Photosensitive resin composition and method for forming a resist pattern

Abstract

The objective is to provide a photosensitive resin composition containing a dye that exhibits excellent hue stability and, consequently, is less susceptible to deterioration of its photosensitive properties even after long-term storage, by suppressing structural changes in the dye during storage. [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 dye, and (E) an antioxidant, wherein the (D) dye comprises one or two selected from the group consisting of (D1) a dye having a triphenylmethane structure and (D2) a dye having a triphenylmethyl cation structure, and the (E) antioxidant comprises a specific compound represented by N-isopropyl-N'-phenyl-p-phenylenediamine.

Description

Technical Field

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

Background Art

[0002] Printed wiring boards are generally manufactured using photolithography. In the photolithography method, first, a photosensitive resin composition layer is formed on a substrate, and a resist pattern is formed by performing exposure and development on this photosensitive resin composition layer. Then, after performing an etching process or a plating process on the substrate to form a conductor pattern, the resist pattern is removed to form a desired wiring pattern on the substrate.

[0003] In the photolithography method, as a method for forming a photosensitive resin layer on a substrate, for example, a method of applying a solution of a photosensitive resin composition on a substrate and drying it; a method of laminating a photosensitive resin composition layer of a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin composition layer) on a substrate; etc. are used. In the manufacturing process of printed wiring boards, among the above, the method using a dry film resist is widely adopted.

[0004] Regarding the photosensitive resin composition constituting the photosensitive resin composition layer, various configurations have been proposed from the viewpoint of further improving photosensitivity, resolution, adhesion, etc. (for example, Patent Documents 1 to 3).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

[0006] In photosensitive resin compositions, dyes are often included in the photosensitive resin layer to improve handling characteristics such as the development of hue contrast before and after exposure and visibility during foreign object inspection. Such dyes can be categorized into those that absorb in the visible light region and those that do not. A dry film resist comprising a photosensitive resin composition layer containing a dye that absorbs in the visible light region is typically perceived as colored. On the other hand, dyes that do not absorb in the visible light region usually transform into chromogenic materials that absorb in the visible light region after the exposure process. In a dry film resist comprising a photosensitive resin composition layer containing such dyes, the exposed areas usually develop color after exposure, resulting in a hue contrast between the exposed and unexposed areas.

[0007] However, some of these dyes undergo structural changes during storage due to undesirable reactions, resulting in the chromogenic component migrating to the dechromogenic component, or vice versa. These structural changes in the dyes are thought to be caused by reactive radicals generated from, for example, additives in the dry film or oxygen molecules in the atmosphere. If the dyes in dry film undergo such structural changes during storage, it can not only impair the appearance of the dry film but also affect its photosensitive properties.

[0008] Therefore, the present invention aims to provide a photosensitive resin composition containing a dye that exhibits excellent hue stability and, consequently, is less susceptible to damage to its photosensitive properties even after long-term storage, by suppressing structural changes of the dye during storage, and a method for forming a resist pattern using the same. [Means for solving the problem]

