Photosensitive resin laminate, method for forming resist pattern, and method for manufacturing wiring board

Abstract

Provided is a photosensitive resin laminate comprising a support and a photosensitive resin layer containing a photosensitive resin composition, the photosensitive resin composition containing the following components: 　(A) a compound having an ethylenically unsaturated bond; 　(B) an alkali-soluble resin; and 　(C) a polymerization initiator, wherein 　the component (A) contains (A1) a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule, 　the component (C) contains a hexaarylbiimidazole compound, and 　the component (C) content is at least 4.0% by mass of the total solid content of the photosensitive resin composition.

Description

Photosensitive resin laminate, method for forming resist pattern, and method for manufacturing wiring board

[0001] The present invention relates to a photosensitive resin laminate, a method for forming a resist pattern, and a method for manufacturing a wiring board.

[0002] Printed circuit boards are generally manufactured using a photolithography process. Photolithography is a method of forming a desired wiring pattern on a substrate through the following steps: First, a layer containing a photosensitive resin composition is formed on the substrate, and a resist pattern is formed by pattern exposure and development of the coating film. Next, a conductor pattern is formed by etching or plating. After that, the desired wiring pattern is formed on the substrate by removing the resist pattern on the substrate.

[0003] Generally, in photolithography processes, resist patterns are formed by methods such as coating a solution of a photosensitive resin composition onto a substrate and drying it, or by laminating a resist layer of a dry film resist (a photosensitive resin laminate including a resist layer and a support film) onto a substrate.

[0004] In the manufacture of printed circuit boards, photosensitive resin laminates are frequently used. In the production and use of photosensitive resin laminates, the type, combination, and content of compounds containing ethylenically unsaturated bonds are important factors, as are their developability, flexibility, resist pattern formation properties, and peelability, as well as their productivity.

[0005] For example, Patent Document 1 discloses a photosensitive element comprising a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having a fluorene skeleton in its molecule, and (C) a photopolymerization initiator. For example, Patent Document 2 discloses a photosensitive resin laminate comprising a photosensitive resin layer and a support layer, the photosensitive resin composition comprising (a) an alkali-soluble resin containing carboxyl groups and having an acid equivalent of 100 to 600: 20 to 90% by mass, (b) a photopolymerizable unsaturated compound: 5 to 70% by mass, and (c) a photopolymerization initiator: 0.1 to 20% by mass, wherein (b) the photopolymerizable unsaturated compound contains (b-1) a photopolymerizable unsaturated compound having a fluorene skeleton in an amount of 3 to 19% by mass relative to the total sum of the above components (a) and (b).

[0006] Japanese Patent Publication No. 2005-331771 Japanese Patent Publication No. 2009-053388

[0007] However, although the photosensitive resin composition described in Patent Document 1 has a predetermined peelability, there was room for further improvement in terms of resist pattern formation and developability. Similarly, although the photosensitive resin composition described in Patent Document 2 has a predetermined resist pattern formation, there was room for further improvement in terms of developability and peelability. In this specification, excellent resist pattern formation means excellent in both resolution and adhesion.

[0008] The object of the present invention is to provide a photosensitive resin laminate, a method for forming a resist pattern, and a method for manufacturing a wiring board that have excellent resist pattern formation properties, developability, and peelability.

[0009] The present invention is as follows:

[0010] [1] A photosensitive resin laminate comprising a support and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition contains the following components: (A) a compound having an ethylenically unsaturated bond, (B) an alkali-soluble resin, and (C) a polymerization initiator, the component (A) contains (A1) a compound having three or more aromatic rings in one molecule and one or more ethylenically unsaturated bonds, the component (C) contains a hexaarylbiimidazole compound, and the content of the component (C) is 4.0% by mass or more based on the total solid content of the photosensitive resin composition. Photosensitive resin laminate. [2] The photosensitive resin laminate according to [1], wherein (A1) is a compound having a structure in which three or more aromatic rings are bonded to one carbon atom in one molecule and one or more ethylenically unsaturated bonds. [3] The photosensitive resin laminate according to [1] or [2], wherein (A1) contains a fluorene skeleton, or a methylidene tris(phenyl) skeleton or an ethylidene tris(phenyl) skeleton in the molecule. [4] The photosensitive resin laminate according to any one of [1] to [3], wherein (A1) contains a fluorene skeleton in the molecule. [5] The photosensitive resin laminate according to any one of [1] to [4], wherein (A1) is a compound having a fluorene skeleton in the molecule and 2 to 4 (meth)acryloyl groups. [6] The photosensitive resin laminate according to any one of [1] to [5], wherein (A1) is represented by the following general formula (I): [In the formula, X is independently S or O, R １ , R ２ , R ３ and R ４ each independently represents an alkylene group having 1 to 10 carbon atoms, R ５ , R ６ , R ７ , R ８、 R ９ and R １０ are each independently a hydrogen atom or a methyl group, a and b are 0 or 1, and m, n, o and p are each independently 0 to 30.]. The photosensitive resin laminate according to any one of [1] to [5], containing the compound represented by the formula. [7] The photosensitive resin laminate according to any one of [1] to [5], wherein (A1) is represented by the following general formula (II): [In the formula, R １ and R ２Each of these independently represents an alkylene group having 1 to 10 carbon atoms, and R ５ and R ６ A photosensitive resin laminate according to any one of [1] to [6], comprising a compound represented by ], wherein (A1) is a compound having two (meth)acryloyl groups. [8] A photosensitive resin laminate according to any one of [1] to [7], wherein (A1) is a compound having two (meth)acryloyl groups. [9] A photosensitive resin laminate according to any one of [1] to [8], wherein the main chain end of (A1) is a methacryloyl group.

[10] The repeating unit in the general formulas (I) and (II), R １ O, R ２ O, R ３ O, and R ４ A photosensitive resin laminate according to any one of [6] to [9], wherein O is ethylene oxide (EO) or propylene oxide (PO).

[11] A photosensitive resin laminate according to any one of [6] to

[10] , wherein the total number of moles of repeating units in general formulas (I) and (II) (the sum of m + n + o + p in general formula (I) and the sum of (2 × m) + (2 × n) in general formula (II)) is 30 moles or less.

[12] A photosensitive resin laminate according to any one of [6] to

[11] , wherein the total number of moles of repeating units in general formulas (I) and (II) (the sum of m + n + o + p in general formula (I) and the sum of (2 × m) + (2 × n) in general formula (II)) is 5 moles or more.

[13] The photosensitive resin laminate according to any one of [1] to

[12] , wherein (A1) contains a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton in the molecule.

[14] The (A1) is the following general formula (III): [In the formula, X is independently S or O, and R １ , R ２ and R ３ Each of these independently represents an alkylene group having 1 to 10 carbon atoms, and R ４ , R ５ , R ６ and R ７A photosensitive resin laminate according to any one of [1] to

[13] , comprising a compound represented by [A1].

[15] The above (A1) is the following general formula (IV): [In the formula, R １ , R ２ and R ３ Each of these independently represents an alkylene group having 1 to 10 carbon atoms, and R ４ , R ５ , R ６ and R ７ A photosensitive resin laminate according to any one of [1] to

[14] , comprising a compound represented by [ ], wherein each is independently a hydrogen atom or a methyl group, and m, n and o are independently 0 to 30.

[16] The repeating unit in the general formulas (III) and (IV), R １ O, R ２ O and R ３A photosensitive resin laminate according to

[14] or

[15] , wherein O is ethylene oxide (EO) or propylene oxide (PO).

[17] A photosensitive resin laminate according to any one of

[14] to

[16] , wherein the total number of moles of repeating units in the general formulas (III) and (IV) (the sum of m + n + o in the general formula (III) and the sum of (2 × m) + (2 × n) + (2 × o) in the general formula (IV)) is 0 to 50 moles.

[18] A photosensitive resin laminate according to any one of

[14] to

[17] , wherein the total number of moles of repeating units in the general formulas (III) and (IV) (the sum of m + n + o in the general formula (III) and the sum of (2 × m) + (2 × n) + (2 × o) in the general formula (IV)) is 5 moles or more.

[19] The photosensitive resin laminate according to any one of [1] to

[18] , wherein the total content of component (A) and component (B) in the photosensitive resin composition is 80% by mass or more, based on the total solid content mass of the photosensitive resin composition.

[20] The photosensitive resin laminate according to any one of [1] to

[19] , wherein the content of component (B) is 70% by mass or less, based on the total content of component (A) and component (B).

[21] The photosensitive resin laminate according to any one of [1] to

[20] , wherein the photosensitive resin composition further comprises (D) a polymerization inhibitor.

[22] The photosensitive resin laminate according to any one of [1] to

[21] , wherein component (A) further comprises (A2) a compound having two or fewer aromatic rings in one molecule and having an ethylenically unsaturated bond.

[23] The photosensitive resin laminate according to

[22] , wherein (A2) comprises a compound having two or more ethylenically unsaturated bonds.

[24] The photosensitive resin laminate according to

[22] , wherein (A2) comprises a compound having three or more ethylenically unsaturated bonds.

[25] The photosensitive resin laminate according to

[22] , wherein (A2) comprises a compound having three to six ethylenically unsaturated bonds.

[26] The photosensitive resin laminate according to any one of

[22] to

[25] , wherein (A2) does not have quaternary carbon and comprises a compound having three or more ethylenically unsaturated bonds.

[27] The photosensitive resin laminate according to any one of

[22] to

[25] , wherein (A2) does not have quaternary carbon and comprises a compound having three to six ethylenically unsaturated bonds.

[28] A compound that does not have a quaternary carbon and has three or more ethylenically unsaturated bonds has the following general formula (V): [In the formula, h is between 1 and 20, each i is a natural number between 1 and h, each k, li, and j are independently between 0 and 30, R ９ , and R １１ Each of these independently represents either a hydrogen atom or a methyl group, and R １２ , and R １４ Each of these is an alkylene group having 1 to 10 carbon atoms, with the following general formula (VI): [In the formula, R １５ and R １６ Each of these is an alkylene group having 1 to 10 carbon atoms. The group represented by ] and the following general formula (VII): [In the formula, R １７[1] is an alkylene group having 1 to 10 carbon atoms.

[22] is one selected from the group consisting of groups represented by [1].

[33] A photosensitive resin laminate according to

[26] comprising a (poly)glycerin-based (meth)acrylate represented by [1].

[29] A photosensitive resin laminate according to

[28] , wherein in the general formula (V), h is 2 to 20.

[30] A photosensitive resin laminate according to any one of

[22] to

[29] , wherein (A2) is a compound containing a methacryloyl group.

[31] A photosensitive resin laminate according to any one of

[22] to

[30] , wherein (A2) is a compound having one ethylenically unsaturated bond.

[32] A photosensitive resin laminate according to any one of [1] to

[31] , wherein component (B) comprises a copolymer having structural units derived from styrene and benzyl (meth)acrylate.

[33] The photosensitive resin laminate according to any one of [1] to

[32] , wherein the component (B) contains constituent units derived from styrene, and the component (B) contains 30% by mass or more of styrene.

[34] The photosensitive resin laminate according to any one of [1] to

[33] , wherein the content of constituent units derived from styrene in the component (B) is 50% by mass or less.

[35] The photosensitive resin laminate according to any one of [1] to

[34] , wherein the weight-average molecular weight of the component (B) is 17,500 or more.

[36] The photosensitive resin laminate according to any one of [1] to

[35] , wherein the weight-average molecular weight of the component (B) is 50,000 or less.

[37] The photosensitive resin laminate according to any one of [1] to

[36] , wherein the component (B) contains constituent units derived from (meth)acrylic acid, and the content of constituent units derived from (meth)acrylic acid is 15% by mass or more and 35% by mass or less.

[38] The photosensitive resin laminate according to any one of [1] to

[37] , wherein the component (B) comprises a constituent unit derived from a monomer having at least one ethylenically unsaturated bond in the molecule and containing a hydroxyl group.

[39] The photosensitive resin laminate according to any one of [1] to

[38] , wherein the Tg of the component (B), calculated by Fox's formula, is 375 K or more and 400 K or less.

[40] Na at a concentration of 1% by mass ２ CO ３A photosensitive resin laminate according to any one of [1] to

[39] , wherein the minimum development time per 1 μm of film thickness of the photosensitive resin layer when developing by spraying an aqueous solution at 30°C is 0.6 seconds or more and 1.1 seconds or less.

[41] A photosensitive resin laminate according to any one of [1] to

[40] , further comprising a protective film.

[42] A method for forming a resist pattern using a photosensitive resin laminate according to any one of [1] to

[41] , comprising the following steps: a lamination step of laminating a photosensitive resin layer onto a substrate; an exposure step of exposing the photosensitive resin layer; and a development step of developing and removing the unexposed portion of the photosensitive resin layer.

[43] A method for manufacturing a wiring board using a photosensitive resin laminate as described in any of [1] to

[41] , comprising the following steps: a lamination step of laminating a photosensitive resin layer onto a substrate; an exposure step of exposing the photosensitive resin layer to light; a developing step of developing and removing the unexposed portion of the photosensitive resin layer to form a resist pattern; a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed to form a conductor pattern; and a peeling step of peeling the resist pattern from the substrate; a method for manufacturing a wiring board.

[0011] According to the present invention, it is possible to provide a photosensitive resin laminate comprising a resist layer containing a photosensitive resin composition that has excellent developability, resist pattern formation properties, and peelability, a method for forming a resist pattern, and a method for manufacturing a wiring board.

