WO2016104585A1 - 感光性樹脂組成物、並びにこれを用いた感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法 - Google Patents

感光性樹脂組成物、並びにこれを用いた感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法 Download PDF

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WO2016104585A1
WO2016104585A1 PCT/JP2015/085985 JP2015085985W WO2016104585A1 WO 2016104585 A1 WO2016104585 A1 WO 2016104585A1 JP 2015085985 W JP2015085985 W JP 2015085985W WO 2016104585 A1 WO2016104585 A1 WO 2016104585A1
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photosensitive resin
mass
resin composition
group
resist pattern
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PCT/JP2015/085985
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English (en)
French (fr)
Japanese (ja)
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壮和 粂
小野　博史
桃子 宗像
大橋　武志
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日立化成株式会社
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Priority to JP2016566433A priority Critical patent/JPWO2016104585A1/ja
Publication of WO2016104585A1 publication Critical patent/WO2016104585A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present disclosure relates to a photosensitive resin composition, a photosensitive element using the same, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.
  • photosensitive resin composition As a resist material used for etching treatment or plating treatment, a photosensitive resin composition and a layer formed using this photosensitive resin composition (hereinafter referred to as “photosensitive”).
  • a photosensitive element having a structure in which a resin layer is also formed on a support and a protective layer is disposed on the photosensitive resin layer is widely used.
  • the printed wiring board is manufactured, for example, by the following procedure using the photosensitive element. That is, first, the photosensitive resin layer of the photosensitive element is laminated on a circuit forming substrate such as a copper-clad laminate. At this time, the surface opposite to the surface (hereinafter also referred to as the “lower surface” of the photosensitive resin layer) in contact with the support of the photosensitive resin layer (hereinafter also referred to as the “upper surface” of the photosensitive resin layer). Is laminated so as to be in close contact with the circuit forming surface of the circuit forming substrate. Therefore, when the protective layer is disposed on the upper surface of the photosensitive resin layer, the laminating operation is performed while peeling off the protective layer. Lamination is performed by thermocompression bonding the photosensitive resin layer to a circuit forming substrate (normal pressure laminating method).
  • the photosensitive resin layer is pattern-exposed through a mask film or the like.
  • the support is peeled off at any timing before or after exposure.
  • the unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed with a developer.
  • an etching process or a plating process is performed to form a conductor pattern, and finally a cured portion of the photosensitive resin layer is peeled and removed.
  • a projection exposure method has recently been introduced in which a photosensitive resin layer is exposed by irradiating an actinic ray on which a photomask image is projected onto a photosensitive resin layer through a lens.
  • the projection exposure method can ensure high alignment as compared with the contact exposure method using a mask film or the like. Therefore, in recent years when circuit formation on printed wiring boards is required to be miniaturized, the projection exposure method has received much attention.
  • An ultra-high pressure mercury lamp or the like is used as a light source used in the projection exposure method.
  • an exposure machine using i-line monochromatic light having an exposure wavelength of 365 nm is often used, but an exposure machine using h-line monochromatic light having an exposure wavelength of 405 nm or ihg mixed line may also be used.
  • the projection exposure method generally uses monochromatic light and split exposure to obtain high resolution, so the amount of irradiation energy is low due to monochromatic light, and the exposure time tends to be longer due to split exposure. There is.
  • the contact exposure method generally employs the ihg mixed line and batch exposure method, the exposure time tends to be shortened. Therefore, from the viewpoint of improving efficiency during mass production, the illuminance of the projection exposure machine is designed to be higher than that of the contact exposure machine, and the exposure time per projection exposure machine is Tend to be shorter than
  • the projection exposure apparatus In order to improve resolution, it has been studied to improve the crosslinking density of the photosensitive resin layer.
  • the projection exposure apparatus has a short exposure time per time, and it is very difficult to increase the reactivity of the exposure part.
  • a photosensitive resin composition suitable for the exposure environment of a projection exposure machine specifically, a photosensitive resin composition capable of forming a resist pattern with excellent resolution even when a projection exposure method is used is required. ing.
  • the present disclosure has been made in view of the above-described problems of the prior art, and when a resist pattern is formed using a projection exposure method, a photosensitive resin composition capable of forming a resist pattern with excellent resolution, and the use thereof. It is an object of the present invention to provide a photosensitive element, a resist pattern forming method, and a printed wiring board manufacturing method.
  • the present disclosure provides (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a photosensitizer, and (E) A polymerization inhibitor is contained, and the content of the (E) polymerization inhibitor is 100 mass of the total solid content of the photopolymerizable compound having the (A) binder polymer and the (B) ethylenically unsaturated bond.
  • the photosensitive resin composition is provided in an amount of 0.03 to 0.3 parts by mass with respect to parts.
  • Such a photosensitive resin composition can form a resist pattern having excellent resolution when the resist pattern is formed using the projection exposure method by having the above-described configuration.
  • the photosensitive resin composition of the present disclosure is useful as a photosensitive resin composition for projection exposure, and in particular, high resolution, high aspect ratio, high adhesion, high imaging property, and high workability are required. It is useful as a photosensitive resin composition for projection exposure for producing an ultrahigh-density wiring board.
  • the (E) polymerization inhibitor may include a compound represented by the following general formula (I).
  • R 5 represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, an aryl group, a mercapto group, or an alkyl mercapto group having 1 to 10 carbon atoms.
  • An alkyl group represents a carboxyalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic group, m represents an integer of 2 or more selected so that m + n is 6 or less, n Represents an integer of 0 or more selected so that m + n is 6 or less.
  • R 5 may be the same or different.
  • a resist pattern having a higher resolution and a higher aspect ratio can be formed.
