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

Abstract

To provide a photosensitive resin composition which enables formation of a resin film that facilitates fine pattern formation with a thick film without discoloration of copper, and is excellent in copper migration resistance, adhesion to a base material and reliability, a photosensitive resin film, a photosensitive dry film, and a pattern formation method using them.SOLUTION: A photosensitive resin composition contains (A) a silicone resin having an acid crosslinkable group, (B) an oxazoline compound or its derivative, and (C) a photoacid generator.SELECTED DRAWING: None

Description

[Technical field]

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

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

[0003] In response to this, a photosensitive silicone composition has been proposed that contains a silicone polymer containing a silphenylene skeleton as a main component (Patent Document 2). The photosensitive silicone composition has improved chemical resistance to photoresist stripping solutions and the like, but further improvements are desired in terms of the level of fineness achieved by pattern formation and copper migration resistance. In addition, discoloration due to copper corrosion has been observed when a pattern is formed on copper using the photosensitive silicone composition, and improvements are also desired in this regard. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2002-88158 A [Patent Document 2] JP 2008-184571 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and can easily form a fine pattern with a thick film without discoloration of copper, and has excellent copper migration resistance and adhesion to a substrate, and is used for protecting electric and electronic components. An object of the present invention is to provide a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method using the same, which can form a resin film (resin layer) excellent in reliability as a film or a film for substrate adhesion.

Means for Solving the Problems

[0006] In order to solve the above problems, in the present invention, (A) A silicone resin having an acid-crosslinkable group, (B) An oxazoline compound or a derivative thereof, and (C) A photoacid generator A photosensitive resin composition characterized by containing the above components is provided.

[0007] With such a photosensitive resin composition of the present invention, it is possible to easily form a fine pattern with a thick film without discoloration of copper, and to have excellent copper migration resistance and adhesion to a substrate, and to form a resin film (resin layer) excellent in reliability as a film for protecting electric and electronic components or a film for substrate adhesion.

[0008] In this case, it is preferable that the (A) silicone resin is represented by the following formula (A1).

Chemical Formula

[0009] Such component (A) can form a good resin film. The resulting resin film has good adhesion to laminates, substrates, and the like, good pattern-forming ability, and good crack resistance and heat resistance.

[0010] Furthermore, the silicone resin (A) preferably contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4). [ka] [In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and 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 1 +a 2 +a 3 <1, 0 1 +b 2 +b 3 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1. 1 is a divalent group represented by the following formula (X1). 2 is a divalent group represented by the following formula (X2). 3 is a divalent group represented by the following formula (X3). 4 is a divalent group represented by the following formula (X4). [ka] ​​ (In the formula, Y 1 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or a fluorene-9,9-diyl group. R 11 and R 12 are each independently a hydrogen atom or a methyl group. R 13 and R 14 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy 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. The dashed line is a bond.)

Chemical formula

Chemical formula

Chemical formula

[0011] Such component (A) can form a better resin film, and by combining the above repeating units, a resin film having desired properties can be formed.

[0012] It is preferable that the composition further contains a crosslinking agent (D).

[0013] In this case, the (D) crosslinking agent is preferably at least one selected from the group consisting of nitrogen-containing compounds containing two or more methylol groups and / or alkoxymethyl groups on average per molecule, selected from melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having two or more methylol groups or alkoxymethyl groups on average per molecule; and epoxy compounds having two or more epoxy groups on average per molecule.

[0014] Such a component (D) can facilitate pattern formation and also further increase the strength of the cured product.

[0015] It is preferable that the composition further contains a solvent (E).

[0016] By including such a component (E), the viscosity of the composition can be suitably adjusted, and workability can be improved.

[0017] The present invention also provides a photosensitive resin film obtained from the above photosensitive resin composition.

[0018] The photosensitive resin film of the present invention can be formed into a thick film with fine patterns without discoloring copper, and has excellent copper migration resistance and adhesion to substrates, making it highly reliable as a protective film for electric and electronic components and for bonding substrates.

[0019] The present invention also provides a photosensitive dry film comprising a support film and the above-mentioned photosensitive resin film on the support film.

[0020] The photosensitive dry film of the present invention is solid, and the photosensitive resin film does not contain a solvent, so there is no risk of bubbles caused by the evaporation of the solvent remaining inside the photosensitive resin film and between the photosensitive dry film and the substrate having irregularities. Furthermore, when the photosensitive dry film is adhered to a substrate having irregularities, the photosensitive resin film conforms to the irregularities and covers the substrate, achieving high flatness. In particular, the photosensitive resin film has low viscoelasticity, so that a higher flatness can be achieved.

[0021] The present invention also relates to a method for producing a photosensitive resin film on a substrate using the photosensitive resin composition, (ii) exposing the photosensitive resin film to light; and (iii) A method for forming a pattern, comprising the step of developing the exposed photosensitive resin film with a developer to form a pattern.

[0022] The present invention also relates to a method for manufacturing a photosensitive dry film, comprising the steps of: (i') forming a photosensitive resin film on a substrate using the photosensitive dry film; (ii) exposing the photosensitive resin film to light; and (iii) A method for forming a pattern, comprising the step of developing the exposed photosensitive resin film with a developer to form a pattern.

[0023] The pattern formation method of the present invention can easily form a fine pattern in a thick film without discoloring the copper, and can efficiently form a resin film that is highly reliable as a film for protecting electric and electronic components, a film for bonding substrates, etc.

[0024] In the present invention, it is preferable to further include a step (iv) of post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

[0025] This makes it possible to increase the crosslink density of the photosensitive resin composition and remove remaining volatile components, and is preferable from the standpoints of adhesion to the substrate, heat resistance and strength, electrical properties, and adhesive strength.

[0026] In the present invention, the photosensitive resin composition is preferably a material for a film for protecting electric / electronic parts, and is also preferably a material for a film for bonding substrates to bond two substrates together.

[0027] The photosensitive resin composition of the present invention is useful as such a material. Effect of the Invention

[0028] The photosensitive resin composition of the present invention can form a film in a wide range of thickness, and furthermore, by the pattern forming method described below, it is possible to form a thick, fine and perpendicular pattern without discoloration of copper. The film obtained by using the photosensitive resin composition and photosensitive dry film of the present invention is excellent in adhesion to substrates, electronic components, semiconductor elements, etc., particularly substrates used for circuit boards, mechanical properties, electrical insulation, copper migration resistance, and chemical resistance. In addition, the film has high reliability as an insulating protective film, and can be suitably used as a film forming material for protecting various electric and electronic components such as circuit boards, semiconductor elements, and display elements, and as a film forming material for bonding substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above-mentioned object, and as a result have found that the above-mentioned object can be achieved by a photosensitive resin composition comprising (A) a silicone resin having an acid crosslinkable group, (B) an oxazoline compound or a derivative thereof, and (C) a photoacid generator, and have thus completed the present invention.

[0030] That is, the present invention provides: (A) a silicone resin having an acid crosslinkable group, (B) an oxazoline compound or a derivative thereof, and (C) Photoacid generator The photosensitive resin composition is characterized by comprising:

[0031] The photosensitive resin composition of the present invention can easily form a thick, fine pattern without discoloring copper, and can form a resin film (resin layer) that is excellent in various film properties such as copper migration resistance and adhesion to substrates used in substrates, electronic components, semiconductor elements, etc., particularly circuit boards, and is highly reliable as a protective film for electric / electronic components, a film for bonding substrates, etc. This photosensitive resin composition can provide a photosensitive resin film and a photosensitive dry film, and a pattern forming method using these can be provided.

