WO2020066633A1 - Photosensitive resin composition, method for forming resist pattern, and method for manufacturing plated shaped body - Google Patents

Photosensitive resin composition, method for forming resist pattern, and method for manufacturing plated shaped body Download PDF

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Publication number
WO2020066633A1
WO2020066633A1 PCT/JP2019/035753 JP2019035753W WO2020066633A1 WO 2020066633 A1 WO2020066633 A1 WO 2020066633A1 JP 2019035753 W JP2019035753 W JP 2019035753W WO 2020066633 A1 WO2020066633 A1 WO 2020066633A1
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Prior art keywords
resist pattern
resin composition
photosensitive resin
meth
acrylate
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PCT/JP2019/035753
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French (fr)
Japanese (ja)
Inventor
優 木村
石川　弘樹
朋之 松本
佐藤　慶一
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Jsr株式会社
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Priority to CN201980052361.1A priority Critical patent/CN112585535B/en
Priority to KR1020217008561A priority patent/KR102706084B1/en
Priority to JP2020548403A priority patent/JP7331855B2/en
Publication of WO2020066633A1 publication Critical patent/WO2020066633A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a plated molded article.
  • connection terminals such as wiring and bumps of semiconductor elements and display elements such as liquid crystal displays and touch panels have been increasingly miniaturized due to increasing demands for high-density mounting.
  • wiring and bumps are formed by plating, and as described in Patent Document 1, a photosensitive resin composition is applied on a substrate having a metal foil such as copper to form a resist coating film.
  • the resist film is manufactured by exposing and developing the resist coating film using a mask to form a resist pattern, and plating the substrate using the resist pattern as a mask.
  • a portion of the resist coating film where a resist for wiring is formed densely is a bright area (bright field,
  • the portion where the resist for bumps is sparsely formed is a dark region (dark field) where the exposure amount is relatively small.
  • the resist coating film is required to have such a property that a resist pattern is formed with high precision in both the bright field and the dark field even if the effective exposure amount is somewhat different between the bright field and the dark field.
  • a resist composition having a wide common exposure latitude (Exposure Latitude, also referred to as “EL” for short) in which the exposure ranges in which a good resist pattern can be formed in both the dark field and the bright field overlap.
  • the exposure allowance means a range of exposure in which a resist pattern can be formed with high accuracy.
  • the present invention provides a photosensitive resin composition having a wide common exposure latitude (EL) in a dark field and a bright field, and can form a fine resist pattern with high accuracy in both a dark field and a bright field. It is an object of the present invention to provide a method for forming a resist pattern, and a method for manufacturing a plated object capable of manufacturing a fine plated object with high accuracy.
  • EL exposure latitude
  • the present invention that achieves the above object relates to, for example, the following [1] to [8].
  • a polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D) are contained, and the content of the thiol compound (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the compound (A), and the content of the polymerization inhibitor (D) is 1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound (A).
  • Characteristic photosensitive resin composition [2] The photosensitive resin composition according to [1], wherein the thiol compound (C) is a polyfunctional thiol compound (C-1).
  • a method of manufacturing a plated object comprising a step of performing plating on the substrate using a resist pattern formed by the method for forming a resist pattern according to [7] as a mask.
  • the present invention can provide a photosensitive resin composition having a wide common exposure latitude (EL) in a dark field and a bright field.
  • EL exposure latitude
  • the photosensitive resin composition it is possible to provide a method of forming a resist pattern capable of forming a fine resist pattern with high accuracy in both a bright field and a dark field.
  • the resist pattern formed by the method for forming a resist pattern it is possible to provide a method of manufacturing a plated molded article capable of producing an accurate and fine plated molded article.
  • FIG. 1 is an electron microscope photograph of the resist patterns of Examples 1B and 2B and Comparative Example 3B.
  • FIG. 2 is an electron microscope photograph of a plated product using a 2 ⁇ m 1L / 1S resist pattern in EOP as a mask.
  • the photosensitive resin composition of the present invention contains a polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D).
  • the content is 5 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound (A)
  • the content of the polymerization inhibitor (D) is 1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound (A). 10 parts by mass.
  • the photosensitive resin composition of the present invention has a wide common EL in a dark field and a bright field. As described above, when the common EL of the photosensitive resin composition is narrow, a difference easily occurs in the accuracy of the formed resist pattern between the bright field and the dark field. There are several possible reasons why the common EL of the photosensitive resin composition becomes narrower. Among them, the present inventor has found that (1) the diffusion length of radicals generated when the photosensitive resin composition is exposed is long. And (2) the sensitivity of the photosensitive resin composition to exposure light was low.
  • the diffusion length of the radical is long, in addition to the area exposed to the exposure light in the resist coating film formed from the photosensitive resin composition, the radical generated by the exposure diffuses over a wide range, exceeding the expected range. The radical reaction proceeds, and the accuracy of the resist pattern decreases. For this reason, it is considered that the exposure range in which a highly accurate resist pattern can be formed is limited, and the common EL becomes narrow.
  • the extent and extent to which the radical reaction proceeds depend on the amount of radicals generated and the diffusion length. Since the amount of generated radicals differs between the bright field and the dark field, a difference occurs in the precision of the resist pattern between the bright field and the dark field.
  • a certain amount of a polymerization inhibitor is added to the photosensitive resin composition in order to suppress the diffusion length of the radical.
  • a polymerization inhibitor when a polymerization inhibitor is added, the sensitivity is greatly reduced. Therefore, a fixed amount of a thiol compound, particularly a polyfunctional thiol compound, capable of increasing the sensitivity is added to the photosensitive resin composition. That is, the polymerization inhibitor suppresses the adverse effects caused by the long diffusion length of the radical, and the thiol compound suppresses the adverse effects caused by the decrease in sensitivity caused by the addition of the polymerization inhibitor.
  • the present invention achieves a wide common EL by the combined effect of the polymerization inhibitor and the thiol compound.
  • the common EL of the photosensitive resin composition of the present invention is usually at least 8%, preferably at least 10%, more preferably at least 15%. Therefore, when forming a resist pattern using the photosensitive resin composition of the present invention, even a fine resist pattern, the selectable exposure range is wide, the formation of the resist pattern is simple, and in line with the purpose The resist pattern can be easily formed in both the bright field and the dark field.
  • a region corresponding to the formation of a resist pattern of 1: 1 line and space of 2 ⁇ m (hereinafter abbreviated as “1 L / 1S of 2 ⁇ m”) is referred to as a bright field and a line of 1/3 line and space of 2 ⁇ m.
  • a region corresponding to the formation of a resist pattern in a space (hereinafter abbreviated as “1 L / 3S of 2 ⁇ m”) is defined as a dark field.
  • the common EL forms a fine resist pattern with high precision in a bright field when an exposure amount at which a 2 ⁇ m 1L / 1S resist pattern is optimally formed is an optimal exposure amount (hereinafter, also referred to as “EOP”).
  • EOP optimal exposure amount
  • the ratio of the exposure amount range in which the possible exposure amount range overlaps with the exposure amount range in which a fine resist pattern can be accurately formed in the dark field is shown as a ratio to the optimum exposure amount.
  • the polymerizable compound (A) is a component that undergoes radical polymerization by an active species generated from a photoradical polymerization initiator upon exposure, and preferably has at least one ethylenically unsaturated double bond in one molecule.
  • a (meth) acrylate compound having a (meth) acryloyl group and a compound having a vinyl group are preferable.
  • the (meth) acrylate compound is classified into a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound, and any compound may be used.
  • Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate.
  • polyfunctional (meth) acrylate compound examples include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane PO (propylene oxide) modified tri (meth) acrylate, and tetramethylolpropane.
  • Epoxy (meth) acrylate bisphenol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxymethyl ethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyester (Meth) acrylate (trifunctional or higher), and the like reaction product of phthalic acid and epoxy acrylate.
  • the polymerizable compound (A) a commercially available compound can be used as it is.
  • Commercially available compounds include, for example, Aronix M-210, M-309, M-310, M-320, M-400, M-7100, M-8030, M-8060, M-8100, M-9050, M-240, M-245, M-6100, M-6200, M-6250, M-6300, M-6400, M-6500 ( KAYARAD @ R-551, R-712, TMPTA, HDDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-604, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.), Viscort # 295, 300, 260, 312, and 335 P, the 360, the same GPT, the same 3PA, the 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.
  • polymerizable compounds (A) may be used alone or in combination of two or more.
  • the content ratio of the polymerizable compound (A) in the present photosensitive resin composition is usually from 5 to 90% by mass, preferably from 10 to 70% by mass, more preferably from 15 to 50% by mass in the solid content.
  • solid content refers to all components other than the solvent contained in the photosensitive resin composition.
  • the photo-radical polymerization initiator (B) is a compound that generates radicals upon irradiation with exposure light and starts radical polymerization of the polymerizable compound (A).
  • the photopolymerization initiator (B) include oxime compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azides
  • Examples include compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds.
  • an oxime-based photoradical polymerization initiator (B1) particularly a photoradical polymerization initiator having an oxime ester structure, is preferable.
  • the photoradical polymerization initiator having an oxime ester structure may have geometric isomers due to the double bond of the oxime, but these are not distinguished and all are included in the photoradical polymerization initiator (B).
  • Examples of the photoradical polymerization initiator having an oxime ester structure include WO2010 / 146883, JP-A-2011-132215, JP-T-2008-506749, JP-T-2009-519904, and JP-T-2009-5191991. Photo-radical polymerization initiators described in the gazette are mentioned.
  • photoradical polymerization initiator having an oxime ester structure examples include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and 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-methyl Benzoyl) -9H-carbazol-3-yl] ethane-1-imine and N-acetoxy-1- [9-ethyl-6- ⁇ 2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl ⁇ -9H-carbazol-3-yl] ethane-1-imine, ethanone, 1- [9-ethyl-ethy
  • photopolymerization initiators (B) may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (B) in the present photosensitive resin composition is generally 1 to 40 parts by mass, preferably 3 to 35 parts by mass, more preferably 5 to 35 parts by mass based on 100 of the polymerizable compound (A). 3030 parts by mass.
  • a suitable radical amount is obtained, and excellent resolution is obtained.
  • the thiol compound (C) improves the sensitivity of the photosensitive resin composition, and achieves a wide common EL in both the bright field and the dark field due to the combined effect with the polymerization inhibitor (D). Is a component that contributes to
  • the thiol compound (C) may be either a monofunctional thiol compound or a polyfunctional thiol compound, but is preferably a polyfunctional thiol compound (C-1) from the viewpoint of further increasing the sensitivity of the photosensitive resin composition to exposure light. Is preferred.
  • the monofunctional thiol compound is a compound having one thiol group (mercapto group) in a molecule. Examples of the monofunctional thiol compound include stearyl-3-mercaptopropionate.
  • the polyfunctional thiol compound (C-1) is a compound having two or more thiol groups (mercapto groups) in a molecule.
  • a low molecular weight compound having a molecular weight of 100 or more is preferable, and specifically, the molecular weight is more preferably 100 to 1,500, and further preferably 150 to 1,000.
  • the number of functional groups of the polyfunctional thiol compound (C-1) is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 4.
  • the number of functional groups is large, the film strength is excellent, while when the number of functional groups is small, the storage stability is excellent. In the case of the above range, these can be compatible.
  • an aliphatic polyfunctional thiol compound is preferable.
  • the thiol group in the polyfunctional thiol compound (C-1) may be a primary thiol group, a secondary thiol group, or a tertiary thiol group. From the viewpoint of properties, it is preferably a primary or secondary thiol group, and more preferably a secondary thiol group. Further, from the viewpoint of storage stability, a secondary or tertiary thiol group is preferable, and a secondary thiol group is more preferable.