  • the content of the (D) photosensitizer is a solid content of the photopolymerizable compound having the (A) binder polymer and the (B) ethylenically unsaturated bond. 1.0 mass part or less may be sufficient with respect to 100 mass parts of total amounts.
  • the present disclosure also provides a photosensitive element comprising a support and a photosensitive resin layer formed on the support using the photosensitive resin composition of the present disclosure described above.
  • Such a photosensitive element includes a photosensitive resin layer formed using the photosensitive resin composition of the present disclosure described above, when a resist pattern is formed using a projection exposure method, the photosensitive element has excellent resolution and an aspect ratio. A high resist pattern can be formed.
  • the present disclosure also includes a step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition of the present disclosure described above or the photosensitive element of the present disclosure described above, and an activity in which an image of a photomask is projected.
  • a method for forming a resist pattern comprising a step of exposing the photosensitive resin layer through a lens using light rays and a step of removing an unexposed portion of the photosensitive resin layer from a substrate by development.
  • the method for forming such a resist pattern includes a step of forming a photosensitive resin layer using the photosensitive resin composition of the present disclosure described above or the photosensitive element of the present disclosure described above, the resist pattern is formed using a projection exposure method. Can form a resist pattern with excellent resolution and a high aspect ratio.
  • the present disclosure further provides a method for manufacturing a printed wiring board including a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the above-described method for forming a resist pattern of the present disclosure.
  • the printed wiring board manufacturing method forms a resist pattern by the resist pattern forming method of the present disclosure described above, it can form a resist pattern with excellent resolution and a high aspect ratio.
  • a method for producing a printed wiring board suitable for increasing the density can be provided.
  • a photosensitive resin composition capable of forming a resist pattern having excellent resolution and a high aspect ratio, and a photosensitive element and a resist pattern using the same. And a method for producing a printed wiring board can be provided.
  • (meth) acrylic acid means at least one of acrylic acid and methacrylic acid corresponding thereto.
  • (meth) acrylate means at least one of acrylic acid and methacrylic acid corresponding thereto.
  • process is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
  • the numerical range indicated by using “to” in this specification indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view.
  • the photosensitive resin composition according to this embodiment includes (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a photosensitizer, and (E) A polymerization inhibitor is contained, and the content of the (E) polymerization inhibitor is 100 mass of the total solid content of the photopolymerizable compound having the (A) binder polymer and the (B) ethylenically unsaturated bond.
  • the present invention relates to a photosensitive resin composition that is 0.03 to 0.3 parts by mass with respect to parts.
  • (A) Binder polymer examples of the (A) binder polymer (hereinafter also referred to as “component (A)”) that can be used in the photosensitive resin composition according to this embodiment include acrylic resins, styrene resins, epoxy resins, and amides. Resin, amide epoxy resin, alkyd resin, phenol resin and the like. From the standpoint of further improving alkali developability, an acrylic resin may be included. These can be used individually by 1 type or in combination of 2 or more types.
  • the binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. That is, it can be said that (A) the binder polymer has a structural unit derived from the polymerizable monomer.
  • the polymerizable monomer include polymerizable styrene derivatives substituted at the ⁇ -position or aromatic ring such as styrene, vinyl toluene, ⁇ -methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl, and the like.
  • -Ethers of vinyl alcohol such as n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester such as benzyl methacrylate, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl Ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (Meth) acrylic acid, ⁇ -bromoacrylic acid, ⁇ -chloroacrylic acid, ⁇ -furyl (meth) acrylic acid, ⁇ -styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Examples thereof include maleic acid monoesters such as monoethyl
  • (meth) acrylic acid alkyl ester may be used from the viewpoint of further improving developability.
  • examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (II) and compounds in which the alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like.
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group having 1 to 12 carbon atoms represented by R 7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an undecyl group.
  • Dodecyl groups structural isomers of these groups, and the like.
  • Examples of the (meth) acrylic acid alkyl ester represented by the general formula (II) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic.
  • Acid butyl ester (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic Examples include acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, and the like. These can be used individually by 1 type or in combination of 2 or more types.
  • the binder polymer may contain a carboxyl group from the viewpoint of further improving the alkali developability.
  • the (A) binder polymer containing a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.
  • the polymerizable monomer having a carboxyl group may be (meth) acrylic acid or methacrylic acid.
  • the acid value of the (A) binder polymer containing a carboxyl group may be 50 to 250 mgKOH / g.
  • the carboxyl group content of the binder polymer improves the alkali developability and the alkali resistance in a balanced manner. From the viewpoint, it may be 12 to 50% by mass, 12 to 40% by mass, 15 to 35% by mass, or 15 to 30% by mass.
  • the carboxyl group content is 12% by mass or more, alkali developability tends to be improved, and when it is 50% by mass or less, alkali resistance tends to be excellent.
  • the content of the structural unit derived from the polymerizable monomer having a carboxyl group in the binder polymer (A) correlates with the blending ratio of the polymerizable monomer having a carboxyl group, 12 to 50 mass. %, 12-40 mass%, 15-35 mass%, or 15-30 mass%.
  • the binder polymer may use styrene or a styrene derivative as a polymerizable monomer from the viewpoint of further improving the adhesion and chemical resistance.
  • the content thereof (the blending ratio of styrene or styrene derivative with respect to the total amount of polymerizable monomer used in the binder polymer) further improves adhesion and chemical resistance. From the standpoint of making it, it may be 10 to 60% by mass or 15 to 50% by mass. When the content is 10% by mass or more, the adhesion tends to be improved.
  • “chemical resistance” means resistance to chemicals (developer, water, etching solution, etc.) used in a resist pattern forming method or a printed wiring board manufacturing method described later. .