[0032] The present invention will be described in detail below, but the present invention is not limited thereto.

[0033] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a silicone resin having an acid crosslinkable group, (B) an oxazoline compound, and (C) a photoacid generator, and may further contain other components, such as (D) a crosslinking agent, (E) a solvent, and other additives, as necessary. Each component will be described below.

[0034] [(A) Silicone resin having an acid crosslinkable group] (A) The silicone resin contains an acid crosslinkable group in the molecule. Here, the acid crosslinkable group means a group in which functional groups can be chemically bonded directly or via a crosslinking agent by the action of an acid. As the acid crosslinkable group, an epoxy group and a phenolic hydroxy group are preferable. The epoxy group and the phenolic hydroxy group may contain only one of them, or may contain both of them.

[0035] As the silicone resin having the acid crosslinkable group, those represented by the following formula (A1) are preferable.

Chemical formula

[0036] In formula (A1), R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms, preferably those having 1 to 6 carbon atoms. k is an integer of 1 to 600, preferably an integer of 1 to 400, and more preferably an integer of 1 to 200. a and b represent the composition ratio (molar ratio) of each repeating unit, and are numbers satisfying 0 < a < 1, 0 < b < 1, and a + b = 1. X is a divalent organic group containing an epoxy group and / or a phenolic hydroxy group.

[0037] The hydrocarbyl group may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, hexyl group, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclohexyl group; aryl groups such as phenyl group, etc. Among these, the methyl group and the phenyl group are preferable due to the ease of obtaining raw materials.

[0038] As the silicone resin represented by formula (A1), those containing the 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) are particularly preferable.

Chemical formula

[0039] In formulas (a1) and (b1), X 1 is a divalent group represented by the following formula (X1). [ka] (In the formula, the dashed lines represent bonds.)

[0040] In formula (X1), Y 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11 and R 12 R is each independently a hydrogen atom or a methyl group. 13 and R 14 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer of 0 to 7. 1 and q 2 are each independently an integer of 0 to 2.

[0041] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclopropyl and cyclobutyl. The saturated hydrocarbyloxy group may be linear, branched, or cyclic, and specific examples thereof include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and structural isomers thereof; cyclic saturated hydrocarbyloxy groups such as cyclopropyloxy and cyclobutyloxy.

[0042] In formulas (a2) and (b2), X 2 is a divalent group represented by the following formula (X2). [ka] (In the formula, the dashed lines represent bonds.)

[0043] In formula (X2), Y 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 21 and R 22 R is each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer of 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. The saturated hydrocarbyl group and the saturated hydrocarbyloxy group include R 13 and R 14 Examples of the examples are similar to those given in the description of .

[0044] In formulas (a3) ​​and (b3), X 3 is a divalent group represented by the following formula (X3). [ka] (In the formula, the dashed lines represent bonds.)

[0045] In formula (X3), R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer of 0 to 7.

[0046] In formulas (a4) and (b4), X 4 is a divalent group represented by the following formula (X4). [ka] (In the formula, the dashed lines represent bonds.)

[0047] In formula (X4), R 41 and R 42 R is each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. 1 and u 2 are each independently an integer of 0 to 7. v is an integer of 0 to 600, preferably an integer of 0 to 400, and more preferably an integer of 0 to 200. As the hydrocarbyl group, R 1 ~R 4 Examples of the examples are similar to those given in the description of .

[0048] The silicone resin of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, and more preferably 5,000 to 200,000. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0049] In the formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and 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 1 +a 2 +a 3 <1, 0 1 +b 2 +b 3 <1 and a 1 +a 2 +a 3 +a 4 +b​​1 +b 2 +b 3 +b 4 = 1, but 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 = 1 is more preferable, and 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 It is more preferable that the number satisfies =1. Furthermore, from the viewpoint of reaction, 0 2 <1, and 0.2≦b 2 ≦0.95, and more preferably 0.3≦b 2 ​It is even more preferable that it is ≦0.9.

[0050] The repeating units may be bonded randomly or as a block polymer. When there are two or more siloxane units in each repeating unit, the siloxane units may all be the same or may contain two or more different types of siloxane units. When there are two or more different types of siloxane units, the siloxane units may be bonded randomly or may contain a plurality of blocks of the same type of siloxane units. In the silicone resin, the silicone (siloxane unit) content is preferably 30 to 80% by mass.

[0051] The silicone resin of component (A) functions to provide film-forming ability, and the resulting resin film has good adhesion to laminates and substrates, good pattern-forming ability, crack resistance, and heat resistance.

[0052] The silicone resin of the component (A) may use one type alone, or two or more types in combination.

[0053] [(A) Method for producing silicone resin] The silicone resin of component (A) can be produced by hydrosilylation reaction using an organosilicon compound having an acid crosslinking group as a raw material. The organosilicon compound as the raw material may be appropriately selected according to the silicone resin having an acid crosslinking group of interest. When component (A) is a silicone resin represented by formula (A1), for example, it can be produced by addition polymerization of a compound represented by the following formula (1), a compound represented by the following formula (2), at least one selected from a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5), and, if necessary, a compound represented by the following formula (6) in the presence of a metal catalyst. [ka] (In the formula, R 1 ~R 4 and k are the same as above.)

[0054] [ka] (In the formula, R 11 ~R 14 , R 21 ~R 24 , R 31 , R 32 , R 41 ~R 44 , Y 1 , Y 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 above.)

[0055] The metal catalyst includes platinum group metals such as platinum (including platinum black), rhodium, and palladium; 2 PtCl 4 xH 2 O, H 2 PtCl 6 xH 2 O, NaHPtCl 6 xH 2 O, KHPtCl 6 xH 2 O, Na 2 PtCl 6 xH 2 OK 2 PtCl 4 xH 2 O, PtCl 4 xH 2 O, PtCl 2 , Na 2 PtCl 4 xH 20 (wherein x is preferably an integer of 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, as described in U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, as described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinic acid salts with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes); and the like can be used.

[0056] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 parts by mass, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the total of the raw material compounds.

[0057] In the addition polymerization reaction, a solvent may be used as necessary. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferable.

[0058] The polymerization temperature is preferably 40 to 150°C, more preferably 60 to 120°C, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time. The polymerization time varies depending on the type and amount of the resin to be obtained, but is preferably about 0.5 to 100 hours, more preferably 0.5 to 30 hours, in order to prevent the intrusion of moisture into the polymerization system. After the reaction is completed, if a solvent is used, it can be distilled off to obtain the silicone resin of component (A).

[0059] The reaction method is not particularly limited, but for example, in the case of reacting a compound represented by formula (1), a compound represented by formula (2), at least one selected from a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5), and optionally a compound represented by formula (6), a method can be mentioned in which first, at least one selected from a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5), and optionally a compound represented by formula (6) are mixed and heated, a metal catalyst is added to the mixture, and then the compound represented by formula (1) and the compound represented by formula (2) are dropwise added over 0.1 to 5 hours.

[0060] The compounds are preferably blended such that the molar ratio of the total of the hydrosilyl groups contained in the compound represented by formula (1) and the compound represented by formula (2) to the total of the alkenyl groups contained in at least one selected from the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5), and optionally the compound represented by formula (6), is preferably 0.67 to 1.67, more preferably 0.83 to 1.25.

[0061] The Mw of the resulting resin can be controlled by using a monoallyl compound such as o-allylphenol or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight regulator.

