Photosensitive resin composition and method for forming resist pattern

Abstract

A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photoinitiator, (D) a sensitizer, and (E) polymerization inhibitors, wherein (C) the photoinitiator includes one or more selected from a 2,4,5-triallyl imidazole dimer and an acridine compound, the contained amount of (C) the photoinitiator is 5.0 mass% or more with respect to the total mass of solid content of the photosensitive resin composition, (D) the sensitizer contains a specific compound represented by the compound described by formula (D1-1), and (E) the polymerization inhibitors include (E1) a first polymerization inhibitor selected from nitroso compounds and nitroxyl radicals and (E2) a second polymerization inhibitor other than the first polymerization inhibitor.

Description

Photosensitive resin composition and method for forming a resist pattern

[0001] The present invention relates to a photosensitive resin composition and a method for forming a resist pattern.

[0002] Printed circuit boards are generally manufactured using photolithography. In photolithography, a photosensitive resin composition layer is first formed on the substrate, and a resist pattern is formed by exposing and developing this photosensitive resin composition layer. Then, a conductive pattern is formed on the substrate by etching or plating, and after that, the resist pattern is removed to form the desired wiring pattern on the substrate.

[0003] In photolithography, methods for forming a photosensitive resin layer on a substrate include, for example, applying a solution of a photosensitive resin composition to the substrate and drying it; or laminating a photosensitive resin composition layer of a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin composition layer) onto the substrate. In the manufacturing process of printed circuit boards, the method using dry film resist is widely adopted.

[0004] Various configurations have been proposed for the photosensitive resin composition that constitutes the photosensitive resin composition layer, from the viewpoint of further improving light sensitivity, resolution, adhesion, etc. (for example, Patent Documents 1 to 3).

[0005] Japanese Patent Publication No. 2015-161723, Japanese Patent Publication No. 59-142258, Japanese Patent Publication No. 2003-140329

[0006] Photosensitive resin compositions used in photolithography contain, for example, binder polymers, compounds having ethylenically unsaturated bonds, photopolymerization initiators, sensitizers, etc. In recent years, there has been a trend to increase the content of polymerization initiators in photosensitive resin compositions in order to improve the photosensitivity of the composition and the adhesion of the resulting resist pattern to the substrate. Increasing the content of polymerization initiators in a photosensitive resin composition does indeed improve photosensitivity and adhesion.

[0007] However, conventional photosensitive resin compositions still lack sufficient photosensitivity. Furthermore, increasing the content of polymerization initiators in the photosensitive resin composition can lead to unintended polymerization of compounds containing ethylenically unsaturated bonds during storage, impairing storage stability. When compounds containing ethylenically unsaturated bonds in the photosensitive resin composition undergo unintended polymerization, the viscosity of the composition increases, affecting handling properties, coating properties, and potentially impacting photosensitive characteristics.

[0008] Therefore, the first objective of the present invention is to provide a photosensitive resin composition having higher photosensitivity compared to those known in the prior art. The second objective of the present invention is to provide a photosensitive resin composition having high photosensitivity, high adhesion of the resulting resist pattern to a substrate, and excellent storage stability. The third objective of the present invention is to provide a method for forming a resist pattern using the above-mentioned photosensitive resin composition.

[0009] The present invention, which achieves the above objectives, is as follows:

[0010] <Aspect 1> A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a sensitizer, and (E) a polymerization inhibitor, wherein the (C) photopolymerization initiator comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, the content of the (C) photopolymerization initiator is 5.0% by mass or more with respect to the total mass of the solids of the photosensitive resin composition, the (D) sensitizer comprises a compound represented by the following general formula (D1), and the (E) polymerization inhibitor comprises (E1) a first polymerization inhibitor selected from nitroso compounds and nitroxyl radicals, and (E2) a second polymerization inhibitor other than the first polymerization inhibitor. {In formula (D1), R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １ and R ２When it is an alkyl group, each terminal may be bonded to the 6-position carbon or 8-position carbon of the coumarin skeleton to form a heterocyclic ring containing nitrogen.} {Aspect 2} The photosensitive resin composition according to aspect 1, wherein the (E1) first polymerization inhibitor contains one or more selected from the compounds represented by the following general formulas (E1-1) and (E1-2). {R in formula (E1-1) １２ and R １３ are each a hydrocarbon group which may have a substituent.} {In formula (E1-2), R １４ is a hydrocarbon group which may have a substituent, M ｍ＋ is an ion of a metal selected from aluminum, cobalt, iron, and copper, and m is the valence of the ion of the metal.} {Aspect 3} The photosensitive resin composition according to aspect 1 or 2, wherein the content of the (C) photoinitiator is 5.5 parts by mass or more and 8.0 parts by mass or less with respect to 100 parts by mass in total of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond. {Aspect 4} The photosensitive resin composition according to aspect 3, wherein the content of the (C) photoinitiator is 5.5 parts by mass or more and 7.0 parts by mass or less with respect to 100 parts by mass in total of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond. {Aspect 5} When the content of the (C) photoinitiator with respect to 100 parts by mass in total of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond is Wc (parts by mass), and the content of the (D) sensitizer is W Ｄ (parts by mass), the ratio W Ｄ of the content Wc of the (C) photoinitiator to the content W Ｃ of the (D) sensitizer is W ＤA photosensitive resin composition according to any one of embodiments 1 to 4, wherein the (E2) second polymerization inhibitor comprises a phenolic polymerization inhibitor. Aspect 6 A photosensitive resin composition according to any one of embodiments 1 to 5, wherein the (E2) second polymerization inhibitor comprises a phenolic polymerization inhibitor. Aspect 7 A photosensitive resin composition according to any one of embodiments 1 to 6, wherein the (E2) second polymerization inhibitor comprises 4-t-butylcatechol. Aspect 8 A photosensitive resin composition according to any one of embodiments 1 to 7, wherein the compound represented by formula (D1) is a compound represented by the following general formula (D1-1). <Aspect 9> The photosensitive resin composition according to any one of aspects 1 to 8, wherein the (D) sensitizer further comprises a compound having a skeleton selected from the group consisting of anthracene, triarylamine, dialkylbenzophenone, oxazole, pyrazoline, and coumarin (excluding the compound represented by formula (D1)). <Aspect 10> The photosensitive resin composition according to aspect 9, wherein the (D) sensitizer further comprises a compound having an anthracene skeleton. <Aspect 11> The photosensitive resin composition according to aspect 10, wherein the compound having an anthracene skeleton is a compound represented by the following general formula (D2). {In formula (D2), R ４ and R ５Each of these is independently a hydrogen atom, a C1-C20 alkyl group, a C1-C5 alkoxyl group, or a C6-C20 aryl group.} <Aspect 12> The photosensitive resin composition according to any one of aspects 1 to 11, wherein the (A) alkali-soluble polymer contains structural units derived from styrene in an amount of 35% by mass or more and 75% by mass or less, based on the total mass of structural units derived from all monomers contained in the (A) alkali-soluble polymer. <Aspect 13> The photosensitive resin composition according to aspect 12, wherein the (A) alkali-soluble polymer contains structural units derived from styrene in an amount of 40% by mass or more and 75% by mass or less, based on the total mass of structural units derived from all monomers contained in the (A) alkali-soluble polymer. <Aspect 14> The photosensitive resin composition according to any one of aspects 1 to 13, wherein the (A) alkali-soluble polymer contains structural units derived from hydroxyethyl (meth)acrylate. 《Aspect 15》A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a sensitizer, and (E) a polymerization inhibitor, wherein the (C) photopolymerization initiator comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, the content of the (C) photopolymerization initiator is 5.0% by mass or more with respect to the total mass of the solids of the photosensitive resin composition, the (D) sensitizer comprises a compound represented by the following general formula (D1), and the content of the (C) photopolymerization initiator is Wc (parts by mass) and the content of the (D) sensitizer is W Ｄ When the amount is (parts by mass), the content of the sensitizer (D) is W Ｄ The ratio of the content Wc of the (C) photopolymerization initiator to the above W Ｃ / W Ｄ A photosensitive resin composition having a value of 12.0 or higher. {In formula (D1), R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １ and R ２If is an alkyl group, its ends may bond to the 6th or 8th carbon of the coumarin skeleton to form a nitrogen-containing heterocycle.} <Aspect 16> A photosensitive resin composition laminate comprising a support film and a photosensitive resin composition layer on the support film, wherein the photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of aspects 1 to 15. <Aspect 17> A method for forming a resist pattern comprising: laminating a photosensitive resin composition layer on a substrate; exposing the photosensitive resin composition layer; and developing the photosensitive resin composition layer after exposure; wherein the photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of aspects 1 to 15.

[0011] According to the present invention, firstly, a photosensitive resin composition having high photosensitivity is provided. Secondly, a photosensitive resin composition is provided that has high photosensitivity, high adhesion of the resulting resist pattern to a substrate, and excellent storage stability. Thirdly, a method for forming a resist pattern using the above-mentioned photosensitive resin composition is provided.

[0012] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. Throughout this specification, if there are multiple structures represented by the same reference numerals in the general formula within a single molecule, they may be identical or different. The present invention is not limited to the following embodiments and may be carried out with various modifications within the scope of its gist.

