Photosensitive resin composition, method for manufacturing a resist pattern film, and method for manufacturing a plated object

Abstract

To provide a photosensitive resin composition which can suppress whitening of a non-exposure part and enables formation of a resist patterned film excellent in developability and resolution, a manufacturing method of a resist patterned film which can form the resist patterned film, and a manufacturing method of a plated molded article using the resist patterned film.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble resin, (B1) a polymerizable compound having at least two of (meth)acryloyl groups and hydroxy groups in one molecule and a ring structure, (C) a photo-radical polymerization initiator, (D) at least one compound selected from the group consisting of a nitrogen-containing heterocyclic compound (d1) containing two or more nitrogen atoms, a thiol compound (D2) and a polymerization initiator (d3), and (F) a solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a method for manufacturing a resist pattern film, and a method for manufacturing a plated molded article.

Background Art

[0002] In recent years, connection elements such as bumps of semiconductor elements and display elements such as liquid crystal displays and touch panels need to be arranged on a substrate with high precision.

[0003] Generally, bumps and the like are plated molded articles, and as described in Patent Document 1, a thick film resist pattern is formed on a substrate having a metal foil such as copper, and the thick film resist pattern is used as a mask (mold) for plating. It is manufactured by performing plating.

[0004] Among thick film resist patterns, there is an increasing demand for resist patterns having a film thickness region (≧250 μm) that requires the photosensitive resin composition to be applied to the substrate three times.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, when the film thickness region (≧250 μm) requires the photosensitive resin composition to be applied three times, it has been found that there is a problem that the unexposed portion (the portion that is originally dissolved in the developing process) turns white due to the influence of the heat history during heat drying.

[0007] The present invention aims to provide a photosensitive resin composition that can suppress whitening of unexposed areas and form a resist pattern film with excellent developability and resolution, a method for manufacturing the resist pattern film, and a method for manufacturing a plated object using the resist pattern film. [Means for solving the problem]

[0008] The present invention, which achieves the aforementioned objectives, relates, for example, to the following [1] to

[14] . [1] (A) Alkali-soluble resin, (B1) A polymerizable compound having at least two (meth)acryloyl groups and hydroxyl groups in one molecule, and having a ring structure, (C) Photoradical polymerization initiator, (D) At least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds (d1) containing two or more nitrogen atoms, thiol compounds (d2), and polymerization inhibitors (d3), and (F) Solvent A photosensitive resin composition containing [a specific substance].

[0009] [2] The photosensitive resin composition according to [1], wherein the polymerizable compound (B1) has at least two structures represented by the following formula (1) in one molecule. [ka] [In formula (1), R 1 * indicates a hydrogen atom or a methyl group. * indicates a bonding bond.

[0010] [3] The photosensitive resin composition according to [1] or [2], wherein the ring structure of the polymerizable compound (B1) is an alicyclic hydrocarbon structure.

[0011] [4] A photosensitive resin composition according to any one of [1] to [3], further containing a polymerizable compound (B2) other than the polymerizable compound (B1).

[0012] [5] The photosensitive resin composition according to any one of claims [1] to [4], wherein the photo radical polymerization initiator (C) contains an oxime-based photo radical polymerization initiator (C1).

[0013] [6] The photosensitive resin composition according to [5], wherein the photo radical polymerization initiator (C) further contains a non-oxime-based photo radical polymerization initiator (C2).

[0014] [7] The photosensitive resin composition according to any one of claims [1] to [6], wherein the compound (D) contains the nitrogen-containing heterocyclic compound (d1).

[0015] [8] The photosensitive resin composition according to any one of [1] to [7], which contains the compound (D) in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound (B1).

[0016] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the alkali-soluble resin (A) has a phenolic hydroxyl group-containing structural unit represented by the following formula (2). [Chemical formula] [In formula (2), R 2 represents a hydrogen atom or a methyl group.]

[0017]

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the content of the phenolic hydroxyl group-containing structural unit in 100% by mass of the alkali-soluble resin (A) is in the range of 1 to 40% by mass.

[0018]

[11] A method for manufacturing a resist pattern film, comprising the steps of: (1) applying a photosensitive resin composition described in any one of items [1] to

[10] onto a substrate to form a resin coating film; (2) exposing the resin coating film to light; and (3) developing the resin coating film after exposure.

[0019]

[12] A method for producing a resist pattern film according to

[11] , which involves forming a resist pattern film on a copper film.

[0020]

[13] A method for manufacturing a resist pattern film according to

[11] or

[12] , wherein the thickness of the resin coating film formed in step (1) is 250 μm or more.

[0021]

[14] A method for manufacturing a plated object, comprising the step of using a resist pattern film manufactured by any of the manufacturing methods described in

[11] to

[13] as a mask to perform a plating treatment on the substrate. [Effects of the Invention]

[0022] According to the photosensitive resin composition of the present invention, it is possible to suppress whitening of unexposed areas and suitably produce a resist pattern film with excellent developability and resolution. [Modes for carrying out the invention]

[0023] [Photosensitive resin composition] The photosensitive resin composition of the present invention is a resin composition for forming a resist pattern film. The photosensitive resin composition contains an alkali-soluble resin (A), a polymerizable compound (B1) having at least two (meth)acryloyl groups and hydroxyl groups in one molecule and having a cyclic structure, a photoradical polymerization initiator (C), at least one compound (D) selected from the group consisting of nitrogen-containing heterocyclic compounds (d1) containing two or more nitrogen atoms, thiol compounds (d2), and polymerization inhibitors (d3), and a solvent (F). It may further contain polymerizable compounds other than compound (B1) (B2), and surfactants, etc., as needed.