[0062] [(B) Oxazoline compound or its derivative] The oxazoline compound of the component (B) is a compound having a structure represented by the following formula (B1). [ka]

[0063] The oxazoline compound is not particularly limited, and commercially available products can be used. Specifically, 2-amino-2-oxazoline, 2,2'-(1,3-phenylene)bis(2-oxazoline), 2,2'-(1,4-phenylene)bis(2-oxazoline), 2,2'-(2,6-pyridinediyl)bis(4-isopropyl-2-oxazoline), 2,2'-(4,6-m-xylylenediyl)bis(4-isopropyl-2-oxazoline), 2,2'-bis(2-oxazoline), 2,2'-(2,6-pyridinediyl)bis(4-phenyl-2-oxazoline), 4-tert-butyl-2-(2-pyridyl)oxazoline, 2-phenyl 2,2'-isopropylidenebis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis(4-isopropyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2-isopropyl-2-oxazoline, 2-methyl-2-oxazoline, 2,2'-(diethylmethylene)bis(4-benzyl-2-oxazoline), 5-phenylbenzoxazole-2-thiol, 2-propyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, and the like. Among these, 2,2'-(1,3-phenylene)bis(2-oxazoline), 2,2'-(1,4-phenylene)bis(2-oxazoline, 2,2'-bis(2-oxazoline), 4,4-dimethyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-methyl-2-oxazoline, 2-propyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, 4-tert-butyl-2-(2-pyridyl)oxazoline, and 2,2'-isopropylidenebis(4-phenyl-2-oxazoline) are preferred.

[0064] By adding an oxazoline compound or a derivative thereof, a clear contrast of the amount of acid generated by the photoacid generator is provided between the exposed and unexposed parts, improving the resolution, suppressing the change in sensitivity after exposure, reducing the substrate dependency or environmental dependency, and improving the exposure margin and pattern shape. In addition, a pattern can be formed without discoloration of copper. In addition, a good catalytic effect is exhibited during post-curing, and a cured film excellent in reliability and migration resistance can be obtained.

[0065] Without being bound by any particular theory, it is speculated that such an effect is brought about by the fact that the oxazoline compound or a derivative thereof of component (B) has both basicity that can appropriately control the migration of generated acid and can also exhibit a catalytic effect that increases the reactivity of the acid crosslinking group upon heating, and coordination ability that can suppress copper migration.

[0066] When the acid crosslinkable group is an epoxy group, it is possible to incorporate basic compounds or their salts, such as quaternary ammonium salts, tertiary amines and their salts, and imidazole-based compounds, which are known as curing agents or curing assistants for epoxy resins, into the composition from the viewpoint of improving curing properties. On the other hand, depending on the basicity (strength), the acid generated from the photoacid generator may be neutralized, decreasing the reactivity of the acid crosslinkable group. In addition, as nitrogen-containing heterocyclic compounds capable of suppressing the migration of copper ions, compounds having one nitrogen atom in a nitrogen-containing heterocyclic ring such as piperidine and pyridine; compounds having two nitrogen atoms in a nitrogen-containing heterocyclic ring such as imidazole, pyrazole, pyrazoline, pyrazolidine, pyrimidine, and pyridazine; compounds having three nitrogen atoms in a nitrogen-containing heterocyclic ring such as 1,2,3-triazole, 1,2,4-triazole, and triazine; and compounds having four nitrogen atoms in a nitrogen-containing heterocyclic ring such as 1H-tetrazole are known (JP Patent Publication 2012-181281). These nitrogen-containing heterocyclic compounds also have corresponding base strengths. However, a composition that does not contain component (B) combined with a silicone resin having an acid crosslinkable group is inferior in the ultimate resolution and shape in pattern formation, cannot suppress copper migration and discoloration, and the resulting pattern has poor reliability, adhesiveness, and solvent resistance. In particular, although a diaminotriazine compound having an imidazole ring used as a curing agent or curing accelerator for an epoxy resin is known to suppress copper discoloration (see Japanese Patent Laid-Open No. 7-033766), even when such a compound is blended, copper discoloration cannot be suppressed, and the properties of the formed pattern are also inferior. Thus, the present invention can exhibit excellent effects that cannot be predicted from the prior art by combining (A) a silicone resin having an acid crosslinkable group and (B) an oxazoline compound or a derivative thereof.

[0067] Also, although it is known that a compound having an oxazoline skeleton can react with a carboxyl group in a polymer and be crosslinkable (see Japanese Patent Laid-Open No. 2009-003369), in the present invention, even if component (A) and other components do not contain a carboxyl group in their structures, the above excellent effects can be exhibited.

[0068] The content of component (B) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 3 parts by mass, per 100 parts by mass of component (A). If the content of component (B) is 0.01 part by mass or more, sufficient effects can be obtained, and if it is 10 parts by mass or less, the compatibility with component (A) is good, and there is no risk of problems such as a decrease in transparency, which is preferable. Component (B) can be used alone or in combination of two or more.

[0069] [(C) Photoacid generator] The photoacid generator of component (C) is not particularly limited as long as it decomposes upon light irradiation to generate an acid, but those that decompose upon light having a wavelength of 190 to 500 nm and generate an acid are preferable. The photoacid generator serves as a curing catalyst. Since the photosensitive resin composition of the present invention has excellent compatibility with the photoacid generator, a wide range of photoacid generators can be used.

[0070] Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, and iminosulfonate derivatives.

[0071] Examples of the onium salt include a sulfonium salt represented by the following formula (C1) and an iodonium salt represented by the following formula (C2). [ka]

[0072] In formulas (C1) and (C2), R 101 ~R 105 are each independently a saturated hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. - is a non-nucleophilic counterion.

[0073] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and structural isomers thereof; and cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. The aryl group includes phenyl, naphthyl, and biphenylyl. The aralkyl group includes benzyl and phenethyl.

[0074] Examples of the substituent include an oxo group, a saturated hydrocarbyl group having 1 to 12 carbon atoms, a saturated hydrocarbyloxy group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an arylthio group having 6 to 24 carbon atoms. The hydrocarbyl group and the hydrocarbyl moiety of the saturated hydrocarbyloxy group may be linear, branched, or cyclic, and specific examples thereof include R 101 ~R 105 Examples of the saturated hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0075] R 101 ~R 105 Preferred examples of the aryl group include saturated hydrocarbyl groups which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, or a 2-oxocyclohexyl group; aryl groups which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, a 2-, 3-, or 4-methoxyphenyl group, a 2-, 3-, or 4-ethoxyphenyl group, a 3- or 4-tert-butoxyphenyl group, a 2-, 3-, or 4-methylphenyl group, a 2-, 3-, or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, or a biphenylylthiophenyl group; and aralkyl groups which may have a substituent such as a benzyl group or a phenethyl group. Of these, aryl groups which may have a substituent and aralkyl groups which may have a substituent are more preferred.

[0076] Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ion; borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion; and phosphate ions such as hexafluorophosphate ion and tris(pentafluoroethyl)trifluorophosphate ion.

[0077] The diazomethane derivative includes a compound represented by the following formula (C3). [ka]

[0078] In formula (C3), R 111 and R 112 each independently represents a saturated hydrocarbyl group having 1 to 12 carbon atoms, a halogenated saturated hydrocarbyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0079] The saturated hydrocarbyl group may be linear, branched, or cyclic. Specific examples thereof include R 101 ~R 105 Examples of the halogenated saturated hydrocarbyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like.