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

[0010] Appearance 1: (A) Alkali-soluble polymer, (B) Compounds having an ethylenically unsaturated bond, (C) Photopolymerization initiator, (D) Dyes, and (E) Antioxidants A photosensitive resin composition comprising, The aforementioned (D) dye is (D1) Dyes having a triphenylmethane structure, and (D2) Dye having a triphenylmethyl cation structure It includes one or two selected from the group consisting of, The aforementioned (E) antioxidant includes a compound represented by any of the following formulas (E1) to (E3): Photosensitive resin composition. [ka] {In formula (E1), Ar1 is an arylene group having 6 to 12 carbon atoms, and the two R1s are each independently a hydrocarbon group having 1 to 12 carbon atoms, and one or more hydrogen atoms of the hydrocarbon group R1 may be substituted with a hydroxyl group or a halogen atom; In formula (E2), the two Ar2 groups are each independently a group having 6 to 24 carbon atoms and possessing an aromatic ring, and the compound represented by formula (E1) is excluded from (E2); In (E3), n1 is an integer from 0 to 6, n2 is 0 or 1, except when n1 is 1 or greater, n2 is 1, and any multiple R2 and R3 are each independently alkyl groups having 1 to 6 carbon atoms, and R4 is a hydrogen atom, an alkalkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. <Aspect 2> The photosensitive resin composition according to aspect 1, wherein the compound represented by formula (E1) is the compound represented by the following formula (E-1). [ka] {In equation (E1), R1 has the same meaning as R1 in equation (E1) above.} Aspect 3: The photosensitive resin composition according to Aspect 1 or 2, wherein in the formula (E-1), each R1 is independently an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a group represented by the following formula. [Chemical formula] {In the above formula, R9 is a hydrogen atom or a methyl group, R 10 is an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, and n is an integer from 0 to 6.} A group represented by.} Aspect 4: The photosensitive resin composition according to any one of Aspects 1 to 3, wherein the compound represented by the formula (E2) is a compound represented by the following formula (E2-1) or (E2-2). [Chemical formula] In formulas (E2-1) and (E2-2), R5 to R7 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.} Aspect 5: The photosensitive resin composition according to any one of Aspects 1 to 4, wherein the compound represented by the formula (E3) is a compound represented by the following formula (E3-1) or (E3-2). [Chemical formula] {In formulas (E3-1) and (E3-2), R2 to R4 have the same meanings as R2 to R4 in the formula (E3), respectively, and n1 is an integer from 0 to 2.} Aspect 6: The photosensitive resin composition according to any one of Aspects 1 to 5, wherein the (D) dye contains both the (D1) dye and the (D2) dye. Aspect 7: The photosensitive resin composition according to any one of Aspects 1 to 6, wherein the content of the (E) antioxidant is 0.001% by mass or more and 0.1% by mass or less based on the total mass of the solid content of the photosensitive resin composition. Aspect 8: The (D) dye is contains leuco crystal violet as the (D1) dye, and contains diamond green as the (D2) dye, A photosensitive resin composition according to any one of embodiments 1 to 7. [Aspect 9] A photosensitive resin composition according to any one of aspects 1 to 8, further comprising one or more antioxidants selected from the group consisting of compounds having two or more phenolic hydroxyl groups, nitroso compounds, compounds having a phenothiazine skeleton, and compounds having a phenoxazine skeleton. <Aspect 10> The photosensitive resin composition according to any one of aspects 1 to 9, wherein the alkali-soluble polymer (A) has structural units derived from (meth)acrylic acid and structural units derived from alkyl (meth)acrylate substituted with a hydroxyl group. <Aspect 11> 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 10. A laminate of a photosensitive resin composition. <Aspect 12> 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 10. A method for forming a resist pattern. [Effects of the Invention]

[0011] According to the present invention, a photosensitive resin composition containing a dye is provided that has excellent hue stability and, consequently, does not easily lose its photosensitive properties even after long-term storage, by suppressing structural changes of the dye during storage, and a method for forming a resist pattern using the same is provided. [Modes for carrying out the invention]

[0012] The following describes in detail an embodiment for carrying out the present invention (hereinafter referred to as "this embodiment"). Throughout this specification, if multiple structures represented by the same sign 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.

[0013] 《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) Dyes, and (E) Antioxidants A photosensitive resin composition comprising, The aforementioned (D) dye is (D1) Dyes having a triphenylmethane structure, and (D2) Dye having a triphenylmethyl cation structure It includes one or two selected from the group consisting of, The aforementioned (E) antioxidant includes a compound represented by any of the following formulas (E1) to (E3): It is a photosensitive resin composition.

[0014] [ka]

[0015] {In formula (E1), Ar1 is an arylene group having 6 to 12 carbon atoms, and the two R1s are each independently a hydrocarbon group having 1 to 12 carbon atoms, and one or more hydrogen atoms of the hydrocarbon group R1 may be substituted with a hydroxyl group or a halogen atom; In formula (E2), the two Ar2 groups are each independently a group having 6 to 24 carbon atoms and possessing an aromatic ring, and the compound represented by formula (E1) is excluded from (E2); In (E3), n1 is an integer from 0 to 6, n2 is 0 or 1, except when n1 is 1 or greater, n2 is 1, and any multiple R2 and R3 are each independently alkyl groups having 1 to 6 carbon atoms, and R4 is a hydrogen atom, an alkalkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms.

[0016] The photosensitive resin composition of this embodiment may contain (E) an antioxidant and (F) other antioxidants. Furthermore, the photosensitive resin composition of this embodiment may optionally contain any component in addition to components (A) to (E), or components (A) to (F).

[0017] <(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.

[0018] (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.

[0019] (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.

[0020] (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.

[0021] (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.

[0022] (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.

[0023] (A) If the alkali-soluble polymer has structural units derived from alkyl (meth)acrylates substituted with hydroxyl groups, the content thereof may be 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% 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, 30% by mass or less, or 25% by mass or less.

[0024] (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.

[0025] (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 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, based on the total mass of structural units derived from all monomers contained in (A) the alkali-soluble polymer.

[0026] (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.

[0027] (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, or 5% by mass or more, and may be 50% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less, based on the total mass of structural units derived from all monomers contained in the alkali-soluble polymer (A).

