Photosensitive Resin Composition and Method for Forming Resist Pattern

Abstract

To provide a photosensitive resin composition having high photosensitivity, high adhesion of the resulting resist pattern to a substrate, and excellent storage stability. 【Solution means】A photosensitive resin composition containing (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 based on the total mass of the solid content of the photosensitive resin composition, (D) the sensitizer contains specific compounds typified by coumarin 1, coumarin 102, etc., and (E) the polymerization inhibitor contains (E1) a first polymerization inhibitor which is a nitroso compound and (E2) a second polymerization inhibitor other than the nitroso compound.

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 a photolithography method. 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 treatment or a plating treatment 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] For 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

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, there has been a tendency to increase the content of the polymerization initiator contained in the composition. When the content of the polymerization initiator in the photosensitive resin composition increases, the photosensitivity and adhesion are certainly 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, coatability, etc., and may also affect the photosensitive properties.

[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 (D) sensitizer contains a compound represented by the following general formula (D1), and the (E) polymerization inhibitor is (E1) a first polymerization inhibitor that is a nitroso compound, and (E2) a second polymerization inhibitor other than a nitroso compound and includes a photosensitive resin composition. [Chemical formula] {In formula (D1), R1 to R3 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. When R1 and R2 are alkyl groups, their terminals may each be bonded to the 6-position carbon or 8-position carbon of the coumarin skeleton to form a heterocyclic ring containing nitrogen.} <<Aspect 2>> The content of the (C) photoinitiator is 5.5 parts by mass or more and 8.0 parts by mass or less with respect to a total of 100 parts by mass of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond. The photosensitive resin composition according to aspect 1. <<Aspect 3>> The content of the (C) photoinitiator is 5.5 parts by mass or more and 7.0 parts by mass or less with respect to a total of 100 parts by mass of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond. The photosensitive resin composition according to aspect 2. <<Aspect 4>> When the content of the (C) photoinitiator with respect to a total of 100 parts by mass of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond is Wc (parts by mass), and the content of the (D) sensitizer is W D (parts by mass), the ratio W D of the content Wc of the (C) photoinitiator to the content W C of the (D) sensitizer is 12.0 or more. The photosensitive resin composition according to any one of aspects 1 to 3. D <<Aspect 5>> The (E2) second polymerization inhibitor contains a phenolic polymerization inhibitor. The photosensitive resin composition according to any one of aspects 1 to 4. ​Aspect 6: The photosensitive resin composition according to any one of Aspects 1 to 5, wherein the (E2) second polymerization inhibitor contains 4-t-butylcatechol. Aspect 7: The photosensitive resin composition according to any one of Aspects 1 to 6, wherein the compound represented by the formula (D1) is a compound represented by the following formula (D1-1). [Chemical formula] Aspect 8: The photosensitive resin composition according to any one of Aspects 1 to 7, wherein the (D) sensitizer further contains a compound having a skeleton selected from the group consisting of anthracene, triarylamine, dialkylbenzophenone, oxazole, pyrazoline, and coumarin (excluding the compound represented by the formula (D1)). Aspect 9: The photosensitive resin composition according to Aspect 8, wherein the (D) sensitizer further contains 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). [Chemical formula] {In the formula (D2), R4 and R5 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.} Aspect 11: The photosensitive resin composition according to any one of Aspects 1 to 10, wherein the (A) alkali-soluble polymer contains a structural unit derived from styrene in a range of 35% by mass or more and 75% by mass or less based on the total mass of the structural units derived from all the monomers contained in the (A) alkali-soluble polymer. Aspect 12: The photosensitive resin composition according to Aspect 11, wherein the (A) alkali-soluble polymer contains a structural unit derived from styrene in a range of 40% by mass or more and 75% by mass or less based on the total mass of the structural units derived from all the monomers contained in the (A) alkali-soluble polymer. 《Aspect 13》The photosensitive resin composition according to any one of Aspects 1 to 12, wherein the (A) alkali-soluble polymer contains a structural unit derived from hydroxyethyl (meth) acrylate. 《Aspect 14》A photosensitive resin composition laminate comprising a support film and a photosensitive resin composition layer on the support film, wherein the photosensitive resin composition layer is a layer composed of the photosensitive resin composition according to any one of Aspects 1 to 13. Photosensitive resin composition laminate. 《Aspect 15》Laminating a photosensitive resin composition layer on a substrate; Exposing the photosensitive resin composition layer; and Developing the exposed photosensitive resin composition layer; A method for forming a resist pattern, comprising: wherein the photosensitive resin composition layer is a layer composed of the photosensitive resin composition according to any one of Aspects 1 to 13. Method for forming a resist pattern.

Advantages of the Invention

[0010] According to the present invention, there are provided a photosensitive resin composition having high photosensitivity, high adhesion of the resulting resist pattern to a substrate, and excellent storage stability, and a method for forming a resist pattern using the same.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Throughout this specification, when a plurality of structures represented by the same reference numeral in a general formula are present in one molecule, they may be the same as or different from each other. The present invention is not limited to the following embodiments, and various modifications may be made within the scope of the gist thereof.

[0012] 《Photosensitive Resin Composition》 The photosensitive resin composition of the present embodiment is (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 (D) sensitizer contains a compound represented by the following general formula (D1), and The (E) polymerization inhibitor (E1) A first polymerization inhibitor which is a nitroso compound, and (E2) A second polymerization inhibitor other than a nitroso compound containing: A photosensitive resin composition.

[0013] [Chemical formula]

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

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

[0016] 〈(A) Alkali-soluble polymer〉 The (A) alkali-soluble polymer contained in the photosensitive resin composition of this embodiment refers to a polymer that dissolves in an alkaline aqueous solution. (A) The alkali-soluble polymer may be, for example, (a1) Those having a structural unit derived from an unsaturated acidic monomer, It preferably has a structural unit derived from an unsaturated acidic monomer and a structural unit derived from one or more selected from the group consisting of (a2) a styrene derivative, (a3) an alkyl (meth) acrylate substituted with a hydroxyl group, (a4) an alkyl (meth) acrylate, (a5) a (meth) acrylate 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 anhydride having one polymerizable unsaturated group in one molecule. (a1) Examples of the unsaturated acidic monomer 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 the unsaturated acidic monomer, (meth) acrylic acid is particularly preferable.

[0018] (A) The content ratio of the structural unit derived from the (a1) unsaturated acidic monomer in the alkali-soluble polymer may be 5% by mass or more and 100% by mass or less, preferably 10% by mass or more and 50% by mass or less, based on the total mass of the structural units derived from all the monomers contained in the (A) alkali-soluble polymer. From the viewpoint of obtaining a resist pattern excellent in resolution and developability during resist pattern formation and excellent in adhesion to the substrate, it is preferable to adjust the content ratio of the structural unit derived from the (a1) unsaturated acidic monomer within the above range. The content ratio of the structural unit derived from the (a1) unsaturated acidic monomer 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, or 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 according to the above criteria.

[0019] (A) Since the alkali-soluble polymer has a structural unit derived from a (a2) styrene derivative, the heat resistance of the resulting resist pattern can be further improved without impairing other functions. Examples of the (a2) styrene derivative include styrene, oxystyrene, acetoxystyrene, alkylstyrene, halogenoalkylstyrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer, etc. One or more selected from these may be used. As the (a2) styrene derivative, styrene is particularly preferable.