[0080] Examples of the aryl group which may have a substituent include a phenyl group, an alkoxyphenyl group such as a 2-, 3- or 4-methoxyphenyl group, a 2-, 3- or 4-ethoxyphenyl group, or a 3- or 4-tert-butoxyphenyl group, an alkylphenyl group such as a 2-, 3- or 4-methylphenyl group, a 2-, 3- or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group, and an aryl halide group such as a fluorophenyl group, a chlorophenyl group, or a 1,2,3,4,5-pentafluorophenyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, etc.

[0081] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)trifluoromethanesulfonate, p-Toluenesulfonate, (p-tert-butoxyphenyl)phenylsulfonium, trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenyl butanesulfonate Sulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate Cyclohexylphenylsulfonium, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate,Examples of the borate include tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0082] Specific examples of the diazomethane derivative include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis( tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

[0083] Specific examples of the glyoxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis- Examples of the dimethylglyoxime include o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0084] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like.

[0085] Specific examples of the disulfone derivative include diphenyl disulfone and dicyclohexyl disulfone.

[0086] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0087] Specific examples of the sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0088] Specific examples of the imide-yl sulfonate derivative include phthalimide-yl triflate, phthalimide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl triflate, 5-norbornene-2,3-dicarboximide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0089] Specific examples of the oxime sulfonate derivative include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile, α-(p-tolylsulfonium oxyimino)-p-methoxyphenylacetonitrile, and the like.

[0090] Specific examples of the iminosulfonate derivative include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, and the like.

[0091] Also suitable for use are 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like.

[0092] From the viewpoint of photocurability, the content of the (C) component 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 the (A) component. If the content of the (C) component is 0.05 parts by mass or more, sufficient acid is generated to sufficiently proceed with the crosslinking reaction, and if the content is 20 parts by mass or less, an increase in the absorbance of the photoacid generator itself can be suppressed, and there is no risk of problems such as a decrease in transparency, which is preferable. The (C) component may be used alone or in combination of two or more types.

[0093] [(D) Crosslinking agent] The photosensitive resin composition of the present invention preferably further contains a crosslinking agent as component (D). The crosslinking agent has the function of reacting with the acid crosslinking group in component (A) and other crosslinking groups, if any, to increase the degree of crosslinking of the cured product. For example, when the above-mentioned component (A) contains a phenolic hydroxy group or R 13 , R 14 , R 23 or R 24 When the component (A) has a saturated hydrocarbyloxy group represented by the formula (A1), it undergoes a condensation reaction with the saturated hydrocarbyloxy group represented by the formula (A2), and serves as a component that facilitates pattern formation and further increases the strength of the cured product. From this viewpoint, it is preferable to combine the (D) crosslinking agent with a silicone resin having an acid crosslinkable group represented by the formula (A1).

[0094] Preferred examples of the crosslinking agent include melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds containing, on average, two or more methylol groups and / or alkoxymethyl groups per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having, on average, two or more methylol groups or alkoxymethyl groups per molecule; and epoxy compounds having, on average, two or more epoxy groups per molecule.

[0095] The melamine compound may be one represented by the following formula (D1). [ka]

[0096] In formula (D1), R 201 ~R 206 are each independently a methylol group, a saturated hydrocarbyloxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, and at least one of them is a methylol group or a saturated hydrocarbyloxymethyl group. Examples of the saturated hydrocarbyloxymethyl group include alkoxymethyl groups such as a methoxymethyl group and an ethoxymethyl group.

[0097] Examples of the melamine compound represented by the formula (D1) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.

[0098] The melamine compound represented by formula (D1) can be obtained, for example, by first modifying a melamine monomer with formaldehyde by methylolation according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol, preferably a lower alcohol, for example an alcohol having 1 to 4 carbon atoms.

[0099] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0100] Examples of the glycoluril compound include tetramethylol glycoluril and tetrakis(methoxymethyl) glycoluril.

[0101] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0102] 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.

[0103] The modified melamine condensate may be obtained by addition condensation polymerization of a compound represented by formula (D1) or a multimer thereof (e.g., an oligomer such as a dimer or trimer) with formaldehyde until a desired molecular weight is reached. As the addition condensation polymerization method, a conventionally known method may be adopted. The modified melamine represented by formula (D1) may be used alone or in combination of two or more.

[0104] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0105] The modified urea condensate can be obtained, for example, by modifying a urea condensate having a desired molecular weight with formaldehyde by methylolation according to a known method, or by further modifying the urea condensate by alkoxylation with an alcohol.

[0106] Examples of the phenol compound having two or more methylol groups or alkoxymethyl groups on average per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and the like.

[0107] Examples of the epoxy compound having two or more epoxy groups on average per molecule include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, triphenol alkane type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene-modified phenol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene ring-containing epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic type epoxy resins.

[0108] When the (D) component is contained, its content is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the (A) component. If it is 0.5 parts by mass or more, sufficient curability can be obtained upon light irradiation, and if it is 50 parts by mass or less, the proportion of the (A) component in the photosensitive resin composition does not decrease, so that a sufficient effect can be exerted in the cured product. The (D) component may be used alone or in a mixture of two or more types.

[0109] [(E) Solvent] The photosensitive resin composition of the present invention may further contain a solvent as component (E). The solvent is not particularly limited as long as it is capable of dissolving components (A) to (D) and various additives described below, but organic solvents are preferred because they have excellent solubility in these components.

[0110] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. In particular, ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof, which have the best solubility for the photoacid generator, are preferred.

[0111] From the viewpoints of compatibility and viscosity of the photosensitive resin composition, the amount of the component (E) used is preferably 50 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and particularly preferably 50 to 100 parts by mass, per 100 parts by mass of the component (A). The component (E) may be used alone or in combination of two or more kinds.

[0112] [Other additives] The photosensitive resin composition of the present invention may contain other additives in addition to the above-mentioned components. Examples of the other additives include surfactants commonly used to improve coatability.

[0113] The surfactant is preferably a nonionic one, and examples thereof include fluorine-based surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, fluorine-containing organosiloxane compounds, etc. Commercially available surfactants can be used, and examples thereof include Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141, S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne (registered trademark) DS-401, DS-4031, DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant is preferably 0.05 to 1 part by mass relative to 100 parts by mass of component (A).

[0114] The photosensitive resin composition of the present invention may contain a silane coupling agent as another additive. By containing a silane coupling agent, the adhesion of the coating obtained from the composition to the adherend can be further improved. Examples of the silane coupling agent include an epoxy group-containing silane coupling agent and an aromatic group-containing aminosilane coupling agent. These can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited, but when contained, it is preferably 0.01 to 5 mass% in the photosensitive resin composition of the present invention.

[0115] The photosensitive resin composition of the present invention can be prepared by a conventional method, for example, by mixing the above-mentioned components with stirring, and then filtering the mixture with a filter or the like to remove solids, if necessary.

[0116] The photosensitive resin composition of the present invention thus prepared is suitably used, for example, as a protective film for semiconductor elements, a protective film for wiring, a coverlay film, a solder mask, a material for insulating films for through-hole electrodes (for TSV), and further as an adhesive between laminated substrates in three-dimensional stacking.

[0117] [Pattern formation method using photosensitive resin composition] The pattern forming method using the photosensitive resin composition of the present invention comprises the steps of: (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. It includes.

[0118] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, silicon wafers for through-hole electrodes, silicon wafers thinned by backside polishing, plastic or ceramic substrates, and substrates having metals such as Ni and Au on the entire surface or part of the substrate by ion sputtering or plating. Substrates having irregularities may also be used.