  • Examples of the aliphatic polyfunctional thiol compound include pentaerythritol tetrakis (3-mercaptobutyrylate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (3-mercaptobutyryloxyethyl) ) -1,3,5-Triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), tri Methylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) And dipentaerythris Tall hexakis (3-mercaptopropionat
  • C-1 Commercial products of the aliphatic polyfunctional thiol compound (C-1) include, for example, Karenz MT-PE-1, Karenz MT-BD-1, Karenz MT-NR-1, TPMB, and TEMB (all of Showa Denko KK) ), TMMP, TEMPIC, PEMP, EGMP-4, and DPMP (all manufactured by Sakai Chemical Industry Co., Ltd.).
  • thiol compounds (C) may be used alone or in combination of two or more. From the viewpoint of realizing a wide common EL by a combined effect with the polymerization inhibitor (D), the content of the thiol compound (C) is, as described above, based on 100 parts by mass of the polymerizable compound (A). The amount is 5 to 50 parts by mass, preferably 5 to 35 parts by mass, more preferably 5 to 25 parts by mass.
  • the polymerization inhibitor (D) is a component that suppresses the diffusion length of radicals and contributes to the realization of a wide common EL by a combined effect with the thiol compound (C). Further, the polymerization inhibitor (D) can also contribute to improving the storage stability of the photosensitive resin composition.
  • Examples of the polymerization inhibitor (D) include hydroquinone, monoesters of hydroquinone, N-nitrosodiphenylamine, benzoquinone, phenothiazine, p-methoxyphenol, pt-butylcatechol, N-phenylnaphthylamine, and 2,6-diphenyl. -T-butyl-p-methylphenol, chloranil, pyrogallol.
  • phenolic polymerization inhibitors (D-1) such as hydroquinone, p-methoxyphenol, and catechol are preferable.
  • Commercial products of the polymerization inhibitor (D) include, for example, Irganox 1010 (manufactured by BASF) and Kinopower QS20 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.). These polymerization inhibitors (D) may be used alone or in combination of two or more.
  • the content of the polymerization inhibitor (D) is, as described above, based on 100 parts by mass of the polymerizable compound (A).
  • the amount is 1 to 10 parts by mass, preferably 3 to 8 parts by mass, more preferably 4 to 6 parts by mass.
  • the photosensitive resin composition of the present invention preferably contains an alkali-soluble resin (E).
  • E alkali-soluble resin
  • resistance to a plating solution can be imparted to the resist, and development can be performed with an alkali developing solution.
  • the alkali-soluble resin (E) is a resin having a property of dissolving in an alkaline developer to such an extent that the desired development processing can be performed.
  • Examples of the alkali-soluble resin (E) include, for example, JP-A-2008-276194, JP-A-2003-241372, JP-T-2009-53730, WO2010 / 001691, JP-A-2011-123225, Known alkali-soluble resins described in Japanese Unexamined Patent Application Publication No. 2009-222923 and JP-A-2006-243161 are exemplified.
  • examples of the alkali-soluble resin (E) include simple resins having an acidic functional group such as (meth) acrylic acid, maleic acid, p-hydroxystyrene, isopropenylphenol, and hydroxyphenyl (meth) acrylate. And resins having structural units derived from other monomers such as styrene, N-phenylmaleimide, n-butyl (meth) acrylate, isobrenyl (meth) acrylate, and isobornyl vinyl ether. .
  • the weight average molecular weight (Mw) of the alkali-soluble resin (E) in terms of polystyrene measured by gel permeation chromatography is generally 1,000 to 1,000,000, preferably 2,000 to 50,000, Preferably it is in the range of 3,000 to 20,000.
  • the alkali-soluble resin (E) preferably has a phenolic hydroxyl group from the viewpoint of improving the plating solution resistance of the resist.
  • the alkali-soluble resin (E) may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin (E) is usually 50 to 300 parts by mass, preferably 100 to 250 parts by mass, based on 100 parts by mass of the polymerizable compound (A).
  • the content of the alkali-soluble resin is in the above range, a resist excellent in plating solution resistance can be formed.
  • the photosensitive resin composition of the present invention may contain, as other components, a solvent, a surfactant, an adhesion aid, a sensitizer, an inorganic filler, and the like, as long as the object and properties of the present invention are not impaired. .
  • a solvent a surfactant, an adhesion aid, a sensitizer, an inorganic filler, and the like.
  • 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, propylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; Ethyl acetate, butyl acetate, ethoxy
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent may be such that the solid content of the photosensitive resin composition is 5 to 80% by mass.
  • the photosensitive resin composition of the present invention can be produced by uniformly mixing the above components.
  • the method for forming a resist pattern according to the present invention includes the steps of: (1) forming a resin coating film by applying the above-described photosensitive resin composition on a substrate; (2) exposing the resin coating film; (3) a step of developing the resin coating film.
  • the photosensitive resin composition is applied on a substrate to form a resin coating film.
  • the substrate is not particularly limited as long as it is a substrate on which the resin coating film can be formed.
  • a semiconductor substrate, a glass substrate, a silicon substrate and a semiconductor plate, a glass plate, various metal films are provided on the surface of the silicon plate. And the like.
  • the shape of the substrate is not particularly limited. It may have a flat plate shape or a shape in which a concave portion (hole) is provided in a flat plate like a silicon wafer.
  • a copper film may be provided at the bottom of the concave portion as in the TSV structure.
  • the method for applying the photosensitive resin composition is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an ink jet method.
  • the method is preferred.
  • the rotation speed is usually 800 to 3000 rpm, preferably 800 to 2000 rpm
  • the rotation time is usually 1 to 300 seconds, preferably 5 to 200 seconds.
  • the resulting coating film is heated and dried, for example, at 50 to 250 ° C. for about 1 to 30 minutes.
  • the thickness of the resin coating film is generally 0.1 to 300 ⁇ m, preferably 1 to 100 ⁇ m.
  • the plated object is wiring, it is usually 0.1 to 50 ⁇ m, and the plated object is a bump.
  • it is an electrode, it is usually 1 to 300 ⁇ m. Since the effect of oxygen inhibition becomes more pronounced as the thickness of the resin coating becomes thinner, it is preferable that the thickness be in the above-described range when a plated molded article is manufactured.
  • step (2) the resin coating film is exposed. That is, the resin coating film is selectively exposed so as to obtain a resist pattern in step (3).
  • the coating film is usually exposed through a desired photomask, for example, using a contact aligner, a stepper, or a scanner.
  • the exposure light light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is usually used.
  • the amount of exposure varies depending on the type and amount of components in the coating film, the thickness of the coating film, and the like. However, when i-line is used for the exposure light, it is usually from 1 to 10,000 mJ / cm 2 .
  • the photosensitive resin composition used for forming the resin coating film has a wide common EL in both the dark field and the bright field, the fine resin having the bright field and the dark field in the step (2) is used. Even when a proper resist pattern is formed, a resist pattern suitable for the purpose can be satisfactorily formed.
  • a heat treatment can be performed after the exposure.
  • the conditions of the heat treatment after the exposure are appropriately determined depending on the types and the amounts of the components in the resin coating film, the thickness of the coating film, and the like, and are usually 70 to 180 ° C. for 1 to 60 minutes.
  • step (3) the exposed resin coating is developed.
  • a resist pattern is formed.
  • the developer include 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.
  • An aqueous solution of 0] -5-nonane can be used. Further, an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above-mentioned alkalis can also be used as the developer.
  • a water-soluble organic solvent such as methanol or ethanol or a surfactant
  • the development time varies depending on the type and proportion of each component in the composition, the thickness of the coating film, and the like, but is usually 30 to 600 seconds.
  • the method of development may be any of a puddle method, a dipping method, a paddle method, a spray method, a shower development method and the like.
  • the resist pattern prepared as described above can be further cured by performing additional exposure (hereinafter, referred to as “post-exposure”) or heating according to the intended use.
  • Post-exposure can be performed by the same method as the above-mentioned exposure.
  • the exposure amount is not particularly limited, but is preferably 100 to 10,000 mJ / cm 2 when a high-pressure mercury lamp is used. Heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 60 to 200 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 5 to 60 minutes in an oven. do it.
  • a cured film having a pattern having better characteristics can be obtained.
  • the resist pattern may be washed with running water or the like. Thereafter, air drying may be performed using an air gun or the like, or drying may be performed under heating using a hot plate or an oven.
  • a method of manufacturing a plated object according to the present invention includes a step of performing a plating process on the substrate using the resist pattern formed by the above-described method for forming a resist pattern as a mask.
  • Examples of the plated object include a bump, a wiring, and the like.
  • the formation of the resist pattern is performed according to the above-described method of forming a resist pattern.
  • Examples of the plating treatment include wet plating such as electrolytic plating, electroless plating, and hot-dip plating, and dry plating such as chemical vapor deposition and sputtering.
  • plating is usually performed by electrolytic plating.
  • a pretreatment such as an ashing process, a flux process, and a desmear process can be performed on the inner wall surface of the resist pattern.
  • a layer formed on the inner wall of the resist pattern by sputtering or electroless plating can be used as a seed layer, and when a substrate having a metal film on the surface is used as the substrate, the metal film is seeded. It can also be used as a layer.
  • the barrier layer may be formed before forming the seed layer, and the seed layer may be used as the barrier layer.
  • the plating solution used in the electrolytic plating process include a copper plating solution containing copper sulfate or copper pyrophosphate; a gold plating solution containing gold potassium cyanide; and a nickel plating solution containing nickel sulfate or nickel carbonate; Is mentioned.
  • the conditions of the electrolytic plating can be appropriately selected depending on the type of the plating solution and the like.
  • the current density is usually 10 to 90 ° C. and the current density is 0.1 to 100 A / dm 2 .
  • solder copper pillar bumps can be formed by first performing copper plating, then performing nickel plating, and then performing molten solder plating.
  • the thickness of the plated object varies depending on the application, but is, for example, usually 1 to 300 ⁇ m for a bump electrode and 0.1 to 50 ⁇ m for a wiring.
  • a resist pattern is formed using the above-described photosensitive resin composition. Therefore, even if the resist pattern is a fine resist pattern, a resist pattern suitable for the purpose can be easily formed. For this reason, in the method of manufacturing a plated object of the present invention using the resist pattern formed by the above-described method of forming a resist pattern, a fine plated object can be accurately and simply manufactured.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is a value calculated by gel permeation chromatography in terms of polystyrene under the following conditions.
  • Surfactant (F1) diglycerin ethylene oxide (average number of moles added: 18) adduct perfluorononenyl ether (product name "Fantagent FTX-218", manufactured by Neos Corporation)
  • Example 1B The photosensitive resin composition of Example 1A is applied to a substrate having a copper sputter film on a 6-inch silicon wafer by spin coating, and heated at 110 ° C. for 180 seconds on a hot plate to have a film thickness of 12 ⁇ m. A resin coating was formed.
  • the resin coating film was formed in a region corresponding to the formation of a 2 ⁇ m 1L / 1S resist pattern (hereinafter referred to as a “BF corresponding region”). ) And a region corresponding to the formation of a 2 ⁇ m 1L / 3S resist pattern (hereinafter, referred to as a “DF corresponding region”). Exposure was carried out 25 shot a shot that was increased from 20mJ / cm 2 by 10mJ / cm 2 to 260mJ / cm 2.
  • FIG. 1 shows a photograph of the electron microscope of Example 1B.
  • Example 1B a resist pattern was formed in the same manner as in Example 1B except that the photosensitive resin composition shown in Table 2 was used, and the exposure amount range in the BF corresponding region and the DF corresponding region, and the overlapping exposure The amount range, as well as the common EL, were measured. Table 2 shows the evaluation results.
  • FIG. 1 shows a photograph of an electron microscope of Example 2B and Comparative Example 3B.
  • Example 1C ⁇ Manufacture of plated objects>
  • the substrate having the resist pattern formed in Example 1B was subjected to an ashing process.
  • the substrate after the ashing treatment was immersed in 1 liter of a copper plating solution (product name “MICROFAB Cu300”, manufactured by EEJA) at 25 ° C. for 15 minutes to perform an electrolytic plating reaction.
