WO2007129589A1 - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
WO2007129589A1
WO2007129589A1 PCT/JP2007/059020 JP2007059020W WO2007129589A1 WO 2007129589 A1 WO2007129589 A1 WO 2007129589A1 JP 2007059020 W JP2007059020 W JP 2007059020W WO 2007129589 A1 WO2007129589 A1 WO 2007129589A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive resin
group
mass
resin composition
resist pattern
Prior art date
Application number
PCT/JP2007/059020
Other languages
French (fr)
Japanese (ja)
Inventor
Yukari Himeda
Hiroaki Tomita
Teruhiko Adachi
Original Assignee
Asahi Kasei Emd Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Emd Corporation filed Critical Asahi Kasei Emd Corporation
Priority to JP2008514438A priority Critical patent/JP5188391B2/en
Publication of WO2007129589A1 publication Critical patent/WO2007129589A1/en

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Classifications

    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means

Definitions

  • the present invention uses a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate in which the photosensitive resin composition is laminated on a support, and the photosensitive resin laminate.
  • the present invention relates to a photosensitive resin composition that provides a resist pattern suitable for the manufacture of tape substrates, semiconductor bumps, ITO electrodes and members in the field of flat panel displays, such as address electrodes and electromagnetic wave shields.
  • a printed wiring board has been manufactured by a photolithography method.
  • the photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure an exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer.
  • a method of forming a conductor pattern on a substrate by forming a resist pattern on the substrate, forming a conductor pattern by etching or clinging, and then peeling and removing the resist pattern on the substrate.
  • a photosensitive resin laminate (hereinafter also referred to as a “dry film resist”) in which a layer (hereinafter also referred to as a “photosensitive resin layer”) having a strength of the photosensitive resin composition and a protective layer as necessary is sequentially laminated. Any of the methods of laminating to the substrate is used. In the production of printed wiring boards, the latter dry film resist is often used. [0004] A method for producing a printed wiring board using the dry film resist will be briefly described below.
  • the dry film resist has a protective layer
  • it is peeled off from the photosensitive resin layer.
  • the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order.
  • the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays emitted from an ultra-high pressure mercury lamp, for example, i-line (365 nm) through a photomask having a wiring pattern.
  • an ultra-high pressure mercury lamp for example, i-line (365 nm)
  • the support is peeled off.
  • resist pattern (hereinafter simply referred to as “resist pattern”) cured on the substrate by dissolving or dispersing and removing the unexposed portion of the photosensitive resin layer with a developing solution, for example, an aqueous solution having weak alkalinity. Let it form.
  • a known etching process or pattern fitting process is performed using the formed resist pattern as a protective mask.
  • the resist pattern is peeled from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.
  • a high-sensitivity initiator or sensitizer is used in order to increase the sensitivity for improving productivity and to deal with direct drawing by a laser.
  • these compositions have good sensitivity, but have a problem that they develop color or lose color when stored for a long time at high temperatures where the hue stability is low.
  • Patent Document 1 discloses a photosensitive resin composition to which phenols such as rhodium, idroquinone and catechol are added in order to improve the hue stability of the photosensitive composition.
  • Patent Document 2 discloses o tert butyl. Photopolymerizable composition containing phenol derivatives and heterocyclic thiol compounds
  • Patent Document 3 describes a photopolymerizable mixture containing an epoxy group-containing compound
  • Patent Document 4 describes a photosensitive resin composition containing alkanolamine and malachite green.
  • the hue stability of these photosensitive resin compositions is not fully satisfactory, and further improvement in hue stability is required.
  • Patent Document 5 features a polymer binder, an ethylenically unsaturated compound, a leuco dye, an organic halogen compound, and a phosphorous acid ester as a composition having high storage stability even at high temperatures.
  • a photosensitive composition is described. However, what is shown here is the prevention of coloration of colorless leuco dyes during high-temperature storage! / There is no description or suggestion regarding the anti-bleaching effect. Moreover, it is considered that a resist pattern cannot be formed with the disclosed photosensitive composition.
  • the leuco dye is colorless, it is generally known as a chromogenic dye because it changes to a colored dye by acid.
  • a leuco dye is used as a material for image recording by heat sensitivity or pressure sensitivity.
  • Patent Document 5 discloses a leuco dye, and a specific example thereof is leucocrystal violet! Although leuco crystal violet itself is colorless, it changes to a crystal violet dye by acid and turns purple.
  • the basic dye in the invention of the present application is itself colored and does not change its hue when it can be oxidized. This also shows that the coloring mechanism for leuco dyes during high-temperature storage is completely different from the decoloring mechanism for basic dyes.
  • Patent Document 1 US Patent No. 3042515
  • Patent Document 2 JP-A-60-2945
  • Patent Document 3 JP-A-11161001
  • Patent Document 4 JP-A-6-148883
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-219690
  • the present invention has excellent sensitivity, resolution, and adhesion, color development and decoloration during storage of a dry film, no problem, and good hue stability, which can be developed with an alkaline aqueous solution.
  • Photosensitive resin composition, photosensitive resin laminate using the photosensitive resin composition, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and the resist pattern The purpose is to provide usage.
  • R is hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, a pyridyl group, or 1 carbon atom. ⁇ 6 alkoxy groups.
  • N aryl amino acid represented by the following general formula ( ⁇ ): 0.001 to 1.0% by mass, characterized in that it contains any one of (1) to (3) Photosensitive resin composition.
  • R is an aryl group.
  • B and C are each independently a linear or branched alkyl group having 3 or more carbon atoms, or NR (R is a hydrogen atom or an alkyl group), and A is an aryl group.
  • a 0 or 1
  • the addition polymerizable monomer having at least one terminal ethylenically unsaturated group contains at least one of the following general formula (IV) or (V): (1) to (6 ).
  • the photosensitive resin composition according to any one of the above.
  • the repeating unit of-(DO)-and-(E-O)- may be a block structure None of them may be on the bisphenol group side.
  • ml, m2, nl, and n2 are each independently 0 or a positive integer, and their sum is 2-30.
  • [Chemical 4] (Wherein R and R are each independently H or CH; and F and G are carbon
  • the-(FO) — and — (G—O) — repeating units have a block structure Either of them may or may not be on the cyclohexyl group side.
  • pl, p2, q1, and q2 are each independently 0 or a positive integer, and the sum thereof is 2 to 30. )
  • a photosensitive resin laminate obtained by laminating the photosensitive resin composition according to any one of (1) to (7) on a support.
  • a resist pattern forming method including a lamination step, an exposure step, and a development step for forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to (8).
  • a method for producing a printed wiring board comprising a step of etching or attaching a substrate on which a resist pattern is formed by the method according to (9) or (10).
  • a lead frame manufacturing method including a step of etching a substrate on which a resist pattern is formed by the method according to (9) or (10).
  • a method for manufacturing a semiconductor package comprising a step of etching or attaching a substrate on which a resist pattern is formed by the method according to (9) or (10).
  • a method for producing a substrate having a concavo-convex pattern comprising a step of processing a substrate on which a resist pattern is formed by the method according to (9) or (10) by sand blasting.
  • the present invention is a photosensitive resin composition that is excellent in sensitivity, resolution, and adhesiveness, has good hue stability, and can be developed with an alkaline aqueous solution, and a photosensitive resin using the photosensitive resin composition.
  • the present invention provides a resin laminate, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and a use of the resist pattern, and manufactures a printed wiring board, a lead frame, and a semiconductor package. It can be suitably used for the production of flat displays.
  • the photosensitive resin composition of the present invention includes (a) an ⁇ , ⁇ unsaturated carboxyl group-containing monomer as a copolymerization component, an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500, 000 thermoplastic copolymer: 20 to 90% by mass, (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) photoinitiator: 0.01 ⁇ 30 mass%, (d) Phosphite ester compound: 0.01 to 5 mass%, (e) Basic dye: 0.001 to 0.3 mass% as essential components.
  • thermoplastic copolymer includes a, j8-unsaturated carboxyl group-containing monomer as a copolymerization component, and has an acid equivalent of 100 to 600, and a weight. Use an average molecular weight of 5,000 to 500,000.
  • the carboxyl group in the thermoplastic copolymer is necessary for the photosensitive resin composition to have developability and releasability with respect to a developing solution and a peeling solution comprising an alkaline aqueous solution.
  • the acid equivalent is preferably 100-600 forces, more preferably 250-450. To ensure compatibility with other components in the solvent or composition, particularly (b) addition polymerizable monomer described later From the viewpoint, it is 100 or more, and from the viewpoint of maintaining developability and peelability, it is 600 or less.
  • the acid equivalent means the mass (gram) of the thermoplastic copolymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by potentiometric titration with 0.1 ImolZL NaOH aqueous solution using Hiranuma Reporting Titer (COM-555).
  • the weight average molecular weight of the thermoplastic polymer of the present invention is preferably 5,000 to 500,000. From the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to the developer, it is 5,000 or more, and from the viewpoint of maintaining developability, it is 500,000 or less. More preferably, the weight average molecular weight is 20,000 force 100,000.
  • the weight average molecular weight in this case is a weight average molecular weight measured by gel permeation chromatography (GPC) using a standard polystyrene (Showa Denko Co., Ltd. Shodex STANDARD SM-105) calibration curve. .
  • the weight average molecular weight can be measured under the following conditions using gel permeation chromatography manufactured by JASCO Corporation.
  • thermoplastic copolymer is preferably a copolymer that has at least one or more of the first monomer described later and at least one or more of the second monomer described later.
  • the first monomer is a monomer containing a, j8 unsaturated carboxyl group in the molecule.
  • examples thereof include (meth) acrylic acid, fumaric acid, cinnamate, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Of these, (meth) acrylic acid is particularly preferable.
  • the second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule.
  • the amount of the thermoplastic polymer contained in the photosensitive resin composition of the present invention is in the range of 20 to 90% by mass, and preferably in the range of 25 to 70% by mass. This amount is 20% by mass or more from the viewpoint of maintaining alkali developability, and is 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.
  • the addition polymerizable monomer having at least one terminal ethylenically unsaturated group used in the photosensitive resin composition of the present invention is not particularly limited, but from the viewpoint of resolution and adhesion, the following general formula It is desirable to contain the compound represented by (IV).
  • R and R are each independently H or CH, and D and E have 2 carbon atoms.
  • the repeating unit of-(DO)-and-(E-O)- may be a block structure None of them may be on the bisphenol group side.
  • ml, m2, nl, and n2 are each independently 0 or a positive integer, and their sum is 2-30.
  • Examples of the compound represented by the above general formula (IV) include 2, 2 bis ⁇ (4 attaryloxypolyethyleneoxy) phenol ⁇ propane or 2,2 bis ⁇ (4-methacryloxypolyethyleneoxy) phenol. -Le ⁇ Propane.
  • the polyethyleneoxy group possessed by the compound includes monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octa Ethyleneoxy, nonaethyleneoxy, decaethyleneoxy, undecaethyleneoxy, dodecaethyleneoxy, tridecaethyleneoxy, tetradecaethyleneoxy, and pentadecaethylene Xy group power is a group power selected A compound that is any group selected is preferred. Further, 2,2bis ⁇ (4-aryloxypolyalkyleneoxy) phenol ⁇ propane or 2,2bis ⁇ (4-methacryloxypolyalkyleneoxy) phenol ⁇ propane can be mentioned.
  • Examples of the polyalkyleneoxy group possessed by the compound include a mixture of an ethyleneoxy group and a propyleneoxy group, an adduct having a block structure or a random structure having an otaethyleneoxy group and a dipropyleneoxy group, and a tetra structure.
  • An adduct having a block structure of an ethyleneoxy group and a tetrapropyleneoxy group or an adduct having a random structure is preferable.
  • 2,2bis ⁇ (4-methacryloxypentaethyleneoxy) phenol ⁇ propane is most preferred.
  • the repeating units (FO) and one (GO) — may be a block structure. Any of them may be on the cyclohexyl group side.
  • pl, p2, ql and q2 are each independently 0 or a positive integer, and their sum is 2 to 30 o)
  • Examples of the compound represented by the general formula (V) include 2, 2 bis ⁇ (4-ataryloxypolyethyleneoxy) cyclohexyl ⁇ propane or 2,2 bis ⁇ (4-methacryloxypolyoxyethylene) cyclohexane. Hexyl ⁇ propane.
  • Polyethyleneoxy group possessed by the compound is monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octaethylene Group consisting of oxy group, nonaethyleneoxy group, decaethyleneoxy group, undeethylene ethyleneoxy group, dodecaethyleneoxy group, tridecaethyleneoxy group, tetradecaethyleneoxy group, and pentadecaethyleneoxy group Compounds that are any group selected from are preferred.
  • the polyalkyleneoxy group possessed by the compound include a mixture of an ethoxy group and a propyloxy group, an adduct having a block structure or a random structure having an octaethyleneoxy group and a dipropyleneoxy group, and An adduct with a block structure or a random structure of a tetraethyleneoxy group and a tetrapropyleneoxy group is preferred.
  • 2,2-bis ⁇ (4-methacryloxypentaethyleneoxy) cyclohexyl ⁇ propane is most preferred.
  • the content is 5 to 40% by mass in the photosensitive resin composition. It is preferably contained, more preferably 10 to 30% by mass. This amount is 5% by mass or more from the viewpoint of high resolution and high adhesion, and 40% by mass or less from the viewpoint of suppressing cold flow and resist pattern peeling delay.
  • a polyfunctional group (meth) acrylate having a urethane group for example, there may also be mentioned urethane compounds of xamethylene diisocyanate and alcohols such as nonapropylene glycol monomethacrylate, and polyfunctional (meth) acrylate of isocyanurate ester compounds.
  • the amount of the (b) addition polymerizable monomer contained in the photosensitive resin composition of the present invention is more preferably in the range of 5 to 75% by mass with respect to the entire photosensitive resin composition.
  • the range is 15 to 70% by weight. This amount is 5% by mass or more from the viewpoint of suppressing poor curing and development time delay, and is 75% by mass or less from the viewpoint of suppressing cold flow and resist pattern peeling delay.
  • the photosensitive resin composition of the present invention contains (c) a photopolymerization initiator.
  • the amount of the (c) photopolymerization initiator contained in the photosensitive resin composition of the present invention is in the range of 0.01 to 30% by mass, more preferably 0.05 to: LO% by mass. .
  • the viewpoint power for obtaining sufficient sensitivity is also preferably 0.01% by mass or more.
  • light is sufficiently transmitted to the surface (bottom surface) of the resist pattern that is in contact with the substrate, providing excellent high resolution and adhesion. From the standpoint of obtaining good properties, 30% by mass or less is preferable.
  • a hexaarylbisimidazole derivative (hereinafter referred to as triarylimidazolyl dimer) is preferably used.
  • the triarylimidazolyl dimer include, for example, 2- (0-chlorophenol) -4,5 diphenyl-imidazolyl dimer (hereinafter referred to as 2,2,1bis) , 4,, 5, 5, 1 tetraphenyl 1, 1, 1 bisimidazole), 2, 2 ', 5 Tris 1 (o-cross-mouthed) 1— (3, 4 dimethoxy (Phenol) 4, 5, 5, 1-diphenyl imidazolyl dimer, 2, 4 bis (o-cross-phase) —5— (3,4 Dimethoxyphenol) —Diphenol-Louimidazolyl dimer 2, 4, 5 Tris-(o black-mouthed) monodiphenyl imidazolidyl dimer, 2— (o black-mouthed phenol
  • 2-(. Single-mouthed phenol) 4,5 diphenyl-imidazolyl dimer is a photopolymerization initiator having a high effect on resolution and strength of a cured film, and is preferably used.
  • Photopolymerization initiators other than hexarylbisimidazole include, for example, quinones such as 2-ethyl anthraquinone, otaethyl anthraquinone, 1,2-benzanthraquinone, 2, 3 Benzanthraquinone, 2 Phenylanthraquinone, 2, 3 Diphenyl Ninoleanthraquinone, 1 Black mouth anthraquinone, 1, 4 Naphthoquinone, 9, 10 Phenylanthraquinone, 2-Methyl-1, 4 Naphthoquinone, 2, 3 Dimethylanthraquinone Rollo 2-methylanthraquinone,
  • Aromatic ketones such as benzophenone, Michler's ketone [4,4,1bis (dimethinoreamino) benzophenone], and 4,4,1bis (jetylamino) benzophenone, benzoin, Benzoin ethers, such as benzoin ether, benzoin ether, methyl benzoin, and ethyl benzoin,
  • Examples of the combination of the above thixanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and dimethylaminobenzoate, a combination of 2-chlorothioxanthone and dimethylaminobenzoate, and isopropyl thixanthone and dimethylaminobenzoate. Combination with acid ethyl is mentioned.
  • the (C) atharidine compound represented by the following general formula (I) is preferably used as the photopolymerization initiator.
  • R represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, a pyridyl group, or an alkoxy group having 1 to 6 carbon atoms.