[0020] When the (A) alkali-soluble polymer has a structural unit derived from a (a2) styrene derivative, the content ratio 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 the structural units derived from all the monomers contained in the (A) 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) Alkyl (meth) acrylate substituted with a hydroxyl group is a monomer in which one or more of the hydrogen atoms of the alkyl group of alkyl (meth) acrylate are substituted with a hydroxyl group. (A) Since the alkali-soluble polymer has a structural unit derived from a (a3) alkyl (meth) acrylate substituted with a hydroxyl group, the developability during resist pattern formation and the adhesion of the resulting resist pattern to the substrate can be further improved without impairing other functions. Examples of the (a3) alkyl (meth) acrylate substituted with a hydroxyl group include As the alkyl (meth) acrylate substituted with one hydroxyl group, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc. As the alkyl (meth)acrylate substituted with two hydroxyl groups, for example, glycerin mono (meth)acrylate, etc. are; Each is exemplified, and one or more selected from these may be used. (a3) As the alkyl (meth)acrylate substituted with a hydroxyl group, particularly, hydroxyethyl (meth)acrylate is preferable.

[0022] (A) When the alkali-soluble polymer has a structural unit derived from (a3) alkyl (meth)acrylate substituted with a hydroxyl group, its content ratio 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 the structural units derived from all the monomers contained in (A) the alkali-soluble polymer, 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 the alkyl (meth)acrylate 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) As the alkyl (meth)acrylate, particularly, 2-ethylhexyl (meth)acrylate is preferable.

[0024] (A) When the alkali-soluble polymer has a structural unit derived from (a4) alkyl (meth)acrylate, its content ratio may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total mass of the structural units derived from all the monomers contained in (A) the alkali-soluble polymer, and may be 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less.

[0025] (a5) As the (meth)acrylate having an alicyclic ring or an aromatic ring, Examples of the (meth)acrylate having an alicyclic ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, etc.; Examples of the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.; Each of them may be mentioned, and one or more selected from these may be used. The "dicyclopentanyl" group in the above means a "tricyclo[5.2.1.0 2,6 decane-8-yl" group. As the alkyl (meth)acrylate in (a4), particularly, one or two selected from the group consisting of 2-ethylhexyl (meth)acrylate and benzyl (meth)acrylate are preferable.

[0026] When the alkali-soluble polymer in (A) has a structural unit derived from the (meth)acrylate having an alicyclic ring or an aromatic ring in (a5), its content ratio may be 1% by mass or more, or 3% by mass or more, based on the total mass of the structural units derived from all the monomers contained in the alkali-soluble polymer in (A), and may be 30% by mass or less, 20% by mass or less, or 10% by mass or less.

[0027] Examples of the other monomers in (a6) include 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, etc., and one or more selected from these may be used.

[0028] (A) When the alkali-soluble polymer has a structural unit derived from (a6) other monomers, the content ratio may be 1% by mass or more and 20% by mass or less based on the total mass of the structural units derived from all the monomers contained in the (A) alkali-soluble polymer.

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

[0030] Regarding the (A) alkali-soluble polymer, the weight average molecular weight in terms of polystyrene 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) The alkali-soluble polymer can be synthesized by polymerizing one type of monomer described above or copolymerizing two or more types of monomers. The polymerization or copolymerization may preferably be carried out in a suitable solvent, preferably in the presence of a suitable polymerization initiator. As the solvent, for example, acetone, methyl ethyl ketone, isopropanol, ethanol, etc. can be used. As the polymerization initiator, for example, radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile can be used. The polymerization reaction may be in batch mode or continuous mode.

[0032] In the photosensitive resin composition of this embodiment, as the (A) alkali-soluble polymer, only one type may be used, or two or more types may be mixed and used. As the (A) alkali-soluble polymer, for example, a polymer having structural units derived from (a1) (meth)acrylic acid as an unsaturated acidic monomer, (a2) a styrene derivative, (a3) an alkyl (meth)acrylate substituted with a hydroxyl group, and (a4) an alkyl (meth)acrylate, and a polymer having structural units derived from (a1) (meth)acrylic acid as an unsaturated acidic 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 Mixing and using them are also included in the preferred embodiments of the present invention.

[0033] In the photosensitive resin composition of this embodiment, the content of the (A) alkali-soluble polymer (total content when two or more (A) alkali-soluble polymers are included) is 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 the (A) alkali-soluble polymer within this range, the edge fuse resistance when storing the photosensitive resin composition as a dry film resist can be improved, and the development time when forming a resist pattern can be set within an appropriate range. "Edge fuse resistance" is the performance of suppressing the seepage of the photosensitive resin composition layer from the film end face of the dry film resist, and is a particularly required performance when storing the dry film resist wound in a roll shape.

[0034] 〈(B) Compound having an ethylenically unsaturated bond〉 (B) The compound having an ethylenically unsaturated bond may be a compound containing 1, 2, or 3 or more (for example, 3, 4, 5, or 6) ethylenically unsaturated bonds in one molecule. (B) The ethylenically unsaturated bond in the compound having an ethylenically unsaturated bond is preferably contained in the molecule in the form of (meth)acrylate. Therefore, the (B) compound having an ethylenically unsaturated bond may be, for example, a monofunctional, difunctional, or trifunctional or higher (for example, trifunctional, tetrafunctional, pentafunctional, or hexafunctional) (meth)acrylate compound.

[0035] Examples of the monofunctional (meth)acrylate compound include alkylene oxide-modified phenol (meth)acrylate, alkylene oxide-modified nonylphenol (meth)acrylate, alkylene oxide-modified 2-ethylhexyl (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ω-carboxy-polycaprolactone mono (meth)acrylate, phthalic acid monohydroxyethyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 1-naphthalenemethyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, tetradecyl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-decyl-1-tetradecanyl (meth)acrylate, isobornyl (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. One or more of these may be used.

[0036] Examples of the bifunctional (meth)acrylate compound include alkyldi (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, tetramethylene glycoloxylated (hydrogenated) bisphenol A di (meth)acrylate. One or more of these may be used.

[0037] Examples of commercially available difunctional (meth)acrylate compounds include, for example, 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 Oligo (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 (registered trademark) 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.); Funacryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, FA-240A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Resonac Co., Ltd.); DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel Allnex 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 (above, manufactured by Arkema Co., Ltd.); KAYARAD (registered trademark) NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684 (above, manufactured by Nippon Kayaku Co., Ltd.); etc. can be mentioned.

[0038] Examples of trifunctional or higher functional (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, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, alkylene oxide-modified glycerin tri(meth)acrylate, 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. One or more selected from these may be used.

[0039] Examples of commercially available trifunctional or higher functional (meth)acrylate compounds include NK Ester (registered trademark) A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, A-9550, A-DPH-12E, TPOA-50, NK Oligo (registered trademark) UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Light Acrylate (registered trademark) TMP-A, cPE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.); FA-731A (manufactured by Resona Co., Ltd.); 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 (registered trademark) 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.); etc. can be mentioned.

[0040] In the photosensitive resin composition of this embodiment, the content of the compound (B) having an ethylenically unsaturated bond (total content when two or more compounds (B) having an ethylenically unsaturated bond are included) may be 20% by mass or more, 30% by mass or more, or 40% by mass or more, based on the mass of the total solid content of the photosensitive resin composition, and may be 60% by mass or less, 50% by mass or less, or 45% by mass or less. By setting the content of the compound (B) having an ethylenically unsaturated bond within this range, the tackiness, resolution, and edge fuse resistance of the photosensitive resin composition are further improved.