  • the content of the structural unit derived from styrene or a styrene derivative in (A) the binder polymer is correlated with the blending ratio of the styrene or styrene derivative, and may be 10 to 60% by mass. It may be mass%.
  • the binder polymer may use (meth) acrylic acid benzyl ester as a polymerizable monomer from the viewpoint of further improving the resolution and aspect ratio.
  • the content of (meth) acrylic acid benzyl ester in the binder polymer may be 15 to 50% by mass from the viewpoint of further improving the resolution and aspect ratio.
  • binder polymers can be used singly or in combination of two or more.
  • binder polymer (A) used in combination of two or more include, for example, two or more binder polymers composed of different polymerizable monomers, two or more binder polymers having different weight average molecular weights, and different degrees of dispersion. 2 or more types of binder polymers.
  • the binder polymer can be produced by a usual method. Specifically, for example, it can be produced by radical polymerization of (meth) acrylic acid alkyl ester, (meth) acrylic acid, styrene and the like.
  • the weight average molecular weight of the binder polymer is 20,000 to 300,000, 40,000 to 150,000, 40,000 to 120,000, from the viewpoint of improving mechanical strength and alkali developability in a balanced manner. Alternatively, it may be 50,000 to 80,000.
  • the weight average molecular weight of the binder polymer is 20,000 or more, the developer resistance tends to be excellent, and when it is 300,000 or less, the development time tends to be suppressed.
  • the weight average molecular weight in this specification is a value measured by a gel permeation chromatography method (GPC) and converted by a calibration curve created using standard polystyrene.
  • the content of the (A) binder polymer is 30 to 80 parts by weight, 40 to 75 parts by weight, or 50 to 70 parts by weight with respect to 100 parts by weight of the total solid content of the component (A) and the component (B) described later. It may be. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.
  • the photosensitive resin composition according to the present embodiment includes (B) a photopolymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as “component (B)”).
  • component (B) can be used without particular limitation as long as it is a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule.
  • component (B) examples include urethane monomers such as compounds obtained by reacting an ⁇ , ⁇ -unsaturated carboxylic acid with a polyhydric alcohol, bisphenol type (meth) acrylate compounds, and (meth) acrylate compounds having a urethane bond.
  • urethane monomers such as compounds obtained by reacting an ⁇ , ⁇ -unsaturated carboxylic acid with a polyhydric alcohol, bisphenol type (meth) acrylate compounds, and (meth) acrylate compounds having a urethane bond.
  • the component (B) may contain a bisphenol type (meth) acrylate compound from the viewpoint of improving the resolution, adhesion, and resist bottom generation suppression in a well-balanced manner.
  • the bisphenol type (meth) acrylate compound may be a compound represented by the following general formula (III).
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a methyl group.
  • X and Y each independently represent an ethylene group or a propylene group, and XO and YO each independently represent an oxyethylene group (hereinafter sometimes referred to as “EO group”) or an oxypropylene group (hereinafter referred to as “PO”). May be referred to as a “group”).
  • EO group oxyethylene group
  • PO oxypropylene group
  • p 1 , p 2 , q 1 and q 2 each independently represent a numerical value of 0 to 40. However, both p 1 + q 1 and p 2 + q 2 are 1 or more.
  • p 1 + p 2 is 1 to 40
  • q 1 + q 2 is 0 to 20
  • p 1 + p 2 is 0 to 20
  • q 1 + q 2 is 1 to 40. Since p 1 , p 2 , q 1 and q 2 indicate the number of structural units of the EO group or PO group, a single molecule indicates an integer value, and an aggregate of a plurality of types of molecules indicates an average rational number. Show. Note that the EO group and the PO group may be continuously present in blocks or randomly.
  • Examples of the compound represented by the general formula (III) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy). Polypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, and the like. These can be used individually by 1 type or in combination of 2 or more types.
  • Examples of commercially available bisphenol (meth) acrylate compounds include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (“BPE-200” manufactured by Shin-Nakamura Chemical Co., Ltd.). ), 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (“BPE-500” manufactured by Shin-Nakamura Chemical Co., Ltd., or “FA-321M” manufactured by Hitachi Chemical Co., Ltd.), 2,2- Bis (4- (methacryloxypentadecaethoxy) phenyl) propane (“BPE-1300” manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane (Kyoeisha Chemical Co., Ltd.) “BP-2EM” manufactured by company (EO group: 2.6 (average value))) and the like.
  • BPE-200 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane
  • the content of the bisphenol type (meth) acrylate compound is 1 to 50% by mass and 1 to 45% by mass with respect to the total solid content of the component (A) and the component (B) from the viewpoint of improving chemical resistance. It may be 1 to 40% by mass, or 3 to 25% by mass.
  • the content of the bisphenol type (meth) acrylate compound is 30 to 99% by mass, 50 to 97% by mass, or 60% with respect to the total solid content of the component (B) from the viewpoint of improving chemical resistance. It may be up to 95% by mass.
  • a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid may be contained.
  • a compound for example, polyalkylene glycol di (meth) acrylate having both an EO group and a PO group in the molecule can be used.
  • the content of the compound obtained by reacting the polyhydric alcohol with the ⁇ , ⁇ -unsaturated carboxylic acid is 1 to 10% by mass, or 3 to 3% with respect to the total solid content of the component (A) and the component (B). It may be 7% by mass.
  • the content of the compound obtained by reacting the polyhydric alcohol with the ⁇ , ⁇ -unsaturated carboxylic acid is 1 to 30% by mass, or 3 to 20% by mass with respect to the total solid content of the component (B). It may be.
