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WO2025070065A1 - Composition de résine photosensible, élément photosensible, procédé de formation de motif de résine photorésine et procédé de fabrication de substrat de câblage - Google Patents

Composition de résine photosensible, élément photosensible, procédé de formation de motif de résine photorésine et procédé de fabrication de substrat de câblage Download PDF

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Publication number
WO2025070065A1
WO2025070065A1 PCT/JP2024/032544 JP2024032544W WO2025070065A1 WO 2025070065 A1 WO2025070065 A1 WO 2025070065A1 JP 2024032544 W JP2024032544 W JP 2024032544W WO 2025070065 A1 WO2025070065 A1 WO 2025070065A1
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WIPO (PCT)
Prior art keywords
mass
meth
photosensitive
resin composition
acrylate
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PCT/JP2024/032544
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English (en)
Japanese (ja)
Inventor
裕亮 坂下
茜 大野
敬司 小野
真生 成田
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Resonac Corp
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Resonac Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • 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

  • This disclosure relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a wiring board.
  • photosensitive resin compositions and photosensitive elements comprising a layer formed on a support using the photosensitive resin composition (hereinafter also referred to as a "photosensitive layer”) are widely used as resist materials used in etching or plating processes.
  • the wiring board is manufactured, for example, by the following procedure. First, the photosensitive layer of the photosensitive element is laminated onto the circuit-forming substrate (photosensitive layer formation process). Next, a predetermined portion of the photosensitive layer is exposed to light to form a photocured portion (exposure process). At this time, the support is peeled off before or after exposure. Thereafter, the area of the photosensitive layer other than the photocured portion is removed from the substrate, and a resist pattern, which is a cured product of the photosensitive resin composition, is formed on the substrate (development process). Next, the obtained resist pattern is used as a resist and subjected to etching or plating to form a conductor pattern on the substrate (circuit formation process), and finally the resist is peeled off and removed (peeling process).
  • a conventional exposure method is to use a mercury lamp as the light source and expose through a photomask.
  • a direct imaging exposure method called LDI Laser Direct Imaging
  • LDI Laser Direct Imaging
  • This direct imaging exposure method has better alignment accuracy than exposure methods that use a photomask, and can produce highly detailed patterns, so it is being introduced for the production of high-density packaging boards.
  • Patent Document 1 discloses a photosensitive resin composition that uses a specific photosensitizer to provide excellent sensitivity and resolution.
  • Patent Document 2 discloses a photosensitive resin composition that uses a specific alkali-soluble polymer and a compound having an ethylenic double bond to provide excellent sensitivity and resolution.
  • photosensitive resin compositions are required to form resist patterns such as via hole patterns with high resolution, for example to form copper pillars that connect IC chips and wiring boards for semiconductor packages.
  • resist patterns such as via hole patterns with high resolution
  • the thicker the photosensitive layer formed using a photosensitive resin composition the more difficult it is to cure uniformly to the bottom, making it difficult to form a resist pattern with sufficient resolution and adhesion.
  • resist patterns with excellent adhesion tend to take a long time to peel off. Therefore, photosensitive resin compositions are required to form resist patterns with excellent adhesion and resolution, as well as to have excellent peelability after curing.
  • the present disclosure aims to provide a photosensitive resin composition that is excellent in resolution, adhesion, and peelability, a photosensitive element that uses the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a wiring board.
  • a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a sensitizer, wherein the photopolymerizable compound contains a monofunctional (meth)acrylate having a bicyclo skeleton, and the content of the monofunctional (meth)acrylate having a bicyclo skeleton is less than 5.0 parts by mass per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.
  • a photosensitive element comprising a support and a photosensitive layer formed on the support using the photosensitive resin composition according to any one of [1] to [4] above.
  • a method for forming a resist pattern comprising the steps of: forming a photosensitive layer on a substrate using the photosensitive element described in [6] above; irradiating at least a portion of the photosensitive layer with active light to form a photocured portion; and removing an unphotocured portion of the photosensitive layer from the substrate to form a resist pattern.