[0028] (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.

[0029] (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).

[0030] In the photosensitive resin composition of this embodiment, (A) the alkali-soluble polymer is particularly, (a1) It may have a structural unit derived from (meth)acrylic acid as an unsaturated acid monomer and (a3) ​​a structural unit derived from an alkyl (meth)acrylate substituted with a hydroxyl group. (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.

[0031] (A) For alkali-soluble polymers, the weight-average molecular weight in polystyrene terms, as measured by gel permeation chromatography, may be 5,000 or more, 10,000 or more, 15,000 or more, or 20,000 or more, and may be 100,000 or less, 80,000 or less, 60,000 or less, 50,000 or less, or 45,000 or less.

[0032] (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.

[0033] 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.

[0034] 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.

[0035] (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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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, 25% by mass or more, or 30% 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 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.

[0042] (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.

[0043] 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 0.40 or more, 0.50 or more, 0.60 or more, or 0.70 or more, and may be 1.0 or less, 0.90 or less, 0.80 or less, or 0.75 or less.

[0044] Specific examples of compounds having an ethylenically unsaturated bond in the photosensitive resin composition of this embodiment include, but are not limited to, the following. A polyethylene glycol dimethacrylate (product name "BPE-500") in which an average of 5 moles of EO are added to each end of a bisphenol A molecule. Hexamethacrylate of polyethylene glycol with a total of 13 moles of EO attached to the six ends of dipentaerythritol; Tetramethacrylate, in which a total of 9 moles of EO are attached to each of the four ends of pentaerythritol; Dodecapropylene glycol dimethacrylate; Dimethacrylate of polyalkylene glycosides, in which an average of 2 moles of PO and an average of 6 moles of EO are attached to each end of bisphenol A; Epoxy acrylate (product name "EA-1020" above); 4-Nonylphenyl-heptaethylene glycol;-Dipropylene glycol acrylate; etc. In the above, "EO" is an abbreviation for ethylene oxide, and "PO" is an abbreviation for propylene oxide. Furthermore, the number of alkylene glycols such as EO or PO added indicates the average number per mole of the compound.

[0045] (C) Photopolymerization 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.

[0046] Examples of (C) photopolymerization initiators in the photosensitive resin composition of this embodiment include biimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, coumarin derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, halogen compounds, etc., and one or more selected from these may be used.

[0047] 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.

[0048] 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; Examples of aromatic ketone compounds include benzophenone, Michla's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone; Each of these may be listed, and one or more of the above may be used for each.

[0049] Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 10-phenyl-9-anthraceneboronic acid, etc., and one or more selected from these may be used.

[0050] 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;

[0051] 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; Examples of pyrazoline derivatives 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;

[0052] 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.

[0053] 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 10.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.5% by mass or less, or 6.0% by mass or less.

[0054] In the photosensitive resin composition of this embodiment, the (C) photopolymerization initiator preferably contains a biimidazole compound. In this case, (C) the photopolymerization initiator may consist only of a biimidazole compound, or it may contain a biimidazole compound and a photopolymerization initiator other than a biimidazole compound. In the latter case, the photopolymerization initiator other than the biimidazole compound preferably contains a compound that has the function of promoting the generation of radicals of other components by irradiation with light (active light such as ultraviolet rays), and more preferably contains one or more selected from the group consisting of pyrazoline derivatives, coumarin derivatives, and anthracene derivatives.

[0055] The content of the biimidazole compound may be 50% by mass or more, 70% by mass or more, 80% by mass or more, or 85% by mass or more, based on the total mass of the (C) photopolymerization initiator, and may be 100% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less.

[0056] <(D) Dye> The (D) dye in the photosensitive resin composition of this embodiment is (D1) Dyes having a triphenylmethane structure, and (D2) Dye having a triphenylmethyl cation structure It includes one or two types selected from the group consisting of the following.

[0057] These dyes are incorporated into the photosensitive resin composition of this embodiment for the purpose of improving the expression of hue contrast before and after exposure, visibility during foreign object inspection, and other handling characteristics. (D1) The dye having a triphenylmethane structure is incorporated into the photosensitive resin composition of this embodiment in the form of a decolorized material that does not absorb in the visible light region. However, during storage, heat, light, or other stimuli may generate radicals, acids, bases, or other reactive substances caused by additives in the dry film or oxygen molecules in the atmosphere. In this case, the (D1) dye, which is originally a decolorized material, may undergo a structural change through reaction with the above-mentioned reactive substances and be converted into a chromogenic material that absorbs in the visible light region. On the other hand, the dye having a (D2) triphenylmethyl cation structure is incorporated into the photosensitive resin composition of this embodiment in the form of a chromogenic material that absorbs in the visible light region. However, during storage, reactive substances may be generated due to the same stimuli as described above. In this case, the (D2) dye, which is originally a chromogenic material, may undergo a structural change through reaction with the reactive substance and be converted into a dechromogenic material that does not absorb in the visible light region.