[0119] The photosensitive resin film may be formed, for example, by applying the photosensitive resin composition onto a substrate and pre-heating (pre-baking) as necessary. The application method may be a known method, such as a dip method, a spin coating method, or a roll coating method. The amount of the photosensitive resin composition applied may be appropriately selected depending on the purpose, but it is preferable to apply the composition so that the thickness of the resulting photosensitive resin film is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0120] In order to improve the film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent and the amount of the dropped solvent can be appropriately selected depending on the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as PGME, etc. are preferable, but it is also possible to use a solvent used in the photosensitive resin composition.

[0121] Here, in order to efficiently carry out the photocuring reaction, pre-baking may be carried out as necessary to evaporate the solvent etc. Pre-baking can be carried out, for example, at 40 to 140° C. for about 1 minute to 1 hour.

[0122] Next, (ii) the photosensitive resin film is exposed to light. In this case, the exposure is preferably performed with light having a wavelength of 10 to 600 nm, and more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such wavelengths include light of various wavelengths generated by a radiation generator, such as ultraviolet rays such as g-rays, h-rays, and i-rays, and far ultraviolet rays (248 nm, 193 nm). Of these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is 10 to 10,000 mJ / cm. 2 is preferred.

[0123] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out. The material of the photomask is not particularly limited, but is preferably one that blocks light of the wavelengths. For example, a photomask having a light-shielding film made of chromium or the like is preferably used.

[0124] Furthermore, in order to enhance the development sensitivity, a post-exposure bake (PEB) may be performed. The PEB is preferably performed at 40 to 150° C. for 0.5 to 10 minutes. The exposed portion is crosslinked by the PEB to form an insolubilized pattern that is insoluble in an organic solvent, which is a developer.

[0125] After exposure or PEB, (iii) the photosensitive resin film is developed with a developer to form a pattern. As the developer, for example, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as PGME are preferred, but it is also possible to use a solvent used in the photosensitive resin composition. As a development method, a normal method, for example, a method of immersing a substrate on which a pattern has been formed in the developer, can be mentioned. The non-exposed portion is dissolved and removed by organic solvent development to form a pattern. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a resin film having a desired pattern.

[0126] Furthermore, (iv) the film on which the pattern is formed may be post-cured using an oven or a hot plate, preferably at 100 to 250°C, more preferably at 130 to 220°C. If the post-curing temperature is 100 to 250°C, the crosslink density of the photosensitive resin composition can be increased and the remaining volatile components can be removed, which is preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, electrical properties, and adhesive strength. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. If the photosensitive resin composition of the present invention is used, a film having excellent various film properties can be obtained even if the post-curing is performed at a relatively low temperature of 200°C or less. The film thickness of the film (cured film) after post-curing is usually 1 to 200 μm, preferably 5 to 50 μm.

[0127] When it is not necessary to form a pattern, for example when it is desired to simply form a uniform film, in step (ii) of the pattern formation method, the film can be formed by exposing the film to light of an appropriate wavelength without using the photomask.

[0128] [Board bonding method] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. An example of a method for bonding substrates is a method in which a substrate on which a film is formed using the photosensitive resin composition of the present invention is bonded to a second substrate under suitable conditions of heat and pressure so that an adhesive bond is formed between the two substrates. Either or both of the substrate on which the film is formed and the second substrate may be chipped by dicing or the like. As bonding conditions, a heating temperature of 50 to 200°C and a time of 1 to 60 minutes are preferred. A wafer bonder device may be used as a bonding device to bond wafers together under reduced pressure while applying a load, or chip-wafer or chip-chip bonding may be performed using a flip chip bonder device. The adhesive layer formed between the substrates has a higher bonding strength by a post-curing treatment described later, resulting in permanent adhesion.

[0129] The substrates that have been attached (bonded) are post-cured under the same conditions as in step (iv) described above, thereby increasing the crosslink density of the coating and increasing the substrate adhesive strength. A crosslinking reaction occurs due to heating during bonding, but the crosslinking reaction does not cause a side reaction accompanied by degassing, so that bonding defects (voids) are not induced, particularly when used as a substrate adhesive.

[0130] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin coating obtained from the photosensitive resin composition on the support film.

[0131] The photosensitive dry film (support film and photosensitive resin film) is solid, and since the photosensitive resin film does not contain a solvent, there is no risk of air bubbles caused by the evaporation of the solvent remaining inside the photosensitive resin film or between the photosensitive resin film and the uneven substrate.

[0132] The thickness of the photosensitive resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm, from the viewpoints of flatness on an uneven substrate, step coverage, and substrate lamination spacing.

[0133] In addition, the viscosity and fluidity of the photosensitive resin film are closely related, and the photosensitive resin film can exhibit appropriate fluidity in an appropriate viscosity range, and can penetrate deep into narrow gaps and strengthen adhesion to the substrate by softening the resin. Therefore, from the viewpoint of fluidity, the viscosity of the photosensitive resin film is preferably 10 to 5000 Pa·s, more preferably 30 to 2000 Pa·s, and even more preferably 50 to 300 Pa·s at 80 to 120°C. In the present invention, the viscosity is a value measured using a rotational viscometer.

[0134] When the photosensitive dry film of the present invention is adhered to a substrate having irregularities, the photosensitive resin film conforms to the irregularities and covers the substrate, achieving high flatness. In particular, the photosensitive resin film has low viscoelasticity, achieving higher flatness. Furthermore, when the photosensitive resin film is adhered to the substrate in a vacuum environment, the occurrence of gaps between the substrate and the photosensitive resin film can be more effectively prevented.

[0135] The photosensitive dry film of the present invention can be produced by applying the photosensitive resin composition onto a support film and drying it to form a photosensitive resin film. As a production device for the photosensitive dry film, a film coater for producing a pressure-sensitive adhesive product can be used. Examples of the film coater include a comma coater, a comma reverse coater, a multi-coater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three-bottom reverse coater, and a four-bottom reverse coater.

[0136] When the support film is unwound from the unwinding shaft of the film coater and passed through the coater head of the film coater, the photosensitive resin composition is applied to the support film in a predetermined thickness, and then the film is passed through a hot air circulating oven at a predetermined temperature and time, and dried on the support film to form a photosensitive resin film, thereby producing a photosensitive dry film. In addition, if necessary, the photosensitive dry film is passed through a laminating roll at a predetermined pressure together with a protective film unwound from another unwinding shaft of the film coater to bond the photosensitive resin film on the support film to the protective film, and then the film is wound up on the winding shaft of the film coater to produce a photosensitive dry film with a protective film. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0137] The support film may be a single-layer film made of a single film, or a multi-layer film made of a plurality of laminated films. Examples of the material of the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate is preferred because it has appropriate flexibility, mechanical strength, and heat resistance. These films may be subjected to various treatments such as corona treatment and release agent coating. Commercially available products may be used, such as Therapeel WZ (RX), Therapeel BX8 (R) (all manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (all manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (all manufactured by Teijin DuPont Films Co., Ltd.), PET38×1-A3, PET38×1-V8, and PET38×1-X08 (all manufactured by Nippa Corporation).

[0138] The protective film may be the same as the support film described above, but polyethylene terephthalate and polyethylene are preferred because they have appropriate flexibility. Commercially available products may be used, and examples of polyethylene terephthalate include those already exemplified, and examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE film type 0 (manufactured by Nippa Co., Ltd.).

[0139] The thickness of each of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoints of stability in the production of the photosensitive dry film and prevention of curling, ie, winding tendency around the core.