[0013] 《Photosensitive Resin Composition》 First, the first photosensitive resin composition described as embodiment 15 above will be explained. The first photosensitive resin composition in the present invention is a photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a sensitizer, and (E) a polymerization inhibitor, wherein the (C) photopolymerization initiator comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, the content of the (C) photopolymerization initiator is 5.0% by mass or more with respect to the total mass of the solids of the photosensitive resin composition, the (D) sensitizer comprises a compound represented by the following general formula (D1), and the content of the (C) photopolymerization initiator is Wc (parts by mass) and the content of the (D) sensitizer is W Ｄ When the amount is (parts by mass), the content of the sensitizer (D) is W Ｄ The ratio of the content Wc of the (C) photopolymerization initiator to the above W Ｃ / W Ｄ However, it is a photosensitive resin composition with a value of 12.0 or higher.

[0014]

[0015] {In formula (D1), R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １ and R ２ If it is an alkyl group, its terminals may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.

[0016] The photosensitive resin composition of this embodiment has higher photosensitivity compared to those known in the prior art.

[0017] The photosensitive resin composition of this embodiment may optionally contain any components in addition to components (A) to (E).

[0018] <(A) Alkali-soluble polymer> The (A) alkali-soluble polymer contained in the first photosensitive resin composition refers to a polymer that dissolves in an alkaline aqueous solution. The (A) alkali-soluble polymer may, for example, have a structural unit derived from an (a1) unsaturated acidic monomer, and it is preferable that it has a structural unit derived from an (a1) unsaturated acidic monomer and a structural unit derived from one or more selected from the group consisting of (a2) styrene derivatives, (a3) ​​alkyl (meth)acrylates substituted with hydroxyl groups, (a4) alkyl (meth)acrylates, (a5) (meth)acrylates having alicyclic or aromatic rings, and (a6) other monomers.

[0019] (a1) The unsaturated acidic monomer may be, for example, a carboxylic acid or carboxylic acid anhydride having one polymerizable unsaturated group in one molecule. (a1) Examples of unsaturated acidic monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid anhydride, maleic acid half-ester, etc., and one or more selected from these may be used. (a1) As the unsaturated acidic monomer, (meth)acrylic acid is particularly preferred.

[0020] (A) The content of structural units derived from (a1) unsaturated acidic monomers in the alkali-soluble polymer may be 5% by mass or more and 100% by mass or less, and preferably 10% by mass or more and 50% by mass or less, based on the total mass of structural units derived from all monomers contained in the alkali-soluble polymer (A). Adjusting the content of structural units derived from (a1) unsaturated acidic monomers to the above range is preferable from the viewpoint of obtaining a resist pattern that is excellent in resolution and developability when forming a resist pattern and has excellent adhesion to the substrate. The content of structural units derived from (a1) unsaturated acidic monomers may be 12% by mass or more, 14% by mass or more, 16% by mass or more, 18% by mass or more, or 20% by mass or more, based on the above criteria, and may be 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 28% by mass or less.

[0021] (A) The alkali-soluble polymer has structural units derived from (a2) styrene derivatives, which allows for further improvement of the heat resistance of the resulting resist pattern without impairing other functions. Examples of (a2) styrene derivatives include styrene, oxystyrene, acetoxystyrene, alkylstyrene, halogenoalkylstyrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer, etc., and one or more selected from these may be used. Styrene is particularly preferred as the (a2) styrene derivative.

[0022] (A) If the alkali-soluble polymer has structural units derived from (a2) styrene derivatives, the content thereof may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more, based on the total mass of structural units derived from all monomers contained in (A) the alkali-soluble polymer, and may be 75% by mass or less, 70% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less.

[0023] (a3) A alkyl (meth)acrylate substituted with a hydroxyl group is a monomer in which one or more hydrogen atoms of the alkyl group of the alkyl (meth)acrylate are substituted with a hydroxyl group. (A) By having an alkali-soluble polymer have structural units derived from (a3) ​​alkyl (meth)acrylate substituted with a hydroxyl group, the developability during resist pattern formation and the adhesion of the resulting resist pattern to the substrate can be further improved without impairing other functions. (a3) ​​Examples of alkyl (meth)acrylates substituted with a hydroxyl group include: an alkyl (meth)acrylate substituted with one hydroxyl group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc.; and an alkyl (meth)acrylate substituted with two hydroxyl groups such as glycerin mono (meth)acrylate, etc.; and one or more selected from these may be used. (a3) Among alkyl (meth)acrylates substituted with hydroxyl groups, hydroxyethyl (meth)acrylate is particularly preferred.

[0024] (A) If the alkali-soluble polymer has structural units derived from alkyl (meth)acrylates substituted with hydroxyl groups, the content thereof may be 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total mass of structural units derived from all monomers contained in the alkali-soluble polymer (A), and may be 50% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less.

[0025] (a4) Examples of alkyl (meth)acrylates 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-ethylhexyl (meth)acrylate, etc., and one or more selected from these may be used. (a4) 2-ethylhexyl (meth)acrylate is particularly preferred as the alkyl (meth)acrylate.

[0026] (A) If the alkali-soluble polymer has structural units derived from (a4) alkyl (meth)acrylate, the content thereof may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less, based on the total mass of structural units derived from all monomers contained in (A) the alkali-soluble polymer.

[0027] (a5) Examples of (meth)acrylates having an alicyclic or aromatic ring include: As an alicyclic (meth)acrylate, for example, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, etc.; As an aromatic (meth)acrylate, for example, benzyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.; and one or more selected from these may be used. The "dicyclopentanyl" group in the above is "tricyclo[5.2.1.0 ２，６ ] This refers to the "decane-8-yl" group. (a4) As the alkyl (meth)acrylate, one or two selected from the group consisting of 2-ethylhexyl (meth)acrylate and benzyl (meth)acrylate are particularly preferred.

[0028] (A) If the alkali-soluble polymer has structural units derived from (a5) alicyclic or aromatic rings (meth)acrylate, the content thereof may be 1% by mass or more, 3% by mass or more, 30% by mass or less, 20% by mass or less, or 10% by mass or less, based on the total mass of structural units derived from all monomers contained in the alkali-soluble polymer (A).

[0029] (a6) Other monomers include, for example, 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 trimethylolpropane formal (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and one or more selected from these may be used.

[0030] (A) If the alkali-soluble polymer has structural units derived from (a6) other monomers, the content thereof may be 1% by mass or more and 20% by mass or less, based on the total mass of structural units derived from all monomers contained in the alkali-soluble polymer (A).

[0031] In the first photosensitive resin composition, (A) the alkali-soluble polymer may particularly have (a1) structural units derived from (meth)acrylic acid as an unsaturated acid monomer and (a2) structural units derived from a styrene derivative, or (a1) structural units derived from (meth)acrylic acid as an unsaturated acid monomer, (a2) structural units derived from a styrene derivative and (a3) ​​structural units derived from an alkyl (meth)acrylate substituted with a hydroxyl group, or (a1) structural units derived from (meth)acrylic acid as an unsaturated acid monomer, (a2) structural units derived from a styrene derivative, (a3) ​​structural units derived from an alkyl (meth)acrylate substituted with a hydroxyl group and (a4) structural units derived from one or two selected from the group consisting of alkyl (meth)acrylate and (a5) (meth)acrylate having an alicyclic or aromatic ring.

[0032] (A) For alkali-soluble polymers, the weight-average molecular weight in polystyrene terms, measured by gel permeation chromatography, may be 10,000 or more, 15,000 or more, 20,000 or more, 25,000 or more, or 30,000 or more, and may be 100,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, or 55,000 or less.

[0033] (A) Alkali-soluble polymers can be synthesized by polymerization of one monomer or copolymerization of two or more monomers as described above. Polymerization or copolymerization may be carried out preferably in a suitable solvent and preferably in the presence of a suitable polymerization initiator. Examples of solvents that can be used include acetone, methyl ethyl ketone, isopropanol, and ethanol. Examples of polymerization initiators that can be used include radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile. The polymerization reaction may be carried out in batch or continuous order.

[0034] In the first photosensitive resin composition, (A) the alkali-soluble polymer may be used alone or as a mixture of two or more types. As (A) the alkali-soluble polymer, for example, a polymer having (a1) (meth)acrylic acid as an unsaturated acid monomer, (a2) a styrene derivative, (a3) ​​an alkyl (meth)acrylate substituted with a hydroxyl group, and (a4) a structural unit derived from an alkyl (meth)acrylate, and a polymer having (a1) (meth)acrylic acid as an unsaturated acid monomer, (a2) a styrene derivative, (a3) ​​an alkyl (meth)acrylate substituted with a hydroxyl group, and (a5) a structural unit derived from an alicyclic or aromatic ring, is also included in the preferred embodiments of the present invention.

[0035] The content of (A) alkali-soluble polymer in the first photosensitive resin composition (total content if two or more types of (A) alkali-soluble polymers are included) may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, based on the mass of the total solids of the photosensitive resin composition, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. By adjusting the content of (A) alkali-soluble polymer within this range, the edge-fusing resistance when storing the photosensitive resin composition as a dry film resist can be improved, and the development time when forming the resist pattern can be kept within an appropriate range. "Edge-fusing resistance" refers to the ability to suppress the seepage of the photosensitive resin composition layer from the film edge of the dry film resist, and is a performance that is particularly required when storing the dry film resist wound in a roll.

[0036] <(B) Compounds having ethylenically unsaturated bonds> (B) Compounds having ethylenically unsaturated bonds may be compounds containing one, two, or three or more ethylenically unsaturated bonds (for example, three, four, five, or six) in one molecule. (B) The ethylenically unsaturated bonds in compounds having ethylenically unsaturated bonds are preferably contained in the molecule in the form of (meth)acrylate. Therefore, (B) Compounds having ethylenically unsaturated bonds may be, for example, monofunctional, difunctional, or trifunctional or more (for example, trifunctional, tetrafunctional, pentafunctional, or heptahical) (meth)acrylate compounds.