[0041] The content of the compound (B) having an ethylenically unsaturated bond may be 0.3 times or more, 0.4 times or more, 0.5 times or more, or 0.6 times or more, 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, relative to the content of the alkali-soluble polymer (A).

[0042] As the compound (B) having an ethylenically unsaturated bond in the photosensitive resin composition of this embodiment, it is preferable to include a difunctional or higher (meth)acrylate compound. In this case, only a difunctional or higher (meth)acrylate compound may be used, or a difunctional or higher (meth)acrylate compound may be used in combination with one or more selected from a monofunctional (meth)acrylate compound and a trifunctional or higher (meth)acrylate compound. The ratio of the difunctional (meth)acrylate compound to the total mass of the compound (B) having an ethylenically unsaturated bond may be 0.50 or more, 0.60 or more, 0.70 or more, 0.80, 0.90 or more, or 0.95 or more.

[0043] ≪Component (C): Polymerization initiator≫ The (C) photoinitiator in the photosensitive resin composition of the present embodiment is preferably a compound that generates radicals upon irradiation with light (actinic rays such as ultraviolet rays). The (C) photoinitiator may be a compound that exhibits one or more of the functions of initiating the polymerization of the (B) compound having an ethylenically unsaturated bond by the radicals generated upon light irradiation and promoting the generation of radicals in other components to promote the polymerization of the (B) compound having an ethylenically unsaturated bond.

[0044] Examples of the (C) photoinitiator in the photosensitive resin composition of the present embodiment include biimidazole-based compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, ester compounds of N-aryl amino acids, halogen compounds, etc. One or more selected from these may be used.

[0045] The biimidazole compound may be, for example, a dimer of rofin (2,4,5-triaryl imidazole). Specific examples thereof include, for example, 2-(o-chlorophenyl)-4,5-diphenyl biimidazole (alias: 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-diphenyl biimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl biimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenyl biimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenyl biimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,5-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,6-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4,6-(Trifluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4,5-tetrafluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4,6-tetrafluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4,5,6-pentafluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, etc. may be mentioned, and one or more selected from these may be used.,

[0046] Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc.; Examples of the quinone compound 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-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc.; Each is mentioned, and one or more selected from these may be used respectively., Examples of the aromatic ketone compound include benzophenone. Note that dialkylbenzophenone corresponds to "other sensitizers" among the (D) sensitizers described 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-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, etc.; Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc.; Examples of benzoin compounds and benzoin ether compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc.;

[0048] Examples of dialkyl ketal compounds include benzyl dimethyl ketal, benzyl diethyl ketal, etc.; Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.; Examples of dialkylamino benzoic acid ester compounds include ethyl dimethylamino benzoate, ethyl diethylamino benzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4-(dimethylamino)benzoate, etc.; Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc.; Examples of the acridine compound include 1,7-bis(9,9'-acridinyl)heptane, 9-phenylacridine, etc.;

[0049] Examples of the ester compound of N-aryl amino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, octyl ester of N-phenylglycine, etc.; Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethyl phenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compound, diallyl iodonium compound, etc.; Each is listed, and one or more selected from the above may be used respectively.

[0050] The (C) photoinitiator in the photosensitive resin composition of this embodiment preferably contains a biimidazole-based compound.

[0051] The content of the (C) photoinitiator in the photosensitive resin composition of this embodiment (the total content when two or more (C) photoinitiators 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, and may be 15.0% by mass or less, 12.0% by mass or less, 10.0% by mass or less, or 9.0% by mass or less based on the mass of the total solid content of the photosensitive resin composition.

[0052] 《(D) Sensitizer》 The photosensitive resin composition of this embodiment contains a (D) sensitizer. The (D) sensitizer has a function of promoting the photopolymerization reaction of a compound (B) having an ethylenically unsaturated bond by absorbing the irradiation light during exposure and transmitting its energy to a (C) photoinitiator. The (D) sensitizer in the photosensitive resin composition of this embodiment contains a compound represented by the following general formula (D1). [Chemical formula] {In formula (D1), R1 to R3 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. When R1 and R2 are alkyl groups, their terminals may each be bonded to the 6-position carbon or 8-position carbon of the coumarin skeleton to form a heterocyclic ring containing nitrogen.}

[0053] The alkyl groups of R1 to R3 may be linear or branched. The number of carbon atoms of the alkyl groups of R1 to R3 is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 3. As described above, when R1 and R2 are alkyl groups, their terminals may each be bonded to the 6-position carbon or 8-position carbon of the coumarin skeleton to form a heterocyclic ring containing nitrogen. In this case, the terminal of the alkyl group of R1 may be bonded to the 6-position carbon of the coumarin skeleton, and the terminal of the alkyl group of R2 may be bonded to the 8-position carbon of the coumarin skeleton to form a heterocyclic condensed ring containing nitrogen as a whole. When the terminal of the alkyl group of R1 or R2 is bonded to the 6-position carbon or 8-position carbon of the coumarin skeleton to form a heterocyclic ring containing nitrogen, the number of carbon atoms of 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 (Coumarin 1) represented by the following formula (D1-1) and the compound (Coumarin 102) represented by (D1-2).

[0055] [Chemical formula]

[0056] In the photosensitive resin composition of this embodiment, the (D) sensitizer may contain only the compound represented by the above formula (D1), or may contain other sensitizers together with the compound represented by the above formula (D1). When the (D) sensitizer contains other sensitizers together with the compound represented by the above formula (D1), changes in the absorbance and photosensitivity of the composition in the wavelength region near the exposure wavelength (for example, h-line or i-line) can be made gentle. As a result, fluctuations in photosensitivity due to variations in the exposure wavelength are reduced, making it easier to obtain a photosensitive resin composition with good wavelength dependence. Examples of other sensitizers include compounds having a skeleton selected from the group consisting of anthracene, triarylamine, dialkylbenzophenone, oxazole, pyrazoline, and coumarin (excluding the compound represented by the above formula (D1)), etc., and one or more selected from these may be used.

[0057] Examples of the compound having an anthracene skeleton include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, the compound represented by the following general formula (D2), etc., and one or more selected from these may be used.

[0058]

Chemical formula

[0059] In formula (D2), R4 and R5 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. Examples of the compound represented by the above formula (D2) include, for example, anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, etc. As the compound having an anthracene skeleton, the compound represented by the above formula (D2) is preferable.

[0060] Examples of the compound having a triarylamine skeleton include compounds having a triphenylamine skeleton, and specifically, for example, triphenylamine and the like may be used.

[0061] Examples of the compound having a dialkylbenzophenone skeleton include Michler's ketone (4,4'-bis(dimethylamino)benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, and the like. Examples of the compound having an oxazole skeleton include oxazolone (2-phenyl-4-ethoxymethyleneoxazole-5(4H)-one) and the like. Examples of the compound 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, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, and the like. Each of them may be mentioned, and one or more selected from these may be used respectively.

[0062] From the compounds having a coumarin skeleton as other sensitizers, the compound represented by the above formula (D1) is excluded. Examples of compounds having a coumarin skeleton as other sensitizers include 3-benzoyl-7-diethylaminocoumarin, 3-phenyl-7-(diethylamino)coumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one, ethyl 2,3,6,7-tetrahydro-11-oxo-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinoline-10-carboxylate (Coumarin 314), 3-phenyl-7-(diethylamino)coumarin, 3-trifluoromethyl-7-(dimethylamino)coumarin (Coumarin 152), 3-trifluoromethyl-6-methyl-7-(ethylamino)coumarin (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]quinolin-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. One or more selected from these may be used.