  • Specific compounds of the above general formula (I) include, for example, 9 phenylacridine, 9- (4'-tolyl) atalysine, 9- (4'-methoxyphenol) atalysine, 9- (4'-hydroxy (Phenol) Atalidine, 9-Acetylaminoacridine, Benz [a] Phenazine, 9-Methylbenz [a] Phenazine, 2-Styrylquinoline, 9 Ethylatridine, 9 Chloroethylacridine, 9-Methoxyacrylidine, 9 Ethoxy 9- (4-Methylphenyl) atalysine, 9- (4-N-propylphenol) atalysine, 9 (4 n-butylphenol) atalysine, 9- ( 4-tert-Butylphenol) Atariji 9- (4-Methoxyphenyl) atalysine, 9- (4-Ethoxyphenyl) atalysine, 9— (4-
  • a dimer of an ataridin compound can also be used.
  • Nonane 1 9 methylataridin 1, 6 bis (9-atalidinyl) hexane, 1, 7 bis (9- atalyzyl) heptane, 1, 8 bis (9- atalyzyl) otatan, 1, 9 bis (9- attaridyl) )
  • Nonane 1 9 methylataridin 1, 6 bis (9-atalidinyl) hexane, 1, 7 bis (9- atalyzyl) heptane, 1, 8 bis (9- atalyzyl) otatan, 1, 9 bis (9- attaridyl)
  • Nonane 1 9 methylataridin 1, 6 bis (9-atalidinyl) hexane
  • a pyrazoline compound represented by the following general formula (III) is contained as a photopolymerization initiator.
  • the content is 0.001% by mass or more with respect to the entire photosensitive resin composition, from the viewpoint of improving sensitivity and resolution, and the compatibility of the photosensitive resin composition and From the viewpoint of dispersibility in the developer, it is preferably 10% by mass or less based on the entire photosensitive resin composition. More preferably, from 0.005 to 5 mass 0/0, more preferably 0.05 to 2 mass 0/0.
  • B and C are each independently a linear or branched alkyl group having 3 or more carbon atoms.
  • NR R is a hydrogen atom or an alkyl group
  • A is an aryl group, a heterocyclic group,
  • each of B and C is preferably a linear or branched alkyl group having 3 to 12 carbon atoms.
  • Virazolin compounds represented by the above general formula ( ⁇ ) include 1-Fellow 3- (4-tert-Butylstyryl) -5- (4-tert-Butyl-phenol) pyrazoline, 1,5 bis 1- (4-tertbutylbutyl) 3- (4-tert-butylstyryl) pyrazoline, 1-loop 3- (4-tert-octylstyryl) -5- (4-tert-octyl roof) ) —Pyrazoline, 1,5 Bis— (4—tert-octyl roofyl) — 3— (4-tert-octylstyryl) Pyrazoline, 1 Fluoro 3— (4 dodecyl styryl) 5— (4 —Dodecyl roofing oil) —Virazoline, 1— (4—Dodecyl roofing oil) —3— (4 —Dodecyl roofing oil) —5— (4—Dodecyl roofing oil) —Virazoline, 1—
  • the amount of the (d) phosphite ester compound contained in the photosensitive resin composition of the present invention is in the range of 0.01 to 5% by mass with respect to the entire photosensitive resin composition, preferably 0.1 The range is from 1 to 3% by mass.
  • the hue stability of the photosensitive composition is good at 0.01% by mass or more, and the curability is good at 5% by mass or less.
  • phosphite compounds include 2, 4, 8, 10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d F] [l, 3, 2] dioxaphosfenpine, 2,2-methylenebis (4,6 di tert butylphenol) octyl phosphite, bis (2,4 ditert butylphenol) penta Erythritol diphosphite, tris (2,4 di-ter t-butylphenol) phosphite, 4, 4, -butylidenebis (3-methyl-6-tbutylphenol di-tridecylphosphite, 4, 4, Isopropylidene-di-phenol alkyl phosphite, tris-isodecyl phosphite 4.
  • propyl propylene di-phenol alkyl phosphite the alkyl group
  • the amount of the basic dye (e) contained in the photosensitive resin composition of the present invention is in the range of 0.001 to 0.3% by mass, preferably 0, based on the total photosensitive resin composition.
  • the range is 01 to 0.112% by mass.
  • the point power at which sufficient colorability can be recognized is preferably 0.001% by mass or more and 0.3% by mass or less from the viewpoint of maintaining hue stability.
  • Basic Green 1 [633-03-03] for example, Aiz en (registered trademark) Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.
  • Malachite green oxalate [2437—29—8] for example, Aizen (registered trademark) Malachite Green, trade name, manufactured by Hodogaya Igaku Kogyo
  • Brilliant Green [633—03—4] Fuchsin [6 32 — 99—5], Methyl violet [603—47—4], Methyl violet 2B [8004— 8 7-3], Crystal Violet [548—62—9], Methyl Green [82—94—0], Victoria Blue B [2580—56—5], Basic Blue 7 [2390—60—5]
  • Aizen Victoria Pure Blue BOH trade name, manufactured by Hodogaya Chemical Co., Ltd.
  • Rhodamine B [81—88—9] Rhodamine B [81—88—9]
  • (c) In the case of using the above-mentioned ataridine compound as a photopolymerization initiator, it is preferable to use (f) an organic halogen compound in combination from the viewpoint of sensitivity.
  • the organic halogen compound (f) include tribromomethyl phenol sulfone, 2-tribromomethyl sulfopyridine, or s-triazine compound represented by the following general formula (VI).
  • R, R and R each represent a substituent, and at least one of them is a trihalomethyl group.
  • R, R and R may be the same or different
  • the amount of the organic halogen compound is preferably 0.01 to 3% by mass with respect to the photosensitive resin composition.
  • the content is 0.01% by mass or more, a good contrast is exhibited between the exposed portion and the unexposed portion, and when the content is 3% by mass or less, the hue stability is good.
  • N-aryl amino acid represented by the following general formula ( ⁇ ).
  • R is an aryl group.
  • the content of N-aryl amino acid is preferably 0.001 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, and still more preferably relative to the entire photosensitive resin composition. 0.04 to 0.3 mass%.
  • the viewpoint power of sensitivity is preferably 0.001% by mass or more and 1.0% by mass or less from the viewpoint of hue stability.
  • N-aryl amino acids include N-phenylglycine, N- (p black-mouthed phenyl) glycine, N- (p bromophenol) glycine, N- (p cyanophyl). Glycine, N— (p-methylphenol) glycine, N-butyl N-phenolglycine, N-ethyl —N-phenylglycine, N-propyl-N-phenylglycine, N-methyl-N-phenylglycine, N— (p-bromophenol -N) N-methylglycine, N- (p-phenyl) N ethylglycine.
  • the photosensitive resin composition of the present invention may contain a leuco dye so that the presence or absence of photosensitivity can be visually determined.
  • leuco dyes include leuco crystal violet and leucomalachite green.
  • Sufficient coloring (color development) can be recognized From the viewpoint, the content is preferably 0.01% by mass or more and 5% by mass or less from the viewpoint of hue stability and good image characteristics with respect to the entire photosensitive resin composition.
  • the photosensitive resin composition contains a carboxybenzotriazole compound. That is.
  • Examples of the carboxybenzotriazole compound include 4 carboxy 1, 2, 3-benzotriazole, 5 carboxy 1, 2, 3 benzotriazole, N- (N, N di2-ethylhexyl) aminomethylenecarboxy. Examples include benzotriazole, N— (N, N di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N— (N, N di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.
  • the photosensitive resin composition contains benzotriazoles and Z or a radical polymerization inhibitor. It is preferable to make it.
  • radical polymerization inhibitors include ⁇ -methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-ditert-butyl-p-cresol, 2,2, -me.
  • examples include tylene bis (4-methyl-6-tert-butylphenol), 2,2, monomethylene bis (4-ethyl-6-tert-butylphenol), nitrosohydroxyhydroxyamine aluminum salt, and diphenylnitrosamine.
  • benzotriazoles examples include 1, 2, 3 benzotriazole, 1-, 2, 3 benzotriazole, bis (N-2-ethylhexyl) aminomethylene 1, 2, 3 —Benzotriazole, bis (N—2ethylhexyl) aminomethylene-1,2,3 tolyltriazole, and bis (N—2hydroxyethyl) aminomethylene-1,2,3 benzotriazole.
  • the amount of addition in the case of containing a radical polymerization inhibitor, a benzotriazole compound, and a carboxybenzotriazole compound is preferably 0.01 to 3% by mass with respect to the photosensitive resin compound. More preferably, it is 0.05 to 1% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of imparting hue stability to the photosensitive resin composition. In addition, the viewpoint power for maintaining sensitivity is more preferably 3% by mass or less.
  • the photosensitive resin composition of the present invention may contain a plasticizer, if necessary.
  • plasticizers include polyethylene glycol, polypropylene glycol, glycol esters such as polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, and polyoxyethylene polyoxy Propylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalates such as jetyl phthalate, o-toluenesulfonic acid amide, p-toluene Sulfonic acid amide, Tributyl citrate, Triethyl taenoate, Triethyl acetyl citrate, Triacetyl acetyl sulfonate n-propyl, acetyl que Acid tri - n-butyl.
  • the addition amount is preferably 5 to 50% by mass, more preferably 5 to 30% by mass in the photosensitive resin composition.
  • the viewpoint power of 5% by mass or more is preferred because it suppresses the delay in development time and imparts flexibility to the cured film, and 50% by mass or less is preferred from the viewpoint of suppressing insufficient curing and cold flow.
  • the photosensitive resin composition of the present invention may be a photosensitive resin composition preparation solution to which a solvent is added.
  • Suitable solvents include ketones typified by methyl ethyl ketone (MEK), as well as alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition such that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa ⁇ sec at 25 ° C.
  • the photosensitive resin layered product of the present invention has a protective layer on the surface of the photosensitive resin layer opposite to the support of the photosensitive resin layer, if necessary, as a supporting force to support the photosensitive resin layer and the layer. Also good.
  • the support used here is preferably transparent so as to transmit light emitted from the exposure light source.
  • a support include, for example, polyethylene terephthalate film, polybulualcohol film, polychlorinated bull film, and bull chloride copolymer film.
  • films include films, polyvinylidene chloride films, vinylidene chloride copolymer films, polymethyl methacrylate copolymer films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films can be stretched if necessary.
  • the haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 / ⁇ ⁇ is preferably used because the strength needs to be maintained.
  • an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and easily peeled in terms of adhesion to the photosensitive resin layer. It is possible.
  • a polyethylene film and a polypropylene film can be preferably used as the protective layer.
  • a film having excellent peelability disclosed in JP-A-59-202457 can be used.
  • the thickness of the protective layer is 10 to: L 00 m is preferred, and a force of 10 to 50 m is preferred.
  • the thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 5 to 10 O ⁇ m, more preferably 7 to 60 / ⁇ ⁇ . As the thickness is thinner, the resolution is improved, and as the thickness is thicker, the film strength is improved.
  • a conventionally known method can be adopted as a method of laminating a support, a photosensitive resin layer, and if necessary, a protective layer in order to produce the photosensitive resin laminate of the present invention.
  • the photosensitive resin composition used for the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation liquid, and first coated on the support using a bar coater or a roll coater. And drying, and a photosensitive resin layer made of the photosensitive resin composition is laminated on the support.
  • a photosensitive resin laminate can be prepared by laminating a protective layer on the photosensitive resin layer.
  • a resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a laminating process, an exposure process, and a developing process. An example of a specific method is shown.
  • a laminating process is performed using a laminator.
  • the photosensitive resin laminate has a protective layer
  • the photosensitive resin layer is heated on the substrate surface with a laminator. Crimp and laminate.
  • the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary.
  • the heating temperature at this time is generally 40 to 160 ° C.
  • substrate of the obtained resist pattern improves by performing this thermocompression bonding twice or more.
  • a two-stage laminator equipped with two rolls may be used for crimping, or it may be repeatedly crimped through the roll several times.
  • an exposure process is performed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask.
  • the exposure amount is determined from the light source illuminance and the exposure time. It can be measured using a photometer.
  • the exposure process use a maskless exposure method.
  • maskless exposure exposure is performed directly on the substrate by a drawing apparatus without using a photomask.
  • the light source a semiconductor laser having a wavelength of 350 to 410 nm and an ultrahigh pressure mercury lamp are used.
  • the drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.
  • a developing process is performed using a developing device. Exclude any support on the photosensitive resin layer after exposure. Subsequently, the unexposed area is removed by using a developer such as an alkaline aqueous solution to obtain a resist pattern. Na CO or K CO as alkaline aqueous solution
  • a surfactant, an antifoaming agent, and a small amount of an organic solvent for promoting development may be mixed.
  • the temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 20 to 40 ° C.
  • the force at which a resist pattern can be obtained by the above-described steps.
  • a heating step of 100 to 300 ° C can be further performed.
  • hot air, infrared, or far-infrared heating furnaces can be used.
  • the method for producing a printed wiring board of the present invention includes a copper-clad laminate or a flexible board as a substrate. After the resist pattern is formed on the substrate by the above-described resist pattern forming method, the following steps are performed.
  • a step of forming a conductor pattern using a known method such as an etching method or a fitting method is performed on the copper surface of the substrate exposed by development.
  • a desired printed wiring board is obtained by performing a peeling process in which the resist pattern is peeled off with an aqueous solution having alkalinity stronger than that of the developer.
  • the alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. It is possible to add a small amount of water-soluble solvent to the stripping solution.
  • the temperature of the stripping solution in the stripping process is preferably in the range of 40 to 70 ° C! /.
  • the lead frame manufacturing method of the present invention is performed by performing the following steps after forming a resist pattern on a metal plate of copper, copper alloy, or iron-based alloy as a substrate by the above-described resist pattern forming method.
  • a step of etching the substrate exposed by development to form a conductor pattern is performed. Thereafter, a desired lead frame is obtained by performing a peeling process in which the resist pattern is peeled by the same method as the above-described printed wiring board manufacturing method.
  • the method for manufacturing a semiconductor package of the present invention is performed by forming a resist pattern by the above-described resist pattern forming method on a wafer on which a circuit as an LSI has been formed as a substrate, and then performing the following steps.
  • a step of forming a conductor pattern by performing columnar plating with copper or solder on the opening exposed by development is performed. Thereafter, by performing a peeling step of peeling the resist pattern by the same method as the method for manufacturing a printed wiring board described above, and further performing a step of removing a thin metal layer other than the columnar tack by etching, Obtain the desired semiconductor package.
  • the resist pattern is formed by the sandblasting method using the resist pattern forming method described above. It can be used as a protective mask member when processing the substrate.
  • the substrate examples include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material.
  • a resist pattern is formed on these substrates by the same method as the above-described resist pattern forming method. After that, the resist pattern upper force blasting material formed is blown to the desired depth and the sandblasting process is performed, and the resist pattern portion remaining on the substrate is removed from the substrate with a stripping solution.
  • the substrate can have a fine concavo-convex pattern.
  • known materials are used, for example,
  • the photosensitive resin laminates in Examples and Comparative Examples were produced as follows.
  • the photosensitive resin composition having the composition shown in Table 1 is thoroughly stirred and mixed, and uniformly applied to the surface of a 16 m-thick polyethylene terephthalate film (Mitsubishi Polyester R310-16) as a support using a bar coater.
  • a photosensitive resin layer was formed by drying for 4 minutes in a 95 ° C dryer.
  • the thickness of the photosensitive resin layer was 40 m.
  • Table 2 describes the symbols shown in Table 1.
  • Etch solution resistance, resolution, adhesion, and tenting properties are evaluated using a 1.6 mm thick copper clad laminate with 35 ⁇ m rolled copper foil, and the surface is wet pafrol polished (manufactured by 3M Corporation). Scotch Bright (registered trademark) HD # 600, twice).
  • the roll temperature was adjusted to 105 ° C using a hot roll laminator (AL-70, manufactured by Asahi Kasei Co., Ltd.) on a copper-clad laminate that had been leveled and preheated to 60 ° C. Laminated at ° C. Air pressure is 0.335MPa and laminating speed is 1.5 va./min.
  • A-70 manufactured by Asahi Kasei Co., Ltd.
  • a 21-step tablet made by Stofer is placed on a polyethylene terephthalate film as a support, and a super high pressure mercury lamp (OMW, HMW-201KB) is placed on the photosensitive resin layer for the evaluation.
  • OMW super high pressure mercury lamp
  • This exposure method is referred to as a batch exposure method.
  • the number of step tablet steps is 8 by the following sensitivity evaluation using a direct-drawing exposure system (Hitachi Via Mechatas Co., Ltd., DI exposure machine DE-1AH, light source: GaN blue-violet diode, dominant wavelength 407 ⁇ 3 nm) Exposure was performed with an exposure amount (this exposure method is a direct drawing type exposure method).
  • the unexposed portion of the photosensitive resin layer was dissolved and removed in a time twice as long as the minimum development time.
  • the minimum development time was defined as the minimum time required for the photosensitive resin layer in the unexposed area to be completely dissolved.
  • the substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed using a 21-step tablet manufactured by Stofer, whose brightness was changed from transparent to black in 21 levels. After exposure, Development was performed with a development time twice as long as the minimum development time, and the cured resist film remained completely!
  • Adhesive strength value exceeds 0 m and 50 m or less.
  • Adhesion value exceeds 50 m.
  • the present invention includes printed wiring board manufacturing, IC chip mounting lead frame manufacturing, metal mask manufacturing, packages such as BGA and CSP manufacturing, tape substrates such as COF and TAB manufacturing, semiconductor bump manufacturing, ITO electrodes and addresses. It can be used in a method for producing an electrode, an electromagnetic wave shield, for example, a partition wall of a flat panel display.

