Photosensitive resin composition and method for forming a resist pattern

Abstract

To provide a photosensitive resin composition that has high light sensitivity, high adhesion of the resulting resist pattern to the substrate, and excellent storage stability. [Solution] 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 content of (C) the photopolymerization initiator is 5.0% by mass or more with respect to the total mass of the solids of the photosensitive resin composition, (D) the sensitizer comprises a specific compound represented by coumarin 1, coumarin 102, etc., and (E) the polymerization inhibitor comprises (E1) a first polymerization inhibitor which is a nitroso compound, and (E2) a second polymerization inhibitor which is not a nitroso compound.

Description

[Technical Field]

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

[0002] Printed circuit boards are generally manufactured using photolithography. In photolithography, a photosensitive resin composition layer is first formed on a 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, a method for forming a photosensitive resin layer on a substrate is, for example, A method of applying a solution of a photosensitive resin composition onto a substrate and drying it; A method for 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 a substrate; These are used. In the manufacturing process of printed circuit boards, the method using dry film resist is widely adopted among the above methods.

[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). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2015-161723 [Patent Document 2] Japanese Patent Application Publication No. 59-142258 [Patent Document 3] Japanese Patent Application Laid-Open No. 2003-140329 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] The photosensitive resin composition used in the photolithography method contains, for example, a binder polymer, a compound having an ethylenically unsaturated bond, a photopolymerization initiator, a sensitizer, and the like. In recent years, for the purpose of improving the photosensitivity of the photosensitive resin composition and the adhesion of the resulting resist pattern to the substrate, the content of the polymerization initiator contained in the composition has a tendency to increase. When the content of the polymerization initiator in the photosensitive resin composition increases, the photosensitivity and adhesion are surely improved. However, when the content of the polymerization initiator in the photosensitive resin composition is increased, unintended polymerization of the compound having an ethylenically unsaturated bond may easily occur during storage, and the storage stability may be impaired. When the compound having an ethylenically unsaturated bond in the photosensitive resin composition undergoes unintended polymerization, the viscosity of the composition increases, which affects the handleability, coating property, etc., and may also affect the photosensitive characteristics.

[0007] Therefore, an object of the present invention is to provide a photosensitive resin composition having high photosensitivity, high adhesion of the resulting resist pattern to the substrate, and excellent storage stability, and a method for forming a resist pattern using the same.

[0008] The present invention for achieving the above object is as follows.

[0009] <<Aspect 1>>(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 A photosensitive resin composition containing The content of the (C) photopolymerization initiator is 5.0% by mass or more based on the total mass of the solid content of the photosensitive resin composition. The aforementioned (D) sensitizer contains a compound represented by the following general formula (D1), and The aforementioned (E) polymerization inhibitor is (E1) A nitroso compound acting as a first polymerization inhibitor, and (E2) Second polymerization inhibitors other than nitroso compounds including, Photosensitive resin composition. [ka] {In formula (D1), R1 to R3 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. If R1 and R2 are alkyl groups, their ends may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.} <Aspect 2> The photosensitive resin composition according to aspect 1, 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. <Aspect 3> The photosensitive resin composition according to aspect 2, 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. <Aspect 4> The content of (C) photopolymerization initiator is Wc (parts by mass) and the content of (D) sensitizer is W D When (mass part), The content of the aforementioned (D) sensitizer 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 according to any one of embodiments 1 to 3, wherein the value is 12.0 or higher. <Aspect 5> The photosensitive resin composition according to any one of aspects 1 to 4, wherein the (E2) second polymerization inhibitor comprises a phenolic polymerization inhibitor. <Aspect 6> The photosensitive resin composition according to any one of aspects 1 to 5, wherein the (E2) second polymerization inhibitor comprises 4-t-butylcatechol. <Aspect 7> The photosensitive resin composition according to any one of aspects 1 to 6, wherein the compound represented by formula (D1) is the compound represented by the following formula (D1-1). [ka] Appearance 8: The photosensitive resin composition according to any one of Appearances 1 to 7, 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 9> The photosensitive resin composition according to aspect 8, wherein the (D) sensitizer further comprises a compound having an anthracene skeleton. <Aspect 10> The photosensitive resin composition according to aspect 9, wherein the compound having an anthracene skeleton is a compound represented by the following general formula (D2). [ka] {In formula (D2), R4 and R5 are each independently a hydrogen atom, a C1-C20 alkyl group, a C1-C5 alkoxyl group, or a C6-C20 aryl group.} <Aspect 11> The photosensitive resin composition according to any one of aspects 1 to 10, 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). <Aspect 12> The photosensitive resin composition according to aspect 11, 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). <Aspect 13> The photosensitive resin composition according to any one of aspects 1 to 12, wherein the alkali-soluble polymer (A) contains structural units derived from hydroxyethyl (meth)acrylate. <Aspect 14> comprising a support film and a photosensitive resin composition layer on the support film, The photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of embodiments 1 to 13. A laminate of a photosensitive resin composition. <Aspect 15> 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; A method for forming a resist pattern, including, The photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of embodiments 1 to 13. A method for forming a resist pattern. [Effects of the Invention]

[0010] The present invention provides a photosensitive resin composition that has high photosensitivity, high adhesion of the resulting resist pattern to a substrate, and excellent storage stability, as well as a method for forming a resist pattern using the same. [Modes for carrying out the invention]

[0011] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. Throughout this specification, if multiple structures represented by the same symbols in a general formula exist within a single molecule, they may be identical or different from one another. The present invention is not limited to the following embodiments, and may be implemented with various modifications within the scope of its gist.