  • the resist pattern was stripped using a resist stripper (product name “ELPAC THB-S17”, manufactured by JSR Corporation) to produce a plated model.
  • FIG. 2 is an electron micrograph of a plated product using a 2 ⁇ m 1L / 1S resist pattern in EOP as a mask.

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Abstract

The present invention is a photosensitive resin composition characterized by containing a polymerizable compound (A), a light radical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D), the content of the thiol compound (C) being 5-50 mass parts to 100 mass parts of the polymerizable compound (A), and the content of the polymerization inhibitor (D) being 1-10 mass parts to 100 mass parts of the polymerizable compound (A). The present invention makes it possible to provide a photosensitive resin composition having wide exposure latitude (EL) in both bright fields and dark fields. Using the photosensitive resin composition, it is possible to provide a method for forming a resist pattern with which it is possible to form a fine resist pattern having good accuracy in both bright fields and dark fields. Using a resist pattern formed using the method for forming a resist pattern, it is possible to provide a method for manufacturing a plated shaped body with which it is possible to manufacture a fine plated shaped body having good accuracy.

Description

感光性樹脂組成物、レジストパターンの形成方法、およびメッキ造形物の製造方法Photosensitive resin composition, method for forming resist pattern, and method for producing plated object
　本発明は、感光性樹脂組成物、レジストパターンの形成方法、およびメッキ造形物の製造方法に関する。 The present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a plated molded article.
　近年、半導体素子や、液晶ディスプレイやタッチパネル等の表示素子の配線やバンプ等の接続端子は、高密度に実装することに対する要求が高まっていることから、微細化が進んでいる。 In recent years, connection terminals such as wiring and bumps of semiconductor elements and display elements such as liquid crystal displays and touch panels have been increasingly miniaturized due to increasing demands for high-density mounting.
　一般的に、配線やバンプなどはメッキ造形物であり、特許文献１に記載されるように、銅等の金属箔を有する基板上に感光性樹脂組成物を塗布してレジスト塗膜を形成し、そのレジスト塗膜にマスクを用いて露光および現像を行って、レジストパターンを形成し、そのレジストパターンをマスクにして、基板上にメッキを行うことで製造される。 In general, wiring and bumps are formed by plating, and as described in Patent Document 1, a photosensitive resin composition is applied on a substrate having a metal foil such as copper to form a resist coating film. The resist film is manufactured by exposing and developing the resist coating film using a mask to form a resist pattern, and plating the substrate using the resist pattern as a mask.
　このため、配線やバンプ等の微細化にともない、その製造に用いられるレジストパターンも微細化が必要になってきている。 (4) For this reason, with miniaturization of wirings, bumps, and the like, the miniaturization of resist patterns used in the manufacture thereof is also required.
特開２００６－２８５０３５号公報JP 2006-285035 A
　ネガ型のレジスト塗膜にマスクを用いて露光を行うとき、レジスト塗膜において、配線用のレジストが密に形成されるような部分は、相対的に露光量が多くなる明領域（ブライトフィールド、Bright-Field）となり、バンプ用のレジストが疎に形成されるような部分は、相対的に露光量が少なくなる暗領域（ダークフィールド、Dark-Field）となる。 When performing exposure using a mask on a negative resist coating film, a portion of the resist coating film where a resist for wiring is formed densely is a bright area (bright field, The portion where the resist for bumps is sparsely formed is a dark region (dark field) where the exposure amount is relatively small.
　レジストパターンが微細化すると、露光光の回析、漏れ光、基板からの露光光の反射の影響が強くなり、ブライトフィールドとダークフィールドとにおいて、レジスト塗膜に対する実質的な露光量（実行露光量）が異なってくる。そのことに起因して、ブライトフィールドとダークフィールドとにおいて、形成されるレジストパターンの精度に差が生じるという不具合が生じる。そのため、ブライトフィールドとダークフィールドとにおいて、実行露光量がある程度異なったとしても、ブライトフィールドとダークフィールドとの両方においてレジストパターンが高精度で形成されるような性質がレジスト塗膜に要求される。すなわち、ダークフィールドおよびブライトフィールドの両方において良好なレジストパターンが形成できる露光量の範囲が重複する、広い共通の露光量余裕度（Exposure Latitude、略して「ＥＬ」ともいう）を有するレジスト組成物が求められる。ここで、露光量余裕度（ＥＬ）とは、レジストパターンが高精度で形成され得る露光量の範囲を意味する。 As the resist pattern becomes finer, the effects of diffraction of exposure light, leakage light, and reflection of exposure light from the substrate become stronger, and a substantial exposure amount (effective exposure amount) to the resist coating film in a bright field and a dark field. ) Will be different. As a result, there arises a problem that a difference occurs in the accuracy of the formed resist pattern between the bright field and the dark field. For this reason, the resist coating film is required to have such a property that a resist pattern is formed with high precision in both the bright field and the dark field even if the effective exposure amount is somewhat different between the bright field and the dark field. That is, a resist composition having a wide common exposure latitude (Exposure Latitude, also referred to as “EL” for short) in which the exposure ranges in which a good resist pattern can be formed in both the dark field and the bright field overlap. Desired. Here, the exposure allowance (EL) means a range of exposure in which a resist pattern can be formed with high accuracy.
　本発明は、ダークフィールドおよびブライトフィールドにおいて広い共通の露光量余裕度（ＥＬ）を有する感光性樹脂組成物を提供すること、ダークフィールドおよびブライトフィールドの両方において精度良く、微細なレジストパターンを形成できるレジストパターンの形成方法を提供すること、および精度良く、微細なメッキ造形物を製造できるメッキ造形物の製造方法を提供すること、を目的とする。 The present invention provides a photosensitive resin composition having a wide common exposure latitude (EL) in a dark field and a bright field, and can form a fine resist pattern with high accuracy in both a dark field and a bright field. It is an object of the present invention to provide a method for forming a resist pattern, and a method for manufacturing a plated object capable of manufacturing a fine plated object with high accuracy.
　前記目的を達成する本発明は、例えば下記［１］～［８］に関する。
［１］　重合性化合物（Ａ）、光ラジカル重合開始剤（Ｂ）、チオール化合物（Ｃ）、および重合禁止剤（Ｄ）を含有し、前記チオール化合物（Ｃ）の含有量が、前記重合性化合物（Ａ）１００質量部に対して５～２０質量部、前記重合禁止剤（Ｄ）の含有量が、前記重合性化合物（Ａ）１００質量部に対して１～５質量部であることを特徴とする感光性樹脂組成物。
［２］　前記チオール化合物（Ｃ）が多官能チオール化合物（Ｃ－１）である、前記［１］に記載の感光性樹脂組成物。
［３］　前記チオール化合物（Ｃ）１００質量物に対して、前記重合禁止剤（Ｄ）の含有量が２０～８０質量部である、前記［１］または［２］に記載の感光性樹脂組成物。
［４］　前記重合禁止剤（Ｄ）がフェノール系重合禁止剤（Ｄ－１）である前記［１］～［３］のいずれかに記載の感光性樹脂組成物。
［５］　前記光ラジカル重合開始剤（Ｂ）がオキシム系光ラジカル重合開始剤（Ｂ１）である、前記［１］～［４］のいずれかに記載の感光性樹脂組成物。
［６］　さらに、アルカリ可溶性樹脂（Ｅ）を含有する、前記［１］～［５］に記載の感光性樹脂組成物。
［７］　前記［１］～［６］のいずれかに記載の感光性樹脂組成物を基板上に塗布して樹脂塗膜を形成する工程（１）、前記樹脂塗膜を露光する工程（２）、露光後の樹脂塗膜を現像する工程（３）、を有することを特徴とするレジストパターンの形成方法。
［８］　前記［７］に記載のレジストパターンの形成方法によって形成したレジストパターンをマスクにして、前記基板に対してメッキ処理を行う工程を有することを特徴とするメッキ造形物の製造方法。 The present invention that achieves the above object relates to, for example, the following [1] to [8].
[1] A polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D) are contained, and the content of the thiol compound (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the compound (A), and the content of the polymerization inhibitor (D) is 1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound (A). Characteristic photosensitive resin composition.
[2] The photosensitive resin composition according to [1], wherein the thiol compound (C) is a polyfunctional thiol compound (C-1).
[3] The photosensitive resin composition according to [1] or [2], wherein the content of the polymerization inhibitor (D) is 20 to 80 parts by mass based on 100 parts by mass of the thiol compound (C). Stuff.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the polymerization inhibitor (D) is a phenolic polymerization inhibitor (D-1).
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photo-radical polymerization initiator (B) is an oxime-based photo-radical polymerization initiator (B1).
[6] The photosensitive resin composition according to any one of [1] to [5], further containing an alkali-soluble resin (E).
[7] A step (1) of applying the photosensitive resin composition according to any of the above [1] to [6] on a substrate to form a resin coating, and a step of exposing the resin coating (2). ), And a step (3) of developing the resin coating film after exposure.
[8] A method of manufacturing a plated object, comprising a step of performing plating on the substrate using a resist pattern formed by the method for forming a resist pattern according to [7] as a mask.
　本発明は、ダークフィールドおよびブライトフィールドにおいて広い共通の露光量余裕度（ＥＬ）を有する感光性樹脂組成物を提供することができる。前記感光性樹脂組成物を用いて、ブライトフィールドとダークフィールドとの両方において精度良く、微細なレジストパターンを形成することができる、レジストパターンの形成方法を提供することができる。前記レジストパターンの形成方法により形成したレジストパターンを用いて、精度の良い、微細なメッキ造形物を製造することができる、メッキ造形物の製造方法を提供することができる。 The present invention can provide a photosensitive resin composition having a wide common exposure latitude (EL) in a dark field and a bright field. By using the photosensitive resin composition, it is possible to provide a method of forming a resist pattern capable of forming a fine resist pattern with high accuracy in both a bright field and a dark field. By using the resist pattern formed by the method for forming a resist pattern, it is possible to provide a method of manufacturing a plated molded article capable of producing an accurate and fine plated molded article.
図１は、実施例１Ｂ、２Ｂおよび比較例３Ｂのレジストパターンの電子顕微鏡の写真である。FIG. 1 is an electron microscope photograph of the resist patterns of Examples 1B and 2B and Comparative Example 3B. 図２は、ＥＯＰにおける２μｍの１Ｌ／１Ｓレジストパターンをマスクとしたメッキ造形物の電子顕微鏡の写真である。FIG. 2 is an electron microscope photograph of a plated product using a 2 μm 1L / 1S resist pattern in EOP as a mask.
［感光性樹脂組成物］
　本発明の感光性樹脂組成物は、重合性化合物（Ａ）、光ラジカル重合開始剤（Ｂ）、チオール化合物（Ｃ）、および重合禁止剤（Ｄ）を含有し、前記チオール化合物（Ｃ）の含有量が、前記重合性化合物（Ａ）１００質量部に対して５～５０質量部、前記重合禁止剤（Ｄ）の含有量が、前記重合性化合物（Ａ）１００質量部に対して１～１０質量部である。 [Photosensitive resin composition]
The photosensitive resin composition of the present invention contains a polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D). The content is 5 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound (A), and the content of the polymerization inhibitor (D) is 1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound (A). 10 parts by mass.
　本発明の感光性樹脂組成物は、ダークフィールドおよびブライトフィールドにおいて広い共通のＥＬを有する。
　前述のとおり、感光性樹脂組成物の共通のＥＬが狭いと、ブライトフィールドとダークフィールドとにおいて、形成されるレジストパターンの精度に差が生じやすくなる。感光性樹脂組成物の共通のＥＬが狭くなる理由として、いくつか考えられるが、その中でも本発明者は、（１）感光性樹脂組成物に露光をしたときに発生するラジカルの拡散長が長すぎること、および（２）感光性樹脂組成物の露光光に対する感度が低いこと、に着目した。 The photosensitive resin composition of the present invention has a wide common EL in a dark field and a bright field.
