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

Abstract

The invention provides a photosensitive resin composition, a photosensitive resin coating film, a photosensitive dry film, and a pattern forming method using the photosensitive resin composition, the photosensitive resin coating film, and the photosensitive dry film, the photosensitive resin composition can easily form a thick and fine pattern in a state of no copper discoloration. And a resin coating having excellent copper migration resistance, adhesion to a base material, and reliability can be formed. The photosensitive resin composition is characterized by comprising (A) a silicone resin having an acid-crosslinkable group, (B) an oxazoline compound or a derivative thereof, and (C) a photoacid generator.

Description

Technical Field

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

[0002] Conventionally, photosensitive polyimide compositions, photosensitive epoxy resin compositions, photosensitive silicone compositions, and the like have been used as photosensitive protective films for semiconductor elements or insulating films for multilayer printed circuit boards. Among them, a photosensitive silicone composition having excellent flexibility has been proposed as a photosensitive material for protecting the above substrates or circuits (Patent Document 1). Although the photosensitive silicone composition can be cured at low temperatures and can form a coating having excellent reliability such as moisture-resistant adhesion, it has a problem of poor chemical resistance to photoresist stripping solutions such as N-methyl-2-pyrrolidone, which has a strong solubility.

[0003] In view of this, a photosensitive silicone composition having a silicone-type polymer containing a silphenylene skeleton as a main component has been proposed (Patent Document 2). Although the photosensitive silicone composition has improved chemical resistance to photoresist stripping liquids and the like, it is desired to further improve the level of miniaturization achieved by patterning and the property of resisting copper migration. In addition, when the photosensitive silicone composition is used to form a pattern on copper, discoloration of the copper due to corrosion is observed, and this point is also desired to be improved.

[0004] Prior art literature

[0005] Patent Literature

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

[0007] Patent Document 2: Japanese Patent Application Publication No. 2008-184571 Summary of the invention

[0008] 1. Technical issues to be resolved

[0009] The present invention has been made in view of the above circumstances, and its object is to provide a photosensitive resin composition, a photosensitive resin coating, a photosensitive dry film, and a pattern forming method using the photosensitive resin composition, the photosensitive resin coating, and the photosensitive dry film. The photosensitive resin composition can be easily formed into a thick film and a fine pattern without copper discoloration, and can form a resin coating (resin layer) that has excellent copper migration resistance and adhesion to a substrate and is excellent in reliability when used as a coating for protecting electric and electronic parts or a coating for bonding substrates.

[0010] (II) Technical solution

[0011] In order to solve the above technical problems, the present invention provides a photosensitive resin composition, which comprises:

[0012] (A) a silicone resin having an acid crosslinkable group,

[0013] (B) an oxazoline compound or a derivative thereof, and

[0014] (C) Photoacid generator.

[0015] The photosensitive resin composition of the present invention can be easily formed into a thick film and a fine pattern without copper discoloration, and can form a resin coating (resin layer) that has excellent resistance to copper migration and adhesion to a substrate and is excellent in reliability when used as a coating for protecting electric and electronic parts or a coating for bonding substrates.

[0016] In this case, the (A) silicone resin is preferably a silicone resin represented by the following formula (A1).

[0017]

[0018] In the formula, R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; k is an integer of 1 to 600; a and b represent the composition ratio (molar ratio) of each repeating unit, which is a number 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 hydroxyl group.

[0019] The component (A) described above can form a favorable resin coating, and the obtained resin coating has favorable adhesion to a laminate, a substrate, etc., favorable pattern forming ability, crack resistance, and heat resistance.

[0020] Furthermore, the silicone resin (A) preferably includes repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4).

[0021]

[0022] In the formula, R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; k is an integer from 1 to 600; a 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and satisfies 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; X 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);

[0023]

[0024] Where Y 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 11 and R 12 are each independently a hydrogen atom or a methyl group; R 13 and R 14 Each is independently a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms; 1 and p 2 Each independently represents an integer from 0 to 7; q 1 and q 2 Each is independently an integer from 0 to 2; the dotted line is a connecting bond;

[0025]

[0026] Where Y 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 21 and R 22 are each independently a hydrogen atom or a methyl group; R 23 and R 24 Each independently represents a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms; 1 and r 2 Each independently represents an integer from 0 to 7; s 1 and 2 Each is independently an integer from 0 to 2; the dotted line is a connecting bond;

[0027]

[0028] In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group; 1 and t 2 Each is independently an integer from 0 to 7; the dotted line is a connecting bond;

[0029]

[0030] In the formula, R 41 and R 42 are each independently a hydrogen atom or a methyl group; R 43 and R 44 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; 1 and u 2 Each is independently an integer from 0 to 7; v is an integer from 0 to 600; and the dotted line is a connecting bond.

[0031] If it is the above-mentioned (A) component, a better resin film can be formed. In addition, by combining the above-mentioned repeating units, a resin film having desired characteristics can be formed.

[0032] Furthermore, it is preferred to contain (D) a cross-linking agent.

[0033] At this time, the (D) cross-linking agent is preferably at least one selected from a nitrogen-containing compound selected from melamine compounds, cyanamide compounds, glycoluril compounds and urea compounds containing an average of more than two hydroxymethyl groups and / or alkoxymethyl groups in one molecule; an amino condensate modified by formaldehyde or formaldehyde-alcohol; a phenol compound having an average of more than two hydroxymethyl groups or alkoxymethyl groups in one molecule; and an epoxy compound having an average of more than two epoxy groups in one molecule.

[0034] The component (D) described above can facilitate patterning and further improve the strength of the cured product.

[0035] Furthermore, it is preferred to contain (E) a solvent.

[0036] By including the above-mentioned component (E), the viscosity of the composition can be appropriately adjusted, and the workability can be improved.

[0037] In addition, the present invention provides a photosensitive resin film obtained from the photosensitive resin composition.

[0038] The photosensitive resin coating of the present invention can provide a thick film and a fine pattern without discoloring copper, and has excellent resistance to copper migration and adhesion to a substrate, and has high reliability when used as a coating for protecting electric and electronic parts or for substrate bonding.

[0039] In addition, the present invention provides a photosensitive dry film, which comprises a support film, and the photosensitive resin coating film is provided on the support film.

[0040] Since the photosensitive dry film of the present invention is solid and the photosensitive resin coating does not contain a solvent, there is no need to worry about bubbles remaining inside the photosensitive resin coating and between the photosensitive resin coating and the substrate with uneven surfaces due to volatilization. In addition, when the photosensitive dry film is closely attached to the substrate with uneven surfaces, the photosensitive resin coating will follow and cover the uneven surfaces, thereby achieving high flatness. In particular, since the photosensitive resin coating has low viscoelasticity, it can achieve higher flatness.

[0041] In addition, the present invention provides a pattern forming method, characterized in that it comprises the following steps:

[0042] (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition;

[0043] (ii) exposing the photosensitive resin film to light; and

[0044] (iii) a step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0045] In addition, the present invention provides a pattern forming method, characterized in that it comprises the following steps:

[0046] (i') a process of forming a photosensitive resin coating on a substrate using the photosensitive dry film;

[0047] (ii) exposing the photosensitive resin film to light; and

[0048] (iii) a step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0049] The pattern forming method of the present invention can easily form a thick film and a fine pattern without copper discoloration, and can effectively form a resin film with excellent reliability when used as a film for protecting electric and electronic parts or a film for bonding substrates.

[0050] The present invention preferably further comprises the following steps:

[0051] (iv) a step of post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

[0052] This increases the crosslinking density of the photosensitive resin composition and enables removal of residual volatile components, which is preferred from the viewpoints of adhesion to the substrate, heat resistance and strength, electrical characteristics, and adhesive strength.

[0053] In the present invention, the photosensitive resin composition is preferably a material for a coating film for protecting electric and electronic parts, and is also preferably a material for a coating film for bonding two substrates together.

[0054] The photosensitive resin composition of the present invention is useful as the above-mentioned material.

[0055] (III) Beneficial effects

[0056] The photosensitive resin composition of the present invention can form a coating within a wide range of film thicknesses, and further, can form a thick film with excellent fine verticality without copper discoloration by a pattern forming method described later. The coating obtained by using the photosensitive resin composition and the photosensitive dry film of the present invention has excellent adhesion, mechanical properties, electrical insulation, copper migration resistance, and chemical resistance to substrates, electronic parts, semiconductor elements, etc., especially to substrates for circuit substrates. In addition, the coating has high reliability as an insulating protective film and can be suitably used as a material for forming a coating for protecting various electrical and electronic parts such as circuit substrates, semiconductor elements, and display elements, or a material for forming a coating for bonding substrates. DETAILED DESCRIPTION

[0057] In order to achieve the above-mentioned object, the inventors of the present invention have conducted intensive research and found that the above-mentioned object can be achieved by a photosensitive resin composition comprising (A) a silicone resin having an acid crosslinking group, (B) an oxazoline compound or its derivative and (C) a photoacid generator, thereby completing the present invention.