[0012] 《Photosensitive resin composition》 The photosensitive resin composition of this embodiment is (A) Alkali-soluble polymer, (B) Compounds having an ethylenically unsaturated bond, (C) Photopolymerization initiator, (D) Sensitizers, and (E) Polymerization inhibitors A photosensitive resin composition comprising, The content of the aforementioned (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 aforementioned (D) sensitizer contains a compound represented by the following general formula (D1), and The aforementioned (E) polymerization inhibitor is (E1) A nitroso compound acting as a first polymerization inhibitor, and (E2) Second polymerization inhibitors other than nitroso compounds including, It is a photosensitive resin composition.

[0013] [ka]

[0014] {In formula (D1), R1 to R3 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. If R1 and R2 are alkyl groups, their ends may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.}

[0015] The photosensitive resin composition of this embodiment may optionally contain any components in addition to components (A) to (E).

[0016] <(A) Alkali-soluble polymer> The alkali-soluble polymer (A) contained in the photosensitive resin composition of this embodiment refers to a polymer that dissolves in an alkaline aqueous solution. (A) Alkali-soluble polymers are, for example, (a1) It may have structural units derived from unsaturated acidic monomers, Preferably, the structural unit has (a1) a structural unit derived from an unsaturated acidic monomer and (a2) a structural unit derived from one or more selected from the group consisting of styrene derivatives, (a3) ​​alkyl (meth)acrylates substituted with hydroxyl groups, (a4) alkyl (meth)acrylates, (a5) (meth)acrylates having an alicyclic or aromatic ring, and (a6) other monomers.

[0017] (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 anhydride, maleic acid half-ester, etc., and one or more selected from these may be used. (a1) As an unsaturated acidic monomer, (meth)acrylic acid is particularly preferred.

[0018] (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.

[0019] (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. (a2) Styrene is particularly preferred as the styrene derivative.

[0020] (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, or 35% 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 70% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less.

[0021] (a3) A hydroxyl-substituted alkyl (meth)acrylate 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) The alkali-soluble polymer has structural units derived from (a3) ​​alkyl (meth)acrylate substituted with a hydroxyl group, which further improves the developability during resist pattern formation and the adhesion of the resulting resist pattern to the substrate without impairing other functions. (a3) ​​The alkyl (meth)acrylate substituted with a hydroxyl group is: Examples of alkyl (meth)acrylates substituted with one hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; Examples of alkyl (meth)acrylates substituted with two hydroxyl groups include glycerin mono(meth)acrylate; Each of these is listed, and you may use one or more selected from them. (a3) Among alkyl (meth)acrylates substituted with a hydroxyl group, hydroxyethyl (meth)acrylate is particularly preferred.

[0022] (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.

[0023] (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) Among the alkyl (meth)acrylates, 2-ethylhexyl (meth)acrylate is particularly preferred.

[0024] (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.

[0025] (a5) As for (meth)acrylates having an alicyclic or aromatic ring, Examples of alicyclic (meth)acrylates include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate; Examples of (meth)acrylates having an aromatic ring include benzyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. Each of these is listed, and you may use one or more selected from them. The "dicyclopentanyl" group in the above refers to "tricyclo[5.2.1.0 2,6 ] Decane-8-yl means the 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.

[0026] (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).

[0027] (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.

[0028] (A) If the alkali-soluble polymer has structural units derived from (a6) other monomers, the proportion of such units 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).

[0029] In the photosensitive resin composition of this embodiment, (A) the alkali-soluble polymer is particularly, (a1) It may have structural units derived from (meth)acrylic acid as an unsaturated acid monomer and (a2) structural units derived from a styrene derivative. (a1) A structural unit derived from (meth)acrylic acid as an unsaturated acid monomer, (a2) a structural unit derived from a styrene derivative, and (a3) ​​a structural unit derived from an alkyl (meth)acrylate substituted with a hydroxyl group. Preferably, the structural unit has (a1) a structural unit derived from (meth)acrylic acid as an unsaturated acid monomer, (a2) a structural unit derived from a styrene derivative, (a3) ​​a structural unit derived from an alkyl (meth)acrylate substituted with a hydroxyl group, and (a4) a structural unit derived from one or two selected from the group consisting of alkyl (meth)acrylates and (a5) (meth)acrylates having an alicyclic or aromatic ring.

[0030] (A) For alkali-soluble polymers, the weight-average molecular weight in polystyrene terms, as 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.

[0031] (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 can be carried out in a batch or continuous manner.

[0032] In the photosensitive resin composition of this embodiment, (A) the alkali-soluble polymer may be used alone or as a mixture of two or more types. (A) As an alkali-soluble polymer, for example, (a1) a polymer having (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 alkyl (meth)acrylate, (a1) a polymer having structural units derived from (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 (meth)acrylate having an alicyclic or aromatic ring. Using a mixture of these is also included in preferred embodiments of the present invention.

[0033] The content of (A) alkali-soluble polymer in the photosensitive resin composition of this embodiment (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 solid content 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.