[0037] Examples of monofunctional (meth)acrylate compounds 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, isoamyl (meth)acrylate, Examples include 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, 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl (meth)acrylate, etc., and one or more selected from these may be used.

[0038] Examples of bifunctional (meth)acrylate compounds 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, ethoxylated propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycoxified (hydrogenated) bisphenol A di(meth)acrylate. One or more selected from these may be used.

[0039] Examples of commercially available bifunctional (meth)acrylate compounds include NK Ester® 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-300, A-BPE-4, A-BPE-10, A-BPE-20, HD-N, NOD-N, DOD-N, NPG, and 701. 2G, 3G, 4G, 9G, 14G, 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, NK original Go (registered trademark) UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA and EA-1020 (all 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 Resonac 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, S R508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR Examples include 9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema Co., Ltd.); KAYARAD® NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684 (all manufactured by Nippon Kayaku Co., Ltd.); and others.

[0040] Examples of trifunctional or more (meth)acrylate compounds 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, and alkylene oxide-modified trimethylolpropane tri(meth)acrylate. Examples include alkylene oxide-modified tri(meth)acrylate of glycerin, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and one or more selected from these may be used.

[0041] Examples of commercially available (meth)acrylate compounds with three or more functionalities include, NK Ester® 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, 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, cPE-4A, cPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.); FA-731A (manufactured by Resonac Corporation); TMPTA, EBECRYL 160S, OTA 480, 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.); and others.

[0042] The content of compounds having (B) ethylenically unsaturated bonds in the first photosensitive resin composition (total content if two or more compounds having (B) ethylenically unsaturated bonds are included) may be 20% by mass or more, 30% by mass or more, or 40% by mass or more, and may be 60% by mass or less, 50% by mass or less, or 45% by mass or less, based on the mass of the total solids of the photosensitive resin composition. By setting the content of compounds having (B) ethylenically unsaturated bonds within this range, the tackiness, resolution, and edge fusing resistance of the photosensitive resin composition are further improved.

[0043] (B) The content of compounds having ethylenically unsaturated bonds may be 0.3 times or more, 0.4 times or more, 0.5 times or more, or 0.6 times or more, relative to the content of alkali-soluble polymers in (A), and may be 3.0 times or less, 2.5 times or less, 2.0 times or less, 1.5 times or less, 1.0 times or less, or 0.9 times or less.

[0044] The (B) compound having an ethylenically unsaturated bond in the first photosensitive resin composition preferably includes a bifunctional (meth)acrylate compound. In this case, only a bifunctional (meth)acrylate compound may be used, or a bifunctional (meth)acrylate compound may be used in combination with one or more selected from monofunctional (meth)acrylate compounds and trifunctional (meth)acrylate compounds. The ratio of the bifunctional (meth)acrylate compound to the total mass of the (B) compounds having an ethylenically unsaturated bond may be 0.50 or more, 0.60 or more, 0.70 or more, 0.80, 0.90 or more, or 0.95 or more.

[0045] <<Component (C): Polymerization Initiator>> The (C) photopolymerization initiator in the first photosensitive resin composition is a compound that generates radicals upon irradiation with light (active light such as ultraviolet light). The (C) photopolymerization initiator may be a compound that exhibits one or more of the following functions: the function of initiating the polymerization of the (B) compound having an ethylenically unsaturated bond by the radicals generated by light irradiation, and the function of promoting the polymerization of the (B) compound having an ethylenically unsaturated bond by promoting the generation of radicals in other components.

[0046] The (C) photopolymerization initiator in the first photosensitive resin composition comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds. When the (C) photopolymerization initiator comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, the photosensitivity of the composition is increased, and preferably further, various properties such as viscosity stability, crystal precipitation, adhesion, resolution, and developability are improved.

[0047] 2,4,5-triarylimidazole dimers include, for example, 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), 2,2'-(o-chlorophenyl)-4,4',5,5'-bis-(m-methoxyphenyl)biimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-chlorophenyl)-tetrakiss-4. 4',5,5'-(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-(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',5,5'-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,Examples include 6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, and 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, and one or more selected from these may be used.

[0048] Examples of acridine compounds include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine, and one or more selected from these may be used.

[0049] The (C) photopolymerization initiator in the first photosensitive resin composition may include a 2,4,5-triarylimidazole dimer and an acridine compound, along with other photopolymerization initiators. Examples of other photopolymerization initiators include N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, N-aryl amino acid ester compounds, halogen compounds, etc., and may be one or more selected from these.

[0050] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine; 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; and one or more selected from these may be used for each. An example of an aromatic ketone compound is benzophenone. Dialkylbenzophenone falls under the category of "other sensitizers" in (D) sensitizers, which will be discussed later.

[0051] 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-morpholinopropanone-1; 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; and examples of benzoin compounds and benzoin ether compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime.

[0052] Examples of dialkylketal compounds include benzyldimethylketal and benzyldiethylketal; 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; 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;

[0053] 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, octyl ester of N-phenylglycine, and the like; 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, diallylodonium compounds, etc., and one or more selected from the above may be used for each.

[0054] The content of (C) photopolymerization initiator in the first photosensitive resin composition (total content if two or more types of (C) photopolymerization initiators are included) may be 5.0% by mass or more, 5.2% by mass or more, 5.5% by mass or more, or 6.0% by mass, and may be 15.0% by mass or less, 12.0% by mass or less, 10.0% by mass or less, or 9.0% by mass or less, based on the mass of the total solids content of the photosensitive resin composition.

[0055] In the first photosensitive resin composition, the total content of one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more, based on the total mass of (C) the photopolymerization initiator, or it may be 100% by mass, and no other photopolymerization initiators may be included.

[0056] (D) Sensitizer The first photosensitive resin composition contains (D) sensitizer. The (D) sensitizer has the function of absorbing the irradiation light during exposure and transferring its energy to the (C) photopolymerization initiator, thereby promoting the photopolymerization reaction of the compound having an (B) ethylenically unsaturated bond. The (D) sensitizer in the first photosensitive resin composition contains a compound represented by the following general formula (D1). {In formula (D1), R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １ and R ２ If it is an alkyl group, its terminals may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.

[0057] R １ ~R ３ The alkyl group may be linear or branched. １ ~R ３ The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3. As described above, R １ and R ２If is an alkyl group, its terminals may be bonded to the 6th or 8th carbon of the coumarin skeleton to form a nitrogen-containing heterocycle. In this case, R １ The alkyl group terminus is bonded to the 6th carbon of the coumarin skeleton, and R ２ The alkyl group terminus may bond to the 8th carbon of the coumarin skeleton, forming a nitrogen-containing heterofused ring overall. １ or R ２ When the terminal of the alkyl group is bonded to the 6th or 8th carbon of the coumarin skeleton to form a nitrogen-containing heterocycle, the number of carbon atoms in this alkyl group is preferably 2 to 4, and more preferably 2 or 3.

[0058] The compound represented by the above formula (D1) is preferably one or two selected from the group consisting of the compound represented by the following formulas (D1-1) (coumarin 1) and the compound represented by (D1-2) (coumarin 102).

[0059]

[0060] The (D) sensitizer in the first photosensitive resin composition may contain only the compound represented by formula (D1), or it may contain the compound represented by formula (D1) along with other sensitizers. When the (D) sensitizer contains the compound represented by formula (D1) along with other sensitizers, the changes in the absorbance and photosensitivity of the composition in the wavelength region near the exposure wavelength (e.g., h-line or i-line) can be made more gradual. This reduces fluctuations in photosensitivity due to variations in exposure wavelength, making it easier to obtain a photosensitive resin composition with good wavelength dependence. Examples of other sensitizers include compounds having a skeleton selected from the group consisting of anthracene, triarylamine, dialkylbenzophenone, oxazole, pyrazoline, and coumarin (excluding the compound represented by formula (D1)), and one or more selected from these may be used.

[0061] Examples of compounds having an anthracene skeleton include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and compounds represented by the following general formula (D2). One or more of these may be used.

[0062]

[0063] {In formula (D2), R ４ and R ５ Each of these is independently a hydrogen atom, a C1-C20 alkyl group, a C1-C5 alkoxyl group, or a C6-C20 aryl group. Examples of compounds represented by the above formula (D2) include anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-diphenylanthracene. As compounds having an anthracene skeleton, compounds represented by the above formula (D2) are preferred.

[0064] Examples of compounds having a triarylamine skeleton include compounds having a triphenylamine skeleton, and more specifically, triphenylamine may be one example.

[0065] Examples of compounds having a dialkylbenzophenone skeleton include Michlaz ketone (4,4'-bis(dimethylamino)benzophenone) and 4-methoxy-4'-dimethylaminobenzophenone; examples of compounds having an oxazole skeleton include oxazolone (2-phenyl-4-ethoxymethyleneoxazole-5(4H)-one); examples of compounds having a pyrazoline skeleton include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline; Each of these can be listed, and one or more can be selected from these for each case.

[0066] The compound represented by formula (D1) above is excluded from the list of compounds having a coumarin skeleton to be used as other sensitizers. Examples of compounds having a coumarin skeleton to be used as other sensitizers include 3-benzoyl-7-diethylaminocoumarin, 3-phenyl-7-(diethylamino)coumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]chyloridine-11-one, 2,3,6,7-tetrahydro-11-oxo-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinoridine-10-carboxylate ethyl(coumarin 314), 3-phenyl-7-(diethylamino)coumarin, 3-trifluoromethyl-7-(dimethylamino)coumarin (coumarin 152), and 3-trifluoromethyl-6-methyl-7-(ethylamino)coumarin Examples include (coumarin 307), 3-trifluoromethyl-7-(ethylamino)coumarin (coumarin 500), 3-methyl-6-methyl-7-(ethylamino)coumarin (coumarin 2), 2,3,6,7,10,11-hexahydro-1H,5H-cyclopenta[3,4][1]benzopyrano[6,7,8-ij]quinoridine-12(9H)-one (coumarin 106), 1,2-dihydro-7-(dimethylamino)cyclopenta[c][1]benzopyran-4(3H)-one, 7-(dimethylamino)-2,3-dihydrocyclopenta[c][1]benzopyran-4(1H)-one (coumarin 138), 3-(2-benzimidazolyl)-7-(diethylamino)coumarin (coumarin 7), and others, and one or more selected from these may be used.