[0012] The following describes in detail an exemplary embodiment of the present invention (hereinafter abbreviated as "this embodiment"). The present invention is not limited to this embodiment and can be implemented in various modifications within the scope of its gist. In this specification, the upper and lower limits of each numerical range can be arbitrarily combined. Furthermore, in this embodiment, the upper or lower limit of a numerical range can be replaced with the value shown in the example. In this specification, numerical ranges indicated using "~" include the upper and lower numerical limits. The term "process" in the following description includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as the function of that "process" is achieved.

[0013] Furthermore, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means acryloyl group or methacryloyl group, and "(meth)acrylate" means "acrylate" or "methacrylate".

[0014] <Photosensitive Resin Laminate> In one embodiment, the photosensitive resin laminate of this embodiment comprises a support and a photosensitive resin layer containing a photosensitive resin composition. In particular, the photosensitive resin composition constituting the photosensitive resin laminate provided in one aspect of this embodiment comprises the following components: (A) a compound having an ethylenically unsaturated bond, (B) an alkali-soluble resin, and (C) a polymerization initiator. In particular, in the photosensitive resin laminate of this embodiment, the photosensitive resin composition includes (A) a compound having an ethylenically unsaturated bond, which is (A1) a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule. In one embodiment, the photosensitive resin laminate of this embodiment includes a photosensitive resin composition containing a hexaarylbiimidazole compound as (C) a polymerization initiator, wherein the content of (C) the polymerization initiator is 4.0% by mass or more of the total solid content of the photosensitive resin composition.

[0015] The present inventors have found that by combining a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule as component (A1) of the photosensitive resin composition of this embodiment, the developability, resolution, adhesion, and peelability are improved. In other words, according to this embodiment, it is possible to provide a photosensitive resin composition with excellent developability, resolution, adhesion, and peelability, a method for forming a resist pattern, and a method for manufacturing a wiring board.

[0016] <Support> The support according to this embodiment is a layer or film for supporting the photosensitive resin layer, and is preferably a transparent substrate film that transmits active light.

[0017] Examples of transparent substrate films include films made from synthetic resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate (PET), cellulose triacetate, and cycloolefin polymer. Among these, it is preferable to use a high-quality film with fewer internal foreign matter. Specifically, as high-quality films, polyethylene terephthalate (PET) film, cellulose triacetate film, or cycloolefin polymer film are preferred, and polyethylene terephthalate (PET) film, which has appropriate flexibility and strength, is more preferably used. Among PET films, it is more preferable to use PET films synthesized using a Ti-based catalyst, PET films with a small diameter and low lubricant content, PET films containing lubricant on only one side of the film, thin-film PET films, PET films with a smoothing treatment on at least one side, or PET films with a roughening treatment such as plasma treatment on at least one side. This allows the light to be exposed to the photosensitive resin layer without being blocked by internal foreign matter, thereby improving the resolution of the photosensitive resin composition.

[0018] The thickness of the support film is preferably 5 μm to 25 μm, and more preferably 6 μm to 20 μm. A thinner support film reduces the number of internal foreign matter, thus preventing a decrease in resolution. However, if the film is too thin, it can lead to stretching deformation in the winding direction due to tension during the coating and winding manufacturing process, tearing due to minute scratches, or insufficient film strength resulting in wrinkles during lamination.

[0019] At least one side of the support may be subjected to a smoothing treatment using a calendering device or the like. This reduces the surface roughness of one side of the support, particularly the side that comes into contact with the photosensitive resin composition layer described later, thereby improving the effects of this embodiment.

[0020] The haze of the support is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01% to 0.95%, from the viewpoint of improving the parallelism of the light rays irradiated onto the photosensitive resin layer and obtaining higher resolution after exposure and development of the photosensitive resin laminate.

[0021] <Photosensitive Resin Layer> The photosensitive resin layer according to this embodiment includes a photosensitive resin composition. In one embodiment, the photosensitive resin layer according to this embodiment is a resist layer. The thickness of the photosensitive resin layer according to this embodiment is preferably 3 to 100 μm, more preferably 3 to 50 μm, and even more preferably 5 to 30 μm. The closer the thickness of the photosensitive resin layer is to 3 μm, the better the resolution, and the closer it is to 100 μm, the better the film strength, so it can be appropriately selected according to the application. When the thickness of the photosensitive resin layer according to this embodiment is 3 to 100 μm, it can be suitably used for applications such as copper wiring formation for printed circuit boards, copper wiring formation for package substrates, bump formation, copper pillar formation, and copper wiring formation for redistribution layers. When the thickness of the photosensitive resin layer according to this embodiment is 5 to 30 μm, it can be suitably used for applications such as copper wiring formation for printed circuit boards, copper wiring formation for package substrates, and copper wiring formation for redistribution layers. The thickness of the photosensitive resin layer according to this embodiment may be greater than 100 μm and less than or equal to 500 μm. Having the photosensitive resin layer thickness within this range makes it suitable for use in bump formation and copper pillar formation.

[0022] The photosensitive resin layer according to this embodiment contains Na at a concentration of 1% by mass. ２ CO ３When developing by spraying an aqueous solution at 30°C, the minimum development time is preferably 0.6 seconds or more and 1.1 seconds or less per 1 μm of film thickness. It is believed that a good balance between adhesion and resolution is achieved when the minimum development time is within the above range. Although not bound by theory, it is presumed that the mechanism by which a good balance between adhesion and resolution is achieved when the minimum development time is within the above range is that a minimum development time of 0.6 seconds or more allows sufficient penetration of the developer solution into the vicinity of the substrate surface between adjacent patterns during resist pattern formation, and a minimum development time of 1.1 seconds or less prevents stress on the resist pattern and swelling of the resist pattern during development. In this disclosure, the minimum development time is the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve, and may be determined by visual inspection.

[0023] <Photosensitive resin composition> The photosensitive resin composition of this embodiment comprises (A) a compound having an ethylenically unsaturated bond, (B) an alkali-soluble resin, and (C) a polymerization initiator.

[0024] - (A) Compounds having ethylenically unsaturated bonds The photosensitive resin composition of this embodiment includes (A) a compound having ethylenically unsaturated bonds (hereinafter referred to as component (A)). Component (A) includes (A1) a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule (hereinafter referred to as component (A1)). In this embodiment, component (A1) is not particularly limited as long as it is a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule. In one embodiment, the photosensitive resin composition of this embodiment includes, in addition to component (A1), component (A) further includes (A2) a compound having two or fewer aromatic rings in one molecule and having ethylenically unsaturated bonds (hereinafter referred to as component (A2)). The photosensitive resin composition of this embodiment, by including component (A1) as component (A), exhibits good developability, resolution, adhesion, and peelability.

[0025] - (A1) A compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule. In one embodiment, component (A1) is a compound having a structure in which three or more aromatic rings are bonded to one carbon atom in one molecule, and having one or more ethylenically unsaturated bonds. In one embodiment, component (A1) contains a fluorene skeleton, or a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton in its molecule. In one embodiment, component (A1) contains at least one compound containing a fluorene skeleton, or a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton in its molecule. In one embodiment, component (A1) contains a fluorene skeleton in its molecule. In one embodiment, component (A1) contains a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton in its molecule.

[0026] When component (A1) contains a fluorene skeleton within its molecule, the resist pattern formed using this photosensitive resin composition containing component (A1) exhibits excellent adhesion and resolution (resist pattern formation). This is because fluorene is rigid due to its unique structure having a cardioid (hinge) structure and numerous aromatic rings. In this disclosure, a cardioid (hinge) structure refers to a structure in which the aromatic rings of the main chain and the fluorenes of the side chains are orthogonal in three directions.

[0027] In this embodiment, from the viewpoint of adhesion and resolution, it is preferable that the main chain terminus of component (A1) is a (meth)acryloyl group, and more preferably a methacryloyl group. In this embodiment, from the viewpoint of adhesion and resolution, it is preferable that component (A1) is a compound having one or more (meth)acryloyl groups, and more preferably a compound having two (meth)acryloyl groups. In this embodiment, component (A1) may be a compound having two or more (meth)acryloyl groups. In this embodiment, from the viewpoint of adhesion and resolution, it is preferable that component (A1) is a compound having a fluorene skeleton in the molecule and having two to four (meth)acryloyl groups.

[0028] (A1) Component is given by the following general formula (I): [In the formula, X is independently S or O, and R １ , R ２ , R ３ and R ４ Each of these independently represents an alkylene group having 1 to 10 carbon atoms, and R ５ , R ６ , R ７ , R ８ , R ９ and R １０ It is preferable to include a compound represented by [where each is independently a hydrogen atom or a methyl group, a and b are 0 or 1, and m, n, o and p are independently 0 to 30].

[0029] Examples of component (A1), which is a compound having a fluorene skeleton within the molecule and 2 to 4 (meth)acryloyl groups, include 9,9-bis(4-hydroxyphenyl)fluororange(meth)acrylate, 9,9-bis(4-hydroxy-3-methylphenyl)fluororange(meth)acrylate, 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol di(meth)acrylate, and 9,9-bis(4-hydroxyphenyl)-9H-fluorene-3,6-diol di(meth)acrylate. Furthermore, examples of component (A1), which is a compound having a fluorene skeleton within the molecule and having 2 to 4 (meth)acryloyl groups, include di(meth)acrylates of polyalkylene glycols obtained by adding alkylene oxides to both ends of 9,9-bis(4-hydroxyphenyl)fluorene, di(meth)acrylates of polyalkylene glycols obtained by adding alkylene oxides to both ends of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, di(meth)acrylates of polyalkylene glycols obtained by adding alkylene oxides to both ends of 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol, and di(meth)acrylates of polyalkylene glycols obtained by adding alkylene oxides to both ends of 9,9-bis(4-hydroxyphenyl)-9H-fluorene-3,6-diol.

[0030] (A1) Component is given by the following general formula (II): [In the formula, R １ and R ２ Each of these independently represents an alkylene group having 1 to 10 carbon atoms, and R ５ and R ６It is preferable to include a compound represented by ] where each is independently a hydrogen atom or a methyl group, and m and n are independently 0 to 30. Examples of component (A1), which is a compound having a fluorene skeleton in the molecule and 2 to 4 (meth)acryloyl groups, include 9,9-bis(4-aminophenyl)fluorenetetra(meth)acrylate and tetra(meth)acrylate of polyalkylene glycol obtained by adding an alkylene oxide to 9,9-bis(4-aminophenyl)fluorene.

[0031] From the viewpoint of flexibility and adhesion, m, n, o, and p in general formulas (I) and (II) are each preferably independently between 0 and 30, more preferably between 1 and 20, even more preferably between 2 and 10, even more preferably between 2 and 8, and particularly preferably between 3 and 7. In this disclosure, when the (A1) component represented by general formulas (I) and (II): a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule (hereinafter also referred to as a polyfunctional (meth)acrylate having a fluorene skeleton) consists of a single type of molecule, m, n, o, and p can be expressed as integer values. Furthermore, when the (A1) polyfunctional (meth)acrylate having a fluorene skeleton represented by general formulas (I) and (II) consists of multiple types of molecules, m, n, o, and p can be expressed as number average values.

[0032] Furthermore, when a polyfunctional (meth)acrylate having a (A1) fluorene skeleton represented by general formula (I) consists of multiple types of molecules, a and b can be expressed as number average values.

[0033] In this disclosure, the R in the formula of a polyfunctional (meth)acrylate having a fluorene skeleton represented by general formula (I) (A1) １ O, R ２ O, R ３ O, and R ４ O is referred to as the repeating unit in general formula (I). In this disclosure, R in the formula of (A1) polyfunctional (meth)acrylate having a fluorene skeleton represented by general formula (II) １ O and R ２O is referred to as the repeating unit in general formula (II). In this disclosure, the total number of moles of repeating units is expressed as the sum of m + n + o + p in general formula (I), and as the sum of (2 × m) + (2 × n) in general formula (II). The total number of moles of repeating units in general formulas (I) and (II) is preferably 30 moles or less. From the viewpoint of resolution and adhesion, the total number of moles of repeating units in general formulas (I) and (II) is preferably 25 moles or less, more preferably 21 moles or less, even more preferably 17 moles or less, and particularly preferably 13 moles or less. In one embodiment, the total number of moles of repeating units in general formulas (I) and (II) is preferably 2 moles or more. From the viewpoint of developability, the total number of moles of repeating units in general formulas (I) and (II) is preferably 2 moles or more, more preferably 4 moles or more, even more preferably 5 moles or more, particularly preferably 6 moles or more, and most preferably 8 moles or more. Herein, in this specification, the total number of moles of repeating units in general formulas (I) and (II) is the number of moles of repeating units per mole of a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule.

[0034] From the viewpoint of adhesion and resolution, R in general formulas (I) and (II) ５ , R ６ , R ７ , R ８、 R ９ and R １０ It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0035] From the viewpoint of adhesion and resolution, R in general formulas (I) and (II) １ O, R ２ O, R ３ O and R ４O is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 2 to 10 carbon atoms, and still more preferably an alkylene group having 2 to 4 carbon atoms, and is particularly preferably an ethylene group and / or a propylene group. Examples of alkylene groups having 2 to 4 carbon atoms include an ethylene group, a propylene group, a trimethylene group, a butylene group, and a tetramethylene group. In one embodiment, R is the repeating unit in general formulas (I) and (II). １ O, R ２ O, R ３ O, and R ４ O includes ethylene oxide (EO) or propylene oxide (PO).