Abstract

A photosensitive resin composition which is excellent in sensitivity, resolution, and adhesion, has satisfactory hue stability with respect to coloring and color fading during dry film storage, and can be developed with an alkaline aqueous solution; a layered photosensitive-resin product including the photosensitive resin composition; a method of forming a resist pattern on a substrate with the layered photosensitive-resin product; and a use of the resist pattern. The photosensitive resin composition is characterized by comprising: (a) 20-90 mass% thermoplastic copolymer which contains comonomer units derived from an α,β-unsaturated carboxylated monomer and has an acid equivalent of 100-600 and a weight-average molecular weight of 5,000-500,000; (b) 5-75 mass% addition-polymerizable monomer having at least one terminal ethylenically unsaturated group; (c) 0.01-30 mass% photopolymerization initiator; (d) 0.01-5 mass% phosphorous ester compound; and (e) 0.001-0.3 mass% basic dye.

Description

明 細 書  Specification
感光性樹脂組成物  Photosensitive resin composition
技術分野  Technical field
[0001] 本発明は、アルカリ性水溶液によって現像可能な感光性榭脂組成物、該感光性榭 脂組成物を支持体上に積層した感光性榭脂積層体、該感光性榭脂積層体を用いて 基板上にレジストパターンを形成する方法、及び該レジストパターンの用途に関する The present invention uses a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate in which the photosensitive resin composition is laminated on a support, and the photosensitive resin laminate. A method for forming a resist pattern on a substrate and use of the resist pattern
。さらに詳しくは、プリント配線板の製造、フレキシブルプリント配線板の製造、 ICチッ プ搭載用リードフレーム（以下、リードフレームという）の製造、金属箔精密加工、例え ば、メタルマスク製造、半導体パッケージ、例えば、 BGA(Ball Grid Array)や CS P (Chip Size Package)の製造、 TAB (Tape Automated Bonding)や COF ( Chip On Film:半導体 ICをフィルム状の微細配線板上に搭載したもの）に代表さ れるテープ基板の製造、半導体バンプの製造、フラットパネルディスプレイ分野にお ける ITO電極、部材、例えばアドレス電極や電磁波シールドの製造に好適なレジスト パターンを与える感光性榭脂組成物に関する。 . More specifically, the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for IC chip mounting (hereinafter referred to as lead frames), the precision processing of metal foils, such as the manufacture of metal masks, semiconductor packages such as , Represented by BGA (Ball Grid Array) and CS P (Chip Size Package) manufacturing, TAB (Tape Automated Bonding) and COF (Chip On Film: semiconductor IC mounted on a film-like fine wiring board) The present invention relates to a photosensitive resin composition that provides a resist pattern suitable for the manufacture of tape substrates, semiconductor bumps, ITO electrodes and members in the field of flat panel displays, such as address electrodes and electromagnetic wave shields.
背景技術  Background art
[0002] 従来、プリント配線板はフォトリソグラフィ一法によって製造されて 、る。フォトリソダラ フィ一法とは、感光性榭脂組成物を基板上に塗布し、パターン露光して該感光性榭 脂組成物の露光部を重合硬化させ、未露光部を現像液で除去して基板上にレジスト パターンを形成し、エッチング又はめつき処理を施して導体パターンを形成した後、 該レジストパターンを該基板上カゝら剥離除去することによって、基板上に導体パター ンを形成する方法を言う。  Conventionally, a printed wiring board has been manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure an exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer. A method of forming a conductor pattern on a substrate by forming a resist pattern on the substrate, forming a conductor pattern by etching or clinging, and then peeling and removing the resist pattern on the substrate. Say.
[0003] 上記のフォトリソグラフィ一法においては、感光性榭脂組成物を基板上に塗布する にあたって、感光性榭脂組成物の溶液を基板に塗布して乾燥させる方法、または支 持体、感光性榭脂組成物力もなる層（以下、「感光性榭脂層」ともいう。）、及び必要 によっては保護層、を順次積層した感光性榭脂積層体 (以下、「ドライフィルムレジス ト」ともいう。）を基板に積層する方法のいずれかが使用される。そして、プリント配線 板の製造においては、後者のドライフィルムレジストが使用されることが多い。 [0004] 上記のドライフィルムレジストを用いてプリント配線板を製造する方法について、以 下に簡単に述べる。 [0003] In the photolithography method described above, when the photosensitive resin composition is applied onto the substrate, a solution of the photosensitive resin composition is applied to the substrate and dried, or a support or photosensitive material is used. A photosensitive resin laminate (hereinafter also referred to as a “dry film resist”) in which a layer (hereinafter also referred to as a “photosensitive resin layer”) having a strength of the photosensitive resin composition and a protective layer as necessary is sequentially laminated. Any of the methods of laminating to the substrate is used. In the production of printed wiring boards, the latter dry film resist is often used. [0004] A method for producing a printed wiring board using the dry film resist will be briefly described below.
[0005] まず、ドライフィルムレジストが保護層を有する場合には、感光性榭脂層からこれを 剥離する。次いで、ラミネーターを用いて基板、例えば銅張積層板の上に、該基板、 感光性榭脂層、支持体の順序になるよう、感光性榭脂層及び支持体を積層する。次 いで、配線パターンを有するフォトマスクを介して、該感光性榭脂層を超高圧水銀灯 が発する紫外線、例えば i線（365nm)で露光することによって、露光部分を重合硬 化させる。次いで支持体を剥離する。次いで、現像液、例えば弱アルカリ性を有する 水溶液により感光性榭脂層の未露光部分を溶解又は分散除去して、基板上に硬化 したレジストパターン (以下、単に「レジストパターン」と略称する。）を形成させる。次 いで、形成されたレジストパターンを保護マスクとして公知のエッチング処理、又はパ ターンめつき処理を行う。最後に、該レジストパターンを基板から剥離して導体パター ンを有する基板、すなわちプリント配線板を製造する。  [0005] First, when the dry film resist has a protective layer, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays emitted from an ultra-high pressure mercury lamp, for example, i-line (365 nm) through a photomask having a wiring pattern. Next, the support is peeled off. Next, a resist pattern (hereinafter simply referred to as “resist pattern”) cured on the substrate by dissolving or dispersing and removing the unexposed portion of the photosensitive resin layer with a developing solution, for example, an aqueous solution having weak alkalinity. Let it form. Next, a known etching process or pattern fitting process is performed using the formed resist pattern as a protective mask. Finally, the resist pattern is peeled from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.
[0006] 近年のプリント配線板における配線間隔の微細化に伴 、、ドライフィルムレジストに は高解像性の要求が増してきている。また生産性向上の観点力も高感度化も求めら れている。一方で、露光方式も用途に応じ多様ィ匕しており、レーザーによる直接描画 、つまりフォトマスクを不要とするマスクレス露光が近年急激な広がりを見せている。マ スクレス露光の光源としては波長 350〜410nmの光、とくに i線または h線（405nm) が用いられる場合が多い。従って、これらの波長域の光源に対して高感度、かつ高 解像度のレジストパターンを形成できることが重要視されている。  [0006] With the recent miniaturization of wiring intervals in printed wiring boards, demands for high resolution are increasing for dry film resists. In addition, there is a demand for higher productivity and higher sensitivity. On the other hand, there are various exposure methods depending on the application, and direct drawing by laser, that is, maskless exposure that does not require a photomask, has been spreading rapidly in recent years. As a light source for maskless exposure, light having a wavelength of 350 to 410 nm, particularly i-line or h-line (405 nm) is often used. Therefore, it is important to be able to form a resist pattern with high sensitivity and high resolution for light sources in these wavelength ranges.
[0007] ドライフィルムレジスト用の感光性榭脂組成物において、生産性向上を図るための 高感度化や、レーザーによる直接描画に対応するために高感度の開始剤又は増感 剤を使用するのが一般的であるが、これらの組成物は感度がよい反面、色相安定性 が低ぐ高温下および、長時間保存した場合発色したり、脱色したりするという問題が ある。  [0007] In a photosensitive resin composition for a dry film resist, a high-sensitivity initiator or sensitizer is used in order to increase the sensitivity for improving productivity and to deal with direct drawing by a laser. However, these compositions have good sensitivity, but have a problem that they develop color or lose color when stored for a long time at high temperatures where the hue stability is low.
[0008] 特許文献 1には感光性組成物の色相安定性を向上させるために、フエノール類、 例えば、ノ、イドロキノン、カテコールを添加した感光性榭脂組成物、特許文献 2には o tert ブチルフエノール誘導体と複素環チオールィ匕合物とを含む光重合性組成 物、特許文献 3にはエポキシ基を有する化合物を含有する光重合可能な混合物、特 許文献 4にはアルカノールァミンとマラカイトグリーンを含有する感光性榭脂組成物が 記載されて!、る。しかしながらこれらの感光性榭脂組成物の色相安定性は十分満足 のいくものではなぐ更なる色相安定性の向上が要求されている。 [0008] Patent Document 1 discloses a photosensitive resin composition to which phenols such as rhodium, idroquinone and catechol are added in order to improve the hue stability of the photosensitive composition. Patent Document 2 discloses o tert butyl. Photopolymerizable composition containing phenol derivatives and heterocyclic thiol compounds Patent Document 3 describes a photopolymerizable mixture containing an epoxy group-containing compound, and Patent Document 4 describes a photosensitive resin composition containing alkanolamine and malachite green. However, the hue stability of these photosensitive resin compositions is not fully satisfactory, and further improvement in hue stability is required.
[0009] 特許文献 5には、高温下においても保存安定性の高い組成物として、高分子結合 剤、エチレン性不飽和化合物、ロイコ染料、有機ハロゲンィ匕合物および亜リン酸エス テルを特徴とする感光性組成物が記載されている。しかし、ここに示されているのは、 無色であるロイコ染料の高温貯蔵時の発色を防止すると!/、う効果であって、有色であ る塩基性染料を用いた場合の高温貯蔵時の脱色防止効果にっ 、ては、何らの記載 も示唆もない。しかも、開示されている感光性組成物ではレジストパターンの形成が 出来ないと考えられる。 [0009] Patent Document 5 features a polymer binder, an ethylenically unsaturated compound, a leuco dye, an organic halogen compound, and a phosphorous acid ester as a composition having high storage stability even at high temperatures. A photosensitive composition is described. However, what is shown here is the prevention of coloration of colorless leuco dyes during high-temperature storage! / There is no description or suggestion regarding the anti-bleaching effect. Moreover, it is considered that a resist pattern cannot be formed with the disclosed photosensitive composition.
[0010] ロイコ染料は無色であるが、酸ィ匕により有色染料に変化するため一般に発色性染 料として知られている。ロイコ染料は、感熱ゃ感圧による画像記録の材料として用い られている。特許文献 5には、ロイコ染料の開示があり、その具体例としてロイコクリス タルバイオレットが挙げられて!/、る。ロイコクリスタルバイオレットはそれ自体は無色で あるが、酸ィ匕によりクリスタルバイオレット染料に変化して、紫色に発色する。本願発 明における塩基性染料は、それ自体が有色であり、また酸化されうる状態で色相が 変化することは起こらない。このことからも、高温貯蔵時のロイコ染料に関する発色の 機構と、塩基性染料に関する脱色の機構は全く異なることが分かる。  [0010] Although the leuco dye is colorless, it is generally known as a chromogenic dye because it changes to a colored dye by acid. A leuco dye is used as a material for image recording by heat sensitivity or pressure sensitivity. Patent Document 5 discloses a leuco dye, and a specific example thereof is leucocrystal violet! Although leuco crystal violet itself is colorless, it changes to a crystal violet dye by acid and turns purple. The basic dye in the invention of the present application is itself colored and does not change its hue when it can be oxidized. This also shows that the coloring mechanism for leuco dyes during high-temperature storage is completely different from the decoloring mechanism for basic dyes.
[0011] このような理由から、ドライフィルムレジスト用の塩基性染料を含む感光性榭脂組成 物であって、高感度、高解像度、密着性に優れ、かつドライフィルムレジスト保存時の 脱色の問題のない、色相安定性に優れた感光性榭脂組成物が望まれていた。  [0011] For these reasons, a photosensitive resin composition containing a basic dye for dry film resists, which has high sensitivity, high resolution, excellent adhesion, and a problem of decoloration during storage of dry film resists. There has been a demand for a photosensitive resin composition having no hue and excellent hue stability.
特許文献 1 :米国特許第 3042515号明細書  Patent Document 1: US Patent No. 3042515
特許文献 2：特開昭 60 - 2945公報  Patent Document 2: JP-A-60-2945
特許文献 3 :特開平 1一 161001号公報  Patent Document 3: JP-A-11161001
特許文献 4：特開平 6— 148883号公報  Patent Document 4: JP-A-6-148883
特許文献 5 :特開 2004— 219690号公報  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-219690
発明の開示 発明が解決しょうとする課題 Disclosure of the invention Problems to be solved by the invention
[0012] 本発明は、感度、解像度、及び密着性に優れ、ドライフィルム保存時の発色及び脱 色と!/ヽつた問題のな!、色相安定性が良好で、アルカリ性水溶液によって現像しうる感 光性榭脂組成物、該感光性榭脂組成物を用いた感光性榭脂積層体、該感光性榭 脂積層体を用いて基板上にレジストパターンを形成する方法、及び該レジストパター ンの用途を提供することを目的とする。  [0012] The present invention has excellent sensitivity, resolution, and adhesion, color development and decoloration during storage of a dry film, no problem, and good hue stability, which can be developed with an alkaline aqueous solution. Photosensitive resin composition, photosensitive resin laminate using the photosensitive resin composition, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and the resist pattern The purpose is to provide usage.
課題を解決するための手段  Means for solving the problem
[0013] 上記目的は、本発明の次の構成によって達成することができる。 The above object can be achieved by the following configuration of the present invention.
(1) (a) α , β 不飽和カルボキシル基含有単量体を共重合成分として含み、酸当 量で 100〜600、重量平均分子量が 5, 000〜500, 000の熱可塑性共重合体： 20 〜90質量％、 (b)少なくとも一つの末端エチレン性不飽和基を有する付加重合性モ ノマー： 5〜75質量％、（c)光重合開始剤： 0. 01〜30質量％、（d)亜リン酸エステル 化合物： 0. 01〜5質量％、（e)塩基性染料: 0. 001-0. 3質量％を含有することを 特徴とする感光性榭脂組成物。  (1) (a) Thermoplastic copolymer containing an α, β unsaturated carboxyl group-containing monomer as a copolymerization component and having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000: 20 to 90% by mass, (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) photopolymerization initiator: 0.01 to 30% by mass, (d 1) Phosphorous ester compound: 0.01 to 5% by mass; (e) Basic dye: 0.001 to 0.3% by mass;
(2)上記 (c)光重合開始剤として、へキサァリールビスイミダゾール誘導体を含有す ることを特徴とする（1)記載の感光性榭脂組成物。  (2) The photosensitive resin composition according to (1), which contains a hexaarylbisimidazole derivative as the photopolymerization initiator (c).
(3)上記 (c)光重合開始剤として、下記一般式 (I)で表されるアタリジン化合物を含有 し、更に (f)有機ハロゲンィ匕合物： 0. 01〜3質量％を含有することを特徴とする（1) 又は（2)に記載の感光性榭脂組成物。  (3) As the photopolymerization initiator (c), an atalidine compound represented by the following general formula (I) is contained, and (f) an organic halogen compound: 0.01 to 3% by mass. (1) The photosensitive resin composition according to (2), wherein
[0014] [化 1]  [0014] [Chemical 1]
Figure imgf000005_0001
Figure imgf000005_0001
[0015] (式中、 Rは水素、炭素数 1〜6のアルキル基、ァリール基、ピリジル基、又は炭素数 1 〜6のアルコシキル基である。） [In the formula, R is hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, a pyridyl group, or 1 carbon atom. ˜6 alkoxy groups. )
(4)下記一般式 (Π)で表される N ァリールアミノ酸: 0. 001〜1. 0質量％を含有す ることを特徴とする（1)〜（3)のいずれか一つに記載の感光性榭脂組成物。  (4) N aryl amino acid represented by the following general formula (Π): 0.001 to 1.0% by mass, characterized in that it contains any one of (1) to (3) Photosensitive resin composition.
[0016] R -NHCH COOH (II)  [0016] R -NHCH COOH (II)
1 2  1 2
(式中、 Rはァリール基である。 )  (In the formula, R is an aryl group.)
(5) (c)光重合開始剤として、下記一般式 (III)で表されるビラゾリンィ匕合物: 0. 001 〜 10質量％を含有することを特徴とする（1)〜 (4)のいずれか一つに記載の感光性 榭脂組成物。  (5) (c) As a photopolymerization initiator, it contains virazolin compound represented by the following general formula (III): 0.001 to 10% by mass of (1) to (4) The photosensitive resin composition as described in any one.
[0017] [化 2]  [0017] [Chemical 2]
Figure imgf000006_0001
Figure imgf000006_0001
[0018] (式中 B及び Cは、それぞれ独立に、炭素数 3以上の直鎖または分枝鎖のアルキル 基、又は NR (Rは水素原子、またはアルキル基)であり、 Aは、ァリール基、複素環 [In the formula, B and C are each independently a linear or branched alkyl group having 3 or more carbon atoms, or NR (R is a hydrogen atom or an alkyl group), and A is an aryl group. , Heterocycle
2  2
基、及び炭素数 3以上の直鎖または分枝鎖のアルキル基力 なる群力 選ばれる置 換基を表す。 aは 0又は 1であり、 b = c = lである。 )  A group and a group power consisting of a straight-chain or branched alkyl group having 3 or more carbon atoms. a is 0 or 1, and b = c = 1. )
(6) (d)亜リン酸エステル化合物力 2, 4, 8, 10—テトラー tert ブチルー 6— [3— ( 3 -メチル 4—ヒドロキシ 5— tert -ブチルフエ-ル）プロポキシ]ジベンゾ [d、 f ] [1, 3, 2]ジォキサホスフェンピン、 2, 2—メチレンビス（4, 6 ジ一 tert—ブチルフ 工 -ル）ォクチルホスファイト、ビス（2, 4 ジ tert ブチルフエ-ル）ペンタエリスリ トールージホスファイト、トリス（2, 4 ジ—tert ブチルフエ-ル）ホスファイト、 4, 4， -ブチリデンビス（3—メチル— 6— t—ブチルフエ-ル—ジ—トリデシルホスフアイト、 4、 4， 一イソプロピリデンージ—フエノールアルキルホスファイト、及びトリスイソデシル フォスファイトからなる群より選ばれる少なくとも一つの化合物である（1)〜（5)のいず れか一つに記載の感光性榭脂組成物。 (6) (d) Phosphite Compound Strength 2, 4, 8, 10-Tetra-tert-butyl-6- [3- (3-Methyl-4-hydroxy 5-tert-butylphenol) propoxy] dibenzo [d, f ] [1, 3, 2] dioxaphosfenpine, 2,2-methylenebis (4,6 di-tert-butyl phosphine octyl phosphite), bis (2,4 di tert-butyl phenol) pentaerythri Tall diphosphite, tris (2,4 di-tert butylphenol) phosphite, 4, 4, At least selected from the group consisting of 3-butylidenebis (3-methyl-6-t-butylphenol-di-tridecyl phosphite, 4, 4, monoisopropylidenedi-phenol alkyl phosphite, and trisisodecyl phosphite The photosensitive resin composition according to any one of (1) to (5), which is one compound.
(7) (b)少なくとも一つの末端エチレン性不飽和基を有する付加重合性モノマーが下 記一般式 (IV)または (V)の少なくとも 1種を含むことを特徴とする（ 1)〜（6)の 、ずれ か一つに記載の感光性榭脂組成物。  (7) (b) The addition polymerizable monomer having at least one terminal ethylenically unsaturated group contains at least one of the following general formula (IV) or (V): (1) to (6 ). The photosensitive resin composition according to any one of the above.
[0019] [化 3]  [0019] [Chemical 3]
Figure imgf000007_0001
Figure imgf000007_0001
[0020] (式中、 R及び Rは、それぞれ独立に Hまたは CHであり、 Dおよび Eは、炭素数が 2 [0020] (wherein R and R are each independently H or CH; D and E each have 2 carbon atoms)
1 2 3  one two Three
〜4個のアルキレン基であり、それぞれ同一であっても異なっていてもよぐ異なって いる場合、 - (D-O)—及び—（E— O)—の繰り返し単位は、ブロック構造であって もなくてもよく、又そのいずれがビスフエ-ル基側であっても良い。 ml、 m2、 nl、及 び n2は、それぞれ独立に 0又は正の整数であり、これらの合計は、 2〜30である。） [0021] [化 4]
Figure imgf000008_0001
(式中、 R及び Rは、それぞれ独立に Hまたは CHである。また、 Fおよび Gは、炭素 In the case where they are the same or different, the repeating unit of-(DO)-and-(E-O)-may be a block structure None of them may be on the bisphenol group side. ml, m2, nl, and n2 are each independently 0 or a positive integer, and their sum is 2-30. ) [0021] [Chemical 4]