[0058] Therefore, a photosensitive resin composition containing one or two selected from the group consisting of (D1) dye and (D2) dye may change in hue during storage. If the hue of a photosensitive resin composition changes, it can not only impair the appearance of the composition but also potentially affect its photosensitive properties. In this embodiment, the photosensitive resin composition contains (E) an antioxidant compound with a specific structure, which suppresses the generation of the above-mentioned reactive substances and (D) suppresses the change in hue of the composition due to structural changes of the dye.

[0059] (D1) Examples of dyes having a triphenylmethane structure include leucocrystal violet, leucomalachite green, leucocrystal violet lactone, and the leuco form of compounds corresponding to (D2) dyes. One or more selected from these may be used. Leucocrystal violet is preferred as the (D1) dye. (D2) Examples of dyes having a triphenylmethyl cation structure include Diamond Green, Crystal Violet, Basic Blue 7, Coomassie Brilliant Blue, Green S, Diamond Green, Thymol Blue, Fast Green FCF, Phenolsulfonphthalein, Fuchsin, Brilliant Blue FCF, Malachite Green, Methyl Blue, New Fuchsin (Basic Violet 2), Pararosalinine (Pararoseaniline), etc., and one or more selected from these may be used. (D2) Diamond Green is preferred as the dye.

[0060] The photosensitive resin composition of this embodiment may contain both the (D1) dye and the (D2) dye, and in particular, it may contain leucocrystal violet as the (D1) dye and diamond green as the (D2) dye.

[0061] If the photosensitive resin composition of this embodiment contains a dye having a (D1) triphenylmethane structure, the amount thereof may be 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, or 0.4% by mass or more, based on the mass of the total solids of the photosensitive resin composition, and may be 1.2% by mass or less, 1.0% by mass or less, 1.0% by mass or less, 0.8% by mass or less, or 0.6% by mass or less. If the photosensitive resin composition of this embodiment contains a dye having a (D2) triphenylmethyl cation structure, the amount thereof may be 0.01% by mass or more, 0.02% by mass or more, or 0.03% by mass or more, and may be 0.10% by mass or less, 0.08% by mass or less, or 0.05% by mass or less, based on the mass of the total solids of the photosensitive resin composition.

[0062] (E) Antioxidants In this embodiment, (E) the antioxidant includes a compound represented by any of the following formulas (E1) to (E3). (E) The antioxidant has the function of suppressing the generation of radicals and other reactive substances that occur during storage, and (D) suppressing discoloration of the components. More specifically, (E) the antioxidant is thought to reduce the hue change of (D) the pigment by capturing radicals generated in the composition through the action of nitrogen atoms bonded to the aromatic ring, thereby suppressing unwanted reactions between the reactive radicals and (D) the pigment.

[0063] [ka] {In formula (E1), Ar1 is an arylene group having 6 to 12 carbon atoms, and the two R1s are each independently a hydrocarbon group having 1 to 12 carbon atoms, and one or more hydrogen atoms of the hydrocarbon group R1 may be substituted with a hydroxyl group or a halogen atom; In formula (E2), the two Ar2 groups are each independently a group having 6 to 24 carbon atoms and possessing an aromatic ring, and the compound represented by formula (E1) is excluded from (E2); In (E3), n1 is an integer from 0 to 6, n2 is 0 or 1, except when n1 is 1 or greater, n2 is 1, and any multiple R2 and R3 are each independently alkyl groups having 1 to 6 carbon atoms, and R4 is a hydrogen atom, an alkalkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms.

[0064] In formula (E1), Ar1 is an arylene group having 6 to 12 carbon atoms. Examples of such arylene groups include phenylene (-C6H4-), trilene (-C6(CH3)H3-), xylylene (-C6(CH3)2H2-), and naphthylene (-C 10 H6-), methylnaphthylene group (-C 10 Examples include (CH3)H5-). Of these, a phenylene group is preferred as Ar1. That is, the compound represented by formula (E1) may be the compound represented by the following formula (E-1).

[0065] [ka]

[0066] {In equation (E1-1), R1 has the same meaning as R1 in equation (E1) above.}

[0067] The two R1 groups in formula (E1-1) are each independently a hydrocarbon group having 1 to 12 carbon atoms, and one or more hydrogen atoms of the hydrocarbon group R1 may be substituted with a hydroxyl group or a halogen atom. Examples of R1 include an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and the following formula (R);

[0068] [ka]

[0069] {In formula (R), R9 is a hydrogen atom or a methyl group, R 10 is an alkylene group having 1 to 6 carbon atoms, which may be substituted with a hydroxyl group, and n is an integer from 0 to 6. Examples include groups represented by}.