As described above, when the common EL of the photosensitive resin composition is narrow, a difference easily occurs in the accuracy of the formed resist pattern between the bright field and the dark field. There are several possible reasons why the common EL of the photosensitive resin composition becomes narrower. Among them, the present inventor has found that (1) the diffusion length of radicals generated when the photosensitive resin composition is exposed is long. And (2) the sensitivity of the photosensitive resin composition to exposure light was low.
　ラジカルの拡散長が長いと、感光性樹脂組成物から形成されたレジスト塗膜における露光光が当たったエリア以外にも、露光により発生したラジカルが広範囲に拡散し、想定していた範囲を超えてラジカル反応が進むことになり、レジストパターンの精度が低下する。このため、高精度のレジストパターンを形成できる露光量範囲が制限され、共通のＥＬが狭くなると考えられる。ラジカル反応が進む範囲および程度は、ラジカルの発生量と拡散長に依存する。ラジカルの発生量はブライトフィールドとダークフィールドとでは異なるので、ブライトフィールドとダークフィールドとでレジストパターンの精度に差が生じるようになる。 If the diffusion length of the radical is long, in addition to the area exposed to the exposure light in the resist coating film formed from the photosensitive resin composition, the radical generated by the exposure diffuses over a wide range, exceeding the expected range. The radical reaction proceeds, and the accuracy of the resist pattern decreases. For this reason, it is considered that the exposure range in which a highly accurate resist pattern can be formed is limited, and the common EL becomes narrow. The extent and extent to which the radical reaction proceeds depend on the amount of radicals generated and the diffusion length. Since the amount of generated radicals differs between the bright field and the dark field, a difference occurs in the precision of the resist pattern between the bright field and the dark field.
　また、感光性樹脂組成物の露光光に対する感度が低いと、露光量を増やす必要があることになるので、漏れ光の影響が大きくなる。このため、感度の低さが共通のＥＬに影響すると考えられる。 (4) When the sensitivity of the photosensitive resin composition to exposure light is low, the amount of exposure needs to be increased, so that the influence of light leakage increases. Therefore, it is considered that the low sensitivity affects the common EL.
　そこで、本発明においては、ラジカルの拡散長を抑えるために、感光性樹脂組成物に重合禁止剤を一定量添加する。一方、重合禁止剤を入れると感度が大幅に下がるので、感度を高めることが可能なチオール化合物、特に多官能チオール化合物を感光性樹脂組成物に一定量添加する。つまり、重合禁止剤によって、ラジカルの長い拡散長に起因する弊害を抑制し、重合禁止剤の添加により生じる、感度の低下に起因する弊害をチオール化合物によって抑制する。さらに、多官能チオールの添加により、基板とレジスト塗膜との接着性が強くなり、レジストパターンの精度がより向上する。以上のとおり、本発明は、重合禁止剤とチオール化合物との複合的な効果により、広い共通のＥＬを実現したものである。 Therefore, in the present invention, a certain amount of a polymerization inhibitor is added to the photosensitive resin composition in order to suppress the diffusion length of the radical. On the other hand, when a polymerization inhibitor is added, the sensitivity is greatly reduced. Therefore, a fixed amount of a thiol compound, particularly a polyfunctional thiol compound, capable of increasing the sensitivity is added to the photosensitive resin composition. That is, the polymerization inhibitor suppresses the adverse effects caused by the long diffusion length of the radical, and the thiol compound suppresses the adverse effects caused by the decrease in sensitivity caused by the addition of the polymerization inhibitor. Further, by the addition of the polyfunctional thiol, the adhesiveness between the substrate and the resist coating film is increased, and the accuracy of the resist pattern is further improved. As described above, the present invention achieves a wide common EL by the combined effect of the polymerization inhibitor and the thiol compound.
　本発明の感光性樹脂組成物が有する共通のＥＬは、通常８％以上、好ましくは１０％以上、より好ましくは１５％以上である。このため、本発明の感光性樹脂組成物を用いてレジストパターンを形成するときには、微細なレジストパターンであっても選択できる露光量範囲が広く、レジストパターンの形成が簡便であり、目的に沿ったレジストパターンをブライトフィールドおよびダークフィールドの両方において容易に形成することができる。 The common EL of the photosensitive resin composition of the present invention is usually at least 8%, preferably at least 10%, more preferably at least 15%. Therefore, when forming a resist pattern using the photosensitive resin composition of the present invention, even a fine resist pattern, the selectable exposure range is wide, the formation of the resist pattern is simple, and in line with the purpose The resist pattern can be easily formed in both the bright field and the dark field.
　なお、本明細書では、２μｍ寸法の１対１ラインアンドスペース（以下、「２μｍの１Ｌ／１Ｓ」と略す）のレジストパターンの形成に対応する領域をブライトフィールド、２μｍ寸法の１対３ラインアンドスペース（以下、「２μｍの１Ｌ／３Ｓ」と略す）のレジストパターンの形成に対応する領域をダークフィールドとする。共通のＥＬは、２μｍの１Ｌ／１Ｓレジストパターンが最適に形成される露光量を最適露光量（以下、「ＥＯＰ」ともいう）としたとき、ブライトフィールドにおいて、精度良く、微細なレジストパターンを形成できる露光量範囲と、ダークフィールドにおいて、精度良く、微細なレジストパターンを形成できる露光量範囲とが重複する露光量範囲の、前記最適露光量に対する割合を示す。 In the present specification, a region corresponding to the formation of a resist pattern of 1: 1 line and space of 2 μm (hereinafter abbreviated as “1 L / 1S of 2 μm”) is referred to as a bright field and a line of 1/3 line and space of 2 μm. A region corresponding to the formation of a resist pattern in a space (hereinafter abbreviated as “1 L / 3S of 2 μm”) is defined as a dark field. The common EL forms a fine resist pattern with high precision in a bright field when an exposure amount at which a 2 μm 1L / 1S resist pattern is optimally formed is an optimal exposure amount (hereinafter, also referred to as “EOP”). The ratio of the exposure amount range in which the possible exposure amount range overlaps with the exposure amount range in which a fine resist pattern can be accurately formed in the dark field is shown as a ratio to the optimum exposure amount.
　重合性化合物（Ａ）は、露光により光ラジカル重合開始剤から発生する活性種によりラジカル重合する成分であり、好ましくは、１分子中に少なくとも１個のエチレン性不飽和二重結合を有する。 The polymerizable compound (A) is a component that undergoes radical polymerization by an active species generated from a photoradical polymerization initiator upon exposure, and preferably has at least one ethylenically unsaturated double bond in one molecule.
　重合性化合物（Ａ）としては、（メタ）アクリロイル基を有する（メタ）アクリレート化合物、ビニル基を有する化合物が好ましい。前記（メタ）アクリレート化合物は、単官能性（メタ）アクリレート化合物と多官能性（メタ）アクリレート化合物とに分類されるが、いずれの化合物であってもよい。 As the polymerizable compound (A), a (meth) acrylate compound having a (meth) acryloyl group and a compound having a vinyl group are preferable. The (meth) acrylate compound is classified into a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound, and any compound may be used.
　上記単官能性（メタ）アクリレート化合物としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシルアミル（メタ）アクリレート、ラウリル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、グリセロール（メタ）アクリレート、エチレングリコールモノメチルエーテル（メタ）アクリレート、エチレングリコールモノエチルエーテル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシポリプロピレングリコール（メタ）アクリレート、トリシクロ〔５．２．１．０2,6〕デカジエニル（メタ）アクリレート、トリシクロ〔５．２．１．０2,6〕デカニル（メタ）アクリレート、トリシクロ〔５．２．１．０2,6〕デセニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、アクリル酸アミド、メタクリル酸アミド、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、ｔｅｒｔ－オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７－アミノ－３，７－ジメチルオクチル（メタ）アクリレートなどが挙げられる。 Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. ) Acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) ) Acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) ) Acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl amyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl ( (Meth) acrylate, phenoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, glycerol (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, tricyclo [5. 2.1.0 2,6 ] decadienyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decanyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decenyl (meth) ) Acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, cyclohexyl (meth) acrylate, acrylamide, methacrylamide, diacetone (meth) acrylamide, isobutoxime Tyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, tert-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl ( (Meth) acrylate and the like.
　上記多官能性（メタ）アクリレート化合物としては、例えば、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンＰＯ（propylene oxide）変性トリ（メタ）アクリレート、テトラメチロールプロパンテトラ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ビスフェノールＡのジグリシジルエーテルに（メタ）アクリル酸を付加させたエポキシ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリロイルオキシエチルエーテル、ビスフェノールＡジ（メタ）アクリロイルオキシメチルエチルエーテル、ビスフェノールＡジ（メタ）アクリロイルオキシエチルオキシエチルエーテル、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ポリエステル（メタ）アクリレート（三官能以上）、フタル酸とエポキシアクリレートとの反応物などが挙げられる。 Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane PO (propylene oxide) modified tri (meth) acrylate, and tetramethylolpropane. Tetra (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tris (2-hydroxyethyl) (Meth) acrylic acid was added to isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, and diglycidyl ether of bisphenol A. Epoxy (meth) acrylate, bisphenol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxymethyl ethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyester (Meth) acrylate (trifunctional or higher), and the like reaction product of phthalic acid and epoxy acrylate.
　重合性化合物（Ａ）として、市販されている化合物をそのまま用いることができる。市販されている化合物としては、例えば、アロニックスＭ－２１０、同Ｍ－３０９、同Ｍ－３１０、同Ｍ－３２０、同Ｍ－４００、同Ｍ－７１００、同Ｍ－８０３０、同Ｍ－８０６０、同Ｍ－８１００、同Ｍ－９０５０、同Ｍ－２４０、同Ｍ－２４５、同Ｍ－６１００、同Ｍ－６２００、同Ｍ－６２５０、同Ｍ－６３００、同Ｍ－６４００、同Ｍ－６５００（以上、東亞合成（株）製）、ＫＡＹＡＲＡＤ Ｒ－５５１、同Ｒ－７１２、同ＴＭＰＴＡ、同ＨＤＤＡ、同ＴＰＧＤＡ、同ＰＥＧ４００ＤＡ、同ＭＡＮＤＡ、同ＨＸ－２２０、同ＨＸ－６２０、同Ｒ－６０４、同ＤＰＣＡ－２０、ＤＰＣＡ－３０、同ＤＰＣＡ－６０、同ＤＰＣＡ－１２０（以上、日本化薬（株）製）、ビスコート＃２９５、同３００、同２６０、同３１２、同３３５ＨＰ、同３６０、同ＧＰＴ、同３ＰＡ、同４００（以上、大阪有機化学工業（株）製）などが挙げられる。 と し て As the polymerizable compound (A), a commercially available compound can be used as it is. Commercially available compounds include, for example, Aronix M-210, M-309, M-310, M-320, M-400, M-7100, M-8030, M-8060, M-8100, M-9050, M-240, M-245, M-6100, M-6200, M-6250, M-6300, M-6400, M-6500 ( KAYARAD @ R-551, R-712, TMPTA, HDDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-604, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.), Viscort # 295, 300, 260, 312, and 335 P, the 360, the same GPT, the same 3PA, the 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.
　これらの重合性化合物（Ａ）は、１種単独で用いてもよく、２種以上を併用してもよい。
　本感光性樹脂組成物における重合性化合物（Ａ）の含有割合は、固形分中、通常５～９０質量％であり、好ましくは１０～７０質量％、より好ましくは１５～５０質量％である。なお、本発明において、「固形分」とは、感光性樹脂組成物に含まれる溶剤以外の全成分をいう。 These polymerizable compounds (A) may be used alone or in combination of two or more.
The content ratio of the polymerizable compound (A) in the present photosensitive resin composition is usually from 5 to 90% by mass, preferably from 10 to 70% by mass, more preferably from 15 to 50% by mass in the solid content. In the present invention, “solid content” refers to all components other than the solvent contained in the photosensitive resin composition.