[0034] (B) Compounds containing 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) In compounds having an ethylenically unsaturated bond, the ethylenically unsaturated bond is preferably contained in the molecule in the form of a (meth)acrylate. Therefore, (B) the compound having an ethylenically unsaturated bond may be, for example, a monofunctional, difunctional, or trifunctional (e.g., trifunctional, tetrafunctional, pentfunctional, or hexafunctional) (meth)acrylate compound.

[0035] 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.

[0036] 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 of these may be selected and used.

[0037] Examples of commercially available bifunctional (meth)acrylate compounds include, NK Ester (registered trademark) 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, 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® 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, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema Co., Ltd.); 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.); These are some examples.

[0038] 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.

[0039] 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.); 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.); These are some examples.

[0040] The content of compounds having (B) ethylenically unsaturated bonds in the photosensitive resin composition of this embodiment (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.

[0041] (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, 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.

[0042] In the photosensitive resin composition of this embodiment, (B) the compound having an ethylenically unsaturated bond preferably includes a (meth)acrylate compound with two or more functions. In this case, only a (meth)acrylate compound with two or more functions may be used, or a (meth)acrylate compound with two or more functions may be used in combination with one or more selected from monofunctional (meth)acrylate compounds and trifunctional (meth)acrylate compounds. (B) The ratio of the difunctional (meth)acrylate compound to the total mass of compounds having ethylenically unsaturated bonds 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.

[0043] (C) Ingredient: Polymerization initiator In the photosensitive resin composition of this embodiment, (C) the photopolymerization initiator is preferably 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 (B) a compound having an ethylenically unsaturated bond by radicals generated by light irradiation, and the function of promoting the polymerization of (B) a compound having an ethylenically unsaturated bond by promoting the generation of radicals in other components.

[0044] Examples of the (C) photopolymerization initiator in the photosensitive resin composition of this embodiment include biimidazole compounds, 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, acridine compounds, N-aryl amino acid ester compounds, halogen compounds, etc., and one or more selected from these may be used.

[0045] Biimidazole compounds may be, for example, dimers of rophine(2,4,5-triarylimidazole), and specific examples include, for example, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,2',5-tris-(o-chlorophenyl)- 4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl) 2,2'-Bis-(2,4',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) 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,Examples include 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-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and one or more selected from these may be used.

[0046] 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; Each of these can be listed, and you may use one or more selected from them. Examples of aromatic ketone compounds include benzophenone. Dialkylbenzophenone falls under the category of "other sensitizers" in (D) sensitizers, which will be discussed later.

[0047] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Examples of 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;

[0048] Examples of dialkylketal compounds include benzyldimethyl ketal and benzyldiethyl ketal; Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorthioxanthone; Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate; Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime; Examples of acridine compounds include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine;

[0049] Examples of ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine; 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, diallyloidonium compounds, etc. Each of these may be listed, and one or more of the above may be used for each.

[0050] In the photosensitive resin composition of this embodiment, the (C) photopolymerization initiator preferably contains a biimidazole compound.

[0051] The content of (C) photopolymerization initiator in the photosensitive resin composition of this embodiment (total content if two or more types of (C) photopolymerization initiators are included) may be 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, or 4.5% by mass or more, based on the mass of the total solid content of the photosensitive resin composition, 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.

[0052] (D) Sensitizer The photosensitive resin composition of this embodiment includes (D) a sensitizer. The (D) sensitizer has the function of absorbing the irradiation light during exposure and transferring its energy to (C) a photopolymerization initiator, thereby promoting the photopolymerization reaction of a compound having (B) an ethylenically unsaturated bond. The (D) sensitizer in the photosensitive resin composition of this embodiment includes a compound represented by the following general formula (D1). [ka] {In formula (D1), R1 to R3 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. If R1 and R2 are alkyl groups, their ends may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle.}

[0053] The alkyl groups R1 to R3 may be linear or branched. The number of carbon atoms in the alkyl groups R1 to R3 is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3. As described above, when R1 and R2 are alkyl groups, their ends may be bonded to the 6th or 8th carbon of the coumarin skeleton, respectively, to form a nitrogen-containing heterocycle. In this case, the end of the alkyl group of R1 may be bonded to the 6th carbon of the coumarin skeleton, and the end of the alkyl group of R2 may be bonded to the 8th carbon of the coumarin skeleton, forming a nitrogen-containing heterocondensed ring as a whole. When the terminal end of the R1 or R2 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.

[0054] 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).

[0055] [ka]

[0056] The (D) sensitizer in the photosensitive resin composition of this embodiment 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. As a result, fluctuations in photosensitivity due to variations in exposure wavelength are reduced, making it easier to obtain a photosensitive resin composition with good wavelength dependence. Other sensitizers include, for example, compounds having a skeleton selected from the group consisting of anthracene, triarylamine, dialkylbenzophenone, oxazole, pyrazoline, and coumarin (excluding the compound represented by formula (D1) above), and one or more selected from these may be used.

[0057] 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.

[0058] [ka]

[0059] {In formula (D2), R4 and R5 are each 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 a compound having an anthracene skeleton, the compound represented by the above formula (D2) is preferred.

[0060] Examples of compounds having a triarylamine skeleton include compounds having a triphenylamine skeleton, and more specifically, triphenylamine may be one example.

[0061] Examples of compounds having a dialkylbenzophenone skeleton include Michla's 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, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline; Each of these can be listed, and you may use one or more selected from them.