[0067] The other sensitizer in the first photosensitive resin composition preferably includes a compound having an anthracene skeleton.

[0068] The content of (D) sensitizer in the first photosensitive resin composition (total content if two or more types of (D) sensitizers are included, or content including other sensitizers if the (D) sensitizer includes other sensitizers) may be 0.10% by mass or more, 0.15% by mass or more, 0.20% by mass or more, 0.25% by mass or more, 0.30% by mass or more, or 0.35% by mass or more, based on the mass of the total solid content of the photosensitive resin composition, and may be 0.80% by mass or less, 0.70% by mass or less, 0.60% by mass or less, 0.50% by mass or less, or 0.40% by mass or less. When the sensitizer (D) contains other sensitizers together with the compound represented by formula (D1) above, the mass ratio of the other sensitizers to the total mass of the sensitizer (D) may be 50% by mass or less, less than 50% by mass, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, or 5% by mass or less. When using other sensitizers, the effect of using other sensitizers will be realized if the other sensitizers are contained in an amount of 1% by mass or more or 3% by mass or more relative to the total mass of the sensitizer (D).

[0069] In the first photosensitive resin composition, the content of (C) a photopolymerization initiator is Wc (parts by mass) and the content of (D) a sensitizer is W, based on 100 parts by mass of the total of (A) the content of alkali-soluble polymer and (B) the content of compound having an ethylenically unsaturated bond. Ｄ When (parts by mass) is used, the content of (D) the sensitizer is W Ｄ (C) Ratio of photopolymerization initiator content Wc Ｃ / W Ｄ The value is 12.0 or higher. As described above, (D) the sensitizer has the function of absorbing the irradiation light during exposure and transferring its energy to (C) the photopolymerization initiator. Therefore, in order to transfer the light energy absorbed by (D) the sensitizer to (C) the photopolymerization initiator without loss, the content W of (D) the sensitizer is Ｄ (C) Ratio of photopolymerization initiator content Wc Ｃ / W ＤA larger value is preferable. On the other hand, from the viewpoint of the adhesion of the resulting resist pattern to the substrate, there is an optimal content for the sensitizer. That is, if the sensitizer content increases excessively, the amount of light that reaches the bottom of the photosensitive resin composition layer during exposure decreases, and the adhesion of the resulting resist pattern to the substrate tends to be impaired.

[0070] From this perspective, (D) the amount of sensitizer is W Ｄ (C) Ratio of photopolymerization initiator content Wc Ｃ / W Ｄ It is preferably 12.0 or higher, and may be 13.0 or higher, 13.2 or higher, 13.5 or higher, 14.0 or higher, or 15.0 or higher. On the other hand, relative W Ｃ / W Ｄ If the ratio is made excessively large, (D) there will be (C) photopolymerization initiators that do not benefit from the effect of the sensitizer, and the photosensitivity per unit content of (C) photopolymerization initiator will actually decrease, making it impossible to maintain a good balance between the thermal stability and photosensitivity of the photosensitive resin composition. To avoid this, ratio W Ｃ / W Ｄ For example, this could be 60.0 or less, 50.0 or less, 40.0 or less, 30.0 or less, 25.0 or less, or 20.0 or less.

[0071] (E) Polymerization Inhibitor The first photosensitive resin composition contains (E) a polymerization inhibitor. The (E) polymerization inhibitor has the function of improving the thermal stability and resolution of the photosensitive resin composition by preventing the unintended polymerization of compounds having (B) ethylenically unsaturated bonds. Preferably, the (E) polymerization inhibitor in the first photosensitive resin composition contains (E1) a first polymerization inhibitor selected from nitroso compounds and nitroxyl radicals, and (E2) a second polymerization inhibitor other than the first polymerization inhibitor. The (E1) first polymerization inhibitor is thought to mainly contribute to improving the thermal stability of the photosensitive resin composition, and the (E2) second polymerization inhibitor is thought to mainly contribute to improving the resolution of the photosensitive resin composition layer. However, the present invention is not bound by any particular theory.

[0072] (E1) The nitroso compound among the first polymerization inhibitors may be, for example, a compound represented by the following general formula (E1) or a metal salt thereof.

[0073]

[0074] {In formula (E1), R １１ This is a hydrocarbon group which may have substituents, -NHR １２ , or -NR １２ R １３ R １２ and R １３ Each of these is independently a hydrocarbon group which may have substituents.} R in formula (EI) １１ From the viewpoint of fully obtaining the effects intended by the present invention, for example, the following are used: saturated or unsaturated linear or branched linear hydrocarbon groups having 1 to 20 carbon atoms (e.g., methyl group); saturated or unsaturated monocyclic or polycyclic cyclic hydrocarbon groups having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.); monocyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms (e.g., phenyl group, etc.); aralkyl groups having 7 to 20 carbon atoms (e.g., phenylmethyl group, phenylethyl group, etc.); condensed polycyclic aromatic hydrocarbon groups having 10 to 20 carbon atoms (e.g., naphthyl group, etc.); and -NHR １２ and -NR １２ R １３ {R １２ and R １３ Each of these is independently a hydrocarbon group which may have substituents. Preferably, it is one or a combination of two or more selected from the group consisting of};

[0075] - NHR １２ and -NR １２ R １３Preferably, each of these is independently selected from the group consisting of: a saturated or unsaturated monocyclic or polycyclic cyclic hydrocarbon group having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.); a monocyclic aromatic hydrocarbon group having 6 to 20 carbon atoms (e.g., phenyl group, etc.); an aralkyl group having 7 to 20 carbon atoms (e.g., phenylmethyl group, phenylethyl group, etc.); and a condensed polycyclic aromatic hydrocarbon group having 10 to 20 carbon atoms (e.g., naphthyl group, etc.), and is either one or a combination of two or more.

[0076] Also, R １１ ~R １３ One or more of the hydrogen atoms in the compound may be substituted with a group having a heteroatom. Here, the heteroatom may be, for example, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, etc. The halogen atom may be, for example, a chlorine atom, a bromine atom, an iodine atom, etc.

[0077] R in equation (E1) １１ The preferred group is a phenyl group, naphthyl group, aminophenyl group, hydroxyphenyl group, thiohydroxyphenyl group, chlorophenyl group, aminonaphthyl group, hydroxynaphthyl group, thiohydroxynaphthyl group, or chloronaphthyl group, and more preferably a phenyl group, naphthyl group, aminophenyl group, hydroxyphenyl group, aminonaphthyl group, or hydroxynaphthyl group. In formula (E1), R １２ and R １３ Preferably, each of these groups is independently a C1-C10 alkyl group, a phenyl group, a naphthyl group, a C1-C10 aminoalkyl group, a C1-C10 hydroxyalkyl group, a C1-C10 thiohydroxyalkyl group, a C1-C10 chloroalkyl group, an aminophenyl group, a hydroxyphenyl group, a thiohydroxyphenyl group, a chlorophenyl group, an aminonaphthyl group, a hydroxynaphthyl group, a thiohydroxynaphthyl group, or a chloronaphthyl group; more preferably a C1-C10 alkyl group or a phenyl group; and even more preferably a methyl group or a phenyl group.

[0078] The nitroso compound among the (E1) first polymerization inhibitors in the first photosensitive resin composition may be a metal salt of the compound represented by the general formula (E1) described above.

[0079] When the nitroso compound is a compound represented by the above general formula (E1), the nitroso compound may be, for example, a compound represented by the following general formula (E1-1).

[0080] {R in equation (E1-1) １２ and R １３ These are, respectively, R in the above formula (E1). １１ ga-NR １２ R １３ R in the case of １２ and R １３ This is the same as above.} In the first photosensitive resin composition, by including (E) a polymerization inhibitor, which is a compound represented by the above formula (E1-1), the composition has excellent photosensitivity and resolution, and the adhesion of the resulting resist pattern is also excellent. Examples of the (E1) first polymerization inhibitor in the first composition include N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodipropylamine, N-nitrosodibutylamine, N-nitrosodiethanolamine, N-nitrosodiisopropanolamine, N-nitroso-N-methylaniline, N-nitrosodiphenylamine, N,N-diethyl-N-nitrosoaniline, 5-nitroso-8-quinolinol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, N-nitroso-N-phenylhydroxylamine, and one or more selected from these may be used. (E1) As the first polymerization inhibitor, N-nitrosodiphenylamine or 1-nitroso-2-naphthol is preferred from the viewpoint of the resolution of the composition and the adhesion of the resist pattern.

[0081] When the nitroso compound is a metal salt of the compound represented by the above general formula (E1), the nitroso compound may be, for example, in the form of a salt in which the non-bonding electron pair of an amine is added to a suitable metal atom. In this case, examples of the metal atom include aluminum, cobalt, iron, copper, and the like. The nitroso compound that is a metal salt of the compound represented by the above general formula (E1) may be, for example, a compound represented by the following general formula (E1-2). {In the formula (E1-2), R １４ is a hydrocarbon group that may have a substituent, M ｍ＋ is an ion of a metal selected from aluminum, cobalt, iron, and copper, and m is the valence of the ion of the metal.} In the above general formula (E1-2), it is described that the negative charge of the anion on the left is localized on one oxygen atom, but this negative charge may be delocalized to the O-N-N-O unit and may be in the form of a complex compound coordinated to the metal atom by two oxygen atoms.