  • the EO group and the PO group may be present continuously in blocks or randomly.
  • the PO group may be either an oxy-n-propylene group or an oxyisopropylene group.
  • the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.
  • polyalkylene glycol di (meth) acrylates having both EO groups and PO groups include, for example, poly having EO groups: 6 (average value) and PO groups: 12 (average value). And alkylene glycol di (meth) acrylate (“FA-023M”, “FA-024M” manufactured by Hitachi Chemical Co., Ltd.).
  • the content of the component (B) is 20 to 70 parts by mass, 25 to 60 parts by mass, or 30 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) and (B). Also good. When the content of the component (B) is within this range, in addition to the resolution of the photosensitive resin composition, the adhesiveness, and the suppression of resist skirt generation, the photosensitivity and the coating property are also improved.
  • the photosensitive resin composition according to the present embodiment contains at least one (C) photopolymerization initiator (hereinafter also referred to as “component (C)”).
  • component (C) is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators.
  • component (C) examples include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as propanone-1, quinones such as alkyl anthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl)- 2,4,5-triarylimidazole dimer such as 4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1, Acridine derivatives such as 7- (9,9′-acridinyl) heptane Can be mentioned. These can be used individually by 1 type or in
  • 2,4,5-triarylimidazole dimer may be contained from the viewpoint of further improving the resolution.
  • Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- And (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.
  • 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer may be contained.
  • 2,4,5-triarylimidazole dimer examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, It is commercially available as a product name) manufactured by Tsuchiya Chemical Industry Co., Ltd.
  • Component (C) contains at least one of 2,4,5-triarylimidazole dimer from the viewpoint of further improving photosensitivity and adhesion and further suppressing the light absorption of component (C).
  • 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer may be included.
  • the 2,4,5-triarylimidazole dimer may have a symmetric structure or an asymmetric structure.
  • the content of the component (C) is 0.01 to 30 parts by weight, 0.1 to 10 parts by weight, 1 to 7 parts by weight with respect to 100 parts by weight of the total solid content of the components (A) and (B). It may be 1 to 6 parts by mass, 1 to 5 parts by mass, or 2 to 5 parts by mass.
  • the content of the component (C) is 0.01 parts by mass or more, the photosensitivity, resolution, and adhesion tend to be improved, and when it is 30 parts by mass or less, the shape of the resist pattern tends to be excellent.
  • the photosensitive resin composition according to the present embodiment includes (D) a photosensitizer (hereinafter also referred to as “component (D)”). By containing the component (D), the absorption wavelength of actinic rays used for exposure can be effectively used.
  • component (D) a photosensitizer
  • component (D) examples include pyrazolines, dialkylaminobenzophenones, anthracene, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes , Naphthalimides, triarylamines and the like. These can be used individually by 1 type or in combination of 2 or more types.
  • (D) Content of component is 1.0 mass part or less, 0.5 mass part or less, 0.15 mass part or less with respect to 100 mass parts of solid content total of (A) component and (B) component, 0 .12 parts by mass or less, or 0.1 parts by mass or less may be used.
  • the content of the component (D) is 1.0 part by mass or less with respect to 100 parts by mass of the total solid content of the component (A) and the component (B)
  • the resist pattern shape deterioration and the generation of the resist residue are further suppressed.
  • the lower limit value of the content of the component (D) is 0. 0 with respect to 100 parts by mass of the total solid content of the components (A) and (B), from the viewpoint of easily obtaining high photosensitivity and high resolution. It may be 01 parts by mass or more.
  • the photosensitive resin composition according to the present embodiment includes (E) a polymerization inhibitor (hereinafter also referred to as “component (E)”).
  • component (E) a polymerization inhibitor
  • the exposure amount required in order to photocure the photosensitive resin composition can be adjusted to the optimal exposure amount for exposing with a projection exposure machine.
  • the component (E) may contain a compound represented by the following general formula (I) from the viewpoint of further improving the resolution.
  • R 5 represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, an aryl group, a mercapto group, or 1 to 10 carbon atoms.
  • R 5 may be the same or different.
  • the aryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.
  • R 5 may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms from the viewpoint of further improving the compatibility with the component (A).
  • the alkyl group having 1 to 20 carbon atoms represented by R 5 may be an alkyl group having 1 to 4 carbon atoms.
  • m may be 2 or 3, or 2 from the viewpoint of further improving the resolution.
  • Examples of the compound represented by the general formula (I) include catechol, resorcinol (resorcin), 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3 -Ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl Catechol, 3-tert-butylcatechol, 4-tert-butylcatechol, alkylcatechol such as 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol (orcine), 2 -Ethyl resorcino Alkyl, resorcinol such as 4-ethyl resorcinol, 2-propyl resorcinol, 4-
  • alkylcatechol may be used from the viewpoint of further improving the resolution.
  • the content of the component (E) is 0.03 to 0.3 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) and (B), 0.03 to 0.2 parts by mass, It may be 0.05 to 0.15 parts by mass, or 0.05 to 0.1 parts by mass. (E) By making content of a component 0.3 mass part or less, exposure time can be shortened, it can contribute to the efficiency improvement of mass production, By making it 0.03 mass part or more, The photoreaction of the exposed portion can be sufficiently advanced, and the resist swelling can be suppressed and the resolution can be improved by improving the reaction rate.
  • the content of the component (E) is 0.05 to 0.4 parts by mass, 0.05 to 0.2 parts by mass, or 0.05 to 0.2 parts by mass with respect to 100 parts by mass of the solid content of the component (A). 0.1 mass part may be sufficient.
  • content of (E) component is 0.05 mass part or more with respect to (A) component, there exists a tendency which can improve the thermal stability of the photosensitive resin composition, and is 0.4 mass part or less. When it is, there exists a tendency which can suppress yellowing of the photosensitive resin composition.