[0062] The compound represented by formula (D1) above is excluded from the list of compounds containing a coumarin skeleton that can be used as other sensitizers. Other compounds containing a coumarin skeleton that can be used as sensitizers include, for example, 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), etc., and one or more selected from these may be used.

[0063] In the photosensitive resin composition of this embodiment, it is preferable that the other sensitizers include compounds having an anthracene skeleton.

[0064] In the photosensitive resin composition of this embodiment, the content of the (D) sensitizer (total content when two or more (D) sensitizers are included, content including other sensitizers when the (D) sensitizer contains other sensitizers) is 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 (D) sensitizer contains other sensitizers together with the compound represented by the above formula (D1), the mass ratio of the other sensitizer to the total mass of the (D) sensitizer 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, if the other sensitizers are contained at 1% by mass or more or 3% by mass or more based on the total mass of the (D) sensitizer, the effects of using the other sensitizers will be manifested.

[0065] In the photosensitive resin composition of this embodiment, 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, the content of the (C) photoinitiator is taken as Wc (parts by mass), and the content of the (D) sensitizer is taken as W D (parts by mass), when the content of the (D) sensitizer is taken as W D The ratio W C of the content Wc of the (C) photoinitiator to the content W of the (D) sensitizer D is preferably 12.0 or more. As described above, the (D) sensitizer has a function of absorbing the irradiation light during exposure and transmitting its energy to the (C) photoinitiator. Therefore, in order to transmit the energy of the light absorbed by the (D) sensitizer to the (C) photoinitiator without loss, the ratio W D of the content Wc of the (C) photoinitiator to the content W of the (D) sensitizer C / W D is preferably larger. On the other hand, from the viewpoint of the adhesion of the resulting resist pattern to the substrate, there is an optimal amount of sensitizer to be included. That is, if the amount of sensitizer is excessively increased, 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.

[0066] 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, but 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, ratio W C / W D If (D) is made excessively large, (C) there will be photopolymerization initiators that do not benefit from the effect of the sensitizer, and the photosensitivity per unit amount 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, 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.

[0067] (E) Polymerization inhibitors The photosensitive resin composition of this embodiment contains (E) a polymerization inhibitor. (E) The polymerization inhibitor has the function of preventing (B) compounds having ethylenically unsaturated bonds from unintentionally polymerizing, thereby improving the thermal stability and resolution of the photosensitive resin composition. The (E) polymerization inhibitor in the photosensitive resin composition of this embodiment includes (E1) a first polymerization inhibitor which is a nitroso compound, and (E2) a second polymerization inhibitor which is not a nitroso compound. (E1) The first polymerization inhibitor is thought to primarily contribute to improving the thermal stability of the photosensitive resin composition, and (E2) the second polymerization inhibitor is thought to primarily contribute to improving the resolution of the photosensitive resin composition layer. However, the present invention is not bound by any particular theory.

[0068] (E1) The nitroso compound may be, for example, a compound represented by the following general formula (E1).

[0069] [ka]

[0070] {In formula (E1), R 11 This is a hydrocarbon group which may have substituents, -NHR 12 , or -NR 12 R 13 Show, R 12 and R 13 These are, independently, hydrocarbon groups that may have substituents. R in equation (EI) 11 From the viewpoint of fully obtaining the effects of this embodiment, for example, A saturated or unsaturated linear or branched chain hydrocarbon group having 1 to 20 carbon atoms (e.g., a 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 with 6 to 20 carbon atoms (e.g., phenyl group); Aralkyl groups with 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 groups); 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. It is preferable that the selected item be one or a combination of two or more items chosen from the group consisting of the following:

[0071] -NHR 12 and -NR 12 R 13 Each of them operates independently. 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 with 6 to 20 carbon atoms (e.g., phenyl group); Aralkyl groups 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); It is preferable that the selected item be one or a combination of two or more items chosen from the group consisting of the following:

[0072] 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.

[0073] R in equation (E1) 11 As for, Phenyl group, naphthyl group, aminophenyl group, hydroxyphenyl group, thiohydroxyphenyl group, chlorophenyl group, aminonaphthyl group, hydroxynaphthyl group, thiohydroxynaphthyl group, or chloronaphthyl group are preferred. Phenyl group, naphthyl group, aminophenyl group, hydroxyphenyl group, aminonaphthyl group, or hydroxynaphthyl group are more preferred. R in equation (E1) 12 and R 13 In that sense, each is independent, Preferably, 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. A C1-C10 alkyl group or a phenyl group is more preferable. A methyl group or a phenyl group is even more preferred.

[0074] In the photosensitive resin composition of this embodiment, the (E1) first polymerization inhibitor preferably contains a compound represented by the following general formula (E1-1). [ka]

[0075] {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 this case 12 and R 13 It is the same as this. In the photosensitive resin composition of this embodiment, the polymerization inhibitor (E) contains a compound represented by the above formula (E1-1), resulting in excellent photosensitivity and resolution, as well as excellent adhesion of the resulting resist pattern. Examples of the (E1) first polymerization inhibitor in this embodiment 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.

[0076] (E1) The first polymerization inhibitor may be in the form of a complex compound in which the non-bonding electron pair of the amine is attached to a suitable metal atom. In this case, examples of metal atoms include aluminum, cobalt, and iron. An example of the (E1) first polymerization inhibitor in the form of a complex compound is N-nitroso-N-phenylhydroxylamine aluminum.