[0058] That is, the present invention is a photosensitive resin composition, characterized in that it comprises:

[0059] (A) a silicone resin having an acid crosslinkable group,

[0060] (B) an oxazoline compound or a derivative thereof, and

[0061] (C) Photoacid generator.

[0062] The photosensitive resin composition of the present invention can be easily formed into a thick film and a fine pattern without copper discoloration, and can form a resin coating (resin layer) having excellent film properties such as resistance to copper migration, adhesion to substrates, electronic parts, semiconductor elements, etc., especially to base materials for circuit substrates, and excellent reliability as a coating for protecting electric and electronic parts or a coating for bonding substrates. The photosensitive resin composition can provide a photosensitive resin coating and a photosensitive dry film, and can provide a pattern forming method using the photosensitive resin composition, the photosensitive resin coating and the photosensitive dry film.

[0063] Hereinafter, the present invention will be described in detail, but the present invention is not limited to these contents.

[0064] [Photosensitive resin composition]

[0065] The photosensitive resin composition of the present invention comprises (A) a silicone resin having an acid crosslinkable group, (B) an oxazoline compound and (C) a photoacid generator, and may further contain components other than the above components, such as (D) a crosslinking agent, (E) a solvent, and other additives as required.

[0066] Hereinafter, each component will be described.

[0067] [(A) Silicone resin having an acid crosslinkable group]

[0068] The silicone resin of component (A) contains an acid crosslinkable group in the molecule. The acid crosslinkable group refers to a group in which functional groups can be chemically bonded to each other directly or via a crosslinking agent through the action of an acid. As the acid crosslinkable group, epoxy groups and phenolic hydroxyl groups are preferred. Only one of epoxy groups and phenolic hydroxyl groups may be contained, or both may be contained.

[0069] As the silicone resin having an acid crosslinkable group, a silicone resin represented by the following formula (A1) is preferred.

[0070]

[0071] In formula (A1), R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group 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 hydroxyl group.

[0072] The hydrocarbon group may be any of linear, branched, and cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, hexyl, and isomers of these groups; cyclic saturated hydrocarbon groups such as cyclohexyl; and aryl groups such as phenyl. Among them, methyl and phenyl are preferred because of easy access to raw materials.

[0073] The silicone resin represented by formula (A1) is particularly preferably a silicone resin containing repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4) (hereinafter referred to as repeating units a1 to a4 and b1 to b4, respectively).

[0074]

[0075] In the formula, R 1 ~R 4 and k and the above R 1 ~R 4 and k are the same.

[0076] In formula (a1) and (b1), X 1 It is a divalent group represented by the following formula (X1).

[0077]

[0078] In the formula, the dotted line is the connecting bond.

[0079] In formula (X1), Y 1 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 11 and R 12 Each is independently a hydrogen atom or a methyl group. 13 and R 14 Each is independently a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms. 1 and p 2 Each independently represents an integer from 0 to 7. 1 and q2 Each independently represents an integer from 0 to 2.

[0080] The saturated hydrocarbon group may be any one of straight chain, branched chain, and cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, and isomers of these groups; cyclic saturated hydrocarbon groups such as cyclopropyl and cyclobutyl. The saturated hydrocarbon oxy group may be any one of straight chain, branched chain, and cyclic. Specific examples thereof include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and isomers of these groups; cyclic saturated hydrocarbon oxy groups such as cyclopropyl and cyclobutyl.

[0081] In formula (a2) and (b2), X 2 It is a divalent group represented by the following formula (X2).

[0082]

[0083] In the formula, the dotted line is the connecting bond.

[0084] In formula (X2), Y 2 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 21 and R 22 Each is independently a hydrogen atom or a methyl group. 23 and R 24 Each is independently a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms. 1 and r 2 Each independently represents an integer from 0 to 7. 1 and 2 Each independently represents an integer of 0 to 2. As the saturated hydrocarbon group and the saturated hydrocarbon oxy group, there can be cited those having the same 13 and R 14 The saturated hydrocarbon group and the saturated hydrocarbon oxy group exemplified in the description of are the same groups.

[0085] In formula (a3) ​​and (b3), X 3 It is a divalent group represented by the following formula (X3).

[0086]

[0087] In the formula, the dotted line is the connecting bond.

[0088] In formula (X3), R 31 and R 32 Each independently represents a hydrogen atom or a methyl group. 1 and t 2 Each independently represents an integer from 0 to 7.

[0089] In formula (a4) and (b4), X 4 It is a divalent group represented by the following formula (X4).

[0090]

[0091] In the formula, the dotted line is the connecting bond.

[0092] In formula (X4), R 41 and R 42 Each is independently a hydrogen atom or a methyl group. 43 and R 44 Each is independently a hydrocarbon group having 1 to 8 carbon atoms. 1 and u 2 Each independently represents an integer of 0 to 7. v represents an integer of 0 to 600, preferably an integer of 0 to 400, and more preferably an integer of 0 to 200. Examples of the hydrocarbon group include 1 ~R 4 The same groups as the hydrocarbon groups exemplified in the description of .

[0093] The weight average molecular weight (Mw) of the silicone resin of the component (A) is preferably 3000 to 500000, and more preferably 5000 to 200000. In the present invention, Mw is a polystyrene-converted measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.

[0094] In 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 satisfies 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 +b3 +b 4 =1, preferably 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, preferably satisfying 0≤a 1 ≤0.7, 0≤a 2 ≤0.7, 0≤a 3 ≤0.7, 0≤a 4 ≤0.7, 0≤b 1 ≤0.9, 0≤b 2 ≤0.9, 0≤b 3 ≤0.9, 0≤b 4 ≤0.9、0.1≤a 1 +a 2 +a 3 ≤0.7、0.3≤b 1 +b 2 +b 3 ≤0.9 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1. Furthermore, from the perspective of the reaction, it is preferred that 0 < b 2 <1, more preferably 0.2≤b 2 ≤0.95, more preferably 0.3≤b 2 ≤0.9.

[0095] The aforementioned repeating units can be randomly bonded or bonded as block polymers. In addition, when the siloxane units in each repeating unit are more than 2, each siloxane unit can be exactly the same or can include two or more different siloxane units. When including two or more different siloxane units, the siloxane units can be randomly bonded or can include blocks of multiple siloxane units of the same kind. In addition, in the silicone resin, the organosilicon (siloxane unit) content is preferably 30 to 80% by mass.

[0096] The silicone resin of the component (A) functions to impart film-forming ability. The obtained resin film has good adhesion to a laminate, a substrate, etc., good pattern-forming ability, crack resistance, and heat resistance.

[0097] The silicone resin of the component (A) may be used alone or in combination of two or more.

[0098] [(A) Method for preparing silicone resin]

[0099] The silicone resin of component (A) can be prepared by using an organosilicon compound having an acid crosslinking group as a raw material and utilizing a hydrosilylation reaction. The organosilicon compound of the raw material can be appropriately selected according to the target silicone resin having an acid crosslinking group. When component (A) is a silicone resin represented by formula (A1), it can be prepared, for example, by the following method: in the presence of a metal catalyst, a compound represented by the following formula (1), a compound represented by the following formula (2), a compound selected from the group consisting of 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 a compound represented by the following formula (6) as required are subjected to addition polymerization.

[0100]

[0101] In the formula, R 1 ~R 4 and k and the above R 1 ~R 4 and k are the same.

[0102]

[0103] 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 、p2 ,q 1 ,q 2 、r 1 、r 2 、s 1 、s 2 ,t 1 ,t 2 、u 1 、u 2 and v and the above 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 Same as v.

[0104] As the metal catalyst, platinum (including platinum black), rhodium, palladium and other platinum group metal monomers can be used; platinum chloride, chloroplatinic acid and chloroplatinates such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2PtCl4·xH2O (wherein x is preferably an integer of 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, Alcohol-modified chloroplatinic acid described in U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, complexes of chloroplatinic acid and olefins described in U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662 and U.S. Pat. No. 3,775,452); substances in which platinum group metals such as platinum black or palladium are supported on carriers such as alumina, silica and carbon; rhodium-olefin complexes, tris(triphenylphosphine)rhodium chloride (so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid or chloroplatinates and vinyl-containing siloxanes (especially vinyl-containing cyclic siloxanes), etc.