  • dyes such as malachite green, Victoria pure blue, brilliant green, and methyl violet, tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, and triphenyl are used.
  • Photo-coloring agents such as amine, diethylaniline, o-chloroaniline, and tertiary butyl catechol, thermo-coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, adhesion imparting
  • Additives such as an agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent are each 0.01 parts per 100 parts by mass of the total solid content of the component (A) and the component (B). Up to 20 parts by mass can be contained. These additives can be used alone or in combination of two or more.
  • the photosensitive resin composition according to the present embodiment can contain at least one organic solvent as required.
  • the organic solvent normally can be especially used without a restriction
  • the photosensitive resin composition according to the present embodiment dissolves the component (A), the component (B), the component (C), the component (D), and the component (E) in the organic solvent.
  • it can be used as a solution having a solid content of 30 to 60% by mass (hereinafter also referred to as “coating solution”).
  • solid content refers to the component in compositions other than the substance to volatilize, such as a water
  • the volatile substance refers to a substance having a boiling point of 155 ° C. or lower under atmospheric pressure.
  • the coating solution can be used for forming a photosensitive resin layer as follows, for example.
  • the said coating liquid is apply
  • the metal plate examples include a metal plate made of an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron, or stainless steel. From the viewpoint of further improving durability, copper, a copper-based alloy, or A metal plate made of an iron-based alloy may be used.
  • an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron, or stainless steel. From the viewpoint of further improving durability, copper, a copper-based alloy, or A metal plate made of an iron-based alloy may be used.
  • the photosensitive element which concerns on this embodiment is related with the photosensitive element provided with a support body and the photosensitive resin layer formed using the said photosensitive resin composition on the said support body.
  • the photosensitive element 1 which concerns on this embodiment is a photosensitive resin derived from the support body 2 and the said photosensitive resin composition formed on the support body 2, as the schematic cross section of the example is shown in FIG. Layer 3 and other layers such as a protective layer 4 provided as necessary.
  • the polymer film which has heat resistance and solvent resistance such as polyester, such as a polypropylene, polyethylene, and a polyethylene terephthalate, can be used, for example.
  • the thickness of the support may be 1 to 100 ⁇ m, 1 to 50 ⁇ m, or 1 to 30 ⁇ m. There exists a tendency which can suppress that a support body is torn when peeling a support body because the thickness of a support body is 1 micrometer or more. Moreover, there exists a tendency for the fall of resolution to be suppressed because the thickness of a support body is 100 micrometers or less.
  • the photosensitive element 1 may further include a protective layer 4 that covers the surface of the photosensitive resin layer 3 opposite to the surface facing the support 2 as necessary.
  • the protective layer may have a lower adhesive strength to the photosensitive resin layer than the adhesive strength of the support to the photosensitive resin layer, or may be a low fish eye film.
  • fish eye refers to a foreign material of a material taken into the film when the material constituting the protective layer is melted by heat, kneaded, extruded, and produced by a biaxial stretching casting method, This means undissolved materials, oxidized degradation products, and the like. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
  • a polymer film having heat resistance and solvent resistance such as polyester such as polypropylene, polyethylene, polyethylene terephthalate, etc.
  • polyester such as polypropylene
  • polyethylene polyethylene
  • polyethylene terephthalate etc.
  • Examples of commercially available products include polyethylene terephthalate films such as PS series such as Alfane MA-410 and E-200C manufactured by Oji Paper Co., Ltd., polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and PS-25 manufactured by Teijin Limited.
  • the protective layer may be the same as the above support.
  • the thickness of the protective layer may be 1 to 100 ⁇ m, 5 to 50 ⁇ m, 5 to 30 ⁇ m, or 15 to 30 ⁇ m.
  • the thickness of the protective layer is 1 ⁇ m or more, there is a tendency that the protective layer is prevented from being broken when the photosensitive resin layer and the support are laminated on the substrate while peeling off the protective layer. Further, it may be 100 ⁇ m or less from the viewpoint of easily obtaining economic benefits.
  • the photosensitive element which concerns on this embodiment can be manufactured as follows, for example. A step of preparing a coating solution in which the photosensitive resin composition is dissolved in the organic solvent; a step of coating the coating solution on a support to form a coating layer; and drying the coating layer to form a photosensitive resin. And a step of forming a layer.
  • coating solution onto the support can be performed by a known method using, for example, roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, spray coating, or the like.
  • the drying of the coating layer is not particularly limited as long as at least part of the organic solvent can be removed from the coating layer, but may be dried at 70 to 150 ° C. for 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is 2% by mass or less based on the total amount of the photosensitive resin composition excluding the organic solvent from the viewpoint of suppressing the diffusion of the organic solvent in the subsequent step. May be.
  • the thickness of the photosensitive resin layer in the photosensitive element can be appropriately selected depending on the application, but it may be 1 to 200 ⁇ m, 5 to 100 ⁇ m, or 10 to 50 ⁇ m after drying.
  • the thickness of the photosensitive resin layer is 1 ⁇ m or more, industrial coating becomes easy and productivity tends to be improved.
  • the thickness of the photosensitive resin layer is 200 ⁇ m or less, the photosensitivity is high and the photocurability at the bottom of the resist is excellent, so that a resist pattern having excellent resolution and aspect ratio tends to be formed.
  • the thickness of the photosensitive resin layer in the photosensitive element is less than 30 ⁇ m in terms of the resolution from the viewpoint of further improving the resolution. It may be 25 ⁇ m or less.