[0077] In the photosensitive resin composition of this embodiment, the (E2) second polymerization inhibitor is a polymerization inhibitor other than the (E1) first polymerization inhibitor (nitroso compound). The (E2) second polymerization inhibitor may be, for example, a phenolic polymerization inhibitor, a phenothiazine polymerization inhibitor, a phenoxazine polymerization inhibitor, etc.

[0078] Preferred phenolic polymerization inhibitors are phenol compounds having two or more phenolic hydroxyl groups. Specifically, examples include hydroquinone, catechol, 4-t-butylcatechol, pyrogallol, gallic acid, and methyl gallate. Examples of phenothiazine polymerization inhibitors include phenothiazines and the like. Examples of phenoxazine-based banned substances include phenoxazine, etc. (E2) As the second polymerization inhibitor, 4-t-butylcatechol or phenothiazine is preferred. In the photosensitive resin composition of this embodiment, one or more of the above-mentioned (E2) second polymerization inhibitors may be used.

[0079] In the photosensitive resin composition of this embodiment, the content of (E1) first polymerization inhibitor (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 content 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 content of the photosensitive resin composition, from the viewpoint of balancing the storage stability of the composition with the photosensitivity and resolution. In the photosensitive resin composition of this embodiment, 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).

[0080] In the photosensitive resin composition of this embodiment, 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 solid content 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 solid content of the photosensitive resin composition, from the viewpoint of balancing the photosensitivity of the composition and the adhesion of the obtained resist pattern to the substrate. In the photosensitive resin composition of this embodiment, when the total mass of the photosensitive resin composition is 100% by mass, (E1) the content W of the first polymerization inhibitor E1 And, (E2) the 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.

[0081] <Optional ingredients> The photosensitive resin composition of this embodiment may contain any components in addition to the components (A) to (E) described above. The optional component may be one or more selected from, for example, pigments, adhesion aids, plasticizers, rust inhibitors, solvents, etc.

[0082] 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 pigments 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 of these may be selected and used.

[0083] If the photosensitive resin composition of this embodiment contains a dye, its content (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 solid content of the photosensitive resin composition.

[0084] Examples of adhesion enhancers include benztriazoles and carboxybenztriazoles, and one or more selected from these may be used. If the photosensitive resin composition of this embodiment contains an adhesion aid, the amount thereof 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 may be 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.

[0085] 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.

[0086] 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.

[0087] 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; Phthalates 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 attached to both ends of bisphenol A, and ethylene glycol, which has ethylene oxide attached to both ends of bisphenol A; Aluminum salts to which 1 to 3 moles of nitrosophenylhydroxylamine have been added; These are some examples.

[0088] 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.

[0089] 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 is The invention comprises a support film and a photosensitive resin composition layer on the support film, The aforementioned photosensitive resin composition layer is a layer made of the photosensitive resin composition of this embodiment described above. It is a laminate of a photosensitive resin composition. In this embodiment, the photosensitive resin composition laminate 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."

[0090] <Support film> The support film has the function of supporting the photosensitive resin composition layer in the photosensitive resin composition laminate of this embodiment and maintaining the shape of the laminate. The support film preferably has transparency that allows light (such as ultraviolet light or other active light) to pass through when the photosensitive resin composition layer is exposed.

[0091] 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 film with high film quality and low internal foreign matter as the support film. Examples of high-quality films include, for example, PET films synthesized using titanium (Ti) 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 undergoing a flattening treatment, such as calendering, on at least one side.

[0092] 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 is preferable for the support film, but a haze of 0.01% or more does not pose a practical problem.

[0093] <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 as described above. The thickness of the photosensitive resin composition layer may be 3 μm to 200 μm, 3 μm to 100 μm, or 3 μm to 50 μm. Generally, thinner layers of the photosensitive resin composition layer result in higher resolution, while thicker layers tend to increase film strength. The thickness of the photosensitive resin composition layer may be appropriately set according to the application, taking into consideration the balance between resolution and film strength.

[0094] 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 included in the photosensitive resin layer include ketones such as methyl ethyl ketone and acetone; alcohols such as methanol, ethanol, and isopropanol; toluene; and the like. The solvent content 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 solid content of the photosensitive resin composition.

[0095] <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. For example, polyethylene, polypropylene, stretched polypropylene, polyester film, etc., are preferred materials for the protective film. The thickness of the protective film is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm. To allow the protective film to be easily peeled from the photosensitive resin composition layer, a release layer may be formed on the side of the protective film facing the photosensitive resin composition layer. 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.

[0096] <Method for manufacturing a photosensitive resin composition laminate> The photosensitive resin composition laminate of this embodiment is, for example, Prepare a coating solution containing the photosensitive resin composition and solvent of this embodiment; Applying the above coating liquid onto a support film to form a coating film; Removing the solvent from the coating film and forming a photosensitive resin composition layer on the support film; and Laminating a protective film onto a photosensitive resin composition layer; It may be manufactured by a method that includes [a certain component].

[0097] Examples of solvents used in the preparation of coating solutions 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.

[0098] 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 by, for example, leaving the support film on which the coating has been formed to stand 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 lamination of the protective film onto the photosensitive resin composition layer may be carried out according to a standard method.