[0105] The amount of the catalyst used is a catalytic amount, and is generally preferably 0.001 to 0.1 parts by mass, and more preferably 0.01 to 0.1 parts by mass, relative to 100 parts by mass of the total amount of the raw material compounds.

[0106] 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 preferred.

[0107] From the perspective of not deactivating the catalyst and completing the polymerization in a short time, the polymerization temperature is preferably 40 to 150° C., more preferably 60 to 120° C. The polymerization time varies depending on the type and amount of the obtained resin, but in order to prevent moisture from entering the polymerization system, it is preferably about 0.5 to 100 hours, more preferably 0.5 to 30 hours. After the reaction is completed, if a solvent is used, the solvent can be distilled off to obtain the silicone resin of component (A).

[0108] The reaction method is not particularly limited. For example, when reacting a compound represented by formula (1), a compound represented by formula (2), at least one selected from the group consisting of a compound represented by formula (3), a compound represented by formula (4) and a compound represented by formula (5), with a compound represented by formula (6) which is present as required, the following method can be cited: first, after mixing and heating at least one selected from the group consisting of a compound represented by formula (3), a compound represented by formula (4) and a compound represented by formula (5) and a compound represented by formula (6) which is present as required, a metal catalyst is added to the mixed solution, and then the compound represented by formula (1) and the compound represented by formula (2) are added dropwise over a period of 0.1 to 5 hours.

[0109] The compounds are blended in such a manner that the total amount of the hydrosilyl groups possessed by the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.67 to 1.67, more preferably 0.83 to 1.25, in terms of molar ratio, relative to the total amount of alkenyl groups possessed by at least one compound selected from the group consisting of the compound represented by formula (3), the compound represented by formula (4) and the compound represented by formula (5) and the compound represented by formula (6) which is present as required.

[0110] The Mw of the obtained resin can be controlled by using a monoallyl compound such as o-allylphenol or a monohydrogenated silane or monohydrogenated siloxane such as triethylhydrogenated silane as a molecular weight modifier.

[0111] [(B) Oxazoline compound or its derivative]

[0112] (B) The oxazoline compound of the component is a compound having a structure represented by the following formula (B1).

[0113]

[0114] The oxazoline compound is not particularly limited, and commercially available products can be used. Specific examples thereof include 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-xylenediyl)bis(4-isopropyl-2-oxazoline), 2,2'-bis(2-oxazoline), 2,2'-(2,6-pyridinediyl)bis(4-phenyl-2-oxazoline), and 4-tert-butyl-2-(2-pyridine)bis(4-isopropyl-2-oxazoline). Oxazoline, 2-phenyl (2-oxazoline), 4,4-dimethyl-2-oxazoline, 2-ethyl-2-oxazoline, 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-phenylbenzothiazole-2-thiol, 2-propyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, etc.

[0115] Among them, 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.

[0116] By adding an oxazoline compound or a derivative thereof, a clear contrast of the amount of acid generated by the photoacid generator is given to the exposed portion and the unexposed portion, thereby increasing the resolution, suppressing the sensitivity change after exposure, reducing substrate dependence or environmental dependence, and improving exposure latitude and pattern shape. In addition, a pattern that is not accompanied by copper discoloration can be formed. In addition, a good catalyst effect can be shown during post-curing, and a cured film with excellent reliability and anti-migration properties can be obtained.

[0117] The above-mentioned effect is not bound by a specific theory, but it is speculated that the effect is caused by the following reasons: the oxazoline compound or its derivative of component (B) has both basicity and coordination ability, and the basicity can appropriately control the migration of the generated acid, and can also show a catalytic effect of increasing the reactivity of the acid crosslinking group by heating, and the coordination ability can inhibit the migration of copper.

[0118] In the case where the acid crosslinking group is an epoxy group, from the perspective of improving curability, it is conceivable to mix a basic compound or its salt, such as a quaternary ammonium salt, a tertiary amine and its salt, an imidazole compound, etc., which is known as a curing agent or curing aid for epoxy resin, into the composition. However, due to its basicity (strength), there is a concern that it will neutralize the acid generated by the photoacid generator, thereby reducing the reactivity of the acid crosslinking group.

[0119] In addition, as nitrogen-containing heterocyclic compounds that can inhibit copper ion migration, there are known compounds having one nitrogen atom in the nitrogen-containing heterocyclic ring, such as piperidine and pyridine; compounds having two nitrogen atoms in the nitrogen-containing heterocyclic ring, such as imidazole, pyrazole, pyrazoline, pyrazolidine, pyrimidine, pyridazine; compounds having three nitrogen atoms in the nitrogen-containing heterocyclic ring, such as 1,2,3-triazole, 1,2,4-triazole, triazine; and compounds having four nitrogen atoms in the nitrogen-containing heterocyclic ring, such as 1H-tetrazole (Japanese Patent Publication No. 2012-181281). These nitrogen-containing heterocyclic compounds also have their own corresponding base strengths.

[0120] However, the composition not including the component (B) combined with the silicone resin (A) having an acid crosslinkable group has poor limiting resolution and shape when forming a pattern, cannot suppress copper migration and discoloration, and the obtained pattern lacks reliability, adhesion, and solvent resistance. In particular, although it is known that diaminotriazine compounds having an imidazole ring used as a curing agent or curing accelerator for epoxy resins can suppress copper discoloration (see Japanese Patent Publication No. 7-033766), even if such compounds are added, copper discoloration cannot be suppressed, and the characteristics of the formed pattern are also poor.

[0121] In contrast, the present invention can achieve excellent effects that could not be expected from the prior art by combining (A) a silicone resin having an acid crosslinkable group with (B) an oxazoline compound or a derivative thereof.

[0122] It is also known that compounds having an oxazoline skeleton can react with carboxyl groups in polymers to form crosslinks (see Japanese Patent Application Publication No. 2009-003369). However, in the present invention, even if component (A) or other components do not contain carboxyl groups in their structures, the above-mentioned excellent effects can still be exerted.

[0123] The content of component (B) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of component (A). If the content of component (B) is 0.01 parts by mass or more, sufficient effects can be obtained. If it is 10 parts by mass or less, compatibility with component (A) is good, and there is no need to worry about the problem of decreased transparency, so it is preferred. Component (B) can be used alone or in combination of two or more.

[0124] [(C) Photoacid generator]

[0125] The photoacid generator of component (C) is not particularly limited as long as it is a component that is decomposed by light irradiation to generate acid, and preferably is decomposed by light with a wavelength of 190 to 500 nm to generate acid. The photoacid generator is a curing catalyst. The photosensitive resin composition of the present invention has excellent compatibility with the photoacid generator, and a wide range of photoacid generators can be used.

[0126] Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, imide-yl-sulfonate derivatives, oximesulfonate derivatives, and iminosulfonate derivatives.

[0127] Examples of the onium salt include sulfonium salts represented by the following formula (C1) and iodonium salts represented by the following formula (C2).

[0128]

[0129] In formula (C1) and (C2), R 101 ~R 105 Each is independently a saturated hydrocarbon 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. - It is a non-nucleophilic counter ion.

[0130] The saturated hydrocarbon group may be any of a linear, branched, or cyclic group. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these groups; cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the aryl group include phenyl, naphthyl, biphenyl, and the like. Examples of the aralkyl group include benzyl, phenethyl, and the like.

[0131] Examples of the substituent include an oxo group, a saturated hydrocarbon group having 1 to 12 carbon atoms, a saturated hydrocarbon oxy 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. In addition, the hydrocarbon moiety of the saturated hydrocarbon group and the saturated hydrocarbon oxy group may be any of a linear, branched, and cyclic shape. Specific examples thereof include the following: 101 ~R 105The saturated hydrocarbon groups represented are the same groups as exemplified above.

[0132] As R 101 ~R 105 , preferably methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl or other saturated hydrocarbon groups with or without substituents; phenyl, naphthyl, biphenyl, 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl or 4-ethoxyphenyl, 3-tert-butoxyphenyl or 4-tert-butoxyphenyl, 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyloxyphenyl, biphenylthiophenyl or other aryl groups with or without substituents; benzyl, phenethyl or other aralkyl groups with or without substituents. Among them, aryl groups with or without substituents and aralkyl groups with or without substituents are more preferred.