　光ラジカル重合開始剤（Ｂ）は、露光光の照射によりラジカルを発生し、重合性化合物（Ａ）のラジカル重合を開始させる化合物である。
　光重合開始剤（Ｂ）としては、例えば、オキシム系化合物、有機ハロゲン化化合物、オキシジアゾール化合物、カルボニル化合物、ケタール化合物、ベンゾイン化合物、アクリジン化合物、有機過酸化化合物、アゾ化合物、クマリン化合物、アジド化合物、メタロセン化合物、ヘキサアリールビイミダゾール化合物、有機ホウ酸化合物、ジスルホン酸化合物、オニウム塩化合物、アシルホスフィン（オキシド）化合物が挙げられる。これらの中でも、感度の点から、オキシム系光ラジカル重合開始剤（Ｂ１）、特にオキシムエステル構造を有する光ラジカル重合開始剤が好ましい。 The photo-radical polymerization initiator (B) is a compound that generates radicals upon irradiation with exposure light and starts radical polymerization of the polymerizable compound (A).
Examples of the photopolymerization initiator (B) include oxime compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azides Examples include compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, from the viewpoint of sensitivity, an oxime-based photoradical polymerization initiator (B1), particularly a photoradical polymerization initiator having an oxime ester structure, is preferable.
　オキシムエステル構造を有する光ラジカル重合開始剤にはオキシムの二重結合に起因する幾何異性体が存在しうるが、これらは区別されず、いずれも光ラジカル重合開始剤（Ｂ）に含まれる。 光 The photoradical polymerization initiator having an oxime ester structure may have geometric isomers due to the double bond of the oxime, but these are not distinguished and all are included in the photoradical polymerization initiator (B).
　オキシムエステル構造を有する光ラジカル重合開始剤としては、例えば、ＷＯ２０１０／１４６８８３号公報、特開２０１１－１３２２１５号公報、特表２００８－５０６７４９号公報、特表２００９－５１９９０４、および特表２００９－５１９９９１号公報に記載光ラジカル重合開始剤が挙げられる。 Examples of the photoradical polymerization initiator having an oxime ester structure include WO2010 / 146883, JP-A-2011-132215, JP-T-2008-506749, JP-T-2009-519904, and JP-T-2009-5191991. Photo-radical polymerization initiators described in the gazette are mentioned.
　オキシムエステル構造を有する光ラジカル重合開始剤の具体例としては、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－エトキシカルボニルオキシ－ １－フェニルプロパン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－アセトキシ－１－ ［９ －エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、およびＮ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）（イルガキュアOXE-02）等が挙げられる。 Specific examples of the photoradical polymerization initiator having an oxime ester structure include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and 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-methyl Benzoyl) -9H-carbazol-3-yl] ethane-1-imine and N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl {-9H-carbazol-3-yl] ethane-1-imine, ethanone, 1- [9-ethyl- - (2-methylbenzoyl) -9H- carbazol-3-yl] -, 1-(O-acetyl oxime) (IRGACURE OXE-02), and the like.
　これらの光重合開始剤（Ｂ）は、１種単独で用いてもよく、２種以上を併用してもよい。
　本感光性樹脂組成物における光重合開始剤（Ｂ）の含有量は、重合性化合物（Ａ）１００に対して、通常１～４０質量部であり、好ましくは３～３５質量、より好ましくは５～３０質量部である。光ラジカル重合開始剤（Ｂ）の含有量が前記範囲内であると、好適なラジカル量が得られ、優れた解像度が得られる。 These photopolymerization initiators (B) may be used alone or in combination of two or more.
The content of the photopolymerization initiator (B) in the present photosensitive resin composition is generally 1 to 40 parts by mass, preferably 3 to 35 parts by mass, more preferably 5 to 35 parts by mass based on 100 of the polymerizable compound (A). ３０30 parts by mass. When the content of the photo-radical polymerization initiator (B) is within the above range, a suitable radical amount is obtained, and excellent resolution is obtained.
　チオール化合物（Ｃ）は、前述のとおり、感光性樹脂組成物の感度を向上させ、重合禁止剤（Ｄ）との複合的な効果により、ブライトフィールドおよびダークフィールドの両方における広い共通のＥＬの実現に寄与する成分である。 As described above, the thiol compound (C) improves the sensitivity of the photosensitive resin composition, and achieves a wide common EL in both the bright field and the dark field due to the combined effect with the polymerization inhibitor (D). Is a component that contributes to
　チオール化合物（Ｃ）は、単官能チオール化合物および多官能チオール化合物のいずれでもよいが、感光性樹脂組成物の露光光に対する感度をより高める観点から、多官能チオール化合物（Ｃ－１）であることが好ましい。
　単官能チオール化合物とは、チオール基（メルカプト基）を分子内に１個有する化合物である。単官能チオール化合物としては、例えばステアリル－３－メルカプトプロピオネート等を挙げることができる。
　多官能チオール化合物（Ｃ－１）とは、チオール基（メルカプト基）を分子内に２個以上有する化合物である。多官能チオール化合物としては、分子量１００以上の低分子化合物が好ましく、具体的には、分子量１００～１，５００であることがより好ましく、１５０～１，０００が更に好ましい。 The thiol compound (C) may be either a monofunctional thiol compound or a polyfunctional thiol compound, but is preferably a polyfunctional thiol compound (C-1) from the viewpoint of further increasing the sensitivity of the photosensitive resin composition to exposure light. Is preferred.
The monofunctional thiol compound is a compound having one thiol group (mercapto group) in a molecule. Examples of the monofunctional thiol compound include stearyl-3-mercaptopropionate.
The polyfunctional thiol compound (C-1) is a compound having two or more thiol groups (mercapto groups) in a molecule. As the polyfunctional thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable, and specifically, the molecular weight is more preferably 100 to 1,500, and further preferably 150 to 1,000.
　多官能チオール化合物（Ｃ－１）の官能基数としては、２～１０官能が好ましく、２～８官能がより好ましく、２～４官能が更に好ましい。官能基数が大きくなると膜強度に優れる一方、官能基数が小さいと保存安定性に優れる。上記範囲の場合、これらを両立することができる。 数 The number of functional groups of the polyfunctional thiol compound (C-1) is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 4. When the number of functional groups is large, the film strength is excellent, while when the number of functional groups is small, the storage stability is excellent. In the case of the above range, these can be compatible.
　多官能チオール化合物（Ｃ－１）としては、脂肪族多官能チオール化合物が好ましい。脂肪族多官能チオール化合物の好ましい例としては、脂肪族炭化水素基と、－Ｏ－、－Ｃ（＝Ｏ）－の組み合わせからなる化合物であって、脂肪族炭化水素基の水素原子の少なくとも２つがチオール基で置換された化合物が例示される。 As the polyfunctional thiol compound (C-1), an aliphatic polyfunctional thiol compound is preferable. Preferred examples of the aliphatic polyfunctional thiol compound include a compound composed of a combination of an aliphatic hydrocarbon group and —O—, —C (＝ O) —, wherein at least two hydrogen atoms of the aliphatic hydrocarbon group are present. Compounds in which one is substituted with a thiol group are exemplified.
　多官能チオール化合物（Ｃ－１）におけるチオール基は、第一級チオール基であっても、第二級チオール基であっても、第三級チオール基であってもよいが、感度及び耐薬品性の観点から、第一級又は第二級チオール基であることが好ましく、第二級チオール基であることがより好ましい。また、保存安定性の観点からは、第二級又は第三級チオール基であることが好ましく、第二級チオール基であることがより好ましい。 The thiol group in the polyfunctional thiol compound (C-1) may be a primary thiol group, a secondary thiol group, or a tertiary thiol group. From the viewpoint of properties, it is preferably a primary or secondary thiol group, and more preferably a secondary thiol group. Further, from the viewpoint of storage stability, a secondary or tertiary thiol group is preferable, and a secondary thiol group is more preferable.
　脂肪族多官能チオール化合物としては、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールエタントリス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリス［（３－メルカプトプロピオニルオキシ）エチル］イソシアヌレート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、テトラエチレングリコールビス（３－メルカプトプロピオネート）、及び、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）等を挙げることができ、これらの中でも、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、及び、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン等がより好ましい。 Examples of the aliphatic polyfunctional thiol compound include pentaerythritol tetrakis (3-mercaptobutyrylate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (3-mercaptobutyryloxyethyl) ) -1,3,5-Triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), tri Methylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) And dipentaerythris Tall hexakis (3-mercaptopropionate) and the like, among which 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 is more preferred.
　脂肪族多官能チオール化合物（Ｃ－１）の市販品としては、例えば、カレンズＭＴ－ＰＥ－１、カレンズＭＴ－ＢＤ－１、カレンズＭＴ－ＮＲ－１、ＴＰＭＢ、ＴＥＭＢ（以上、昭和電工（株）製）、ＴＭＭＰ、ＴＥＭＰＩＣ、ＰＥＭＰ、ＥＧＭＰ－４、及び、ＤＰＭＰ（以上、堺化学工業（株）製）等が挙げられる。 Commercial products of the aliphatic polyfunctional thiol compound (C-1) include, for example, Karenz MT-PE-1, Karenz MT-BD-1, Karenz MT-NR-1, TPMB, and TEMB (all of Showa Denko KK) ), TMMP, TEMPIC, PEMP, EGMP-4, and DPMP (all manufactured by Sakai Chemical Industry Co., Ltd.).
　これらのチオール化合物（Ｃ）は、１種単独で用いてもよく、２種以上を併用してもよい。
　重合禁止剤（Ｄ）との複合的な効果により、広い共通のＥＬを実現する観点から、チオール化合物（Ｃ）の含有量は、前述のとおり、重合性化合物（Ａ）１００質量部に対して５～５０質量部であり、好ましくは５～３５質量、より好ましくは５～２５質量部である。 These thiol compounds (C) may be used alone or in combination of two or more.
From the viewpoint of realizing a wide common EL by a combined effect with the polymerization inhibitor (D), the content of the thiol compound (C) is, as described above, based on 100 parts by mass of the polymerizable compound (A). The amount is 5 to 50 parts by mass, preferably 5 to 35 parts by mass, more preferably 5 to 25 parts by mass.
　重合禁止剤（Ｄ）は、前述のとおり、ラジカルの拡散長を抑制し、チオール化合物（Ｃ）との複合的な効果により、広い共通のＥＬの実現に寄与する成分である。また、重合禁止剤（Ｄ）は、感光性樹脂組成物の保存安定性の向上にも寄与し得る。 As described above, the polymerization inhibitor (D) is a component that suppresses the diffusion length of radicals and contributes to the realization of a wide common EL by a combined effect with the thiol compound (C). Further, the polymerization inhibitor (D) can also contribute to improving the storage stability of the photosensitive resin composition.
　重合禁止剤（Ｄ）としては、例えば、ヒドロキノン、ヒドロキノンのモノエステル化物、Ｎ－ニトロソジフェニルアミン、ベンゾキノン、フェノチアジン、ｐ－メトキシフェノール、ｐ－ｔ－ブチルカテコール、Ｎ－フェニルナフチルアミン、２，６－ジ－ｔ－ブチル－ｐ－メチルフェノール、クロラニール、ピロガロールが挙げられる。 Examples of the polymerization inhibitor (D) include hydroquinone, monoesters of hydroquinone, N-nitrosodiphenylamine, benzoquinone, phenothiazine, p-methoxyphenol, pt-butylcatechol, N-phenylnaphthylamine, and 2,6-diphenyl. -T-butyl-p-methylphenol, chloranil, pyrogallol.
　重合禁止剤（Ｄ）としては、ヒドロキノン、ｐ－メトキシフェノール、カテコール等のフェノール系重合禁止剤（Ｄ－１）が好ましい。
　重合禁止剤（Ｄ）の市販品としては、例えば、Ｉｒｇａｎｏｘ　１０１０（ＢＡＳＦ社製）、キノパワーＱＳ２０（川崎化成工業（株）製）等が挙げられる。
　これらの重合禁止剤（Ｄ）は、１種単独で用いてもよく、２種以上を併用してもよい。 As the polymerization inhibitor (D), phenolic polymerization inhibitors (D-1) such as hydroquinone, p-methoxyphenol, and catechol are preferable.