[0036] Polyfunctional (meth)acrylates having a fluorene skeleton represented by general formulas (I) and (II) can be synthesized, for example, by the following method, but the synthesis method of the compound (A1) in this embodiment, which has three or more aromatic rings and one or more ethylenically unsaturated bonds in a single molecule, is not limited thereto. A compound having a fluorene skeleton is reacted with a compound having a hydroxyl group, a thiol group, or an amino group as a reactive group to obtain a compound having a reactive group at the end of the fluorene skeleton. Next, the reactive group is reacted with an alkylene oxide to obtain a compound having a fluorene skeleton with an alkylene oxide-modified end. Then, the hydroxyl group at the end of the compound is reacted with acrylic acid or methacrylic acid to obtain a polyfunctional (meth)acrylate having a fluorene skeleton represented by general formulas (I) and (II). These reactions may be carried out in any order. For example, without introducing the repeating unit alkylene oxide, a polyfunctional (meth)acrylate having a fluorene skeleton represented by general formulas (I) and (II) can be obtained by reacting a compound having a reactive group such as a hydroxyl group, thiol group, or amino group at the end of the fluorene skeleton with acrylic acid or methacrylic acid. Specifically, commercially available polyfunctional (meth)acrylates having a fluorene skeleton represented by general formulas (I) and (II) include trade names EA-0200 and EA-0300 from Osaka Gas Chemical Co., Ltd., and trade name A-BPEF from Shin Nakamura Chemical Industry Co., Ltd.

[0037] When component (A1) contains a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton within its molecule, the resist pattern formed using the photosensitive resin composition containing component (A1) exhibits excellent flexibility, adhesion, and developability.

[0038] In this embodiment, from the viewpoint of adhesion and resolution, component (A1) is preferably a compound having a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton in the molecule and having 2 to 4 (meth)acryloyl groups.

[0039] Component (A1) is given by the following general formula (III): [wherein X is, independently of each other, S or O, and R １ , R ２ and R ３ each independently represents an alkylene group having 1 to 10 carbon atoms, and R ４ , R ５ , R ６ and R ７ each independently represents a hydrogen atom or a methyl group, and m, n and o are each independently 0 to 30. ] It is preferable to contain the compound represented by. It is a compound having a methylidene tris(phenyl) skeleton or an ethylidene tris(phenyl) skeleton in such a molecule. Examples of the component (A1) include 1,1,1-tris(4-hydroxyphenyl)methane tri(meth)acrylate and 1,1,1-tris(4-hydroxyphenyl)ethane tri(meth)acrylate, trimethacrylate of a compound obtained by adding an alkylene oxide to 1,1,1-tris(4-hydroxyphenyl)methane, trimethacrylate of a compound obtained by adding an alkylene oxide to 1,1,1-tris(4-hydroxyphenyl)ethane, and the like.

[0040] The component (A1) is represented by the following general formula (IV): [wherein, R １ , R ２ and R ３ each independently represents an alkylene group having 1 to 10 carbon atoms, and R ４ , R ５ , R ６ and R ７is, independently of each other, a hydrogen atom or a methyl group, and m, n, and o are each independently from 0 to 30. ] It is preferable to contain the compound represented by. As the component (A1) which is a compound having a methylidene tris(phenyl) skeleton or an ethylidene tris(phenyl) skeleton in such a molecule, for example, 1,1,1-tris(4-aminophenyl)methane hexa(meth)acrylate, 1,1,1-tris(4-aminophenyl)ethane hexa(meth)acrylate, hexamethacrylate of a compound obtained by adding an alkylene oxide to 1,1,1-tris(4-aminophenyl)methane, and hexamethacrylate of a compound obtained by adding an alkylene oxide to 1,1,1-tris(4-aminophenyl)ethane, etc. are mentioned.

[0041] From the viewpoints of flexibility and adhesion, it is preferable that m, n, and o in the general formulas (III) and (IV) are each independently from 0 to 30, more preferably from 1 to 20, still more preferably from 2 to 10, even more preferably from 2 to 8, and particularly preferably from 3 to 8. In the present disclosure, when the polyfunctional (meth)acrylate having a methylidene tris(phenyl) skeleton or an ethylidene tris(phenyl) skeleton represented by the general formulas (III) and (IV) consists of a single type of molecule, m, n, and o can be represented by integer values. Also, when the polyfunctional (meth)acrylate having a methylidene tris(phenyl) skeleton or an ethylidene tris(phenyl) skeleton represented by the general formulas (III) and (IV) consists of a plurality of types of molecules, m, n, and o can be represented by number average values.

[0042] In the present disclosure, R in the formula of the polyfunctional (meth)acrylate having a methylidene tris(phenyl) skeleton or an ethylidene tris(phenyl) skeleton represented by the general formulas (III) and (IV) １ O, R ２ O, and R ３O is referred to as the repeating unit in general formulas (III) and (IV). In this disclosure, the total number of moles of the repeating unit is expressed as the sum of m + n + o in general formula (III), and as the sum of (2 × m) + (2 × n) + (2 × o) in general formula (IV). The total number of moles of the repeating unit in general formulas (III) and (IV) is preferably 0 to 50 moles, more preferably 1 to 50 moles, and even more preferably 2 to 30 moles. From the viewpoint of resolution and adhesion, the total number of moles of the repeating unit in general formulas (III) and (IV) is preferably 50 moles or less, more preferably 30 moles or less, even more preferably 25 moles or less, particularly preferably 22 moles or less, and most preferably 19 moles or less. In one embodiment, the total number of moles of the repeating unit in general formulas (III) and (IV) is preferably 5 moles or more. From the viewpoint of developability, the total number of moles of repeating units in general formulas (III) and (IV) is preferably 5 moles or more, more preferably 7 moles or more, even more preferably 9 moles or more, particularly preferably 11 moles or more, and most preferably 13 moles or more.

[0043] From the viewpoint of adhesion and resolution, in general formulas (III) and (IV), R ４ , R ５ , R ６ and R ７ It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0044] From the viewpoint of adhesion and resolution, R in general formulas (III) and (IV) １ O, R ２ O, and R ３O is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 2 to 10 carbon atoms, and still more preferably an alkylene group having 2 to 4 carbon atoms, and is particularly preferably an ethylene group and / or a propylene group. Examples of alkylene groups having 2 to 4 carbon atoms include an ethylene group, a propylene group, a trimethylene group, a butylene group, and a tetramethylene group. In one embodiment, R is the repeating unit in general formulas (III) and (IV). １ O, R ２ O and R ３ O includes ethylene oxide (EO) or propylene oxide (PO).

[0045] Component (A1) represented by general formulas (III) and (IV): A compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule (hereinafter also referred to as a polyfunctional (meth)acrylate having a methylidenttrisphenyl skeleton or ethylidenttrisphenyl skeleton) can be synthesized, for example, by the following method, but the method for synthesizing the compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule of (A1) according to this embodiment is not limited to this. A compound having a methylidenttrisphenyl skeleton or ethylidenttrisphenyl skeleton is reacted with a compound having a hydroxyl group, a thiol group, or an amino group as a reactant to obtain a compound having a reactant at the end of the methylidenttrisphenyl skeleton or ethylidenttrisphenyl skeleton. Next, the reactant is reacted with an alkylene oxide to obtain a compound having a methylidenttrisphenyl skeleton or ethylidenttrisphenyl skeleton with its terminals modified by alkylene oxide. Then, by reacting the hydroxyl group at the end of the compound with acrylic acid or methacrylic acid, a polyfunctional (meth)acrylate having a methylidenttrisphenyl skeleton or ethylidenttrisphenyl skeleton represented by general formulas (III) and (IV) can be obtained. These reactions may be carried out in any order. For example, without introducing a repeating unit (alkylene oxide), a polyfunctional (meth)acrylate having a methylidenttrisphenyl skeleton or ethylidenttrisphenyl skeleton represented by general formulas (III) and (IV) can be obtained by directly reacting a compound having a hydroxyl group, thiol group, or amino group at the end of the methylidenttrisphenyl skeleton or ethylidenttrisphenyl skeleton with acrylic acid or methacrylic acid.

[0046] In the photosensitive resin composition of this embodiment, the content of the compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule of (A1) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 9% by mass or more, based on the total solid content mass of the photosensitive resin composition. Furthermore, in the photosensitive resin composition of this embodiment, the content of the compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule of (A1) is preferably 50% by mass or less, more preferably 48% by mass or less, even more preferably 45% by mass or less, even more preferably 43% by mass or less, and particularly preferably 40% by mass or less, based on the total solid content mass of the photosensitive resin composition.

[0047] Furthermore, (A1) a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in a single molecule may be used alone or in combination of two or more compounds.

[0048] - (A2) Compounds having two or fewer aromatic rings per molecule and having ethylenically unsaturated bonds In this embodiment, (A2) Compounds having two or fewer aromatic rings per molecule and having ethylenically unsaturated bonds (hereinafter referred to as (A2) component) are compounds other than (A1) component, and are not particularly limited as long as they have two or fewer aromatic rings per molecule and have ethylenically unsaturated bonds. It is preferable that (A2) component includes compounds having two or more ethylenically unsaturated bonds, and from the viewpoint of improving resolution, it is preferable that it includes compounds having two to six ethylenically unsaturated bonds. Furthermore, (A2) component may be a single compound or two or more compounds may be used in combination. By including (A2) component in (A) component, the adhesion of the photosensitive resin composition of this embodiment to the substrate and the peelability of the resist pattern are improved.

[0049] Component (A2) is preferably a compound containing a (meth)acryloyl group, and more preferably a compound containing a methacryloyl group.

[0050] (A2) Component may include a compound having two ethylenically unsaturated bonds. Examples of compounds having two ethylenically unsaturated bonds include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, tetramethylene glycoxized (hydrogenated) bisphenol A di(meth)acrylate, and polyester di(meth)acrylate.

[0051] The above compound having two ethylenically unsaturated bonds may contain an alkylene group having 1 to 10 carbon atoms as a repeating unit in one molecule, for example, the following general formula (VI): [In the formula, R １５ and R １６ Each of these is an alkylene group having 1 to 10 carbon atoms. The group represented by ] and the following general formula (VII): [In the formula, R １７ is an alkylene group having 1 to 10 carbon atoms. It may further contain one or more repeating units selected from the group consisting of groups represented by ].

[0052] Among these, from the viewpoint of excellent adhesion to the substrate, the compound having the two ethylenically unsaturated bonds may include a di(meth)acrylate compound having an aromatic ring, may include a di(meth)acrylate compound having a bisphenol A structure, and the following general formula (VIII): (In the formula, R ２２ and R ２３ Each is independently a hydrogen atom or a methyl group, R １８ O, R １９ O, R ２０ O and R ２１The compound may contain the following: O is independently an oxyalkylene group, q, r, s, and t are independently integers from 0 to 40, t+q is from 1 to 40, and r+s is from 0 to 20.

[0053] R １８ O, R １９ O, R ２０ O and R ２１ Preferably, O is independently an oxyethylene group and an oxypropylene group. For compounds having a bisphenol A structure, from the viewpoint of resolution and adhesion, the average value of q + r + s + t is preferably 20 or less, more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. The average value of q + r + s + t may be 2 or more. Each of q, r, s, and t is independently preferably 0 to 10, and more preferably 2 to 8.

[0054] Examples of commercially available compounds having two ethylenically unsaturated bonds include NK esters (registered trademarks) A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, ABE-2, ABE-2.2, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, A-ABE-30, and A-BP. P-3, HD-N, NOD-N, DOD-N, NPG, 701, 2G, 3G, 4G, 9G, 14G, 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-300, BPE-5 00, BPE-900, BPE-1300N, NK Oligo (registered trademark) UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate® 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, NP-A, MPD-A, 1.6HX-A, 1.9ND-A, DCP-A, BP-4EAL, BP-4PA, HPP-A, Light Ester G-201P (all manufactured by Kyoeisha Chemical Co., Ltd.) Funcryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, FA-240A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Showa Denko Materials Co., Ltd.) DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel Ornex Co., Ltd.), SR212,SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema Co., Ltd.) Examples include KAYARAD® NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

[0055] Component (A2) preferably contains a compound that can increase the crosslinking density during exposure, from the viewpoint of improving resolution, and preferably contains a compound having three or more ethylenically unsaturated bonds. For example, the compound contained in component (A2) may be a compound having three to six ethylenically unsaturated bonds. In other words, component (A2) may contain a compound having three to six ethylenically unsaturated bonds.

[0056] Examples of compounds having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, dipentaerythritol (tetra / penta / hexa)(meth)acrylate, sorbitol (tri / tetra / penta / hexa)(meth)acrylate, and polyglycerin (tetra / penta / hexa / deca)(meth)acrylate.

[0057] Compounds having three or more ethylenically unsaturated bonds may contain alkylene groups having 1 to 10 carbon atoms as repeating units in a single molecule, for example, the following general formula (VI): [In the formula, R １５and R １６ Each of these is an alkylene group having 1 to 10 carbon atoms. The group represented by ] and the following general formula (VII): [In the formula, R １７ is an alkylene group having 1 to 10 carbon atoms. It may further contain one or more repeating units selected from the group consisting of groups represented by ].