[0133] Examples of the non-nucleophilic counter ions include halide ions such as chloride ion and bromide ion; fluoroalkane sulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; aryl sulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkane sulfonate ions such as methanesulfonate ion and butanesulfonate ion; fluoroalkane sulfonyl imide ions such as trifluoromethanesulfonyl imide ions; fluoroalkane sulfonyl methide ions such as tris(trifluoromethanesulfonyl)methide ion; borate ions such as tetraphenylborate ion and tetrakis(pentafluorophenyl)borate ion; phosphate ions such as hexafluorophosphate ion and tris(pentafluoroethyl)trifluorophosphate ion, and the like.

[0134] Examples of the diazomethane derivative include compounds represented by the following formula (C3).

[0135]

[0136] In formula (C3), R 111 and R 112 Each is independently a saturated hydrocarbon group having 1 to 12 carbon atoms, a halogenated saturated hydrocarbon 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.

[0137] The saturated hydrocarbon group may be any of a linear, branched, or cyclic type. Specific examples thereof include the following: 101 ~R 105The saturated hydrocarbon group represented by is the same as the saturated hydrocarbon group exemplified above. Examples of the halogenated saturated hydrocarbon group include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl.

[0138] Examples of the aryl group which may or may not have a substituent include phenyl; alkoxyphenyl groups such as 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl or 4-ethoxyphenyl, 3-tert-butoxyphenyl or 4-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; halogenated aryl groups such as fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl, etc. Examples of the aralkyl group include benzyl and phenethyl.

[0139] 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)phenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tri(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, and trimethylsulfonium p-toluenesulfonate. trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl) trifluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(trifluoromethanesulfonyl) methylate ([4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide), triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate, and the like.

[0140] Specific examples of the diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, and bis(isopropylsulfonyl)diazomethane. diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

[0141] 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-pentanedioneglyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, Oxime, bis-o-(methylsulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butylsulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime bis-(2-(4-(2-(2-(4-(2-(2-(4-(2-(2-(2-(4-piperidinyl)sulfonyl)-α-dimethylglyoxime), bis-(2-(4-piperidinyl)sulfonyl)-α-dimethylglyoxime, bis-(2-(2-(4-piperidinyl)sulfonyl)-α-dimethylglyoxime), bis-(2-(2-(4-piperidinyl)sulfonyl)-α-dimethylglyoxime, bis-(2-(2-(2-piperidinyl)sulfonyl)-α-dimethylglyoxime, bis ...

[0142] Specific examples of the β-ketosulfone derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0143] Specific examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0144] Specific examples of the nitrobenzyl sulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0145] Specific examples of the sulfonic acid ester derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0146] Specific examples of the imido-sulfonate derivatives include phthalimido-trifluoromethanesulfonate, phthalimido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthyl imide.

[0147] Specific examples of the oxime sulfonate derivatives include α-(phenylsulfonyloxyimino)-4-methylphenylacetonitrile and α-(p-tolylsulfonyloxyimino)-p-methoxyphenylacetonitrile.

[0148] Specific examples of the imidosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-methylene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-methylene)-(2-methylphenyl)-acetonitrile.

[0149] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be preferably used.

[0150] From the perspective of photocurability, the content of component (C) is preferably 0.05 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of component (A). If the content of component (C) is 0.05 parts by mass or more, sufficient acid will be generated, and the crosslinking reaction will be fully carried out. If it is 20 parts by mass or less, the increase in the absorbance of the photoacid generator itself can be suppressed, and there is no need to worry about the problem of decreased transparency, so it is preferred. Component (C) can be used alone or in combination of two or more.

[0151] [(D) Cross-linking agent]

[0152] The photosensitive resin composition of the present invention further preferably comprises 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 when there are other crosslinking groups, thereby increasing the crosslinking degree of the cured product. For example, when the aforementioned component (A) has a phenolic hydroxyl group or R 13 , R 14 , R 23 or R 24 When the saturated hydrocarbon oxy group represented by (A) is present, the crosslinking agent (D) is a component that undergoes a condensation reaction with these groups and facilitates the formation of a pattern, and further improves the strength of the cured product. From this perspective, the crosslinking agent (D) is preferably combined with the silicone resin having an acid crosslinkable group represented by formula (A1) of the component (A).

[0153] As the cross-linking agent, preferred are melamine compounds, cyanamide compounds, glycoluril compounds or urea compounds containing an average of more than 2 hydroxymethyl groups and / or alkoxymethyl groups in one molecule; amino condensates modified by formaldehyde or formaldehyde-alcohol; phenol compounds having an average of more than 2 hydroxymethyl groups or alkoxymethyl groups in one molecule; and epoxy compounds having an average of more than 2 epoxy groups in one molecule.

[0154] Examples of the melamine compound include melamine compounds represented by the following formula (D1).

[0155]

[0156] In formula (D1), R 201 ~R 206 Each is independently a hydroxymethyl group, a saturated hydrocarbon oxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, and at least one is a hydroxymethyl group or a saturated hydrocarbon oxymethyl group. Examples of the saturated hydrocarbon oxymethyl group include alkoxymethyl groups such as methoxymethyl and ethoxymethyl.

[0157] Examples of the melamine compound represented by the formula (D1) include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, and hexaethoxymethylmelamine.

[0158] The melamine compound represented by formula (D1) can be obtained, for example, by first modifying the melamine monomer by hydroxymethylation with formaldehyde according to a known method, or further modifying it by alkoxylation with an alcohol. In addition, the alcohol is preferably a lower alcohol, such as an alcohol having 1 to 4 carbon atoms.

[0159] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0160] Examples of the glycoluril compound include tetrakishydroxymethyl glycoluril and tetrakis(methoxymethyl) glycoluril.

[0161] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0162] Examples of the amino condensate modified by formaldehyde or formaldehyde-alcohol include melamine condensate modified by formaldehyde or formaldehyde-alcohol, and urea condensate modified by formaldehyde or formaldehyde-alcohol.

[0163] As the modified melamine condensate, there can be cited the modified melamine condensate obtained by subjecting the compound represented by formula (D1) or its polymer (e.g., oligomers such as dimers and trimers) to addition polycondensation with formaldehyde to a desired molecular weight. In addition, as the addition polycondensation method, an existing known method can be adopted. In addition, the modified melamine represented by formula (D1) can be used alone or in combination of two or more.

[0164] Examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate, and the like.

[0165] The modified urea condensate can be obtained, for example, by modifying a urea condensate having a desired molecular weight by methylolating it with formaldehyde according to a known method, or further modifying it by alkoxylating it with an alcohol.

[0166] Examples of the phenol compound having an average of two or more hydroxymethyl groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2′,6,6′-tetramethoxymethylbisphenol A.

[0167] Examples of the epoxy compound having an average of two or more epoxy groups in one molecule include bisphenol-type epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin, novolac-type epoxy resins such as phenol novolac-type epoxy resin and cresol novolac-type epoxy resin, 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, heterocyclic epoxy resins, and the like.

[0168] When the component (D) is included, the content of the component (D) 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 component (A). If it is 0.5 parts by mass or more, sufficient curability can be obtained during light irradiation, and if it is 50 parts by mass or less, since the proportion of the component (A) in the photosensitive resin composition does not decrease, sufficient effects can be exhibited in the cured product. The component (D) may be used alone or in combination of two or more.

[0169] [(E) Solvent]

[0170] 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 can dissolve components (A) to (D) and various additives described below, but an organic solvent is preferred due to its excellent solubility in the above components.

[0171] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentanone; 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. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof, which have the best solubility for the photoacid generator.

[0172] From the perspective of compatibility with the photosensitive resin composition and viscosity, the amount of component (E) 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 relative to 100 parts by mass of component (A). Component (E) may be used alone or in combination of two or more.

[0173] [Other additives]

[0174] In addition to the above-mentioned components, the photosensitive resin composition of the present invention may further include other additives. Examples of other additives include surfactants commonly used to improve coating properties.

[0175] As the surfactant, nonionic surfactant is preferred, for example, fluorine-based surfactants can be listed, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl oxide amines, fluorinated organic silicone compounds, etc. These surfactants can use commercial products, for example, Fluorad (registered trademark) FC-430 (manufactured by 3M Limited Inc.), 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), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Among them, 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 the component (A).

[0176] 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 by the composition to the adherend can be further improved. As the silane coupling agent, epoxy-containing silane coupling agents, aromatic group-containing aminosilane coupling agents, etc. can be listed. These silane coupling agents can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited. When the silane coupling agent is contained, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0177] The photosensitive resin composition of the present invention can be prepared by a conventional method, for example, by stirring and mixing the above components, and then filtering using a filter or the like as needed to remove solid components, thereby preparing the photosensitive resin composition of the present invention.

[0178] The photosensitive resin composition of the present invention prepared in the above manner is suitable for use as materials such as protective films for semiconductor elements, protective films for wiring, covering films, solder resists, insulating films for through-electrodes (for TSV), and adhesives between laminated substrates during three-dimensional lamination.