[0063] Other sensitizers in the photosensitive resin composition of this embodiment preferably include a compound having an anthracene skeleton.

[0064] In the photosensitive resin composition of this embodiment, the content of the (D) sensitizer (the total content when two or more (D) sensitizers are included, and the content including other sensitizers when the (D) sensitizer contains other sensitizers) may be 0.10% by mass or more, 0.15% by mass or more, 0.20% by mass or more, 0.25% by mass or more, 0.30% by mass or more, or 0.35% by mass or more, based on the mass of the total solid content of the photosensitive resin composition, and may be 0.80% by mass or less, 0.70% by mass or less, 0.60% by mass or less, 0.50% by mass or less, or 0.40% by mass or less. When the (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, when the content of the (C) photopolymerization initiator is Wc (parts by mass) and the content of the (D) sensitizer is W D (parts by mass), when the content of the (D) sensitizer is W D the ratio W C of the content Wc of the (C) photopolymerization initiator 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) photopolymerization initiator. Therefore, in order to transmit the energy of the light absorbed by the (D) sensitizer to the (C) photopolymerization initiator without loss, the ratio W D of the content Wc of the (C) photopolymerization initiator to the content W of the (D) sensitizer C is preferably larger. D On the other hand, from the viewpoint of the adhesion of the resulting resist pattern to the substrate, there is an appropriate point in the content of the sensitizer. That is, when the content of the sensitizer increases excessively, the amount of light reaching 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 instead.

[0066] From such a viewpoint, (D) the content of the sensitizer is W D The ratio W of the content Wc of the (C) photoinitiator to C / W D is preferably 12.0 or more, and may be 13.0 or more, 13.2 or more, 13.5 or more, 14.0 or more, or 15.0 or more. On the other hand, if the ratio W C / W D is made too large, there will be a (C) photoinitiator that does not enjoy the effect of the (D) sensitizer, and the photosensitivity per unit content of the (C) photoinitiator will rather decrease, and it will not be possible to maintain a good balance between the thermal stability and photosensitivity of the photosensitive resin composition. To avoid this, the ratio W C / W D may be, for example, 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 inhibitor>> The photosensitive resin composition of this embodiment contains an (E) polymerization inhibitor. The (E) polymerization inhibitor has a function of preventing the (B) compound having an ethylenically unsaturated bond from polymerizing unintentionally and improving the thermal stability and resolution of the photosensitive resin composition. The (E) polymerization inhibitor in the photosensitive resin composition of this embodiment includes a first polymerization inhibitor (E1) which is a nitroso compound and a second polymerization inhibitor (E2) other than the nitroso compound. It is considered that the (E1) first polymerization inhibitor mainly contributes to the improvement of the thermal stability of the photosensitive resin composition, and the (E2) second polymerization inhibitor mainly contributes to the improvement of the resolution of the photosensitive resin composition layer. However, the present invention is not restricted by a specific theory.

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

[0069] [Chemical formula]

[0070] {In formula (E1), R 11 represents a hydrocarbon group which may have a substituent, -NHR 12 , or -NR 12 R 13 ; R 12 and R 13 each independently represent a hydrocarbon group which may have a substituent.} R 11 in formula (EI) is, from the viewpoint of fully obtaining the effects of the present embodiment, for example, a saturated or unsaturated, linear or branched chain hydrocarbon group having 1 to 20 carbon atoms (e.g., methyl group, etc.); a saturated or unsaturated, monocyclic or polycyclic cyclic hydrocarbon group having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.); a monocyclic aromatic hydrocarbon group having 6 to 20 carbon atoms (e.g., phenyl group, etc.); an aralkyl group having 7 to 20 carbon atoms (e.g., phenylmethyl group, phenylethyl group, etc.); a condensed polycyclic aromatic hydrocarbon group having 10 to 20 carbon atoms (e.g., naphthyl group, etc.); and -NHR 12 and -NR 12 R 13 {R 12 and R 13 each independently represent a hydrocarbon group which may have a substituent.}; It is preferably one selected from the group consisting of, or a combination of two or more thereof.

[0071] -NHR 12 and -NR 12 R 13 each independently are A saturated or unsaturated, monocyclic or polycyclic cyclic hydrocarbon group having 3 to 20 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.); A monocyclic aromatic hydrocarbon group having 6 to 20 carbon atoms (e.g., phenyl group, etc.); An aralkyl group having 7 to 20 carbon atoms (e.g., phenylmethyl group, phenylethyl group, etc.); and A condensed polycyclic aromatic hydrocarbon group having 10 to 20 carbon atoms (e.g., naphthyl group, etc.); It is preferably one selected from the group consisting of, or a combination of two or more thereof.

[0072] Also, one or more of the hydrogen atoms in R 11 ~R 13 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] As R 11 in formula (E1), a phenyl group, a naphthyl group, an aminophenyl group, a hydroxyphenyl group, a thihydroxyphenyl group, a chlorophenyl group, an aminonaphthyl group, a hydroxynaphthyl group, a thihydroxynaphthyl group, or a chloronaphthyl group is preferred, a phenyl group, a naphthyl group, an aminophenyl group, a hydroxyphenyl group, an aminonaphthyl group, or a hydroxynaphthyl group is more preferred. As R 12 and R 13 in formula (E1), each independently, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a naphthyl group, an aminoalkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a thihydroxyalkyl group having 1 to 10 carbon atoms, a chloroalkyl group having 1 to 10 carbon atoms, an aminophenyl group, a hydroxyphenyl group, a thihydroxyphenyl group, a chlorophenyl group, an aminonaphthyl group, a hydroxynaphthyl group, a thihydroxynaphthyl group, or a chloronaphthyl group is preferred, An alkyl group having 1 to 10 carbon atoms or a phenyl group is more preferable, and a methyl group or a phenyl group is even more preferable.

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

Chemical formula

[0075] {In formula (E1-1), R 12 and R 13 are the same as R 11 in the above formula (E1) when R 12 is -NR 13 R 12 and R 13 .} In the photosensitive resin composition of this embodiment, since the (E) polymerization inhibitor contains the compound represented by the above formula (E1-1), it has excellent photosensitivity and resolution, and the adhesion of the resulting resist pattern is also excellent. 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, etc. One or more selected from these may be used. As the (E1) first polymerization inhibitor, N-nitrosodiphenylamine or 1-nitroso-2-naphthol is preferable from the viewpoints 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 unshared electron pair of an amine is added to a suitable metal atom. In this case, examples of the metal atom include aluminum, cobalt, iron, etc. Examples of the (E1) first polymerization inhibitor in the form of a complex compound include aluminum N-nitroso-N-phenylhydroxylamine, etc.

[0077] The (E2) second polymerization inhibitor in the photosensitive resin composition of this embodiment 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-based polymerization inhibitor, a phenoxazine-based polymerization inhibitor, etc.

[0078] As the phenolic polymerization inhibitor, a phenolic compound having two or more phenolic hydroxyl groups is preferable. Specifically, for example, hydroquinone, catechol, 4-t-butylcatechol, pyrogallol, gallic acid, methyl gallate, etc. can be mentioned. Examples of the phenothiazine-based polymerization inhibitor include phenothiazine. Examples of the phenoxazine-based polymerization inhibitor include phenoxazine. As the (E2) second polymerization inhibitor, 4-t-butylcatechol or phenothiazine is preferable. As the (E2) second polymerization inhibitor in the photosensitive resin composition of this embodiment, one or more selected from the above may be used.