  • the lower limit of the thickness of the photosensitive resin layer is not particularly limited as long as the photosensitive resin layer can be formed, but from the viewpoint of further improving the throughput, the thickness after drying may be 1 ⁇ m or more, 5 ⁇ m or more, or 7 ⁇ m or more. Good.
  • the photosensitive element according to the present embodiment may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, or a gas barrier layer, if necessary.
  • an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, or a gas barrier layer, if necessary.
  • the form of the photosensitive element according to this embodiment is not particularly limited.
  • a sheet shape may be sufficient and the shape wound up by the roll shape on the core may be sufficient.
  • the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, or ABS (acrylonitrile-butadiene-styrene copolymer).
  • an end face separator may be installed on the end face of the roll-shaped photosensitive element roll thus obtained, and from the viewpoint of edge fusion resistance, a moisture-proof end face separator is installed. Also good. As a packing method, it may be wrapped in a black sheet with low moisture permeability.
  • the photosensitive element according to the present embodiment can be suitably used, for example, for a resist pattern forming method described later.
  • the resist pattern forming method includes (i) a step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition or the photosensitive element (hereinafter referred to as “(i) photosensitive property”. (Also referred to as “resin layer forming step”) and (ii) a step of exposing the photosensitive resin layer through a lens using an actinic ray onto which an image of a photomask is projected (hereinafter also referred to as “(ii) exposure step”). ) And (iii) a step of removing the unexposed portion of the photosensitive resin layer from the substrate by development (hereinafter also referred to as “(iii) development step”), and other steps as necessary May be included.
  • Photosensitive resin layer forming step a photosensitive resin layer is formed on a substrate using the photosensitive resin composition or the photosensitive element.
  • substrate for circuit formation provided with the insulating layer and the conductor layer formed on the insulating layer, or die pads (base material for lead frames) etc., such as an alloy base material, is used. It is done.
  • Examples of the method for forming the photosensitive resin layer on the substrate include a method in which a coating liquid containing the photosensitive resin composition is applied and then dried, a method using the photosensitive element, and the like.
  • a photosensitive element having a protective layer after removing the protective layer, the photosensitive resin layer of the photosensitive element is pressure-bonded to the substrate while heating, so that the photosensitive resin layer is formed on the substrate. Can be formed. Thereby, the laminated body provided with a board
  • Heating at the time of pressure bonding may be performed at a temperature of 70 to 130 ° C., and pressure bonding may be performed at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf / cm 2 ), but these conditions are necessary. It can be selected as appropriate. If the photosensitive resin layer of the photosensitive element is heated to 70 to 130 ° C., it is not necessary to preheat the substrate in advance, but in order to further improve the adhesion and followability, the substrate is preheated. It can also be done.
  • (Ii) Exposure process In the exposure process, by irradiating at least a part of the photosensitive resin layer formed on the substrate with actinic rays through a lens using actinic rays onto which an image of a photomask is projected, The exposed portion irradiated with actinic rays is photocured to form a photocured portion (latent image).
  • the photosensitive resin layer is formed using the photosensitive element, when the support existing on the photosensitive resin layer is transmissive to actinic rays, it can be irradiated with actinic rays through the support.
  • the photosensitive resin layer is irradiated with actinic rays after the support is removed.
  • a method (projection exposure method) in which an actinic ray on which an image of a photomask is projected is irradiated in an image form through a lens is used. That is, the photosensitive resin composition of the present embodiment can be applied to a method (projection exposure method) in which an actinic ray onto which an image of a photomask is projected is irradiated in an image form through a lens. From the viewpoint of improving productivity, the projection exposure method may be used alone or in combination with an exposure method other than the projection exposure method.
  • a direct drawing exposure method such as a method of irradiating an actinic ray in an image form through a negative mask pattern called an artwork (mask exposure method), an LDI (Laser Direct Imaging) exposure method, or the like.
  • a direct drawing exposure method such as a method of irradiating an actinic ray in an image form through a negative mask pattern called an artwork (mask exposure method), an LDI (Laser Direct Imaging) exposure method, or the like.
  • Examples include a method of irradiating actinic rays in an image form.
  • the light source of the actinic ray is not particularly limited as long as it is a known light source that is usually used.
  • a laser that effectively emits ultraviolet rays such as a solid-state laser such as a semiconductor laser such as a gallium nitride blue-violet laser, is used. Moreover, you may use what radiates
  • a light source capable of emitting i-line monochromatic light with an exposure wavelength of 365 nm a light source capable of emitting h-line monochromatic light with an exposure wavelength of 405 nm, or ihg mixed-line exposure
  • a light source capable of emitting actinic light having a wavelength may be used, and a light source capable of emitting i-line monochromatic light having an exposure wavelength of 365 nm may be used.
  • Examples of the light source capable of emitting i-line monochromatic light having an exposure wavelength of 365 nm include an ultrahigh pressure mercury lamp.
  • (Iii) Development Step In the development step, the unexposed portion (uncured portion) of the photosensitive resin layer is removed from the substrate by development. By the development process, a resist pattern including a photocured portion obtained by photocuring the photosensitive resin layer is formed on the substrate. When the support is present on the photosensitive resin layer, the support is removed, and then the unexposed portions other than the exposed portions are removed by development. Development methods include wet development and dry development.
  • wet development can be performed by a known wet development method using a developer corresponding to the photosensitive resin composition.
  • the wet development method include a dipping method, a paddle method, a high pressure spray method, a method using brushing, slapping, scrubbing, rocking immersion, etc., and from the viewpoint of improving resolution, a high pressure spray method is used. There may be.
  • These wet development methods may be developed singly or in combination of two or more methods.
  • the developer is appropriately selected according to the configuration of the photosensitive resin composition.