[0058] Compounds containing three or more ethylene unsaturated bonds and containing alkylene groups with 1 to 10 carbon atoms as repeating units include, for example, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, glycerin alkylene oxide-modified tri(meth)acrylate, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, and alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa). Other examples include (meth)acrylate, alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, alkylene oxide-modified sorbitol (tri / tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified polyglycerin (tetra / penta / hexa / hepta / octa / nona / deca)(meth)acrylate (for example, ethylene oxide-modified diglycerin tetramethacrylate and ethylene oxide-modified tetraglycerin hexamethacrylate). From the viewpoint of excellent developability and flexibility, it is preferable that the above component (A2) contains alkylene oxide-modified glycerin tri(meth)acrylate or alkylene oxide-modified polyglycerin (tetra / penta / hexa / hepta / octa / nona / deca)(meth)acrylate (for example, ethylene oxide-modified diglycerin tetramethacrylate and ethylene oxide-modified tetraglycerin hexamethacrylate).

[0059] Examples of commercially available compounds having three or more ethylenically unsaturated bonds include NK esters (registered trademark) A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, and A-TMM- 3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, A-9550, A-DPH-12E, TPOA-50, NK Oligo® UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.) Light Acrylate® TMP-A, CPE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-731A (manufactured by Resonac Co., Ltd.), TMPTA, EBECRYL 160S, OTA480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel Ornex Co., Ltd.) Examples include SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema Co., Ltd.), KAYARAD® GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.).

[0060] The photosensitive resin composition of this embodiment preferably contains component (A2): a compound having two or fewer aromatic rings per molecule and an ethylene unsaturated bond, which is a compound that does not have a quaternary carbon and has three or more ethylenically unsaturated bonds per molecule, or a compound that does not have a quaternary carbon and has three to six ethylenically unsaturated bonds per molecule.

[0061] A resist pattern formed using a photosensitive resin composition containing a compound as component (A2) that does not have quaternary carbon atoms and has three or more ethylenically unsaturated bonds in one molecule, or a compound as component (A2) that does not have quaternary carbon atoms and has three to six ethylenically unsaturated bonds in one molecule, is presumed to have high flexibility because it does not contain quaternary carbon atoms. Furthermore, high flexibility of the resist pattern leads to good developability. Therefore, a resist pattern formed using a photosensitive resin composition containing a compound as component (A2) that does not have quaternary carbon atoms and has three or more ethylenically unsaturated bonds in one molecule, or a compound as component (A2) that does not have quaternary carbon atoms and has three to six ethylenically unsaturated bonds in one molecule, is presumed to exhibit excellent developability.

[0062] Furthermore, compounds that do not contain quaternary carbon atoms and have 3 to 6 ethylenically unsaturated bonds in one molecule are presumed to have a strong resist pattern because the structure in component (A2) becomes complexly bonded during curing by exposure due to the presence of 3 to 6 ethylenically unsaturated bonds in one molecule. Therefore, it is presumed that resist patterns formed using a photosensitive resin composition containing a compound that does not contain quaternary carbon atoms and has 3 to 6 ethylenically unsaturated bonds in one molecule will have excellent toughness. In particular, when component (A1): a compound having 3 or more aromatic rings and 1 or more ethylenically unsaturated bonds in one molecule is used in combination with component (A2), it is possible to balance the rigidity of component (A1) with the toughness derived from component (A2), which is presumed to result in excellent flexibility, resolution, and adhesion.

[0063] Compounds that do not have quaternary carbon atoms and have 3 to 6 ethylenically unsaturated bonds in one molecule include glycerin tri(meth)acrylate, sorbitol (tri / tetra / penta / hexa)(meth)acrylate, polyglycerin (tetra / penta / hexa)(meth)acrylate, alkylene oxide-modified glycerin tri(meth)acrylate, alkylene oxide-modified sorbitol (tri / tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified polyglycerin (tetra / penta / hexa / hepta / octa / nona / deca)(meth)acrylate.

[0064] A compound that does not have a quaternary carbon and has three or more (in one embodiment, three to six) ethylenically unsaturated bonds is given by the following general formula (V): [In the formula, h is between 1 and 20, each i is a natural number between 1 and h, each k, li, and j are independently between 0 and 30, R ９ , and R １１ Each of these independently represents either a hydrogen atom or a methyl group, and R １２ , and R １４ Each of these is an alkylene group having 1 to 10 carbon atoms, with the following general formula (VI): [In the formula, R １５ and R １６ Each of these is an alkylene group having 1 to 10 carbon atoms. The group represented by ] and the following general formula (VII): [In the formula, R １７ is an alkylene group having 1 to 10 carbon atoms. It is one selected from the group consisting of groups represented by ]. It is preferable to include a (poly)glycerin-based (meth)acrylate represented by ].

[0065] The (poly)glycerin-based (meth)acrylate represented by the general formula (V) is preferably such that h is independently 1 to 20, and more preferably 2 to 20, from the viewpoint of developability, resolution, and adhesion.

[0066] When the content of constituent units derived from (meth)acrylic acid, styrene, and benzyl (meth)acrylate in component (B) described below is within the above-described predetermined range, when a photosensitive resin composition is used in which component (A2) contains a compound that does not have quaternary carbon and has three or more ethylenically unsaturated bonds in one molecule, or a compound that does not have quaternary carbon and has three to six ethylenically unsaturated bonds in one molecule, a good balance between developability and flexibility and rigidity can be achieved, and effects of excellent flexibility, resolution and adhesion can be easily obtained.

[0067] From the viewpoint of improving peelability, component (A2) may include a compound having one ethylenically unsaturated bond.

[0068] For example, compounds having one ethylenically unsaturated bond include alkylene oxide-modified phenol (meth)acrylate, alkylene oxide-modified nonylphenol (meth)acrylate, alkylene oxide-modified 2-ethylhexyl (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ω-carboxy-polycaprolactone mono (meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 1-naphthalenemethyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, isopropyl Examples include myr(meth)acrylate, hexyl(meth)acrylate, isodecyl(meth)acrylate, n-lauryl(meth)acrylate, tetradecyl(meth)acrylate, n-stearyl(meth)acrylate, isostearyl(meth)acrylate, behenyl(meth)acrylate, 2-decyl-1-tetradecanyl(meth)acrylate, isobolonyl(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, 1H,1H,5H-octafluoropentyl(meth)acrylate, and 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl(meth)acrylate.

[0069] The upper limit of the ratio of component (A1) to component (A2) (i.e., the ratio of the content of component (A1) to the content of component (A2)) is preferably 4 or less, more preferably 3.5 or less, and even more preferably 3 or less. The lower limit of the ratio of component (A1) to component (A2) is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.12 or more, even more preferably 0.15 or more, and particularly preferably 0.20 or more.

[0070] In particular, the upper limit of the ratio of component (A1) to the total amount of compounds having three or more ethylenically unsaturated bonds in component (A2) (i.e., the ratio of the content of component (A1) to the total amount of compounds having three or more ethylenically unsaturated bonds in component (A2)) is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less. The lower limit of the ratio of component (A1) to the total amount of compounds having three or more ethylenically unsaturated bonds in component (A2) is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.12 or more, even more preferably 0.15 or more, particularly preferably 0.20 or more, and most preferably 0.25 or more.

[0071] The content of (A) the compound having an ethylenically unsaturated bond in the photosensitive resin composition of this embodiment is preferably 30% by mass or more, and preferably 35% by mass or more, based on the total solid content mass of the photosensitive resin composition, from the viewpoint of sensitivity, tackiness, and conformability. Furthermore, the content of (A) the compound having an ethylenically unsaturated bond in the photosensitive resin composition is preferably 50% by mass or less, preferably 45% by mass or less, and preferably 43% by mass or less, based on the total solid content mass of the photosensitive resin composition, from the viewpoint of edge fusion properties, tackiness, and resolution. In one embodiment, the content of (A) the compound having an ethylenically unsaturated bond in the photosensitive resin composition of this embodiment is preferably 20% by mass or more and 60% by mass or less, based on the total solid content mass of the photosensitive resin composition, from the viewpoint of resolution, adhesion, and peelability.

[0072] Furthermore, from the viewpoint of flexibility, resolution, and adhesion, the ratio of the content of compounds having three or more ethylenically unsaturated groups to the total amount of compounds having ethylenically unsaturated bonds (A) contained in the photosensitive resin composition of this embodiment (i.e., the ratio of the content of compounds having three or more ethylenically unsaturated groups / the total amount of compounds having ethylenically unsaturated bonds (A)) is preferably 0.95 or less, and more preferably 0.90 or less.

[0073] Furthermore, from the viewpoint of edge fusion properties, tack properties, and resolution, the upper limit of the ratio of the content of (A) a compound having an ethylenically unsaturated bond to the content of (B) an alkali-soluble resin contained in the photosensitive resin composition of this embodiment (i.e., the ratio of the content of (A) a compound having an ethylenically unsaturated bond / the content of (B) an alkali-soluble resin) is preferably 1.4 or less, more preferably 1.3 or less, even more preferably 1.2 or less, even more preferably 1.1 or less, particularly preferably 1.0 or less, and most preferably 0.9 or less. The lower limit of the ratio of the content of (A) a compound having an ethylenically unsaturated bond / the content of (B) an alkali-soluble resin is preferably 0.50 or more, more preferably 0.60 or more, even more preferably 0.70 or more, even more preferably 0.75 or more, and particularly preferably 0.80 or more.

[0074] In this embodiment, the photosensitive resin composition preferably has a value of 0.10 moles to 0.30 moles of ethylenically unsaturated bonds per 100 g of solid content. By setting it to 0.10 moles or more, the photosensitive resin composition components can be leached out from the cured resist pattern during the water washing step after development, preventing contamination during the water washing step. By setting it to 0.30 moles or less, the cured resist pattern can be chipped and detached during the water washing step after development, preventing contamination during the water washing step.

[0075] The amount of ethylenically unsaturated bonds per 100 g of solids in the photosensitive resin composition of this embodiment is preferably 0.10 moles or more, more preferably 0.11 moles or more, even more preferably 0.12 moles or more, and even more preferably 0.13 moles or more. Furthermore, the amount of ethylenically unsaturated bonds per 100 g of solids in the photosensitive resin composition of this embodiment is preferably 0.30 moles or less, more preferably 0.28 moles or less, even more preferably 0.25 moles or less, even more preferably 0.22 moles or less, particularly preferably 0.20 moles or less, particularly more preferably 0.18 moles or less, and extremely preferably 0.15 moles or less. The amount of ethylenically unsaturated bonds per 100 g of solids in the photosensitive resin composition of this embodiment is more preferably 0.10 moles to 0.25 moles, even more preferably 0.10 moles to 0.20 moles, even more preferably 0.11 moles to 0.20 moles, and extremely preferably 0.11 moles to 0.15 moles.

[0076] (B) Alkali-soluble resin In this embodiment, (B) alkali-soluble resin (hereinafter also referred to as component (B)) is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers and at least one of the second monomers described later.

[0077] The first monomer is a monomer having a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semi-ester. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of excellent adhesion and resolution.

[0078] The copolymerization ratio of the first monomer is preferably in the range of 10 to 50% by mass, based on the total mass of all monomer components. From the viewpoint of excellent developability, adhesion, and resolution, it is preferable that the copolymerization ratio be 10% by mass or more, more preferably 15% by mass or more, even more preferably 18% by mass or more, and even more preferably 21% by mass or more. From the viewpoint of excellent adhesion and resolution, it is preferable that the copolymerization ratio be 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 27% by mass or less. When two or more types of monomers are polymerized and used as the first monomer, it is preferable that the sum of their copolymerization ratios falls within the above range.

[0079] The second monomer is a monomer that has at least one ethylenically unsaturated bond in its molecule and does not have a carboxyl group. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glyceryl mono (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobol (meth)acrylates such as nyl(meth)acrylate, nonylphenoxypolyethylene glycol(meth)acrylate, pentamethylpiperidyl(meth)acrylate, tetramethylpiperidyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, phenoxyethyl(meth)acrylate, ethyl carbitol(meth)acrylate, methoxyethyl(meth)acrylate, methoxytriethylene glycol(meth)acrylate, methoxypolyethylene glycol(meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, cyclic trimethylolpropaneformal(meth)acrylate, 3,3,5-trimethylcyclohexyl(meth)acrylate, etc. Examples include styrene derivatives such as styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, N-phenylmaleimide, styrene dimers, and styrene trimers; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile.

[0080] (B) The weight-average molecular weight Mw of the alkali-soluble resin is preferably 10,000 to 60,000. (B) It is preferable to have a weight-average molecular weight Mw of 60,000 or less from the viewpoint of achieving both flexibility and resolution of the resist pattern, more preferably 55,000 or less, even more preferably 50,000 or less, and particularly preferable 40,000 or less from the same viewpoint. From the viewpoint of flexibility, resolution and adhesion, it is preferable to have a weight-average molecular weight Mw of 10,000 or more, more preferably 12,000 or more, even more preferably 14,000 or more, and particularly preferable 17,500 or more.

[0081] (B) The polydispersity of the alkali-soluble resin (Mw / Mn: weight-average molecular weight / number-average molecular weight) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0082] (B) The alkali-soluble resin may be used alone or in a mixture of two or more types. When two or more (B) components are used in a mixture, it is preferable that the monomer content of the multiple (B) components be selected such that the weight-average molecular weight and polydispersity weight-average value, with the content ratio of one type of (B) component as the weight of each component, falls within the following range. In this disclosure, the weight-average value is the value obtained by multiplying the weight ratio of each type of alkali-soluble resin to the total weight of the mixed (B) components by the weight-average molecular weight or polydispersity of each type of alkali-soluble resin, and then summing the results. (B) The weight-average average value of the weight-average molecular weight of component (B) is preferably 10,000 or more, or 15,000 or more, or 17,500 or more, or 20,000 or more, and preferably 60,000 or less, or 55,000 or less, or 50,000 or less, or 40,000 or less.