[0024] <Alkali-soluble resin (A)> The alkali-soluble resin (A) is a resin that has the property of dissolving in an alkaline developer to a degree that allows for the desired developing process. Examples of alkali-soluble resins include those described in Japanese Patent Publication No. 2008-276194, Japanese Patent Publication No. 2003-241372, Japanese Patent Publication No. 2009-531730, WO2010 / 001691, Japanese Patent Publication No. 2011-123225, Japanese Patent Publication No. 2009-222923, and Japanese Patent Publication No. 2006-243161. The weight-average molecular weight (Mw) of the alkali-soluble resin (A) in terms of polystyrene, as measured by gel permeation chromatography, is preferably in the range of 1,000 to 1,000,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 20,000.

[0025] Furthermore, the alkali-soluble resin (A) is preferably one having phenolic hydroxyl groups, as this improves the developability and pattern shape of the resist pattern film. As the alkali-soluble resin (A) having phenolic hydroxyl groups, an alkali-soluble resin (A1) having a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2)") is preferred.

[0026] [ka] [In formula (2), R 2 [This represents a hydrogen atom or a methyl group.]

[0027] By using an alkali-soluble resin (A1) having structural unit (2), a resist pattern that is less prone to swelling during the plating process can be obtained. As a result, lifting or peeling of the resist pattern from the substrate does not occur, and even when the plating process is carried out for a long time, it is possible to prevent the plating solution from seeping into the interface between the substrate and the resist pattern. Furthermore, resolution can also be improved.

[0028] The content of structural unit (2) in the alkali-soluble resin (A1) having structural unit (2) is preferably in the range of 1 to 40% by mass, more preferably in the range of 5 to 30% by mass. By having a structural unit (2) content within the above range, that is, by using monomers that lead to structural unit (2) in such amounts, the molecular weight of the alkali-soluble resin (A1) can be sufficiently increased. Furthermore, a resist pattern that is less prone to swelling during the plating process can be obtained.

[0029] ≪Monomer (2')≫ Alkali-soluble resins (A1) having structural unit (2) can be obtained by polymerization using, for example, hydroxyl group-containing aromatic vinyl compounds (hereinafter also referred to as "monomer (2')") such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and p-isopropenylphenol as part of the raw material monomer. These monomers (2') may be used individually or in combination of two or more.

[0030] Among these monomers (2'), p-hydroxystyrene and p-isopropenylphenol are preferred, and p-hydroxystyrene is more preferred, in that they yield a resin composition capable of forming a resist pattern with excellent resistance to long-term plating treatment.

[0031] ≪Monomer (I)≫ The alkali-soluble resin (A1) having structural unit (2) may further have structural units derived from other monomers copolymerizable with monomer (2') (hereinafter also referred to as "monomer (I)").

[0032] Examples of monomers (I) include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene; Heteroatom-containing alicyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; (meth)acrylic acid derivatives having a glycol structure, such as phenoxydiethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxydipropylene glycol (meth)acrylate, phenoxytripropylene glycol (meth)acrylate, phenoxytetrapropylene glycol (meth)acrylate, lauroxydiethylene glycol (meth)acrylate, lauroxytriethylene glycol (meth)acrylate, lauroxytetraethylene glycol (meth)acrylate, lauroxydipropylene glycol (meth)acrylate, lauroxytripropylene glycol (meth)acrylate, and lauroxytetrapropylene glycol (meth)acrylate; Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile; Conjugated diolefins such as 1,3-butadiene and isoprene; Carboxyl group-containing vinyl compounds such as acrylic acid and methacrylic acid; (Meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanyl (meth)acrylate; Examples include p-hydroxyphenyl(meth)acrylamide. These monomers (I) may be used individually or in combination of two or more.

[0033] Among these monomers (I), styrene, acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tricyclodecanyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and p-hydroxyphenyl (meth)acrylamide are preferred.

[0034] Alkali-soluble resins (A1) can be produced, for example, by radical polymerization. Polymerization methods include emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

[0035] <Polymerizable compound (B1)> Polymerizable compound (B1) (hereinafter also referred to as "compound (B1)") is polymerized at the radical polymerizable unsaturated double bond groups in the exposed area by the action of radicals generated from the photoradical polymerization initiator (C) when a coating film is formed by applying the negative-type photosensitive resin composition of the present invention onto a substrate and the coating film is exposed to light.

[0036] Compound (B1) has at least two (meth)acryloyl groups and at least two hydroxyl groups in one molecule, and has a ring structure. As for compound (B1), compound (B1a), which has at least two structures represented by the following formula (1) in one molecule, is preferred because, in the method for forming a resist pattern film, it is possible to form a resist pattern film without corrosion of the substrate, especially the copper film on a substrate having a copper film on its surface, even when the development speed is increased.

[0037] [ka] [In formula (1), R 1 * indicates a hydrogen atom or a methyl group. * indicates a bonding bond.

[0038] The method for forming the resist pattern film makes it possible to form the resist pattern film without corroding the substrate, especially the copper film on substrates with a copper film on their surface, even when the development speed is increased. This effect is thought to be due to the characteristic action of compound (B1) contained in the resin film formed on the substrate.