  • a method for producing a wiring board comprising the step of etching or plating a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to [7] above to form a conductor pattern.
  • the present disclosure provides a photosensitive resin composition that is excellent in resolution, adhesion, and peelability, a photosensitive element that uses the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a wiring board.
  • FIG. 1 is a schematic cross-sectional view illustrating one embodiment of a photosensitive element.
  • the term “process” includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.
  • the term “layer” includes structures that are formed on the entire surface as well as structures that are formed on a portion of the surface when observed in a plan view.
  • a numerical range indicated using “ ⁇ ” indicates a range that includes the numerical values before and after " ⁇ " as the minimum and maximum values, respectively.
  • the upper or lower limit of a numerical range of a certain stage may be replaced by the upper or lower limit of a numerical range of another stage.
  • the upper or lower limit of the numerical range may be replaced by the values shown in the examples.
  • (meth)acrylate means at least one of "acrylate” and its corresponding “methacrylate”.
  • EO refers to ethylene oxide
  • EO-modified compound refers to a compound having an oxyethylene group
  • PO refers to propylene oxide
  • a "PO-modified” compound refers to a compound having an oxypropylene group.
  • the amount of each component in a photosensitive resin composition means the total amount of the multiple substances present in the composition when the composition contains multiple substances corresponding to each component, unless otherwise specified.
  • solid content refers to the non-volatile content in the photosensitive resin composition excluding volatile substances (water, solvent, etc.).
  • solid content refers to components other than the solvent that do not volatilize and remain when the photosensitive resin composition is dried, as described below, and includes components that are liquid, syrup-like, or waxy at room temperature (25°C).
  • the photosensitive resin composition according to the present embodiment contains (A) a binder polymer (hereinafter, sometimes referred to as "(A) component”); (B) a photopolymerizable compound (hereinafter, sometimes referred to as “(B) component”); (C) a photopolymerization initiator (hereinafter, sometimes referred to as “(C) component”); and (D) a sensitizer (hereinafter, sometimes referred to as "(D) component”).
  • A a binder polymer
  • (B) a photopolymerizable compound hereinafter, sometimes referred to as "(B) component”
  • C a photopolymerization initiator
  • D a sensitizer
  • the photopolymerizable compound contains a monofunctional (meth)acrylate having a bicyclo skeleton, and the content of the monofunctional (meth)acrylate having a bicyclo skeleton in the photosensitive resin composition is less than 5.0 parts by mass relative to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.
  • the photosensitive resin composition according to the present embodiment contains such a specific photopolymerizable compound in a specific range, and is therefore excellent in resolution, adhesion and peelability, and can be suitably used for thick film applications. Each component will be described below.
  • the photosensitive resin composition contains one or more kinds of component (A).
  • component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, and phenol resins.
  • Component (A) may contain an acrylic resin from the viewpoint of alkaline developability.
  • the acrylic resin is a resin having a structural unit (monomer unit) derived from a (meth)acryloyl group-containing compound.
  • the (meth)acryloyl group-containing compound is a compound that contains a (meth)acryloyl group.
  • examples of the (meth)acryloyl group-containing compound include hydroxyalkyl (meth)acrylate, (meth)acrylic acid, (meth)acrylic acid alkyl ester, (meth)acrylic acid aryl ester, (meth)acrylic acid cycloalkyl ester, acrylamide such as diacetone acrylamide, (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, ⁇ -bromoacrylic acid, ⁇ -chloroacryl
  • the acrylic resin may be, for example, a polymer (a) having at least one unit selected from the group consisting of (meth)acrylic acid units, (meth)acrylic acid alkyl ester units, (meth)acrylic acid aryl ester units, and hydroxyalkyl (meth)acrylate units.
  • the (meth)acrylic acid unit is a structural unit derived from (meth)acrylic acid.