[0070] Examples of the aryl group having 6 to 12 carbon atoms in R1 of formula (E1-1) include phenyl, tolyl, xylyl, mesityl, juryl, and naphthyl groups, of which phenyl, 1-naphthyl, or 2-naphthyl groups are preferred. In formula (E1-1), the C1-C12 alkyl group R1 may be linear or branched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. When these alkyl groups have 3 or more carbon atoms, 2-alkyl groups are preferred. Examples of such alkyl groups include 2-propyl, 2-butyl, 2-(4-methyl)pentyl, 2-hexyl, and 2-octyl groups.

[0071] In formula (E1-1), R1 is represented by the above formula (R), and R9 is preferably a methyl group. 10 Preferably, the group is a hydroxyalkylene group having 2 to 6 carbon atoms. Specifically, with the carbon atom at position 1 being the side that bonds with the N atom, examples include a 2-hydroxyethylene group, a 2-hydroxypropylene group, a 3-hydroxypropylene group, or a 2-hydroxybutylene group, a 3-hydroxybutylene group, a 4-hydroxybutylene group, etc. In the group represented by the above formula (R), n is preferably 0 or 1. Furthermore, in formula (E1-1), if one of the two R1 groups is a group represented by formula (R), it is preferable that the other group is not a group represented by formula (R).

[0072] In formula (E1-1), the two R1NH- groups may be in the ortho, meta, or para positions relative to each other, but it is preferable that they be in the para positions relative to each other. Examples of compounds represented by formula (E1-1) include, for example, the compounds represented by the following formulas (E1-1-1) to (E1-1-9).

[0073] [ka]

[0074] [ka]

[0075] In formula (E2), the two Ar2 groups are each independently a group with 6 to 24 carbon atoms that has an aromatic ring. However, the compound represented by formula (E1) above is excluded from (E2). Groups having an Ar2 aromatic ring include, for example, the phenyl group (C6H5-) and the naphthyl group (C6H5-). 10 Examples include H7-). These phenyl and naphthyl groups may be substituted with alkyl or aralkyl groups. The compound represented by formula (E2) may be the compound represented by (E2-1) or (E2-2).

[0076] [ka]

[0077] In formulas (E2-1) and (E2-2), R5 to R7 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0078] In formula (E2-1), the C1-C12 alkyl group R5 may be linear or branched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of aralkyl groups with 7 to 12 carbon atoms in R5 of formula (E2-1) include methylphenyl group, ethylphenyl group, propylphenyl group, etc., with 2-(2-phenyl)propyl group, 2-(1-phenyl)propyl group, etc. being preferred. In (E2-1), the two R5 atoms may both be hydrogen atoms. However, it is preferable that the two R5 atoms are not both hydrogen atoms. In formula (E2-1), the two R5 atoms may be in the ortho, meta, or para position relative to the N atom, but it is preferable that they be in the para position. Examples of compounds represented by formula (E2-1) include, for example, the compounds represented by the following formulas (E2-2-1) to (E2-1-4).

[0079] [ka]

[0080] In formula (E2-2), the C1-C12 alkyl groups R6 and R7 may be linear or branched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of aralkyl groups with 7 to 12 carbon atoms in R6 and R7 of formula (E2-2) include methylphenyl group, ethylphenyl group, propylphenyl group, and the like. Specifically, examples of compounds represented by formula (E2-2) include the compound represented by the following formula (E2-2-1).

[0081] [ka]

[0082] In formula (E3), the C1-C6 alkyl groups R2 and R3 may be linear or branched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of alkoxyl groups having 1 to 12 carbon atoms in R2 and R3 of formula (E3) include methoxyl, ethoxyl, and propoxyl groups. R2 and R3 are preferably alkyl groups having 1 to 6 carbon atoms, and in particular, methyl groups or t-butyl groups are preferred. Examples of alkoxyl groups with 1 to 12 carbon atoms for R4 include methoxyl, ethoxyl, and propoxyl groups. When R4 is an alkoxyl group, it is preferably located at position 6 of the dihydroquinoline ring. Examples of compounds represented by formula (E3) include those represented by the following formulas (E3-1) or (E3-2).

[0083] [ka] {In equations (E3-1) and (E3-2), R2 to R4 have the same meaning as R2 to R4 in equation (E3), respectively, and n1 is an integer between 0 and 2.}

[0084] Examples of compounds represented by formula (E3-1) include, for example, the compounds represented by the following formulas (E3-1-1) and (E3-1-2).