[0099] Method for forming a resist pattern In yet another aspect of the present invention, a method for forming a resist pattern is provided. The method for forming the resist pattern in this embodiment is: Laminating a photosensitive resin composition layer onto a substrate; Exposing the photosensitive resin composition layer to light; and Developing the photosensitive resin composition layer after exposure; A method for forming a resist pattern, including, The aforementioned photosensitive resin composition layer is a layer made of the photosensitive resin composition of this embodiment described above. This is a method for forming a resist pattern.

[0100] 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. If desired, the substrate may be prepared before use. Surface preparation of the substrate may be performed, for example, by cleaning the substrate with an aqueous H2SO4 solution with a concentration of about 10% by mass.

[0101] Lamination of a photosensitive resin composition layer onto a substrate is, for example, Peeling a protective film from a photosensitive resin composition laminate; and The photosensitive resin composition of the photosensitive resin composition laminate, from which the protective film has been removed, is heat-pressed onto the substrate surface; This may be done by a method that includes [a certain element].

[0102] Heat bonding may be performed, for example, using a laminator equipped with rolls, or by laminating a photosensitive resin composition laminate, from which the protective film has been removed, onto the substrate surface and then passing it through rolls. The heating temperature during heat bonding can be, for example, 40°C to 160°C, and preferably 80°C to 120°C. Heat sealing may be performed under reduced pressure if desired. The heat-sealing operation may be performed only once or two or more times. If the heat-sealing 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 with the protective film removed and the substrate may be passed through the rolls multiple times.

[0103] 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 through 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.

[0104] The photosensitive resin composition layer after exposure is then developed. In this case, 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 radiation; 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.

[0105] The photosensitive resin composition layer after exposure is then optionally heated as described above and subsequently 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 should be removed before development. Development is performed by bringing the photosensitive resin composition layer, after exposure, into contact with a developer solution. The developer may be an alkaline aqueous solution, and specifically, aqueous solutions of Na2CO3, K2CO3, 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, an aqueous solution of Na2CO3 with a concentration of about 0.2% to 2% by mass is common. For example, surfactants, defoamers, small amounts of organic solvents to accelerate development may be added to the alkaline aqueous solution used as the developer. The temperature of the developer during development is preferably kept approximately constant at 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.

[0106] 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 carried out, for example, at a temperature of 60°C to 300°C for a time of 1 minute to 120 minutes. The heating may be carried out using a heating furnace that uses, for example, hot air, infrared rays, or far-infrared rays. [Examples]

[0107] The embodiment will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following embodiments.

[0108] <Manufacturing of alkali-soluble polymers (A-1) to (A-4)> The monomers of the types and quantities shown in Table 1, along with 3.0 parts by mass of azobisisobutyronitrile, were mixed and stirred to prepare solution (a). A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube was charged with 200 parts by mass of methyl ethyl ketone and 100 parts by mass of ethanol. The temperature of the liquid was adjusted to 80°C while blowing nitrogen gas into the flask and stirring. The liquid temperature was maintained at 80°C, and while continuing to blow in 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 continued to blow in nitrogen gas and stir for another 2 hours at 80°C.

[0109] 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 in nitrogen gas and stir, the entire volume of solution (b) was added dropwise over 10 minutes at a constant dropping rate. After the addition was complete, the reaction mixture was kept at 80°C for a further 3 hours, during which time nitrogen gas was blown in and stirring continued. Subsequently, the temperature was raised to 90°C, and nitrogen gas was blown in and stirring continued at 90°C for a further 2 hours.

[0110] Afterward, stirring was stopped, but the nitrogen gas injection continued, and the liquid was allowed to cool to room temperature (25°C). Through the above procedure, solutions containing each of the alkali-soluble polymers (A-1) to (A-4) were obtained. The weight-average molecular weights of alkali-soluble polymers (A-1) to (A-4), measured by gel permeation chromatography (GPC) and converted to polystyrene, are shown in accordance with Table 1. GPC was measured under the following conditions. Measuring device Pump: PU-4580, manufactured by JASCO Corporation. Degasser: Manufactured by JASCO Corporation, model DG-2080-53 Column oven: JASCO Corporation, CO-1560 Columns: Shodex® GPC columns manufactured by Resonaq Corporation, model names "KF-80Y" and "KF-806M," connected in series in that order. Eluent: Tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05mL / min Detector: JASCO Corporation, differential refractometer, model name "RI-1530"

[0111] [Table 1]

[0112] Example 1 (1) Preparation for forming a photosensitive resin composition layer (1-1) Preparation of a compounding solution 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 moles 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 aluminum N-nitroso-N-phenylhydroxylamine as a primary polymerization inhibitor; and (E2) 0.01 parts by mass of 4-t-butylcatechol as a second polymerization inhibitor; and As a pigment, 0.4 parts by mass of leucocrystal violet, and Diamond Green 0.03 parts by mass The mixture was stirred to prepare a formulation for forming a photosensitive resin composition layer.

[0113] In the above, the amounts mentioned refer to the amounts of each active ingredient as solid content. Furthermore, the amount of ethanol added was set to an amount that resulted in a solid content concentration of 60% by mass in the prepared solution.