  • the content of the (meth)acrylic acid unit may be 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total amount of monomer units constituting polymer (a) (100% by mass), from the viewpoint of resolution and adhesion, and may be 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less.
  • the (meth)acrylic acid alkyl ester unit is a structural unit derived from a (meth)acrylic acid alkyl ester.
  • the alkyl group of the (meth)acrylic acid alkyl ester may be, for example, 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, a undecyl group, a dodecyl group, or a structural isomer thereof, and from the viewpoint of peelability, may be an alkyl group having 1 to 4 carbon atoms.
  • the content of the (meth)acrylic acid alkyl ester units may be 1 mass % or more, 2 mass % or more, or 3 mass % or more based on the total amount of monomer units constituting polymer (a) from the viewpoint of peelability, and may be 30 mass % or less, 20 mass % or less, 10 mass % or less, or 8 mass % or less from the viewpoint of resolution and adhesion.
  • the (meth)acrylic acid aryl ester unit is a structural unit derived from an (meth)acrylic acid aryl ester.
  • Examples of the (meth)acrylic acid aryl ester include benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate.
  • the content of the (meth)acrylic acid aryl ester unit may be 5 mass% or more, 10 mass% or more, 15 mass% or more, or 20 mass% or more, and may be 40 mass% or less, 35 mass% or less, 30 mass% or less, or 25 mass% or less, based on the total amount of the monomer units constituting the polymer (a), from the viewpoint of resolution and adhesion.
  • Hydroxyalkyl (meth)acrylate units are structural units derived from hydroxyalkyl (meth)acrylates.
  • hydroxyalkyl (meth)acrylates include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and hydroxyhexyl (meth)acrylate.
  • the hydroxyalkyl (meth)acrylate unit when the number of carbon atoms in the alkyl portion is 3 or more, it may have a branched structure.
  • the content of the hydroxyalkyl (meth)acrylate units may be 0.5% by mass or more, 0.75% by mass or more, or 1.0% by mass or more based on the total amount of monomer units constituting polymer (a) from the viewpoint of dispersibility, and may be 20% by mass or less, 15% by mass or less, or 8% by mass or less from the viewpoint of water absorbency.
  • the polymer (a) may have structural units derived from styrene or a styrene derivative (hereinafter also referred to as "styrene-based units") in order to further improve the resolution and adhesion of the photosensitive resin composition.
  • styrene-based units structural units derived from styrene or a styrene derivative (hereinafter also referred to as "styrene-based units") in order to further improve the resolution and adhesion of the photosensitive resin composition.
  • styrene derivatives include vinyl toluene, ⁇ -methyl styrene, p-methyl styrene, and p-ethyl styrene.
  • the content of the styrene-based units may be 35% by mass or more, 40% by mass or more, 43% by mass or more, or 45% by mass or more based on the total amount of monomer units constituting polymer (a) from the viewpoint of resolution, and may be 70% by mass or less, 60% by mass or less, 50% by mass or less, or 48% by mass or less from the viewpoint of developability.
  • Polymer (a) may further have structural units derived from other monomers in addition to those mentioned above.
  • examples of other monomers include acrylonitrile, vinyl alcohol ethers such as vinyl n-butyl ether, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.
  • the (A) component may contain a binder polymer other than the polymer (a), or may consist of only the polymer (a). From the viewpoints of adhesion and resolution, the content of the polymer (a) in the (A) component may be 50 to 100% by mass, or 80 to 100% by mass, based on the total amount of the (A) component.
  • the acid value of the polymer (a) may be 100 mgKOH/g or more, 120 mgKOH/g or more, 140 mgKOH/g or more, 150 mgKOH/g or more, 160 mgKOH/g or more, or 170 mgKOH/g or more from the viewpoint of developability, and may be 250 mgKOH/g or less, 240 mgKOH/g or less, 230 mgKOH/g or less, 200 mgKOH/g or less, or 190 mgKOH/g or less from the viewpoint of adhesion (resistance to developing solution) of the cured product of the photosensitive resin composition.