Commercial products of the polymerization inhibitor (D) include, for example, Irganox 1010 (manufactured by BASF) and Kinopower QS20 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.).
These polymerization inhibitors (D) may be used alone or in combination of two or more.
　チオール化合物（Ｃ）との複合的な効果により、広い共通のＥＬを実現する観点から、重合禁止剤（Ｄ）の含有量は、前述のとおり、重合性化合物（Ａ）１００質量部に対して１～１０質量部であり、好ましくは３～８質量、より好ましくは４～６質量部である。 From the viewpoint of realizing a wide common EL by the combined effect with the thiol compound (C), the content of the polymerization inhibitor (D) is, as described above, based on 100 parts by mass of the polymerizable compound (A). The amount is 1 to 10 parts by mass, preferably 3 to 8 parts by mass, more preferably 4 to 6 parts by mass.
　本発明の感光性樹脂組成物は、アルカリ可溶性樹脂（Ｅ）を含有することが好ましい。感光性樹脂組成物がアルカリ可溶性樹脂（Ｅ）を含有すると、レジストにメッキ液に対する耐性を付与することができ、且つ現像をアルカリ現像液にて行うことができる。 感光 The photosensitive resin composition of the present invention preferably contains an alkali-soluble resin (E). When the photosensitive resin composition contains an alkali-soluble resin (E), resistance to a plating solution can be imparted to the resist, and development can be performed with an alkali developing solution.
　アルカリ可溶性樹脂（Ｅ）は、目的とする現像処理が可能な程度にアルカリ性の現像液に溶解する性質を有する樹脂である。アルカリ可溶性樹脂（Ｅ）としては、例えば、特開２００８－２７６１９４号公報、特開２００３－２４１３７２号公報、特表２００９－５３１７３０号公報、ＷＯ２０１０／００１６９１号公報、特開２０１１－１２３２２５号公報、特開２００９－２２２９２３号公報、および特開２００６－２４３１６１号公報等に記載の公知のアルカリ可溶性樹脂が挙げられる。より具体的には、アルカリ可溶性樹脂（Ｅ）としては、例えば、（メタ）アクリル酸、マレイン酸、ｐ－ヒドロキシスチレン、イソプロペニルフェノール、およびヒドロキシフェニル（メタ）アクリレート等の酸性官能基を有する単量体由来の構造単位、ならびにスチレン、Ｎ－フェニルマレイミド、ｎ－ブチル（メタ）アクリレート、イソブルニル（メタ）アクリレート、およびイソボルニルビニルエーテル等のその他単量体由来の構造単位を有する樹脂が挙げられる。 The alkali-soluble resin (E) is a resin having a property of dissolving in an alkaline developer to such an extent that the desired development processing can be performed. Examples of the alkali-soluble resin (E) include, for example, JP-A-2008-276194, JP-A-2003-241372, JP-T-2009-53730, WO2010 / 001691, JP-A-2011-123225, Known alkali-soluble resins described in Japanese Unexamined Patent Application Publication No. 2009-222923 and JP-A-2006-243161 are exemplified. More specifically, examples of the alkali-soluble resin (E) include simple resins having an acidic functional group such as (meth) acrylic acid, maleic acid, p-hydroxystyrene, isopropenylphenol, and hydroxyphenyl (meth) acrylate. And resins having structural units derived from other monomers such as styrene, N-phenylmaleimide, n-butyl (meth) acrylate, isobrenyl (meth) acrylate, and isobornyl vinyl ether. .
　アルカリ可溶性樹脂（Ｅ）のゲルパーミエーションクロマトグラフィーにより測定されたポリスチレン換算の重量平均分子量（Ｍｗ）は、通常、１，０００～１，０００，０００、好ましくは２，０００～５０，０００、より好ましくは３，０００～２０，０００の範囲にある。 The weight average molecular weight (Mw) of the alkali-soluble resin (E) in terms of polystyrene measured by gel permeation chromatography is generally 1,000 to 1,000,000, preferably 2,000 to 50,000, Preferably it is in the range of 3,000 to 20,000.
　アルカリ可溶性樹脂（Ｅ）は、レジストのメッキ液耐性が向上する点で、フェノール性水酸基を有することが好ましい。
　アルカリ可溶性樹脂（Ｅ）は１種単独で用いてもよく、２種以上を併用してもよい。 The alkali-soluble resin (E) preferably has a phenolic hydroxyl group from the viewpoint of improving the plating solution resistance of the resist.
The alkali-soluble resin (E) may be used alone or in combination of two or more.
　アルカリ可溶性樹脂（Ｅ）の含有量は、重合性化合物（Ａ）１００質量部に対して、通常５０～３００質量部、好ましくは１００～２５０質量部である。アルカリ可溶性樹脂の含有量が前記範囲にあると、メッキ液耐性に優れたレジストの形成が可能となる。 含有 The content of the alkali-soluble resin (E) is usually 50 to 300 parts by mass, preferably 100 to 250 parts by mass, based on 100 parts by mass of the polymerizable compound (A). When the content of the alkali-soluble resin is in the above range, a resist excellent in plating solution resistance can be formed.
　本発明の感光性樹脂組成物は、その他の成分として、溶剤、界面活性剤、接着助剤、増感剤、無機フィラー等を、本発明の目的および特性を損なわない範囲で含有してもよい。
　本発明の感光性樹脂組成物は、溶剤を含有することで、取り扱い性が向上したり、粘度の調節が容易になったり、保存安定性が向上したりする。 The photosensitive resin composition of the present invention may contain, as other components, a solvent, a surfactant, an adhesion aid, a sensitizer, an inorganic filler, and the like, as long as the object and properties of the present invention are not impaired. .
When the photosensitive resin composition of the present invention contains a solvent, the handleability is improved, the viscosity is easily adjusted, and the storage stability is improved.
　溶剤としては、
メタノール、エタノール、プロピレングリコールなどのアルコール類；
テトラヒドロフラン、ジオキサンなどの環状エーテル類；
エチレングリコール、プロピレングリコールなどのグリコール類；
エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルなどのアルキレングリコールモノアルキルエーテル類；
エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートなどのアルキレングリコールモノアルキルエーテルアセテート類；
トルエン、キシレンなどの芳香族炭化水素類；
アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、４－ヒドロキシ－４－メチル－２－ペンタノンなどのケトン類；
酢酸エチル、酢酸ブチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、乳酸エチルなどのエステル類；
Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルホルムアニリド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、γ－ブチロラクトン、炭酸エチレン、炭酸プロピレン、フェニルセロソルブアセテートなどが挙げられる。 As the solvent,
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, propylene glycol monoethyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Ethyl acetate, butyl acetate, ethoxy acetate, ethyl hydroxyacetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3 Esters such as ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and ethyl lactate;
N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl 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, phenyl cellosolve acetate and the like.
　溶剤は１種単独で用いてもよく、２種以上を併用してもよい。
　溶剤の含有量は、膜厚０．１～１００μｍのレジストパターンを形成する場合、本感光性樹脂組成物の固形分が、５～８０質量％となる量とすることができる。
　本発明の感光性樹脂組成物は、上記成分を均一に混合することにより製造することができる。 The solvent may be used alone or in combination of two or more.
When a resist pattern having a thickness of 0.1 to 100 μm is formed, the content of the solvent may be such that the solid content of the photosensitive resin composition is 5 to 80% by mass.
The photosensitive resin composition of the present invention can be produced by uniformly mixing the above components.
［レジストパターンの形成方法］
　本発明のレジストパターンの形成方法は、前述の感光性樹脂組成物を基板上に塗布して樹脂塗膜を形成する工程（１）、前記樹脂塗膜を露光する工程（２）、露光後の樹脂塗膜を現像する工程（３）、を有することを特徴とする。 [Method of forming resist pattern]
The method for forming a resist pattern according to the present invention includes the steps of: (1) forming a resin coating film by applying the above-described photosensitive resin composition on a substrate; (2) exposing the resin coating film; (3) a step of developing the resin coating film.
　工程（１）では、前記感光性樹脂組成物を基板上に塗布して樹脂塗膜を形成する。
　基板としては、前記樹脂塗膜を形成することができる基板であれば特に制限はなく、例えば半導体基板、ガラス基板、シリコン基板および半導体板、ガラス板、シリコン板の表面に各種金属膜などを設けて形成される基板などを挙げることができる。基板の形状には特に制限はない。平板状であってもシリコンウェハーのように平板に凹部（穴）を設けてなる形状であってもよい。凹部を備え、さらに表面に銅膜を有する基板の場合、ＴＳＶ構造のように、その凹部の底部に銅膜が設けられてもよい。 In the step (1), the photosensitive resin composition is applied on a substrate to form a resin coating film.
The substrate is not particularly limited as long as it is a substrate on which the resin coating film can be formed. For example, a semiconductor substrate, a glass substrate, a silicon substrate and a semiconductor plate, a glass plate, various metal films are provided on the surface of the silicon plate. And the like. The shape of the substrate is not particularly limited. It may have a flat plate shape or a shape in which a concave portion (hole) is provided in a flat plate like a silicon wafer. In the case of a substrate having a concave portion and further having a copper film on the surface, a copper film may be provided at the bottom of the concave portion as in the TSV structure.
　感光性樹脂組成物の塗布方法としては、特に限定されず、例えば、スプレー法、ロールコート法、スピンコート法、スリットダイ塗布法、バー塗布法、インクジェット法を採用することができ、特にスピンコート法が好ましい。スピンコート法の場合、回転速度は通常は８００～３０００ｒｐｍ、好ましくは８００～２０００ｒｐｍであり、回転時間は通常は１～３００秒間、好ましくは５～２００秒間である。感光性樹脂組成物をスピンコートした後は、例えば５０～２５０℃で１～３０分間程度、得られた塗膜を加熱乾燥する。 The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an ink jet method. The method is preferred. In the case of the spin coating method, the rotation speed is usually 800 to 3000 rpm, preferably 800 to 2000 rpm, and the rotation time is usually 1 to 300 seconds, preferably 5 to 200 seconds. After spin-coating the photosensitive resin composition, the resulting coating film is heated and dried, for example, at 50 to 250 ° C. for about 1 to 30 minutes.
　樹脂塗膜の膜厚は、一般的には、０．１～３００μｍ、好ましくは１～１００μｍであり、メッキ造形物が配線である場合は、通常、０．１～５０μｍ、メッキ造形物がバンプ電極である場合は、通常１～３００μｍである。樹脂塗膜の膜厚は薄膜であるほど、酸素阻害の影響が顕著に現れるので、メッキ造形物を製造する場合、膜厚は上述の範囲とすることが好ましい。 The thickness of the resin coating film is generally 0.1 to 300 μm, preferably 1 to 100 μm. When the plated object is wiring, it is usually 0.1 to 50 μm, and the plated object is a bump. When it is an electrode, it is usually 1 to 300 μm. Since the effect of oxygen inhibition becomes more pronounced as the thickness of the resin coating becomes thinner, it is preferable that the thickness be in the above-described range when a plated molded article is manufactured.
　工程（２）では、前記樹脂塗膜を露光する。すなわち、工程（３）においてレジストパターンが得られるように前記樹脂塗膜を選択的に露光する。
　選択的な露光は、通常、所望のフォトマスクを介して、例えばコンタクトアライナー、ステッパーまたはスキャナーを用いて、上記塗膜に対して露光を行う。露光光としては、通常、波長２００～５００ｎｍの光（例：ｉ線（３６５ｎｍ））を用いる。露光量は、塗膜中の成分の種類、配合量、塗膜の厚さなどによって異なるが、露光光にｉ線を使用する場合、通常、１～１０，０００ｍＪ／ｃｍ2である。 In step (2), the resin coating film is exposed. That is, the resin coating film is selectively exposed so as to obtain a resist pattern in step (3).