[0114] (1-2) Evaluation of viscosity stability Seven samples were prepared by filling 20 mL glass containers completely with the resulting solution and sealing them to prevent air from entering. Of the seven samples, the viscosity of one was measured immediately after preparation using an E-type viscometer, and this measurement was taken as the initial viscosity. The remaining six samples were left standing in an oven preheated to 50°C. Samples in the oven were removed one by one each day from 1 to 6 days after the start of standing, and their 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 sample solidified to the point where viscosity measurement was no longer possible, was determined and evaluated according to the following criteria. A (Good): If the number of days required for the viscosity change to occur according to the above criteria was 5 days or more. C (Defective): If the number of days required for the viscosity change to occur as per the above criteria is less than 5 days.

[0115] (2) Photosensitive resin composition laminate (2-1) Manufacturing of photosensitive resin composition laminates A 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "QS71") was used as a support film. The above-mentioned preparation solution was applied to its surface using a bar coater, and the film was left to stand in a 95°C dryer for 2.5 minutes to remove the solvent. Through the above procedure, 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 surface of the photosensitive resin composition layer opposite to the support film.

[0116] (2-2) Evaluation of crystal precipitation properties When manufacturing photosensitive resin composition laminates, crystal precipitation may be observed in the formed photosensitive resin composition layer. The formation of crystals in the photosensitive resin composition layer may interfere with exposure according to a predetermined pattern. Therefore, the obtained photosensitive resin composition laminate was 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. B (Good): When crystal precipitation is observed in a portion of the photosensitive resin composition layer. C (Defective): When crystal precipitation is observed across the entire surface of the photosensitive resin composition layer.

[0117] (3) Various evaluations An evaluation substrate was prepared using the photosensitive resin composition laminate manufactured as described above. A resist pattern was formed by exposure, heating, and development, and the h-line sensitivity, i-line sensitivity, adhesion, resolution, and developability were evaluated. In each evaluation, 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. However, the exposure method was adopted differently depending on the evaluation item, as follows: H-line sensitivity: Exposure using a direct writing exposure machine (manufactured by Oak Manufacturing Co., Ltd., model "FDi-3") with a Stuffer 41-step step tablet as the mask. i-line sensitivity: Exposure using a projection exposure system (manufactured by Ushio Inc., model "UX-23101") with a 41-step stufer tablet as the mask. Adhesion, resolution, and developability: Direct exposure using a direct imaging exposure machine (manufactured by Oak Manufacturing Co., Ltd., model "FDi-3") with a predetermined direct imaging (DI) exposure pattern.

[0118] (3-1) Formation of the resist pattern (3-1-1) Fabrication of evaluation board 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 washed with a 10 mass% H2SO4 aqueous solution, then washed with pure water to smooth the surface. The surface of the copper-clad laminate was preheated to 50°C after surface preparation. An evaluation substrate was prepared by laminating the photosensitive resin composition laminate obtained above onto the surface of a 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.

[0119] (3-1-2) Measurement of the optimal exposure Two hours after lamination, evaluation substrates were directly exposed using a direct imaging exposure machine (Oak Manufacturing Co., Ltd., model "FDi-3") with a predetermined direct imaging (DI) exposure pattern. Exposure was performed using a 41-step step tablet as a mask, and the optimal exposure amount was determined to be the amount that resulted in a maximum of 15 remaining film steps after development. (3-1-3) Exposure Two hours after lamination, the evaluation substrates were exposed to light using the method specified for each evaluation. The exposure amount was set to the optimal exposure amount determined in "(3-2-2) Measurement of Optimal Exposure Amount".

[0120] (3-1-4) Heating Two minutes after exposure, the evaluation substrate was heated by placing it in a forced-air constant-temperature incubator (manufactured by Yamato Scientific Co., Ltd., model "DKM600") set to 70°C for 30 seconds. (3-1-5) Development After peeling the support film from the evaluation substrate after exposure and heating, a resist pattern was formed on the copper-clad laminate by spraying a 1% by mass Na2CO3 aqueous solution, heated to 30°C, onto the photosensitive resin composition layer using a dry film developing machine manufactured by Fuji Kiko Co., Ltd. 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.

[0121] (3-2) Evaluation of h-line sensitivity The maximum number of remaining film stages after development, when exposed using a direct-writing exposure machine (manufactured by Oak Manufacturing Co., Ltd., model "FDi-3") with a Stuffer 41-step step tablet as a mask, 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 The maximum number of remaining film stages after development, when exposed using a projection exposure system (Ushio Inc., model "UX-23101") with a 41-step Stuffer tablet as a mask, 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.

[0122] (3-4) Evaluation of adhesion The resist patterns obtained by directly exposing the material with a predetermined direct imaging (DI) exposure pattern using a direct writing exposure machine (Oak Manufacturing Co., Ltd., model "FDi-3") were observed at 100x magnification using an optical microscope. The presence or absence of pattern breaks 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 breaks or defects were observed in either the L / S = 5 μm / 200 μm or 8 μm / 200 μm regions. B (Good): Pattern breakage or defects were observed in the L / S = 5 μm / 200 μm region, but neither pattern breakage nor defects were observed in the 8 μm / 200 μm region. C (Defective): If folds or defects are found in both the L / S = 5μm / 200μm and 8μm / 200μm regions.