Figure imgf000008_0001
(Wherein R and R are each independently H or CH; and F and G are carbon
3 4 3  3 4 3
数が 2〜4個のアルキレン基であり、それぞれ同一であっても異なっていてもよぐ 異なっている場合、 - (F-O)—及び—（G— O)—の繰り返し単位は、ブロック構造 であってもなくてもよぐそのいずれがシクロへキシル基側であっても良い。 pl、 p2、 q 1、及び q2は、それぞれ独立に 0又は正の整数であり、これらの合計は、 2〜30であ る。） When the number is 2 to 4 alkylene groups, which may be the same or different, the-(FO) — and — (G—O) — repeating units have a block structure Either of them may or may not be on the cyclohexyl group side. pl, p2, q1, and q2 are each independently 0 or a positive integer, and the sum thereof is 2 to 30. )
(8) (1)〜（7)のいずれか一項に記載の感光性榭脂組成物を支持体上に積層して なる感光性榭脂積層体。  (8) A photosensitive resin laminate obtained by laminating the photosensitive resin composition according to any one of (1) to (7) on a support.
(9) (8)記載の感光性榭脂積層体を用いて、基板上に感光性榭脂層を形成するラミ ネート工程、露光工程、及び現像工程を含む、レジストパターン形成方法。  (9) A resist pattern forming method including a lamination step, an exposure step, and a development step for forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to (8).
(10)前記露光工程において、直接描画して露光する事を特徴とする（9)に記載のレ ジストパターン形成方法。  (10) The resist pattern forming method according to (9), wherein in the exposure step, direct exposure is performed by drawing.
(11) (9)又は（10)に記載の方法によってレジストパターンを形成した基板を、エッチ ングする力またはめつきする工程を含むプリント配線板の製造方法。  (11) A method for producing a printed wiring board, comprising a step of etching or attaching a substrate on which a resist pattern is formed by the method according to (9) or (10).
(12) (9)又は（10)に記載の方法によってレジストパターンを形成した基板を、エッチ ングする工程を含むリードフレームの製造方法。 (13) (9)又は（10)に記載の方法によってレジストパターンを形成した基板を、エッチ ングする力またはめつきする工程を含む半導体パッケージの製造方法。 (12) A lead frame manufacturing method including a step of etching a substrate on which a resist pattern is formed by the method according to (9) or (10). (13) A method for manufacturing a semiconductor package, comprising a step of etching or attaching a substrate on which a resist pattern is formed by the method according to (9) or (10).
(14) (9)又は（10)に記載の方法によってレジストパターンを形成した基板を、サンド ブラストによって加工する工程を含む凹凸パターンを有する基材の製造方法。  (14) A method for producing a substrate having a concavo-convex pattern, comprising a step of processing a substrate on which a resist pattern is formed by the method according to (9) or (10) by sand blasting.
発明の効果  The invention's effect
[0023] 本発明は、感度、解像度、及び密着性に優れ、色相安定性の良好な、アルカリ性 水溶液によって現像しうる感光性榭脂組成物、該感光性榭脂組成物を用いた感光 性榭脂積層体、該感光性榭脂積層体を用いて基板上にレジストパターンを形成する 方法、及び該レジストパターンの用途を提供し、プリント配線板の製造、リードフレー ムの製造、半導体パッケージの製造、平面ディスプレイの製造に好適に使用すること ができる。  [0023] The present invention is a photosensitive resin composition that is excellent in sensitivity, resolution, and adhesiveness, has good hue stability, and can be developed with an alkaline aqueous solution, and a photosensitive resin using the photosensitive resin composition. The present invention provides a resin laminate, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and a use of the resist pattern, and manufactures a printed wiring board, a lead frame, and a semiconductor package. It can be suitably used for the production of flat displays.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0024] 以下、本発明について具体的に説明する。  Hereinafter, the present invention will be specifically described.
[0025] <感光性榭脂組成物 >  <Photosensitive resin composition>
本発明の感光性榭脂組成物には、（a) α , β 不飽和カルボキシル基含有単量体 を共重合成分として含み、酸当量で 100〜600、重量平均分子量が 5, 000〜500, 000の熱可塑性共重合体： 20〜90質量％、（b)少なくとも一つの末端エチレン性不 飽和基を有する付加重合性モノマー： 5〜75質量％、（c)光重合開始剤： 0. 01〜3 0質量％、（d)亜リン酸エステルイ匕合物： 0. 01〜5質量％、（e)塩基性染料: 0. 001 〜0. 3質量％を必須成分として含む。  The photosensitive resin composition of the present invention includes (a) an α, β unsaturated carboxyl group-containing monomer as a copolymerization component, an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500, 000 thermoplastic copolymer: 20 to 90% by mass, (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) photoinitiator: 0.01 ~ 30 mass%, (d) Phosphite ester compound: 0.01 to 5 mass%, (e) Basic dye: 0.001 to 0.3 mass% as essential components.
(a)熱可塑性共重合体  (a) Thermoplastic copolymer
本発明の感光性榭脂組成物において、（a)熱可塑性共重合体としては、 a , j8—不 飽和カルボキシル基含有単量体を共重合成分として含む、酸当量で 100〜600、重 量平均分子量が 5, 000〜500, 000のものを用いる。  In the photosensitive resin composition of the present invention, (a) the thermoplastic copolymer includes a, j8-unsaturated carboxyl group-containing monomer as a copolymerization component, and has an acid equivalent of 100 to 600, and a weight. Use an average molecular weight of 5,000 to 500,000.
[0026] 熱可塑性共重合体中のカルボキシル基は、感光性榭脂組成物がアルカリ水溶液 カゝらなる現像液や剥離液に対して、現像性や剥離性を有するために必要である。酸 当量は、 100〜600力好ましく、より好ましくは 250〜450である。溶媒または組成物 中の他の成分、特に後述する（b)付加重合性モノマーとの相溶性を確保するという 観点から 100以上であり、また、現像性や剥離性を維持するという観点から 600以下 である。ここで、酸当量とは、その中に 1当量のカルボキシル基を有する熱可塑性共 重合体の質量 (グラム）をいう。なお、酸当量の測定は、平沼レポ一ティングタイトレー ター（COM— 555)を用い、 0. ImolZLの NaOH水溶液で電位差滴定法により行 われる。 [0026] The carboxyl group in the thermoplastic copolymer is necessary for the photosensitive resin composition to have developability and releasability with respect to a developing solution and a peeling solution comprising an alkaline aqueous solution. The acid equivalent is preferably 100-600 forces, more preferably 250-450. To ensure compatibility with other components in the solvent or composition, particularly (b) addition polymerizable monomer described later From the viewpoint, it is 100 or more, and from the viewpoint of maintaining developability and peelability, it is 600 or less. Here, the acid equivalent means the mass (gram) of the thermoplastic copolymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by potentiometric titration with 0.1 ImolZL NaOH aqueous solution using Hiranuma Reporting Titer (COM-555).
[0027] 本発明の熱可塑性重合体の重量平均分子量は、 5, 000から 500, 000であること が好ましい。ドライフィルムレジストの厚みを均一に維持し、現像液に対する耐性を得 るという観点から 5, 000以上であり、また、現像性を維持するという観点から 500, 00 0以下である。より好ましくは、重量平均分子量は、 20, 000力 100, 000である。こ の場合の重量平均分子量とは、ゲルパーミエーシヨンクロマトグラフィー（GPC)により 標準ポリスチレン（昭和電工 (株）製 Shodex STANDARD SM— 105)の検量線 を用いて測定した重量平均分子量のことである。該重量平均分子量は、 日本分光（ 株)製ゲルパーミエーシヨンクロマトグラフィーを使用して、以下の条件で測定すること ができる。  [0027] The weight average molecular weight of the thermoplastic polymer of the present invention is preferably 5,000 to 500,000. From the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to the developer, it is 5,000 or more, and from the viewpoint of maintaining developability, it is 500,000 or less. More preferably, the weight average molecular weight is 20,000 force 100,000. The weight average molecular weight in this case is a weight average molecular weight measured by gel permeation chromatography (GPC) using a standard polystyrene (Showa Denko Co., Ltd. Shodex STANDARD SM-105) calibration curve. . The weight average molecular weight can be measured under the following conditions using gel permeation chromatography manufactured by JASCO Corporation.
示差屈折率計: RI— 1530  Differential refractometer: RI— 1530
ポンプ： PU— 1580  Pump: PU— 1580
デガッサー： DG— 980— 50  Degasser: DG—980—50
カラムオーブン： CO— 1560  Column oven: CO— 1560
カラム：順に KF— 8025、 KF- 806M X 2, KF— 807  Column: KF-8025, KF-806M X 2, KF—807 in order
溶離液: THF  Eluent: THF
熱可塑性共重合体は、後述する第一の単量体の少なくとも 1種以上と後述する第 二の単量体の少なくとも一種以上力 なる共重合体であることが好ましい。  The thermoplastic copolymer is preferably a copolymer that has at least one or more of the first monomer described later and at least one or more of the second monomer described later.
[0028] 第一の単量体は、分子中に a , j8 不飽和カルボキシル基を含有する単量体であ る。例えば、（メタ）アクリル酸、フマル酸、ケィ皮酸、クロトン酸、ィタコン酸、マレイン 酸無水物、及びマレイン酸半エステルがあげられる。中でも、特に (メタ）アクリル酸が 好ましい。  [0028] The first monomer is a monomer containing a, j8 unsaturated carboxyl group in the molecule. Examples thereof include (meth) acrylic acid, fumaric acid, cinnamate, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Of these, (meth) acrylic acid is particularly preferable.
[0029] 第二の単量体は、非酸性で、分子中に重合性不飽和基を少なくとも一個有する単 量体である。例えば、メチル (メタ）アタリレート、ェチル (メタ）アタリレート、 n—プロピ ル (メタ）アタリレート、 iso—プロピル (メタ）アタリレート、 n—ブチル (メタ）アタリレート、 iso—ブチル（メタ）アタリレート、 tert—ブチル（メタ）アタリレート、 2—ヒドロキシェチル (メタ）アタリレート、 2—ヒドロキシプロピル (メタ）アタリレート、シクロへキシル (メタ）ァ タリレート、 2—ェチルへキシル (メタ）アタリレート、ベンジル (メタ）アタリレート、酢酸ビ -ル、（メタ)アクリロニトリル、スチレン、及び重合可能なスチレン誘導体が挙げられる 。 中でも、特にメチル (メタ）アタリレート、 n—ブチル (メタ）アタリレート、スチレン、ベン ジル (メタ）アタリレート、が好ましい。 [0029] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (Meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meta ) Atarylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, (meth) acrylonitrile , Styrene, and polymerizable styrene derivatives. Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable.
[0030] 本発明の感光性榭脂組成物中に含有される熱可塑性重合体の量は、 20〜90質 量％の範囲であり、好ましくは、 25〜70質量％の範囲である。この量は、アルカリ現 像性を維持するという観点から 20質量％以上であり、また、露光によって形成される レジストパターンがレジストとしての性能を十分に発揮するという観点から 90質量％ 以下である。  [0030] The amount of the thermoplastic polymer contained in the photosensitive resin composition of the present invention is in the range of 20 to 90% by mass, and preferably in the range of 25 to 70% by mass. This amount is 20% by mass or more from the viewpoint of maintaining alkali developability, and is 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.
[0031] (b)付加重合性モノマー  [0031] (b) Addition polymerizable monomer
本発明の感光性榭脂組成物に用いる (b)少なくとも一つの末端エチレン性不飽和 基を有する付加重合性モノマーとしては、特に限定されないが、解像性および密着 性の観点から、下記一般式 (IV)で示される化合物を含有することが望ま 、。  The addition polymerizable monomer having at least one terminal ethylenically unsaturated group used in the photosensitive resin composition of the present invention is not particularly limited, but from the viewpoint of resolution and adhesion, the following general formula It is desirable to contain the compound represented by (IV).
[0032] [化 5]  [0032] [Chemical 5]
Figure imgf000011_0001
[0033] (式中、 R及び Rは、それぞれ独立に Hまたは CHであり、 Dおよび Eは、炭素数が 2
Figure imgf000011_0001
[In the formula, R and R are each independently H or CH, and D and E have 2 carbon atoms.
1 2 3 one two Three
〜4個のアルキレン基であり、それぞれ同一であっても異なっていてもよぐ異なって いる場合、 - (D-O)—及び—（E— O)—の繰り返し単位は、ブロック構造であって もなくてもよく、又そのいずれがビスフエ-ル基側であっても良い。 ml、 m2、 nl、及 び n2は、それぞれ独立に 0又は正の整数であり、これらの合計は、 2〜30である。） 上記一般式 (IV)で示される化合物としては、例えば、 2, 2 ビス { (4 アタリロキシ ポリエチレンォキシ）フエ-ル}プロパンまたは 2, 2 ビス { (4ーメタクリロキシポリェチ レンォキシ)フエ-ル}プロパンがあげられる。該化合物が有するポリエチレンォキシ 基は、モノエチレンォキシ基、ジエチレンォキシ基、トリエチレンォキシ基、テトラエチ レンォキシ基、ペンタエチレンォキシ基、へキサエチレンォキシ基、ヘプタエチレンォ キシ基、ォクタエチレンォキシ基、ノナエチレンォキシ基、デカエチレンォキシ基、ゥ ンデカエチレンォキシ基、ドデカエチレンォキシ基、トリデカエチレンォキシ基、テトラ デカエチレンォキシ基、及びペンタデカエチレンォキシ基力 なる群力 選択される いずれかの基である化合物が好ましい。また、 2, 2 ビス { (4—アタリロキシポリアル キレンォキシ）フエ-ル}プロパンまたは 2, 2 ビス { (4ーメタクリロキシポリアルキレン ォキシ)フエ-ル}プロパンがあげられる。該化合物が有するポリアルキレンォキシ基 としては、エチレンォキシ基とプロピレンォキシ基の混合物が挙げられ、オタタエチレ ンォキシ基とジプロピレンォキシ基のブロック構造の付加物またはランダム構造の付 加物、及びテトラエチレンォキシ基とテトラプロピレンォキシ基のブロック構造の付カロ 物またはランダム構造の付加物が好ましい。これらの中でも、 2, 2 ビス { (4—メタク リロキシペンタエチレンォキシ）フエ-ル}プロパンが最も好ましい。  In the case where they are the same or different, the repeating unit of-(DO)-and-(E-O)-may be a block structure None of them may be on the bisphenol group side. ml, m2, nl, and n2 are each independently 0 or a positive integer, and their sum is 2-30. ) Examples of the compound represented by the above general formula (IV) include 2, 2 bis {(4 attaryloxypolyethyleneoxy) phenol} propane or 2,2 bis {(4-methacryloxypolyethyleneoxy) phenol. -Le} Propane. The polyethyleneoxy group possessed by the compound includes monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octa Ethyleneoxy, nonaethyleneoxy, decaethyleneoxy, undecaethyleneoxy, dodecaethyleneoxy, tridecaethyleneoxy, tetradecaethyleneoxy, and pentadecaethylene Xy group power is a group power selected A compound that is any group selected is preferred. Further, 2,2bis {(4-aryloxypolyalkyleneoxy) phenol} propane or 2,2bis {(4-methacryloxypolyalkyleneoxy) phenol} propane can be mentioned. Examples of the polyalkyleneoxy group possessed by the compound include a mixture of an ethyleneoxy group and a propyleneoxy group, an adduct having a block structure or a random structure having an otaethyleneoxy group and a dipropyleneoxy group, and a tetra structure. An adduct having a block structure of an ethyleneoxy group and a tetrapropyleneoxy group or an adduct having a random structure is preferable. Of these, 2,2bis {(4-methacryloxypentaethyleneoxy) phenol} propane is most preferred.
[0034] また、本発明の感光性榭脂組成物において、（b)付加重合性モノマーとして、下記 一般式 (V)で示される化合物を含有することは解像性の観点力も望ま 、。  [0034] In addition, in the photosensitive resin composition of the present invention, it is desirable that (b) a compound represented by the following general formula (V) as the addition-polymerizable monomer has a viewpoint of resolution.
[0035] [化 6]
Figure imgf000013_0001
(式中、 R及び Rは、それぞれ独立に Hまたは CHである。また、 Fおよび Gは、炭素 [0035] [Chemical 6]
Figure imgf000013_0001
(Wherein R and R are each independently H or CH; and F and G are carbon
3 4 3  3 4 3
数が 2〜4個のアルキレン基であり、それぞれ同一であっても異なっていてもよぐ異 なっている場合、 (F-O) 及び一（G O)—の繰り返し単位は、ブロック構造で あってもなくてもよぐそのいずれがシクロへキシル基側であっても良い。 pl、 p2、 ql 、及び q2は、それぞれ独立に 0又は正の整数であり、これらの合計は、 2〜30である o ) When the number of alkylene groups is 2 to 4, and they may be the same or different, the repeating units (FO) and one (GO) — may be a block structure. Any of them may be on the cyclohexyl group side. pl, p2, ql and q2 are each independently 0 or a positive integer, and their sum is 2 to 30 o)
上記一般式 (V)で示される化合物としては、例えば、 2, 2 ビス { (4—アタリロキシ ポリエチレンォキシ）シクロへキシル }プロパンまたは 2, 2 ビス { (4ーメタクリロキシポ リエチレンォキシ）シクロへキシル }プロパンがあげられる。該化合物が有するポリェチ レンォキシ基は、モノエチレンォキシ基、ジエチレンォキシ基、トリエチレンォキシ基、 テトラエチレンォキシ基、ペンタエチレンォキシ基、へキサエチレンォキシ基、ヘプタ エチレンォキシ基、ォクタエチレンォキシ基、ノナエチレンォキシ基、デカエチレンォ キシ基、ゥンデ力エチレンォキシ基、ドデカエチレンォキシ基、トリデカエチレンォキ シ基、テトラデカエチレンォキシ基、及びペンタデカエチレンォキシ基力 なる群から 選択されるいずれかの基である化合物が好ましい。また、 2, 2 ビス { (4—アタリロキ シポリアルキレンォキシ）シクロへキシル }プロパンまたは 2, 2 ビス { (4—メタクリロキ シポリアルキレンォキシ）シクロへキシル }プロパンがあげられる。該化合物が有する ポリアルキレンォキシ基としては、エトキシ基とプロピルォキシ基の混合物が挙げられ 、ォクタエチレンォキシ基とジプロピレンォキシ基のブロック構造の付加物またはラン ダム構造の付加物、及びテトラエチレンォキシ基とテトラプロピレンォキシ基のブロッ ク構造の付加物またはランダム構造の付加物が好ましい。これらの中でも、 2, 2—ビ ス { (4ーメタクリロキシペンタエチレンォキシ）シクロへキシル }プロパンが最も好ましい Examples of the compound represented by the general formula (V) include 2, 2 bis {(4-ataryloxypolyethyleneoxy) cyclohexyl} propane or 2,2 bis {(4-methacryloxypolyoxyethylene) cyclohexane. Hexyl} propane. Polyethyleneoxy group possessed by the compound is monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octaethylene Group consisting of oxy group, nonaethyleneoxy group, decaethyleneoxy group, undeethylene ethyleneoxy group, dodecaethyleneoxy group, tridecaethyleneoxy group, tetradecaethyleneoxy group, and pentadecaethyleneoxy group Compounds that are any group selected from are preferred. In addition, 2, 2 bis {(4- talyloxypolyalkyleneoxy) cyclohexyl} propane or 2, 2 bis {(4-methacryloxy Cypolyalkyleneoxy) cyclohexyl} propane. Examples of the polyalkyleneoxy group possessed by the compound include a mixture of an ethoxy group and a propyloxy group, an adduct having a block structure or a random structure having an octaethyleneoxy group and a dipropyleneoxy group, and An adduct with a block structure or a random structure of a tetraethyleneoxy group and a tetrapropyleneoxy group is preferred. Of these, 2,2-bis {(4-methacryloxypentaethyleneoxy) cyclohexyl} propane is most preferred.
[0037] 上記一般式 (IV)又は (V)で表される化合物が本発明の感光性榭脂組成物に含ま れる場合の含有量は、感光性榭脂組成物中に 5〜40質量％含まれることが好ましく 、より好ましくは 10〜30質量％である。この量は、高解像度、高密着性を発現すると いう観点から 5質量％以上であり、また、コールドフロー、及びレジストパターンの剥離 遅延を抑えるという観点から 40質量％以下である。 [0037] When the compound represented by the general formula (IV) or (V) is contained in the photosensitive resin composition of the present invention, the content is 5 to 40% by mass in the photosensitive resin composition. It is preferably contained, more preferably 10 to 30% by mass. This amount is 5% by mass or more from the viewpoint of high resolution and high adhesion, and 40% by mass or less from the viewpoint of suppressing cold flow and resist pattern peeling delay.
[0038] 本発明の感光性榭脂組成物に用いる（b)付加重合性モノマーとしては、上記の化 合物以外にも少なくとも 1つの末端エチレン性不飽和基を有する公知の化合物を使 用できる。  [0038] As the (b) addition polymerizable monomer used in the photosensitive resin composition of the present invention, a known compound having at least one terminal ethylenically unsaturated group can be used in addition to the above compound. .
[0039] 例えば、 4ーノユルフェ-ルヘプタエチレングリコールジプロピレングリコールアタリ レート、 2—ヒドロキシー 3—フエノキシプロピルアタリレート、フエノキシへキサエチレン グリコールアタリレート、無水フタル酸と 2—ヒドロキシプロピルアタリレートとの半エス テルィ匕合物とプロピレンォキシドとの反応物（日本触媒化学製、商品名 OE— A 20 0)、 4—ノルマルォクチルフエノキシペンタプロピレングリコールアタリレート、 1, 6— へキサンジオール (メタ）アタリレート、 1, 4—シクロへキサンジオールジ (メタ）アタリレ ート、またポリオキシアルキレングリコールジ (メタ）アタリレート、例えば、ポリプロピレ ングリコールジ (メタ）アタリレート、ポリエチレングリコールジ (メタ）アタリレート、ポリオ キシエチレンポリオキシプロピレングリコールジ (メタ）アタリレート、 2—ジ（p—ヒドロキ シフエ-ル）プロパンジ (メタ）アタリレート、グリセロールトリ（メタ）アタリレート、ペンタ エリスリトールペンタ（メタ）アタリレート、トリメチロールプロパントリグリシジルエーテル トリ（メタ）アタリレート、 2, 2—ビス（4—メタクリロキシペンタエトキシフエ-ル）プロパン [0039] For example, 4-no-lulfeptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, phthalic anhydride and 2-hydroxypropyl acrylate Reaction product of ester compound and propylene oxide (product name OE—A 20 0, manufactured by Nippon Shokubai Chemical Co., Ltd.), 4-normaloctylphenoxypentapropylene glycol acrylate, 1,6-hexanediol ( (Meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, and polyoxyalkylene glycol di (meth) acrylate, such as polypropylene glycol di (meth) acrylate, polyethylene glycol di (meta ) Atalylate, polyoxyethylene Lioxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, penta erythritol penta (meth) acrylate, trimethylol propane tri Glycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenol) propane