[0179] [Pattern forming method using photosensitive resin composition]

[0180] The pattern forming method using the photosensitive resin composition of the present invention comprises the following steps:

[0181] (i) a process of forming a photosensitive resin coating on a substrate using the photosensitive resin composition of the present invention;

[0182] (ii) exposing the photosensitive resin film to light; and

[0183] (iii) a step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0184] Step (i) is a step of forming a photosensitive resin coating on a substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, silicon wafers for through-electrodes, silicon wafers thinned by back grinding, plastic or ceramic substrates, and substrates having a metal such as Ni or Au on the entire surface or a portion of the substrate by ion sputtering or electroplating. In addition, a substrate having projections and depressions may be used.

[0185] As a method for forming a photosensitive resin coating, for example, a method of coating the photosensitive resin composition on a substrate and preheating (prebaking) as needed can be cited. The coating method can be a known method, and can be cited as a dipping method, a spin coating method, a roller coating method, etc. The coating amount of the photosensitive resin composition can be appropriately selected according to the purpose, and it is preferably coated in a manner that the film thickness of the obtained photosensitive resin coating is 0.1 to 200 μm, and more preferably coated in a manner that the film thickness of the obtained photosensitive resin coating is 1 to 150 μm.

[0186] For the purpose of improving the uniformity of the film thickness on the substrate surface, a solvent may be dripped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dripped and its amount may be appropriately selected according to the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as PGME, etc. are preferred, and the solvent used in the photosensitive resin composition may also be used.

[0187] In order to effectively perform the photocuring reaction, pre-baking may be performed as necessary to evaporate the solvent, etc. The pre-baking may be performed at 40 to 140° C. for about 1 minute to 1 hour, for example.

[0188] Next, (ii) the photosensitive resin coating is exposed. At this time, the exposure is preferably carried out using light with a wavelength of 10 to 600 nm, and more preferably using light with a wavelength of 190 to 500 nm. As the light of the above-mentioned wavelength, for example, light of various wavelengths generated by a radiation generating device, for example, ultraviolet rays such as g-line, h-line, i-line, far ultraviolet rays (248nm, 193nm), etc. can be listed. Among them, light with a wavelength of 248 to 436nm is particularly preferred. The exposure amount is preferably 10 to 10000 mJ / cm 2 .

[0189] The exposure can be performed through a photomask. The photomask can be, for example, a film in which a desired pattern is hollowed out. In addition, the material of the photomask is not particularly limited, but is preferably a material that shields the light of the above wavelength, for example, a material having a chromium or the like as a light-shielding film is suitable.

[0190] Furthermore, in order to improve the development sensitivity, a post-exposure heat treatment (PEB) may be performed. PEB is preferably set at 40 to 150° C. and 0.5 to 10 minutes. Through PEB, the exposed part is cross-linked to form an insoluble pattern that is insoluble in an organic solvent as a developer.

[0191] After exposure or PEB, (iii) the photosensitive resin coating is developed using 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 solvents used in photosensitive resin compositions can also be used. As a developing method, conventional methods can be used, for example, a method in which a substrate having a pattern formed thereon is immersed in the developer, etc. By developing with an organic solvent, the non-exposed portion is dissolved and removed, thereby forming a pattern. Then, cleaning, rinsing, drying, etc. are performed as needed to obtain a resin coating having a desired pattern.

[0192] Furthermore, (iv) an oven or a hot plate can be used, preferably at 100 to 250°C, more preferably at 130 to 220°C, to post-cure the patterned coating. If the post-curing temperature is 100 to 250°C, the cross-linking density of the photosensitive resin composition can be increased, and the remaining volatile components can be removed, which is preferred from the perspective 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, even if the post-curing is performed at a relatively low temperature below 200°C, a coating with excellent various film properties can be obtained. The film thickness of the coating (cured coating) after post-curing is generally 1 to 200 μm, preferably 5 to 50 μm.

[0193] When patterning is not required, for example, when only a uniform coating is desired to be formed, the coating may be formed by exposing to light of an appropriate wavelength without using the photomask in step (ii) of the patterning method.

[0194] [Method of bonding substrates]

[0195] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. As a method for bonding substrates, there can be cited a method of bonding a substrate with a film formed thereon to a second substrate in a manner that forms an adhesive bond between the two substrates using the photosensitive resin composition of the present invention under suitable heat and pressure conditions. Either or both of the substrate with a film formed thereon and the second substrate may sometimes be chipped by cutting or the like. As bonding conditions, it is preferably set to a heating temperature of 50 to 200°C and for 1 to 60 minutes. As a bonding device, a wafer bonder can be used to bond wafers to each other under reduced pressure while applying a load, or a flip-chip bonding machine can be used to implement chip-wafer bonding or chip-chip bonding. The bonding force of the bonding layer formed between the substrates will increase due to the post-curing treatment described later, forming a permanent bond.

[0196] By post-curing the attached (bonded) substrate under the same conditions as in the aforementioned step (iv), the crosslinking density of the coating increases, and the substrate bonding strength can be improved. In addition, although a crosslinking reaction is induced by heating during bonding, since a side reaction accompanied by degassing does not occur in the crosslinking reaction, particularly when used as a substrate adhesive, bonding defects (voids) will not be induced.

[0197] [Photosensitive dry film]

[0198] The photosensitive dry film of the present invention comprises a support film, and a photosensitive resin coating film obtained from the photosensitive resin composition is disposed on the support film.

[0199] Since the photosensitive dry film (support film and photosensitive resin coating) is solid and the photosensitive resin coating does not contain a solvent, there is no need to worry about bubbles remaining inside the photosensitive resin coating and between the photosensitive resin coating and the concavo-convex substrate due to the volatilization of the solvent.

[0200] From the viewpoints of flatness on a substrate having projections and depressions, coverage of step differences, and substrate stacking intervals, the film thickness of the photosensitive resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0201] In addition, the viscosity of the photosensitive resin coating is closely related to fluidity. The photosensitive resin coating can exhibit appropriate fluidity within an appropriate viscosity range, can enter deep into narrow gaps, and can enhance adhesion to the substrate by softening the resin. Therefore, from the perspective of its fluidity, the viscosity of the photosensitive resin coating is preferably 10 to 5000 Pa·s at 80 to 120°C, more preferably 30 to 2000 Pa·s, and further preferably 50 to 300 Pa·s. In addition, in the present invention, the viscosity is a measured value measured by a rotational viscometer.

[0202] When the photosensitive dry film of the present invention is closely attached to a substrate having uneven surfaces, the photosensitive resin coating will follow and cover the uneven surfaces, thereby achieving high flatness. In particular, the photosensitive resin coating can achieve higher flatness due to its low viscoelasticity. Furthermore, if the photosensitive resin coating is closely attached to the substrate in a vacuum environment, it is possible to more effectively prevent a gap from being generated therebetween.

[0203] The photosensitive dry film of the present invention can be manufactured in the following manner: the photosensitive resin composition is coated on a support film and dried to form a photosensitive resin coating. As a manufacturing device for the photosensitive dry film, a film coater commonly used for manufacturing adhesive products can be used. As the film coater, for example, 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 3-roll bottom reverse coater, a 4-roll bottom reverse coater, etc. can be cited.

[0204] The photosensitive dry film can be manufactured in the following manner: when the support film is unwound from the unwinding shaft of the coating machine and passed through the coating head of the coating machine, the photosensitive resin composition is coated on the support film with a specified thickness, and then passed through a hot air circulation oven at a specified temperature and time, and dried on the support film to form a photosensitive resin coating. In addition, the photosensitive dry film with a protective film can be manufactured in the following manner: as needed, the photosensitive dry film and the protective film unwound from the other unwinding shaft of the coating machine are passed through a laminating roller under a specified pressure, and the photosensitive resin coating on the support film is laminated with the protective film, and then wound on the winding shaft of the coating machine. At this time, the temperature is preferably 25~150°C, the time is preferably 1~100 minutes, and the pressure is preferably 0.01~5MPa.

[0205] The support film can be a monolayer film composed of a single film, or a multilayer film stacked with multiple films. As the material of the film, synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate can be listed. Among them, polyethylene terephthalate is preferred from the perspective of having appropriate flexibility, mechanical strength, and heat resistance. These films can be films that have been subjected to various treatments such as corona treatment or stripping agent coating. These films can use commercially available products, for example, Cerapeel WZ (RX), Cerapeel BX8 (R) (the above, manufactured by TORAY ADVANCED FILM CO., LTD.), E7302, E7304 (the above, manufactured by TOYOBO Co., Ltd.), Purex G31, Purex G71T1 (the above, manufactured by Teijin DuPont Films Japan Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (the above, manufactured by NIPPA Co., Ltd.), etc.