[0140] [Patterning method using photosensitive dry film] The pattern forming method using the photosensitive dry film of the present invention includes the steps of: (i') forming a photosensitive resin film on a substrate using the photosensitive dry film of the present invention; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. It includes.

[0141] First, in step (i'), a photosensitive resin film is formed on a substrate using a photosensitive dry film. Specifically, the photosensitive resin film of the photosensitive dry film is attached to the substrate to form the photosensitive resin film on the substrate. In addition, when the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film, and then the photosensitive resin film of the photosensitive dry film is attached to the substrate. The attachment can be performed, for example, using a film attachment device.

[0142] The substrate may be the same as that described in the pattern forming method using a photosensitive resin composition. The film laminating device is preferably a vacuum laminator. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is adhered to the substrate on a table at a predetermined temperature in a vacuum chamber at a predetermined vacuum degree using a laminating roll at a predetermined pressure. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum degree is preferably 50 to 500 Pa.

[0143] In order to obtain a photosensitive resin film of the required thickness, the film may be laminated multiple times as necessary. The number of laminations is, for example, about 1 to 10 times, which can obtain a photosensitive resin film with a thickness of 10 to 1000 μm, particularly about 100 to 500 μm.

[0144] In order to efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as necessary. Pre-baking can be performed, for example, at 40 to 140° C. for about 1 minute to 1 hour.

[0145] As in the case of the pattern forming method using the photosensitive resin composition, the photosensitive resin film attached to the substrate can be patterned by (ii) exposing the photosensitive resin film to light, (iii) developing the exposed photosensitive resin film with a developer to form a pattern, and (iv) performing a post-curing treatment as necessary. Note that the support film of the photosensitive dry film is peeled off before pre-baking or PEB, or removed by other methods depending on the process.

[0146] The photosensitive resin composition of the present invention can be a material for a film for protecting electric / electronic parts, or a material for a film for bonding substrates for bonding two substrates together.

[0147] The film obtained from the photosensitive resin composition has excellent mechanical properties such as solder resistance, heat resistance, low substrate warpage, and crack resistance, copper migration resistance, and adhesion to substrates, and is suitably used as a protective film for electric / electronic parts such as semiconductor elements and a film for bonding substrates. These films can also be formed using the photosensitive dry film of the present invention.

[0148] As described above, the present invention can provide a photosensitive resin composition that can easily form a fine pattern in a thick film without discoloring copper, and that can form a resin film (resin layer) that is excellent in various film properties such as copper migration resistance and adhesion to substrates used for substrates such as boards, electronic components, and semiconductor elements, particularly circuit boards, and that is highly reliable as a film for protecting electric / electronic components or a film for bonding boards, etc.; and further, the present invention can provide a photosensitive resin film and a photosensitive dry film formed using the photosensitive resin composition, and a pattern forming method using these. EXAMPLES

[0149] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. The weight average molecular weight (Mw) was measured by GPC using a TSKgel Super HZM-H (manufactured by Tosoh Corporation) column under analysis conditions of a flow rate of 0.6 mL / min, an elution solvent of THF, and a column temperature of 40° C., with monodisperse polystyrene as the standard.

[0150] The compounds (S-1) to (S-6) used in the synthesis examples are shown below. [ka]

[0151] [1] Synthesis of silicone resin [Synthesis Example 1] Into a 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser, 215.0 g (0.5 mol) of compound (S-6) was added, followed by 2000 g of toluene, 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 67.9 g (0.35 mol) of compound (S-4) and compound (S-5) (y 1 453.0 g (0.15 mol) of dimethylformamide (H2O4, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups=1 / 1 (molar ratio)). After completion of the addition, the mixture was heated to 100° C. and aged for 6 hours, after which toluene was removed from the reaction solution by distillation under reduced pressure to obtain Silicone Resin A-1. Silicone Resin A-1 is 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the silicone resin contained repeating units a2 and b2. The Mw of the silicone resin A-1 was 62,000, and the silicone content was 61.6% by mass.

[0152] [Synthesis Example 2] Into a 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser, 53.00 g (0.20 mol) of compound (S-2) and 117.6 g (0.30 mol) of compound (S-1) were added, followed by the addition of 2000 g of toluene and heating to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 48.5 g (0.25 mol) of compound (S-4) and 48.5 g (0.25 mol) of compound (S-5) (y 1 755.0 g (0.25 mol) of dimethylformamide (H2O3=40, Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups=1 / 1 (molar ratio)). After completion of the addition, the mixture was heated to 100° C. and aged for 6 hours, after which toluene was removed from the reaction solution by vacuum distillation to obtain Silicone Resin A-2. Silicone Resin A-2 was prepared by the following procedure: 1 It was confirmed by H-NMR (manufactured by Bruker) that the silicone resin A-2 contained repeating units a1, a3, b1, and b3. The Mw of the silicone resin A-2 was 83,000, and the silicone content was 77.5% by mass.

[0153] [Synthesis Example 3] Into a 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser, 27.9 g (0.15 mol) of compound (S-3), 19.6 g (0.05 mol) of compound (S-1), and 129.0 g (0.30 mol) of compound (S-6) were added, followed by adding 2000 g of toluene and heating to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 87.3 g (0.45 mol) of compound (S-4) and compound (S-5) (y 1 79.3 g (0.05 mol) of dimethylformamide (H2O20, Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups=1 / 1 (molar ratio)). After completion of the addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was removed from the reaction solution by vacuum distillation to obtain Silicone Resin A-3. Silicone Resin A-3 was prepared by the following procedure: 1 It was confirmed by H-NMR (manufactured by Bruker) that the resin contained repeating units a1, a2, a4, b1, b2, and b4. Silicone resin A-3 had an Mw of 24,000 and a silicone content of 31.2% by mass.

[0154] [2] Preparation of photosensitive resin composition [Examples 1 to 8 and Comparative Examples 1 to 16] The components were mixed according to the amounts shown in Tables 1 to 3, and then the mixture was stirred at room temperature to dissolve. The mixture was then microfiltered through a 1.0 μm Teflon (registered trademark) filter to prepare the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 16.

[0155] [Table 1]

[0156] [Table 2]

[0157] [Table 3]

[0158] In Tables 1 to 3, B-1 to B-6 and B'-1 to B'-6 are as follows: Compounds B-1 to B-6 correspond to the component (B) of the present invention, but compounds B'-1 to B'-6 do not. [ka]

[0159] [ka]

[0160] In Tables 1 to 3, the photoacid generators PAG-1 to 3 are as follows. [ka]

[0161] In Tables 1 to 3, the crosslinking agents CL-1 and CL-2 are as follows. [ka]

[0162] In Table 2, Resin A'-1 is as follows: It should be noted that Resin A'-1 does not fall under the category of component (A) of the present invention. [ka]

[0163] [3] Preparation of photosensitive dry film Using a die coater as a film coater and a polyethylene terephthalate film (thickness 38 μm) as a support film, the photosensitive resin compositions listed in Tables 1 to 3 were applied onto the support film. Next, the film was dried by passing through a hot air circulating oven (length 4 m) set at 100° C. for 5 minutes to form a photosensitive resin film on the support film, thereby obtaining a photosensitive dry film. A polyethylene film (thickness 50 μm) was laminated as a protective film from above the photosensitive resin film at a pressure of 1 MPa using a laminating roll to produce a photosensitive dry film with a protective film. The thickness of each photosensitive resin film was 80 μm. The thickness of the photosensitive resin film was measured using an optical interference film thickness measuring instrument (F50-EXR manufactured by Filmetrics Inc.).

