Photosensitive resin composition and photosensitive element

Abstract

To provide a photosensitive resin composition which can achieve a resist pattern good in adhesion / resolution and suppress gelation even after long-term storage.SOLUTION: The photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a biimidazole photopolymerization initiator. The photosensitive resin composition further contains the following component: (D) a component having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylalkylenediamine skeleton. The component (A) has (a) a compound having a hydroxy group and (b) styrene as monomer components of its constituent unit.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition and a photosensitive element. [Background technology]

[0002] Printed wiring boards are generally manufactured using a photolithography process. Photolithography is a method for forming a desired wiring pattern on a substrate by the following steps. That is, first, a layer made of a photosensitive resin composition is formed on a substrate, and the coating film is pattern-exposed and developed to form a resist pattern. Next, a conductor pattern is formed by etching or plating. Thereafter, the resist pattern on the substrate is removed to form the desired wiring pattern on the substrate.

[0003] In recent years, with the miniaturization and high density of electronic devices, there is a demand for finer wiring than ever before on wiring boards. As a manufacturing method for wiring boards that meets such demands, MSAP (Modified Semi-Additive Process) and SAP (Semi-Additive Process) have attracted attention. In order to form fine wiring in these methods, for example, it is necessary to form a resist pattern with a line width of 12 μm or less using a cured film that has excellent adhesion and resolution.

[0004] Here, with the aim of providing a photosensitive resin composition capable of obtaining a cured film excellent in adhesion, resolution, etc., a photosensitive resin composition containing an alkali-soluble polymer having a hydroxyalkyl (meth)acrylate unit has been proposed (for example, see Patent Document 1).

[0005] In addition, it is known to use a benzotriazole compound for the purposes of preventing discoloration of a substrate after formation of a resist pattern and improving the storage stability of a photosensitive resin composition (see, for example, Patent Documents 2 to 5). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2014 / 125884 [Patent Document 2] JP 2013-246387 A [Patent Document 3] JP 2016-139154 A [Patent Document 4] JP 2020-076945 A [Patent Document 5] JP 2009-180795 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, the photosensitive resin composition described in Patent Document 1 may cause a problem that the composition becomes unable to be applied as time passes due to the progress of gelation of the composition. Such gelation has a negative effect on the production efficiency of photosensitive elements. In addition, Patent Documents 2 to 5 do not consider the gelation of the photosensitive resin composition. Furthermore, Patent Documents 1 to 5 leave room for improvement from the standpoint of improving the resolution of the resist pattern and from the standpoint of improving the adhesion of the resist pattern to a substrate (for example, a copper substrate).

[0008] The present invention has been proposed in view of the above-mentioned circumstances. That is, an object of the present invention is to provide a photosensitive resin composition that can realize a resist pattern having good adhesion and resolution and can suppress gelation even after long-term storage, and to provide a photosensitive element obtained by using such a photosensitive resin composition. [Means for solving the problem]

[0009] One aspect of the present invention is as follows. [1] Ingredients include: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, A photosensitive resin composition comprising: The photosensitive resin composition comprises the following components: (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton, and The monomer component of the structural unit of the component (A) is (a) a compound having a hydroxy group, and (b) Styrene The photosensitive resin composition has the following structure. [2] 2. The photosensitive resin composition according to item 1, wherein in the component (A), the compound having a hydroxy group (a) is 2-hydroxyethyl methacrylate. [3] 3. The photosensitive resin composition according to item 1 or 2, wherein the ratio of the (b) monomer component having styrene in the component (A) is 40 mass% or more. [4] 4. The photosensitive resin composition according to any one of items 1 to 3, wherein the component (A) has a weight average molecular weight of less than 50,000. [5] The photosensitive resin composition according to any one of items 1 to 4, wherein the component (D) is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton in one molecule. [6] 6. The photosensitive resin composition according to any one of items 1 to 5, wherein the component (D) is a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or a long-chain alkylenediamine skeleton. [7] 7. The photosensitive resin composition according to any one of items 1 to 6, wherein the (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton is an alkylamine or alkylalkylenediamine having 16 or more carbon atoms. [8] 8. The photosensitive resin composition according to any one of items 1 to 7, wherein the component (D) has a carboxyl group. [9] 9. The photosensitive resin composition according to any one of items 1 to 8, wherein the (d1) triazole skeleton has a carboxybenzotriazole structure.

[10] 10. The photosensitive resin composition according to any one of items 1 to 9, wherein the component (C) comprises a hexaarylbiimidazole compound.

[11] A photosensitive element comprising: a support film; and a photosensitive resin layer formed on the support film, the photosensitive resin layer including a photosensitive resin composition, The photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photoinitiator, and (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton, The component (A) has as its constituent monomer components: (a) a compound having a hydroxy group, and (b) Styrene The photosensitive element has the following structure:

[12] 12. The photosensitive element according to item 11, wherein in the component (A), the compound having a hydroxy group (a) is 2-hydroxyethyl methacrylate.

[13] 13. The photosensitive element according to item 11 or 12, wherein in the component (A), the ratio of the monomer component having styrene (b) is 40% by mass or more.

[14] 14. The photosensitive element according to any one of items 11 to 13, wherein the weight average molecular weight of the component (A) is less than 50,000.

[15] 15. The photosensitive element according to any one of items 11 to 14, wherein the component (D) is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton in one molecule.

[16] 16. The photosensitive element according to any one of items 11 to 15, wherein the component (D) is a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or a long-chain alkylenediamine skeleton.

[17] 17. The photosensitive element according to any one of items 11 to 16, wherein the (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton is an alkylamine or alkylalkylenediamine having 16 or more carbon atoms.

[18] 18. The photosensitive element according to any one of items 11 to 17, wherein the component (D) has a carboxyl group.

[19] 19. The photosensitive element according to any one of items 11 to 18, wherein the (d1) triazole skeleton has a carboxybenzotriazole structure.