[0085] [ka]

[0086] Examples of compounds represented by formula (E3-2) include, for example, the compounds represented by the following formulas (E3-2-1) to (E3-2-3).

[0087] [ka]

[0088] The content of (E) antioxidant in the photosensitive resin composition of this embodiment may be 0.001% by mass or more and 0.1% by mass or less with respect to the total mass of solids in the photosensitive resin composition. If the content of (E) antioxidant is 0.001% by mass or more with respect to the total mass of solids in the photosensitive resin composition, the photosensitive resin composition can be given sufficiently high hue stability. On the other hand, if the content of (E) antioxidant is 0.1% by mass or less with respect to the total mass of solids in the photosensitive resin composition, the effect on the photosensitive properties of the dry film is small and sufficiently high resolution performance can be maintained. The content of (E) antioxidant in the photosensitive resin composition of this embodiment may be, for example, 0.003% by mass or more, 0.003% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.015% by mass or more, 0.02% by mass or more, 0.03% by mass or more, or 0.05% by mass or more, relative to the total mass of the solids of the photosensitive resin composition, and may be, for example, 0.09% by mass or less, 0.08% by mass or less, 0.07% by mass or less, or 0.06% by mass or less.

[0089] (F) Other antioxidants The photosensitive resin composition of this embodiment may contain (F) other antioxidants in addition to (E) antioxidants described above. Examples of (F) other antioxidants include compounds having two or more phenolic hydroxyl groups, nitroso compounds, compounds having a phenothiazine skeleton, compounds having a phenoxazine skeleton, alkylene oxide compounds having a glycidyl group, sulfur-based antioxidants (excluding compounds having a phenothiazine skeleton), and one or more selected from these may be included.

[0090] Examples of compounds having two or more phenolic hydroxyl groups include hydroquinone, t-butylcatechol, and pyrogallol. Examples of nitroso compounds include N-nitrosodiphenylamine, nitrosophenylhydroxyamine aluminum salt (for example, an aluminum salt with 3 moles of nitrosophenylhydroxylamine added), diphenylnitrosamine, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0091] Examples of compounds having a phenothiazine skeleton include phenothiazines. Examples of compounds having a phenoxazine skeleton include phenoxazine.

[0092] Examples of alkylene oxide compounds having a glycidyl group include hydrogenated bisphenol A diglycidyl ether (e.g., manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 4000"), neopentyl glycol diglycidyl ether (e.g., manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 1500NP"), nonaethylene glycol diglycidyl ether (e.g., manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 400E"), bisphenol A-propylene oxide 2 molar adduct diglycidyl ether (e.g., manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 3002"), and 1,6-hexanediol diglycidyl ether (e.g., manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 1600"). Compounds containing a phenothiazine skeleton are excluded from sulfur-based antioxidants. Examples of sulfur-based antioxidants include 3-laurylthiopropionic acid, 3,3'-thiodipropionic acid dilauryl, 2-mercaptobenzimidazole, and pentaerythritol tetrakis[3-laurylthiopropionate].

[0093] (F) Other antioxidants include one or more selected from the group consisting of compounds having two or more phenolic hydroxyl groups, nitroso compounds, compounds having a phenothiazine skeleton, and compounds having a phenoxazine skeleton.

[0094] The content of (F) other antioxidants in the photosensitive resin composition of this embodiment may be 0.5% by mass or less with respect to the total mass of the solid content of the photosensitive resin composition. When (F) or other antioxidants are added to the photosensitive resin composition of this embodiment, if the content is 0.001% by mass or more relative to the total mass of solids in the photosensitive resin composition, the effect of adding (F) or other antioxidants will be realized, and the hue stability of the photosensitive resin composition will be further improved. On the other hand, if the content of (F) or other antioxidants is 0.5% by mass or less relative to the total mass of solids in the photosensitive resin composition, the effect on the photosensitive properties of the composition will be small, and it will be suitable for use in pattern forming applications.

[0095] The content of (F) other antioxidants in the photosensitive resin composition of this embodiment (total content if two or more types of (F) other antioxidants are included) may be 0.003% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and may be 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, or 0.1% by mass or less, based on the total mass of the solids of the photosensitive resin composition.

[0096] <Optional ingredients> The photosensitive resin composition of this embodiment may contain any optional components in addition to components (A) to (E) or components (A) to (F). The optional component may be one or more selected from, for example, adhesion promoters, plasticizers, rust inhibitors, solvents, etc.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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; These are some examples.

[0101] 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.