[0039] When forming a resist pattern film on a substrate, increasing the development speed makes the substrate portion beneath the holes (pores) formed in the resin film more susceptible to corrosion. For example, in the case of a substrate with a copper film on its surface, needle-shaped defects appear in the copper film portion beneath the holes. This defect is particularly noticeable when forming resist patterns on TSV (Total Stabilized Veneer). The cause of the defects is thought to be that during development, the developer solution remains in the holes and is not discharged, resulting in the copper film being in contact with the alkaline developer solution for an extended period, causing the copper to corrode.

[0040] Compound (B1) remaining on the copper film can be easily removed, for example, by a washing operation after development, such as contact with water. Therefore, compound (B1) does not affect the subsequent manufacturing of plated objects such as bumps. The reason why compound (B1) is easily removed by washing is thought to be that the proportion of hydroxyl groups in compound (B1) is not high, and the affinity of compound (B1) to the copper film is not too strong. In particular, in the case of compound (B1a), since the proportion of hydroxyl groups in compound (B1a) is defined within a certain range by formula (1), it is thought that an affinity for the copper film is achieved such that a certain amount remains on the copper film during development and is completely removed by subsequent washing.

[0041] Compound (B1) contains at least one ring structure, preferably 1 to 3 ring structures. The ring structure contained in compound (B1) is not particularly limited, but it is preferably an alicyclic hydrocarbon structure. Here, the term "alicyclic hydrocarbon structure" refers to a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and may be monocyclic or polycyclic.

[0042] Examples of alicyclic hydrocarbon structures include cycloalkane rings such as cyclohexane rings, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane rings, and bicycloalkene rings such as norbornene, but are not limited to these. Among these, cycloalkane rings are preferred, more preferably cycloalkane rings having 4 to 7 carbon atoms, and even more preferably cyclohexane rings.

[0043] Examples of compound (B1) include compounds obtained by the reaction of epoxy (meth)acrylate with carboxylic acids, alcoholic compounds, or phenolic compounds, as well as diglycidyl ethers, or reaction products of diglycidyl carboxylates with (meth)acrylic acid.

[0044] Examples of carboxylic acid compounds include alicyclic dicarboxylic acids such as hexahydrophthalic acid and hexahydroterephthalic acid, aromatic dicarboxylic acids such as phthalic acid and terephthalic acid, aromatic tricarboxylic acids such as trimesic acid, and aromatic tetracarboxylic acids such as benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and oxydiphthalic acid. Examples of alcoholic and phenolic compounds include alicyclic diols such as cyclohexanediol, biphenols and their derivatives, bisphenol A and its derivatives, biphenol ethers and their derivatives, novolac oligomers and their derivatives, and other phenol derivatives.

[0045] Examples of diglycidyl ethers include alicyclic diglycidyl ethers such as hydrogenated bisphenol A diglycidyl ether, and aromatic diglycidyl ethers such as bisphenol A type epoxy resin.

[0046] Examples of diglycidyl carboxylates include diglycidyl phthalate, diglycidyl terephthalate, diglycidyl hexahydrophthalate, and diglycidyl hexahydroterephthalate. These can be used individually or in combination of two or more types. These reactions can be carried out according to standard procedures.

[0047] Specific examples of compound (B1) include polymerizable compound (B11) used in the examples described later. When compound (B1) is a polymerizable compound having a hydroxyl group and a ring structure, such as compound (B11), it is possible to suppress pattern swelling while exhibiting good developability, thereby forming a resist pattern film with excellent developability and pattern shape.

[0048] The content of compound (B1) in the photosensitive resin composition of the present invention is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and particularly preferably 1 to 20 parts by mass, per 100 parts by mass of alkali-soluble resin (A). When the content of compound (B1) is within this range, it is possible to suppress the generation of residue after development while maintaining a good shape during pattern formation, especially when forming a resin film with a high film thickness.

[0049] <Polymerizable compounds other than polymerizable compounds (B1) (B2)> The photosensitive resin composition of the present invention preferably contains a polymerizable compound (B2) other than the polymerizable compound (B1) mentioned above. When a polymerizable compound (B2) other than the polymerizable compound (B1) (hereinafter also referred to as "compound (B2)") is added to the photosensitive resin composition, the development speed of the resin film decreases, allowing the development speed of the resin film to be adjusted. Adding compound (B2) is effective when the development speed of the resin film is too fast.

[0050] Compound (B2) includes 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloyloxyethyl) ether of bisphenol A, and ethoxylated bisphenol A. Compounds having two ethylenically unsaturated double bonds, such as sphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylol Lupropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tri(meth)acrylate and acid anhydride Reactants with substances, reaction products of dipentaerythritol penta(meth)acrylate and acid anhydrides, tripentaerythritol hepta(meth)acrylate and acid anhydrides, caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate,Examples include compounds having three ethylenically unsaturated double bonds, such as caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol tetra(meth)acrylate, caprolactone-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate, reaction products of caprolactone-modified pentaerythritol tri(meth)acrylate with acid anhydrides, reaction products of caprolactone-modified dipentaerythritol penta(meth)acrylate with acid anhydrides, and caprolactone-modified tripentaerythritol hepta(meth)acrylate with acid anhydrides.

[0051] Examples of commercially available compounds (B2) include Aronics M-8060 (manufactured by Toagosei Co., Ltd.), A9300-1CL (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and epoxy ester 70PA (manufactured by Kyoeisha Chemical Co., Ltd.).