  • the acid value of the polymer (a) can be adjusted by the content of the structural unit (e.g., (meth)acrylic acid unit) constituting the polymer (a).
  • the acid value of the other binder polymer may also be within the above range.
  • the weight average molecular weight (Mw) of the polymer (a) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, 35,000 or more, 40,000 or more, or 45,000 or more from the viewpoint of adhesion (resistance to developing solution) of the cured product of the photosensitive resin composition and ease of forming a thick-film resist pattern, and may be 100,000 or less, 80,000 or less, 60,000 or less, or 50,000 or less from the viewpoint of developability.
  • the dispersity (Mw/Mn) of the polymer (a) may be, for example, 1.0 or more or 1.5 or more, and may be 3.0 or less or 2.5 or less from the viewpoint of adhesion and resolution.
  • the Mw of the other binder polymer may also be within the above range.
  • the weight average molecular weight and dispersity can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, they can be measured under the conditions described in the Examples. For compounds with low molecular weights, if it is difficult to measure the weight average molecular weight using the above-mentioned method, the molecular weight can be measured using another method and the average calculated.
  • GPC gel permeation chromatography
  • the content of component (A) may be 20% by mass or more, 30% by mass or more, or 40% by mass or more based on the total solid content of the photosensitive resin composition from the viewpoint of film formability, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 65% by mass or less from the viewpoint of sensitivity and resolution.
  • the content of the (A) component may be 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more, based on 100 parts by mass of the total amount of the (A) component and the (B) component, from the viewpoint of film formability, and may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less, based on the viewpoint of sensitivity and resolution.
  • the photosensitive resin composition contains, as the component (B), a monofunctional (meth)acrylate having a bicyclo skeleton (hereinafter also referred to as "component (b1)") from the viewpoint of releasability, and, from the viewpoints of adhesion and resolution, the content of the component (b1) is less than 5.0 parts by mass per 100 parts by mass of the total amount of the component (A) and the component (B).
  • component (b1) a monofunctional (meth)acrylate having a bicyclo skeleton
  • Examples of the (b1) component include dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
  • the content of component (b1) may be 1.0 to 4.5 parts by mass, 1.5 to 4.0 parts by mass, 2.0 to 3.5 parts by mass, or 2.5 to 3.3 parts by mass per 100 parts by mass of the total amount of components (A) and (B), from the viewpoint of achieving both adhesion, resolution, and releasability.
  • the (B) component may contain a bifunctional (meth)acrylate (hereinafter also referred to as "(b2) component”), which is a compound having two (meth)acryloyl groups.
  • the (b2) component include bisphenol A type (meth)acrylates such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and EO-modified polypropylene glycol di(meth)acrylate; and
  • the (b2) component is preferably bisphenol A type (meth)acrylate, and more preferably 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane.
  • the content of the (b2) component may be 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, or 35 parts by mass or more, and may be 65 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less, relative to 100 parts by mass of the total amount of the (A) component and the (B) component.
  • the content of the (b2) component may be 20 to 65 parts by mass, 25 to 60 parts by mass, 30 to 50 parts by mass, or 35 to 45 parts by mass, relative to 100 parts by mass of the total amount of the (A) component and the (B) component.
  • the (B) component may further contain a compound having three or more (meth)acryloyl groups (hereinafter also referred to as the "(b3)" component).
  • the (b3) component include trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO-PO-modified trimethylolpropane tri(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, EO-modified ditrimethylolpropane tetra(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and tetramethylolmethane tetra(meth)acrylate.
  • the content of the (b3) component may be 1 mass% or more, 5 mass% or more, or 10 mass% or more, and may be 25 mass% or less, 20 mass% or less, or 15 mass% or less, based on the total amount of the (B) component.