[0082] R in the formula (E1-2) １４ may be, for example, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a naphthyl group, an aminoalkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a thiohydroxyalkyl group having 1 to 10 carbon atoms, a chloroalkyl group having 1 to 10 carbon atoms, an aminophenyl group, a hydroxyphenyl group, a thiohydroxyphenyl group, a chlorophenyl group, an aminonaphthyl group, a hydroxynaphthyl group, a thiohydroxynaphthyl group, a chloronaphthyl group, and the like, and a methyl group, a phenyl group, a naphthyl group, an aminophenyl group, a hydroxyphenyl group, a thiohydroxyphenyl group, a chlorophenyl group, an aminonaphthyl group, a hydroxynaphthyl group, a thiohydroxynaphthyl group, a chloronaphthyl group, and the like are preferred.

[0083] Examples of the nitroso compound represented by the above general formula (E1-2) include N-nitroso-N-phenylhydroxylamine aluminum and the like.

[0084] (E1) The nitroxyl radical among the first polymerization inhibitors is a stable radical having a nitroso structure. The nitroxyl radical may be, for example, a compound (radical) represented by the following general formula (E1-3). {In formula (E1-3), R １５ ~R １８ are each independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, a naphthyl group, an aminoalkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a thiohydroxyalkyl group having 1 to 10 carbon atoms, a chloroalkyl group having 1 to 10 carbon atoms, an aminophenyl group, a hydroxyphenyl group, a thiohydroxyphenyl group, a chlorophenyl group, an aminonaphthyl group, a hydroxynaphthyl group, a thiohydroxynaphthyl group, or a chloronaphthyl group, and R １９ and R ２０ are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R １９ and R ２０ may be bonded to each other to form a ring.}

[0085] The substituents that R １９ and R ２０ in formula (E1-3) may have include, for example, a hydroxyl group, a carboxyl group, an alkoxyl group, an acetyl group, a halogenated acetyl group, an oxyl group, an alkynyloxyl group, a (meth)acryloyloxy group, an amino group, etc. The ring formed by R １９ and R ２０ bonding to each other may be, for example, a 5-membered ring, a 6-membered ring, or a 7-membered ring, or may be a condensed ring. These rings may have the above substituents.

[0086] As the nitroxyl radical, R １９ and R ２０These elements may be cyclic radicals formed by bonding with each other to create a ring. Specific examples of such nitroxyl radicals include, as radicals having a five-membered ring, for example, 2,2,5,5-tetramethylpyrrolidine-N-oxyl, 3-carboxy-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 3-hydroxy-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 2,2,5,5-tetramethyl-3-pyrroline-1-oxyl, etc.; as radicals having a six-membered ring, for example, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, Examples include 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamide-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-(2-iodoacetamide)-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-(2-propynyloxy)-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine-N-oxyl, etc.; and as radicals having a 7-membered ring, for example, (2,2,7,7-tetramethyl-5-oxo-1,4-diazepan-1-yl)oxydanil, etc.; Examples of radicals having a condensed ring include 2-adamantane-N-oxyl and 1-methyl-2-adamantane-N-oxyl.

[0087] The (E2) second polymerization inhibitor in the first photosensitive resin composition is a polymerization inhibitor other than the (E1) first polymerization inhibitor. The (E2) second polymerization inhibitor may be, for example, a phenolic polymerization inhibitor, a phenothiazine polymerization inhibitor, a phenoxazine polymerization inhibitor, etc.

[0088] As phenolic polymerization inhibitors, phenolic compounds having two or more phenolic hydroxyl groups are preferred, specifically, for example, hydroquinone, catechol, 4-t-butylcatechol, pyrogallol, gallic acid, methyl gallate, etc. As phenothiazine polymerization inhibitors, phenothiazine, etc. As phenoxazine polymerization inhibitors, phenoxazine, etc. As (E2) second polymerization inhibitors, 4-t-butylcatechol or phenothiazine are preferred. As the (E2) second polymerization inhibitor in the first photosensitive resin composition, one or more selected from the above may be used.

[0089] In the first photosensitive resin composition, the content of (E) polymerization inhibitor (total content if two or more (E) polymerization inhibitors are included) may be 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, or 0.007% by mass or more, based on the mass of the total solids of the photosensitive resin composition, and may be 0.100% by mass or less, 0.080% by mass or less, 0.060% by mass or less, 0.040% by mass or less, 0.030% by mass or less, 0.020% by mass or less, or 0.015% by mass or less, based on the mass of the total solids of the photosensitive resin composition, from the viewpoint of improving the storage stability of the composition and maintaining photosensitivity.

[0090] The content of (E1) first polymerization inhibitor in the first photosensitive resin composition (total content if two or more types of (E1) first polymerization inhibitors are included) may be 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, or 0.007% by mass or more, based on the mass of the total solids of the photosensitive resin composition, and may be 0.050% by mass or less, 0.040% by mass or less, 0.030% by mass or less, 0.020% by mass or less, or 0.015% by mass or less, based on the mass of the total solids of the photosensitive resin composition, from the viewpoint of balancing the storage stability of the composition with the photosensitivity and resolution. In the first photosensitive resin composition, the ratio of the content of the compound represented by formula (E1-1) to the content of the first polymerization inhibitor (E1) may be, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, or the entire amount of the first polymerization inhibitor (E1) may be the compound represented by formula (E1-1).

[0091] In the first photosensitive resin composition, the content of (E2) second polymerization inhibitor (total content if two or more types of (E2) second polymerization inhibitors are included) may be 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, or 0.007% by mass or more, based on the mass of the total solids of the photosensitive resin composition, and may be 0.050% by mass or less, 0.040% by mass or less, 0.030% by mass or less, 0.020% by mass or less, or 0.015% by mass or less, based on the mass of the total solids of the photosensitive resin composition. In the first photosensitive resin composition, when the mass of the total solids of the photosensitive resin composition is 100% by mass, the content W of (E1) first polymerization inhibitor Ｅ１ And, (E2) Content of the second polymerization inhibitor W Ｅ２ W Ｅ１ / W Ｅ２ It may be 0.25 or higher, 0.50 or higher, 0.60 or higher, 0.70 or higher, 0.80 or higher, or 0.90 or higher, and may be 4.00 or lower, 3.00 or lower, 2.00 or lower, 1.50 or lower, 1.25 or lower, or 1.10 or lower.

[0092] <Optional Components> The first photosensitive resin composition may contain optional components in addition to components (A) to (E) described above. The optional components may be one or more selected from, for example, dyes, adhesion aids, plasticizers, rust inhibitors, solvents, etc.

[0093] Dyes may be included in the photosensitive resin composition for the purpose of improving handling characteristics such as the expression of hue contrast before and after exposure and visibility during foreign object inspection. Examples of dyes include leucocrystal violet, leucomalachite green, leucocrystal violet lactone, diamond green, crystal violet, basic blue 7, coomassie brilliant blue, green S, diamond green, thymol blue, fast green FCF, phenolsulfonphthalein, fuchsin, brilliant blue FCF, malachite green, methyl blue, new fuchsin (basic violet 2), pararosalinine (pararoseaniline), etc., and one or more selected from these may be used.

[0094] If the first photosensitive resin composition contains a dye, its content (or total content if it contains two or more dyes) may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, and may be 1.0% by mass or less, 0.8% by mass or less, or 0.5% by mass or less, based on the mass of the total solids of the photosensitive resin composition.

[0095] Examples of adhesion aids include benztriazoles and carboxybenztriazoles, and one or more selected from these may be used. If the first photosensitive resin composition contains an adhesion aid, its content may be 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, or 0.04% by mass or more, and 0.30% by mass or less, 0.20% by mass or less, or 0.10% by mass or less, based on the total mass of the solids of the photosensitive resin composition.

[0096] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0097] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, and mixtures thereof. Of these, a mixture of 4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole is preferred. In this case, the mixing ratio of the two is preferably about 1:1 by mass.

[0098] Examples of plasticizers include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; phthalate esters such as diethyl phthalate; organic acid derivatives such as o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate; polyhydric alcohols such as propylene glycol, which has propylene oxide added to both ends of bisphenol A, and ethylene glycol, which has ethylene oxide added to both ends of bisphenol A; and aluminum salts to which 1 to 3 moles of nitrosophenylhydroxylamine have been added.

[0099] The plasticizer content is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, based on the total solid content mass of the photosensitive resin composition. When this percentage is 1% by mass or more, delays in development time are easily suppressed, and the resulting resist pattern is easily given appropriate flexibility. When this percentage is 50% by mass or less, insufficient curing of the resist pattern and edge fusing of the photosensitive resin composition laminate tend to be suppressed.

[0100] Next, the second photosensitive resin composition described as Embodiment 1 above will be explained. The second photosensitive resin composition in the present invention is a photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a sensitizer, and (E) a polymerization inhibitor, wherein the (C) photopolymerization initiator comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, the content of the (C) photopolymerization initiator is 5.0% by mass or more with respect to the total mass of the solids of the photosensitive resin composition, the (D) sensitizer comprises a compound represented by the following general formula (D1), and the (E) polymerization inhibitor comprises (E1) a first polymerization inhibitor selected from nitroso compounds and nitroxyl radicals, and (E2) a second polymerization inhibitor other than the first polymerization inhibitor.