[0052] The amount of compound (B2) can be appropriately determined depending on the purpose. For example, it is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 15 to 50 parts by mass, per 100 parts by mass of alkali-soluble resin (A). When the content of compound (B2) is within this range, a good balance is achieved in the photosensitive resin composition regarding coatability, developability, sensitivity, and resolution.

[0053] <Photoradical polymerization initiator (C)> The photoradical polymerization initiator (C) is a compound that generates radicals upon irradiation with light, thereby initiating the radical polymerization of compound (B1).

[0054] The content of the photoradical polymerization initiator (C) is preferably 1 to 40 parts by mass, more preferably 3 to 35 parts by mass, and particularly preferably 3 to 20 parts by mass, per 100 parts by mass of the polymerizable compound (B1). When the content of the photoradical polymerization initiator (C) is within the above range, a suitable amount of radicals is obtained, and excellent resolution is obtained.

[0055] Photoradical polymerization initiators (C) are broadly classified into oxime-based photoradical polymerization initiators (C1) and non-oxime-based photoradical polymerization initiators (C2). Among these, oxime-based photoradical polymerization initiators (C1), particularly those having an oxime ester structure, are preferred from the viewpoint of sensitivity.

[0056] Photoradical polymerization initiators having an oxime ester structure may have geometric isomers due to the double bond in the oxime, but these are not distinguished and are both included in photoradical polymerization initiator (C).

[0057] Examples of photoradical polymerization initiators having an oxime ester structure include those described in WO2010 / 146883, JP 2011-132215, JP 2008-506749, JP 2009-519904, and JP 2009-519991.

[0058] Specific examples of photoradical polymerization initiators having an oxime ester structure include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine.

[0059] Examples of commercially available photoradical polymerization initiators having an oxime ester structure include TR-PBG-3057 (manufactured by TRONLY Co., Ltd.) and ADEKA Arcluz NCI-930 (manufactured by ADEKA Corporation).

[0060] On the other hand, examples of non-oxime photoradical polymerization initiators (C2) include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, acylphosphine (oxide) compounds are preferred in terms of developability.

[0061] Examples of acylphosphine (oxide) compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0062] Examples of commercially available acylphosphine (oxide) compounds include Omnirad TPO₄H (manufactured by IGM Resins BV) and Omnirad 819 (manufactured by IGM Resins BV).

[0063] These photoradical polymerization initiators (C) may be used individually or in combination of two or more. A preferred embodiment is the use of at least one oxime-based photoradical polymerization initiator (C1) and at least one non-oxime-based photoradical polymerization initiator (C2). The combination of an oxime-based photoradical polymerization initiator (C1) and a non-oxime-based photoradical polymerization initiator (C2) is preferred because the oxime-based photoradical polymerization initiator (C1) increases the degree of curing of the pattern surface, and the non-oxime-based photoradical polymerization initiator (C2) increases the degree of curing of the inside of the pattern, thereby improving the overall shape of the pattern.

[0064] <Compound (D)> Compound (D) is at least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds (d1) containing two or more nitrogen atoms, thiol compounds (d2), and polymerization inhibitors (d3). Among these, the photosensitive resin composition containing a nitrogen-containing heterocyclic compound (d1) is preferred because it has little effect on sensitivity.

[0065] Compound (D) is presumed to suppress the whitening of unexposed areas, which is thought to be due to thermal crosslinking, by suppressing thermal polymerization on the copper substrate surface.

[0066] The content of compound (D) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of polymerizable compound (B1). When the content of compound (D) is within the above range, whitening of the unexposed areas can be suppressed.

[0067] Nitrogen-containing heterocyclic compounds (d1) containing two or more nitrogen atoms Since nitrogen-containing heterocyclic compounds (d1) containing two or more nitrogen atoms readily coordinate to copper, it is presumed that forming a protective film on the copper surface can prevent polymerizable compounds from forming crosslinks due to heat.

[0068] The nitrogen-containing heterocyclic compound (d1) contains two or more nitrogen atoms, preferably three or more. It is presumed that heterocyclic compounds containing only one nitrogen atom have a weaker interaction with copper, resulting in a less effective protective agent by forming a protective film.

[0069] The nitrogen-containing heterocyclic compound (d1) is not particularly limited, but examples include imidazoles, triazoles, and purine derivatives, with imidazoles and triazoles being preferred. These may be used individually or in combination of two or more.

[0070] Imidazoles are not particularly limited, but examples include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-butylimidazole, 2-t-butylimidazole, 2-pentylimidazole, 2-hexylimidazole, 2-heptylimidazole, 2-(1-ethylpentyl)imidazole, 2-octylimidazole, 2- Nonylimidazole, 2-decylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 2-tetradecylimidazole, 2-pentadecylimidazole, 2-hexadecylimidazole, 2-heptadecylimidazole, 2-(1-methylpentyl)imidazole, 2-(1-ethylpentyl)imidazole, 2-(1-heptyldecyl)imidazole, 2-( 5-Hexenyl)imidazole, 2-(9-octenyl)imidazole, 2-(8-heptadecenyl)imidazole, 2-(4-chlorobutyl)imidazole, 2-(9-hydroxynonyl)imidazole, 2-ethyl-4-methylimidazole, 2-undecyl-4-methylimidazole, 2-heptadecyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2 Examples include -(1-naphthyl)imidazole, 2-(1-naphthyl)-4-methylimidazole, 2-(2-naphthyl)imidazole, 2-(2-naphthyl)-4-methylimidazole, 2-methyl-4-phenylimidazole, 4-phenylimidazole, 4-methylimidazole, 4-isopropylimidazole, 4-octylimidazole, 2,4,5-trimethylimidazole, and benzimidazole. Benzenimidazole is particularly preferred.