、が挙げられる。また、ウレタン基を含有する多官能基 (メタ）アタリレート、例えば、へ キサメチレンジイソシァネートとアルコール類、例えば、ノナプロピレングリコールモノ メタタリレートとのウレタンィ匕物、及びイソシァヌル酸エステルイ匕合物の多官能 (メタ）ァ タリレートも挙げられる。 . In addition, a polyfunctional group (meth) acrylate having a urethane group, for example, There may also be mentioned urethane compounds of xamethylene diisocyanate and alcohols such as nonapropylene glycol monomethacrylate, and polyfunctional (meth) acrylate of isocyanurate ester compounds.
これらは、単独で使用しても、 2種類以上併用しても構わない。  These may be used alone or in combination of two or more.
[0040] 本発明の感光性榭脂組成物中に含有される (b)付加重合性モノマーの量は、感光 性榭脂組成物全体に対して 5〜75質量％の範囲であり、より好ましい範囲は 15〜7 0質量％である。この量は、硬化不良、及び現像時間の遅延を抑えるという観点から 5質量％以上であり、また、コールドフロー、及びレジストパターンの剥離遅延を抑え るという観点から 75質量％以下である。 [0040] The amount of the (b) addition polymerizable monomer contained in the photosensitive resin composition of the present invention is more preferably in the range of 5 to 75% by mass with respect to the entire photosensitive resin composition. The range is 15 to 70% by weight. This amount is 5% by mass or more from the viewpoint of suppressing poor curing and development time delay, and is 75% by mass or less from the viewpoint of suppressing cold flow and resist pattern peeling delay.
[0041] (c)光重合開始剤 [0041] (c) Photopolymerization initiator
本発明の感光性榭脂組成物には、（c)光重合開始剤が含まれる。本発明の感光性 榭脂組成物に含有される（c)光重合開始剤の量は、 0. 01〜30質量％の範囲であり 、より好ましい範囲は 0. 05〜： LO質量％である。十分な感度を得るという観点力も 0. 01質量％以上が好ましぐまた、レジストパターンの基板と接触している面 (底面）に まで光を充分に透過させ、良好な高解像性および密着性を得ると ヽぅ観点から 30質 量％以下が好ましい。  The photosensitive resin composition of the present invention contains (c) a photopolymerization initiator. The amount of the (c) photopolymerization initiator contained in the photosensitive resin composition of the present invention is in the range of 0.01 to 30% by mass, more preferably 0.05 to: LO% by mass. . The viewpoint power for obtaining sufficient sensitivity is also preferably 0.01% by mass or more. Also, light is sufficiently transmitted to the surface (bottom surface) of the resist pattern that is in contact with the substrate, providing excellent high resolution and adhesion. From the standpoint of obtaining good properties, 30% by mass or less is preferable.
[0042] 光重合開始剤としては、へキサァリールビスイミダゾール誘導体 (以下、トリアリール イミダゾリル二量体）が好ましく用いられる。トリアリールイミダゾリル二量体としては、 例えば、 2—（0—クロロフェ-ル）ー4, 5 ジフエ-ルイミダゾリル二量体（以下、 2, 2 ，一ビス（2 クロ口フエ-ル）一 4, 4， , 5, 5，一テトラフエ-ル一 1, 1，一ビスイミダゾ ール、とも言う）、 2, 2' , 5 トリス一（o クロ口フエ-ル）一 4— (3, 4 ジメトキシフエ -ル） 4，， 5，一ジフエ-ルイミダゾリル二量体、 2, 4 ビス一（o クロ口フエ-ル） —5— (3, 4 ジメトキシフエ-ル）—ジフエ-ルイミダゾリル二量体、 2, 4, 5 トリス - (o クロ口フエ-ル）一ジフエ-ルイミダゾリル二量体、 2— (o クロ口フエ-ル） - ビス— 4, 5 - (3, 4 ジメトキシフエ-ル）—イミダゾリル二量体、 2, 2，—ビス—（2— フルオロフェ-ル）一4, 4，， 5, 5，一テトラキス一（3—メトキシフエ-ル）一イミダゾリ ルニ量体、 2, 2,—ビス—（2, 3 ジフルォロメチルフエ-ル）— 4, 4，， 5, 5 ,—テト ラキス一（3—メトキシフエ-ル）一イミダゾリル二量体、 2, 2，一ビス一（2, 4 ジフル オロフェ-ル）一4, 4，， 5, 5，一テトラキス一（3—メトキシフエ-ル）一イミダゾリル二 量体、 2, 2，一ビス一（2, 5 ジフルオロフェ-ル）一4, 4，， 5, 5，一テトラキス一（3 ーメトキシフエ-ル） イミダゾリル二量体、 2, 2，—ビス一（2, 6 ジフルオロフェ- ル） 4, 4，， 5, 5，ーテトラキスー（3—メトキシフエ-ル） イミダゾリル二量体、 2, 2， ビス一（2, 3, 4 トリフノレオ口フエ-ノレ） 4, 4，， 5, 5，ーテトラキスー（3—メトキシ フエ-ル）—イミダゾリル二量体、 2, 2，—ビス—（2, 3, 5 トリフルオロフェ-ル）—4 , 4' , 5, 5，一テトラキス一（3—メトキシフエ-ル）一イミダゾリル二量体、 2, 2，一ビス — (2, 3, 6—トリフノレオ口フエ-ノレ） 4, 4，， 5, 5，一テトラキス一（3—メトキシフエ- ル）—イミダゾリル二量体、 2, 2，—ビス— (2, 4, 5 卜リフルオロフェ -ル）—4, 4，， 5, 5，ーテトラキスー（3—メトキシフエ-ル） イミダゾリル二量体、 2, 2，一ビス一（2,[0042] As the photopolymerization initiator, a hexaarylbisimidazole derivative (hereinafter referred to as triarylimidazolyl dimer) is preferably used. Examples of the triarylimidazolyl dimer include, for example, 2- (0-chlorophenol) -4,5 diphenyl-imidazolyl dimer (hereinafter referred to as 2,2,1bis) , 4,, 5, 5, 1 tetraphenyl 1, 1, 1 bisimidazole), 2, 2 ', 5 Tris 1 (o-cross-mouthed) 1— (3, 4 dimethoxy (Phenol) 4, 5, 5, 1-diphenyl imidazolyl dimer, 2, 4 bis (o-cross-phase) —5— (3,4 Dimethoxyphenol) —Diphenol-Louimidazolyl dimer 2, 4, 5 Tris-(o black-mouthed) monodiphenyl imidazolidyl dimer, 2— (o black-mouthed phenol)-bis— 4, 5-(3, 4 dimethoxyphenol- ) -Imidazolyl dimer, 2, 2, -bis- (2-fluorophenol) 1,4,4,5,5, monotetrakis (3-methoxyphenol) monoimidazolyl dimer, 2, 2, —bis— (2, 3 di Ruoromechirufue - Le) - 4, 4 ,, 5, 5, - Tet Rakisu one (3 Metokishifue - Le) Single imidazolyl dimer, 2, 2, single-bis one (2, 4 difluoromethyl Oroferol) 1, 4, 4, 5, 5, 1, tetrakis mono (3-methoxyphenol) monoimidazolyl dimer, 2, 2, mono bis (2, 5 difluorophenol) 1, 4, 4 ,, 5, 5, 1-tetrakis (3-methoxyphenol) imidazolyl dimer, 2, 2, -bis- (2,6 difluorophenol) 4, 4 ,, 5, 5, 5-tetrakis (3-methoxyphenol) -I) azolyl dimer, 2, 2, bis- (2, 3, 4 trifnoreo oral phenol) 4, 4 ,, 5, 5, -tetrakis (3-methoxyphenol) -imidazolyl dimer, 2, 2, -bis- (2, 3, 5 trifluorophenol) -4, 4 ', 5, 5, monotetrakis mono (3-methoxyphenol) monoimidazolyl dimer, 2, 2, mono Bis — (2, 3, 6-Trifnoreo Mouth-Fu-Nole) 4, 4 ,, 5, 5, 1 Tetrakis mono (3-methoxyphenol) —imidazolyl dimer, 2, 2, —bis— (2, 4, 5 卜Fluorophenol) -4, 4, 4, 5, 5, -tetrakis (3-methoxyphenol) imidazolyl dimer, 2, 2, 1 bis (2,
4, 6—トリフルオロフェ -ル） 4, 4，， 5, 5，一テトラキス一（3—メトキシフエ-ル）一 イミダゾリル二量体、 2, 2，—ビス—（2, 3, 4, 5—テ卜ラフルオロフェ-ル）—4, 4，，4, 6-trifluorophenol) 4, 4, 5, 5, 5, monotetrakis (3-methoxyphenol) monoimidazolyl dimer, 2, 2, -bis- (2, 3, 4, 5 —Tetrafluorofeles) —4, 4,
5, 5，ーテトラキスー（3—メトキシフエ-ル） イミダゾリル二量体、 2, 2，一ビス一（2, 3, 4, 6—テトラフルオロフェ-ル）一4, 4' , 5, 5，一テトラキス一（3—メトキシフエ- ル）一イミダゾリル二量体、及び 2, 2，一ビス一（2, 3, 4, 5, 6 ペンタフルオロフェ -ル） 4, 4，， 5, 5，ーテトラキスー（3—メトキシフエ-ル） イミダゾリル二量体が挙 げられる。特に、 2— (。一クロ口フエ-ル） 4, 5 ジフエ-ルイミダゾリル二量体は解 像性や硬化膜の強度に対して高い効果を有する光重合開始剤であり、好ましく用い られる。 5,5, -Tetrakis (3-methoxyphenol) imidazolyl dimer, 2, 2, 1bis (2, 3, 4, 6-tetrafluorophenol) 1, 4, 4 ', 5, 5, 1 Tetrakis mono (3-methoxyphenol) monoimidazolyl dimer, and 2, 2, monobis (2, 3, 4, 5, 6 pentafluorophenol) 4, 4, 5, 5, 5, tetrakisto ( 3-Methoxyphenol) Imidazolyl dimer. In particular, 2-(. Single-mouthed phenol) 4,5 diphenyl-imidazolyl dimer is a photopolymerization initiator having a high effect on resolution and strength of a cured film, and is preferably used.
[0043] これらは単独でもよ 、し又は 2種類以上組み合わせて用いてもょ 、。  [0043] These may be used alone or in combination of two or more.
[0044] また、へキサァリールビスイミダゾール以外の光重合開始剤としては、例えば、キノ ン類、例えば、 2—ェチルアントラキノン、オタタエチルアントラキノン、 1, 2—べンズァ ントラキノン、 2, 3 ベンズアントラキノン、 2 フエ二ルアントラキノン、 2, 3 ジフエ 二ノレアントラキノン、 1 クロ口アントラキノン、 1, 4 ナフトキノン、 9, 10 フエナント ラキノン、 2—メチルー 1, 4 ナフトキノン、 2, 3 ジメチルアントラキノン、及び 3 ク ロロ一 2—メチルアントラキノン、 [0044] Photopolymerization initiators other than hexarylbisimidazole include, for example, quinones such as 2-ethyl anthraquinone, otaethyl anthraquinone, 1,2-benzanthraquinone, 2, 3 Benzanthraquinone, 2 Phenylanthraquinone, 2, 3 Diphenyl Ninoleanthraquinone, 1 Black mouth anthraquinone, 1, 4 Naphthoquinone, 9, 10 Phenylanthraquinone, 2-Methyl-1, 4 Naphthoquinone, 2, 3 Dimethylanthraquinone Rollo 2-methylanthraquinone,
芳香族ケトン類、例えば、ベンゾフエノン、ミヒラーズケトン [4, 4，一ビス（ジメチノレアミ ノ）ベンゾフエノン]、及び 4, 4，一ビス（ジェチルァミノ）ベンゾフエノン、ベンゾイン、 ベンゾインエーテル類、例えば、ベンゾインェチルエーテル、ベンゾインフエ-ルェ 一テル、メチルベンゾイン、及びェチルベンゾイン、 Aromatic ketones such as benzophenone, Michler's ketone [4,4,1bis (dimethinoreamino) benzophenone], and 4,4,1bis (jetylamino) benzophenone, benzoin, Benzoin ethers, such as benzoin ether, benzoin ether, methyl benzoin, and ethyl benzoin,
ベンジルジメチルケタール、ベンジルジェチルケタール、チォキサントン類とアルキル ァミノ安息香酸の組み合わせ、アタリジン類、並びにォキシムエステル類、例えば、 1 —フエ-ル一 1, 2—プロパンジオン一 2— O ベンゾインォキシム、及び 1—フエ-ル —1, 2—プロパンジオン— 2—（O エトキシカルボ-ル）ォキシムが挙げられる。 なお、上述のチォキサントン類とアルキルアミノ安息香酸の組み合わせとしては、例 えばェチルチオキサントンとジメチルァミノ安息香酸ェチルとの組み合わせ、 2—クロ ルチオキサントンとジメチルァミノ安息香酸ェチルとの組み合わせ、及びイソプロピル チォキサントンとジメチルァミノ安息香酸ェチルとの組み合わせがあげられる。  Benzyl dimethyl ketal, benzyl jetyl ketal, combinations of thixanthones and alkylaminobenzoic acids, atalidines, and oxime esters such as 1-phenol-1,2-propanedione-1-Obenzoinoxime, And 1-phenyl-1,2,2-propanedione-2- (O ethoxycarbol) oxime. Examples of the combination of the above thixanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and dimethylaminobenzoate, a combination of 2-chlorothioxanthone and dimethylaminobenzoate, and isopropyl thixanthone and dimethylaminobenzoate. Combination with acid ethyl is mentioned.
[0045] 中でも、（C)光重合開始剤として下記一般式 (I)で表されるアタリジンィ匕合物は好ま しく用いられる。  [0045] Among them, the (C) atharidine compound represented by the following general formula (I) is preferably used as the photopolymerization initiator.
[0046] [化 7]  [0046] [Chemical 7]
Figure imgf000017_0001
Figure imgf000017_0001
[0047] (式中、 Rは水素、炭素数 1〜6のアルキル基、ァリール基、ピリジル基、又は炭素数 1 〜6のアルコシキル基である。 ) (In the formula, R represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, a pyridyl group, or an alkoxy group having 1 to 6 carbon atoms.)
上記一般式 (I)の具体的な化合物としては、例えば、 9 フエ二ルァクリジン、 9一 ( 4'—トリル）アタリジン、 9— (4'—メトキシフエ-ル）アタリジン、 9— (4'—ヒドロキシフ ェ -ル）アタリジン、 9—ァセチルアミノアクリジン、ベンズ [a]フエナジン、 9—メチルベ ンズ [a]フエナジン、 2—スチリルキノリン、 9 ェチルアタリジン、 9 クロロェチルァク リジン、 9ーメトキシァクリジン、 9 エトキシアタリジン、 9一（4 メチルフエニル）アタリ ジン、 9— (4—ェチルフエ-ル）アタリジン、 9— (4— n—プロピルフエ-ル）アタリジン 、 9 （4 n—ブチルフエ-ル）アタリジン、 9—(4—tert ブチルフエ-ル）アタリジ ン、 9— (4—メトキシフエ-ル）アタリジン、 9— (4—エトキシフエ-ル）アタリジン、 9— ( 4—ァセチルフエ-ル）アタリジン、 9— (4—ジメチルァミノフエ-ル）アタリジン、 9— ( 4—クロ口フエ-ル）アタリジン、 9— (4—ブロモフエ-ル）アタリジン、 9— (3—メチル フエ-ル）アタリジン、 9— (3— tert—ブチルフエ-ル）アタリジン、 9— (3—ァセチル フエ-ル）アタリジン、 9— (3—ジメチルァミノフエ-ル）アタリジン、 9— (3—ジェチル ァミノフエ-ル）アタリジン、 9— (3—クロ口フエ-ル）アタリジン、 9— (3—ブロモフエ- ル）アタリジン、 9— (2 ピリジル）アタリジン、 9— (3 ピリジル）アタリジン、 9— (4— ピリジル)アタリジンが挙げられる。 Specific compounds of the above general formula (I) include, for example, 9 phenylacridine, 9- (4'-tolyl) atalysine, 9- (4'-methoxyphenol) atalysine, 9- (4'-hydroxy (Phenol) Atalidine, 9-Acetylaminoacridine, Benz [a] Phenazine, 9-Methylbenz [a] Phenazine, 2-Styrylquinoline, 9 Ethylatridine, 9 Chloroethylacridine, 9-Methoxyacrylidine, 9 Ethoxy 9- (4-Methylphenyl) atalysine, 9- (4-N-propylphenol) atalysine, 9 (4 n-butylphenol) atalysine, 9- ( 4-tert-Butylphenol) Atariji 9- (4-Methoxyphenyl) atalysine, 9- (4-Ethoxyphenyl) atalysine, 9— (4-acetylethyl) atalidine, 9— (4-Dimethylaminophenol) ataridin, 9 — (4—Black-mouthed) Atalidine, 9— (4-Bromophenyl) Atalidine, 9— (3-Methylphenol) Atridine, 9— (3— tert-Butylphenol) Atridine, 9— 9- (3-Diethylaminophenol) Atharidin, 9- (3-Demethylaminophenol) Atharidin, 9- (3-Cholesterol-Fail) Ataridin, 9 — (3-Bromophenyl) atalysine, 9— (2 Pyridyl) atalysine, 9— (3 Pyridyl) atalysine, 9— (4-Pyridyl) atalysine.
[0048] 更にアタリジンィ匕合物の 2量体も使用できる。例えば 1, 6 ビス（9—アタリジニル） へキサン、 1, 7 ビス（9—アタリジ-ル）ヘプタン、 1, 8 ビス（9—アタリジ-ル）オタ タン、 1, 9 ビス（9—アタリジ-ル）ノナン一 9 メチルアタリジンが挙げられる。  [0048] A dimer of an ataridin compound can also be used. For example, 1, 6 bis (9-atalidinyl) hexane, 1, 7 bis (9- atalyzyl) heptane, 1, 8 bis (9- atalyzyl) otatan, 1, 9 bis (9- attaridyl) ) Nonane 1 9 methylataridin.
[0049] 本発明にお 、て、 (c)光重合開始剤として、下記一般式 (III)で表されるピラゾリン 化合物を含有することは、本発明の好ましい実施形態である。ビラゾリンィ匕合物を含 有する場合の含有量は、感度および解像度が向上するという観点より、感光性榭脂 組成物全体に対して 0. 001質量％以上、感光性榭脂組成物の相溶性および現像 液に対する分散性の観点より、感光性榭脂組成物全体に対して 10質量％以下が好 ましい。より好ましくは、 0. 005〜5質量0 /0、更に好ましくは 0. 05〜2質量0 /0である。 [0049] In the present invention, it is a preferred embodiment of the present invention that (c) a pyrazoline compound represented by the following general formula (III) is contained as a photopolymerization initiator. In the case of containing a virazolin compound, the content is 0.001% by mass or more with respect to the entire photosensitive resin composition, from the viewpoint of improving sensitivity and resolution, and the compatibility of the photosensitive resin composition and From the viewpoint of dispersibility in the developer, it is preferably 10% by mass or less based on the entire photosensitive resin composition. More preferably, from 0.005 to 5 mass 0/0, more preferably 0.05 to 2 mass 0/0.
[0050] [化 8]  [0050] [Chemical 8]
Figure imgf000018_0001
Figure imgf000018_0001
(式中 B及び Cは、それぞれ独立に炭素数 3以上の直鎖または分枝鎖のアルキル基 、又は NR (Rは水素原子、またはアルキル基)であり、 Aは、ァリール基、複素環基、(In the formula, B and C are each independently a linear or branched alkyl group having 3 or more carbon atoms. Or NR (R is a hydrogen atom or an alkyl group), A is an aryl group, a heterocyclic group,
2 2
及び炭素数 3以上の直鎖または分枝鎖のアルキル基力 なる群力 選ばれる置換基 を表す。 aは 0又は 1であり、 b = c = lである。 ) And a group power of a linear or branched alkyl group having 3 or more carbon atoms. a is 0 or 1, and b = c = 1. )
式中 B及び Cは、それぞれ独立に炭素数 3以上 12以下の直鎖または分枝鎖のアル キル基が好ましい。 In the formula, each of B and C is preferably a linear or branched alkyl group having 3 to 12 carbon atoms.
上記一般式 (ΠΙ)で表されるビラゾリンィ匕合物としては、 1 フエ-ルー 3— (4-tert ーブチルースチリル）ー5—（4— tert—ブチルーフエ-ル） ピラゾリン、 1, 5 ビス 一（4—tert ブチルーフエ-ル） 3—（4—tert—ブチルースチリル） ピラゾリン、 1 フエ-ルー 3—（4—tert—ォクチルースチリル）ー5—（4—tert—ォクチルーフ ェ-ル）—ピラゾリン、 1, 5 ビス—（4—tert—ォクチルーフエ-ル）— 3— (4—tert ーォクチルースチリル） ピラゾリン、 1 フエ-ルー 3—（4ードデシルースチリル） 5— (4—ドデシルーフエ-ル）—ビラゾリン、 1— (4—ドデシルーフエ-ル）—3— (4 —ドデシルースチュル）—5— (4—ドデシルーフエ-ル）—ビラゾリン、 1— (4—tert ーォクチルーフエ-ル） 3—（4—tert—ブチルースチリル）ー5—（4—tert—ブチ ルーフエ-ル） ピラゾリン、 1一（4—tert—ブチルーフエ-ル）ー3—（4—tert—ォ クチルースチリル） 5—（4—tert—ォクチルーフエ-ル） ピラゾリン、 1一（4ードデ シルーフエ-ル） 3—（4—tert—ブチルースチリル） 5—（4—tert—ブチルーフ ェ -ル）—ピラゾリン、 1— (4—tert—ブチル—フエ-ル）—3— (4—ドデシルースチ リル） 5—（4ードデシルーフエ-ル） ピラゾリン、 1一（4ードデシルーフエ-ル） 3—（4—tert—ォクチルースチリル） 5—（4—tert—ォクチルーフエ-ル） ピラゾ リン、 1一（4—tert—ォクチルーフエ-ル） 3—（4ードデシルースチリル）ー5—（4 —ドデシル—フエ-ル）—ビラゾリン、 1— (2, 4 ジブチル—フエ-ル）—3— (4 ド デシルースチリル）—5— (4—ドデシルーフエ-ル）—ビラゾリン、 1—フエ-ルー 3— (3, 5—ジ—tert—ブチルースチリル）ー5—（3, 5—ジ tert—ブチルーフエ-ル） —ビラゾリン、 1—フエ-ル— 3— (2, 6 ジ— tert—ブチル—スチリル）— 5— (2, 6 —ジ— tert—ブチル—フエ-ル）—ピラゾリン、 1—フエ-ル— 3— (2, 5 ジ— tert —ブチル—スチリル）— 5— (2, 5 ジ— tert—ブチル—フエ二ル）—ピラゾリン、 1— フエ-ル— 3— (2, 6 ジ— n—ブチル—スチリル）— 5— (2, 6 ジ— n—ブチル— フエ二ル）一ピラゾリン、 1— (4— tert—ブチル一フエ-ル）一 3— (3, 5 ジ tert—ブチルーフエ-ル） ピラゾリン、 1ー（3, 5 ジ—tert ブチルーフエ-ル )ー3—（3, 5—ジ—tert—ブチルースチリル）ー5—（3, 5—ジ—tert—ブチルーフ ェニル） ピラゾリン、が挙げられる。 Virazolin compounds represented by the above general formula (ΠΙ) include 1-Fellow 3- (4-tert-Butylstyryl) -5- (4-tert-Butyl-phenol) pyrazoline, 1,5 bis 1- (4-tertbutylbutyl) 3- (4-tert-butylstyryl) pyrazoline, 1-loop 3- (4-tert-octylstyryl) -5- (4-tert-octyl roof) ) —Pyrazoline, 1,5 Bis— (4—tert-octyl roofyl) — 3— (4-tert-octylstyryl) Pyrazoline, 1 Fluoro 3— (4 dodecyl styryl) 5— (4 —Dodecyl roofing oil) —Virazoline, 1— (4—Dodecyl roofing oil) —3— (4 —Dodecyl roofing oil) —5— (4—Dodecyl roofing oil) —Virazoline, 1— (4—tert) ) 3- (4-tert-Butylstyryl) -5- (4-tert-Butyl roofing) Pyrazo Phosphorus, 1 1 (4-tert-butylphenol) -3— (4-tert-octylstyryl) 5— (4-tert-octyl roofyl) Pyrazoline, 1 1 (4-deoxysilane) 3— (4-tert-Butylstyryl) 5- (4-tert-Butylphenol) -pyrazoline, 1- (4-tert-butyl-phenol) -3-3 (4-Dodecylstyryl) 5- (4 Pyrazoline, 1 (4) decyl roofing oil 3— (4—tert-octylstyryl) 5— (4—tert—octyl roofing) Pyrazoline, 1 1 (4—tert—octylofol) ) 3— (4 dodecyl styryl) -5— (4 —dodecyl thiol) —virazoline, 1— (2, 4 dibutyl phthal) —3— (4 dodecyl styryl) —5— (4 —Dodecyl roofing oil) —Virazoline, 1—Fuel-Lo 3— (3, 5-Di-tert-butylstyryl) -5 — (3,5-Di-tert-butyl-phenol) —Virazolin, 1-phenol— 3— (2, 6 Di-tert-butyl-styryl) — 5— (2, 6 —Di-tert-butyl— (Phenol) -Pyrazoline, 1-Phenol— 3— (2, 5 Di- tert —Butyl-styryl) — 5— (2, 5 Di- tert-Butyl-phenyl) —Pyrazoline, 1 — Hue -Ru 3— (2, 6 di- n-butyl-styryl) — 5— (2, 6 di- n-butyl— Phenyl) 1-Pyrazoline, 1— (4-tert-Butyl 1-Fel) 1 3-— (3, 5 Di-tert-Butyl-Fuel) Pyrazoline, 1- (3, 5 Di-tert-Butyl-Fe) 3- (3,5-Di-tert-butylstyryl) -5- (3,5-di-tert-butylphenyl) pyrazoline.
[0053] (d)亜リン酸エステル化合物  [0053] (d) Phosphite compound
本発明の感光性榭脂組成物に含まれる (d)亜リン酸エステルイ匕合物の量は、感光 性榭脂組成物全体に対して 0. 01〜5質量％の範囲であり、好ましくは 0. 1〜3質量 %の範囲である。 0. 01質量％以上で感光性組成物の色相安定性が良好で、 5質量 %以下で硬化性が良好である。亜リン酸エステルイ匕合物としては、例えば、 2, 4, 8, 10—テトラー tert—ブチルー 6— [3— (3—メチルー 4ーヒドロキシ—5—tert—ブチ ルフエ-ル）プロポキシ]ジベンゾ [d、 f] [l, 3, 2]ジォキサホスフェンピン、 2, 2—メ チレンビス（4, 6 ジ tert ブチルフエ-ル）ォクチルホスファイト、ビス（2, 4 ジ tert ブチルフエ-ル）ペンタエリスリトールージホスファイト、トリス（2, 4 ジ—ter t ブチルフエ-ル）ホスファイト、 4, 4，ーブチリデンビス（3—メチルー 6— t ブチル フエ-ル―ジ—トリデシルホスフアイト、 4、 4，イソプロピリデン—ジ—フエノールアルキ ルホスフアイト、トリスイソデシルホスフアイト、が挙げられる。 4、 4，—イソプロピリデン ージ—フエノールアルキルホスファイトにおいて、アルキル基の好ましい炭素数は、 1 2〜15である。  The amount of the (d) phosphite ester compound contained in the photosensitive resin composition of the present invention is in the range of 0.01 to 5% by mass with respect to the entire photosensitive resin composition, preferably 0.1 The range is from 1 to 3% by mass. The hue stability of the photosensitive composition is good at 0.01% by mass or more, and the curability is good at 5% by mass or less. Examples of phosphite compounds include 2, 4, 8, 10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d F] [l, 3, 2] dioxaphosfenpine, 2,2-methylenebis (4,6 di tert butylphenol) octyl phosphite, bis (2,4 ditert butylphenol) penta Erythritol diphosphite, tris (2,4 di-ter t-butylphenol) phosphite, 4, 4, -butylidenebis (3-methyl-6-tbutylphenol di-tridecylphosphite, 4, 4, Isopropylidene-di-phenol alkyl phosphite, tris-isodecyl phosphite 4. In 4, propyl propylene di-phenol alkyl phosphite, the alkyl group preferably has 12 to 15 carbon atoms. That.