[0102] 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."

[0103] <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.

[0104] 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.

[0105] 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.

[0106] <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.

[0107] 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.

[0108] <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.

[0109] <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].

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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].

[0115] 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.

[0116] 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.

[0117] The photosensitive resin composition layer after exposure is then developed. Here, the photosensitive resin composition layer after exposure may be heated before development. The heating temperature is preferably 30 to 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By performing this heating, further improvements in resolution and adhesion are possible. For heating, for example, a heating furnace using hot air, infrared, or far-infrared 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.

[0118] 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.

[0119] 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]

[0120] 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.

[0121] <Manufacturing of alkali-soluble polymers (A-1) and (A-2)> 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.

[0122] 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.

[0123] 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 alkali-soluble polymers (A-1) and (A-2) were obtained, respectively. The weight-average molecular weights of the alkali-soluble polymers (A-1) and (A-2), measured by gel permeation chromatography (GPC) and converted to polystyrene equivalents, are shown in 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"

[0124] [Table 1]

[0125] Example 1 (1) Preparation of a compounding solution for forming a photosensitive resin composition layer (A) As an alkali-soluble polymer, 40 parts by mass of the alkali-soluble polymer (A-1) manufactured above, and Alkali-soluble polymer (A-2) 15 parts by mass; (B) Compounds having an ethylenically unsaturated bond, 25 parts by mass of polyethylene glycol dimethacrylate (component B-1, manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "BPE-500"), in which an average of 5 moles of ethylene oxide are added to each end of bisphenol A. 5 parts by mass of tetramethacrylate (component B-2) obtained by adding an average of 9 moles of ethylene oxide to pentaerythritol, and 5 parts by mass of polyethylene glycol hexamethacrylate (component B-3) obtained by adding 13 moles of ethylene oxide to dipentaerythritol; (C) As a photopolymerization initiator, 4 parts by mass of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (component C-1), and 10-Phenyl-9-Anthraceneboronic acid (component C-2) 0.7 parts by mass; (D) As a pigment, 0.4 parts by mass of leucocrystal violet (component D-1), and Diamond Green (component D-2) 0.02 parts by mass; (E) As an antioxidant, N-isopropyl-N'-phenyl-p-phenylenediamine (compound represented by the above formula (E1-1-1), component E-2) 0.002 parts by mass; and As optional components, 0.05 parts by mass of thiolite F-888 (product name, manufactured by Chiyoda Chemical Co., Ltd., adhesion aid (component G-1)), and Ethanol as a solvent The mixture was stirred to prepare a formulation for forming a photosensitive resin composition layer.

[0126] 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.

[0127] (2) 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.

[0128] (3) Evaluation (3-1) Evaluation of hue stability The photosensitive resin composition laminate obtained above was stored for 72 hours at 50°C and a relative humidity of 45-55%RH. The light transmittance (%) before and after storage was measured, and the rate of change (%pt) was investigated and evaluated according to the following criteria. The rate of change in light transmittance was evaluated for two types of UV light with wavelengths of 600nm and 630nm. A: When the difference in light transmittance (%) before and after storage is within 5%pt (excellent hue stability) B: When the difference in light transmittance (%) before and after storage exceeds 5%pt but is within 10%pt (good hue stability) C; When the difference in light transmittance (%) before and after storage exceeds 10%pt (poor hue stability) Note that "%pt" (percent point) is a unit that represents the difference between two numbers expressed in percentage (%).

[0129] The light transmittance of the photosensitive resin composition laminate was measured using a spectrophotometer, model "U-3010," manufactured by Hitachi High-Technologies Corporation. A polyethylene terephthalate film of the same type as the support film of the laminate was used as a reference, and measurements were taken in the wavelength range of 300 to 700 nm under conditions of a slit width of 4 nm and a scan speed of 600 nm / min.

[0130] (3-2) Evaluation of resolution (3-2-1) 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.

[0131] (3-2-2) 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. (3-2-3) Exposure Two hours after lamination, evaluation substrates were directly exposed using a direct imaging exposure machine (manufactured by Oak Manufacturing Co., Ltd., model "FDi-3") with a predetermined direct imaging (DI) exposure pattern. The drawing patterns used here consisted of 20 different line-space patterns with a line width (L) to space width (S) ratio (L / S) of x / x (x = 1 to 20 μm, varying in 1 μm increments). The exposure amount was set to the optimal exposure amount determined in "(3-2-2) Measurement of Optimal Exposure Amount".

[0132] (3-2-4) 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. (3-2-5) 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.