[0083] (B) The synthesis of alkali-soluble resins is preferably carried out by adding an appropriate amount of radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, and isopropanol, and then heating and stirring. In some cases, the synthesis may be carried out by dropping a portion of the mixture containing monomers and solvents into a reaction solution such as a radical polymerization initiator. After the polymerization reaction is complete, the solvent may be further added to adjust to the desired concentration. (B) In addition to solution polymerization, living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used as means for synthesizing component B.

[0084] The content of (B) alkali-soluble resin in the photosensitive resin composition of this embodiment may be 10% by mass or more, or 20% by mass or more, or 25% by mass or more, or 30% by mass or more, or 35% by mass or more, or 40% by mass or more, or 45% by mass or more, or 50% by mass or more, or 55% by mass or more, or 60% by mass or more, based on the total solid content mass of the photosensitive resin composition. Furthermore, the content of (B) alkali-soluble resin in the photosensitive resin composition of this embodiment may be 90% by mass or less, or 80% by mass or less, or 70% by mass or less, or 60% by mass or less, based on the total solid content mass of the photosensitive resin composition.

[0085] Based on the total solid content mass of the photosensitive resin composition of this embodiment, it is preferable to set the content of (B) alkali-soluble resin to 90% by mass or less from the viewpoint of controlling the development time, and it is preferable to set it to 10% by mass or more from the viewpoint of suppressing the overflow of the photosensitive resin layer from the film edge.

[0086] Among these, from the viewpoint of excellent adhesion to the substrate, it is preferable that component (B) contains either styrene or benzyl (meth)acrylate, or both. In other words, it is preferable that component (B) contains constituent units derived from styrene and / or benzyl (meth)acrylate. In one embodiment, component (B) contains a copolymer having constituent units derived from styrene and benzyl (meth)acrylate. In one embodiment, from the viewpoint of excellent adhesion to the substrate, component (B) contains constituent units derived from styrene. In one embodiment, from the viewpoint of excellent adhesion to the substrate, component (B) contains constituent units derived from benzyl (meth)acrylate. When the alkali-soluble resin (B) contains multiple alkali-soluble resins, it may contain an alkali-soluble resin containing styrene and an alkali-soluble resin containing benzyl (meth)acrylate, respectively.

[0087] Furthermore, from the viewpoint of flexibility, resolution, and adhesion, the total content of component (A) and component (B) contained in the photosensitive resin composition of this embodiment is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more, based on the total solid content mass of the photosensitive resin composition. From the viewpoint of sensitivity, resolution, and adhesion, the total content of component (A) and component (B) contained in the photosensitive resin composition of this embodiment is preferably 98% by mass or less, and more preferably 96% by mass or less, based on the total solid content mass of the photosensitive resin composition.

[0088] In one embodiment, from the viewpoint of excellent developability, component (B) contains constituent units derived from (meth)acrylic acid. When component (B) contains constituent units derived from (meth)acrylic acid, from the viewpoint of developability, the content of constituent units derived from (meth)acrylic acid in component (B) is preferably 12% by mass or more and 40% by mass or less, and more preferably 15% by mass or more and 35% by mass or less.

[0089] If component (B) contains structural units derived from styrene, from the viewpoint of adhesion, the content of styrene (in one embodiment, structural units derived from styrene) in component (B) is preferably 25% by mass or more, or may be 30% by mass or more, or 35% by mass or more. Furthermore, the content of styrene in component (B) may be 80% by mass or less, or may be 75% by mass or less, or may be 70% by mass or less, or may be 65% by mass or less, or may be 60% by mass or less, or may be 50% by mass or less.

[0090] If component (B) contains constituent units derived from styrene, from the viewpoint of adhesion, the styrene content in component (B) may be 25% by mass or more and 80% by mass or less, or 30% by mass or more and 80% by mass or less, or 35% by mass or more and 80% by mass or less.

[0091] (A) When a compound having an ethylenically unsaturated bond is included in component (A1), it is preferable to make component (B) relatively hydrophilic in order to set the developability of the photosensitive resin composition within an appropriate range and to achieve a good balance between resolution and adhesion. Here, when component (B) is hydrophilic, it significantly affects the developability of the photosensitive resin composition, that is, the development time of the photosensitive resin layer containing the photosensitive resin composition. For example, as the hydrophilicity of component (B) improves, the development time of the photosensitive resin layer tends to decrease. Therefore, in this disclosure, "component (B) being relatively hydrophilic" means that it is sufficiently hydrophilic so that the developability of the photosensitive resin composition is controlled within an appropriate range as described later. In one embodiment, component (B) can be made relatively hydrophilic by adjusting the content of styrene-derived constituent units in component (B) to 50% by mass or less.

[0092] In one embodiment, component (B) can be made relatively hydrophilic by including a constituent unit derived from a monomer having at least one ethylenically unsaturated bond in its molecule and containing a hydroxyl group. Examples of monomers having at least one ethylenically unsaturated bond in its molecule and containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glyceryl mono(meth)acrylate, among the compounds listed above as the second monomer.

[0093] In this disclosure, the appropriate range of developability of the photosensitive resin composition or the photosensitive resin layer is, for example, a concentration of 1% by mass of Na. ２ CO ３ This refers to a case where the minimum development time per 1 μm of film thickness of a photosensitive resin layer containing a photosensitive resin composition, when developing by spraying an aqueous solution at 30°C, is 0.6 seconds or more and 1.1 seconds or less. Furthermore, as a means of making the developability of the photosensitive resin composition or the photosensitive resin layer within an appropriate range, it is possible to set the glass transition temperature (Tg) of component (B) within an appropriate range. For example, an appropriate range for the Tg of component (B) is preferably 300K to 400K, more preferably 350K to 400K, and most preferably 375K to 400K. The Tg of component (B) is a value that can be obtained by the following Fox formula. When component (B) contains multiple types of alkali-soluble resins, the Tg of the entire component (B) is obtained by the weighted average value of the Tg of each alkali-soluble resin.

[0094] ≪Glass transition temperature (Tg) determined by Fox's formula≫ The glass transition temperature (Tg) of component (B) is calculated based on Fox's formula. The Tg of component (B) can be controlled by the types and proportions of monomers that make up component (B). By including preferred components in preferred proportions in component (B), it is easier to achieve a preferred Tg.

[0095] For component (B), which consists of n types of monomers, the Fox formula for calculating the Tg (K: Kelvin) of component (B) is as follows: {In the formula, Tg ｉ(K: Kelvin) is the glass transition temperature of a homopolymer composed of each monomer, c ｉ This is expressed by the copolymerization ratio of each monomer.

[0096] In this disclosure, the Tg value of homopolymers composed of monomers forming alkali-soluble polymers is taken from literature (Brandrup, J. Immergut, E. H. eds., Polymer Handbook, Third Edition, John Wiley & Sons, 1989, Chapter VI “GLASS transition temperatures of polymers”, p209). ｉ An example of this is as follows:

[0097]

[0098] Based on the above [Equation 1] and [Table 1], for example, the Tg of component (B) exemplified below can be derived as follows: ・Methacrylic acid / methyl methacrylate / styrene / n-butyl acrylate (mass ratio = 25 / 10 / 60 / 5): Tg = 385K ・Methacrylic acid / styrene / benzyl methacrylate / 2-hydroxyethyl methacrylate (mass ratio = 27 / 50 / 20 / 3): Tg = 388K ・Methacrylic acid / methyl methacrylate / styrene (mass ratio = 21 / 39 / 40): Tg = 396K (mass ratio = 25 / 10 / 65): Tg = 399K (mass ratio = 25 / 50 / 25): Tg = 401K

[0099] Furthermore, from the viewpoint of developability, resolution and adhesion, the content of component (B) in the photosensitive resin composition is preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 63% by mass or less, and particularly preferably 60% by mass or less, based on the total content of component (A) and component (B). Furthermore, the content of component (B) in the photosensitive resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, based on the total content of component (A) and component (B).

[0100] (C) Polymerization Initiator In this embodiment, the photosensitive resin composition preferably contains (C) a polymerization initiator (hereinafter also referred to as component (C)). The (C) polymerization initiator is more preferably a compound that generates radicals in response to active light emitted from an exposure light source, thereby promoting the polymerization of compounds having ethylenically unsaturated bonds. Examples of (C) polymerization initiators include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, coumarins, and halogen compounds. Among these, the photosensitive resin composition of this embodiment preferably contains a hexaarylbiimidazole compound as component (C).

[0101] Examples of hexaarylbiimidazole compounds include rophine dimers, i.e., dimers of 2,4,5-triarylimidazole.

[0102] The rophine dimers, i.e., dimers of 2,4,5-triarylimidazole, include the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), the dimer of 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole, the dimer of 2-(p-methoxyphenyl)-4,5-diphenylimidazole, and the dimer of 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)- 4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis- Su-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis -(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,Examples include 5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.

[0103] From the viewpoint of high sensitivity, resolution, and adhesion, it is preferable that the (C) component contains a rofin dimer, and among these, the 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0104] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

[0105] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0106] Examples of aromatic ketone compounds include benzophenone compounds. Examples of benzophenone compounds include benzophenone, Michla's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. 4,4'-bis(diethylamino)benzophenone is also an example of an aromatic ketone compound, from the viewpoint of sensitizing effect and adhesion.

[0107] In this disclosure, the term "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and 10-phenyl-9-anthraceneboronic acid. From the viewpoint of sensitizing effect and adhesion, 9,10-dibutoxyanthracene or 9,10-diphenylanthracene is preferred, and 9,10-diphenylanthracene is particularly preferred.

[0108] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0109] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Examples of commercially available acylphosphine oxide compounds include Lucilin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0110] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of dialkyl ketal compounds include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorthioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0111] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0112] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0113] As pyrazoline derivatives, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, or 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline are preferred from the viewpoint of adhesion and rectangularity of the resist pattern.

[0114] Examples of ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0115] Examples of coumarins include 7-diethylamino-4-methylcoumarin and coumarin 102.

[0116] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diallylodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0117] The content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 4.0 to 20% by mass, more preferably 4.0 to 10% by mass, even more preferably 4.5 to 10.0% by mass, and particularly preferably 5.0 to 10.0% by mass, based on the total solid content mass of the photosensitive resin composition. In one embodiment, the content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is 4.0% by mass or more, based on the total solid content mass of the photosensitive resin composition. In one embodiment, the content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is 20% by mass or less, based on the total solid content mass of the photosensitive resin composition. By adjusting the content of (C) polymerization initiator within the above range, sufficient sensitivity can be easily obtained, making it easier to transmit light sufficiently to the bottom of the photosensitive resin composition layer, and consequently, easier to achieve improved resolution.

[0118] From the viewpoint of high sensitivity, resolution, and adhesion, the photosensitive resin composition of this embodiment preferably contains a hexaarylbiimidazole compound as (C) polymerization initiator. In this case, the content of the hexaarylbiimidazole compound in the photosensitive resin composition of this embodiment is preferably 3.5 to 12% by mass, and more preferably 4.0 to 10% by mass, based on the total solid content mass of the photosensitive resin composition.

[0119] (C) It is preferable to use an anthracene derivative and a hexaarylbiimidazole compound in combination as the polymerization initiator. The content of the anthracene derivative contained in the polymerization initiator (C) in the photosensitive resin composition of this embodiment is preferably 0.01% by mass or more, based on the total solid content mass of the photosensitive resin composition. In this case, the content of the anthracene derivative contained in the polymerization initiator (C) in the photosensitive resin composition of this embodiment is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less, based on the total solid content mass of the photosensitive resin composition.

[0120] The content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, based on the content of (A) compound having an ethylenically unsaturated bond. Furthermore, the content of (C) polymerization initiator in the photosensitive resin composition of this embodiment is preferably 5% by mass or more, more preferably 6% by mass or more, even more preferably 7% by mass or more, and particularly preferably 7.5% by mass or more, based on the content of (A) compound having an ethylenically unsaturated bond.

[0121] (D) Polymerization inhibitor In this embodiment, the photosensitive resin composition may further contain (D) a polymerization inhibitor. Examples of (D) polymerization inhibitors include free radical polymerization inhibitors, phenolic polymerization inhibitors, hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine, catechol, and derivatives thereof.

[0122] Examples of free radical polymerization inhibitors include nitroso compounds such as p-nitrosophenol, nitrosobenzene, N-nitrosodiphenylamine, isononyl nitrite, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, and N,N'-dinitrosophenylenediamine; salts of nitroso compounds such as aluminum salts to which nitrosophenylhydroxylamine is added by 3 moles; and hindered amine compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine.

[0123] Examples of phenolic polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,2'-methylenebis(4-methyl-6- tert-butylphenol), bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis[3-(3,5 [-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-te Examples include rt-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrene-phenols (e.g., Antege SP, manufactured by Kawaguchi Chemical Industries, Ltd.), tripenzylphenols (e.g., TBP, manufactured by Kawaguchi Chemical Industries, Ltd., phenols having 1 to 3 benzyl groups), and biphenols.