[0206] As the protective film, the same film as the aforementioned support film can be used, but polyethylene terephthalate and polyethylene are preferred from the point of view of having appropriate flexibility. These films can use commercially available products, and as polyethylene terephthalate, commercially available polyethylene terephthalate that has been exemplified can be listed, and as polyethylene, for example, GF-8 (manufactured by Tamapoly CO., LTD.), PE Film 0-Type (manufactured by NIPPA Co., Ltd.) and the like can be listed.

[0207] From the perspective of stability in the manufacture of the photosensitive dry film and prevention of the winding habit around a winding core, i.e., so-called curl, the thickness of the support film and the protective film are preferably 10 to 100 μm, more preferably 25 to 50 μm.

[0208] [Pattern forming method using photosensitive dry film]

[0209] The pattern forming method using the photosensitive dry film of the present invention comprises the following steps:

[0210] (i') a process of forming a photosensitive resin coating on a substrate using the photosensitive dry film of the present invention;

[0211] (ii) exposing the photosensitive resin film to light; and

[0212] (iii) a step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0213] First, in step (i'), a photosensitive resin coating is formed on a substrate using a photosensitive dry film. Specifically, the photosensitive resin coating of the photosensitive dry film is attached to the substrate, thereby forming the photosensitive resin coating 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 coating of the photosensitive dry film is attached to the substrate. The attachment can be performed using, for example, a film attaching device.

[0214] As the substrate, the same substrate as that described in the pattern forming method using a photosensitive resin composition can be cited. As the film laminating device, a vacuum laminator is preferred. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin coating is closely attached to the substrate on a workbench at a specified temperature using a laminating roller at a specified pressure in a vacuum chamber at a specified vacuum degree. In addition, 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.

[0215] In order to obtain a photosensitive resin coating of a desired thickness, the film may be attached multiple times as needed. The number of attachments is, for example, about 1 to 10 times, and a photosensitive resin coating with a film thickness of 10 to 1000 μm, particularly about 100 to 500 μm, can be obtained.

[0216] In order to effectively perform 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 needed. The pre-baking may be performed at 40 to 140° C. for about 1 minute to 1 hour, for example.

[0217] The photosensitive resin film attached to the substrate can be subjected to (ii) exposure of the photosensitive resin film; (iii) developing the exposed photosensitive resin film with a developer to form a pattern; and (iv) post-curing treatment as required to form a pattern. In addition, the support film of the photosensitive dry film is peeled off before pre-baking or PEB according to the process, or removed by other methods.

[0218] The photosensitive resin composition of the present invention can be used as a material for a coating film for protecting electric and electronic parts, or can be used as a material for a coating film for bonding two substrates together.

[0219] The film obtained from the photosensitive resin composition has excellent mechanical properties such as solder resistance, heat resistance, low warpage of the substrate, crack resistance, copper migration resistance, and adhesion to the substrate, and is suitable for use as a film for protecting electrical and electronic parts such as semiconductor elements or a film for bonding substrates. These films can also be formed using the photosensitive dry film of the present invention.

[0220] As described above, the present invention can provide a photosensitive resin composition that can be easily formed into a thick film and a fine pattern without copper discoloration, and can form a resin coating (resin layer) that is excellent in various film properties such as resistance to copper migration and adhesion to substrates, electronic parts, semiconductor elements, etc., especially base materials for circuit substrates, and has excellent reliability when used as a coating for protecting electric and electronic parts or a coating for bonding substrates. Furthermore, the present invention can provide a photosensitive resin coating, a photosensitive dry film formed using the photosensitive resin composition, and a pattern forming method using the photosensitive resin composition, the photosensitive resin coating, and the photosensitive dry film.

[0221] Example

[0222] The following is a more specific description of the present invention by showing synthesis examples, embodiments and comparative examples, but the present invention is not limited to the following embodiments. In addition, the weight average molecular weight (Mw) was measured by GPC using TSKgel Super HZM-H (manufactured by TOSOH CORPORATION) as a chromatographic column, and the analysis conditions of a flow rate of 0.6 mL / min, an eluent of THF, a chromatographic column temperature of 40° C., and monodisperse polystyrene as a standard.

[0223] The following lists compounds (S-1) to (S-6) used in the synthesis examples.

[0224]

[0225] [1] Synthesis of silicone resin

[0226] [Synthesis example 1]

[0227] After adding 215.0 g (0.5 mol) of compound (S-6) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 2000 g of toluene was added and heated to 70° C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5 mass %) was added, and 67.9 g (0.35 mol) of compound (S-4) and 453.0 g (0.15 mol) of compound (S-5) (y were added dropwise over 1 hour. 1 =40, manufactured by Shin-Etsu Chemical Co., Ltd.) (total amount of hydrosilyl groups / total amount of alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, 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. 1H-NMR (manufactured by Bruker KK) confirmed that silicone resin A-1 contained repeating units a2 and b2. The Mw of silicone resin A-1 was 62,000, and the silicone content was 61.6% by mass.

[0228] [Synthesis example 2]

[0229] After adding 53.00 g (0.20 mol) of compound (S-2) and 117.6 g (0.30 mol) of compound (S-1) to a 3L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 2000 g of toluene was added and heated to 70° C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5 mass %) was added, and 48.5 g (0.25 mol) of compound (S-4) and 755.0 g (0.25 mol) of compound (S-5) were added dropwise over 1 hour (y 1 =40, manufactured by Shin-Etsu Chemical Co., Ltd.) (total amount of hydrosilyl groups / total amount of alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was removed from the reaction solution by vacuum distillation to obtain silicone resin A-2. 1 H-NMR (manufactured by Bruker KK) confirmed that silicone resin A-2 contained repeating units a1, a3, b1, and b3. The Mw of silicone resin A-2 was 83,000, and the silicone content was 77.5% by mass.

[0230] [Synthesis example 3]

[0231] In a 3L flask equipped with a stirrer, a thermometer, a nitrogen replacement 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, and then 2000 g of toluene was added and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5 mass %) was added, and 87.3 g (0.45 mol) of compound (S-4) and 79.3 g (0.05 mol) of compound (S-5) were added dropwise over 1 hour (y 1 = 20, manufactured by Shin-Etsu Chemical Co., Ltd.) (total amount of hydrosilyl groups / total amount of alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was removed from the reaction solution by distillation under reduced pressure to obtain silicone resin A-3. 1H-NMR (manufactured by Bruker KK) confirmed that silicone resin A-3 contained repeating units a1, a2, a4, b1, b2, and b4. The Mw of silicone resin A-3 was 24,000, and the silicone content was 31.2% by mass.

[0232] [2] Preparation of photosensitive resin composition

[0233] [Examples 1 to 8 and Comparative Examples 1 to 16]

[0234] The components were blended in the amounts listed in Tables 1 to 3, stirred and dissolved at room temperature, and then microfiltered using a 1.0 μm filter membrane made of Teflon (registered trademark) to prepare photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 16.

[0235] [Table 1]

[0236]

[0237] [Table 2]

[0238]

[0239] [Table 3]

[0240]

[0241] 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 belong to the component (B) of the present invention, but compounds B'-1 to B'-6 do not.

[0242]

[0243]

[0244] In Tables 1 to 3, the photoacid generators PAG-1 to PAG-3 are shown below.

[0245]

[0246] In Tables 1 to 3, the crosslinking agents CL-1 and CL-2 are as follows.

[0247]

[0248] In Table 2, resin A'-1 is as follows. In addition, resin A'-1 does not belong to the (A) component of the present invention.

[0249]

[0250] [3] Preparation of photosensitive dry film

[0251] A die coater was used as a coating machine, a polyethylene terephthalate film (thickness of 38 μm) was used as a support film, and the photosensitive resin compositions described in Tables 1 to 3 were coated on the support film, respectively. Then, it was passed through a hot air circulation oven (length of 4 m) set at 100° C. for 5 minutes, thereby drying, forming a photosensitive resin coating on the support film to obtain a photosensitive dry film. Using a laminating roller, a polyethylene film (thickness of 50 μm) as a protective film was attached to the top of the photosensitive resin coating at a pressure of 1 MPa to prepare a photosensitive dry film with a protective film. The film thickness of each photosensitive resin coating was set to 80 μm. In addition, the film thickness of the photosensitive resin coating was measured by an optical interference film thickness meter (F50-EXR manufactured by Filmetrics, Inc.).