[0164] [4] Evaluation of resin coating (1) Pattern formation and its evaluation The photosensitive dry film with the protective film was peeled off, and the degree of vacuum in the vacuum chamber was set to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), and the photosensitive resin film on the support film was adhered to a migration test substrate (a comb-shaped electrode substrate with copper conductive material, conductive part interval and conductive part width of 10 μm, and conductive part thickness of 4 μm). The temperature condition was 100° C. After returning to normal pressure, the substrate was removed from the vacuum laminator and the support film was peeled off. Next, in order to enhance adhesion to the substrate, preheating was performed at 120° C. for 5 minutes using a hot plate. In order to form a line and space pattern and a contact hole pattern on the obtained photosensitive resin film, exposure was performed using a contact aligner type exposure device through a mask under exposure conditions of a wavelength of 365 nm. After exposure, PEB was performed using a hot plate at 140° C. for 5 minutes, followed by cooling, and spray development with PGMEA for 300 seconds to form a pattern.

[0165] The photosensitive resin film on the substrate on which the pattern was formed by the above method was post-cured in an oven at 170°C for 1 hour while purging with nitrogen. Then, the cross sections of the formed 100μm, 80μm, 60μm, and 40μm contact hole patterns were observed with a scanning electron microscope (SEM), and the smallest hole pattern in which the holes penetrated to the bottom of the film was determined as the limiting resolution. Furthermore, the perpendicularity of the 80μm contact hole pattern was evaluated from the obtained cross-sectional photograph, with a perpendicular pattern being rated as ◎, a pattern in which a reverse taper shape or footing was slightly observed being rated as ○, a pattern in which a reverse taper shape or footing was strongly observed being rated as △, and an opening failure being rated as ×. The results are shown in Tables 4 to 6.

[0166] (2) Evaluation of electrical properties (copper migration) The substrate on which the pattern was formed by the method (1) was used as the substrate for copper migration evaluation, and a test was conducted. The copper migration test was conducted under the conditions of a temperature of 130°C, humidity of 100%, and an applied voltage of 20 V, and the time until a short circuit occurred was confirmed up to an upper limit of 1000 hours. The results are shown in Tables 4 to 6.

[0167] (3) Discoloration of copper surface The photosensitive dry film with the protective film described above was peeled off, and the degree of vacuum in the vacuum chamber was set to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), and the photosensitive resin film on the support film was adhered to a substrate on which a 350 nm sputtered copper film was formed. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Next, in order to enhance adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. In order to form a line and space pattern and a contact hole pattern on the obtained photosensitive resin film, exposure was performed using a contact aligner type exposure device through a mask under exposure conditions of a wavelength of 365 nm. After exposure, PEB was performed using a hot plate for 5 minutes at 140°C, followed by cooling, and spray development was performed with PGMEA for 300 seconds to form a hole pattern of 1 cm x 1 cm. Then, post-curing was performed using an oven at 170°C for 1 hour. Thereafter, the copper surface in the hole was visually observed, and those that were not discolored were marked with an O, and those that were discolored were marked with an X. The results are shown in Tables 4 to 6.

[0168] (4) Evaluation of reliability (adhesion, crack resistance) The photosensitive dry film with the protective film described above was peeled off, and the degree of vacuum in the vacuum chamber was set to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), and the photosensitive resin film on the support film was adhered to a CCL substrate on which 10 mm x 10 mm square silicon chips were laminated. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Next, in order to improve adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. The obtained photosensitive resin film was exposed to light using a contact aligner type exposure device without a mask under exposure conditions of a wavelength of 365 nm. After exposure, PEB was performed on a hot plate at 140°C for 5 minutes, followed by cooling, and post-curing in an oven at 170°C for 1 hour while purging with nitrogen. Thereafter, the substrate on which the resin film was formed was cut using a dicing saw (DAD685, manufactured by DISCO, spindle rotation speed 40000 rpm, cutting speed 20 mm / sec) equipped with a dicing blade to obtain test pieces of 20 mm x 20 mm square so that the circumference of the silicon chip was 5 mm. The obtained test pieces (10 pieces each) were subjected to a heat cycle test (1000 cycles of holding at -55 ° C for 10 minutes and holding at 125 ° C for 10 minutes). The peeling state of the resin film from the wafer after the heat cycle test and the presence or absence of cracks were confirmed. Those that did not peel or crack at all were marked with ○, those that peeled at least one were marked with ×, and those that cracked at least one were marked with ×. The presence or absence of peeling and cracks was confirmed by top-down observation with an optical microscope and cross-sectional SEM observation. The results are shown in Tables 4 to 6.

[0169] (5) Evaluation of adhesive strength (initial: before heat resistance test) The photosensitive dry film with the protective film was prepared by peeling off the protective film, setting the degree of vacuum in the vacuum chamber to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), laminating the photosensitive resin film on the support film onto an 8-inch silicon wafer, and preheating for 5 minutes at 120°C using a hot plate to obtain a substrate (wafer) with a resin film. In addition, a separately prepared 8-inch silicon wafer was cut into a size of 2 mm x 2 mm square using a dicing saw (DAD685 manufactured by DISCO Co., Ltd.) equipped with a dicing blade. Five chips with a size of 2 mm x 2 mm square were bonded to the substrate with the resin film at 130°C and a load of 50 mN via the resin film. Thereafter, the resin film was cured by heating at 170°C for 1 hour, and subjected to an adhesion measurement test. Adhesion measurements were performed using a bond tester (Dage series 4000-PXY manufactured by Dage) to measure the resistance force applied when a semiconductor chip (2mm x 2mm) was peeled off from a base substrate (15mm x 15mm square silicon wafer), and the adhesion of the resin film was evaluated. The test conditions were a test speed of 200μm / sec and a test height of 50μm. The results are shown in Tables 4 to 6. The values ​​are the average of the measured values ​​for each of five test pieces, and a higher value indicates a higher adhesive strength.

[0170] (6) Evaluation of adhesive strength (after heat resistance test) The test pieces for measuring adhesive strength prepared in (5) above were left in an oven heated to 150°C for 2000 hours, and then the test pieces were taken out of the oven and subjected to an adhesive strength measurement test in the same manner as in (5). The results are shown in Tables 4 to 6.

[0171] (7) Evaluation of solvent resistance In order to evaluate the solvent resistance to N-methyl-2-pyrrolidone (NMP), which is often used when forming semiconductor elements, etc., a substrate prepared in the same manner as the wafer for adhesive strength evaluation in (5) was immersed in NMP at 50°C for 1 hour, and then the change in film thickness and appearance were investigated to evaluate the solvent resistance. Those that showed no change in appearance or film thickness were marked with an O, and those that showed swelling, etc. were marked with an X. The results are shown in Tables 4 to 6.