  • alkaline aqueous solution, organic solvent developing solution, etc. are mentioned.
  • an alkaline aqueous solution may be used as the developer.
  • the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, sodium phosphate Alkali metal phosphates such as sodium pyrophosphate and potassium pyrophosphate, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2 -Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like are used.
  • Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, 0 It may be a dilute solution of 1 to 5% by mass sodium tetraborate.
  • the pH of the alkaline aqueous solution used for development may be in the range of 9 to 11, and the temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive resin layer.
  • a surface active agent, an antifoaming agent, a small amount of an organic solvent for accelerating development may be mixed.
  • organic solvent used in the organic solvent developer examples include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, ⁇ -butyrolactone, 3-acetone alcohol, acetone And ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. These organic solvents may be used as an organic solvent developer by adding water in the range of 1 to 20% by mass from the viewpoint of preventing ignition.
  • the method for forming a resist pattern after removing the unexposed portion in the development step, heating at 60 to 250 ° C. or exposure at an exposure amount of 0.2 to 10 J / cm 2 is performed as necessary. It may include a step of further curing the resist pattern.
  • the method for manufacturing a printed wiring board according to the present embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern has been formed by the above-described resist pattern forming method. Other steps such as a removal step may be included.
  • the method for producing a printed wiring board according to the present embodiment can be suitably used for forming a conductor pattern by using the method for forming a resist pattern with the photosensitive resin composition. Application to the forming method is more preferable.
  • the conductor layer of the substrate not covered with the resist pattern is removed by etching to form a conductor pattern.
  • Etching method is appropriately selected according to the conductor layer to be removed.
  • the etching solution include a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, etc., and a ferric chloride solution is used from the point that the etch factor is good. Also good.
  • the plating process copper or solder is plated on the conductor layer of the substrate not covered with the resist pattern, using the resist pattern formed on the substrate provided with the conductor layer as a mask. After the plating treatment, the resist pattern is removed by removing the resist pattern described later, and the conductor layer covered with the resist pattern is etched to form a conductor pattern.
  • the plating treatment method may be electrolytic plating treatment or electroless plating treatment, but may be electroless plating treatment from the viewpoint of further improving the yield.
  • the electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, Examples thereof include gold plating such as hard gold plating and soft gold plating.
  • the resist pattern on the substrate is removed.
  • the resist pattern can be removed by, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step.
  • a strong alkaline aqueous solution for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used.
  • a 1 to 5% by mass aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution may be used from the viewpoint of further improving the peelability.
  • Examples of the resist pattern peeling method include an immersion method and a spray method, and these may be used alone or in combination.
  • a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist pattern by the etching treatment to form the conductor pattern.
  • the etching method at this time is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.
  • the printed wiring board manufacturing method according to the present embodiment can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. Is possible.
  • the method for manufacturing a printed wiring board according to the present embodiment can be suitably used for manufacturing a high-density package substrate, particularly for manufacturing a wiring board by a semi-additive construction method.
  • An example of the manufacturing process of the wiring board by the semi-additive construction method is shown in FIG.
  • FIG. 2A a substrate (circuit forming substrate) in which the conductor layer 40 is formed on the insulating layer 50 is prepared.
  • the conductor layer 40 is, for example, a copper layer.
  • the photosensitive resin layer 30 is formed on the conductor layer 40 of a board
  • FIG. 2C a photocured portion is formed in the photosensitive resin layer 30 by irradiating the photosensitive resin layer 30 with an actinic ray 80 obtained by projecting an image of a photomask on the photosensitive resin layer 30.
  • an actinic ray 80 obtained by projecting an image of a photomask on the photosensitive resin layer 30.
  • a resist pattern 32 that is a photocured portion is formed on the substrate by removing a region other than the photocured portion formed by the exposure step from the substrate by the developing process.
  • the plating layer 60 is formed on the conductor layer 40 of the substrate not covered with the resist pattern by plating using the resist pattern 32 as a mask.
  • FIG. 2F after the resist pattern 32 is peeled off with a strong alkaline aqueous solution, the conductor layer 40 masked by the resist pattern 32 is removed by a flash etching process, and the plated layer 62 and the etching process after the etching process are removed.
  • a conductor pattern 70 including the subsequent conductor layer 42 is formed.
  • the conductor layer 40 and the plating layer 60 may be made of the same material or different materials. When the conductor layer 40 and the plating layer 60 are the same material, the conductor layer 40 and the plating layer 60 may be integrated. Although the projection exposure method has been described with reference to FIG. 2, the resist pattern 32 may be formed by using both a mask exposure method and a direct drawing exposure method.
  • binder polymers (A-1) shown in Tables 1 and 2 below were synthesized according to Synthesis Example 1.
  • a solution b 1.2 g of azobisisobutyronitrile was dissolved in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of methyl cellosolve and 40 g of toluene to prepare a solution b.
  • a mixed solution of methyl cellosolve and toluene having a mass ratio of 3: 2 (hereinafter also referred to as “mixed solution x”). 400g was added, it stirred while blowing nitrogen gas, and it heated to 80 degreeC.
  • the solution a was added dropwise to the mixed solution x in the flask over a period of 4 hours at a constant dropping rate, followed by stirring at 80 ° C. for 2 hours.
  • the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 hours.
  • the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to room temperature to obtain a solution of binder polymer (A-1).
  • the mixed solution x was added to the binder polymer (A-1) solution to prepare a nonvolatile component (solid content) of 50% by mass.
  • the weight average molecular weight of the binder polymer (A-1) was 50,000, and the acid value was 163 mgKOH / g.