[0079] In the photosensitive resin composition of this embodiment, the content of the (E1) first polymerization inhibitor (the total content when two or more (E1) first polymerization inhibitors are included) is based on the mass of the total solid content of the photosensitive resin composition from the viewpoint of balancing the storage stability of the composition, photosensitivity, and resolution. It 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, 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. In the photosensitive resin composition of this embodiment, the ratio of the content of the compound represented by the above formula (E1-1) to the content of the (E1) first polymerization inhibitor 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 total amount of the (E1) first polymerization inhibitor may be the compound represented by the above formula (E1-1).

[0080] In the photosensitive resin composition of this embodiment, the content of the (E2) second polymerization inhibitor (total content when two or more kinds of (E2) second polymerization inhibitors are included) is, from the viewpoint of balancing the photosensitivity of the composition and the adhesion of the resulting resist pattern to the substrate, based on the mass of the total solid content of the photosensitive resin composition, 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, 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. In the photosensitive resin composition of this embodiment, when the mass of the total solid content of the photosensitive resin composition is 100% by mass, the content W of the (E1) first polymerization inhibitor E1 and the content W of the (E2) second polymerization inhibitor E2 and the ratio W E1 / W E2 may be 0.25 or more, 0.50 or more, 0.60 or more, 0.70 or more, 0.80 or more, or 0.90 or more, and may be 4.00 or less, 3.00 or less, 2.00 or less, 1.50 or less, 1.25 or less, or 1.10 or less.

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

[0082] The dye may be included in the photosensitive resin composition for the purpose of improving handleability such as the expressibility of the hue contrast before and after exposure and the visibility during foreign matter inspection. Examples of the pigment include leuco crystal violet, leuco malachite green, leuco crystal 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), pararosaniline (pararosanilin), etc., and one or more selected from these may be used.

[0083] When the photosensitive resin composition of the present embodiment contains a pigment, its content (total content in the case of containing two or more pigments) 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 the adhesion aid include benzotriazoles, carboxybenzotriazoles, etc., and one or more selected from these may be used. When the photosensitive resin composition of the present embodiment contains an adhesion aid, its content may be 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, or 0.04% by mass or more, and 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 solid content of the photosensitive resin composition.

[0085] Examples of the 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, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole, etc.

[0086] Examples of the 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. Among 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 the 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, polyoxyethylene polyoxypropylene monoethyl ether; phthalic acid esters such as diethyl phthalate; organic acid derivatives such as o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate; polyhydric alcohols such as propylene glycol with propylene oxide added to both ends of bisphenol A and ethylene glycol with ethylene oxide added to both ends of bisphenol A; aluminum salts with 1 to 3 moles of nitrosophenylhydroxylamine added thereto; and the like.

[0088] The content of the plasticizer is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on the mass of the total solid content of the photosensitive resin composition. When this ratio is 1% by mass or more, the delay in development time is likely to be suppressed, and appropriate flexibility is likely to be imparted to the resulting resist pattern. When this ratio is 50% by mass or less, there is a tendency to suppress insufficient curing of the resist pattern and edge fusion of the photosensitive resin composition laminate.

[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 includes a support film and a photosensitive resin composition layer on the support film, wherein the photosensitive resin composition layer is a layer composed of the photosensitive resin composition of this embodiment described above. It is a photosensitive resin composition laminate. In the photosensitive resin composition laminate of this embodiment, a protective film may be further 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 supports the photosensitive resin composition layer in the photosensitive resin composition laminate of this embodiment and has a function of maintaining the shape of the laminate. The support film preferably has transparency to transmit light (for example, actinic rays such as ultraviolet rays) irradiated when exposing the photosensitive resin composition layer.

[0091] Examples of the material of the support film include polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, etc. Among these, polyethylene terephthalate (PET) having appropriate flexibility and strength is preferable. Also, as the support film, it is preferable to use a film with high quality as a film and few internal foreign matters. As high-quality films, specifically, for example, PET films synthesized using titanium (Ti)-based catalysts, PET films with small-diameter lubricants and low lubricant content, PET films containing lubricants only on one side of the film, thin-film PET films, PET films with a smoothing treatment applied to at least one side, PET films with a roughening treatment (such as plasma treatment) applied to at least one side, and the like can be mentioned. The support film may be used after being subjected to 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. Although the smaller the haze of the support film, the more preferable it is, there are no practical problems even if it is 0.01% or more.

[0093] 〈Photosensitive resin composition layer〉 In the photosensitive resin composition laminate of the present embodiment, the photosensitive resin composition layer is a layer composed of the photosensitive resin composition of the present embodiment described above. The thickness of the photosensitive resin composition layer may be 3 μm or more and 200 μm or less, 3 μm or more and 100 μm or less, or 3 μm or more and 50 μm or less. The thinner the thickness of the photosensitive resin composition layer, the higher the resolution tends to be, and the thicker the thickness, the higher the film strength tends to be. The thickness of the photosensitive resin composition layer may be appropriately set according to the application in consideration of the balance between the resolution and the film strength.

[0094] As will be described later, the photosensitive resin layer of the photosensitive resin composition laminate may be formed via a step of coating a coating liquid containing a photosensitive resin composition and a solvent on the support film. In this case, the obtained photosensitive resin layer may contain residual solvent derived from the coating liquid. Examples of the solvent that may be contained in the photosensitive resin layer include ketones typified by methyl ethyl ketone and acetone; alcohols typified by methanol, ethanol, and isopropanol; toluene; and the like. The content of the solvent remaining in the photosensitive resin layer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, based on the mass of the total solid content of the photosensitive resin composition.

[0095] 〈Protective Film〉 The protective film is laminated on the side opposite to the support film in the photosensitive resin composition layer and functions as a cover for the photosensitive resin composition layer. Examples of the material of the protective film include polyethylene, polypropylene, stretched polypropylene, polyester film, and the like. The thickness of the protective film is preferably 10 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or less. A release layer may be formed on the surface of the protective film on the side of the photosensitive resin composition layer so that the protective film can be easily peeled off from the photosensitive resin composition layer. Examples of the material of the release layer include silicone resin, alkyd resin, long-chain alkyl resin, acrylic resin, polyolefin resin, and the like. The thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, and still more preferably 0.01 to 0.5 μm.

[0096] 〈Method for Producing Photosensitive Resin Composition Laminate〉 The photosensitive resin composition laminate of the present embodiment can be produced, for example, by preparing a coating liquid containing the photosensitive resin composition and solvent of the present embodiment; coating the above coating liquid on a support film to form a coating film; removing the solvent from the coating film to form a photosensitive resin composition layer on the support film; and laminating a protective film on the photosensitive resin composition layer. It may be produced by a method including the above steps.

[0097] Examples of the solvent used for preparing the coating liquid include ketones, alcohols, etc. Examples of ketones include acetone, methyl ethyl ketone, etc.; examples of alcohols include methanol, ethanol, isopropanol, etc. It is preferable to adjust the amount of the solvent used so that the solid content concentration of the coating liquid is 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 liquid may be appropriately set within the above range depending on the composition of the photosensitive resin composition, the coating method employed, etc.