[0252] [4] Evaluation of resin coating

[0253] (1) Pattern formation and evaluation

[0254] For the photosensitive dry film with a protective film, the protective film is peeled off, and a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) is used to set the vacuum degree in the vacuum chamber to 80Pa, so that the photosensitive resin coating on the support film is closely attached to the substrate used for the migration test (a comb-shaped electrode substrate with a conductive material of copper, a conductive portion spacing and a conductive portion width of 10μm, and a conductive portion thickness of 4μm). The temperature condition is set to 100°C. After returning to normal pressure, the substrate is taken out of the vacuum laminator and the support film is peeled off. Next, in order to improve the adhesion with the substrate, a hot plate is used to preheat at 120°C for 5 minutes. In order to form a line width / spacing (line-and-space) pattern and a contact hole pattern on the obtained photosensitive resin coating, exposure is performed using a contact aligner type exposure device through a mask with an exposure condition of a wavelength of 365nm. After the exposure, PEB was performed at 140° C. for 5 minutes using a hot plate, followed by cooling and spray development using PGMEA for 300 seconds to form a pattern.

[0255] The photosensitive resin coating on the substrate formed with the pattern by the above method was post-cured at 170°C while purging with nitrogen for 1 hour. Then, the cross-sections of the formed 100μm, 80μm, 60μm, and 40μm contact hole patterns were observed by scanning electron microscopy (SEM), and the smallest hole pattern that penetrated the bottom of the film was taken as the limiting resolution. The verticality of the 80μm contact hole pattern was further evaluated based on the obtained cross-sectional photographs, and the vertical pattern was evaluated as ◎, the observation of a slightly inverted tapered profile or footing was evaluated as ○, the observation of a clear inverted tapered profile or footing was evaluated as △, and the poor opening was evaluated as ×. The results are shown in Tables 4 to 6.

[0256] (2) Evaluation of electrical properties (copper migration)

[0257] The substrate patterned by the method (1) was used as a substrate for evaluating copper migration, and the test was conducted. The copper migration test was conducted at a temperature of 130°C, a humidity of 100%, and an applied voltage of 20V, and the time for short circuit occurrence was confirmed with an upper limit of 1000 hours. The results are shown in Tables 4 to 6.

[0258] (3) Discoloration of copper surface

[0259] For the aforementioned photosensitive dry film with a protective film, the protective film is peeled off, and a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) is used to set the vacuum degree in the vacuum chamber to 80 Pa, so that the photosensitive resin coating on the support film is closely attached to the substrate with a 350nm copper-plated film. The temperature condition is set to 100°C. After returning to normal pressure, the substrate is taken out of the vacuum laminator and the support film is peeled off. Then, in order to improve the adhesion with the substrate, a hot plate is used to preheat at 120°C for 5 minutes. In order to form a line width / spacing pattern and a contact hole pattern on the obtained photosensitive resin coating, a contact photolithography type exposure device is used to expose the pattern through a mask at an exposure condition of a wavelength of 365nm. After exposure, a hot plate is used to perform PEB at 140°C for 5 minutes, and then cooled, and PGMEA is used for 300 seconds of spray development to form a 1cm×1cm hole pattern. Then, post-curing was performed at 170° C. for 1 hour in an oven. Then, the copper surface in the hole was observed with the naked eye, and the evaluation of no discoloration was ○, and the evaluation of discoloration was ×. The results are shown in Tables 4 to 6.

[0260] (4) Evaluation of reliability (adhesion, crack resistance)

[0261] For the aforementioned photosensitive dry film with a protective film, the protective film is peeled off, and a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) is used to set the vacuum degree in the vacuum chamber to 80 Pa, so that the photosensitive resin coating on the support film is tightly attached to a 10 mm × 10 mm square CCL substrate stacked with silicon chips. The temperature condition is set to 100°C. After returning to normal pressure, the substrate is taken out of the vacuum laminator and the support film is peeled off. Then, in order to improve the adhesion with the substrate, a hot plate is used to preheat at 120°C for 5 minutes. Without a mask, the obtained photosensitive resin coating is exposed using a contact photolithography type exposure device at an exposure condition of a wavelength of 365nm. After exposure, PEB is performed at 140°C for 5 minutes on a hot plate, and then cooled. An oven is used to post-cure at 170°C for 1 hour while purging with nitrogen. Then, a dicing machine (DAD685, manufactured by DISCO CORPORATION, with a spindle speed of 40,000 rpm and a cutting speed of 20 mm / second) equipped with a dicing blade was used to cut the substrate on which the resin film was formed so that the periphery of the silicon chip was 5 mm, thereby obtaining a 20 mm × 20 mm square test piece. The obtained test pieces (10 pieces each time) were subjected to a thermal cycle test (kept at -55°C for 10 minutes and at 125°C for 10 minutes, and repeated for 1000 times), and the state of the resin film peeling off from the wafer after the thermal cycle test and the presence or absence of cracks were confirmed. All those without peeling and cracking were evaluated as ○, those with only one peeling were evaluated as ×, and those with only one crack were evaluated as ×. In addition, the presence or absence of peeling and cracking was confirmed by bottom-up observation and cross-sectional SEM observation using an optical microscope. The results are shown in Tables 4 to 6.

[0262] (5) Evaluation of Adhesion (Initial Stage: Before Heat Resistance Test)

[0263] For the photosensitive dry film with a protective film, the protective film is peeled off, and a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) is used to set the vacuum degree in the vacuum chamber to 80 Pa, and the photosensitive resin coating on the support film is laminated on an 8-inch silicon wafer. A hot plate is used to preheat it at 120°C for 5 minutes to obtain a substrate (wafer) with a resin film. In addition, a cutting machine with a cutting blade (DAD685 manufactured by DISCO CORPORATION) is used to cut the separately prepared 8-inch silicon wafer into a size of 2mm×2mm square. Five of the 2mm×2mm square chips are bonded to the previous substrate with a resin film at 130°C and a load of 50mN through the resin film. Then, the resin film is cured by heating at 170°C for 1 hour, and it is provided for an adhesion measurement test. In the adhesion measurement, an adhesion tester (Dage series 4000-PXY manufactured by DAGECORPORATION) was used to measure the resistance of the semiconductor chip (2mm×2mm) when it was peeled off from the base substrate (15mm×15mm square silicon wafer), and the adhesion of the resin film was evaluated. Regarding the test conditions, the test speed was 200μm / second and the test height was 50μm. The results are shown in Tables 4 to 6. In addition, the numerical value is the average of the measured values ​​of the 5 test pieces respectively. The higher the numerical value, the higher the adhesion.

[0264] (6) Evaluation of Adhesion (after heat resistance test)

[0265] The test piece for measuring adhesive strength prepared in (5) was placed in an oven heated to 150° C. for 2000 hours, then taken out of the oven and subjected to an adhesive strength measurement test in the same manner as (5). The results are shown in Tables 4 to 6.

[0266] (7) Evaluation of solvent resistance

[0267] In order to evaluate the solvent resistance to N-methyl-2-pyrrolidone (NMP) which is commonly used in the formation of semiconductor elements, etc., a substrate prepared by the same method as the wafer for evaluating the adhesive force in (5) was immersed in NMP at 50°C for 1 hour, and the film thickness change and appearance were investigated to evaluate the solvent resistance. The evaluation of no change in appearance and film thickness was ○, and the evaluation of swelling was ×. The results are shown in Tables 4 to 6.

[0268] [Table 4]

[0269]

[0270] [Table 5]

[0271]

[0272] [Table 6]

[0273]

[0274] As shown in Table 4, the photosensitive resin composition of the present invention (Examples 1 to 8) can form patterns with excellent resolution and shape, and has good electrical properties (anti-copper migration), no discoloration of the copper surface, and excellent reliability (adhesion, crack resistance), adhesion (heat resistance) and solvent resistance.

[0275] However, as shown in Tables 5 and 6, the compositions of Comparative Examples 1 to 4 and 11 to 16 not containing the component (B) of the present invention and Comparative Examples 5 to 10 not containing the component (A) of the present invention had poor limiting resolution and shape when forming patterns, could not suppress copper migration and discoloration, and had poor reliability, adhesion, and solvent resistance.

[0276] In Comparative Examples 11 to 16, although B'-1 to B'-6 added in place of the component (B) of the present invention are components that have been used as curing agents or curing accelerators for epoxy resins in the past, they failed to give satisfactory results as shown above. In particular, although it is known that diaminotriazine compounds having an imidazole ring that are used as curing agents or curing accelerators for epoxy resins can inhibit discoloration of copper (see Japanese Patent Publication No. 7-033766), as shown in the results of Comparative Example 14 in which B'-4 (2,4-diamino-6-(2'-ethyl-4'-methylimidazolyl)ethyl-1,3,5-triazine) as such a compound is added, it is not possible to inhibit discoloration of copper, and the characteristics of the pattern formed are also poor.