[0101] {In formula (D1), R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １ and R ２ If it is an alkyl group, its terminals may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.

[0102] In the second photosensitive resin composition, the content of (C) a photopolymerization initiator is Wc (parts by mass) and the content of (D) a sensitizer is W, based on 100 parts by mass of the total of (A) the content of alkali-soluble polymer and (B) the content of compound having an ethylenically unsaturated bond. Ｄ When (parts by mass) is used, (D) the amount of sensitizer is W Ｄ (C) Ratio of photopolymerization initiator content Wc Ｃ / W Ｄ However, the requirement that it be 12.0 or higher is not mandatory. Nevertheless, in the second photosensitive resin composition as well, relative W Ｃ / W Ｄ It is preferable that it is 12.0 or higher.

[0103] Furthermore, in the second photosensitive resin composition, it is an essential requirement that the polymerization inhibitor (E) includes both (E1) a first polymerization inhibitor selected from nitroso compounds and nitroxyl radicals, and (E2) a second polymerization inhibitor other than the first polymerization inhibitor.

[0104] With regard to the types and amounts of each component in the second photosensitive resin composition, the explanations for the first photosensitive resin composition may be applied, except for matters specifically noted above. The second photosensitive resin composition may contain optional components, and the types and amounts of optional components are the same as in the case of the first photosensitive resin composition.

[0105] Photosensitive Resin Composition Laminate According to another aspect of the present invention, a photosensitive resin composition laminate is provided. The photosensitive resin composition laminate of this embodiment comprises a support film and a photosensitive resin composition layer on the support film, wherein the photosensitive resin composition layer is a layer made of the first photosensitive resin composition or the second photosensitive resin composition described above. The photosensitive resin composition laminate of this embodiment may further have a protective film laminated on the side of the photosensitive resin composition layer opposite to the support film. The photosensitive resin composition laminate of this embodiment is suitable for application as a so-called "dry film resist".

[0106] <Support Film> The support film in the photosensitive resin composition laminate of this embodiment has the function of supporting the photosensitive resin composition layer and maintaining the shape of the laminate. Preferably, the support film has transparency that allows light (for example, active light such as ultraviolet rays) irradiated when the photosensitive resin composition layer is exposed to light to be transmitted.

[0107] Examples of materials for the support film include polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Of these, polyethylene terephthalate (PET), which has appropriate flexibility and strength, is preferred. Furthermore, it is preferable to use a support film that has high film quality and few internal foreign matter. Specific examples of high-quality films include PET films synthesized using titanium (Ti)-based catalysts, PET films with small lubricant diameters and low lubricant content, PET films containing lubricant on only one side, thin-film PET films, PET films with smoothing treatment on at least one side, and PET films with roughening treatment (such as plasma treatment) on at least one side. The support film may be used after planarizing treatment, such as calendering, on at least one side.

[0108] The thickness of the support film may be 5 μm or more, 8 μm or more, 10 μm or more, or 12 μm or more, and may be 30 μm or less, 25 μm or less, 20 μm or less, or 18 μm or less. The haze of the support film may be 1.50% or less, 1.20% or less, 1.00% or less, or 0.95% or less. A lower haze of the support film is preferable, but a haze of 0.01% or more does not pose a practical problem.

[0109] <Photosensitive Resin Composition Layer> The photosensitive resin composition layer in the photosensitive resin composition laminate of this embodiment is a layer made of the photosensitive resin composition of this embodiment described above. The thickness of the photosensitive resin composition layer may be 3 μm or more and 200 μm or less, 3 μm or more and 100 μm or less, or 3 μm or more and 50 μm or less. The thinner the photosensitive resin composition layer, the higher the resolution tends to be, and the thicker the layer, the higher the film strength tends to be. The thickness of the photosensitive resin composition layer may be set appropriately according to the application, taking into consideration the balance between resolution and film strength.

[0110] The photosensitive resin layer of the photosensitive resin composition laminate may be formed by a process of coating a support film with a coating solution containing the photosensitive resin composition and a solvent, as described later. In this case, the resulting photosensitive resin layer may contain residual solvent derived from the coating solution. Examples of solvents that may be contained in the photosensitive resin layer include ketones represented by methyl ethyl ketone and acetone; alcohols represented by methanol, ethanol, and isopropanol; toluene; and the like. The amount of solvent remaining in the photosensitive resin layer is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less, based on the total mass of the photosensitive resin composition.

[0111] <Protective Film> The protective film is laminated on the side of the photosensitive resin composition layer opposite the support film and functions as a cover for the photosensitive resin composition layer. Preferred materials for the protective film include polyethylene, polypropylene, stretched polypropylene, and polyester film. The thickness of the protective film is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm. A release layer may be formed on the side of the protective film facing the photosensitive resin composition layer so that the protective film can be easily peeled off. Examples of materials for the release layer include silicone resin, alkyd resin, long-chain alkyl resin, acrylic resin, and polyolefin resin. The thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[0112] <Method for manufacturing a photosensitive resin composition laminate> The photosensitive resin composition laminate of this embodiment may be manufactured by a method that includes, for example, preparing a coating solution containing the photosensitive resin composition and solvent of this embodiment; applying the above coating solution to a support film to form a coating film; removing the solvent from the coating film to form a photosensitive resin composition layer on the support film; and laminating a protective film on the photosensitive resin composition layer.

[0113] Examples of solvents used in the preparation of the coating solution include ketones and alcohols. Examples of ketones include acetone and methyl ethyl ketone; examples of alcohols include methanol, ethanol, and isopropanol. It is preferable to adjust the amount of solvent used to set the solid content concentration of the coating solution to 30% by mass or more, 40% by mass or more, or 50% by mass or more, and 90% by mass or less, 80% by mass or less, or 70% by mass or less. The solid content concentration of the coating solution may be appropriately set within the above range depending on the composition of the photosensitive resin composition, the coating method used, etc.

[0114] The coating liquid may be applied to the support film using an appropriate coating device such as a bar coater or a roll coater. The solvent may be removed from the coating film by, for example, leaving the support film on which the coating film has been formed in a dryer heated to a predetermined temperature for a predetermined time. The temperature of the dryer may be, for example, 60°C or higher, 80°C or higher, or 90°C or higher, and 150°C or lower, 120°C or lower, or 100°C or lower. The standing time (drying time) may be, for example, 30 seconds or more, 1 minute or more, or 2 minutes or more, and 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less. The protective film may be laminated onto the photosensitive resin composition layer according to a standard method.

[0115] 《Method for Forming a Resist Pattern》 In yet another view of the present invention, a method for forming a resist pattern is provided. The method for forming a resist pattern of this embodiment is a method for forming a resist pattern comprising: laminating a photosensitive resin composition layer on a substrate; exposing the photosensitive resin composition layer to light; and developing the photosensitive resin composition layer after exposure; wherein the photosensitive resin composition layer is a layer made of the photosensitive resin composition of this embodiment described above.

[0116] Examples of substrate materials on which the resist pattern is formed include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). Copper-clad laminates are particularly preferred as the substrate. The substrate may be used after surface preparation if desired. Surface preparation of the substrate can be performed, for example, by applying H2O at a concentration of about 10% by mass. ２ SO ４ This may be done by cleaning the substrate with an aqueous solution or the like.

[0117] The lamination of the photosensitive resin composition layer onto the substrate may be carried out by, for example, a method including: peeling off a protective film from the photosensitive resin composition laminate; and heat-pressing the photosensitive resin composition of the photosensitive resin composition laminate from which the protective film has been peeled onto the substrate surface.

[0118] Heat bonding may be performed, for example, using a laminator equipped with rolls, or by laminating the photosensitive resin composition laminate, from which the protective film has been removed, onto the substrate surface and then passing it through the rolls. The heating temperature during heat bonding can be, for example, 40°C to 160°C, and preferably 80°C to 120°C. Heat bonding may be performed under reduced pressure if desired. The heat bonding operation may be performed only once or two or more times. When the heat bonding operation is performed two or more times, a multi-stage laminator equipped with multiple rolls may be used, or the laminate of the photosensitive resin composition laminate from which the protective film has been removed and the substrate may be passed through the rolls multiple times.

[0119] The photosensitive resin composition layer may be exposed using an exposure machine such as a contact aligner, mirror projection machine, or stepper, either via a patterned photomask or reticle, or directly. The light source for exposure may be, for example, an ultraviolet light source. Exposure may be performed via a support film, or after the support film has been removed. The exposure method is preferably one or more methods selected from the group consisting of projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, with projection exposure or direct imaging exposure being more preferred.

[0120] The photosensitive resin composition layer after exposure is then developed. Here, the photosensitive resin composition layer after exposure may be heated before development. The heating temperature is preferably 30 to 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By performing this heating, further improvements in resolution and adhesion are possible. For heating, for example, a heating furnace using hot air, infrared, or far-infrared rays; a constant temperature bath; a hot plate; an air dryer; an infrared dryer; a hot roll, etc. The heating time is preferably 1 second to 300 seconds, more preferably 5 seconds to 120 seconds.

[0121] The photosensitive resin composition layer after exposure is then optionally heated as described above and then developed. Development removes the unexposed portion of the photosensitive resin composition layer, forming a resist pattern. If exposure is performed via a support film, the support film is removed before development. Development is performed by bringing the photosensitive resin composition layer after exposure into contact with a developer. The developer may be an alkaline aqueous solution, specifically, for example, Na ２ CO ３ _K ２ CO ３ Aqueous solutions of tetramethylammonium hydroxide, etc., are preferred. The type and concentration of the alkaline aqueous solution are selected according to the characteristics of the photosensitive resin composition layer. As the developer, a concentration of 0.2% to 2% by mass of Na is preferred. ２ CO ３ Aqueous solutions are common. The alkaline aqueous solution used as the developer may contain, for example, surfactants, defoamers, and small amounts of organic solvents to accelerate development. The temperature of the developer during development is preferably kept approximately constant within a predetermined temperature selected from the range of 20°C to 40°C. The development method may be appropriately selected from known development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment.