[20] 20. The photosensitive element according to any one of items 11 to 19, wherein the component (C) comprises a hexaarylbiimidazole compound. [twenty one] 21. The photosensitive element according to any one of items 11 to 20, which is a laminate of the support film, the photosensitive resin layer, and a protective film. Effect of the Invention

[0010] According to the present invention, it is possible to provide a photosensitive resin composition which is capable of realizing a resist pattern with excellent adhesion and resolution, and which is also capable of suppressing gelation even after long-term storage. Furthermore, according to the present invention, it is possible to provide a photosensitive element obtained by using the photosensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an exemplary embodiment of the present invention (hereinafter, abbreviated as "the present embodiment") will be described. The present invention is not limited to the present embodiment, and can be practiced with various modifications within the scope of the gist of the present invention. In this specification, the upper limit value and the lower limit value of each numerical range can be arbitrarily combined. In this specification, any numerical range indicated using "to" includes the upper and lower numerical limits.

[0012] [Photosensitive element] The photosensitive element of the present embodiment includes a support film and a photosensitive resin layer containing a photosensitive resin composition formed on the support film. The photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photoinitiator, and (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton, Including, The monomer component of the structural unit of the component (A) is (a) a compound having a hydroxy group, and (b) Styrene has.

[0013] The present inventors Comonomer components as follows: (a) Compounds having a hydroxy group (b) Styrene It has been found that by combining the component (A) having a structural unit derived from with the components (B) to (D), the adhesion and resolution are good and the gelation of the photosensitive resin composition is unlikely to occur. As a result of the investigation, it is considered that in the case of the component (A) having a hydrophilic repeating unit such as hydroxyalkyl (meth)acrylate, metal impurities are likely to be contained in the synthesis process of the component (A) and the preparation process of the photosensitive resin composition, and therefore, gelation tends to occur easily as the crosslinking reaction proceeds in a solution state. That is, according to the present embodiment, it is possible to provide a photosensitive resin composition that has good adhesion and resolution and can suppress gelation, and a photosensitive element using such a photosensitive resin composition can be provided.

[0014] <Support film> The support film of the present embodiment is preferably a layer or film for supporting the photosensitive resin layer, and is preferably a transparent base film that transmits actinic rays.

[0015] Examples of the transparent base film include films made of synthetic resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, etc. In general, polyethylene terephthalate (PET) is preferably used because of its suitable flexibility and strength. Among these, it is preferable to use a high-quality film with few internal foreign matters.Specifically, as the high-quality film, it is more preferable to use a PET film synthesized using a Ti-based catalyst, a PET film with a small lubricant diameter and a small content, a PET film containing a lubricant only on one side of the film, a thin PET film, a PET film with a smoothing treatment on at least one side, a PET film with a roughening treatment such as plasma treatment on at least one side, etc. This allows the exposure light to be irradiated onto the photosensitive resin layer without being blocked by internal foreign matter, and as a result, the resolution of the photosensitive element can be improved.

[0016] The thickness of the support film is preferably 5 to 25 μm, and more preferably 6 to 20 μm. The thinner the support film, the fewer the number of internal foreign objects, and therefore the easier it is to prevent a decrease in resolution, but if the film thickness is less than 5 μm, it is prone to elongation deformation in the winding direction due to tension during the coating and winding manufacturing process, and to tears due to minute scratches, and the strength of the film is insufficient, making it prone to wrinkles during lamination.

[0017] At least one surface of the support film may be subjected to a smoothing treatment using a calendar device or the like. This reduces the surface roughness of one surface of the support film, particularly the surface that comes into contact with the photosensitive resin layer, and can enhance the effects of the present invention.

[0018] The haze of the support film is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01 to 0.95%, from the viewpoint of improving the parallelism of the light beam irradiated to the photosensitive resin layer, thereby making it easier to obtain high resolution after exposure and development of the photosensitive element.

[0019] <Photosensitive resin layer and photosensitive resin composition> The photosensitive resin layer is laminated on a support film. The photosensitive resin layer of the present embodiment contains the photosensitive resin composition of the present embodiment. The photosensitive resin composition of the present embodiment comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, Includes. The photosensitive resin composition comprises the following components: (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton, and The monomer component of the structural unit of the component (A) is (a) a compound having a hydroxy group, and (b) Styrene has.

[0020] <Component (A): Alkali-soluble polymer> In this embodiment, as described above, the component (A) has (a) a compound having a hydroxy group, and (b) a structural unit derived from styrene. In this embodiment, a plurality of (A) components may be used in combination, and in this case, at least one of the (A) components used in combination has (a) a compound having a hydroxyl group and (b) a structural unit derived from styrene. By having a structural unit derived from such a compound, it becomes easier to control the developability of the photosensitive resin layer, and therefore it becomes possible to obtain a resist pattern having excellent adhesion, resolution, etc.

[0021] The (a) compound having a hydroxy group is preferably a hydroxyalkyl (meth)acrylate. As the hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate is preferred, and 2-hydroxyethyl methacrylate is more preferred. This makes it easy to obtain, and yet allows easy control of developability, resulting in a resist pattern with excellent adhesion and resolution. The content of component (a) in component (A) is preferably from 1.0 to 50 mass%, more preferably from 1.0 to 30 mass%, further preferably from 1.0 to 14 mass%, and most preferably from 1.0 to 5.0 mass%.

[0022] The copolymerization ratio of (b) styrene is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total mass of all monomer components, from the viewpoint of excellent adhesion and resolution. The copolymerization ratio is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of excellent developability and resolution.

[0023] The above-mentioned (A) component preferably further has a repeating unit consisting of at least one type of first monomer described below, and more preferably has a repeating unit consisting of at least one type of first monomer and at least one type of second monomer described below.