[0054] (e)塩基性染料  [0054] (e) Basic dye
本発明の感光性榭脂組成物に含まれる (e)塩基性染料の量は、感光性榭脂組成物 全体に対して、 0. 001〜0. 3質量％の範囲であり、好ましくは 0. 01〜0. 12質量％ の範囲である。充分な着色性が認識できる点力も 0. 001質量％以上、色相安定性 維持の観点から 0. 3質量％以下が好ましい。  The amount of the basic dye (e) contained in the photosensitive resin composition of the present invention is in the range of 0.001 to 0.3% by mass, preferably 0, based on the total photosensitive resin composition. The range is 01 to 0.112% by mass. The point power at which sufficient colorability can be recognized is preferably 0.001% by mass or more and 0.3% by mass or less from the viewpoint of maintaining hue stability.
[0055] (e)塩基性染料としては、例えば、べィシックグリーン 1 [633— 03— 4] (例えば Aiz en (登録商標） Diamond Green GH 、商品名、保土谷ィ匕学工業製)、マラカイ トグリーンしゅう酸塩 [2437— 29— 8] (例えば Aizen (登録商標） Malachite Gre en、商品名、保土谷ィ匕学工業製）、ブリリアントグリーン [633— 03— 4]、フクシン [6 32— 99— 5]、メチルバイオレット [603—47—4]、メチルバイオレット 2B[8004— 8 7- 3] ,クリスタルバイオレット [548— 62— 9]、メチルグリーン [82— 94— 0]、ビクト リアブルー B[2580— 56— 5]、べィシックブルー 7[2390— 60— 5] (例えば Aizen Victoria Pure Blue BOH、商品名、保土谷化学工業製）、ローダミン B [81— 88— 9]、ローダミン 6G[989— 38— 8]、べィシックイェロー 2[2465— 27— 2]力挙 げられ、中でもべィシックグリーン 1、マラカイトグリーンしゅう酸塩、べィシックブルー 7 が好ましい。 [0055] (e) As the basic dye, for example, Basic Green 1 [633-03-03] (for example, Aiz en (registered trademark) Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Malachite green oxalate [2437—29—8] (for example, Aizen (registered trademark) Malachite Green, trade name, manufactured by Hodogaya Igaku Kogyo), Brilliant Green [633—03—4], Fuchsin [6 32 — 99—5], Methyl violet [603—47—4], Methyl violet 2B [8004— 8 7-3], Crystal Violet [548—62—9], Methyl Green [82—94—0], Victoria Blue B [2580—56—5], Basic Blue 7 [2390—60—5] ( For example, Aizen Victoria Pure Blue BOH (trade name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81—88—9], Rhodamine 6G [989—38—8], Basic Yellow 2 [2465—27—2] Among them, basic green 1, malachite green oxalate, and basic blue 7 are preferable.
[0056] 本発明の感光性榭脂組成物には、上記以外にも種々の化合物を添加することがで きる。  In addition to the above, various compounds can be added to the photosensitive resin composition of the present invention.
[0057] (c)光重合開始剤として前述のアタリジンィ匕合物を用いる場合には、感度の観点か ら (f)有機ハロゲンィ匕合物を併用することが好ま 、。 (f)有機ハロゲンィ匕合物として は、例えば、トリブロモメチルフエ-ルスルホン、 2—トリブロモメチルスルホ -ルピリジ ン、または下記一般式 (VI)で示される s トリアジンィ匕合物が挙げられる。  [0057] (c) In the case of using the above-mentioned ataridine compound as a photopolymerization initiator, it is preferable to use (f) an organic halogen compound in combination from the viewpoint of sensitivity. Examples of the organic halogen compound (f) include tribromomethyl phenol sulfone, 2-tribromomethyl sulfopyridine, or s-triazine compound represented by the following general formula (VI).
[化 9]  [Chemical 9]
Figure imgf000021_0001
Figure imgf000021_0001
[0058] (式中、 R、 Rおよび Rは置換基を示し、その少なくとも 1つはトリハロメチル基で [In the formula, R, R and R each represent a substituent, and at least one of them is a trihalomethyl group.
1 2 3  one two Three
あり、トリハロメチル基でない場合は、炭素数 1〜6のアルキル基、炭素数 1〜6のアル コキシ基、ァリール基、又は複素環基である。 R、 Rおよび Rは同一でも相違しても  If it is not a trihalomethyl group, it is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, or a heterocyclic group. R, R and R may be the same or different
1 2 3  one two Three
良い。）  good. )
下記一般式 (VI)の具体例としては、 2, 4, 6 トリス（トリクロロメチル）—s トリァジン 、 2 フエ-ル一 4, 6 ビス（トリクロロメチル） s トリァジン、 2— (4—メトキシフエ- ル） 4, 6 ビス（トリクロロメチル） s トリァジン、 2— (4—メトキシナフチル） 4, 6 ビス（トリクロロメチノレ）一 s トリァジン [69432— 40— 2] ( [ ]内は CAS No. ) 、 2- (2Η- 1, 3 ベンゾジォキソールー 5—ィル） 4, 6 ビス（トリクロロメチル） s トリアジン [71255— 78— 2]、 2— (3, 4 ジメトキシフエ-ル）— 4, 6 ビス（トリ クロロメチル） s トリァジン、 2— (4—メトキシスチリル） 4, 6 ビス（トリクロロメチ ル） s トリァジン、 2— (2—メトキシスチリル） 4, 6 ビス（トリクロロメチル） s ト リアジン、 2- (3, 4 ジメトキシスチリル）一 4, 6 ビス（トリクロロメチル） s トリアジ ン、 2— (2, 4 ジメトキシスチリル） 4, 6 ビス（トリクロロメチル） s トリァジン、 2 - (4 ペントキシスチリル） 4, 6 ビス（トリクロロメチル） s トリァジン、 2— (2- フリルェチリデン） 4, 6 ビス（トリクロロメチル） s トリァジン、 2— [2— (5—メチ ルフリル）ェチリデン]—4, 6—ビス（トリクロロメチル） s トリァジンが挙げられる。 (f)有機ハロゲンィ匕合物の量は、感光性榭脂組成物に対して 0. 01〜3質量％が好 ましい。 0. 01質量％以上で露光部と、未露光部の良好なコントラストを発現し、 3質 量％以下で色相安定性が良好である。 Specific examples of the following general formula (VI) include 2,4,6 tris (trichloromethyl) -s triazine, 2-phenyl-1,4-bis (trichloromethyl) s triazine, 2- (4-methoxyphenol) ) 4, 6 bis (trichloromethyl) s triazine, 2— (4-methoxynaphthyl) 4, 6 bis (trichloromethinole) mono s triazine [69432— 40— 2] (in parentheses are CAS No.), 2 -(2Η- 1, 3 Benzodioxol-5-yl) 4, 6 Bis (trichloromethyl) s Triazine [71255— 78— 2], 2— (3,4 Dimethoxyphenyl) — 4, 6 bis (trichloromethyl) s Triazine, 2— (4-methoxystyryl) 4, 6 bis (trichloromethyl) ) S triazine, 2— (2-methoxystyryl) 4,6 bis (trichloromethyl) s triazine, 2- (3,4 dimethoxystyryl) -1,4,6 bis (trichloromethyl) s triazine, 2— (2 , 4 Dimethoxystyryl) 4, 6 bis (trichloromethyl) s triazine, 2-(4 pentoxystyryl) 4, 6 bis (trichloromethyl) s triazine, 2— (2-furylethylidene) 4, 6 bis (trichloromethyl) s triazine, 2- [2- (5-methylfuryl) ethylidene] -4,6-bis (trichloromethyl) s triazine. (f) The amount of the organic halogen compound is preferably 0.01 to 3% by mass with respect to the photosensitive resin composition. When the content is 0.01% by mass or more, a good contrast is exhibited between the exposed portion and the unexposed portion, and when the content is 3% by mass or less, the hue stability is good.
[0059] また、下記一般式 (Π)で表される N—ァリールアミノ酸を含有することは、本発明の 好ましい実施形態である。  [0059] It is a preferred embodiment of the present invention to contain an N-aryl amino acid represented by the following general formula (式).
[0060] R -NHCH COOH (II)  [0060] R -NHCH COOH (II)
1 2  1 2
(式中、 Rはァリール基である。 )  (In the formula, R is an aryl group.)
N—ァリールアミノ酸の含有量は、感光性榭脂組成物全体に対して 0. 001〜1. 0質 量％が好ましぐより好ましくは 0. 01〜0. 5質量％、更に好ましくは 0. 04〜0. 3質 量％である。感度の観点力 0. 001質量％以上、色相の安定性の観点から 1. 0質 量％以下が好ましい。  The content of N-aryl amino acid is preferably 0.001 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, and still more preferably relative to the entire photosensitive resin composition. 0.04 to 0.3 mass%. The viewpoint power of sensitivity is preferably 0.001% by mass or more and 1.0% by mass or less from the viewpoint of hue stability.
[0061] N—ァリールアミノ酸の具体例としては、 N—フエニルグリシン、 N— (p クロ口フエ -ル）グリシン、 N— (p ブロモフエ-ル）グリシン、 N— (p シァノフエ-ル）グリシン 、 N— (p—メチルフエ-ル）グリシン、 N ブチル N—フエ-ルグリシン、 N ェチル —N フエ-ルグリシン、 N プロピル一 N フエ-ルグリシン、 N—メチル N フエ -ルグリシン、 N— (p ブロモフエ-ル） N—メチルグリシン、 N— (p クロ口フエ二 ル） N ェチルグリシンが挙げられる。  [0061] Specific examples of N-aryl amino acids include N-phenylglycine, N- (p black-mouthed phenyl) glycine, N- (p bromophenol) glycine, N- (p cyanophyl). Glycine, N— (p-methylphenol) glycine, N-butyl N-phenolglycine, N-ethyl —N-phenylglycine, N-propyl-N-phenylglycine, N-methyl-N-phenylglycine, N— (p-bromophenol -N) N-methylglycine, N- (p-phenyl) N ethylglycine.
[0062] 本発明の感光性榭脂組成物には、感光の有無を目視で判断できるようにするため 、ロイコ染料を含有することができる。ロイコ染料としては、例えばロイコクリスタルバイ ォレット、ロイコマラカイトグリーンがあげられる。十分な着色性 (発色性）が認識できる 点から、感光性榭脂組成物全体に対して、 0. 01質量％以上、色相安定性の観点、 良好な画像特性が得られる点から 5質量％以下が好ましい。 [0062] The photosensitive resin composition of the present invention may contain a leuco dye so that the presence or absence of photosensitivity can be visually determined. Examples of leuco dyes include leuco crystal violet and leucomalachite green. Sufficient coloring (color development) can be recognized From the viewpoint, the content is preferably 0.01% by mass or more and 5% by mass or less from the viewpoint of hue stability and good image characteristics with respect to the entire photosensitive resin composition.
[0063] さらに、本発明の感光性榭脂組成物の熱安定性、色相安定性を向上させるために 、感光性榭脂組成物にカルボキシベンゾトリァゾールイ匕合物を含有させることは好ま しいことである。 [0063] Further, in order to improve the thermal stability and hue stability of the photosensitive resin composition of the present invention, it is preferable that the photosensitive resin composition contains a carboxybenzotriazole compound. That is.
[0064] カルボキシベンゾトリアゾール化合物としては、例えば、 4 カルボキシ 1, 2, 3— ベンゾトリァゾール、 5 カルボキシ 1, 2, 3 べンゾトリァゾール、 N—(N, N ジ 2—ェチルへキシル）アミノメチレンカルボキシベンゾトリァゾール、 N— (N, N ジ —2—ヒドロキシェチル）アミノメチレンカルボキシベンゾトリァゾール、及び N— (N, N ジ一 2—ェチルへキシル）アミノエチレンカルボキシベンゾトリアゾールが挙げら れる。  [0064] Examples of the carboxybenzotriazole compound include 4 carboxy 1, 2, 3-benzotriazole, 5 carboxy 1, 2, 3 benzotriazole, N- (N, N di2-ethylhexyl) aminomethylenecarboxy. Examples include benzotriazole, N— (N, N di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N— (N, N di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.
[0065] さらに、本発明の感光性榭脂組成物の熱安定性、色相安定性を向上させるために 、感光性榭脂組成物にべンゾトリアゾール類及び Zまたはラジカル重合禁止剤を含 有させることは、好ましいことである。このようなラジカル重合禁止剤としては、例えば 、 ρ—メトキシフエノール、ハイドロキノン、ピロガロール、ナフチルァミン、 tert—ブチ ルカテコール、塩化第一銅、 2, 6 ジ tert—ブチルー p クレゾール、 2, 2，ーメ チレンビス（4—メチル一6— tert—ブチルフエノール）、 2, 2， 一メチレンビス（4 ェ チル— 6— tert—ブチルフエノール）、ニトロソフエ-ルヒドロキシァミンアルミニウム塩 、及びジフヱ-ルニトロソァミンが挙げられる。  [0065] Further, in order to improve the thermal stability and hue stability of the photosensitive resin composition of the present invention, the photosensitive resin composition contains benzotriazoles and Z or a radical polymerization inhibitor. It is preferable to make it. Examples of such radical polymerization inhibitors include ρ-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-ditert-butyl-p-cresol, 2,2, -me. Examples include tylene bis (4-methyl-6-tert-butylphenol), 2,2, monomethylene bis (4-ethyl-6-tert-butylphenol), nitrosohydroxyhydroxyamine aluminum salt, and diphenylnitrosamine.
[0066] ベンゾトリアゾール類としては、例えば、 1, 2, 3 ベンゾトリァゾール、 1—クロ口一 1 , 2, 3 ベンゾトリアゾール、ビス（N— 2 ェチルへキシル）アミノメチレン一 1, 2, 3 —ベンゾトリアゾール、ビス（N— 2 ェチルへキシル）アミノメチレン一 1, 2, 3 トリ ルトリアゾール、及びビス（N— 2 ヒドロキシェチル）アミノメチレン一 1, 2, 3 ベンゾ トリァゾールが挙げられる。  [0066] Examples of the benzotriazoles include 1, 2, 3 benzotriazole, 1-, 2, 3 benzotriazole, bis (N-2-ethylhexyl) aminomethylene 1, 2, 3 —Benzotriazole, bis (N—2ethylhexyl) aminomethylene-1,2,3 tolyltriazole, and bis (N—2hydroxyethyl) aminomethylene-1,2,3 benzotriazole.
[0067] また、ラジカル重合禁止剤、ベンゾトリアゾール化合物、及びカルボキシベンゾトリア ゾール化合物を含有する場合の添加量は、それぞれ、感光性榭脂化合物に対して、 好ましくは 0. 01〜3質量％であり、より好ましくは 0. 05〜1質量％である。この量は、 感光性榭脂組成物に色相安定性を付与するという観点力 0. 01質量％以上が好ま しぐまた、感度を維持するという観点力も 3質量％以下がより好ましい。 [0067] The amount of addition in the case of containing a radical polymerization inhibitor, a benzotriazole compound, and a carboxybenzotriazole compound is preferably 0.01 to 3% by mass with respect to the photosensitive resin compound. More preferably, it is 0.05 to 1% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of imparting hue stability to the photosensitive resin composition. In addition, the viewpoint power for maintaining sensitivity is more preferably 3% by mass or less.
[0068] 本発明の感光性榭脂組成物には、必要に応じて、可塑剤を含有させても良 ヽ。こ のような可塑剤としては、例えば、ポリエチレングリコール、ポリプロピレングリコール、 グリコールエステル類、例えば、ポリオキシプロピレンポリオキシエチレンエーテル、ポ リオキシエチレンモノメチルエーテル、ポリオキシプロピレンモノメチルエーテル、ポリ ォキシエチレンポリオキシプロピレンモノメチルエーテル、ポリオキシエチレンモノエ チルエーテル、ポリオキシプロピレンモノェチルエーテル、ポリオキシエチレンポリオ キシプロピレンモノェチルエーテル、フタル酸エステル類、例えば、ジェチルフタレー ト、 o—トルエンスルフォン酸アミド、 p—トルエンスルフォン酸アミド、クェン酸トリブチ ル、タエン酸トリエチル、ァセチルクェン酸トリエチル、ァセチルクェン酸トリー n—プロ ピル、ァセチルクェン酸トリ— n—ブチルが挙げられる。  [0068] The photosensitive resin composition of the present invention may contain a plasticizer, if necessary. Examples of such plasticizers include polyethylene glycol, polypropylene glycol, glycol esters such as polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, and polyoxyethylene polyoxy Propylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalates such as jetyl phthalate, o-toluenesulfonic acid amide, p-toluene Sulfonic acid amide, Tributyl citrate, Triethyl taenoate, Triethyl acetyl citrate, Triacetyl acetyl sulfonate n-propyl, acetyl que Acid tri - n-butyl.
[0069] 可塑剤を添加する場合の添加量としては、感光性榭脂組成物中に、 5〜50質量％ 含むことが好ましぐより好ましくは、 5〜30質量％である。現像時間の遅延を抑えた り、硬化膜に柔軟性を付与するという観点力 5質量％以上が好ましぐまた、硬化不 足やコールドフローを抑えるという観点から 50質量％以下が好ましい。  [0069] When the plasticizer is added, the addition amount is preferably 5 to 50% by mass, more preferably 5 to 30% by mass in the photosensitive resin composition. The viewpoint power of 5% by mass or more is preferred because it suppresses the delay in development time and imparts flexibility to the cured film, and 50% by mass or less is preferred from the viewpoint of suppressing insufficient curing and cold flow.
[0070] <感光性榭脂組成物調合液 >  [0070] <Photosensitive resin composition formulation>
本発明の感光性榭脂組成物は、溶媒を添加した感光性榭脂組成物調合液としても よい。好適な溶媒としては、メチルェチルケトン (MEK)に代表されるケトン類、並び にアルコール類、例えば、メタノール、エタノール、及びイソプロピルアルコールが挙 げられる。感光性榭脂組成物調合液の粘度が 25°Cで 500〜4000mPa · secとなるよ うに、溶媒を感光性榭脂組成物に添加することが好まし ヽ。  The photosensitive resin composition of the present invention may be a photosensitive resin composition preparation solution to which a solvent is added. Suitable solvents include ketones typified by methyl ethyl ketone (MEK), as well as alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition such that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.
[0071] <感光性榭脂積層体 >  [0071] <Photosensitive resin laminate>
本発明の感光性榭脂積層体は、感光性榭脂層とその層を支持する支持体力 なる 力 必要により、感光性榭脂層の支持体と反対側の表面に保護層を有していても良 い。  The photosensitive resin layered product of the present invention has a protective layer on the surface of the photosensitive resin layer opposite to the support of the photosensitive resin layer, if necessary, as a supporting force to support the photosensitive resin layer and the layer. Also good.
[0072] ここで用いられる支持体としては、露光光源から放射される光を透過する透明なも のが望ましい。このような支持体としては、例えば、ポリエチレンテレフタレートフィル ム、ポリビュルアルコールフィルム、ポリ塩化ビュルフィルム、塩化ビュル共重合体フ イルム、ポリ塩化ビ-リデンフィルム、塩化ビ-リデン共重合フィルム、ポリメタクリル酸 メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン 共重合体フィルム、ポリアミドフィルム、及びセルロース誘導体フィルムが挙げられる。 これらのフィルムは、必要に応じ延伸されたものも使用可能である。ヘーズは 5以下 のものが好ましい。フィルムの厚みは、薄い方が画像形成性及び経済性の面で有利 であるが、強度を維持する必要から、 10〜30 /ζ πιのものが好ましく用いられる。 [0072] The support used here is preferably transparent so as to transmit light emitted from the exposure light source. Examples of such a support include, for example, polyethylene terephthalate film, polybulualcohol film, polychlorinated bull film, and bull chloride copolymer film. Examples thereof include films, polyvinylidene chloride films, vinylidene chloride copolymer films, polymethyl methacrylate copolymer films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films can be stretched if necessary. The haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 / ζ πι is preferably used because the strength needs to be maintained.
[0073] また、感光性榭脂積層体に用いられる保護層の重要な特性は、感光性榭脂層との 密着力につ 、て、支持体よりも保護層の方が充分小さく容易に剥離できることである 。例えば、ポリエチレンフィルム、及びポリプロピレンフィルムが保護層として好ましく 使用できる。また、特開昭 59— 202457号公報に示された剥離性の優れたフィルム を用いることができる。保護層の膜厚は 10〜： L 00 mが好ましぐ 10〜50 m力 り 好ましい。 [0073] Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and easily peeled in terms of adhesion to the photosensitive resin layer. It is possible. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is 10 to: L 00 m is preferred, and a force of 10 to 50 m is preferred.
[0074] 本発明の感光性榭脂積層体における感光性榭脂層の厚みは、好ましくは、 5〜10 O ^ m,より好ましくは、 7〜60 /ζ πιである。厚みが薄いほど解像度は向上し、また、 厚いほど膜強度が向上するので、用途に応じて適宜選択することができる。  [0074] The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 5 to 10 O ^ m, more preferably 7 to 60 / ζ πι. As the thickness is thinner, the resolution is improved, and as the thickness is thicker, the film strength is improved.
支持体、感光性榭脂層、及び必要により、保護層を順次積層して、本発明の感光性 榭脂積層体を作成する方法は、従来知られて ヽる方法を採用することができる。  A conventionally known method can be adopted as a method of laminating a support, a photosensitive resin layer, and if necessary, a protective layer in order to produce the photosensitive resin laminate of the present invention.
[0075] 例えば、感光性榭脂層に用いる感光性榭脂組成物を、前述の感光性榭脂組成物 調合液にしておき、まず支持体上にバーコ一ターやロールコーターを用いて塗布し て乾燥させ、支持体上に該感光性榭脂組成物からなる感光性榭脂層を積層する。  [0075] For example, the photosensitive resin composition used for the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation liquid, and first coated on the support using a bar coater or a roll coater. And drying, and a photosensitive resin layer made of the photosensitive resin composition is laminated on the support.
[0076] 次いで、必要により、該感光性榭脂層上に保護層を積層することにより感光性榭脂 積層体を作成することができる。  [0076] Next, if necessary, a photosensitive resin laminate can be prepared by laminating a protective layer on the photosensitive resin layer.
[0077] <レジストパターン形成方法 >  <Resist pattern formation method>
本発明の感光性榭脂積層体を用いたレジストパターンは、ラミネート工程、露光ェ 程、及び現像工程を含む工程によって形成することができる。具体的な方法の一例 を示す。  A resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a laminating process, an exposure process, and a developing process. An example of a specific method is shown.