  • the photosensitive resin composition may further contain, as component (B), a photopolymerizable compound other than the above-mentioned components (b1), (b2), and (b3).
  • photopolymerizable compounds include, for example, urethane monomers, nonylphenoxypolyethyleneoxy(meth)acrylates, phthalic acid compounds, (meth)acrylic acid alkyl esters, and photopolymerizable compounds having at least one cationic polymerizable cyclic ether group in the molecule (such as oxetane compounds).
  • the other photopolymerizable compounds may be at least one selected from the group consisting of urethane monomers, nonylphenoxypolyethyleneoxy(meth)acrylates, and phthalic acid compounds.
  • nonylphenoxy polyethyleneoxy (meth)acrylates examples include nonylphenoxy triethyleneoxy (meth)acrylate, nonylphenoxy tetraethyleneoxy (meth)acrylate, nonylphenoxy pentaethyleneoxy (meth)acrylate, nonylphenoxy hexaethyleneoxy (meth)acrylate, nonylphenoxy heptaethyleneoxy (meth)acrylate, nonylphenoxy octaethyleneoxy (meth)acrylate, nonylphenoxy nonaethyleneoxy (meth)acrylate, nonylphenoxy decaethyleneoxy (meth)acrylate, and nonylphenoxy undecaethyleneoxy (meth)acrylate.
  • phthalic acid compounds include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate (also known as 3-chloro-2-hydroxypropyl-2-(meth)acryloyloxyethyl phthalate), ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate, and ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate.
  • ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate also known as 3-chloro-2-hydroxypropyl-2-(meth)acryloyloxyethyl phthalate
  • ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate also known as 3-chloro-2-hydroxypropyl-2-(meth
  • the content of component (B) may be 3% by mass or more, 10% by mass or more, or 25% by mass or more based on the total solid content of the photosensitive resin composition from the viewpoints of sensitivity and resolution, and may be 70% by mass or less, 60% by mass or less, or 50% by mass or less from the viewpoint of film formability.
  • the photosensitive resin composition contains one or more kinds of component (C).
  • the component (C) is not particularly limited as long as it is a component that can polymerize component (B), and can be appropriately selected from commonly used photopolymerization initiators.
  • Examples of the (C) component include hexaarylbiimidazole compounds; aromatic ketone compounds such as benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; alkyl aryl ketones; These include quinone compounds such as tribenzone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyl dimethyl ketal; and phosphine oxide compounds such as bis(2,4,6-trimethylbenzo
  • Component (C) may contain a hexaarylbiimidazole compound from the viewpoint of improving the adhesion of the photosensitive layer to a smooth substrate.
  • the aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like.
  • the hydrogen atom bonded to the aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (such as a chlorine atom).
  • the hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer.
  • 2,4,5-triarylimidazole dimer examples include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.
  • the content of component (C) may be 1.0 to 10 parts by mass, 2.0 to 8 parts by mass, 3.0 to 7.0 parts by mass, or 4.0 to 6.0 parts by mass, per 100 parts by mass of the total amount of components (A) and (B). When the content of component (C) is within this range, it becomes easy to improve both photosensitivity and resolution in a well-balanced manner.
  • the photosensitive resin composition according to this embodiment contains the component (D), so that the absorption wavelength of the actinic radiation used for exposure can be effectively utilized.
  • component (D) examples include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
  • Component (D) may contain an anthracene compound from the viewpoint of further improving resolution and adhesion.
  • anthracene compounds include 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-diethoxyanthracene. From the viewpoints of sensitivity, adhesion, resolution, and strippability, the anthracene compound may include 9,10-dibutoxyanthracene.
  • the content of the (D) component may be 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more, or 0.5 parts by mass or more, and may be 1.5 parts by mass or less, 1.0 parts by mass or less, 0.8 parts by mass or less, 0.75 parts by mass or less, or 0.7 parts by mass or less, relative to 100 parts by mass of the total amount of the (A) component and the (B) component.