[0024] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of excellent adhesion and resolution. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means acryloyl group or methacryloyl group, and "(meth)acrylate" means "acrylate" or "methacrylate".

[0025] The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of excellent adhesion and resolution, more preferably 15% by mass or more, even more preferably 18% by mass or more, even more preferably 21% by mass or more, particularly preferably 23% by mass or more, and most preferably 24% by mass or more. The copolymerization ratio of 50% by mass or less is preferable from the viewpoint of excellent adhesion and resolution, more preferably 35% by mass or less, even more preferably 30% by mass or less, even more preferably 29% by mass or less, particularly preferably 27% by mass or less, and most preferably 26% by mass or less. When two or more kinds of first monomers are polymerized and used, the total copolymerization ratio of each monomer is preferably within the above range.

[0026] The second monomer is a monomer that is non-acidic, except for styrene, and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, and tetrahydrofurfuryl. (meth)acrylates such as (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, etc.; styrene derivatives such as methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile.

[0027] The second monomer preferably contains a compound having an aromatic structure. The copolymerization ratio of the monomer having an aromatic structure and styrene is preferably 10 to 90% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of excellent adhesion and resolution, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more. The copolymerization ratio of 90% by mass or less is preferable from the viewpoint of excellent developability, and more preferably 80% by mass or less. When two or more types of second monomers are polymerized and used, the total copolymerization ratio of each monomer is preferably within the above range.

[0028] The compound having an aromatic structure preferably contains benzyl (meth)acrylate. The proportion of benzyl (meth)acrylate is preferably 1 to 60 mass%, more preferably 1 to 30 mass%, and particularly preferably 1 to 20 mass%, based on the total mass of all monomer components.

[0029] The weight average molecular weight Mw of component (A) is preferably from 10,000 to 60,000. From the standpoint of achieving both flexibility and resolution of the resist pattern, it is preferable to have the weight average molecular weight Mw not exceed 60,000, and from the same standpoint it is more preferable to have the weight average molecular weight Mw not exceed 55,000, and even more preferably less than 50,000. From the same viewpoint, the weight average molecular weight Mw is preferably 10,000 or more, more preferably 14,000 or more, and even more preferably 25,000 or more.

[0030] The polydispersity of the component (A) is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, even more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0031] When multiple (A) components are used in combination, it is preferable that the monomer contents, molecular weights, and polydispersities of the multiple (A) components are selected so that the weighted average values, with the content ratios as weights, fall within the above ranges.

[0032] The synthesis of component (A) is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, in addition to solution polymerization, living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

[0033] The proportion of the (A) component to the total solid mass of the photosensitive resin composition may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. Also, it may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0034] It is preferable to set the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition to 90% by mass or less from the viewpoint of controlling the development time, while it is preferable to set the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition to 10% by mass or more from the viewpoint of improving edge fuse resistance, that is, suppressing exudation of the photosensitive resin layer from the film edge.

[0035] <Component (B): Compound having an ethylenically unsaturated bond> In this embodiment, the component (B) preferably contains a (meth)acryloyl group, and more preferably contains a compound having a bifunctional or higher functional ethylenically unsaturated bond. The term "a compound having a bifunctional or higher functional ethylenically unsaturated bond" refers to a compound having two or more ethylenically unsaturated bonds in one molecule.

[0036] The compound having an ethylenically unsaturated bond is preferably a (meth)acrylate compound. For example, from the viewpoint of adhesion and flexibility of the resist pattern, the compound having an ethylenically unsaturated bond preferably includes a bifunctional compound having an ethylenically unsaturated bond and a trifunctional or higher compound having an ethylenically unsaturated bond. The compound having an ethylenically unsaturated bond may include, for example, a tetrafunctional, pentafunctional, or hexafunctional compound having an ethylenically unsaturated bond.

[0037] Examples of compounds having a difunctional ethylenically unsaturated bond include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycosylated (hydrogenated) bisphenol A di(meth)acrylate.

[0038] Commercially available compounds having a bifunctional ethylenically unsaturated bond 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, and 1 4G, 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 (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.), Fancryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, FA-240A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Showa Denko Materials Co., Ltd.), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (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 (manufactured by Arkema Co., Ltd.), KAYARAD (registered trademark) Examples include NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

[0039] Examples of compounds having a trifunctional or higher ethylenically unsaturated bond 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, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0040] Further, examples of the compound having a trifunctional or higher ethylenically unsaturated bond include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0041] Commercially available compounds having three or more functional ethylenically unsaturated bonds include, for example, 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, and 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 Showa Denko Materials 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-Allnex 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) Examples include GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, and DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.).

[0042] The ratio of the compound having an ethylenic unsaturated bond (B) to the total solid content of the photosensitive resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, from the viewpoints of sensitivity, tackiness, and followability, and is preferably 50% by mass or less, more preferably 45% by mass or less, more preferably 42% by mass or less, from the viewpoints of edge fuse resistance, tackiness, and resolution.

[0043] From the viewpoints of edge fuse resistance, tackiness, and resolution, the value of the solid content of the compound having an ethylenic unsaturated bond (B) relative to the solid content of the alkali-soluble polymer (A) contained in the photosensitive resin composition (i.e., the solid content of the compound having an ethylenic unsaturated bond (B) / the solid content of the alkali-soluble polymer (A)) is preferably 1.4 or less, more preferably 1.3 or less, more preferably 1.2 or less, and more preferably 1.1 or less. The lower limit is preferably 0.7 or more, more preferably 0.8 or more, more preferably 0.9 or more, and more preferably 1.0 or more.

[0044] The photosensitive resin composition of the present embodiment preferably has a number of ethylenically unsaturated bonds of 0.1 to 0.3 mol per 100 g of solid content of the photosensitive resin composition. By making it 0.1 mol or more, it is possible to prevent the photosensitive resin component from eluting from the cured resist pattern in the water washing step after development, which would cause contamination of the water washing step. By making it 0.3 mol or less, it is possible to prevent the cured resist pattern from chipping and falling off in the water washing step after development, which would cause contamination of the water washing step.