[0078] まず、ラミネーターを用いてラミネート工程を行う。感光性榭脂積層体が保護層を有 する場合には保護層を剥離した後、ラミネーターで感光性榭脂層を基板表面に加熱 圧着しラミネートする。この場合、感光性榭脂層は基板表面の片面だけにラミネートし ても良いし、必要に応じて両面にラミネートしても良い。この時の加熱温度は一般的 に 40〜160°Cである。また、該加熱圧着を二回以上行うことにより、得られるレジスト パターンの基板に対する密着性が向上する。この時、圧着は二連のロールを備えた 二段式ラミネーターを使用しても良 、し、何回力繰り返してロールに通し圧着しても良 い。 First, a laminating process is performed using a laminator. When the photosensitive resin laminate has a protective layer, after peeling the protective layer, the photosensitive resin layer is heated on the substrate surface with a laminator. Crimp and laminate. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the obtained resist pattern improves by performing this thermocompression bonding twice or more. At this time, a two-stage laminator equipped with two rolls may be used for crimping, or it may be repeatedly crimped through the roll several times.
[0079] 次に、露光機を用いて露光工程を行う。必要ならば支持体を剥離しフォトマスクを 通して活性光により露光する。露光量は、光源照度及び露光時間より決定される。光 量計を用いて測定しても良 、。  Next, an exposure process is performed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time. It can be measured using a photometer.
[0080] 露光工程にお!、ては、マスクレス露光方法を用いてもょ 、。マスクレス露光はフォト マスクを使用せず基板上に直接描画装置によって露光する。光源としては波長 350 〜410nmの半導体レーザーや超高圧水銀灯が用いられる。描画パターンはコンビ ユーターによって制御され、この場合の露光量は、露光光源の照度および基板の移 動速度によって決定される。  [0080] In the exposure process, use a maskless exposure method. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm and an ultrahigh pressure mercury lamp are used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.
[0081] 次に、現像装置を用いて現像工程を行う。露光後、感光性榭脂層上に支持体があ る場合にはこれを除く。続いてアルカリ水溶液カゝらなる現像液を用いて未露光部を現 像除去し、レジストパターンを得る。アルカリ水溶液としては、 Na CO、または K CO  Next, a developing process is performed using a developing device. Exclude any support on the photosensitive resin layer after exposure. Subsequently, the unexposed area is removed by using a developer such as an alkaline aqueous solution to obtain a resist pattern. Na CO or K CO as alkaline aqueous solution
2 3 2 の水溶液が好ましい。これらは感光性榭脂層の特性に合わせて選択される力 0. 2 An aqueous solution of 2 3 2 is preferred. These are selected forces according to the characteristics of the photosensitive resin layer 0.2
3 Three
〜2質量％の濃度の Na CO水溶液が一般的である。該アルカリ水溶液中には、表  An aqueous solution of Na 2 CO with a concentration of ˜2% by weight is common. In the alkaline aqueous solution,
2 3  twenty three
面活性剤、消泡剤、現像を促進させるための少量の有機溶剤を混入させてもよい。 なお、現像工程における該現像液の温度は、 20〜40°Cの範囲で一定温度に保つこ とが好ましい。  A surfactant, an antifoaming agent, and a small amount of an organic solvent for promoting development may be mixed. The temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 20 to 40 ° C.
[0082] 上述の工程によってレジストパターンが得られる力 場合によっては、さらに 100〜 300°Cの加熱工程を行うこともできる。この加熱工程を実施することにより、更なる耐 薬品性向上が可能となる。加熱には、熱風、赤外線、または遠赤外線の各方式の加 熱炉を用いることができる。  [0082] The force at which a resist pattern can be obtained by the above-described steps. Depending on the case, a heating step of 100 to 300 ° C can be further performed. By carrying out this heating step, it is possible to further improve chemical resistance. For heating, hot air, infrared, or far-infrared heating furnaces can be used.
[0083] <プリント配線板の製造方法 >  [0083] <Method for Manufacturing Printed Wiring Board>
本発明のプリント配線板の製造方法は、基板として銅張積層板またはフレキシブル 基板に上述のレジストパターン形成方法によってレジストパターンを形成した後に、 以下の工程を経ることで行われる。 The method for producing a printed wiring board of the present invention includes a copper-clad laminate or a flexible board as a substrate. After the resist pattern is formed on the substrate by the above-described resist pattern forming method, the following steps are performed.
[0084] まず、現像により露出した基板の銅面に既知の方法、例えば、エッチング法、また はめつき法をもちいて導体パターンを形成する工程を行う。  First, a step of forming a conductor pattern using a known method such as an etching method or a fitting method is performed on the copper surface of the substrate exposed by development.
その後、レジストパターンを、現像液よりも強いアルカリ性を有する水溶液により基板 力 剥離する剥離工程を行って所望のプリント配線板を得る。剥離用のアルカリ水溶 液 (以下、「剥離液」ともいう。）についても特に制限はないが、 2〜5質量％の濃度の NaOH、または KOHの水溶液が一般的に用いられる。剥離液にも、少量の水溶性 溶媒を加える事は可能である。なお、剥離工程における該剥離液の温度は、 40〜7 0°Cの範囲であることが好まし！/、。  Then, a desired printed wiring board is obtained by performing a peeling process in which the resist pattern is peeled off with an aqueous solution having alkalinity stronger than that of the developer. The alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. It is possible to add a small amount of water-soluble solvent to the stripping solution. The temperature of the stripping solution in the stripping process is preferably in the range of 40 to 70 ° C! /.
[0085] <リードフレームの製造方法 > [0085] <Lead Frame Manufacturing Method>
本発明のリードフレームの製造方法は、基板として銅、銅合金、または鉄系合金の 金属板に前述のレジストパターン形成方法によってレジストパターンを形成した後に 、以下の工程を経ることで行われる。  The lead frame manufacturing method of the present invention is performed by performing the following steps after forming a resist pattern on a metal plate of copper, copper alloy, or iron-based alloy as a substrate by the above-described resist pattern forming method.
まず、現像により露出した基板をエッチングして導体パターンを形成する工程を行う。 その後、レジストパターンを上述のプリント配線板の製造方法と同様の方法で剥離す る剥離工程を行って、所望のリードフレームを得る。  First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Thereafter, a desired lead frame is obtained by performing a peeling process in which the resist pattern is peeled by the same method as the above-described printed wiring board manufacturing method.
[0086] <半導体パッケージの製造方法 > [0086] <Method for Manufacturing Semiconductor Package>
本発明の半導体パッケージの製造方法は、基板として LSIとしての回路形成が終 了したウェハに前述のレジストパターン形成方法によってレジストパターンを形成した 後に、以下の工程を経ることで行われる。  The method for manufacturing a semiconductor package of the present invention is performed by forming a resist pattern by the above-described resist pattern forming method on a wafer on which a circuit as an LSI has been formed as a substrate, and then performing the following steps.
まず、現像により露出した開口部に銅やはんだによる柱状のめっきを施して、導体パ ターンを形成する工程を行う。その後、レジストパターンを上述のプリント配線板の製 造方法と同様の方法で剥離する剥離工程を行って、更に、柱状めつき以外の部分の 薄い金属層をエッチングにより除去する工程を行うことにより、所望の半導体パッケ一 ジを得る。  First, a step of forming a conductor pattern by performing columnar plating with copper or solder on the opening exposed by development is performed. Thereafter, by performing a peeling step of peeling the resist pattern by the same method as the method for manufacturing a printed wiring board described above, and further performing a step of removing a thin metal layer other than the columnar tack by etching, Obtain the desired semiconductor package.
[0087] <凹凸パターンを有する基材の製造方法 >  [0087] <Method for Producing Substrate Having Concave and Convex Pattern>
前述のレジストパターン形成方法によってレジストパターンをサンドブラスト工法によ り基板に加工を施す時の保護マスク部材として使用することができる。 The resist pattern is formed by the sandblasting method using the resist pattern forming method described above. It can be used as a protective mask member when processing the substrate.
基板としては、例えば、ガラス、シリコンウェハー、アモルファスシリコン、多結晶シリコ ン、セラミック、サファイア、金属材料が挙げられる。これら基板上に、前述のレジスト パターン形成方法と同様の方法によって、レジストパターンを形成する。その後、形 成されたレジストパターン上力 ブラスト材を吹き付け目的の深さに切削するサンドブ ラスト処理工程、基板上に残存したレジストパターン部分を剥離液で基板から除去す る剥離工程を経て、基板上に微細な凹凸パターンを有する基材とすることができる。 上前記サンドブラスト処理工程に用いるブラスト材は公知のものが用いられ、例えば、 Examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material. A resist pattern is formed on these substrates by the same method as the above-described resist pattern forming method. After that, the resist pattern upper force blasting material formed is blown to the desired depth and the sandblasting process is performed, and the resist pattern portion remaining on the substrate is removed from the substrate with a stripping solution. The substrate can have a fine concavo-convex pattern. As the blasting material used in the above sandblasting process, known materials are used, for example,
SiC, SiO 、 Al O 、 CaCO 、 ZrO、ガラス、ステンレスを材質とする 2〜： LOO μ m程 Made of SiC, SiO 2, Al 2 O 3, CaCO 3, ZrO, glass, and stainless steel 2 ~: About LOO μm
2 2 3 3  2 2 3 3
度の微粒子が用いられる。  Degree fine particles are used.
実施例  Example
[0088] 以下、実施例により本発明の実施形態の例をさらに詳しく説明する。  Hereinafter, examples of embodiments of the present invention will be described in more detail by way of examples.
最初に実施例及び比較例の評価用サンプルの作製方法を説明し、次いで、得られ たサンプルについての評価方法およびその評価結果を示す。  First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method for the obtained samples and the evaluation results will be shown.
[0089] 1.評価用サンプルの作製  [0089] 1. Preparation of sample for evaluation
実施例及び比較例における感光性榭脂積層体は次の様にして作製した。  The photosensitive resin laminates in Examples and Comparative Examples were produced as follows.
<感光性樹脂積層体の作製 >  <Production of photosensitive resin laminate>
表 1に示す組成の感光性榭脂組成物をよく攪拌、混合し、支持体として 16 m厚 のポリエチレンテレフタレートフィルム（三菱ポリエステル製 R310— 16)の表面にバ ーコーターを用いて均一に塗布し、 95°Cの乾燥機中で 4分間乾燥して感光性榭脂 層を形成した。感光性榭脂層の厚みは 40 mであった。  The photosensitive resin composition having the composition shown in Table 1 is thoroughly stirred and mixed, and uniformly applied to the surface of a 16 m-thick polyethylene terephthalate film (Mitsubishi Polyester R310-16) as a support using a bar coater. A photosensitive resin layer was formed by drying for 4 minutes in a 95 ° C dryer. The thickness of the photosensitive resin layer was 40 m.
[0090] 次!、で、感光性榭脂層のポリエチレンテレフタレートフィルムを積層して ヽな 、表面 上に、保護層として 22 m厚のポリエチレンフィルム（タマポリ製 GF— 18)を張り合 わせて感光性榭脂積層体を得た。  [0090] Next !, a polyethylene terephthalate film with a photosensitive resin layer was laminated, and a 22 m thick polyethylene film (GF-18 from Tamapoly) was laminated on the surface as a protective layer. A hydrophilic resin laminate was obtained.
[0091] [表 1]
Figure imgf000029_0001
[0091] [Table 1]
Figure imgf000029_0001
[0092] 表 1に示す記号の説明を表 2に示す。 [0092] Table 2 describes the symbols shown in Table 1.
[0093] [表 2] [0093] [Table 2]
Figure imgf000031_0001
Figure imgf000031_0001
[0094] <基板整面> [0094] <Board surface preparation>
エッチング液耐性、解像度、密着性、テンティング性評価用基板は、 35 μ m圧延銅 箔を積層した 1. 6mm厚の銅張積層板を用い、表面を湿式パフロール研磨 (スリーェ ム (株)製、スコッチブライト (登録商標) HD # 600、 2回通し)した。  Etch solution resistance, resolution, adhesion, and tenting properties are evaluated using a 1.6 mm thick copper clad laminate with 35 μm rolled copper foil, and the surface is wet pafrol polished (manufactured by 3M Corporation). Scotch Bright (registered trademark) HD # 600, twice).
<ラミネート >  <Laminate>
感光性榭脂積層体のポリエチレンフィルムを剥がしながら、整面して 60°Cに予熱し た銅張積層板にホットロールラミネーター (旭化成 (株)社製、 AL - 70)により、ロー ル温度 105°Cでラミネートした。エアー圧力は 0. 35MPaとし、ラミネート速度は 1. 5 va./ minとし 7こ。  While peeling off the polyethylene film of the photosensitive resin laminate, the roll temperature was adjusted to 105 ° C using a hot roll laminator (AL-70, manufactured by Asahi Kasei Co., Ltd.) on a copper-clad laminate that had been leveled and preheated to 60 ° C. Laminated at ° C. Air pressure is 0.335MPa and laminating speed is 1.5 va./min.
[0095] <露光 > [0095] <Exposure>
感光性榭脂層に評価に必要なマスクフィルムを支持体であるポリエチレンテレフタ レートフィルム上におき、超高圧水銀ランプ（オーク製作所製、 HMW- 201KB)に より、スト一ファー製 21段ステップタブレットが 8段となる露光量で露光した (この露光 方法を一括露光方法とする)。  A 21-step tablet made by Stofer is placed on a polyethylene terephthalate film as a support, and a super high pressure mercury lamp (OMW, HMW-201KB) is placed on the photosensitive resin layer for the evaluation. Was exposed with an exposure amount of 8 steps (this exposure method is referred to as a batch exposure method).
同様に、直接描画式露光装置（日立ビアメカ-タス (株)製、 DI露光機 DE— 1AH、 光源: GaN青紫ダイオード、主波長 407 ± 3nm)により下記の感度評価によってステ ップタブレット段数が 8となる露光量で露光した (この露光方法を直接描画式露光方 法とする)。  Similarly, the number of step tablet steps is 8 by the following sensitivity evaluation using a direct-drawing exposure system (Hitachi Via Mechatas Co., Ltd., DI exposure machine DE-1AH, light source: GaN blue-violet diode, dominant wavelength 407 ± 3 nm) Exposure was performed with an exposure amount (this exposure method is a direct drawing type exposure method).
[0096] <現像 > [0096] <Development>
ポリエチレンテレフタレートフィルムを剥離した後、アルカリ現像機 (フジ機工製、ドラ ィフィルム用現像機）を用いて 30°Cの 1質量0/ oNa CO水溶液を所定時間スプレー After peeling off the polyethylene terephthalate film, spray it with a 1 mass 0 / oNa CO aqueous solution at 30 ° C for a specified time using an alkali developer (Fuji Kiko Co., Ltd., dry film developer).
2 3  twenty three
し、感光性榭脂層の未露光部分を最小現像時間の 2倍の時間で溶解除去した。この 際、未露光部分の感光性榭脂層が完全に溶解するのに要する最も少ない時間を最 小現像時間とした。  Then, the unexposed portion of the photosensitive resin layer was dissolved and removed in a time twice as long as the minimum development time. At this time, the minimum development time was defined as the minimum time required for the photosensitive resin layer in the unexposed area to be completely dissolved.
[0097] 2.評価方法 [0097] 2. Evaluation method
( 1) 感度評価  (1) Sensitivity evaluation
ラミネート後 15分経過した感度、解像度評価用基板を、透明から黒色に 21段階に明 度が変化しているスト一ファー製 21段ステップタブレットを用いて露光した。露光後、 最小現像時間の 2倍の現像時間で現像し、硬化レジストの膜が完全に残存して!/、る ステップタブレット段数を感度の値とした。 The substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed using a 21-step tablet manufactured by Stofer, whose brightness was changed from transparent to black in 21 levels. After exposure, Development was performed with a development time twice as long as the minimum development time, and the cured resist film remained completely!
[0098] (2)解像性評価 [0098] (2) Resolution evaluation
ラミネート後 15分経過した感度、解像度評価用基板を、露光部と未露光部の幅が 1 ： 1の比率のラインパターンマスクを通して露光した。最小現像時間の 2倍の現像時間 で現像し、レジストパターンのラインが正常に形成されて ヽる最小マスク幅を解像度 の値とし、解像性を下記のようにランク分けした。  The substrate for sensitivity and resolution evaluation 15 minutes after the lamination was exposed through a line pattern mask in which the width of the exposed area and the unexposed area was 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask width at which a resist pattern line was normally formed was defined as the resolution value, and the resolution was ranked as follows.
◎ (優）：解像度の値が 40 μ m以下。  ◎ (Excellent): Resolution value is 40 μm or less.
〇（良）：解像度の値が 40 mを超え、 50 m以下。  ○ (Good): The resolution value exceeds 40 m and is 50 m or less.
X (不可）：解像度の値が 50 mを超える。  X (Not possible): The resolution value exceeds 50 m.
[0099] (3)密着性評価 [0099] (3) Adhesion evaluation
ラミネート後 15分経過した感度、解像度評価用基板を、露光部と未露光部の幅が 1 : 1の比率のラインパターンマスクを通して露光した。最小現像時間の 2倍の現像時間 で現像し、レジストパターンのラインが正常に形成されて ヽる最小マスクライン幅を密 着性の値とし、密着性を下記のようにランク分けした。  The substrate for sensitivity and resolution evaluation 15 minutes after the lamination was exposed through a line pattern mask having a ratio of the exposed area to the unexposed area of 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width at which a resist pattern line was normally formed was defined as the adhesion value, and the adhesion was ranked as follows.
◎ (優）：密着性の値力 0 μ m以下。  ◎ (excellent): Adhesive strength 0 μm or less.
〇（良）：密着性の値力 0 mを超え、 50 m以下。  ○ (Good): Adhesive strength value exceeds 0 m and 50 m or less.
X (不可）：密着性の値が 50 mを超える。  X (No): Adhesion value exceeds 50 m.
[0100] (4)色相安定性評価感光性榭脂積層体力ゝらポリエチレンフィルムを剥がし、 UV-v isスぺクトロメーター（島津製作所 (株）製、 UV— 240)を用いて、波長 600nmの光の 透過率を測定した。この際、スぺクトロメーターのリファレンス側に該感光性榭脂積層 体に用いたのと同じポリエチレンテレフタレートフィルムを入れて、ポリエチレンテレフ タレートフィルム由来の透過率をキャンセルした。温度 50°C、湿度 60%で 3日間保存 した感光性榭脂積層体の透過率と、温度 23°C、湿度 50%で 3日間保存した同じ感 光性榭脂積層体の透過率を比較し、その差により下記の様にランク分けした。 [0100] (4) Hue stability evaluation The polyethylene film is peeled off from the strength of the photosensitive resin laminate, and UV-vis spectrometer (manufactured by Shimadzu Corporation, UV-240) is used. The light transmittance was measured. At this time, the same polyethylene terephthalate film as that used for the photosensitive resin laminate was put on the reference side of the spectrometer to cancel the transmittance derived from the polyethylene terephthalate film. Compare the transmittance of the photosensitive resin laminate stored at 50 ° C and humidity 60% for 3 days with the transmittance of the same photosensitive resin laminate stored at 23 ° C and humidity 50% for 3 days. However, according to the difference, the ranking was as follows.
[0101] ◎ (優）： 600nmにおける透過率の差が士 5%未満 [0101] ◎ (Excellent): Difference in transmittance at 600nm is less than 5%
〇（良）：600nmにおける透過率の差が ± 5%以上、 ± 10%未満  ○ (Good): Difference in transmittance at 600nm is more than ± 5% and less than ± 10%
X (不可）：600nmにおける透過率の差が ± 10%以上 3.評価結果 X (Not possible): The difference in transmittance at 600nm is more than ± 10% 3.Evaluation results
実施例及び比較例の評価結果は表 1に示した。 The evaluation results of Examples and Comparative Examples are shown in Table 1.
なお、表 1における P— 1〜P— 2の値は、固形分である。 In Table 1, the values of P-1 to P-2 are solid contents.
産業上の利用可能性 Industrial applicability
本発明は、プリント配線板の製造、 ICチップ搭載用リードフレーム製造、メタルマス ク製造、パッケージ、例えば BGAや CSPの製造、テープ基板、例えば COFや TAB の製造、半導体バンプの製造、 ITO電極やアドレス電極、電磁波シールド、例えば、 フラットパネルディスプレイの隔壁を製造する方法に利用することができる。  The present invention includes printed wiring board manufacturing, IC chip mounting lead frame manufacturing, metal mask manufacturing, packages such as BGA and CSP manufacturing, tape substrates such as COF and TAB manufacturing, semiconductor bump manufacturing, ITO electrodes and addresses. It can be used in a method for producing an electrode, an electromagnetic wave shield, for example, a partition wall of a flat panel display.