In the selective exposure, the coating film is usually exposed through a desired photomask, for example, using a contact aligner, a stepper, or a scanner. As the exposure light, light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is usually used. The amount of exposure varies depending on the type and amount of components in the coating film, the thickness of the coating film, and the like. However, when i-line is used for the exposure light, it is usually from 1 to 10,000 mJ / cm 2 .
　樹脂塗膜の形成に用いられた感光性樹脂組成物は、前述のとおり、ダークフィールドおよびブライトフィールドの両方において広い共通のＥＬを有することから、工程（２）においてブライトフィールドおよびダークフィールドを有する微細なレジストパターンを形成する場合であっても、目的に沿ったレジストパターンを良好に形成することができる。 As described above, since the photosensitive resin composition used for forming the resin coating film has a wide common EL in both the dark field and the bright field, the fine resin having the bright field and the dark field in the step (2) is used. Even when a proper resist pattern is formed, a resist pattern suitable for the purpose can be satisfactorily formed.
　また、露光後に加熱処理を行うこともできる。露光後の加熱処理の条件は、樹脂塗膜中の成分の種類、配合量、塗膜の厚さなどによって適宜決められるが、通常７０～１８０℃、１～６０分間である。 加熱 Alternatively, a heat treatment can be performed after the exposure. The conditions of the heat treatment after the exposure are appropriately determined depending on the types and the amounts of the components in the resin coating film, the thickness of the coating film, and the like, and are usually 70 to 180 ° C. for 1 to 60 minutes.
　工程（３）では、露光後の樹脂塗膜を現像する。これによりレジストパターンが形成される。
　現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水、エチルアミン、ｎ－プロピルアミン、ジエチルアミン、ジ－ｎ－プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン、１，５－ジアザビシクロ［４．３．０］－５－ノナンの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノール、エタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。 In step (3), the exposed resin coating is developed. As a result, a resist pattern is formed.
Examples of the developer include 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. An aqueous solution of 0] -5-nonane can be used. Further, an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above-mentioned alkalis can also be used as the developer.
　現像時間は、組成物中の各成分の種類、配合割合、塗膜の厚さなどによって異なるが、通常３０～６００秒間である。現像の方法は液盛り法、ディッピング法、パドル法、スプレー法、シャワー現像法などのいずれでもよい。 (4) The development time varies depending on the type and proportion of each component in the composition, the thickness of the coating film, and the like, but is usually 30 to 600 seconds. The method of development may be any of a puddle method, a dipping method, a paddle method, a spray method, a shower development method and the like.
　上記のように作製されたレジストパターンに対し、用途に応じてさらに、追加の露光（以下「後露光」という。）や加熱を行うことによってさらにレジストパターンを硬化させることができる。 レ ジ ス ト The resist pattern prepared as described above can be further cured by performing additional exposure (hereinafter, referred to as “post-exposure”) or heating according to the intended use.
　後露光は、上記露光と同様の方法で行なうことができる。露光量は特に限定されないが、高圧水銀灯使用の場合１００～１０，０００ｍＪ／ｃｍ2が好ましい。加熱については、ホットプレート、オーブンなどの加熱装置を用いて、所定の温度、例えば６０～２００℃で所定の時間、例えばホットプレート上なら５～３０分間、オーブン中では５～６０分間加熱処理をすればよい。この後処理によって、さらに良好な特性を有するパターンの硬化膜を得ることができる。
　レジストパターンは流水等により洗浄してもよい。その後、エアーガンなどを用いて風乾したり、ホットプレートやオーブンなどの加熱下で乾燥させてもよい。 Post-exposure can be performed by the same method as the above-mentioned exposure. The exposure amount is not particularly limited, but is preferably 100 to 10,000 mJ / cm 2 when a high-pressure mercury lamp is used. Heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 60 to 200 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 5 to 60 minutes in an oven. do it. By this post-treatment, a cured film having a pattern having better characteristics can be obtained.
The resist pattern may be washed with running water or the like. Thereafter, air drying may be performed using an air gun or the like, or drying may be performed under heating using a hot plate or an oven.
［メッキ造形物の製造方法］
　本発明のメッキ造形物の製造方法は、前述のレジストパターンの形成方法によって形成したレジストパターンをマスクにして、前記基板に対してメッキ処理を行う工程を有することを特徴とする。 [Manufacturing method of molded objects]
A method of manufacturing a plated object according to the present invention includes a step of performing a plating process on the substrate using the resist pattern formed by the above-described method for forming a resist pattern as a mask.
　前記メッキ造形物としては、バンプ、配線等が挙げられる。
　レジストパターンの形成は、前述のレジストパターンの形成方法に従って行う。
　メッキ処理としては、電解メッキ処理、無電解メッキ処理、および溶融メッキ処理等の湿式メッキ処理、化学気層蒸着、およびスパッタ等の乾式メッキ処理が挙げられる。ウエハーレベルでの加工における配線や接続端子を形成する場合、メッキ処理は通常、電解メッキ処理により行われる。 Examples of the plated object include a bump, a wiring, and the like.
The formation of the resist pattern is performed according to the above-described method of forming a resist pattern.
Examples of the plating treatment include wet plating such as electrolytic plating, electroless plating, and hot-dip plating, and dry plating such as chemical vapor deposition and sputtering. When forming wiring and connection terminals in processing at the wafer level, plating is usually performed by electrolytic plating.
　電解メッキ処理を行う前に、レジストパターンの内壁表面とメッキ液との親和性を高めるため、レジストパターンの内壁表面にアッシング処理、フラックス処理、およびデスミア処理等の前処理を行うことができる。 (4) Before performing the electrolytic plating process, in order to increase the affinity between the inner wall surface of the resist pattern and the plating solution, a pretreatment such as an ashing process, a flux process, and a desmear process can be performed on the inner wall surface of the resist pattern.
　電解メッキ処理の場合、スパッタまたは無電解メッキ処理によりレジストパターン内壁に形成した層をシード層として用いることができ、また、表面に金属膜を有する基板を基板に用いる場合は、前記金属膜をシード層として用いることもできる。 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, and when a substrate having a metal film on the surface is used as the substrate, the metal film is seeded. It can also be used as a layer.
　シード層を形成する前にバリア層を形成してもよく、シード層をバリア層として用いることもできる。
　電解メッキ処理に使用されるメッキ液としては、例えば、硫酸銅、またはピロリン酸銅等を含む銅メッキ液；シアン化金カリウムを含む金メッキ液処理；ならびに硫酸ニッケルまたは炭酸ニッケルを含むニッケルメッキ液；が挙げられる。 The barrier layer may be formed before forming the seed layer, and the seed layer may be used as the barrier layer.
Examples of the plating solution used in the electrolytic plating process include a copper plating solution containing copper sulfate or copper pyrophosphate; a gold plating solution containing gold potassium cyanide; and a nickel plating solution containing nickel sulfate or nickel carbonate; Is mentioned.
　電解メッキ処理の条件は、メッキ液の種類等により適宜選択でき、例えば、硫酸銅を含む電解メッキ処理の場合、通常、温度１０～９０℃電流密度０．１～１００Ａ／ｄｍ2である。 The conditions of the electrolytic plating can be appropriately selected depending on the type of the plating solution and the like. For example, in the case of the electrolytic plating containing copper sulfate, the current density is usually 10 to 90 ° C. and the current density is 0.1 to 100 A / dm 2 .
　メッキ処理は、異なるメッキ処理を順次行うことができる。例えば、はじめに銅メッキ処理を行い、次にニッケルメッキ処理を行い、次に溶融はんだメッキ処理を行うことで、はんだ銅ピラーバンプを形成することができる。 (4) In the plating process, different plating processes can be sequentially performed. For example, solder copper pillar bumps can be formed by first performing copper plating, then performing nickel plating, and then performing molten solder plating.
　メッキ造形物の厚さは、その用途によって異なるが、例えば、バンプ電極の場合、通常、１～３００μｍであり、配線の場合、通常、０．１～５０μｍである。
　前記レジストパターンの形成方法は、前述の感光性樹脂組成物を用いてレジストパターンを形成することから、微細なレジストパターンであっても、目的に沿ったレジストパターンを容易に形成することができる。このため、前述のレジストパターンの形成方法によって形成したレジストパターンを用いる本発明のメッキ造形物の製造方法においては、微細なメッキ造形物を精度良く、簡便に製造することができる。 The thickness of the plated object varies depending on the application, but is, for example, usually 1 to 300 μm for a bump electrode and 0.1 to 50 μm for a wiring.
In the method for forming a resist pattern, a resist pattern is formed using the above-described photosensitive resin composition. Therefore, even if the resist pattern is a fine resist pattern, a resist pattern suitable for the purpose can be easily formed. For this reason, in the method of manufacturing a plated object of the present invention using the resist pattern formed by the above-described method of forming a resist pattern, a fine plated object can be accurately and simply manufactured.
　以下、本発明を実施例に基づいてさらに具体的に説明するが、本発明はこれら実施例に限定されない。以下の実施例等の記載において、「部」は「質量部」の意味で用いる。
　アルカリ可溶性樹脂の重量平均分子量（Ｍｗ）は、下記条件でゲルパーミエーションクロマトグラフィー法におけるポリスチレン換算により算出した値である。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of the examples and the like, “parts” means “parts by mass”.
The weight average molecular weight (Mw) of the alkali-soluble resin is a value calculated by gel permeation chromatography in terms of polystyrene under the following conditions.
　・カラム：東ソー株式会社製カラムのＴＳＫ－ＭおよびＴＳＫ２５００を直列に接続。
　・溶媒：テトラヒドロフラン
　・カラム温度：４０℃
　・検出方法：屈折率法
　・標準物質：ポリスチレン
　・ＧＰＣ装置：東ソー株式会社製、装置名「ＨＬＣ－８２２０－ＧＰＣ」 Column: TSK-M and TSK2500 manufactured by Tosoh Corporation are connected in series.
・ Solvent: tetrahydrofuran ・ Column temperature: 40 ℃
-Detection method: Refractive index method-Standard substance: polystyrene-GPC device: manufactured by Tosoh Corporation, device name "HLC-8220-GPC"
＜感光性樹脂組成物の製造＞
［実施例１Ａ～８Ａ、および比較例１Ａ～７Ａ］
　溶剤としてプロピレングリコールモノメチルエーテルアセテートを用いて、下記表１に示す量の各成分を前記溶剤に、固形分濃度が５５質量％となるよう加えて混合し、カプセルフィルター（孔径３μｍ）で濾過して、実施例１Ａ～８Ａ、および比較例１Ａ～７Ａの感光性樹脂組成物を製造した。なお、表１中に示す各成分の詳細は以下の通りである。
重合性化合物（Ａ１）：ポリエステルアクリレート（製品名「アロニックスＭ－８０６０」、東亜合成（株）製）
光重合開始剤（Ｂ１）：下記式（Ｂ１）に示す化合物 <Production of photosensitive resin composition>
[Examples 1A to 8A and Comparative Examples 1A to 7A]
Using propylene glycol monomethyl ether acetate as a solvent, the components shown in the following Table 1 were added to the solvent so that the solid content concentration became 55% by mass, mixed, and filtered with a capsule filter (pore size: 3 μm). The photosensitive resin compositions of Examples 1A to 8A and Comparative Examples 1A to 7A were produced. The details of each component shown in Table 1 are as follows.