[0122] As a result, a resist pattern can be formed on the substrate. If desired, the obtained resist pattern may be heated. This heating further improves the chemical resistance of the resist pattern. This heating may be performed, for example, at a temperature of 60°C to 300°C for a time of 1 minute to 120 minutes. The heating may be performed using a heating furnace that uses, for example, hot air, infrared rays, or far-infrared rays.

[0123] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0124] <Preparation of Alkali-Soluble Polymers (A-1) to (A-4)> The monomers of the types and amounts shown in Table 1, along with 3.0 parts by mass of azobisisobutyronitrile, were mixed and stirred to prepare solution (a). 200 parts by mass of methyl ethyl ketone and 100 parts by mass of ethanol were charged into a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube. The liquid temperature was adjusted to 80°C while blowing nitrogen gas into the flask and stirring. Maintaining the liquid temperature at 80°C, and continuing to blow nitrogen gas and stir, the entire amount of solution (a) was added dropwise over 4 hours at a constant dropping rate. After the dropwise addition was complete, the reaction mixture was further blown with nitrogen gas and stirred at 80°C for another 2 hours.

[0125] Solution (b) was prepared by adding 0.5 parts by mass of azobisisobutyronitrile to 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol and dissolving it. The reaction mixture in the flask was kept at 80°C, and while continuing to blow nitrogen gas and stir, the entire amount of solution (b) was added dropwise over 10 minutes at a constant dropping rate. After the dropwise addition was complete, the reaction mixture was continued to blow nitrogen gas and stir at 80°C for a further 3 hours. Then, the temperature was raised to 90°C, and the blowing of nitrogen gas and stirring were continued at 90°C for a further 2 hours.

[0126] Subsequently, stirring was stopped, and while nitrogen gas injection continued, the liquid was allowed to cool to room temperature (25°C). Through these operations, solutions containing each of the alkali-soluble polymers (A-1) to (A-4) were obtained. The weight-average molecular weights of the alkali-soluble polymers (A-1) to (A-4), measured by gel permeation chromatography (GPC) and converted to polystyrene equivalents, are shown in Table 1. GPC was performed under the following conditions. Measurement equipment Pump: PU-4580, manufactured by JASCO Corporation Degasser: DG-2080-53, manufactured by JASCO Corporation Column oven: CO-1560, manufactured by JASCO Corporation Column: Shodex® GPC column, model names "KF-80Y" and "KF-806M", manufactured by Resonaq Corporation, connected in series in that order Eluent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 2.05 mL / min Detector: Differential refractometer, model name "RI-1530", manufactured by JASCO Corporation

[0127]

[0128] 《Example 1》 (1) Preparation for forming a photosensitive resin composition layer (1-1) Preparation of the preparation for forming a photosensitive resin composition layer (A) As an alkali-soluble polymer, 54 parts by mass of the alkali-soluble polymer (A-1) prepared above; (B) As a compound having an ethylenically unsaturated bond, 46 parts by mass of polyethylene glycol dimethacrylate (component B-1, manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "BPE-500") obtained by adding an average of 5 mol of ethylene oxide to each end of bisphenol A; (C) As a photopolymerization initiator, 6.0 parts by mass of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (component C-1); (D) As a sensitizer, 0.38 parts by mass of coumarin 1 (7-diethylamino-4-methylcoumarin, the compound represented by the above formula D-1); (E) As a polymerization inhibitor, (E1) 0.01 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum as a first polymerization inhibitor; and (E2) 0.01 parts by mass of 4-t-butylcatechol as a second polymerization inhibitor; and 0.4 parts by mass of leucocrystal violet and 0.03 parts by mass of diamond green as dyes were mixed and stirred to prepare a formulation for forming a photosensitive resin composition layer.

[0129] In the above, the amounts of each active ingredient refer to their solid content. The amount of ethanol added was set to the amount that would result in a solid content concentration of 60% by mass in the prepared solution.

[0130] (1-2) Evaluation of Viscosity Stability Seven samples were prepared by filling 20 mL glass containers to the brim with the obtained preparation solution and sealing them to prevent air from entering. One of the seven samples was measured for viscosity using an E-type viscometer immediately after preparation, and this measurement was taken as the initial viscosity. The remaining six samples were left standing in an oven heated to 50°C. One sample was removed from the oven each day from 1 to 6 days after the start of standing, and its viscosity was measured. The shortest number of days until the measured viscosity increased by 2,000 mPa·sec or more compared to the initial viscosity, or until the viscosity could not be measured, was determined and evaluated according to the following criteria: A (Good): The number of days required for the viscosity change according to the above criteria to occur was 5 days or more. C (Poor): The number of days required for the viscosity change according to the above criteria to occur was less than 5 days.

[0131] (2) Photosensitive resin composition laminate (2-1) Manufacturing of photosensitive resin composition laminate As a support film, a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "QS71") was used, and the above-mentioned preparation solution was applied to its surface using a bar coater, and the solvent was removed by standing it in a 95°C dryer for 2.5 minutes. By the above operation, a photosensitive resin composition layer with a thickness of 25 μm was formed on the support film. Next, a photosensitive resin composition laminate was obtained by attaching a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818") as a protective layer to the side of the photosensitive resin composition layer opposite to the support film.

[0132] (2-2) Evaluation of Crystal Deposition Properties When manufacturing photosensitive resin composition laminates, crystal precipitation may be observed in the formed photosensitive resin composition layer. If crystals form in the photosensitive resin composition layer, exposure according to the predetermined pattern may be interfered with. Therefore, the obtained photosensitive resin composition laminates were visually inspected to check for the presence or absence of crystal precipitation in the photosensitive resin composition layer and evaluated according to the following criteria: A (Excellent): No crystal precipitation was observed at all. B (Good): Crystal precipitation was observed in a part of the photosensitive resin composition layer. C (Poor): Crystal precipitation was observed over the entire surface of the photosensitive resin composition layer.

[0133] (3) Various Evaluations Evaluation substrates were prepared using the photosensitive resin composition laminates manufactured as described above, and resist patterns were formed by exposure, heating, and development. The h-line sensitivity, i-line sensitivity, adhesion, resolution, and developability were evaluated. The method for preparing the evaluation substrate, the method for measuring the optimal exposure amount, the exposure amount, the heating method, and the development method were the same for each evaluation, but the exposure method was adopted according to the evaluation item as follows: h-line sensitivity: Exposure using a direct writing exposure machine (Oak Manufacturing Co., Ltd., model name "FDi-3") with a 41-step stufer tablet as a mask i-line sensitivity: Exposure using a projection exposure device (Ushio Inc., model name "UX-23101") with a 41-step stufer tablet as a mask Adhesion, resolution, and developability: Direct exposure using a direct writing exposure machine (Oak Manufacturing Co., Ltd., model name "FDi-3") with a predetermined drawing pattern for direct imaging (DI) exposure

[0134] (3-1) Formation of resist pattern (3-1-1) Preparation of evaluation substrate A copper-clad laminate with a total thickness of 0.4 mm was prepared by laminating rolled copper foil with a thickness of 18 μm. The surface of this copper-clad laminate was treated with 10 mass% H ２ SO ４ After washing with an aqueous solution, the surface was washed with pure water and smoothed. The surface of the smoothed copper-clad laminate was preheated to 50°C. An evaluation substrate was prepared by laminating the photosensitive resin composition laminate obtained above onto the surface of the copper-clad laminate preheated to 50°C, while peeling off the protective layer, so that the photosensitive resin composition layer was in contact with the surface of the copper-clad laminate. Lamination was performed using a hot roll laminator (Asahi Kasei Corporation, model "AL-700") at a roll temperature of 105°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min.

[0135] (3-1-2) Measurement of Optimal Exposure Two hours after lamination, the evaluation substrate was directly exposed using a direct writing exposure machine (Oak Manufacturing Co., Ltd., model name "FDi-3") with a predetermined direct imaging (DI) exposure pattern. Exposure was performed using a 41-step step tablet as a mask, and the exposure amount that resulted in a maximum of 15 remaining layers after development was defined as the optimal exposure amount. (3-1-3) Exposure Two hours after lamination, the evaluation substrate was exposed using the predetermined method for each evaluation. The exposure amount was the optimal exposure amount determined in "(3-2-2) Measurement of Optimal Exposure Amount".

[0136] (3-1-4) After heating exposure, the evaluation substrate was heated for 30 seconds by placing it in a forced-air constant temperature incubator (manufactured by Yamato Scientific Co., Ltd., model "DKM600") set to 70°C. (3-1-5) After peeling off the support film from the evaluation substrate after development exposure and heating, 1% by mass Na was added using a dry film developer manufactured by Fuji Kiko Co., Ltd., which was heated to 30°C. ２ CO ３ A resist pattern was formed on a copper-clad laminate by developing the photosensitive resin composition layer by spraying an aqueous solution onto it. The shortest development time was defined as the shortest time required for the unexposed portion of the photosensitive resin composition layer to completely dissolve, and the spray time during development was set to twice the shortest development time.