[0045] The number of ethylenically unsaturated bonds per 100 g of solid content of the photosensitive resin composition is preferably 0.1 mol or more, more preferably 0.11 mol or more, more preferably 0.12 mol or more, more preferably 0.13 mol or more, and preferably 0.3 mol or less, preferably 0.28 mol or less, preferably 0.25 mol or less, preferably 0.22 mol or less, preferably 0.20 mol or less, preferably 0.18 mol or less, and preferably 0.15 mol or less. It is more preferably 0.1 mol or more and 0.25 mol or less, even more preferably 0.1 mol or more and 0.2 mol or less, still more preferably 0.11 mol or more and 0.2 mol or less, and extremely preferably 0.11 mol or more and 0.15 mol or less.

[0046] <Component (C): Photopolymerization initiator> In this embodiment, the component (C) can be any compound without particular limitation, but is preferably a hexaarylbiimidazole compound.

[0047] An example of the hexaarylbiimidazole compound is a lophine dimer, that is, a dimer of 2,4,5-triarylimidazole.

[0048] Lophine dimers, i.e., dimers of 2,4,5-triarylimidazole, include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'- Diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3 -methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-( 3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,Examples of such compounds include 5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.

[0049] From the viewpoints of high sensitivity, resolution, and adhesion, it is preferable that the component (C) contains a lophine dimer, and among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferable. In this case, the content of the component (C) (e.g., lophine dimer) in the photosensitive resin composition is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, based on the total solid content in the photosensitive resin composition.

[0050] In addition, as the photopolymerization initiator, it is preferable to further include at least one of the group consisting of N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, ester compounds of N-aryl amino acids, and halogen compounds. As the other photopolymerization initiator, it is more preferable to have an anthracene derivative.

[0051] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. Among these, N-phenylglycine is preferred because of its high sensitizing effect.

[0052] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0053] Examples of aromatic ketone compounds include benzophenone compounds. Examples of benzophenone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4-methoxy-4'-dimethylaminobenzophenone, etc. Examples of aromatic ketone compounds include 4,4'-bis(diethylamino)benzophenone from the viewpoint of sensitizing effect and adhesion.

[0054] In this specification, the term "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, and 1-chloroanthraquinone. From the viewpoint of sensitizing effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0055] 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-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, etc. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0056] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Examples of commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0057] Examples of the benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of the dialkylaminobenzoate compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0058] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0059] As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, availability, etc.

[0060] From the viewpoints of adhesion and rectangularity of the resist pattern, the pyrazoline derivatives preferably include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline.

[0061] Examples of the ester compound of N-arylamino 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, and octyl ester of N-phenylglycine.

[0062] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl 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 compounds, and diaryliodonium compounds. Among these, tribromomethylphenyl sulfone is preferred.

[0063] The total content of the (C) component and other photopolymerization initiators in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content in the photosensitive resin composition. By adjusting the content of the (C) component and other photopolymerization initiators within the above range, sufficient sensitivity can be easily obtained, so that light can easily be transmitted to the bottom of the photosensitive resin layer, and thus high resolution can be easily achieved.

[0064] ≪(D) ​​Component≫ In this embodiment, the photosensitive resin layer contains a component (D) having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton.

[0065] In this specification, (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton refers to an alkylamine or alkylalkylenediamine having 9 or more carbon atoms. The alkylamine or alkylalkylenediamine preferably has 10 or more carbon atoms, more preferably 12 or more carbon atoms, even more preferably 14 or more carbon atoms, and particularly preferably 16 or more carbon atoms. The number of carbon atoms is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0066] Here, the component (D) may be a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylalkylenediamine skeleton in one molecule, or may be a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or long-chain alkylalkylenediamine skeleton.

[0067] (d1) An example of a compound having a triazole skeleton is benzotriazole. Benzotriazole is represented by the following formula (1): [ka] Carboxybenzotriazole represented by the following formula is preferred. By using benzotriazole having a carboxy group, it becomes easier to obtain a preparation of a photosensitive resin composition having good gelation suppression performance. This is thought to be because the carboxy group and the triazole moiety interact with metal impurities to suppress the polymerization reaction.

[0068] (d2) Examples of the compound having a long-chain alkylamine skeleton include compounds represented by the following general formula (2): [ka] (In the formula, R 1 represents a hydrogen atom or a linear or branched alkyl group; R 2 ,R 2 Each ' independently represents a linear or branched alkyl group. 2,R 2 ' has a total of 9 or more carbon atoms.) Examples of the compound include compounds represented by the following formula:

[0069] Specific examples of compounds having such a long-chain alkylamine skeleton include dialkylamines such as dipentylamine, dihexylamine, dioctylamine, and di(2-ethylhexyl)amine. Dialkylamines include those represented by the following formula (2a): [ka] Di(2-ethylhexyl)amine represented by the following formula is particularly preferred.

[0070] Examples of the compound (d2) having a long-chain alkyl alkylenediamine skeleton include compounds represented by the following general formula (3): [ka] (In the formula, R 3 represents a linear or branched alkyl group having 9 or more carbon atoms, and n is an integer of 1 or more. Examples of the compound include compounds represented by the following formula:

[0071] Specific examples of such compounds having a long-chain alkyl alkylenediamine skeleton include those represented by the following formula (3a): [ka] (In the formula, R 3 represents a tallow alkyl group. A tallow alkyl group is a saturated or unsaturated linear aliphatic hydrocarbon having mainly 16 to 18 carbon atoms. Examples of the alkyl propylene diamine compounds include tallow alkyl propylene diamine compounds represented by the following formula: As a compound such as the above formula (3a), Nissan Amine DT (manufactured by NOF Corporation) is an example of a commercially available product.