[0098] The coating liquid may be applied onto the support film by an appropriate coating apparatus such as a bar coater, a roll coater, etc. Removal of the solvent from the coating film may be performed, for example, by leaving the support film on which the coating film is formed in a dryer adjusted to a predetermined temperature for a predetermined time. The temperature of the dryer may be, for example, 60°C or more, 80°C or more, or 90°C or more, and 150°C or less, 120°C or less, or 100°C or less. 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. Lamination of the protective film onto the photosensitive resin composition layer may be performed according to a conventional method.

[0099] 《Method for Forming a Resist Pattern》 According to still another aspect of the present invention, a method for forming a resist pattern is provided. The method for forming a resist pattern of the present embodiment is laminating a photosensitive resin composition layer on a substrate; exposing the photosensitive resin composition layer; and developing the exposed photosensitive resin composition layer; which is a method for forming a resist pattern, and the photosensitive resin composition layer is a layer composed of the photosensitive resin composition of the present embodiment described above. A method for forming a resist pattern.

[0100] Examples of the material of the substrate on which the resist pattern is formed include copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc. As the substrate, a copper-clad laminate is particularly preferable. If desired, the substrate may be used after surface conditioning. The surface conditioning of the substrate may be performed, for example, by cleaning the substrate with an aqueous solution of H2SO4 having a concentration of about 10% by mass.

[0101] The lamination of the photosensitive resin composition layer on the substrate is, for example, peeling the protective film from the photosensitive resin composition laminate; and thermocompression bonding the photosensitive resin composition of the photosensitive resin composition laminate from which the protective film has been peeled to the substrate surface; may be performed by a method including.

[0102] The thermocompression bonding may be performed, for example, using a laminator equipped with a roll, or may be performed by passing the photosensitive resin composition laminate from which the protective film has been peeled through a roll after laminating it on the substrate surface. The heating temperature during thermocompression bonding can be, for example, 40°C or higher and 160°C or lower, and preferably 80°C or higher and 120°C or lower. The thermocompression bonding may be performed under reduced pressure if desired. The thermocompression bonding operation may be performed only once, or may be performed two or more times. When the thermocompression bonding operation is performed two or more times, a multi-stage laminator equipped with multiple rolls may be used, or a method of passing the laminate of the photosensitive resin composition laminate from which the protective film has been peeled and the substrate through a roll multiple times may also be used.

[0103] The exposure of the photosensitive resin composition layer may be performed, for example, using an exposure machine such as a contact aligner, a mirror projection, or a stepper, through a photomask or reticle having a pattern, 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 peeling off the support film. The exposure method is preferably one or more methods selected from the group consisting of projection exposure method, proximity exposure method, contact exposure method, direct imaging exposure method, and electron beam direct drawing method, and more preferably a projection exposure method or a direct imaging exposure method.

[0104] 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 still more preferably 35 to 120 °C. By performing this heating, further improvement in resolution and adhesion can be achieved. For heating, for example, a heating furnace using hot air, infrared rays, or far-infrared rays; a constant temperature bath; a hot plate; a blow dryer; an infrared dryer; a hot roll, etc. may be used. The heating time is preferably 1 second or more and 300 seconds or less, and more preferably 5 seconds or more and 120 seconds or less.

[0105] The photosensitive resin composition layer after exposure is then developed after optionally undergoing the above-described heating. By development, the unexposed portion of the photosensitive resin composition layer is removed to form a resist pattern. When exposure is performed through a support film, the support film is peeled off before development. Development is performed by bringing the photosensitive resin composition layer after exposure into contact with a developer. The developer may be an alkaline aqueous solution. Specifically, for example, 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 Na2CO3 solution with a concentration of about 0.2% by mass or more and 2% by mass or less is common. In the alkaline aqueous solution as the developer, for example, a surfactant, an antifoaming agent, a small amount of organic solvent for accelerating development, etc. may be added. The temperature of the developer during development is preferably maintained substantially constant at a predetermined temperature selected from the range of 20°C or more and 40°C or less. The developing method may be appropriately selected from known developing methods. For example, it may be appropriately selected from the spin spray method, the paddle method, the dipping method with ultrasonic treatment, etc.

[0106] As described above, a resist pattern can be formed on the substrate. If desired, the obtained resist pattern may be heated. By this heating, the chemical resistance of the resist pattern is further improved. This heating may be performed, for example, at a temperature of 60°C or more and 300°C or less for a time of 1 minute or more and 120 minutes or less. The heating may be performed, for example, using a heating furnace of a type that uses hot air, infrared rays, far-infrared rays, etc.

Examples

[0107] Hereinafter, the present embodiment will be described more specifically by giving examples and comparative examples. However, the present invention is not limited to the following examples, etc.

[0108] 〈Production of Alkaline-Soluble Polymers (A-1) to (A-4)〉 After mixing the monomers of the types and amounts shown in Table 1 and 3.0 parts by mass of azobisisobutyronitrile, stirring was performed to prepare solution (a). A flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube was charged with 200 parts by mass of methyl ethyl ketone and 100 parts by mass of ethanol. While blowing nitrogen gas into this flask and stirring, the liquid temperature was adjusted to 80°C. The liquid temperature was maintained at 80 °C, and while continuously blowing in nitrogen gas and stirring, the total amount of the above solution (a) was added dropwise thereto at a constant dropping rate over 4 hours. With respect to the reaction mixture after completion of the dropping, blowing in nitrogen gas and stirring were continued at 80 °C for an additional 2 hours.

[0109] 0.5 part by mass of azobisisobutyronitrile was added to and dissolved in 50 parts by mass of a mixed solution of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol to prepare solution (b). While maintaining the liquid temperature of the reaction mixture in the above flask at 80 °C and continuously blowing in nitrogen gas and stirring, the total amount of the above solution (b) was added dropwise thereto at a constant dropping rate over 10 minutes. With respect to the reaction mixture after completion of the dropping, blowing in nitrogen gas and stirring were continued at 80 °C for an additional 3 hours. Thereafter, the liquid temperature was raised to 90 °C, and blowing in nitrogen gas and stirring were continued at 90 °C for an additional 2 hours.

[0110] Thereafter, stirring was stopped, and while continuously blowing in nitrogen gas, the liquid temperature was allowed to cool to room temperature (25 °C). By the above operations, solutions containing each of the alkali-soluble polymers (A-1) to (A-4) were obtained. The weight average molecular weights in terms of polystyrene, measured by gel permeation chromatography (GPC), of the alkali-soluble polymers (A-1) to (A-4) are shown in accordance with Table 1. GPC was measured under the following conditions. Measuring device Pump: manufactured by JASCO Corporation, PU-4580 Degasser: manufactured by JASCO Corporation, DG-2080-53 Column oven: manufactured by JASCO Corporation, CO-1560 Columns: manufactured by Resonac Co., Ltd., Shodex (registered trademark) GPC columns, model names "KF-80Y" and "KF-806M" connected in series in this order Eluent: tetrahydrofuran Measuring temperature: 40 °C Flow rate: 2.05 mL / min Detector: manufactured by JASCO Corporation, differential refractometer, model name "RI-1530"

[0111]

Table 1

[0112] Example 1 (1) Blending liquid for forming a photosensitive resin composition layer (1-1) Preparation of the blending liquid for forming a photosensitive resin composition layer (A) As the alkali-soluble polymer, 54 parts by mass of the above-produced alkali-soluble polymer (A-1); (B) As the compound having an ethylenically unsaturated bond, 46 parts by mass of dimethacrylate of polyethylene glycol with an average of 5 moles of ethylene oxide added to both ends of bisphenol A (Component B-1, manufactured by Shin-Nakamura Chemical Co., Ltd., product name "BPE-500"); (C) As the photopolymerization initiator, 6.0 parts by mass of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (Component C-1); (D) As the sensitizer, 0.38 parts by mass of coumarin 1 (7-diethylamino-4-methylcoumarin, the compound represented by the above formula D-1); (E) As the polymerization inhibitor, (E1) 0.01 parts by mass of aluminum N-nitroso-N-phenylhydroxylamine as the first polymerization inhibitor; and (E2) 0.01 parts by mass of 4-t-butylcatechol as the second polymerization inhibitor; and As the dye, 0.4 parts by mass of leuco crystal violet, and 0.03 parts by mass of diamond green were blended and stirred to prepare a blending liquid for forming a photosensitive resin composition layer.