[0124] In this disclosure, the terms "hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine and catechol and their derivatives" include both hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine and catechol and compounds derived therefrom. Examples of hydroquinone derivatives include methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 2,6-di-tert-butylhydroquinone. Examples of quinone derivatives include tert-butylbenzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone and 2,5-di-tert-butyl-1,4-benzoquinone.

[0125] Examples of nitrobenzene derivatives include 4-nitrotoluene. Examples of phenothiazine derivatives include 2,8-dioctylphenothiazine, 2-methoxyphenothiazine, 3-methoxyphenothiazine, 2-methylphenothiazine, 2-ethylphenothiazine, 2-trifluoromethylphenothiazine, 3,7-dibutylphenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 2-cyano-8-methoxyphenothiazine, 2-cyanophenothiazine, 2-bromophenothiazine, 2-chlorophenothiazine, bis-(α-dimethylbenzyl)phenothiazine, and bis-(α-methylbenzyl)phenothiazine. Examples of phenoxazine derivatives include 1-methylphenoxazine, 2-methylphenoxazine, 3-methylphenoxazine, 4-methylphenoxazine, 10-methylphenoxazine, 2-hydroxyphenoxazine, 3-hydroxyphenoxazine, 4-hydroxyphenoxazine, 10-bromophenoxazine, 3,7-dimethylphenoxazine, 2,8-dimethylphenoxazine, 1-aminophenoxazine, 2-aminophenoxazine, 3-aminophenoxazine, 2-ethylphenoxazine, 3-ethylphenoxazine, 2-carbonitrile-phenoxazine, 3-carbonitrile-phenoxazine, 2-methoxyphenoxazine, 3-methoxyphenoxazine, and 12H-benzophenoxazine.

[0126] Examples of catechol derivatives include 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol.

[0127] By including phenothiazine or a phenothiazine derivative and a phenolic polymerization inhibitor, the NH group in the phenothiazine moiety and the OH group of the phenolic polymerization inhibitor form hydrogen bonds, preventing the phenolic polymerization inhibitor from volatilizing or diffusing from the photosensitive resin composition layer. In other words, it is possible to provide a photosensitive resin composition with excellent sensitivity and resolution, and a method for forming a resist pattern, that is not affected by manufacturing conditions or storage conditions determined by the film thickness.

[0128] From the above viewpoint, the photosensitive resin composition of this embodiment preferably contains phenothiazine or a phenothiazine derivative as (D) polymerization inhibitor. In this case, the content of phenothiazine or a phenothiazine derivative in the photosensitive resin composition of this embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less, based on the total solid content mass of the photosensitive resin composition of this embodiment. Furthermore, the content of phenothiazine or a phenothiazine derivative in the photosensitive resin composition of this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.002% by mass or more, based on the total solid content mass of the photosensitive resin composition of this embodiment.

[0129] From the viewpoint of resolution, the photosensitive resin composition of this embodiment preferably contains catechol or a catechol derivative as (D) polymerization inhibitor, and more preferably contains 3-tert-butylcatechol or 4-tert-butylcatechol. In this case, the content of catechol or a catechol derivative in the photosensitive resin composition of this embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less, based on the total solid content mass of the photosensitive resin composition of this embodiment. Furthermore, the content of catechol or a catechol derivative in the photosensitive resin composition of this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.002% by mass or more, based on the total solid content mass of the photosensitive resin composition of this embodiment.

[0130] The content of the polymerization inhibitor (D) in the photosensitive resin composition of this embodiment is preferably 0.0001% by mass to 10% by mass, based on the total solid content mass of the photosensitive resin composition of this embodiment. The content of the polymerization inhibitor (D) in this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, even more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more, from the viewpoint of excellent adhesion and resolution. On the other hand, the content of the polymerization inhibitor (D) in this embodiment is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less, from the viewpoint of minimal sensitivity reduction and improved resolution.

[0131] - Additives The photosensitive resin composition according to this embodiment may contain additives such as dyes, adhesion aids, and plasticizers.

[0132] • Dyes In this embodiment, dyes may be included in the photosensitive resin composition. In one embodiment, a color-developing dye that develops color upon light irradiation may be included in the photosensitive resin composition. It is preferable to add dyes to the dry film resist, which is one embodiment of the photosensitive resin laminate provided by this embodiment. By adding dyes, the resist pattern formed on the substrate after development becomes visible with good contrast, and also helps to improve resolution.

[0133] As dyes, diamond green is preferred. As color-developing dyes, for example, combinations of leuco dyes and halogen compounds are known. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [pigment name: leucocrystal violet] and bis(4-dimethylamino-2-methylphenyl)phenylmethane [pigment name: leucomalachite green]. Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane.

[0134] • Adhesion aid In this embodiment, an adhesion aid may be included in the photosensitive resin composition. It is preferable to add an adhesion aid to the dry film resist, which is one embodiment of the photosensitive resin laminate provided by this embodiment. Adding an adhesion aid helps to improve the adhesion of the resist pattern formed on the substrate after development to the copper.

[0135] Preferred adhesion aids include triazoles or benzotriazoles, with benzotriazoles containing a carboxyl group (e.g., carboxybenzotriazole) being more preferred.

[0136] • Plasticizers In this embodiment, additives such as plasticizers may be included in the photosensitive resin composition as needed. Examples of additives such as plasticizers include phthalate esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

[0137] <Photosensitive Resin Laminate> The photosensitive resin laminate of this embodiment comprises a support and a photosensitive resin layer containing a photosensitive resin composition (in one embodiment, a photosensitive resin composition layer), and the support and the photosensitive resin layer are the same as described above. As the photosensitive resin laminate of this embodiment, for example, at least one photosensitive resin layer is laminated on the support, and two or more photosensitive resin layers may be laminated on the support. From the viewpoint of making the effects of this embodiment more pronounced, the photosensitive resin laminate of this embodiment is preferably a dry film resist or a transfer film, and more preferably a dry film resist.

[0138] The photosensitive resin laminate of this embodiment may include a protective film in addition to the support and the photosensitive resin layer. When the photosensitive resin laminate of this embodiment includes the support, the photosensitive resin layer and the protective film, the protective film is attached to the side of the photosensitive resin layer that is not laminated with the support and functions as a cover.

[0139] In this embodiment, the adhesion force between the photosensitive resin composition layer and the support is significantly less than the adhesion force between the photosensitive resin composition layer and the protective film, allowing the protective film to be easily peeled off the photosensitive resin composition layer. For example, polyethylene film, polypropylene film, stretched polypropylene film, polyester film, etc., can be preferably used as the protective film. Among these, polypropylene film or polyester film is more preferable, and among polyester films, polyethylene terephthalate film is even more preferable. Furthermore, a release layer may be provided on the surface of the protective film.

[0140] The thickness of the protective film is preferably 10 to 100 μm, and more preferably 10 to 50 μm. Examples of protective films include Alphan® EM-501, E-200, E-201F, FG-201, MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Trefan® KW37, 2578, 2548, 2500, YM17S, Therapiel® PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, SY (all manufactured by Toray Industries, Inc.), GF-18, GF-818, GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0141] The photosensitive resin laminate of this embodiment may further include an intermediate layer between the support and the photosensitive resin layer, or between the support and the protective film.

[0142] The photosensitive resin laminate, by having an intermediate layer in its laminated structure, allows for exposure even after the support has been peeled off, and also reduces rattle of the sidewalls of the resist pattern caused by scratches or foreign matter on the support. Furthermore, by including an intermediate layer, it is possible to impart any desired functionality, such as oxygen barrier properties, to the photosensitive resin laminate, and consequently, these functionalities can be maintained even after the support has been peeled off.

[0143] The laminated structure of the photosensitive resin laminate is formed by placing an intermediate layer between the temporary support and the photosensitive resin layer in the photosensitive resin laminate described above. Alternatively, it is formed by peeling the temporary support from the photosensitive resin laminate described above to remove the photosensitive resin layer, and then sequentially laminating the support, intermediate layer, and photosensitive resin layer. The placement or lamination of the intermediate layer is carried out by coating the photosensitive resin composition constituting the intermediate layer onto the support or film. The photosensitive resin composition constituting the intermediate layer is the same as described above.

[0144] As described above, the intermediate layer is preferably an oxygen barrier layer and / or a water-soluble resin layer, and more preferably a water-soluble resin layer, from the viewpoint of ensuring exposure performance and functionality even after peeling the support from the photosensitive resin laminate.

[0145] [Photosensitive resin laminate roll] The photosensitive resin laminate described above may be used as a roll-shaped photosensitive resin laminate roll by winding a long photosensitive resin laminate onto a core.

[0146] [Method for forming a resist pattern] A method for forming a resist pattern using the photosensitive resin laminate according to this embodiment includes, for example, the following steps: a lamination step of laminating a photosensitive resin layer (in one embodiment, a photosensitive resin composition layer) constituting the photosensitive resin laminate of this embodiment onto a substrate; an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate; and a development step of developing and removing the unexposed portion of the photosensitive resin layer. Preferably, the steps are carried out in the above order.

[0147] <Lamination Process> Specifically, in the lamination process, after peeling off the protective film from the photosensitive resin laminate of this embodiment, the photosensitive resin layer is heat-pressed onto the substrate surface using a laminator, and laminated once or multiple times. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO), with copper-clad laminates being preferred.Optionally, for example, H at a concentration of about 10% by mass may be used. ２ SO ４The substrate may be cleaned with an aqueous solution or the like to smooth its surface. The heating temperature during lamination is generally 40°C to 160°C. Heat bonding can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the rolls. Heat bonding can be performed under reduced pressure if desired.

[0148] <Exposure Process> In the exposure process, the photosensitive resin layer is exposed to an ultraviolet light source or the like, either through a patterned photomask or reticle, or directly, using an exposure machine such as a contact aligner, mirror projection machine, or stepper. The exposure process may be performed after peeling off the support, or through the support, as desired. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using a light meter. Direct imaging exposure may also be performed in the exposure process. In direct imaging exposure, the substrate is exposed directly by a drawing device without using a photomask. As the light source, a semiconductor laser with a wavelength of 350 nm to 410 nm or an ultra-high pressure mercury lamp is used. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0149] The exposure method used in the exposure process is preferably at least one method selected from projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and is more preferably performed by projection exposure or direct imaging exposure.

[0150] <Heating Step> A heating step may be provided between the exposure step and the development step. The heating temperature is preferably 30°C to 200°C, more preferably 30°C to 150°C, and even more preferably 35°C to 120°C. By performing this heating step, it is possible to improve resolution and adhesion. For heating, a heating furnace using hot air, infrared rays, or far infrared rays, a constant temperature bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, etc., can be used. The heating time is preferably 1 to 300 seconds, more preferably 5 to 120 seconds.

[0151] The elapsed time from the exposure process to the heating process, or more precisely, the elapsed time from the point when exposure is stopped to the point when heating is started, is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds. The elapsed time from the start of heating to the point when heating is stopped is preferably 1 to 120 seconds, and more preferably 5 to 60 seconds.

[0152] <Development Process> In the development process, the unexposed portions of the photosensitive resin layer after exposure are removed using a developing device with a developing solution to form a resist pattern. If there is a support on the photosensitive resin layer after exposure, the support is removed. Subsequently, the unexposed portions are developed and removed using a developing solution consisting of an alkaline aqueous solution to obtain a resist pattern. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected and used from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment.

[0153] As for the alkaline aqueous solution used as a developing solution, Na ２ CO ３ _K ２ CO ３ And aqueous solutions of tetramethylammonium hydroxide, etc. are preferred. The alkaline aqueous solution is selected according to the properties of the photosensitive resin layer, but a concentration of 0.2% to 2% by mass of Na is preferred. ２ CO ３ Aqueous solutions are commonly used. Surface surfactants, defoamers, and small amounts of organic solvents to accelerate development may be added to the alkaline aqueous solution. It is preferable to keep the temperature of the developer solution constant within the range of 20°C to 40°C during the development process.

[0154] The development process preferably includes a water washing step to remove the developer solution contained in the resist pattern after development. The washing water can be pure water, industrial water, or other water selected according to the characteristics of the photosensitive resin layer, but to improve resolution and the shape of the resist pattern, MgSO4 at a concentration of 0.001% to 1% by mass may be used. ４ Polyvalent metal salts such as the above may be added. It is preferable to keep the temperature of the washing water constant within the range of 20°C to 40°C during the washing process.

[0155] A resist pattern can be obtained through the above process, but if desired, a further heat treatment can be performed at 60°C to 300°C for 1 to 120 minutes. This heat treatment can improve the chemical resistance of the resist pattern. For the heat treatment, a heating furnace using hot air, infrared rays, or far-infrared rays can be used.

[0156] To obtain a conductive pattern, a conductive pattern formation step may be performed after the developing step or heating step, in which the substrate on which the resist pattern has been formed is etched or plated.

[0157] <Conductor Pattern Formation Process> The conductor pattern formation process is a process of forming a conductor pattern on the substrate surface (for example, a copper surface) on which a resist pattern has been formed by development, using a known etching method or plating method.

[0158] For example, the following is a method for forming a conductive pattern by plating: After the development process, the substrate is immersed in an acidic degreasing bath such as a 1-50% by mass sulfuric acid aqueous solution at 20-60°C for 1-60 minutes. After rinsing the immersed substrate with water, it is immersed in a 1-50% by mass sulfuric acid aqueous solution at room temperature for 1-60 minutes.