[0072] The use of such long-chain alkylamine or long-chain alkylenediamine compounds makes it easier to obtain a preparation of a photosensitive resin composition having good gelation suppression performance. It is believed that such amine compounds interact with metal impurities in the preparation, and the long-chain alkyl group has high steric hindrance, thereby suppressing the polymerization reaction, thereby suppressing gelation.

[0073] When the component (D) is a compound having a (d1) triazole skeleton and a (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton in one molecule, the compound is a compound derived from the above-mentioned compound and having a (d1) triazole skeleton and a (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton in one molecule.

[0074] Examples of such compounds include those represented by the following general formula (4): [ka] (In the formula, R 4 represents a hydrogen atom or an organic group having 1 or more carbon atoms which may have a substituent. It is believed that the presence of such a compound can interact with metal impurities and inhibit polymerization reactions caused by the impurities.

[0075] R 4 As the organic group having 1 or more carbon atoms represented by the formula (I), a methyl group, an ethyl group, a propyl group, a carboxyl group, a hydroxyalkyl group, and an aminoalkyl group are preferable, and a carboxyl group is particularly preferable. By having a carboxyl group, developability is improved, and a resist pattern with good resolution can be formed.

[0076] In general formula (4), R 2 , R 2 R′ represents an alkyl group which may have a substituent. 2 ,R 2The total number of carbon atoms in ' is 9 or more. It is considered that the total number of carbon atoms is 9 or more, and thus the steric hindrance of the complex formed by the metal impurities and the triazole compound is increased, and the interaction with the compound having an unsaturated bond is reduced, thereby suppressing gelation.

[0077] Examples of the alkyl group which may have a substituent include an n-pentyl group, an n-hexyl group, an n-octyl group, and a 2-ethylhexyl group. Among them, an n-octyl group or a 2-ethylhexyl group having an alkyl group with 8 or more carbon atoms or a branched structure is preferable, and a 2-ethylhexyl group is particularly preferable. It is considered that gelation can be suppressed by having an alkyl group with 8 or more carbon atoms or a branched structure because steric hindrance increases.

[0078] Specific examples of such compounds include 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-benzotriazole, 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-tolyltriazole, 1-(N,N-bis-2-hydroxyethyl)aminomethyl)-1,2,3-benzotriazole, and 1-(N,N-bis(2-ethylhexyl)aminomethyl)-5-carboxy-1,2,3-benzotriazole. Among them, the following formula (4a): [ka] Preferred is 1-(N,N-bis(2-ethylhexyl)aminomethyl)-5-carboxy-1,2,3-benzotriazole represented by the following formula:

[0079] The content of the (D) component in the photosensitive resin composition is preferably 0.01 to 20 mass%, more preferably 0.01 to 1 mass%, and even more preferably 0.01 to 0.1 mass%, based on the total solid content in the photosensitive resin composition. 0.01 to 0.05 mass% is particularly preferred. By adjusting the content of the (D) component within the above range, sufficient gelation suppression performance is achieved, and high resolution and high adhesion are easily achieved.

[0080] Other Ingredients The photosensitive resin composition may contain, if desired, an antioxidant, a stabilizer, a base dye, a sensitizer, a plasticizer, a hindered amine, and the like.

[0081] Examples of base dyes include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc. Among them, Basic Green 1 is preferred from the viewpoint of improving coloring properties, hue stability, and exposure contrast. These can be used alone or in combination of two or more.

[0082] The content of the base dye in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total solid content in the photosensitive resin composition. From the viewpoint of obtaining good coloring properties, the content of the base dye is preferably equal to or more than the above lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the content is preferably equal to or less than the above upper limit.

[0083] Examples of the antioxidant include triphenyl phosphite (e.g., manufactured by ADEKA, trade name: TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., manufactured by ADEKA, trade name: 2112), tris(mononylphenyl)phosphite (e.g., manufactured by ADEKA, trade name: 1178), bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA, trade name: 329K), etc. These can be used alone or in combination of two or more.

[0084] The content of the antioxidant in the photosensitive resin composition is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.3% by mass, based on the total solid content in the photosensitive resin composition. The content of the antioxidant is preferably equal to or more than the lower limit from the viewpoint of favorably expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer. On the other hand, the content of the antioxidant is preferably equal to or less than the upper limit from the viewpoint of favorably expressing the hue stability while suppressing the color development of the resist pattern and improving adhesion.

[0085] The stabilizer can be used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. For example, the stabilizer can be at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used alone or in combination of two or more.

[0086] Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), diphenylnitrosamine, etc. Among them, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred. These can be used alone or in combination of two or more.

[0087] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. These can be used alone or in combination of two or more.

[0088] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total solid content in the photosensitive resin composition. From the viewpoint of imparting good storage stability to the photosensitive resin composition, the total content is preferably equal to or more than the above lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the total content is preferably equal to or less than the above upper limit.

[0089] In this embodiment, a color-developing dye that develops color upon irradiation with light may be included in the photosensitive resin layer. As a color-developing dye, for example, a combination of a leuco dye and a halogen compound is known. As a leuco dye, for example, tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet], tris(4-dimethylamino-2-methylphenyl)methane [leucomalachite green], etc. are listed. As a halogen compound, for example, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, etc. are listed.

[0090] In this embodiment, an additive such as a plasticizer may be contained in the photosensitive resin layer as necessary. Examples of the additive include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

[0091] In this embodiment, a hindered amine compound may be contained in the photosensitive resin layer as necessary. Examples of the hindered amine compound include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine, 2,2,6,6-tetramethylpiperidyl methacrylate, and 1,2,2,6,6-pentamethylpiperidyl methacrylate.

[0092] By including the above hindered amine compound, excessive crosslinking reaction of the resist pattern is suppressed and diffusibility in a stripping solution is improved, so that a resist pattern with excellent strippability can be formed.