[0172] [Table 4]

[0173] [Table 5]

[0174] [Table 6]

[0175] As shown in Table 4, the photosensitive resin compositions of the present invention (Examples 1 to 8) were capable of forming patterns with excellent resolution and shape, and also had good electrical properties (copper migration resistance), no discoloration of the copper surface, and excellent reliability (adhesion, crack resistance), adhesive strength (heat resistance), and solvent resistance. In contrast, as shown in Tables 5 and 6, the compositions of Comparative Examples 1 to 4 and 11 to 16 which do not contain the component (B) of the present invention, and Comparative Examples 5 to 10 which do not contain the component (A) of the present invention, were inferior in limiting resolution and shape in pattern formation, could not suppress copper migration and discoloration, and were inferior in reliability, adhesion, and solvent resistance. In Comparative Examples 11 to 16, B'-1 to B'-6, which are used instead of the component (B) of the present invention, are conventionally used as curing agents or curing assistants for epoxy resins, but as described above, they do not provide satisfactory results. In particular, it is known that diaminotriazine compounds having an imidazole ring, which are used as curing agents or curing accelerators for epoxy resins, can suppress discoloration of copper (see JP-A-7-033766). However, as shown by the results of Comparative Example 14, which contains this compound, B'-4 (2,4-diamino-6-(2'-ethyl-4'-methylimidazolyl)ethyl-1,3,5-triazine), cannot suppress discoloration of copper, and the characteristics of the pattern formed are also poor. Thus, the present invention can exhibit excellent effects that cannot be predicted from the prior art by combining (A) a silicone resin having an acid-crosslinkable group and (B) an oxazoline compound or a derivative thereof.

[0176] From the above results, the photosensitive resin composition and the photosensitive dry film of the present invention can easily form a thick film with fine vertical and fine patterns without discoloration of copper, and exhibited sufficient properties as a photosensitive material. Further, the photosensitive resin film obtained therefrom has high chemical resistance to a photoresist stripper and the like, and also has excellent adhesion, electrical insulation, and copper migration resistance, and high reliability as an insulating protective film, and is suitable for forming a film for protecting various electrical and electronic components such as circuit boards, semiconductor elements, and display elements. According to the present invention, it is possible to provide a more reliable photosensitive resin composition and a photosensitive dry film.

[0177] This specification includes the following aspects. [1]: A photosensitive resin composition comprising (A) a silicone resin having an acid-crosslinkable group, (B) an oxazoline compound or a derivative thereof, and (C) a photoacid generator characterized in that it contains the same. [2]: The photosensitive resin composition according to [1], wherein the (A) silicone resin is represented by the following formula (A1). [Chemical formula] (In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. a and b represent the composition ratio (molar ratio) of each repeating unit, and are numbers satisfying 0 < a < 1, 0 < b < 1, and a + b = 1. X is a divalent organic group containing an epoxy group and / or a phenolic hydroxy group.) [3]: The photosensitive resin composition according to [1] or [2], wherein the (A) silicone resin contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4). [ka] [In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and 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 1 +a 2 +a 3 <1, 0 1 +b 2 +b 3 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1. 1 is a divalent group represented by the following formula (X1). 2 is a divalent group represented by the following formula (X2). 3 is a divalent group represented by the following formula (X3). 4 is a divalent group represented by the following formula (X4). [ka] (In the formula, Y 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11 and R 12 R is each independently a hydrogen atom or a methyl group. 13 and R 14 ​​are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer of 0 to 7. 1 and q 2 are each independently an integer of 0 to 2. The dashed lines represent bonds. [ka] (In the formula, Y 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 21 and R 22 R is each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer of 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. The dashed lines represent bonds. [ka] (In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer of 0 to 7. The dashed lines represent bonds. [ka] (In the formula, R 41 and R 42 R is each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. 1 and u 2are each independently an integer of 0 to 7. v is an integer of 0 to 600. The dashed lines represent bonds. [4]: The photosensitive resin composition according to any one of [1] to [3], further comprising (D) a crosslinking agent. [5]: The photosensitive resin composition according to [4], wherein the (D) crosslinking agent is at least one selected from the group consisting of nitrogen-containing compounds selected from melamine compounds, guanamine compounds, glycoluril compounds and urea compounds containing, on average, two or more methylol groups and / or alkoxymethyl groups in one molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having, on average, two or more methylol groups or alkoxymethyl groups in one molecule, and epoxy compounds having, on average, two or more epoxy groups in one molecule. [6]: The photosensitive resin composition according to any one of [1] to [5], further comprising (E) a solvent. [7]: A photosensitive resin film obtained from any one of the photosensitive resin compositions [1] to [6]. [8]: A photosensitive dry film comprising a support film and the photosensitive resin coating of [7] on the support film. [9]: (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of [1] to [6]; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. A pattern forming method comprising the steps of:

[10] : (i') forming a photosensitive resin film on a substrate using the photosensitive dry film of [8]; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. A pattern forming method comprising the steps of:

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

[12] : The photosensitive resin composition according to any one of [1] to [6], which is a material for a protective film for electric and electronic parts.

[13] : The photosensitive resin composition according to any one of [1] to [6], wherein the photosensitive resin composition is a material for a substrate bonding film for bonding two substrates.

[0178] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. (A) a silicone resin having an acid crosslinkable group, (B) an oxazoline compound or a derivative thereof, and (C) Photoacid generator A photosensitive resin composition comprising:

2. 2. The photosensitive resin composition according to claim 1, wherein the silicone resin (A) is represented by the following formula (A1): 【Chemistry 1】 (In the formula, R １ ~R ４ are each independently a hydrocarbyl 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 are numbers that 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 hydroxy group.

3. The photosensitive resin composition according to claim 2, wherein the silicone resin (A) contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4): 【Chemistry 2】 [In the formula, R １ ~R ４ are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. １ ~a ４ and b １ ~b ４ represents the composition ratio (molar ratio) of each repeating unit, and 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 = 1. １ is a divalent group represented by the following formula (X1): ２ is a divalent group represented by the following formula (X2). ３ is a divalent group represented by the following formula (X3). ４ is a divalent group represented by the following formula (X4). 【Chemistry 3】 (In the formula, Y １ R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. １１ and R １２ are each independently a hydrogen atom or a methyl group. １３ and R １４ are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. １ and p ２ are each independently an integer from 0 to 7. １ and q ２ are each independently an integer of 0 to 2. The dashed lines represent bonds. 【Chemistry 4】 (In the formula, Y ２ R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. ２１ and R ２２ are each independently a hydrogen atom or a methyl group. ２３ and R ２４ are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. １ and r ２ are each independently an integer from 0 to 7. １ and s ２ are each independently an integer of 0 to 2. The dashed lines represent bonds. 【Chemistry 5】 (In the formula, R ３１ and R ３２ are each independently a hydrogen atom or a methyl group. １ and t ２ are each independently an integer from 0 to 7. The dashed lines represent bonds. 【Chemistry 6】 (In the formula, R ４１ and R ４２ R is each independently a hydrogen atom or a methyl group. ４３ and R ４４ are each independently a hydrocarbyl group having 1 to 8 carbon atoms. １ and u ２ are each independently an integer of 0 to 7. v is an integer of 0 to 600. The dashed lines represent bonds.

4. 2. The photosensitive resin composition according to claim 1, further comprising (D) a crosslinking agent.

5. 5. The photosensitive resin composition according to claim 4, wherein the (D) crosslinking agent is at least one selected from the group consisting of nitrogen-containing compounds selected from melamine compounds, guanamine compounds, glycoluril compounds and urea compounds, each containing two or more methylol groups and / or alkoxymethyl groups on average per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having two or more methylol groups or alkoxymethyl groups on average per molecule; and epoxy compounds having two or more epoxy groups on average per molecule.

6. 2. The photosensitive resin composition according to claim 1, further comprising (E) a solvent.

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

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

9. (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 1 to 6; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. A pattern forming method comprising the steps of:

10. (i') forming a photosensitive resin film on a substrate using the photosensitive dry film according to claim 8; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. A pattern forming method comprising the steps of:

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

12. 7. The photosensitive resin composition according to claim 1, which is a material for a protective film for electric / electronic parts.

13. 7. The photosensitive resin composition according to claim 1, which is a material for a substrate bonding film for bonding two substrates.

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