[0071] Triazoles are not particularly limited, but examples include 1,2,3-triazole, 1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-ethyl-1,2,4-triazole, 1-propyl-1,2,4-triazole, 1-isopropyl-1,2,4-triazole, 1-butyl-1,2,4-triazole, 1-methyl-1,2,3-triazole, 1-ethyl-1,2,3-triazole, 1-propyl-1,2,3-triazole, 1-isopropyl-1,2,3-triazole, 1-butyl-1,2,3-triazole, 1-methylbenzotriazole, 1,2,3-benzotriazole, and 5-methyl-1H-benzotriazole. Particularly preferred is 1,2,3-benzotriazole.

[0072] Purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, and 8-amino Examples include adenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and their derivatives.

[0073] Thiol compound (d2) Since the thiol compound (d2), like the nitrogen-containing heterocyclic compound (d1), readily coordinates to copper, it is presumed that forming a protective film on the copper surface can prevent the polymerizable compound from forming crosslinks on the copper surface due to heat.

[0074] The thiol compound (d2) may be either a monofunctional thiol compound or a polyfunctional thiol compound, but from the viewpoint of further increasing the sensitivity of the photosensitive resin composition to exposure light, it is preferable that it be a polyfunctional thiol compound (d2-a). A monofunctional thiol compound is a compound that has one thiol group (mercapto group) in its molecule. Examples of monofunctional thiol compounds include stearyl-3-mercaptopropionate. A polyfunctional thiol compound (d2-a) is a compound having two or more thiol groups (mercapto groups) in its molecule. As a polyfunctional thiol compound, low molecular weight compounds with a molecular weight of 100 or more are preferred; specifically, those with a molecular weight of 100 to 1,500 are more preferred, and those with a molecular weight of 150 to 1,000 are even more preferred.

[0075] The number of functional groups in the polyfunctional thiol compound (d2-a) is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 4. A larger number of functional groups results in superior film strength, while a smaller number of functional groups results in superior storage stability. Within the above range, both of these can be achieved.

[0076] As the polyfunctional thiol compound (d2-a), either an aromatic polyfunctional thiol compound or an aliphatic polyfunctional thiol compound can be used, and as the aromatic polyfunctional thiol compound, a compound having a benzothiazole structure is more preferred.

[0077] Examples of compounds having a benzothiazole structure include benzothiazole and 2-mercaptobenzothiazole. Among these, 2-mercaptobenzothiazole is preferred.

[0078] Examples of aliphatic polyfunctional thiol compounds include pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), and tris[(3-mercaptopropionyloxy)ethyl]iso Examples include cyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate). Among these, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are more preferred.

[0079] Examples of commercially available aliphatic polyfunctional thiol compounds include C3TS-G (manufactured by Shikoku Chemicals Co., Ltd.), Karenz MT-PE-1, Karenz MT-BD-1, Karenz MT-NR-1, TPMB, TEMB (all manufactured by Showa Denko K.K.), TMMP, TEMPIC, PEMP, EGMP-4, and DPMP (all manufactured by Sakai Chemical Industry Co., Ltd.).

[0080] These thiol compounds (C) may be used individually or in combination of two or more.

[0081] Polymerization inhibitor (d3) It is presumed that the polymerization inhibitor (d3) suppresses the thermal crosslinking of polymerizable compounds on the copper surface. Furthermore, the polymerization inhibitor (d3) may also contribute to improving the storage stability of the photosensitive resin composition.

[0082] Examples of polymerization inhibitors (d3) include hydroquinone, hydroquinone monoesters, N-nitrosodiphenylamine, benzoquinone, phenothiazine, p-methoxyphenol, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol, chloranyl, and pyrogallol.

[0083] As the polymerization inhibitor (d3), phenolic polymerization inhibitors (d3-a) such as hydroquinone, p-methoxyphenol, and catechol are preferred. Examples of phenolic polymerization inhibitors (d3-a) include (d31) and (d32), which were used in the examples described later. These polymerization inhibitors (d3) may be used individually or in combination of two or more.

[0084] <Solvent (F)> The photosensitive resin composition of the present invention, by containing a solvent (F), can have its handling properties improved, its viscosity adjusted, and its storage stability improved.

[0085] As for solvent (F), Alcohols such as methanol, ethanol, and propylene glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Glycols such as ethylene glycol and propylene glycol; Alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; Alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Esters such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, hydroxyethyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and ethyl lactate; Examples include N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0086] In the present invention, the amount of ethylene glycol-based solvent used is preferably 50% by mass or more, more preferably 80% by mass or more, based on 100% by mass of the total solvent. By using an ethylene glycol-based solvent as solvent (F) within the above range, it becomes easier to form resin films with significantly different film thicknesses.

[0087] The amount of solvent (F) used is preferably 50 parts by mass or more, more preferably 60 to 300 parts by mass, and particularly preferably 70 to 200 parts by mass, per 100 parts by mass of alkali-soluble resin (A).