[0159] An aqueous solution containing 1 to 15% by mass of copper sulfate, 0.1 to 30% by mass of sulfuric acid, and 1 to 1000 ppm of hydrochloric acid is prepared. Then, a brightener (in one embodiment, Caparaside HL and Caparaside GS manufactured by Attec Co., Ltd.) is added at concentrations of 0.01 to 40 ml / l and 1 to 200 ml / l, respectively, to prepare a copper sulfate plating solution. Using the prepared copper sulfate plating solution, a conductor pattern is formed by plating with a Harling cell uniform plating apparatus (manufactured by Yamamoto Plating Testing Equipment Co., Ltd.) at an applied current of 0.01 to 10 A for 1 to 300 minutes. The thickness of the copper plating film depends on the thickness of the resist pattern, but is preferably 1 μm or more (thickness of resist pattern (μm) - 2 μm) or less. In this disclosure, the thickness of the resist pattern refers to the thickness of the photosensitive resin layer after curing.

[0160] One method for forming conductive patterns by etching is flash etching. In flash etching, the copper seed layer can be removed with a predetermined etching solution. Examples of etching solutions include, but are not limited to, a mixed etching solution of sulfuric acid and hydrogen peroxide (manufactured by Ebara Electric Industries, Ltd.).

[0161] [Method for manufacturing conductor patterns] The method for manufacturing conductor patterns involves, for example, using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern using the resist pattern formation method described above, and then carrying out the conductor pattern formation step.

[0162] <Peeling Process> Furthermore, after forming the conductor pattern by the conductor pattern formation process described above, a peeling process may be performed to peel the resist pattern from the substrate using an aqueous solution that is more alkaline than the developer. By performing the peeling process, a wiring board (in one embodiment, a printed wiring board) having the desired wiring pattern can be obtained.

[0163] The alkaline aqueous solution used for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, but an aqueous solution of NaOH or KOH with a concentration of 2% to 20% by mass, or an organic amine-based stripping solution, is generally used. A small amount of water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohol. The temperature of the stripping solution in the stripping process is preferably in the range of 40°C to 70°C, and the immersion time of the stripping solution is preferably 30 seconds to 60 minutes.

[0164] [Manufacturing Method for Wiring Boards] In one embodiment, the manufacturing method for wiring boards using the photosensitive resin laminate according to this embodiment includes the following steps: a lamination step of laminating a photosensitive resin layer onto a substrate; an exposure step of exposing the photosensitive resin layer to light; a developing step of developing and removing the unexposed portion of the photosensitive resin layer to form a resist pattern; a conductor pattern forming step of etching or plating the substrate on which the resist pattern has been formed to form a conductor pattern; and a peeling step of peeling the resist pattern from the substrate. The lamination step, exposure step, developing step, conductor pattern forming step and peeling step, which are included in the manufacturing method for wiring boards according to this embodiment, are the same as described above.

[0165] In this embodiment, the photosensitive resin laminate can be used in the manufacture of printed circuit boards; lead frames for IC chip mounting; precision metal foil processing such as metal masks; packages such as ball grid arrays (BGAs) and chip-size packages (CSPs); tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); semiconductor bumps; and partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields. Unless otherwise specified, the values ​​of each of the above parameters are measured in accordance with the measurement methods described in the embodiments below.

[0166] [Method for Manufacturing a Photosensitive Resin Laminate] The photosensitive resin laminate according to this embodiment can be manufactured by the method shown below. That is, the method for manufacturing the photosensitive resin laminate of this embodiment is, in one embodiment, a method for manufacturing a photosensitive resin laminate comprising a support and a photosensitive resin layer containing a photosensitive resin composition, and includes the following steps: A preparation step of preparing a photosensitive resin composition solution containing a compound having an ethylenically unsaturated bond which is component (A), an alkali-soluble resin which is component (B), a polymerization initiator which is component (C), and a solvent; a coating step of coating the photosensitive resin composition solution onto the support; and a photosensitive resin layer formation step of heating the support coated with the photosensitive resin composition solution to form a photosensitive resin layer. In one embodiment, component (A) includes a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule (component A1).

[0167] The method for manufacturing a photosensitive resin laminate according to this embodiment makes it possible to produce a photosensitive resin laminate with excellent sensitivity and resolution that is not affected by manufacturing conditions or storage conditions determined by the thickness of the photosensitive resin layer.

[0168] <Formulation Process> This process involves adding a solvent to the above-mentioned (A) compound having an ethylenically unsaturated bond, (B) alkali-soluble resin, and (C) polymerization initiator to prepare a photosensitive resin composition solution.

[0169] Suitable solvents include ketones, such as methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. The solvent may be used alone or a mixture of two or more solvents. The solvent content is preferably 30 to 60% by mass, more preferably 33 to 55% by mass, and even more preferably 35 to 57% by mass, relative to the photosensitive resin composition solution. It is preferable to add the solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition solution is 500 to 4000 mPa·sec at 25°C. The viscosity is measured at 25°C using a Brookfield viscometer (Eikoh Co., Ltd., model DVNext).

[0170] <Coating Process> This process involves coating a photosensitive resin composition solution onto a support. For coating the support with the photosensitive resin composition solution, conventional methods such as coating with a roll coater, spin coater, bar coater, blade coater, curtain coater, and screen printing machine, or spray coating with a spray coater can be used.

[0171] <Photosensitive Resin Layer Formation Process> This process involves heating a support coated with a photosensitive resin composition solution to form a photosensitive resin layer made of the photosensitive resin composition by heating and distilling off the solvent in the photosensitive resin composition solution. The heating temperature of the support coated with the photosensitive resin composition solution is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher. Heating to 70°C or higher accelerates the evaporation of the solvent contained in the photosensitive resin composition solution, thereby improving the production efficiency of the photosensitive resin laminate. The heating temperature of the support coated with the photosensitive resin composition solution is preferably 140°C or lower, more preferably 130°C or lower, and even more preferably 120°C or lower. Maintaining a temperature of 140°C or lower prevents the thermal polymerization of the photosensitive resin composition from progressing. The heating time of the support coated with the photosensitive resin composition solution is preferably 1 to 10 minutes.

[0172] If necessary, the process may include a protective step after the photosensitive resin layer formation step in which a protective layer, such as a protective film, is laminated onto the photosensitive resin layer. The protective layer is applied to the side of the photosensitive resin layer where the support is not laminated and functions as a cover. The protective film used in the protective step is the same as described above.

[0173] Next, this embodiment will be described in more detail with reference to examples and comparative examples. However, this embodiment is not limited to the following examples unless it deviates from its essence. The physical properties in the examples were measured by the following methods.

[0174] (B) The weight-average molecular weight of the alkali-soluble resin was measured by gel permeation chromatography (GPC) and derived by conversion using a calibration curve for standard polystyrene. The GPC conditions are as follows:

[0175] (GPC conditions) Pump: PU-980 manufactured by JASCO Corporation Column: Two columns in total, Shodex KF-80Y / KF-806M Eluent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 2.05 mL / min Detector: RI-1530 manufactured by JASCO Corporation Standard monodisperse polystyrene: TSKgel standard polystyrene manufactured by Tosoh Corporation

[0176] The photosensitive resin laminates were prepared as follows. <Preparation of Photosensitive Resin Laminates> The components (A) to (E) shown in Table 2 below (wherein the numbers for each component indicate the amount (parts by mass) of solids) were mixed to prepare the photosensitive resin compositions (Examples 1 to 34 and Comparative Examples 1 to 12). The photosensitive resin compositions of Examples 1 to 34 and Comparative Examples 1 to 12, along with ethanol measured so that the solids concentration of these photosensitive resin compositions was 60% by mass, were thoroughly stirred and mixed to obtain a formulation containing the photosensitive resin compositions of Examples 1 to 34 and Comparative Examples 1 to 12. A 16 μm thick polyethylene terephthalate film (QS71, manufactured by Toray Industries, Inc.) was used as a support, and these formulations were uniformly applied to its surface using a bar coater (product name: Type A Automatic Applicator, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The mixture was then heated and dried in a 95°C dryer for 2 minutes and 30 seconds to form a 25 μm thick photosensitive resin layer. Next, a 19 μm thick polyethylene film (GF-858, manufactured by Tamapoly Co., Ltd.) was laminated as a protective layer onto the surface of the photosensitive resin layer that did not have the polyethylene terephthalate film laminated on it, to obtain a photosensitive resin laminate containing the photosensitive resin compositions of Examples 1 to 34 and Comparative Examples 1 to 12.

[0177] [Fabrication of performance evaluation substrates] Performance evaluation substrates were fabricated as follows.

[0178] <Substrate Surface Preparation> A 0.4 mm thick copper-clad laminate was prepared by laminating 18 μm thick rolled copper foil. The surface of this substrate was treated with H at a concentration of 10 mass%. ２ SO ４ It was washed with an aqueous solution.

[0179] <Lamination> After peeling off the polyethylene film from the photosensitive resin laminate prepared above and leveling the substrate surface using the method described above, the photosensitive resin laminate prepared above was laminated onto a copper-clad laminate preheated to 50°C using a hot roll laminator (Asahi Kasei Corporation, AL-700) at a roll temperature of 105°C to obtain a substrate for performance evaluation. The air pressure was set to 0.35 MPa and the lamination speed to 1.5 m / min.

[0180] <Exposure Process> Two hours after lamination, the performance evaluation substrate was exposed at a wavelength of 365 nm through a glass mask using a projection exposure machine (UX-44101SM, manufactured by Ushio Inc.). Similarly, the performance evaluation substrate was exposed at a wavelength of 402 nm using a direct imaging exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) with a predetermined direct imaging (DI) exposure pattern.

[0181] <Heating Process> The performance evaluation substrate, one minute after exposure, was heated for 30 seconds in a forced-air constant temperature incubator (DKM600, manufactured by Yamato Scientific Co., Ltd.) set to 60°C.

[0182] <Developing Process> After peeling off the polyethylene terephthalate film (support), an alkaline developer (manufactured by Fuji Kiko Co., Ltd., for dry film) is used at 30°C with a concentration of 1% by mass of Na ２ CO ３ Developing was performed by spraying an aqueous solution for a predetermined period of time. The developing spray time was set to twice the minimum development time, and the post-development rinsing spray time was also set to twice the minimum development time.

[0183] <Plating Process> On a substrate that had been prepared and laminated in the same manner as described above, a resist pattern was formed by exposure using a drawing pattern with a line width (L) / space width (S) (hereinafter referred to as "L / S") of x / x (x = 1 to 20 (varying in 1 μm intervals)) (unit: μm) at an energy level that resulted in 17 remaining steps on the Hitachi 41-step step tablet. After exposure, the same heating and developing process as described above was performed to form a resist pattern. The developed substrate was immersed in an acidic degreasing FRX (10% by mass sulfuric acid aqueous solution, manufactured by Attec Japan Co., Ltd.) bath at 40°C for 4 minutes. After rinsing with water, it was immersed in a 10% by mass sulfuric acid aqueous solution at room temperature for 2 minutes.

[0184] A 121 g / l copper sulfate aqueous solution was prepared and diluted with 19% by mass sulfuric acid until its volume was 3.6 times its original size. Then, concentrated hydrochloric acid was added to a concentration of 200 ppm. Next, caparaside HL and caparaside GS were added as brighteners at concentrations of 0.4 ml / l and 20 ml / l, respectively, to prepare a copper sulfate plating solution. A pre-treated substrate (6 cm × 12.5 cm) for evaluating plating resistance was plated with the prepared copper sulfate plating solution using a Harling cell uniform plating apparatus (manufactured by Yamamoto Plating Testing Equipment Co., Ltd.) at an applied current of 0.4 A for 65 minutes. The thickness of the copper plating film at this time was 20 μm.

[0185] <Stripping Process> "Clean Etch (Registered Trademark) R-100S" (manufactured by Mitsubishi Gas Chemical Company, Inc.) and "Clean Etch (Registered Trademark) R-101" (manufactured by Mitsubishi Gas Chemical Company, Inc.) were mixed in a volume ratio of 1 / 2, and then diluted with pure water to prepare a stripping solution with a concentration of 20% by mass. A performance evaluation substrate that had undergone plating treatment was immersed in the stripping solution, heated to 50°C, for 4 minutes without stirring to strip off the resist pattern.