  • the photosensitive resin composition may further contain one or more other components other than the above-mentioned components.
  • the other components include a polymerization inhibitor, a hydrogen donor (bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet, N-phenylglycine, etc.), a dye (malachite green, etc.), tribromophenyl sulfone, a photocoloring agent, a thermal coloring inhibitor, a plasticizer (p-toluenesulfonamide, etc.), a pigment, a filler, a defoamer, a flame retardant, a stabilizer, an adhesion imparting agent, a leveling agent, a peeling promoter, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent.
  • the content of the other components may be 0.005 parts by mass or more or 0.01 parts
  • the photosensitive resin composition may contain an organic solvent to improve the handling properties of the photosensitive composition and to adjust the viscosity and storage stability.
  • an organic solvent any commonly used organic solvent may be used without any particular restrictions.
  • the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether.
  • the components (A) to (D) may be dissolved in an organic solvent to prepare a solution having a solid content of about 30 to 60% by mass.
  • the photosensitive resin composition according to this embodiment may be in a liquid form or in a film form (photosensitive film).
  • the photosensitive resin composition may be used, for example, as a negative-type photosensitive resin composition.
  • the photosensitive resin composition may be suitably used in the method for forming a resist pattern and the method for manufacturing a wiring board, which will be described later.
  • the photosensitive element of this embodiment includes a support and a photosensitive layer formed on the support, and the photosensitive layer contains the above-mentioned photosensitive resin composition.
  • the content of each component (components (A) to (D) and other components) other than the volatile substance in the photosensitive layer may be within the numerical range of the content of each component in the above-mentioned photosensitive resin composition.
  • FIG. 1 is a schematic cross-sectional view of a photosensitive element according to one embodiment.
  • the photosensitive element 1 comprises a support 2, a photosensitive layer 3 derived from the photosensitive resin composition formed on the support 2, and other layers such as a protective layer 4 that are provided as necessary.
  • the support 2 and the protective layer 4 may each be a polymer film having heat resistance and solvent resistance, for example, a polyester film such as a polyethylene terephthalate film, a polyethylene film, a polyolefin film such as a polypropylene film, etc.
  • the support 2 and the protective layer 4 may each be a film of a hydrocarbon-based polymer other than polyolefin.
  • the film of a hydrocarbon-based polymer containing polyolefin may have a low density, for example, a density of 1.014 g/cm 3 or less.
  • the support 2 and the protective layer 4 may each be a stretched film obtained by stretching the low-density hydrocarbon-based polymer film.
  • the type of the polymer film constituting the protective layer 4 may be the same as or different from the type of the polymer film constituting the support 2.
  • polymer films can be purchased, for example, as polyethylene terephthalate films such as the PS series (e.g., PS-25) manufactured by Teijin Limited, polyethylene films such as NF-15 manufactured by Tamapoly Co., Ltd., or polypropylene films manufactured by Oji Paper Co., Ltd. (e.g., Alphan MA-410, E-200C) and Shin-Etsu Film Co., Ltd.
  • PS series e.g., PS-25
  • polyethylene films such as NF-15 manufactured by Tamapoly Co., Ltd.
  • polypropylene films manufactured by Oji Paper Co., Ltd. e.g., Alphan MA-410, E-200C
  • the thickness of the support 2 may be 1 ⁇ m or more or 5 ⁇ m or more from the viewpoint of suppressing damage to the support 2 when peeling the support 2 from the photosensitive layer 3, and may be 100 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less from the viewpoint of suitable exposure even when exposure is performed through the support 2.
  • the thickness of the protective layer 4 may be 1 ⁇ m or more, 5 ⁇ m or more, or 15 ⁇ m or more from the viewpoint of suppressing damage to the protective layer 4 when the photosensitive layer 3 and the support 2 are laminated onto the substrate while the protective layer 4 is peeled off, and may be 100 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less from the viewpoint of improving productivity.