[0088] <Other ingredients> In addition to the components described above, the resin composition may optionally contain a thermal polymerization inhibitor to improve the storage stability of the resin composition, a surfactant, an adhesion aid to improve the adhesion between the resin film and the substrate, a sensitizer to increase sensitivity, an inorganic filler to improve the strength of the resin film, etc., to the extent that they do not impair the objectives and properties of the present invention.

[0089] <<Surfactants>> Adding surfactants to a resin composition can improve its applicability, defoaming properties, leveling properties, and other characteristics.

[0090] Commercially available surfactants can be used as surfactants. Specific examples of commercially available surfactants include, for example, NBX-15, FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218, FTX-220D, FTX-222D (all manufactured by Neos Co., Ltd.), BM-1000, BM-1100 (both manufactured by BM Chemie Co., Ltd.), Megafac F142D, F172, F173, F183 (all manufactured by Dainippon Ink and Chemicals, Inc.). Examples include Florard FC-135, FC-170C, FC-430, and FC-431 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, S-113, S-131, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Dow Corning Silicone Co., Ltd.).

[0091] <Method for preparing a photosensitive resin composition> The photosensitive resin composition of the present invention can be prepared by uniformly mixing each component. Alternatively, to remove impurities, the mixture may be filtered using a filter or the like after uniformly mixing each component.

[0092] [Method for manufacturing a resist pattern film] The present invention's method for manufacturing a resist pattern film is characterized by comprising the following steps 1 to 3. Step 1: A step of applying the photosensitive resin composition onto a substrate to form a resin coating film. Step 2: Exposure of the resin coating film. Step 3: Developing the resin coating after exposure.

[0093] [Step (1)] In step (1), the photosensitive resin composition is applied to a substrate to form a resin coating. Examples of substrates include semiconductor substrates, glass substrates, silicon substrates, and substrates formed by providing various metal films (particularly copper films are preferred) on the surface of semiconductor plates, glass plates, or silicon plates. There are no particular restrictions on the shape of the substrate. It may be a flat plate or a flat plate with recesses (holes) like a silicon wafer. In the case of a substrate with recesses and a copper film on its surface, the copper film may be provided at the bottom of the recesses, as in a TSV structure.

[0094] As a method for applying the photosensitive composition, for example, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet method can be used, with the spin coating method being particularly preferred. In the case of the spin coating method, the rotation speed is preferably 800 to 3000 rpm, more preferably 800 to 2000 rpm, and the rotation time is preferably 1 to 300 seconds, more preferably 5 to 200 seconds. After spin coating the photosensitive composition, the obtained resin coating film is heat-dried at preferably 50 to 180°C, more preferably 60 to 150°C, and particularly preferably 70 to 130°C for about 1 to 30 minutes.

[0095] The thickness of the resin coating is preferably 200 to 400 μm, and is particularly preferable when forming a pattern with a high film thickness of 250 μm or more, as this is when the effects of the present invention are exhibited.

[0096] [Step (2)] In step (2), the resin coating is exposed to light. That is, the resin coating is selectively exposed to light so that a resist pattern film is obtained in step (3).

[0097] Exposure is typically performed on the resin coating film using a desired photomask, for example, a contact aligner, stepper, or scanner. The exposure light used is typically light with a wavelength of 200-500 nm (e.g., i-line (365 nm)). The exposure dose varies depending on the type and amount of components in the resin coating film, the thickness of the coating film, etc., but when using i-line light, it is preferably 1-10,000 mJ / cm². 2 That is the case.

[0098] Furthermore, heat treatment can be performed after exposure. The conditions for heat treatment after exposure are appropriately determined depending on the type and amount of components in the resin coating, the thickness of the resin coating, etc., but preferably 70 to 180°C for 1 to 60 minutes.

[0099] [Step (3)] In step (3), the resin coating film after exposure is developed. This forms a resist pattern film.

[0100] As a developer, for example, an aqueous solution containing sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonane, etc. can be used. Alternatively, an aqueous solution obtained by adding an appropriate amount of a water-soluble solvent such as methanol or ethanol, or a surfactant, to the aqueous solution of the above alkalis can also be used as a developer.

[0101] The development time varies depending on the type and proportion of each component in the composition, the thickness of the coating, etc., but is preferably 10 to 1200 seconds, more preferably 30 to 1000 seconds, and particularly preferably 60 to 900 seconds. Any development method such as the liquid-filling method, dipping method, paddle method, spray method, or shower development method may be used.

[0102] Depending on the development time, it is likely that the compound (B1) contained in the unexposed portion of the resin coating film will not be completely removed and will remain attached to the substrate in some amount. Therefore, in step (3), after contacting the resin coating film with an alkaline aqueous solution, washing may be performed to remove the compound (B1) remaining on the substrate. Washing can be performed, for example, by bringing water into contact with the substrate. The contact time with water is, for example, 60 to 600 seconds. Contact with water can be performed, for example, by applying running water or by spraying water. Afterward, you can air dry them using an air gun or dry them under heat using a hot plate or oven.

[0103] [Method for manufacturing plated molded objects] The present invention's method for manufacturing a plated object is characterized by comprising the step of performing a plating treatment on a substrate using a resist pattern film formed by the resist pattern film manufacturing method described above as a mask.