[0186] [Evaluation] <Developability> The fabricated performance evaluation substrate was subjected to exposure and development processes according to the above method, and the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was defined as the minimum development time. In this disclosure, the closer the minimum development time is to the ideal development time, the better the developability, and the minimum development time was evaluated according to the following criteria. In this example, the ideal development time for a film thickness of 25 μm was set to 21 seconds. If the developability evaluation value is 2 or higher, it can be suitably used as a photosensitive resin laminate for resist pattern formation. Furthermore, an evaluation of 3 or higher is more preferable, and an evaluation of 4 is particularly preferable. 4: Difference between the minimum development time and 21 seconds is less than 2 seconds 3: Difference between the minimum development time and 21 seconds is 2 seconds or more and less than 5 seconds 2: Difference between the minimum development time and 21 seconds is 5 seconds or more and 10 seconds or less 1: Difference between the minimum development time and 21 seconds is more than 10 seconds

[0187] <Adhesion> A resist pattern was formed on the fabricated performance evaluation substrate using a drawing pattern with a line width (L) / space width (S) (hereinafter referred to as "L / S") of x / 3x (x = 1 to 20 (varying in 1 μm increments)) (unit: μm). The resist pattern was exposed to an energy level that resulted in 17 remaining steps on a Hitachi 41-step step tablet, followed by the heating and developing processes described above. The resist pattern was observed with an optical microscope, and the adhesion was evaluated based on the minimum line width at which the line portion (exposed portion) was formed without meandering or chipping. A smaller line width value indicates higher adhesion, and the following criteria were used to evaluate the adhesion: 4: Minimum line width less than 5 μm; 3: Minimum line width 5 μm or more and less than 6 μm; 2: Minimum line width 6 μm or more and less than 7 μm; 1: Minimum line width 7 μm or more

[0188] <Resolution> A resist pattern was formed on a fabricated performance evaluation substrate using a drawing pattern with a line width (L) / space width (S) (hereinafter referred to as "L / S") of x / x (x = 1 to 20 (varying in 1 μm increments)) (unit: μm). The resist pattern was formed by exposing it to a Hitachi 41-step step tablet with an energy level that resulted in 17 remaining steps, followed by the heating and developing processes described above. The resist pattern was observed with an optical microscope, and the resolution was evaluated by the minimum line width at which the line portions (exposed portions) did not meander or break, and the space portions (unexposed portions) were removed without any residue. A smaller line width value indicates higher resolution, and the following criteria were used to evaluate the resolution: 4: Minimum line width less than 5 μm 3: Minimum line width 5 μm or more and less than 6 μm 2: Minimum line width 6 μm or more and less than 7 μm 1: Minimum line width 7 μm or more

[0189] The resist pattern formation ability was evaluated based on the adhesion evaluation value and the resolution evaluation value. If the sum of the adhesion evaluation value and the resolution evaluation value is 6 or more, the photosensitive resin laminate of this embodiment can be suitably used for resist pattern formation. Furthermore, if the sum of the adhesion evaluation value and the resolution evaluation value is 7 or more, it is more suitable for the photosensitive resin laminate of this embodiment, and if the sum of the adhesion evaluation value and the resolution evaluation value is 8, it is particularly suitable.

[0190] <Evaluation of Peelability> After performing the above plating process on the fabricated performance evaluation substrate, the above peeling process was performed. Peelability was evaluated by the time it took for the cured resist lines between the plating patterns to be completely peeled off. A shorter time indicates higher peelability, and the following criteria were used to evaluate the peelability and determine the evaluation value. If the evaluation value of peelability is 2 or higher, it can be suitably used as the photosensitive resin laminate of this embodiment for printed circuit boards in which plating is performed after the formation of the resist pattern. Furthermore, an evaluation of 3 or higher is more suitable for the photosensitive resin laminate of this embodiment, and an evaluation of 4 is particularly suitable. 4: Less than 50 seconds 3: 50 seconds or more and less than 65 seconds 2: 65 seconds or more and less than 80 seconds 1: 80 seconds or more

[0191] Table 2 shows the evaluation results for the performance evaluation substrate of the example. Table 3 shows the details of the components shown in Table 2. For component (B) in Table 3, the content ratio of each monomer component in components B-1 to B-5 represents the mass ratio of each monomer component.

[0192]

[0193]

[0194]

[0195]

[0196]

[0197] As is clear from Table 2, the embodiments that met the requirements of this embodiment showed good resist pattern formation, peelability, and developability. On the other hand, when component (A) did not contain component (A1), as in Comparative Examples 1 to 12, the resist pattern formation, peelability, and developability were all poor. Also, when the content of polymerization initiator (C) was less than 4.0% by mass of the total solid content of the photosensitive resin composition, as in Comparative Example 12, the resist pattern formation was poor.

[0198] While embodiments of the present invention have been described above, the present invention is not limited thereto and can be modified as appropriate without departing from the spirit of the invention.

[0199] By using the photosensitive resin laminate according to the present invention, excellent resist pattern formation properties, peelability, and developability are obtained, unaffected by coating, drying, or storage conditions of the photosensitive resin laminate. In other words, it can be widely used as a photosensitive resin laminate for resist pattern formation, and is particularly suitable for use in forming resist patterns on printed circuit boards where plating is required after resist pattern formation.

Claims

A photosensitive resin laminate comprising a support and a photosensitive resin layer containing a photosensitive resin composition, The aforementioned photosensitive resin composition comprises the following components: (A) Compounds having ethylenically unsaturated bonds (B) Alkali-soluble resins and (C) Polymerization initiator Includes, The aforementioned component (A) is a compound having three or more aromatic rings and one or more ethylenically unsaturated bonds in one molecule of (A1). Includes, The aforementioned component (C) comprises a hexaarylbiimidazole compound, The content of component (C) is 4.0% by mass or more of the total solid content of the photosensitive resin composition. Photosensitive resin laminate. 　 The photosensitive resin laminate according to claim 1, wherein (A1) is a compound having a structure in which three or more aromatic rings are bonded to one carbon atom in one molecule, and having one or more ethylenically unsaturated bonds. 　 The photosensitive resin laminate according to claim 1, wherein (A1) contains a fluorene skeleton, or a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton within the molecule. 　 The above (A1) is the photosensitive resin laminate according to claim 3, wherein the molecule contains a fluorene skeleton. 　 The photosensitive resin laminate according to claim 3, wherein (A1) is a compound having a fluorene skeleton in its molecule and having 2 to 4 (meth)acryloyl groups. 　 The above (A1) is the following general formula (I): [In the formula, X is independently either S or O, R １ , R ２ , R ３ and R ４ Each of these independently represents an alkylene group having 1 to 10 carbon atoms. R ５ 、 R ６ 、 R ７ 、 R ８ 、 R ９ and R １０ each independently represents a hydrogen atom or a methyl group, a and b are 0 or 1. m, n, o, and p are each independently between 0 and 30. A photosensitive resin laminate according to claim 5, comprising a compound represented by [the specified compound]. 　 The above (A1) is the following general formula (II): [In the formula, R １ and R ２ Each of these independently represents an alkylene group having 1 to 10 carbon atoms. R ５ and R ６ Each of these is independently either a hydrogen atom or a methyl group. m and n are each independently between 0 and 30. A photosensitive resin laminate according to claim 5, comprising a compound represented by [the specified compound]. 　 The photosensitive resin laminate according to claim 6 or 7, wherein (A1) is a compound having two (meth)acryloyl groups. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the main chain end of (A1) is a methacryloyl group. 　 The repeating unit in the above general formulas (I) and (II) is R １ O, R ２ O, R ３ O, and R ４ The photosensitive resin laminate according to claim 6 or 7, wherein O comprises ethylene oxide (EO) or propylene oxide (PO). 　 The photosensitive resin laminate according to claim 10, wherein the total number of moles of repeating units in the general formulas (I) and (II) (the sum of m + n + o + p in the general formula (I) and the sum of (2 × m) + (2 × n) in the general formula (II)) is 30 moles or less. 　 The photosensitive resin laminate according to claim 10, wherein the total number of moles of repeating units in the general formulas (I) and (II) (the sum of m + n + o + p in the general formula (I) and the sum of (2 × m) + (2 × n) in the general formula (II)) is 5 moles or more. 　 The photosensitive resin laminate according to claim 3, wherein (A1) contains a methylidenttrisphenyl skeleton or an ethylidenttrisphenyl skeleton in the molecule. 　 The above (A1) is the following general formula (III): [In the formula, X is independently either S or O, R １ , R ２ and R ３ Each of these independently represents an alkylene group having 1 to 10 carbon atoms. R ４ , R ５ , R ６ and R ７ Each of these is independently either a hydrogen atom or a methyl group. m, n, and o are each independently between 0 and 30. A photosensitive resin laminate according to claim 13, comprising a compound represented by [the specified compound]. 　 The above (A1) is the following general formula (IV): [In the formula, R １ , R ２ and R ３ Each of these independently represents an alkylene group having 1 to 10 carbon atoms. R ４ , R ５ , R ６ and R ７ Each of these is independently either a hydrogen atom or a methyl group. m, n, and o are each independently between 0 and 30. A photosensitive resin laminate according to claim 13, comprising a compound represented by [the specified compound]. 　 The repeating unit in the above general formulas (III) and (IV) is R １ O, R ２ O and R ３ The photosensitive resin laminate according to claim 14 or 15, wherein O comprises ethylene oxide (EO) or propylene oxide (PO). 　 The photosensitive resin laminate according to claim 16, wherein the total number of moles of repeating units in the general formulas (III) and (IV) (the sum of m + n + o in the general formula (III) and the sum of (2 × m) + (2 × n) + (2 × o) in the general formula (IV)) is 0 to 50 moles. 　 The photosensitive resin laminate according to claim 16, wherein the total number of moles of repeating units in the general formulas (III) and (IV) (the sum of m + n + o in the general formula (III) and the sum of (2 × m) + (2 × n) + (2 × o) in the general formula (IV)) is 5 moles or more. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the total content of component (A) and component (B) in the photosensitive resin composition is 80% by mass or more, based on the total solid content mass of the photosensitive resin composition. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the content of component (B) is 70% by mass or less, based on the total content of component (A) and component (B). 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the photosensitive resin composition further comprises (D) a polymerization inhibitor. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the component (A) further comprises a compound having two or fewer aromatic rings in one molecule and having an ethylenically unsaturated bond. 　 The photosensitive resin laminate according to claim 22, wherein (A2) comprises a compound having two or more ethylenically unsaturated bonds. 　 The photosensitive resin laminate according to claim 22, wherein (A2) comprises a compound having three or more ethylenically unsaturated bonds. 　 The photosensitive resin laminate according to claim 22, wherein (A2) comprises a compound having 3 to 6 ethylenically unsaturated bonds. 　 The photosensitive resin laminate according to claim 22, wherein (A2) contains a compound that does not have quaternary carbon atoms and has three or more ethylenically unsaturated bonds. 　 The photosensitive resin laminate according to claim 22, wherein (A2) contains a compound that does not have quaternary carbon atoms and has 3 to 6 ethylenically unsaturated bonds. 　 A compound that does not have the aforementioned quaternary carbon and has three or more ethylenically unsaturated bonds is, The following general formula (V): [In the formula, h is between 1 and 20, Each i is a natural number between 1 and h. Each of k, li, and j is independently between 0 and 30. R ９ 、 and R １１ Each of these independently represents either a hydrogen atom or a methyl group. R １２ 、 and R １４ Each of these is an alkylene group having 1 to 10 carbon atoms, with the following general formula (VI): [In the formula, R １５ and R １６ Each of these is an alkylene group having 1 to 10 carbon atoms. A base represented by, The following general formula (VII): [In the formula, R １７ This is an alkylene group having 1 to 10 carbon atoms. It is one of the groups selected from the group consisting of the bases represented by [the formula shown]. The photosensitive resin laminate according to claim 26, comprising a (poly)glycerin-based (meth)acrylate represented by . 　 The photosensitive resin laminate according to claim 28, wherein in the general formula (V), h is 2 to 20. 　 The photosensitive resin laminate according to claim 22, wherein (A2) is a compound containing a methacryloyl group. 　 The photosensitive resin laminate according to claim 22, wherein (A2) comprises a compound having one ethylenically unsaturated bond. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the component (B) comprises a copolymer having structural units derived from styrene and benzyl (meth)acrylate. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the (B) component contains a constituent unit derived from styrene, and the (B) component contains 30% by mass or more of styrene. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the content of styrene-derived structural units in component (B) is 50% by mass or less. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the weight-average molecular weight of component (B) is 17,500 or more. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the weight-average molecular weight of component (B) is 50,000 or less. 　 The aforementioned component (B) includes a constituent unit derived from (meth)acrylic acid, The photosensitive resin laminate according to any one of claims 1 to 3, wherein the content of the constituent units derived from (meth)acrylic acid is 15% by mass or more and 35% by mass or less. 　 The photosensitive resin laminate according to any one of claims 1 to 3, wherein the component (B) includes a constituent unit derived from a monomer having at least one ethylenically unsaturated bond in its molecule and containing a hydroxyl group. A photosensitive resin laminate according to any one of claims 1 to 3, wherein the Tg of component (B), calculated by Fox's formula, is 375K or more and 400K or less. Na at a concentration of 1% by mass ２ CO ３ The photosensitive resin laminate according to any one of claims 1 to 3, wherein the minimum development time per 1 μm of film thickness of the photosensitive resin layer when developing by spraying an aqueous solution at 30°C is 0.6 seconds or more and 1.1 seconds or less. 　 Furthermore, the photosensitive resin laminate according to any one of claims 1 to 3, comprising a protective film. 　 A method for forming a resist pattern using a photosensitive resin laminate according to any one of claims 1 to 3, comprising the following steps: Lamination process for stacking a photosensitive resin layer onto a substrate; An exposure step of exposing the photosensitive resin layer; A developing step for developing and removing the unexposed portion of the photosensitive resin layer; A method for forming a resist pattern, including the method described above. 　 A method for manufacturing a wiring board using a photosensitive resin laminate according to any one of claims 1 to 3, comprising the following steps: Lamination process for stacking a photosensitive resin layer onto a substrate; An exposure step of exposing the photosensitive resin layer; A developing step to develop and remove the unexposed portion of the photosensitive resin layer to form a resist pattern; A conductor pattern forming step involves etching or plating the substrate on which the resist pattern is formed to form a conductor pattern; and A peeling step for peeling the resist pattern from the substrate; A method for manufacturing a wiring board, including the method described above.

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