  • the photosensitive layer 3 is made of the photosensitive resin composition described above.
  • the thickness of the photosensitive layer 3 after drying may be 30 to 100 ⁇ m. From the viewpoint of forming a resist pattern with a high aspect ratio, the thickness of the photosensitive layer may be 30 ⁇ m or more, 35 ⁇ m or more, 38 ⁇ m or more, 40 ⁇ m or more, or 50 ⁇ m or more, and from the viewpoint of peelability, it may be 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, or 60 ⁇ m or less.
  • the photosensitive element 1 can be obtained, for example, as follows. First, a photosensitive layer 3 is formed on a support 2. The photosensitive layer 3 can be formed, for example, by applying a photosensitive resin composition containing an organic solvent to form a coating layer, and then drying this coating layer. Next, a protective layer 4 is formed on the surface of the photosensitive layer 3 opposite the support 2.
  • the coating layer is formed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, etc.
  • the coating layer is dried so that the amount of organic solvent remaining in the photosensitive layer 3 is, for example, 2 mass% or less, and specifically, for example, at 70 to 150°C for about 5 to 30 minutes.
  • the photosensitive element may further include an intermediate layer between the support 2 and the photosensitive layer 3.
  • the intermediate layer may be a layer containing a water-soluble resin.
  • An example of the water-soluble resin is a resin containing polyvinyl alcohol as a main component.
  • the photosensitive element may not include a protective layer, and may further include other layers, such as a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer, etc.
  • the photosensitive element 1 may be, for example, in the form of a sheet, or may be in the form of a photosensitive element roll wound around a core. In the photosensitive element roll, the photosensitive element 1 is preferably wound with the support 2 on the outside.
  • the core is formed of, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, or the like.
  • An end separator may be provided on the end surface of the photosensitive element roll from the viewpoint of end surface protection, and a moisture-proof end surface separator may be provided from the viewpoint of edge fusion resistance.
  • the photosensitive element 1 may be wrapped, for example, in a black sheet with low moisture permeability.
  • the photosensitive element 1 can be suitably used to form a resist pattern, and can be particularly suitably used in the method for manufacturing a printed wiring board described below.
  • the method for forming a resist pattern of this embodiment includes a step of forming a photosensitive layer on a substrate using the photosensitive resin composition or the photosensitive element (photosensitive layer forming step), a step of irradiating at least a part (predetermined part) of the photosensitive layer with active light to form a photocured part (exposure step), and a step of removing at least a part of the uncured part from the substrate (development step), and may include other steps as necessary.
  • the resist pattern can be said to be a photocured product pattern of the photosensitive resin composition or a relief pattern.
  • the method for forming a resist pattern can also be said to be a method for manufacturing a substrate with a resist pattern.
  • the method of forming the photosensitive layer on the substrate may be, for example, coating and drying the photosensitive resin composition, or removing the protective layer from the photosensitive element, and then pressing the photosensitive layer of the photosensitive element onto the substrate while heating.
  • a laminate consisting of a substrate, a photosensitive layer, and a support, which are laminated in order, is obtained.
  • the substrate is not particularly limited, but is usually a circuit-forming substrate having an insulating layer and a conductor layer formed on the insulating layer, or a die pad (substrate for lead frame) such as an alloy substrate.
  • the surface roughness (Ra) of the substrate may be 200 nm or less, 180 nm or less, or 160 nm or less from the viewpoint of suppressing halation due to unevenness of the substrate and improving resolution, and may be 10 nm or more, 30 nm or more, or 40 nm or more from the viewpoint of improving adhesion of the resist pattern.
  • Ra may be 10 to 200 nm, 30 to 180 nm, or 40 to 160 nm from the viewpoint of maintaining a balance between resolution and adhesion.
  • the photosensitive layer forming step is preferably carried out under reduced pressure from the viewpoint of adhesion and followability.