Polymerizable compound (A1): polyester acrylate (product name "Aronix M-8060", manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (B1): a compound represented by the following formula (B1)
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
光重合開始剤（Ｂ２）：２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド
チオール化合物（Ｃ１）：ペンタエリスリトール テトラキス （３－メルカプトブチレート）（製品名「カレンズＭＴ　ＰＥ１」、昭和電工（株）製）
チオール化合物（Ｃ２）：ステアリル－３－メルカプトプロピオネート（製品名「STMP」、堺化学工業（株）製）
チオール化合物（Ｃ３）：１，４－ビス（３－メルカプトブチリルオキシ）ブタン（製品名「カレンズＭＴ－ＢＤ－１」、昭和電工（株）製）
チオール化合物（Ｃ４）：１,３,５－トリス(２－(３－スルファニルブタノイルオキシ)エチル)－１,３,５－トリアジナン－２,４,６－トリオン（製品名「カレンズＭＴ－ＮＲ－１」、昭和電工（株）製）
重合禁止剤（Ｄ１）：ヒンダードフェノール系重合禁止剤（製品名「Ｉｒｇａｎｏｘ　１０１０」、ＢＡＳＦ社製）
重合禁止剤（Ｄ２）：フェノール系重合禁止剤（製品名「キノパワーＱＳ２０」、川崎化成工業（株）製）
重合禁止剤（Ｄ３）：ｐ－ベンゾキノン
重合禁止剤（Ｄ４）：フェノチアジン
アルカリ可溶性樹脂（Ｅ１）：下記式（Ｅ１）に示す、記号ａ～ｃを付した構造単位を有するアクリル系樹脂（Ｍｗ：８０００、構造単位ａ～ｃの含有割合：ａ／ｂ／ｃ＝５０／３０／２０（質量％）） Photopolymerization initiator (B2): 2,4,6-trimethylbenzoyldiphenylphosphine oxide thiol compound (C1): pentaerythritol tetrakis (3-mercaptobutyrate) (product name "Karenz MT PE1", manufactured by Showa Denko KK) )
Thiol compound (C2): stearyl-3-mercaptopropionate (product name "STMP", manufactured by Sakai Chemical Industry Co., Ltd.)
Thiol compound (C3): 1,4-bis (3-mercaptobutyryloxy) butane (product name "Karenz MT-BD-1", manufactured by Showa Denko KK)
Thiol compound (C4): 1,3,5-tris (2- (3-sulfanylbutanoyloxy) ethyl) -1,3,5-triazinane-2,4,6-trione (product name “Karenz MT-NR -1 ", manufactured by Showa Denko KK
Polymerization inhibitor (D1): hindered phenol polymerization inhibitor (product name "Irganox 1010", manufactured by BASF)
Polymerization inhibitor (D2): phenolic polymerization inhibitor (product name "Kinopower QS20", manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
Polymerization inhibitor (D3): p-benzoquinone polymerization inhibitor (D4): phenothiazine alkali-soluble resin (E1): Acrylic resin (Mw: 8000, content ratio of structural units a to c: a / b / c = 50/30/20 (% by mass))
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
界面活性剤（Ｆ１）：ジグリセリンエチレンオキサイド（平均付加モル数：１８）付加物ペルフルオロノネニルエーテル（製品名「フタージェントＦＴＸ－２１８」、ネオス（株）製） Surfactant (F1): diglycerin ethylene oxide (average number of moles added: 18) adduct perfluorononenyl ether (product name "Fantagent FTX-218", manufactured by Neos Corporation)
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
＜レジストパターンの形成＞
［実施例１Ｂ］
　６インチシリコンウエハ上に銅スパッタ膜を備える基板に、実施例１Ａの感光性樹脂組成物をスピンコート法にて塗布し、ホットプレートにて１１０℃で１８０秒間加熱し、１２μｍの膜厚を有する樹脂塗膜を形成した。 <Formation of resist pattern>
[Example 1B]
The photosensitive resin composition of Example 1A is applied to a substrate having a copper sputter film on a 6-inch silicon wafer by spin coating, and heated at 110 ° C. for 180 seconds on a hot plate to have a film thickness of 12 μm. A resin coating was formed.
　前記樹脂塗膜を、ｉ線露光用ステッパー（装置名「ＮＳＲ－ｉ１２Ｄ」、（株）ニコン製）を用い、２μｍの１Ｌ／１Ｓレジストパターン形成に対応する領域（以下、「ＢＦ対応領域」という）および２μｍの１Ｌ／３Ｓレジストパターン形成に対応する領域（以下、「ＤＦ対応領域」という）を有するフォトマスクを介して露光した。露光は２０ｍＪ／ｃｍ2から１０ｍＪ／ｃｍ2ずつ増やしたショットを２６０ｍＪ／ｃｍ2まで２５ショット行った。 Using a stepper for i-line exposure (device name “NSR-i12D”, manufactured by Nikon Corporation), the resin coating film was formed in a region corresponding to the formation of a 2 μm 1L / 1S resist pattern (hereinafter referred to as a “BF corresponding region”). ) And a region corresponding to the formation of a 2 μm 1L / 3S resist pattern (hereinafter, referred to as a “DF corresponding region”). Exposure was carried out 25 shot a shot that was increased from 20mJ / cm 2 by 10mJ / cm 2 to 260mJ / cm 2.
　露光後の樹脂塗膜を、現像液として２．３８質量％テトラメチルアンモニウムハイドロオキサイド水を用いて液盛り法にて現像し、流水洗浄、乾燥し、レジストパターンを形成した。 (4) The resin coating film after the exposure was developed by a puddle method using 2.38% by mass of tetramethylammonium hydroxide water as a developing solution, washed with running water, and dried to form a resist pattern.
　ＢＦ対応領域において２μｍの１Ｌ／１Ｓレジストパターンを最適に形成する露光量である最適露光量（ＥＯＰ）、ＢＦにおいて、精度良く、微細なレジストパターンを形成できた露光量範囲、およびＤＦにおいて、精度良く、微細なレジストパターンを形成できた露光量範囲、ならびに前記ＢＦにおける露光量範囲と前記ＤＦにおける露光量範囲とが重複する露光量範囲（重複露光量範囲）を、前記レジストパターンを電子顕微鏡観察することにより求めた。 The optimum exposure amount (EOP), which is the exposure amount that optimally forms a 2 μm 1L / 1S resist pattern in the BF-corresponding region, the exposure amount range in which a fine resist pattern can be formed accurately in BF, and the accuracy in DF Observing the resist pattern with an electron microscope, the exposure range in which a fine resist pattern can be formed, and the exposure range in which the exposure range in the BF overlaps the exposure range in the DF (overlapping exposure range). I asked by doing.
　また、前記ＥＯＰに対する前記重複露光量範囲の割合より、ＢＦとＤＦとの共通のＥＬを算出した。
　評価結果を表２に示す。実施例１Ｂの電子顕微鏡の写真を図１に示す。 Further, a common EL of BF and DF was calculated from the ratio of the overlapping exposure amount range to the EOP.
Table 2 shows the evaluation results. FIG. 1 shows a photograph of the electron microscope of Example 1B.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
［実施例２Ｂ～８Ａ、比較例１Ｂ～７Ｂ］
　実施例１Ｂにおいて、表２中に示す感光性樹脂組成物を用いた以外は実施例１Ｂと同様の操作にてレジストパターンを形成し、ＢＦ対応領域およびＤＦ対応領域における露光量範囲、および重複露光量範囲、ならびに共通のＥＬを測定した。評価結果を表２に示す。
　実施例２Ｂおよび比較例３Ｂの電子顕微鏡の写真を図１に示す。 [Examples 2B to 8A, Comparative Examples 1B to 7B]
In Example 1B, a resist pattern was formed in the same manner as in Example 1B except that the photosensitive resin composition shown in Table 2 was used, and the exposure amount range in the BF corresponding region and the DF corresponding region, and the overlapping exposure The amount range, as well as the common EL, were measured. Table 2 shows the evaluation results.
FIG. 1 shows a photograph of an electron microscope of Example 2B and Comparative Example 3B.
＜メッキ造形物の製造＞
［実施例１Ｃ］
　実施例１Ｂで形成したレジストパターンを有する基板をアッシング処理した。アッシング処理後の基板を銅メッキ液（製品名「ＭＩＣＲＯＦＡＢ　Ｃｕ３００」、ＥＥＪＡ社製）１リットル中に２５℃で１５分間浸漬し、電解メッキ反応を行った。次いで、レジストパターンをレジスト剥離液（製品名「ＥＬＰＡＣ　ＴＨＢ－Ｓ１７」、ＪＳＲ（株）製）を用いて剥離し、メッキ造形物を製造した。 <Manufacture of plated objects>
[Example 1C]
The substrate having the resist pattern formed in Example 1B was subjected to an ashing process. The substrate after the ashing treatment was immersed in 1 liter of a copper plating solution (product name “MICROFAB Cu300”, manufactured by EEJA) at 25 ° C. for 15 minutes to perform an electrolytic plating reaction. Next, the resist pattern was stripped using a resist stripper (product name “ELPAC THB-S17”, manufactured by JSR Corporation) to produce a plated model.
　図２は、ＥＯＰにおける２μｍの１Ｌ／１Ｓレジストパターンをマスクとしたメッキ造形物の電子顕微鏡の写真である。 FIG. 2 is an electron micrograph of a plated product using a 2 μm 1L / 1S resist pattern in EOP as a mask.

Claims (8)

  1. 　重合性化合物（Ａ）、光ラジカル重合開始剤（Ｂ）、チオール化合物（Ｃ）、および重合禁止剤（Ｄ）を含有し、前記チオール化合物（Ｃ）の含有量が、前記重合性化合物（Ａ）１００質量部に対して５～５０質量部、前記重合禁止剤（Ｄ）の含有量が、前記重合性化合物（Ａ）１００質量部に対して１～１０質量部であることを特徴とする感光性樹脂組成物。 It contains a polymerizable compound (A), a photoradical polymerization initiator (B), a thiol compound (C), and a polymerization inhibitor (D), and the content of the thiol compound (C) is as follows. 5) 50 parts by mass with respect to 100 parts by mass, and the content of the polymerization inhibitor (D) is 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound (A). Photosensitive resin composition.
  2. 　前記チオール化合物（Ｃ）が多官能チオール化合物（Ｃ－１）である、請求項１に記載の感光性樹脂組成物。 感光 The photosensitive resin composition according to claim 1, wherein the thiol compound (C) is a polyfunctional thiol compound (C-1).
  3. 　前記チオール化合物（Ｃ）１００質量物に対して、前記重合禁止剤（Ｄ）の含有量が２０～８０質量部である、請求項１または２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the content of the polymerization inhibitor (D) is 20 to 80 parts by mass based on 100 parts by mass of the thiol compound (C).
  4. 　前記重合禁止剤（Ｄ）がフェノール系重合禁止剤（Ｄ－１）である請求項１～３のいずれかに記載の感光性樹脂組成物。 感光 The photosensitive resin composition according to any one of claims 1 to 3, wherein the polymerization inhibitor (D) is a phenolic polymerization inhibitor (D-1).
  5. 　前記光ラジカル重合開始剤（Ｂ）がオキシム系光ラジカル重合開始剤（Ｂ１）である、請求項１～４のいずれかに記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the photo-radical polymerization initiator (B) is an oxime-based photo-radical polymerization initiator (B1).
  6. 　さらに、アルカリ可溶性樹脂（Ｅ）を含有する、請求項１～５のいずれかに記載の感光性樹脂組成物。 (6) The photosensitive resin composition according to any one of (1) to (5), further comprising an alkali-soluble resin (E).
  7. 　請求項１～６のいずれかに記載の感光性樹脂組成物を基板上に塗布して樹脂塗膜を形成する工程（１）、前記樹脂塗膜を露光する工程（２）、露光後の樹脂塗膜を現像する工程（３）、を有することを特徴とするレジストパターンの形成方法。 A step (1) of applying the photosensitive resin composition according to any one of claims 1 to 6 on a substrate to form a resin coating, a step (2) of exposing the resin coating, and a resin after exposure. A method for forming a resist pattern, comprising a step (3) of developing a coating film.
  8. 　請求項７に記載のレジストパターンの形成方法によって形成したレジストパターンをマスクにして、前記基板に対してメッキ処理を行う工程を有することを特徴とするメッキ造形物の製造方法。 (8) A method for producing a plated object, comprising: performing a plating process on the substrate using a resist pattern formed by the method for forming a resist pattern according to claim 7 as a mask.
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