  • the acid value was measured by a neutralization titration method. Specifically, 30 g of acetone was added to 1 g of the binder polymer solution, and further uniformly dissolved, and then an appropriate amount of an indicator, phenolphthalein, was added to the binder polymer solution to obtain a 0.1 N aqueous KOH solution. It measured by performing titration using.
  • the weight average molecular weight was measured by a gel permeation chromatography method and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
  • GPC condition Pump Hitachi L-6000 type (manufactured by Hitachi, Ltd.) Column: 3 in total (column specifications: 10.7 mm ⁇ x 300 mm, all manufactured by Hitachi Chemical Co., Ltd.) Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 Eluent: Tetrahydrofuran Sample concentration: 120 mg of a binder polymer having a solid content of 50% by mass was sampled and dissolved in 5 mL of tetrahydrofuran to prepare a sample. Measurement temperature: 25 ° C Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)
  • the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 were obtained by mixing the components shown in Table 1 and Table 2 in the amounts shown in the table (unit: parts by mass). It was.
  • the compounding quantity of (A) component in Table 1 and Table 2 and (B) component all are compounding quantities in solid content.
  • the total content of the polymerization inhibitors (methoquinone and the like) contained in the component (B) is based on the total solid content of the components (A) and (B) (100 % By mass) is less than 0.01% by mass.
  • Photopolymerization initiator * 6 B-CIM (Hodogaya Chemical Co., Ltd., product name) 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole
  • the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 obtained above were each formed on a polyethylene terephthalate film (product name “FB40” manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m (support). It apply
  • FB40 polyethylene terephthalate film
  • a polypropylene film (protective layer) (manufactured by Tamapoly Co., Ltd., product name “NF-15”) is bonded onto the photosensitive resin layer, and the support, the photosensitive resin layer, and the protective layer are laminated in this order. A photosensitive element was obtained.
  • the copper surface of a copper-clad laminate (substrate, manufactured by Hitachi Chemical Co., Ltd., product name “MCL-E-67”), which is a glass epoxy material in which copper foil with a thickness of 12 ⁇ m is laminated on both sides, is equipped with a brush equivalent to # 600 Polishing was performed using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, and dried with an air flow.
  • the polished copper-clad laminate was heated to 80 ° C., and the photosensitive element obtained above was laminated to the copper-clad laminate so that the photosensitive resin layer was in contact with the copper surface while peeling off the protective layer. .
  • Lamination was performed using a 110 ° C. heat roll at a pressure of 0.40 MPa and a roll speed of 1.5 m / min.
  • Exposure is photosensitive with an energy amount (exposure amount) of 100 mJ / cm 2 using a projection exposure apparatus (product name “UX-2240SMXJ-01” manufactured by USHIO INC.) Using a semiconductor laser having a wavelength of 365 nm as a light source. The resin layer was exposed. At this time, other areas not used were covered with a black sheet.
  • the support is peeled off from the test piece, and the photosensitive resin layer is subjected to twice the shortest development time (the shortest time during which the unexposed area is removed) using a 1.0 mass% sodium carbonate aqueous solution at 30 ° C. Spray development was performed over time, and the unexposed area was removed and development processing was performed. In addition, the said shortest development time was calculated
  • step number the number of remaining steps (step number) of the step tablet of the photocured product (resist pattern) formed on the copper clad laminate at each exposure amount was measured.
  • a calibration curve between the exposure amount and the step step number was prepared, and the exposure amount (unit: mJ / cm 2 ) at which the step step number was 11 was obtained, and was used as the photosensitivity of the photosensitive resin composition. The smaller the exposure amount, the better the photosensitivity. The results are shown in Tables 3 and 4.
  • a projection exposure apparatus product name “UX-2240SMXJ-01” manufactured by USHIO INC.
  • a glass mask and a semiconductor laser having a wavelength of 365 nm as the light source
  • the content of the polymerization inhibitor is 0.03 to 0.3 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) and (B). It was confirmed that the resist patterns formed using the photosensitive resin compositions of Examples 1 to 9 were superior in resolution and higher in aspect ratio than Comparative Examples 1 to 7.
  • the photosensitive resin compositions of Examples 1 to 9 have a higher exposure amount and lower sensitivity than the photosensitive resin compositions of Comparative Examples 1 to 7, but this reduction in sensitivity is not necessarily inferior characteristics. In other words, it can be said that the photosensitivity range is suitable for the market demand in the field of semiconductor packages.
  • the resolution ranges from 6 to 7 ⁇ m (comparative example) to 4 It can be said that the effect of improving the thickness to ⁇ 5 ⁇ m (Example) is a very large effect.
  • the content of the polymerization inhibitor is (A) and
  • the photosensitive resin compositions of Examples 1 to 9, which are 0.03 to 0.3 parts by mass with respect to 100 parts by mass of the total solid content of the component (B), can achieve resolution regardless of the type of photosensitizer. It was confirmed that a resist pattern having excellent aspect ratio was obtained.
  • a photosensitive resin composition capable of forming a resist pattern with excellent resolution and a high aspect ratio, and a photosensitive resin using the same. It is possible to provide a conductive element, a resist pattern forming method, and a printed wiring board manufacturing method.
  • SYMBOLS 1 ... Photosensitive element, 2 ... Support, 3,30 ... Photosensitive resin layer, 4 ... Protective layer, 32 ... Resist pattern, 40 ... Conductor layer, 42 ... Conductor layer after an etching process, 50 ... Insulating layer, 60 ... Plating layer, 62 ... Plating layer after etching treatment, 70 ... Conductor pattern, 80 ... Actinic ray.

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  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)
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WO2022030053A1 (ja) * 2020-08-07 2022-02-10 昭和電工マテリアルズ株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法

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