[0137] (3-2) Evaluation of h-line sensitivity When exposed using a direct writing exposure machine (manufactured by Oak Manufacturing Co., Ltd., model name "FDi-3") with a 41-step stufer tablet as a mask, the maximum number of remaining film stages after development is recorded as the h-line sensitivity. Here, if the maximum number of remaining film stages is 12.5 or higher, the h-line sensitivity can be evaluated as good. (3-3) Evaluation of i-line sensitivity When exposed using a projection exposure device (manufactured by Ushio Inc., model name "UX-23101") with a 41-step stufer tablet as a mask, the maximum number of remaining film stages after development is recorded as the i-line sensitivity. Here, if the maximum number of remaining film stages is 12.5 or higher, the i-line sensitivity can be evaluated as good.

[0138] (3-4) Evaluation of Adhesion A resist pattern obtained by directly exposing a resist pattern using a direct writing exposure machine (manufactured by Oak Manufacturing Co., Ltd., model name "FDi-3") with a predetermined direct imaging (DI) exposure pattern was observed at a magnification of 100x using an optical microscope, and the presence or absence of pattern folds and defects in the line and space (L / S) = 5 μm / 200 μm and 8 μm / 200 μm regions was examined and evaluated according to the following criteria. A (Excellent): No pattern folds or defects were found in either the L / S = 5 μm / 200 μm or 8 μm / 200 μm regions. B (Good): Pattern folds or defects were found in the L / S = 5 μm / 200 μm region, but no pattern folds or defects were found in the 8 μm / 200 μm region. C (Poor): Pattern folds or defects were found in either the L / S = 5 μm / 200 μm or 8 μm / 200 μm regions.

[0139] (3-5) Evaluation of Resolution The resist patterns obtained by directly exposing them with a predetermined direct imaging (DI) exposure pattern using a direct writing exposure machine (manufactured by Oak Manufacturing Co., Ltd., model name "FDi-3") were observed with an optical microscope at a magnification of 200x, and the presence or absence of lateral bending, folding, and defects of the pattern, as well as development residuals between patterns, in the line and space (L / S) = 5 μm / 5 μm and 8 μm / 8 μm regions were examined and evaluated according to the following criteria. A (Excellent): No pattern folds or defects, or development residue between patterns, were observed in both the L / S = 5 μm / 5 μm and 8 μm / 8 μm regions. B (Good): Pattern folds or defects, or development residue between patterns, were observed in the L / S = 5 μm / 200 μm region, but no pattern folds or defects, or development residue between patterns, were observed in the 8 μm / 200 μm region. C (Poor): Pattern folds or defects, or development residue between patterns, were observed in both the L / S = 5 μm / 200 μm and 8 μm / 200 μm regions.

[0140] (3-6) The shortest development time was investigated when directly exposed using a developable direct-writing exposure machine (manufactured by Oak Manufacturing Co., Ltd., model name "FDi-3") with a predetermined direct imaging (DI) exposure pattern, and evaluated according to the following criteria: A (Excellent): When the shortest development time was 19 seconds or less B (Good): When the shortest development time was greater than 19 seconds but 23 seconds or less C (Poor): When the shortest development time was greater than 23 seconds

[0141] Examples 2-21 and Comparative Examples 1-4: Except for changing the type and amount of each component as shown in Tables 2-5, a photosensitive resin composition layer forming solution was prepared in the same manner as in Example 1, and various evaluations were performed. The amount of (D) sensitizer was set so that the transmittance of the h line in the resulting photosensitive resin composition layer was the same as in Example 1. The evaluation results are shown in accordance with Tables 2-5. Tables 2-4 show the amount of (D) sensitizer (W Ｄ (C) Amount of photopolymerization initiator (W) relative to ) Ｃ ) ratio (W Ｃ / W Ｄ ) was also shown.

[0142]

[0143]

[0144]

[0145]

[0146] The abbreviations for the components in Tables 2-5 have the same meanings as shown in Table 6.

[0147]

[0148] As can be seen from the table above, the photosensitive resin composition of Comparative Example 1, which does not contain the (C) polymerization initiator specified in this embodiment, was inferior in photosensitivity, as well as in the adhesion and resolution of the resist pattern; the photosensitive resin compositions of Comparative Examples 2 and 3, which do not contain the (D) sensitizer specified in this embodiment, were inferior in h-line sensitivity and i-line sensitivity; and the photosensitive resin composition of Comparative Example 4, in which the amount of (C) photopolymerization initiator added was not the amount specified in this embodiment, was inferior in h-line sensitivity and i-line sensitivity.

[0149] In contrast to these, the photosensitive resin compositions of Examples 1 to 21, which satisfy the requirements specified in this embodiment, were verified to exhibit excellent h-line sensitivity and i-line sensitivity. In particular, the photosensitive resin compositions of Examples 1 to 19, in which the polymerization inhibitor (E) contains both component (E1) and component (E2), showed well-balanced and excellent results in all evaluations, including not only h-line sensitivity and i-line sensitivity, but also viscosity stability, crystal precipitation properties, adhesion, resolution, and developability. From these results, it was verified that the problems of the present invention are solved for the first time by satisfying the requirements specified in this embodiment.

Claims

1. A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a sensitizer, and (E) a polymerization inhibitor, wherein the (C) photopolymerization initiator comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, the content of the (C) photopolymerization initiator is 5.0% by mass or more with respect to the total mass of the solids of the photosensitive resin composition, the (D) sensitizer comprises a compound represented by the following general formula (D1), and the (E) polymerization inhibitor comprises (E1) a first polymerization inhibitor selected from nitroso compounds and nitroxyl radicals, and (E2) a second polymerization inhibitor other than the first polymerization inhibitor. {In formula (D1), R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １ and R ２ If it is an alkyl group, its terminals may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.

2. The photosensitive resin composition according to claim 1, wherein the (E1) first polymerization inhibitor comprises one or more compounds selected from the compounds represented by the following general formulas (E1-1) and (E1-2). {R in equation (E1-1) １２ and R １３ These are each hydrocarbon groups that may have substituents. {In formula (E1-2), R １４ M is a hydrocarbon group which may have substituents. ｍ＋ m is a metal ion selected from aluminum, cobalt, iron, and copper, and m is the valence of the said metal ion.

3. The photosensitive resin composition according to claim 1 or 2, wherein the content of (C) the photopolymerization initiator is 5.5 parts by mass or more and 8.0 parts by mass or less based on 100 parts by mass of the total content of (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond.

4. The photosensitive resin composition according to claim 3, wherein the content of (C) the photopolymerization initiator is 5.5 parts by mass or more and 7.0 parts by mass or less based on 100 parts by mass of the total content of (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond.

5. When the content of the (C) photopolymerization initiator is Wc (parts by mass) and the content of the (D) sensitizer is W Ｄ (parts by mass) with respect to a total of 100 parts by mass of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond, the ratio W Ｄ of the content Wc of the (C) photopolymerization initiator to the content of the (D) sensitizer W Ｃ / W Ｄ is 12.0 or more, the photosensitive resin composition according to any one of claims 1 to 4.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the (E2) second polymerization inhibitor comprises a phenolic polymerization inhibitor.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (E2) second polymerization inhibitor comprises 4-t-butylcatechol.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the compound represented by formula (D1) is the compound represented by the following general formula (D1-1).

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (D) sensitizer further comprises a compound having a skeleton selected from the group consisting of anthracene, triarylamine, dialkylbenzophenone, oxazole, pyrazoline, and coumarin (excluding the compound represented by formula (D1)).

10. The photosensitive resin composition according to claim 9, wherein the (D) sensitizer further comprises a compound having an anthracene skeleton.

11. The photosensitive resin composition according to claim 10, wherein the compound having an anthracene skeleton is a compound represented by the following general formula (D2). {In formula (D2), R ４ and R ５ Each of these is independently a hydrogen atom, a C1-C20 alkyl group, a C1-C5 alkoxyl group, or a C6-C20 aryl group.

12. The photosensitive resin composition according to any one of claims 1 to 11, wherein the alkali-soluble polymer (A) contains structural units derived from styrene in an amount of 35% by mass or more and 75% by mass or less, based on the total mass of structural units derived from all monomers contained in the alkali-soluble polymer (A).

13. The photosensitive resin composition according to claim 12, wherein the alkali-soluble polymer (A) contains structural units derived from styrene in an amount of 40% by mass or more and 75% by mass or less, based on the total mass of structural units derived from all monomers contained in the alkali-soluble polymer (A).

14. The photosensitive resin composition according to any one of claims 1 to 13, wherein the alkali-soluble polymer (A) comprises structural units derived from hydroxyethyl (meth)acrylate.

15. A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a sensitizer, and (E) a polymerization inhibitor, wherein the (C) photopolymerization initiator comprises one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, the content of the (C) photopolymerization initiator is 5.0% by mass or more with respect to the total mass of the solids of the photosensitive resin composition, the (D) sensitizer comprises a compound represented by the following general formula (D1), and the content of the (C) photopolymerization initiator is Wc (parts by mass) and the content of the (D) sensitizer is W Ｄ When the amount is (parts by mass), the content of the sensitizer (D) is W Ｄ The ratio of the content Wc of the (C) photopolymerization initiator to the above W Ｃ / W Ｄ A photosensitive resin composition having a value of 12.0 or higher. {In formula (D1), R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １ and R ２ If it is an alkyl group, its terminals may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.

16. A photosensitive resin composition laminate comprising a support film and a photosensitive resin composition layer on the support film, wherein the photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of claims 1 to 15.

17. A method for forming a resist pattern, comprising: laminating a photosensitive resin composition layer on a substrate; exposing the photosensitive resin composition layer; and developing the photosensitive resin composition layer after exposure, wherein the photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of claims 1 to 15.

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