[0093] Since the flexibility of the cured film after the crosslinking reaction is improved and the peelability is improved, the hindered amine compound preferably has a monofunctional polymerizable group, and 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are particularly preferred.

[0094] The ratio of the hindered amine compound to the total solid content mass of the photosensitive resin composition is preferably 0.001 to 10% by mass. From the viewpoint of excellent releasability, this ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more. On the other hand, from the viewpoint of improving resolution, this ratio is preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0095] The above hindered amine compound may be used as a repeating unit in the alkali-soluble polymer (A).

[0096] The thickness of the photosensitive resin layer is preferably 3 to 100 μm, and more preferably the upper limit is 50 μm. As the thickness of the photosensitive resin layer approaches 3 μm, the resolution improves, and as the thickness approaches 100 μm, the film strength improves, so that the thickness can be appropriately selected according to the application.

[0097] <Protective film> The photosensitive element of the present embodiment may include a protective film in addition to the support film and the photosensitive resin layer. The protective film is laminated on the photosensitive resin layer on the side opposite to the support film, and functions as a cover.

[0098] Since the adhesive strength between the photosensitive resin layer and the protective film is sufficiently smaller than that between the photosensitive resin layer and the support film, the protective film can be easily peeled off from the photosensitive resin layer. For example, a polyethylene film, a polypropylene film, an oriented polypropylene film, a polyester film, etc. can be preferably used as the protective film. In addition, a release layer may be provided on the surface of the protective film.

[0099] The thickness of the protective film is preferably 10 to 100 μm, more preferably 10 to 50 μm. Examples of the protective film include Alphan (registered trademark) EM-501, E-200, E-201F, FG-201, and MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Torayfan (registered trademark) KW37, 2578, 2548, 2500, YM17S, Therapeel (registered trademark) PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, and SY (all manufactured by Toray Industries, Inc.), GF-18, GF-818, and GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0100] [Method of producing photosensitive element] The photosensitive element can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective film on a support film. A step of mixing the photosensitive resin composition with a solvent capable of dissolving the photosensitive resin composition to obtain a photosensitive resin composition preparation liquid (coating liquid); A step of applying the coating liquid onto a support film using a bar coater or a roll coater and drying the coating liquid to form a photosensitive resin layer on the support film; If necessary, a step of laminating a protective film on the photosensitive resin layer; may have the following structure:

[0101] [Photosensitive element roll] The photosensitive element described above may be used as a roll of a long photosensitive element wound around a core.

[0102] [Method of forming resist pattern] A method for forming a resist pattern using the photosensitive element of this embodiment includes the following steps: a lamination step of laminating the photosensitive element to a substrate; an exposure step of exposing a photosensitive resin layer of the photosensitive element to light; and a developing step of developing and removing the unexposed areas of the photosensitive resin layer; preferably in that order.

[0103] Specifically, in the lamination step, after peeling off the protective film from the photosensitive element, the photosensitive resin layer is heated and pressed onto the surface of a support (e.g., a substrate) using a laminator, and laminated once or multiple times. Examples of materials for the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is generally 40°C to 160°C. Heating and pressing can be performed using a laminator equipped with a roll, or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the roll several times. Heating and pressing can be performed under a reduced pressure environment as desired.

[0104] In the exposure step, the photosensitive resin layer is exposed to active light using an exposure machine. The exposure can be performed after peeling off the support, if desired. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using an actinometer. In the exposure step, direct imaging exposure may be performed. In direct imaging exposure, exposure is performed directly on the substrate using a drawing device without using a photomask. As the light source, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm is used. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0105] The light irradiation method used in the exposure step is preferably at least one method selected from the group consisting of projection exposure method, proximity exposure method, contact exposure method, direct imaging exposure method, and electron beam direct writing method, and it is more preferable to use the projection exposure method or the direct imaging exposure method.

[0106] A heating step may be provided between the exposure step and the development step. The heating temperature is preferably about 30 to about 200° C., more preferably 30 to 150° C., and even more preferably 35 to 120° C. By carrying out this heating step, it is possible to improve the resolution and adhesion. For heating, a hot air, infrared, or far infrared heating furnace, a thermostatic bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used.

[0107] The time elapsed from the exposure step to the heating step, more precisely the time elapsed from the time exposure is stopped to the time heating is started, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds.The time elapsed from the time heating is started to the time heating is stopped is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0108] In the development process, the unexposed or exposed parts of the photosensitive resin layer after exposure are removed with a developer using a developing device. If there is a support film on the photosensitive resin layer after exposure, it is removed. Then, the unexposed or exposed parts are developed and removed using a developer consisting of an alkaline aqueous solution to obtain a resist image.

[0109] The alkaline solution is Na 2 CO 3 , K 2 CO 3 The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, but a Na solution having a concentration of 0.2 to 2 mass % is preferable. 2 CO 3 An aqueous solution is generally used. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, etc. may be added to the alkaline aqueous solution. The temperature of the developer in the development step is preferably kept constant within the range of 20 to 40°C.

[0110] The development step preferably includes a washing step for removing the developer contained in the resist pattern after development. The washing water may be selected from pure water, industrial water, and other water depending on the characteristics of the photosensitive resin layer. In order to improve the resolution and the shape of the resist pattern, it is preferable to use MgSO 2 with a concentration of 0.001 to 1% by mass. 4 It is also possible to add a polyvalent metal salt such as the above. The temperature of the washing water in the washing step is preferably kept constant within the range of 20 to 40°C.

[0111] A resist pattern can be obtained by the above steps, but if desired, a heating step can be further performed at 60° C. to 300° C. By performing this heating step, the chemical resistance of the resist pattern can be improved. For the heating step, a heating furnace using hot air, infrared rays, or far infrared rays can be used.

[0112] In order to obtain a conductive pattern, after the developing step or the heating step, a conductive pattern forming step may be performed in which the substrate on which the resist pattern has been formed is etched or plated.