[0104] Examples of plated molded objects include bumps, wiring, and the like. The resist pattern film is formed according to the resist pattern film manufacturing method described above. Examples of the aforementioned plating processes include wet plating processes such as electrolytic plating, electroless plating, and molten metal plating, as well as dry plating processes such as chemical vapor deposition and sputtering. When forming wiring or connection terminals in wafer-level processing, the plating process is usually carried out by electrolytic plating.

[0105] Before performing electroplating, pretreatments such as ashing, fluxing, and desmearing can be applied to the inner wall surface of the resist pattern to increase its affinity with the plating solution.

[0106] In the case of electrolytic plating, a layer formed on the inner wall of the resist pattern by sputtering or electroless plating can be used as a seed layer. Furthermore, if a substrate having a metal film on its surface is used as the substrate, the metal film can also be used as a seed layer.

[0107] A barrier layer may be formed before the seed layer, or the seed layer may be used as the barrier layer. Examples of plating solutions used in electrolytic plating include copper plating solutions containing copper sulfate or copper pyrophosphate; gold plating solutions containing potassium gold cyanide; and nickel plating solutions containing nickel sulfate or nickel carbonate.

[0108] Plating processes can be performed sequentially using different plating treatments. For example, by first performing copper plating, then nickel plating, and then molten solder plating, a solder copper pillar bump can be formed. [Examples]

[0109] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The weight-average molecular weight (Mw) of the alkali-soluble resin was calculated using the polystyrene equivalent in gel permeation chromatography under the following conditions. • Column: TSKgel SuperMultiporeHZ-M manufactured by Tosoh Corporation • Solvent: tetrahydrofuran Column temperature: 40°C • Detection method: Refractive index method • Standard material: Polystyrene • GPC device: Manufactured by Tosoh Corporation, device name "HLC-8320-GPC"

[0110] <Manufacturing of photosensitive resin composition> [Examples 1A-16A, and Comparative Examples 1A-11A] Using propylene glycol monomethyl ether acetate as a solvent, the components shown in Table 1 were added to the solvent in amounts corresponding to the solid content concentrations shown in Table 1, mixed, and filtered through a capsule filter (pore size 1 μm) to produce the photosensitive resin compositions of Examples 1A to 16A and Comparative Examples 1A to 11A.

[0111] [Table 1-1]

[0112] [Table 1-2]

[0113] [Table 1-3]

[0114] The details of each component shown in Table 1 are as follows:

[0115] Acrylic-soluble resin (A11) Acrylic resin having structural units denoted by symbols a to e as shown in the following formula (A11) (Mw: 12000, content ratio of structural units a to e: a / b / c / d / e = 10 / 15 / 25 / 20 / 30 (mass%))

[0116] [ka]

[0117] Acrylic-soluble resin (A12) Acrylic resin having structural units denoted by symbols a to e as shown in the following formula (A12) (Mw: 10000, content ratio of structural units a to e: a / b / c / d / e = 10 / 12 / 25 / 19 / 34 (mass%))

[0118] [ka]

[0119] Acrylic-soluble resin (A13) Acrylic resin having structural units denoted by symbols a to e as shown in the following formula (A13) (Mw: 10000, content ratio of structural units a to e: a / b / c / d / e = 10 / 10 / 25 / 20 / 35 (mass%))

[0120] [ka]

[0121] Acrylic soluble resin (A14) Acrylic resin having structural units denoted by symbols a to e as shown in the following formula (A14) (Mw: 10000, content ratio of structural units a to e: a / b / c / d / e = 10 / 20 / 25 / 15 / 30 (mass%))

[0122] [ka]

[0123] Polymerizable compounds (B11): Compounds shown in the following formula (B11)

[0124] [ka]

[0125] Polymerizable compound (B21): Polyester acrylate (product name "Aronics M-8060", manufactured by Toagosei Co., Ltd.) Polymerizable compound (B22): Product name "A9300-1CL", manufactured by Shin Nakamura Chemical Industry Co., Ltd. Polymerizable compound (B23): Product name "Epoxy Ester 70PA", manufactured by Kyoeisha Chemical Co., Ltd.

[0126] Photoradical polymerization initiator (C11): Product name "TR-PBG-3057", manufactured by TRONLY Co., Ltd. Photoradical polymerization initiator (C12): Product name "ADEKA Arcluz NCI-930", manufactured by ADEKA Corporation. Photoradical polymerization initiator (C21): 2,2-dimethoxy-2-phenylacetophenone (product name "Omnirad 651", manufactured by IGM Resins BV) Photoradical polymerization initiator (C22): 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name "Omnirad TPO H", manufactured by IGM Resins BV) Photoradical polymerization initiator (C23): Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (product name "Omnirad 819", manufactured by IGM Resins BV)

[0127] Nitrogen-containing heterocyclic compound (d11): 1,2,3-benzotriazole Nitrogen-containing heterocyclic compounds (d12): Benzimidazole

[0128] Thiol compound (d21): 2-mercaptobenzothiazole Thiol compound (d22): Product name "C3TS-G", manufactured by Shikoku Chemicals Co., Ltd. Thiol compound (d23): Pentaerythritol tetrakis(3-mercaptobutyrate) (product name "Karenz MT PE1", manufactured by Showa Denko K.K.)

[0129] Polymerization inhibitor (d31): Compound shown in the following formula (d31)

[0130] [ka]

[0131] Polymerization inhibitor (d32): Compound shown in the following formula (d32)

[0132] [ka]

[0133] Other ingredients (E1): Product name "Futergent FTX-218", manufactured by Neos Co., Ltd.