Claims

請求の範囲 The scope of the claims
[1] (a) α , β 不飽和カルボキシル基含有単量体を共重合成分として含み、酸当量 で 100〜600、重量平均分子量が 5, 000〜500, 000の熱可塑性共重合体： 20〜 90質量％、 (b)少なくとも一つの末端エチレン性不飽和基を有する付加重合性モノ マー： 5〜75質量％、（c)光重合開始剤： 0. 01〜30質量％、（d)亜リン酸エステル 化合物： 0. 01〜5質量％、（e)塩基性染料: 0. 001-0. 3質量％を含有することを 特徴とする感光性榭脂組成物。  [1] (a) Thermoplastic copolymer containing an α, β unsaturated carboxyl group-containing monomer as a copolymerization component and having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000: 20 ~ 90% by mass, (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) photopolymerization initiator: 0.01 to 30% by mass, (d) Phosphorous ester compound: 0.01 to 5% by mass, (e) Basic dye: 0.001 to 0.3% by mass A photosensitive resin composition characterized by comprising:
[2] 上記 (c)光重合開始剤として、へキサァリールビスイミダゾール誘導体を含有するこ とを特徴とする請求項 1記載の感光性榭脂組成物。  [2] The photosensitive resin composition according to [1], wherein (c) a hexarylbisimidazole derivative is contained as a photopolymerization initiator.
[3] 上記 (c)光重合開始剤として、下記一般式 (I)で表されるアタリジンィ匕合物を含有し 、更に (f)有機ハロゲンィ匕合物： 0. 01〜3質量％を含有することを特徴とする請求項 1又は 2に記載の感光性榭脂組成物。  [3] As the above (c) photopolymerization initiator, it contains an ataridin compound represented by the following general formula (I), and (f) an organic halogen compound: 0.01 to 3% by mass The photosensitive resin composition according to claim 1 or 2, wherein:
[化 1]  [Chemical 1]
Figure imgf000035_0001
Figure imgf000035_0001
(式中、 Rは水素、炭素数 1〜6のアルキル基、ァリール基、ピリジル基、又は炭素数 1 〜6のアルコシキル基である。 ) (In the formula, R is hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group, a pyridyl group, or an alkoxy group having 1 to 6 carbon atoms.)
[4] 下記一般式 (Π)で表される N—ァリールアミノ酸: 0. 001〜1. 0質量％を含有する ことを特徴とする請求項 1〜3のいずれか一項に記載の感光性榭脂組成物。 [4] The photosensitivity according to any one of claims 1 to 3, comprising N-aryl amino acid represented by the following general formula (Π): 0.001 to 1.0% by mass. Rosin composition.
R -NHCH COOH (II)  R -NHCH COOH (II)
1 2  1 2
(式中、 Rはァリール基である。 )  (In the formula, R is an aryl group.)
[5] (c)光重合開始剤として、下記一般式 (ΠΙ)で表されるビラゾリンィ匕合物： 0. 001〜[5] (c) As a photopolymerization initiator, a virazoline compound represented by the following general formula (ΠΙ):
10質量％を含有することを特徴とする請求項 1〜4のいずれか一項に記載の感光性 榭脂組成物。 [化 2] It contains 10 mass%, The photosensitive resin composition as described in any one of Claims 1-4 characterized by the above-mentioned. [Chemical 2]
Figure imgf000036_0001
Figure imgf000036_0001
(式中 B及び Cは、それぞれ独立に、炭素数 3以上の直鎖または分枝鎖のアルキル 基、又は NR (Rは水素原子、またはアルキル基)であり、 Aは、ァリール基、複素環 (Wherein B and C are each independently a linear or branched alkyl group having 3 or more carbon atoms, or NR (R is a hydrogen atom or an alkyl group), and A is an aryl group, heterocyclic ring
2  2
基、及び炭素数 3以上の直鎖または分枝鎖のアルキル基力 なる群力 選ばれる置 換基を表す。 aは 0又は 1であり、 b = c = lである。 )  A group and a group power consisting of a straight-chain or branched alkyl group having 3 or more carbon atoms. a is 0 or 1, and b = c = 1. )
[6] (d)亜リン酸エステル化合物力 2, 4, 8, 10—テトラー tert—ブチルー 6— [3— (3 ーメチルー 4ーヒドロキシ—5—tert ブチルフエ-ル）プロポキシ]ジベンゾ [d、 f] [1 , 3, 2]ジォキサホスフェンピン、 2, 2—メチレンビス（4, 6 ジ一 tert—ブチルフエ二 ル）ォクチルホスファイト、ビス（2, 4 ジ—tert ブチルフエ-ル）ペンタエリスリトー ルージホスフアイト、トリス（2, 4 ジ tert ブチルフエ-ル）ホスファイト、 4, 4'ーブ チリデンビス（3—メチル—6— t—ブチルフエ-ル―ジ—トリデシルホスフアイト、 4、 4 ，一イソプロピリデン一ジ一フエノールアルキルホスファイト、及びトリスイソデシルフォ スフアイトからなる群より選ばれる少なくとも一つの化合物である請求項 1〜5のいず れか一項に記載の感光性榭脂組成物。  [6] (d) Phosphite compound power 2, 4, 8, 10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tertbutylphenol) propoxy] dibenzo [d, f] [1,3,2] dioxaphosfenpine, 2,2-methylenebis (4,6 di-tert-butylphenyl) octylphosphite, bis (2,4 di-tert-butylphenol) pentaerythris Rito Luthiphosphite, Tris (2,4 di tertbutylbutyl) phosphite, 4,4'-Tylidenebis (3-methyl-6-tert-butylphenol-tri-decylphosphite, 4, 4, The photosensitive resin composition according to any one of claims 1 to 5, which is at least one compound selected from the group consisting of monoisopropylidene, di-diphenol alkyl phosphite, and trisisodecyl phosphate. .
[7] (b)少なくとも一つの末端エチレン性不飽和基を有する付加重合性モノマーが下記 一般式 (IV)または (V)の少なくとも 1種を含むことを特徴とする請求項 1〜6の!、ずれ か一項に記載の感光性榭脂組成物。  (7) (b) The addition polymerizable monomer having at least one terminal ethylenically unsaturated group contains at least one of the following general formula (IV) or (V): The photosensitive resin composition according to claim 1.
[化 3] [Chemical 3]
Figure imgf000037_0001
Figure imgf000037_0001
(式中、 R及び Rは、それぞれ独立に Hまたは CHであり、 Dおよび Eは、炭素数が 2 (In the formula, R and R are each independently H or CH, and D and E have 2 carbon atoms.
1 2 3  one two Three
〜4個のアルキレン基であり、それぞれ同一であっても異なっていてもよぐ異なって いる場合、 - (D-O)—及び—（E— O)—の繰り返し単位は、ブロック構造であって もなくてもよく、又そのいずれがビスフエ-ル基側であっても良い。 ml、 m2、 nl、及 び n2は、それぞれ独立に 0又は正の整数であり、これらの合計は、 2〜30である。） [化 4]  In the case where they are the same or different, the repeating unit of-(DO)-and-(E-O)-may be a block structure None of them may be on the bisphenol group side. ml, m2, nl, and n2 are each independently 0 or a positive integer, and their sum is 2-30. ) [Chemical 4]
Figure imgf000037_0002
(式中、 R及び Rは、それぞれ独立に Hまたは CHである。また、 Fおよび Gは、炭素
Figure imgf000037_0002
(Wherein R and R are each independently H or CH; and F and G are carbon
3 4 3 3 4 3
数が 2〜4個のアルキレン基であり、それぞれ同一であっても異なっていてもよぐ異 なっている場合、 (F-O) 及び一（G O)—の繰り返し単位は、ブロック構造で あってもなくてもよぐそのいずれがシクロへキシル基側であっても良い。 pl、 p2、 ql 、及び q2は、それぞれ独立に 0又は正の整数であり、これらの合計は、 2〜30である o )  When the number of alkylene groups is 2 to 4, and they may be the same or different, the repeating units (FO) and one (GO) — may be a block structure. Any of them may be on the cyclohexyl group side. pl, p2, ql and q2 are each independently 0 or a positive integer, and their sum is 2 to 30 o)
[8] 請求項 1〜7の ヽずれか一項に記載の感光性榭脂組成物を支持体上に積層して なる感光性榭脂積層体。  [8] A photosensitive resin laminate obtained by laminating the photosensitive resin composition according to any one of claims 1 to 7 on a support.
[9] 請求項 8記載の感光性榭脂積層体を用いて、基板上に感光性榭脂層を形成する ラミネート工程、露光工程、及び現像工程を含む、レジストパターン形成方法。 [9] A resist pattern forming method comprising a lamination step, an exposure step, and a development step of forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to claim 8.
[10] 前記露光工程において、直接描画して露光する事を特徴とする請求項 9に記載の レジストパターン形成方法。 10. The resist pattern forming method according to claim 9, wherein in the exposure step, direct exposure is performed by drawing.
[11] 請求項 9又は 10に記載の方法によってレジストパターンを形成した基板を、エッチ ングする力またはめつきする工程を含むプリント配線板の製造方法。 [11] A method for producing a printed wiring board, comprising a step of etching or attaching a substrate on which a resist pattern is formed by the method according to claim 9 or 10.
[12] 請求項 9又は 10に記載の方法によってレジストパターンを形成した基板を、エッチ ングする工程を含むリードフレームの製造方法。 [12] A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern is formed by the method according to claim 9 or 10.
[13] 請求項 9又は 10に記載の方法によってレジストパターンを形成した基板を、エッチ ングする力またはめつきする工程を含む半導体パッケージの製造方法。 [13] A method for manufacturing a semiconductor package, comprising a step of etching or attaching a substrate on which a resist pattern has been formed by the method according to claim 9 or 10.
[14] 請求項 9又は 10に記載の方法によってレジストパターンを形成した基板を、サンド ブラストによって加工する工程を含む凹凸パターンを有する基材の製造方法。 [14] A method for producing a substrate having a concavo-convex pattern comprising a step of processing a substrate on which a resist pattern is formed by the method according to claim 9 or 10 by sand blasting.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009022724A1 (en) * 2007-08-15 2009-02-19 Asahi Kasei E-Materials Corporation Photosensitive resin composition and laminate thereof
JP2009186780A (en) * 2008-02-06 2009-08-20 Hitachi Chem Co Ltd Photosensitive element, resist pattern forming method using the same, and method for manufacturing printed wiring board
JP2010217287A (en) * 2009-03-13 2010-09-30 Hitachi Chem Co Ltd Photosensitive resin composition for laser direct drawing exposure, photosensitive element using the composition, method for forming resist pattern, and method for manufacturing printed wiring board
JP2011028165A (en) * 2009-07-29 2011-02-10 Asahi Kasei E-Materials Corp Photosensitive resin composition
JP2013068936A (en) * 2011-09-06 2013-04-18 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
JP2013080259A (en) * 2008-04-28 2013-05-02 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, forming method of resist pattern, and manufacturing method of print circuit board
JP2013117581A (en) * 2011-12-01 2013-06-13 Asahi Kasei E-Materials Corp Photosensitive resin composition
JP2013246387A (en) * 2012-05-29 2013-12-09 Asahi Kasei E-Materials Corp Photosensitive resin composition
JP2015132834A (en) * 2015-02-24 2015-07-23 三菱製紙株式会社 chemical milling
US9268217B2 (en) 2013-08-09 2016-02-23 Cheil Industries Inc. Photosensitive resin composition and light blocking layer using the same
US9334399B2 (en) 2012-12-12 2016-05-10 Cheil Industries Inc. Photosensitive resin composition and black spacer using the same

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WO2013084283A1 (en) * 2011-12-05 2013-06-13 日立化成株式会社 Method for forming protective film for touch panel electrodes, photosensitive resin composition, and photosensitive element
WO2013084282A1 (en) 2011-12-05 2013-06-13 日立化成株式会社 Method for forming resin cured film pattern, photosensitive resin composition, and photosensitive element
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003057840A (en) * 2001-08-10 2003-02-28 Asahi Kasei Corp Method for manufacturing photo-polymerizable resin composition
JP2003162052A (en) * 2001-11-28 2003-06-06 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element using the same, method for forming resist pattern and method for manufacturing printed wiring board
JP2003186186A (en) * 2001-12-17 2003-07-03 Asahi Kasei Corp Photosensitive resin composition
JP2004184878A (en) * 2002-12-05 2004-07-02 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and its use
JP2004219690A (en) * 2003-01-15 2004-08-05 Sumitomo Seika Chem Co Ltd Photosensitive composition
JP2005215142A (en) * 2004-01-28 2005-08-11 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and laminate
JP2005292289A (en) * 2004-03-31 2005-10-20 Nichigo Morton Co Ltd Photoresist film

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002278051A (en) * 2001-03-19 2002-09-27 Sumitomo Bakelite Co Ltd Positive type photosensitive resin composition and semiconductor device
US20040087687A1 (en) * 2002-10-30 2004-05-06 Vantico A&T Us Inc. Photocurable compositions with phosphite viscosity stabilizers
JP4459751B2 (en) * 2004-08-11 2010-04-28 東京応化工業株式会社 Photosensitive resin composition for sandblasting and photosensitive dry film for sandblasting using the same
JP2006078868A (en) * 2004-09-10 2006-03-23 Asahi Kasei Electronics Co Ltd Photosensitive resin composition for sandblasting

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003057840A (en) * 2001-08-10 2003-02-28 Asahi Kasei Corp Method for manufacturing photo-polymerizable resin composition
JP2003162052A (en) * 2001-11-28 2003-06-06 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element using the same, method for forming resist pattern and method for manufacturing printed wiring board
JP2003186186A (en) * 2001-12-17 2003-07-03 Asahi Kasei Corp Photosensitive resin composition
JP2004184878A (en) * 2002-12-05 2004-07-02 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and its use
JP2004219690A (en) * 2003-01-15 2004-08-05 Sumitomo Seika Chem Co Ltd Photosensitive composition
JP2005215142A (en) * 2004-01-28 2005-08-11 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and laminate
JP2005292289A (en) * 2004-03-31 2005-10-20 Nichigo Morton Co Ltd Photoresist film

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009022724A1 (en) * 2007-08-15 2009-02-19 Asahi Kasei E-Materials Corporation Photosensitive resin composition and laminate thereof
JP5221543B2 (en) * 2007-08-15 2013-06-26 旭化成イーマテリアルズ株式会社 Photosensitive resin composition and laminate thereof
JP2009186780A (en) * 2008-02-06 2009-08-20 Hitachi Chem Co Ltd Photosensitive element, resist pattern forming method using the same, and method for manufacturing printed wiring board
JP2013080259A (en) * 2008-04-28 2013-05-02 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, forming method of resist pattern, and manufacturing method of print circuit board
JP2010217287A (en) * 2009-03-13 2010-09-30 Hitachi Chem Co Ltd Photosensitive resin composition for laser direct drawing exposure, photosensitive element using the composition, method for forming resist pattern, and method for manufacturing printed wiring board
JP2011028165A (en) * 2009-07-29 2011-02-10 Asahi Kasei E-Materials Corp Photosensitive resin composition
JP2013068936A (en) * 2011-09-06 2013-04-18 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
JP2013117581A (en) * 2011-12-01 2013-06-13 Asahi Kasei E-Materials Corp Photosensitive resin composition
JP2013246387A (en) * 2012-05-29 2013-12-09 Asahi Kasei E-Materials Corp Photosensitive resin composition
US9334399B2 (en) 2012-12-12 2016-05-10 Cheil Industries Inc. Photosensitive resin composition and black spacer using the same
US9268217B2 (en) 2013-08-09 2016-02-23 Cheil Industries Inc. Photosensitive resin composition and light blocking layer using the same
JP2015132834A (en) * 2015-02-24 2015-07-23 三菱製紙株式会社 chemical milling

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CN101438208A (en) 2009-05-20

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