[0113] In the above, the blending amounts are the blending amounts as the solid content of each active ingredient. Also, the blending amount of ethanol was set to an amount such that the solid content concentration of the blending liquid became 60% by mass.

[0114] (1-2) Evaluation of viscosity stability The obtained prepared liquid was filled to the brim in a glass container with a volume of 20 mL, and seven samples sealed so that no air entered were prepared. Of the seven samples, one was immediately subjected to viscosity measurement using an E-type viscometer after preparation, and this measured value was taken as the initial viscosity. The remaining six samples were left standing in an oven whose temperature was adjusted to 50 °C. The samples in the oven were taken out one by one each day from 1 day to 6 days after the start of standing, viscosity measurement was performed, and the shortest number of days when the measured value increased by 2,000 mPa·sec or more with respect to the initial viscosity, or when solidification occurred so that viscosity measurement could not be performed, was examined and evaluated according to the following criteria. A (good): when the number of days required for the occurrence of the viscosity change according to the above criteria was 5 days or more C (bad): when the number of days required for the occurrence of the viscosity change according to the above criteria was less than 5 days

[0115] (2) Photosensitive resin composition laminate (2-1) Production of photosensitive resin composition laminate As a support film, a 16-μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "QS71") was used, and the above-prepared liquid was applied to its surface using a bar coater and left standing in a dryer at 95 °C for 2.5 minutes to remove the solvent. By the above operations, a photosensitive resin composition layer with a thickness of 25 μm was formed on the support film. Next, a 19-μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818") was attached as a protective layer to the surface of the above photosensitive resin composition layer on the side opposite to the support film, thereby obtaining a photosensitive resin composition laminate.

[0116] (2-2) Evaluation of crystal precipitation When producing a photosensitive resin composition laminate, crystal precipitation may be observed in the formed photosensitive resin composition layer. When crystals are generated in the photosensitive resin composition layer, exposure according to a predetermined pattern may be hindered. Therefore, the obtained photosensitive resin composition laminate was visually observed to examine the presence or absence of crystal precipitation in the photosensitive resin composition layer, and evaluated according to the following criteria. A (excellent): When no crystal precipitation was observed at all B (good): When crystal precipitation was observed in a part of the photosensitive resin composition layer C (poor): When crystal precipitation was observed over the entire surface of the photosensitive resin composition layer

[0117] (3) Various evaluations An evaluation substrate was fabricated using the photosensitive resin composition laminate manufactured as described above, exposed, heated, and developed to form a resist pattern, and evaluations of h-line sensitivity, i-line sensitivity, adhesion, resolution, and developability were performed. In each evaluation, the method for fabricating the evaluation substrate, the method for measuring the optimum exposure amount, the exposure amount, the heating method, and the developing method were the same, but for the exposure method, the following methods were adopted respectively according to the evaluation items. h-line sensitivity: Exposure was performed using a direct drawing exposure machine (manufactured by Okou Seisakusho Co., Ltd., model name "FDi-3") with a Stouffer 41-step tablet as a mask. i-line sensitivity: Exposure was performed using a projection exposure apparatus (manufactured by Ushio Electric Inc., model name "UX-23101") with a Stouffer 41-step tablet as a mask. Adhesion, resolution, and developability: Direct exposure was performed using a direct drawing exposure machine (manufactured by Okou Seisakusho Co., Ltd., model name "FDi-3") with a drawing pattern for predetermined direct imaging (DI) exposure.

[0118] (3-1) Formation of resist pattern (3-1-1) Fabrication of evaluation substrate A copper-clad laminate with a total thickness of 0.4 mm formed by laminating a rolled copper foil with a thickness of 18 μm was prepared. The surface of this copper-clad laminate was washed with a 10 mass% H2SO4 aqueous solution and then washed with pure water to level the surface. The surface of the copper-clad laminate after leveling was preheated to 50°C. While peeling off the protective layer of the photosensitive resin composition laminate obtained above on the surface of the copper-clad laminate preheated to 50°C, it was laminated so that the photosensitive resin composition layer was in contact with the surface of the copper-clad laminate to produce a substrate for evaluation. The lamination was carried out using a hot roll laminator (manufactured by Asahi Kasei Corporation, model name "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 optimum exposure amount The substrate for evaluation after 2 hours from lamination was directly exposed with a drawing pattern for predetermined direct imaging (DI) exposure using a direct drawing exposure machine (manufactured by Okou Seisakusho Co., Ltd., model name "FDi-3"). The exposure was carried out using a Stouffer 41-step tablet as a mask, and the exposure amount at which the highest remaining film step number after development was 15 steps was defined as the optimum exposure amount. (3-1-3) Exposure The substrate for evaluation after 2 hours from lamination was exposed by the method predetermined for each evaluation. The exposure amount was the optimum exposure amount determined in "(3-2-2) Measurement of the optimum exposure amount".

[0120] (3-1-4) Heating The substrate for evaluation after 2 minutes from exposure was left standing in a forced-air constant-temperature oven set at 70°C (manufactured by Yamato Scientific Co., Ltd., model name "DKM600") for 30 seconds for heating. (3-1-5) Development After peeling off the support film from the substrate for evaluation after exposure and heating, development was carried out by spraying a 1 mass% Na2CO3 aqueous solution adjusted to 30°C onto the photosensitive resin composition layer using a developing machine for dry film manufactured by Fuji Kiko Co., Ltd., to form a resist pattern on the copper-clad laminate. At this time, the shortest time required for the unexposed portion of the photosensitive resin composition layer to completely dissolve was defined as the shortest development time, and the spray time during development was set to twice the shortest development time.

[0121] (3-2) Evaluation of h-line sensitivity When a direct writing exposure system (manufactured by Oak Manufacturing Co., Ltd., model "FDi-3") was used to expose a Stouffer 41-step tablet as a mask, the maximum number of remaining film steps after development was recorded as the h-ray sensitivity. Here, when the maximum number of remaining film steps was 12.5 or more, the h-ray sensitivity was evaluated as good. (3-3) Evaluation of i-line sensitivity When a projection exposure system (manufactured by Ushio Inc., model number "UX-23101") was used to expose a Stouffer 41-step tablet as a mask, the maximum number of remaining film steps after development was recorded as the i-line sensitivity. Here, when the maximum number of remaining film steps was 12.5 or more, the i-line sensitivity was evaluated as good.