[0134] <Manufacturing of resist pattern films> [Example 1B] A photosensitive resin composition of Example 1A was applied to a substrate with a copper sputtered film on a 12-inch silicon wafer by spin coating. The first layer was heated on a hot plate at 120°C or 130°C for 300 seconds, and the second and third layers were heated for 600 seconds each, to form a resin coating with a thickness of 350 μm. The aforementioned coating film was exposed to light through a pattern mask using a stepper (Canon, model "FPA-5520iV"), developed by immersion in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 720 seconds, and then washed with pure water for 480 seconds to attempt the formation of resist pattern films measuring 180 μm (vertical) × 180 μm (horizontal) × 340 μm (depth) and 200 μm (vertical) × 200 μm (horizontal) × 340 μm (depth).

[0135] The "developability" of the photosensitive resin composition was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: The film formed by heating at 130°C three times had a development rate of 50 μm / min or more. B: The development rate of the film formed by heating at 130°C three times was between 40 μm / min and 50 μm / min. C: The film formed by heating at 130°C three times had a development rate of less than 40 μm / min.

[0136] The "pattern shape" of the resist pattern film was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: The pattern is rectangular, and there is no tension at the top of the pattern or indentation at the bottom. B: The pattern is rectangular, but there is a slight tension at the top of the pattern and a slight indentation at the bottom. C: The rectangular shape of the pattern is compromised, and the tension at the top of the pattern and the indentation at the bottom of the pattern are clearly visible.

[0137] The whitening of unexposed areas was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: No whitening was observed even after heating at 130°C three times. B: No whitening was observed with heating at 120°C twice and 130°C once, but some whitening was observed with heating at 130°C three times. Whitening was also observed after heating at 120°C twice and 130°C once.

[0138] Furthermore, the smallest resist pattern film that could be formed among those attempted was determined. The "resolution" of the photosensitive resin composition was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: It resolved patterns up to 180 μm vertically x 180 μm horizontally x 340 μm deep. B: The pattern was resolved down to 200 μm in height, 200 μm in width, and 340 μm in depth. C: A pattern measuring 200 μm vertically x 200 μm horizontally x 340 μm deep could not be resolved.

[0139] [Examples 2B-16B, Comparative Examples 1B-11B] Except for using the photosensitive resin composition shown in Table 2 below instead of the photosensitive resin composition of Example 1A, the resist pattern films of Examples 2B to 16B and Comparative Examples 1B to 11B were formed using the same procedure as in Example 1B, and the degree of development, pattern shape, whitening of unexposed areas, and resolution were evaluated. The evaluation results are shown in Table 2.

[0140] [Table 2]

Claims

1. (A) Alkali-soluble resin, (B1) A polymerizable compound having at least two (meth)acryloyl groups and two hydroxyl groups in one molecule, and having an alicyclic hydrocarbon structure. (C) Photoradical polymerization initiator, (D) At least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds (d1) containing two or more nitrogen atoms and thiol compounds (d2), and (F) solvent It contains, The polymerizable compound (B1) is (i) Reaction products of epoxy (meth)acrylate and alicyclic dicarboxylic acids, and (ii) At least one reaction product selected from the group consisting of reaction products of alicyclic dicarboxylic acid diglycidyl ester and (meth)acrylic acid, The nitrogen-containing heterocyclic compound (d1) is at least one selected from the group consisting of imidazoles, triazoles, and purine derivatives. A photosensitive resin composition wherein the photoradical polymerization initiator (C) comprises an oxime-based photoradical polymerization initiator (C1) and a non-oxime-based photoradical polymerization initiator (C2).

2. The photosensitive resin composition according to claim 1, wherein the polymerizable compound (B1) has at least two structures represented by the following formula (1) in one molecule. 【Chemistry 1】 [In formula (1), R １ * indicates a hydrogen atom or a methyl group. * indicates a bonding bond.

3. The photosensitive resin composition according to claim 1, further containing a polymerizable compound (B2) other than the polymerizable compound (B1).

4. The photosensitive resin composition according to claim 1, wherein the compound (D) comprises the nitrogen-containing heterocyclic compound (d1).

5. The photosensitive resin composition according to claim 1, comprising 0.05 to 20 parts by mass of compound (D) per 100 parts by mass of polymerizable compound (B1).

6. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) has a phenolic hydroxyl group-containing structural unit represented by the following formula (2). 【Chemistry 2】 [In formula (2), R ２ This represents a hydrogen atom or a methyl group.

7. The photosensitive resin composition according to claim 6, wherein the content of the phenolic hydroxyl group-containing structural unit in 100% by mass of the alkali-soluble resin (A) is in the range of 1 to 40% by mass.

8. A method for manufacturing a resist pattern film, comprising the steps of: (1) applying a photosensitive resin composition according to any one of claims 1 to 7 onto a substrate to form a resin coating film; (2) exposing the resin coating film to light; and (3) developing the resin coating film after exposure.

9. A method for producing a resist pattern film according to claim 8, wherein a resist pattern film is formed on a copper film.

10. The method for manufacturing a resist pattern film according to claim 8, wherein the thickness of the resin coating film formed in step (1) is 250 μm or more.

11. A method for manufacturing a plated object, comprising the step of performing a plating treatment on the substrate using a resist pattern film manufactured by the manufacturing method described in claim 8 as a mask.

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