[0123] (3-5) Evaluation of resolution Using a direct writing exposure machine (manufactured by Oak Manufacturing Co., Ltd., model "FDi-3"), the resist patterns obtained by direct exposure with a predetermined direct imaging (DI) exposure pattern were observed at 200x magnification using an optical microscope. The presence or absence of lateral bending, folding, and defects in the line-and-space (L / S) = 5 μm / 5 μm and 8 μm / 8 μm regions, as well as development residuals between patterns, were examined and evaluated according to the following criteria. A (Excellent): No pattern breakage or loss, nor any development residue between patterns, was observed in either the L / S = 5μm / 5μm or 8μm / 8μm regions. B (Good): In the L / S = 5 μm / 200 μm region, pattern folds or defects, or development residue between patterns were observed, but in the 8 μm / 200 μm region, neither pattern folds nor defects, nor development residue between patterns, were observed. C (Defective): If pattern folds or defects, or development residue between patterns, are observed in both the L / S = 5μm / 200μm and 8μm / 200μm regions.

[0124] (3-6) Developability The shortest development time when directly exposed using a direct imaging (DI) exposure pattern (manufactured by Oak Manufacturing Co., Ltd., model "FDi-3") was investigated and evaluated according to the following criteria. A (Excellent): When the minimum development time was 19 seconds or less. B (Good): If the minimum development time was greater than 19 seconds but 23 seconds or less. C (Defective): If the minimum development time exceeds 23 seconds.

[0125] Examples 2-18 and Comparative Examples 1-6 Except for changing the types and amounts of each component as shown in Tables 2 to 4, a photosensitive resin composition layer-forming solution was prepared in the same manner as in Example 1, and various evaluations were performed. (D) The amount of 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 Tables 2-4. Tables 2-4 show (D) the amount of sensitizer (W D (C) Amount of photopolymerization initiator (W) relative to ) C ) ratio (W C / W D ) was also shown.

[0126] [Table 2]

[0127] [Table 3]

[0128] [Table 4]

[0129] The abbreviations for the components in Tables 2-4 have the meanings shown in Table 5.

[0130] [Table 5]

[0131] 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, is 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, exhibit inferior h-line sensitivity and i-line sensitivity; (E) The photosensitive resin compositions of Comparative Examples 4 and 5, which do not satisfy the embodiment specified in this embodiment, in which the polymerization inhibitor contains both component (E1) and component (E2), have inferior viscosity stability of the composition (Comparative Example 4) or inferior adhesion and resolution of the resist pattern (Comparative Example 5); (C) The photosensitive resin composition of Comparative Example 6, in which the amount of photopolymerization initiator was not equal to the amount specified in this embodiment, exhibited inferior h-ray sensitivity and i-ray sensitivity.

[0132] In contrast to these, the photosensitive resin compositions of Examples 1 to 18, which satisfy all the requirements specified in this embodiment, showed well-balanced and excellent results in all evaluations. This demonstrates that the problem of the present invention is solved only by satisfying all the requirements specified in this embodiment.

Claims

1. (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, (C) Photopolymerization initiator, (D) Sensitizers, and (E) Polymerization inhibitors A photosensitive resin composition comprising, 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 contains a compound represented by the following general formula (D1), The (E) polymerization inhibitor is (E1) A nitroso compound, which is a first polymerization inhibitor, and (E2) Second polymerization inhibitors other than nitroso compounds including, Photosensitive resin composition. 【Chemistry 1】 {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 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.

3. The photosensitive resin composition according to claim 2, wherein the content of (C) the photopolymerization initiator is 5.5 parts by mass or more and 7.0 parts by mass or less with respect to 100 parts by mass of the total content of (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond.

4. Wc (parts by mass) is the content of the photopolymerization initiator (C) relative to 100 parts by mass of the total content of (A) alkali-soluble polymer and (B) compound having an ethylenically unsaturated bond, and W is the content of the sensitizer (D). Ｄ When (mass part), 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 The photosensitive resin composition according to claim 1, wherein the coefficient is 12.0 or higher.

5. The photosensitive resin composition according to claim 1, wherein the (E2) second polymerization inhibitor comprises a phenolic polymerization inhibitor.

6. The photosensitive resin composition according to claim 1, wherein the (E2) second polymerization inhibitor comprises 4-t-butylcatechol.

7. The photosensitive resin composition according to claim 1, wherein the compound represented by formula (D1) is the compound represented by the following formula (D1-1). 【Chemistry 2】

8. The photosensitive resin composition according to claim 1, 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)).

9. The photosensitive resin composition according to claim 8, wherein the (D) sensitizer further comprises a compound having an anthracene skeleton.

10. The photosensitive resin composition according to claim 9, wherein the compound having an anthracene skeleton is a compound represented by the following general formula (D2). 【Transformation 3】 {In formula (D2), R ４ and R ５ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms.}

11. The photosensitive resin composition according to claim 1, 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).

12. The photosensitive resin composition according to claim 11, 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).

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

14. The invention comprises a support film and a photosensitive resin composition layer on the support film, The photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of claims 1 to 13. A laminate of a photosensitive resin composition.

15. Laminating a photosensitive resin composition layer onto a substrate; Exposing the photosensitive resin composition layer to light; and Developing the photosensitive resin composition layer after exposure; A method for forming a resist pattern, including, The photosensitive resin composition layer is a layer made of the photosensitive resin composition described in any one of claims 1 to 13. A method for forming a resist pattern.

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