[0122] (3-4) Evaluation of adhesion A resist pattern was obtained by directly exposing a predetermined direct imaging (DI) exposure pattern using a direct imaging exposure machine (manufactured by Oak Manufacturing Co., Ltd., model name "FDi-3"), and the resist pattern was observed at 100x magnification using an optical microscope to check for the presence or absence of pattern folds and defects in the line and space (L / S) = 5 μm / 200 μm and 8 μm / 200 μm regions, and evaluated according to the following criteria. A (Excellent): When neither pattern breakage nor defects were found in both the L / S = 5 μm / 200 μm and 8 μm / 200 μm regions. B (Good): A break or defect in the pattern was confirmed in the L / S = 5 μm / 200 μm region, but neither a break nor a defect in the pattern was confirmed in the 8 μm / 200 μm region. C (Poor): When breaks or defects are found in both the L / S = 5 μm / 200 μm and 8 μm / 200 μm areas

[0123] (3-5) Resolution evaluation Using a direct drawing exposure machine (manufactured by OKU Corporation, model name "FDi-3"), a resist pattern obtained by directly exposing with a drawing pattern for predetermined direct imaging (DI) exposure was observed with an optical microscope at a magnification of 200 times. The horizontal collapse, breakage, and defects of the pattern, and the presence or absence of development residue between the patterns in the regions of line and space (L / S) = 5 μm / 5 μm and 8 μm / 8 μm were examined and evaluated according to the following criteria. A (excellent): When none of the pattern breakage, defects, and development residue between the patterns were confirmed in both the regions of L / S = 5 μm / 5 μm and 8 μm / 8 μm B (good): When pattern breakage or defects, or development residue between the patterns were confirmed in the region of L / S = 5 μm / 200 μm, but none of the pattern breakage, defects, and development residue between the patterns were confirmed in the region of 8 μm / 200 μm C (poor): When pattern breakage or defects, or development residue between the patterns were confirmed in both the regions of L / S = 5 μm / 200 μm and 8 μm / 200 μm

[0124] (3-6) Developability Using a direct drawing exposure machine (manufactured by OKU Corporation, model name "FDi-3"), the shortest development time when directly exposing with a drawing pattern for predetermined direct imaging (DI) exposure was examined and evaluated according to the following criteria. A (excellent): When the shortest development time was 19 seconds or less B (good): When the shortest development time exceeded 19 seconds and was 23 seconds or less C (poor): When the shortest development time exceeded 23 seconds

[0125] 《Examples 2 to 18 and Comparative Examples 1 to 6》 Except that the types and amounts of each component were changed as described in Tables 2 to 4 respectively, a preparation liquid for forming a photosensitive resin composition layer was prepared in the same manner as in Example 1, and various evaluations were performed. (D) The blending amount of the sensitizer was set so that the transmittance of the h-line of the obtained photosensitive resin composition layer would be the same as that in Example 1. The evaluation results are shown in accordance with Tables 2 to 4. Tables 2 to 4 also show the ratio (W D / W C ) of the blending amount (W C ) of the (C) photopolymerization initiator to the blending amount (W D ) of the (D) sensitizer.

[0126] [Table 2]

[0127] [Table 3]

[0128] [Table 4]

[0129] The abbreviations of the components in Tables 2 to 4 have the meanings as shown in Table 5, respectively.

[0130] [Table 5]

[0131] As understood from the above table, the photosensitive resin composition of Comparative Example 1 that does not contain the (C) polymerization initiator specified in this embodiment is inferior in photosensitivity, adhesion, and resolution of the resist pattern; the photosensitive resin compositions of Comparative Examples 2 and 3 that do not contain the (D) sensitizer specified in this embodiment are inferior in h-line sensitivity and i-line sensitivity; the photosensitive resin compositions of Comparative Examples 4 and 5 that do not satisfy the specified aspect of this embodiment that the (E) polymerization inhibitor contains both the (E1) component and the (E2) component are inferior in viscosity stability of the composition (Comparative Example 4) or inferior in adhesion and resolution of the resist pattern (Comparative Example 5); the photosensitive resin composition of Comparative Example 6 in which the blending amount of the (C) photopolymerization initiator does not reach the specified amount in this embodiment was inferior in h-line sensitivity and i-line sensitivity.

[0132] In contrast, the photosensitive resin compositions of Examples 1 to 18 that satisfy all the requirements specified in this embodiment showed excellent results well-balanced in all evaluations. From this, it was verified that by satisfying all the requirements specified in this embodiment, the problems of the present invention are first solved.

Claims

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 comprising: The (C) photopolymerization initiator is one or more selected from 2,4,5-triarylimidazole dimers and acridine compounds, and the content thereof is 5.0% by mass or more based on the total mass of the solid content of the photosensitive resin composition. The (D) sensitizer contains a compound represented by the following general formula (D1), and The (E) polymerization inhibitor is (E1) One or more first polymerization inhibitors selected from a compound represented by the following general formula (E1-1) and aluminum N-nitroso-N-phenylhydroxylamine, and (E2) One or more second polymerization inhibitors selected from phenolic polymerization inhibitors and phenothiazine-based polymerization inhibitors A photosensitive resin composition comprising: A photosensitive resin composition. 【Chemical 1】 {In formula (D1), R １ and R2 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and when R １ and R ２ are alkyl groups, their terminals may each be bonded to the 6-position carbon or 8-position carbon of the coumarin skeleton to form a heterocyclic ring containing nitrogen, and R3 is an alkyl group having 1 to 20 carbon atoms.} 【Chemical 2】 {In formula (E1-1), R 12 is a phenyl group, a naphthyl group, an aminophenyl group, a hydroxyphenyl group, a thiohydroxyphenyl group, a chlorophenyl group, an aminonaphthyl group, a hydroxynaphthyl group, a thiohydroxynaphthyl group, or a chloronaphthyl group, and R 13 is 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.}

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

3. The content of the (C) 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 in total of the content of the (A) alkali-soluble polymer and the content of the (B) compound having an ethylenically unsaturated bond. The photosensitive resin composition according to Claim 2.

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

5. The (E2) second polymerization inhibitor contains a phenolic polymerization inhibitor. The photosensitive resin composition according to Claim 1.

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

7. The photosensitive resin composition according to claim 1, wherein the compound represented by the formula (D1) is a compound represented by the following formula (D1-1). [Chemical Formula 3]

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

9. The photosensitive resin composition according to claim 8, wherein the (D) sensitizer further contains 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). 【Chemical Formula 4】 {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 (A) alkali-soluble polymer contains a structural unit derived from styrene in a range of 35% by mass or more and 75% by mass or less based on the total mass of the structural units derived from all the monomers contained in the (A) alkali-soluble polymer.

12. The photosensitive resin composition according to claim 11, wherein the (A) alkali-soluble polymer contains a structural unit derived from styrene in a range of 40% by mass or more and 75% by mass or less based on the total mass of the structural units derived from all the monomers contained in the (A) alkali-soluble polymer.

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

14. A photosensitive resin composition laminate comprising a support film and a photosensitive resin composition layer on the support film, wherein the photosensitive resin composition layer is a layer composed of the photosensitive resin composition according to any one of claims 1 to 13. Photosensitive resin composition laminate.

15. Laminating a photosensitive resin composition layer on a substrate; Exposing the photosensitive resin composition layer; and Developing the exposed photosensitive resin composition layer; A method for forming a resist pattern, comprising: wherein the photosensitive resin composition layer is a layer composed of the photosensitive resin composition according to any one of claims 1 to 13. Method for forming a resist pattern.

Images