[0113] The method for producing a conductor pattern is, for example, performed by using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then performing a conductor pattern forming step, in which a conductor pattern is formed on the substrate surface (e.g., copper surface) exposed by development using a known etching method or plating method.

[0114] Furthermore, after producing a conductor pattern by the above-mentioned method for producing a conductor pattern, a peeling process can be carried out in which the resist pattern is peeled off from the substrate using an aqueous solution that is more alkaline than the developer, thereby obtaining a wiring board (e.g., a printed wiring board) having a desired wiring pattern.

[0115] The aqueous alkaline solution for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, but an aqueous solution of NaOH or KOH with a concentration of 2 to 5 mass %, or an organic amine stripping solution is generally used. A small amount of a water-soluble solvent may be added to the stripping solution. Examples of the water-soluble solvent include alcohol. The temperature of the stripping solution in the stripping step is preferably within the range of 40 to 70°C.

[0116] In this embodiment, the photosensitive element can be used in the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; precision processing of metal foils such as the manufacture of metal masks; the manufacture of packages such as ball grid arrays (BGAs) and chip size packages (CSPs); the manufacture of tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); the manufacture of semiconductor bumps; and the manufacture of partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields. Unless otherwise specified, the values ​​of the above-mentioned parameters are measured according to the measurement methods in the Examples. EXAMPLES

[0117] The present embodiment will be described in more detail below with reference to examples and comparative examples. The present embodiment is not limited to the following examples. The physical properties in the examples were measured by the following methods.

[0118] <Synthesis of component (A)> The monomers shown in the table were mixed with azobisisobutyronitrile in the amounts shown in the table (units are "parts by mass"). A mixed solution (x) was prepared by mixing methyl cellosolve and toluene in a ratio of 3:2. A mixed solution (x) of 50 parts by mass of methyl cellosolve and 20 parts by mass of toluene was mixed with 0.5 parts by mass of azobisisobutyronitrile to prepare a solution (b). 300 g of the mixed solution (x) was put into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas inlet tube, and the mixture was stirred while blowing nitrogen gas into the flask, and the temperature was raised to 80°C. The mixed solution in the flask was dropped with the solution (a) at a constant dropping rate over 4 hours. The mixture was then stirred at 80°C for 2 hours. Next, solution (b) was added dropwise to the solution in the flask at a constant rate over 10 minutes, and the solution in the flask was then stirred at 80°C for 3 hours. The solution in the flask was then heated to 90°C over 30 minutes and kept at 90°C for 2 hours. Stirring was then stopped and the solution was cooled to room temperature (25°C), yielding solutions of alkali-soluble polymers A1 to A9, respectively. The non-volatile content (solid content) of the solutions of alkali-soluble polymers A1 to A9 was 50 mass% each. The weight average molecular weights (Mw) of the alkali-soluble polymers A1 to A9 are shown in the table.

[0119] The weight average molecular weight was measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene. The GPC conditions were as follows: (GPC conditions) Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name) Columns: 3 in total Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 (above, product name, manufactured by Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

[0120] [Preparation of evaluation samples] <Preparation of photosensitive resin composition and photosensitive element> The components shown in the table (wherein the number of each component indicates the amount (parts by mass) of solid content) were mixed in the amounts shown in the table, and ethanol was added until the solid content concentration reached 60%, followed by thorough stirring. In this way, preparations containing photosensitive resin compositions were obtained (Examples 1A to 20A, and Comparative Examples 1A to 8A). A 16 μm-thick polyethylene terephthalate film (QS71, manufactured by Toray Industries, Inc.) was used as the support film. The above-mentioned preparation was uniformly applied to the surface of the film using a bar coater, and then dried in a dryer at 95° C. for 2 minutes and 30 seconds to form a photosensitive resin layer with a thickness of 25 μm. This resulted in the production of photosensitive resin elements (Examples 1 to 10 and Comparative Examples 1 to 8). Next, a 19 μm polyethylene film (protective film) was attached as a protective layer to the surface of the photosensitive resin layer on the side on which the polyethylene terephthalate film was not laminated.

[0121] <Substrate surface preparation> A 0.4 mm thick copper-clad laminate was prepared by laminating 18 μm rolled copper foil. The surface of this substrate was then immersed in 10 mass% H 2 SO 4 Wash with an aqueous solution.

[0122] <Lamination> While peeling off the polyethylene film (protective film) of the photosensitive element, the photosensitive element was laminated at a roll temperature of 105°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) onto a copper-clad laminate that had been preheated to 50°C after the surface had been prepared by the above method. This resulted in a substrate for evaluation. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min.

[0123] <Exposure> Two hours after lamination, the evaluation substrate was exposed to light using a direct imaging (DI) exposure pattern with a direct imaging exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.).

[0124] <Heating> One minute after exposure, the evaluation substrate was heated for 30 seconds in a constant temperature incubator with a constant airflow (DKM600, manufactured by Yamato Scientific Co., Ltd.) set at 60°C.

[0125] <Development> After peeling off the polyethylene terephthalate film (support film), the film was immersed in an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer) at 30°C with 1% by weight Na 2 CO 3 The aqueous solution was sprayed for a predetermined time (development spray). The development spray time was twice the shortest development time, and after development, a water wash spray was also performed, and the water wash spray time was twice the shortest development time. The shortest time required for the unexposed photosensitive resin layer to completely dissolve was defined as the "shortest development time."

[0126] [evaluation] <Sensitivity> A Hitachi 41-step tablet was placed on the evaluation substrate that had been subjected to the above surface preparation and lamination, and exposure and development were performed. The exposure dose (unit: mJ / cm2) that resulted in 15 remaining steps after development was 2 The sensitivity was evaluated by the following formula: The lower the exposure amount, the higher the sensitivity.