[0277] This shows that the present invention can achieve excellent effects that could not be expected from the prior art by combining (A) a silicone resin having an acid crosslinkable group with (B) an oxazoline compound or a derivative thereof.

[0278] According to the above results, the photosensitive resin composition and photosensitive dry film of the present invention have no copper discoloration, can be easily formed into a thick film and vertical fine pattern, and exhibit sufficient characteristics as a photosensitive material. In addition, the photosensitive resin coating obtained from the photosensitive resin composition and photosensitive dry film of the present invention has high chemical resistance to photoresist stripping liquid, etc., and has excellent adhesion, electrical insulation, and copper migration resistance. It has high reliability when used as an insulating protective film and can be used as a coating material for protecting various electrical and electronic parts such as circuit substrates, semiconductor elements, and display elements. According to the present invention, a photosensitive resin composition and photosensitive dry film with higher reliability can be provided.

[0279] This manual contains the following solutions:

[0280] [1]: A photosensitive resin composition, characterized in that it comprises:

[0281] (A) a silicone resin having an acid crosslinkable group,

[0282] (B) an oxazoline compound or a derivative thereof, and

[0283] (C) Photoacid generator.

[0284] [2]: The photosensitive resin composition according to [1], characterized in that the silicone resin (A) is a silicone resin represented by the following formula (A1):

[0285]

[0286] In the formula, R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; k is an integer of 1 to 600; a and b represent the composition ratio (molar ratio) of each repeating unit, which is a number 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 hydroxyl group.

[0287] [3]: The photosensitive resin composition according to [1] or [2], characterized in that the silicone resin (A) comprises repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4),

[0288]

[0289] In the formula, R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; k is an integer from 1 to 600; a 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and satisfies 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 +a3 +a 4 +b 1 +b 2 +b 3 +b 4 =1; X 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);

[0290]

[0291] Where Y 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 11 and R 12 are each independently a hydrogen atom or a methyl group; R 13 and R 14 Each is independently a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms; 1 and p 2 Each independently represents an integer from 0 to 7; q 1 and q 2 Each is independently an integer from 0 to 2; the dotted line is a connecting bond;

[0292]

[0293] Where Y 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 21 and R 22 are each independently a hydrogen atom or a methyl group; R 23 and R 24 Each independently represents a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms; 1 and r 2 Each independently represents an integer from 0 to 7; s 1 and 2 Each is independently an integer from 0 to 2; the dotted line is a connecting bond;

[0294]

[0295] In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group; 1and t 2 Each is independently an integer from 0 to 7; the dotted line is a connecting bond;

[0296]

[0297] In the formula, R 41 and R 42 are each independently a hydrogen atom or a methyl group; R 43 and R 44 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; 1 and u 2 Each is independently an integer from 0 to 7; v is an integer from 0 to 600; and the dotted line is a connecting bond.

[0298] [4]: The photosensitive resin composition according to any one of [1] to [3], further comprising (D) a cross-linking agent.

[0299] [5]: The photosensitive resin composition according to [4] is characterized in that the (D) crosslinking agent is at least one selected from the group consisting of a nitrogen-containing compound selected from melamine compounds, cyanamide compounds, glycoluril compounds and urea compounds containing an average of more than 2 hydroxymethyl groups and / or alkoxymethyl groups in one molecule; an amino condensate modified by formaldehyde or formaldehyde-alcohol; a phenol compound having an average of more than 2 hydroxymethyl groups or alkoxymethyl groups in one molecule; and an epoxy compound having an average of more than 2 epoxy groups in one molecule.

[0300] [6]: The photosensitive resin composition according to any one of [1] to [5], further comprising (E) a solvent.

[0301] [7]: A photosensitive resin coating obtained from the photosensitive resin composition described in any one of [1] to [6].

[0302] [8]: A photosensitive dry film, characterized in that it comprises a support film and the photosensitive resin coating described in [7] is disposed on the support film.

[0303] [9]: A pattern forming method, characterized in that it comprises the following steps:

[0304] (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition described in any one of [1] to [6];

[0305] (ii) exposing the photosensitive resin film to light; and

[0306] (iii) a step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0307]

[10] : A pattern forming method, characterized in that it comprises the following steps:

[0308] (i') a step of forming a photosensitive resin coating on a substrate using the photosensitive dry film described in [8];

[0309] (ii) exposing the photosensitive resin film to light; and

[0310] (iii) a step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0311]

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

[0312]

[12] : The photosensitive resin composition according to any one of [1] to [6], characterized in that the photosensitive resin composition is a material for a coating for protecting electrical and electronic parts.

[0313]

[13] : The photosensitive resin composition according to any one of [1] to [6], characterized in that the photosensitive resin composition is a material for a coating for bonding two substrates.

[0314] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are examples, and any technical solution having substantially the same structure and achieving the same technical effect as the technical concept described in the claims of the present invention is included in the technical scope of the present invention.

Claims

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

2. The photosensitive resin composition according to claim 1, characterized in that: The (A) silicone resin is a silicone resin represented by the following formula (A1), In the formula, R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; k is an integer of 1 to 600; a and b represent the composition ratio (molar ratio) of each repeating unit, which is a number 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 hydroxyl group.

3. The photosensitive resin composition according to claim 2, characterized in that: The silicone resin (A) comprises repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4), In the formula, R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; k is an integer from 1 to 600; a 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and satisfies 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; X 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); Where Y 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 11 and R 12 are each independently a hydrogen atom or a methyl group; R 13 and R 14 Each is independently a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms; 1 and p 2 Each independently represents an integer from 0 to 7; q 1 and q 2 Each is independently an integer from 0 to 2; the dotted line is a connecting bond; Where Y 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 21 and R 22 are each independently a hydrogen atom or a methyl group; R 23 and R 24 Each independently represents a saturated hydrocarbon group having 1 to 4 carbon atoms or a saturated hydrocarbon oxy group having 1 to 4 carbon atoms; 1 and r 2 Each independently represents an integer from 0 to 7; s 1 and 2 Each is independently an integer from 0 to 2; the dotted line is a connecting bond; In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group; 1 and t 2 Each is independently an integer from 0 to 7; the dotted line is a connecting bond; In the formula, R 41 and R 42 are each independently a hydrogen atom or a methyl group; R 43 and R 44 Each is independently a hydrocarbon group having 1 to 8 carbon atoms; 1 and u 2 Each is independently an integer from 0 to 7; v is an integer from 0 to 600; and the dotted line is a connecting bond.

4. The photosensitive resin composition according to claim 1, characterized in that: It further comprises (D) a cross-linking agent.

5. The photosensitive resin composition according to claim 4, characterized in that: The (D) cross-linking agent is at least one selected from a nitrogen-containing compound selected from melamine compounds, cyanamide compounds, glycoluril compounds and urea compounds, which contains an average of more than 2 hydroxymethyl groups and / or alkoxymethyl groups in one molecule; an amino condensate modified by formaldehyde or formaldehyde-alcohol; a phenol compound having an average of more than 2 hydroxymethyl groups or alkoxymethyl groups in one molecule; and an epoxy compound having an average of more than 2 epoxy groups in one molecule.

6. The photosensitive resin composition according to any one of claims 1 to 5, characterized in that: It further comprises (E) a solvent. 7 . A photosensitive resin coating, obtained from the photosensitive resin composition according to claim 1 .

8. A photosensitive dry film, characterized in that: The photosensitive resin film comprises a support film, and the photosensitive resin film according to claim 7 is provided on the support film.

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

10. A pattern forming method, characterized in that: It includes the following steps: (i') a process of forming a photosensitive resin coating 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 using a developer to form a pattern.

11. The pattern forming method according to claim 9, characterized in that: It further comprises the following steps: (iv) a step of post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

12. The photosensitive resin composition according to any one of claims 1 to 5, characterized in that: The photosensitive resin composition is a material for coating films that protect electrical and electronic parts.

13. The photosensitive resin composition according to claim 6, characterized in that: The photosensitive resin composition is a material for coating films that protect electrical and electronic parts.

14. The photosensitive resin composition according to any one of claims 1 to 5, characterized in that: The photosensitive resin composition is a material for a coating film for bonding two substrates.

15. The photosensitive resin composition according to claim 6, characterized in that: The photosensitive resin composition is a material for a coating film for bonding two substrates.

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