[0133] (3-2-5) Evaluation of resolution The resist pattern after development was observed using an optical microscope, and the resolution was evaluated according to the following criteria, based on the minimum line width at which the line portions (exposed areas) were free from meandering and missing sections, and the space portions (unexposed areas) were completely removed without residue. A: When the resolution is 6 μm or less (good resolution) C: When the resolution is greater than 6 μm (poor resolution)

[0134] Examples 2-15 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. The evaluation results are shown in Tables 2-4.

[0135] [Table 2]

[0136] [Table 3]

[0137] [Table 4]

[0138] The abbreviations for the components in Tables 2-4 have the meanings shown in Table 5. [Table 5]

[0139] As shown in the table above, the photosensitive resin compositions of Comparative Examples 1 to 6, which belong to the prior art, failed to achieve both high resolution and hue stability at wavelengths of 600 nm and 630 nm. In contrast to these, it was found that the photosensitive resin compositions of Examples 1 to 18, which are specific examples of the present invention, can satisfy both of these requirements.

Claims

1. (A) Alkali-soluble polymer, (B) Compounds having an ethylenically unsaturated bond, (C) Photopolymerization initiator, (D) Dyes, and (E) Antioxidants A photosensitive resin composition comprising, The aforementioned (D) dye is (D1) Dyes having a triphenylmethane structure, and (D2) Dye having a triphenylmethyl cation structure It includes one or two selected from the group consisting of, The aforementioned (E) antioxidant includes a compound represented by any of the following formulas (E1) to (E3): Photosensitive resin composition. 【Chemistry 1】 {In formula (E1), Ar １ This is an arylene group with 6 to 12 carbon atoms, and there are two R １ Each of these is independently a hydrocarbon group having 1 to 12 carbon atoms, and R １ One or more hydrogen atoms of the hydrocarbon group may be substituted by a hydroxyl group or a halogen atom; In equation (E2), there are two Ar ２ Each of these is independently a group having 6 to 24 carbon atoms and an aromatic ring, and the compound represented by formula (E1) is excluded from (E2); (E3) In (E3), n1 is an integer from 0 to 6, and n2 is 0 or 1, provided that when n1 is 1 or greater, n2 is 1, and there are multiple R ２ , and R ３ Each of these is an alkyl group having 1 to 6 carbon atoms, and R ４ This is a hydrogen atom, an alkalkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms.

2. The photosensitive resin composition according to claim 1, wherein the compound represented by formula (E1) is the compound represented by the following formula (E-1). 【Chemistry 2】 {In formula (E1), R １ has the same meaning as R １ in the said formula (E1).}{

3. In the above formula (E-1), R １ The photosensitive resin composition according to claim 2, wherein each is independently an aryl group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a group represented by the following formula. 【Transformation 3】 {In the above formula, R ９ R is a hydrogen atom or a methyl group, １０ This is a group represented by}, where n is an alkylene group having 1 to 6 carbon atoms, which may be substituted with a hydroxyl group, and n is an integer from 0 to 6.

4. The photosensitive resin composition according to claim 1, wherein the compound represented by formula (E2) is a compound represented by the following formula (E2-1) or (E2-2). 【Chemistry 4】 In equations (E2-1) and (E2-2), R ５ ~R ７ Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C7-C12 aralkyl group.

5. The photosensitive resin composition according to claim 1, wherein the compound represented by formula (E3) is a compound represented by the following formula (E3-1) or (E3-2). 【Transformation 5】 {In formulas (E3-1) and (E3-2), R ２ ~R ４ These are, respectively, R in formula (E3) above. ２ ~R ４ This has the same meaning, and n1 is an integer between 0 and 2.

6. The photosensitive resin composition according to claim 1, wherein the (D) dye comprises both the (D1) dye and the (D2) dye.

7. The photosensitive resin composition according to claim 1, wherein the content of the antioxidant (E) is 0.001% by mass or more and 0.1% by mass or less with respect to the total mass of the solids of the photosensitive resin composition.

8. The aforementioned (D) dye is The (D1) dye includes leucocrystal violet, The (D2) dye includes diamond green, A photosensitive resin composition according to any one of claims 1 to 7.

9. A photosensitive resin composition according to any one of claims 1 to 7, further comprising one or more antioxidants selected from the group consisting of compounds having two or more phenolic hydroxyl groups, nitroso compounds, compounds having a phenothiazine skeleton, and compounds having a phenoxazine skeleton.

10. The photosensitive resin composition according to any one of claims 1 to 7, wherein the alkali-soluble polymer (A) has structural units derived from (meth)acrylic acid and structural units derived from hydroxyalkyl (meth)acrylate.

11. 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 7. A laminate of a photosensitive resin composition.

12. 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 7. A method for forming a resist pattern.

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