[0127] <Adhesion> The evaluation substrate that had been subjected to the above-mentioned surface preparation and lamination was exposed to light using a drawing pattern in which line width (L) / space width (S) (hereinafter sometimes referred to as "L / S") was x / 3x (x = 1 to 20 (varying at 1 μm intervals)) (unit: μm) with an energy amount that resulted in 17 remaining steps on a Hitachi 41-step step tablet. Thereafter, the above-mentioned heating and development treatments were performed to form a resist pattern. This resist pattern was observed under an optical microscope, and adhesion was evaluated based on the minimum line width that was formed without causing meandering or chipping of the line portion (exposed portion). The smaller this value, the better the adhesion. Those with adhesion of 7 μm or less were considered to pass.

[0128] <Resolution> Using a drawing pattern with L / S of x / x (x=1 to 20 (varying in 1 μm intervals)) (unit: μm), exposure was performed with an energy amount that resulted in 17 remaining steps on a Hitachi 41-step step tablet. The above-mentioned heating and development treatment was then performed to form a resist pattern. This resist pattern was observed under an optical microscope, and the resolution was evaluated based on the smallest line width at which the line portions (exposed portions) were free of meandering and chipping, and no residue was found in the space portions (unexposed portions) (the unexposed portions were removed). The smaller this value, the better the resolution. A resolution of 12 μm or less was considered acceptable.

[0129] <Gelling prevention performance> 25 g of the prepared liquid containing the photosensitive resin composition was placed in a 50 ml brown glass screw bottle (manufactured by Maruemu Co., Ltd.) and stored in a closed state in a hot air circulation incubator (manufactured by Espec Corp.) at 50° C. for 25 hours, 50 hours, 100 hours, and 200 hours, respectively. The liquid after storage was visually inspected, and when the container was tilted 90° and held for 30 seconds, those where flow on the liquid surface was observed were rated as pass, and those where no flow on the liquid surface was observed due to the composition solidifying or the like were rated as fail. Those where no gelation was observed after 50 hours of storage were rated as pass.

[0130] [Table 1]

[0131] [Table 2]

[0132] [Table 3]

[0133] [Table 4]

[0134] [Table 5]

[0135] As is clear from the table, Examples 1 to 20 were excellent in all of adhesion, resolution, and gelation suppression performance.

[0136] In contrast, good results were not obtained in Comparative Examples 1 to 8. That is, in Comparative Examples 4 to 7, which did not include the component (d2) as the component (D), the gelation inhibition performance was unacceptable. On the other hand, in Comparative Example 8, which did not include the component (d1) as the component (D), the adhesion was "unacceptable." Moreover, in Comparative Example 1, in which the component (A) did not include the component (a) as a constituent unit, Comparative Example 2, in which the component (A) did not include the component (b) as a constituent unit, and Comparative Example 3, in which the component (C) did not include the component (C), the adhesion and resolution were "unacceptable." [Industrial Applicability]

[0137] The photosensitive resin composition of the present invention can be used to obtain the photosensitive element of the present invention. The use of such a photosensitive element provides good adhesion, resolution, and gelation suppression performance, and therefore the element can be widely used as a photosensitive element for forming resist patterns on printed wiring boards and the like.

Claims

1. Ingredients: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, A photosensitive resin composition comprising: The photosensitive resin composition comprises the following components: (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylalkylenediamine skeleton having 9 or more carbon atoms; and The component (A) has, as a monomer component of its structural unit, (b) styrene and the proportion of the (b) styrene-containing monomer component in the (A) component is 50 mass% or more based on the total mass of all monomer components; the component (C) contains a hexaarylbiimidazole compound in an amount of 0.5 to 10% by mass based on the total solid content of the photosensitive resin composition; Photosensitive resin composition.

2. 2. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the component (A) is less than 50,000.

3. 3. The photosensitive resin composition according to claim 1, wherein the component (D) is a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or long-chain alkylalkylenediamine skeleton.

4. A photosensitive resin composition according to claim 1 or 2, wherein the component (D) is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylalkylenediamine skeleton within one molecule.

5. 3. The photosensitive resin composition according to claim 1, wherein the long-chain alkylamine or long-chain alkylalkylenediamine skeleton (d2) is an alkylamine or alkylalkylenediamine having 16 or more carbon atoms.

6. The photosensitive resin composition according to claim 1 or 2, wherein the component (D) has a carboxyl group.

7. The photosensitive resin composition according to claim 1 or 2, wherein the triazole skeleton (d1) has a carboxybenzotriazole structure.

8. A photosensitive element comprising: a support film; and a photosensitive resin layer formed on the support film and containing a photosensitive resin composition, The photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylalkylenediamine skeleton having 9 or more carbon atoms, The component (A) contains, as a monomer component of its structural unit, (b) styrene and the proportion of the (b) styrene-containing monomer component in the (A) component is 50 mass% or more based on the total mass of all monomer components; the component (C) contains a hexaarylbiimidazole compound in an amount of 0.5 to 10% by mass based on the total solid content of the photosensitive resin composition; Photosensitive element.

9. The photosensitive element of claim 8 , wherein the weight average molecular weight of component (A) is less than 50,000.

10. 10. The photosensitive element according to claim 8, wherein the component (D) is a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or long-chain alkylalkylenediamine skeleton.

11. A photosensitive element described in claim 8 or 9, wherein the component (D) is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylalkylenediamine skeleton within one molecule.

12. The photosensitive element according to claim 8 or 9, wherein the long-chain alkylamine or long-chain alkylalkylenediamine skeleton (d2) is an alkylamine or alkylalkylenediamine having 16 or more carbon atoms.

13. The photosensitive element according to claim 8 or 9, wherein the component (D) has a carboxyl group.

14. The photosensitive element according to claim 8 or 9, wherein the triazole skeleton (d1) has a carboxybenzotriazole structure.

15. The photosensitive element according to claim 8 or 9, which is a laminate of the support film, the photosensitive resin layer, and a protective film.