  • the photosensitive layer and/or the substrate may be heated at a temperature of 70 to 130° C. during pressure bonding.
  • the pressure bonding may be carried out at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm 2 ), and these conditions are appropriately selected as necessary. If the photosensitive layer is heated to 70 to 130° C., it is not necessary to preheat the substrate in advance, but the substrate may be preheated in order to further improve adhesion and followability.
  • the exposure step at least a part of the photosensitive layer formed on the substrate is irradiated with active light rays, whereby the part irradiated with the active light rays is photocured to form a latent image.
  • the active light rays can be irradiated through the support, but if the support is light-shielding, the support is removed before the photosensitive layer is irradiated with the active light rays.
  • Examples of exposure methods include a method of irradiating active light rays in an image-wise manner through a negative or positive mask pattern called artwork (mask exposure method).
  • a method of irradiating active light rays in an image-wise manner by a projection exposure method may also be used.
  • a method of irradiating active light rays in an image-wise manner by a direct imaging exposure method such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method may also be used.
  • the light source for the actinic rays can be any known light source, including, for example, carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid-state lasers such as YAG lasers, and semiconductor lasers that effectively emit ultraviolet light and visible light.
  • (Developing process) In the development process, at least a part of the uncured portion (other than the photocured portion) of the photosensitive layer is removed from the substrate, thereby forming a resist pattern on the substrate. If a support is present on the photosensitive layer, the support is removed, and then the area other than the photocured portion (also called the unexposed portion) is removed (developed).
  • development methods wet development and dry development, and wet development is widely used.
  • development is performed by a known development method using a developer that is compatible with the photosensitive resin composition.
  • development methods include the dip method, paddle method, spray method, brushing, scrubbing, and rocking immersion. From the viewpoint of improving resolution, the high-pressure spray method may be used as the development method. Development may be performed by combining two or more of these methods.
  • the composition of the developer is appropriately selected depending on the composition of the photosensitive resin composition.
  • the developer include an alkaline aqueous solution and an organic solvent developer.
  • an alkaline aqueous solution may be used as the developer.
  • bases for alkaline aqueous solutions include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonates or bicarbonates; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, and morpholine.
  • the alkaline aqueous solution used for development may be a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, a dilute solution of 0.1 to 5% by mass sodium hydroxide, or a dilute solution of 0.1 to 5% by mass sodium tetraborate.
  • the pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature can be adjusted according to the alkaline developability of the photosensitive layer.
  • a surfactant, an antifoaming agent, or a small amount of an organic solvent to promote development may be mixed into the alkaline aqueous solution.
  • organic solvents used in alkaline aqueous solutions include acetone, ethyl acetate, alkoxyethanols with an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
  • organic solvents used in organic solvent developers include 1,1,1-trichloroethane, N-methyl-2-pyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone.
  • water may be added to these organic solvents in a range of 1 to 20% by weight to form an organic solvent developer.
  • the method for forming a resist pattern in this embodiment may include a step of further curing the resist pattern by heating at about 60 to 250° C. or exposing to light at about 0.2 to 10 J/cm 2 , as necessary, after removing the uncured portions in the development step.
  • the method for manufacturing a wiring board of this embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern has been formed using the above-mentioned resist pattern forming method, and may also include other steps, such as a resist pattern removal step, as necessary.
  • the resist pattern formed on the substrate is used as a mask to etch away the conductive layer provided on the substrate, forming a conductive pattern.
  • the etching method is appropriately selected depending on the conductive layer to be removed. Examples of etching solutions include cupric chloride solution, ferric chloride solution, alkaline etching solution, and hydrogen peroxide-based etching solution.
  • the conductor layer provided on the substrate is plated using the resist pattern formed on the substrate as a mask.
  • the resist is removed by removing the resist pattern as described below, and the conductor layer covered by the resist may be etched to form a conductor pattern.
  • the plating method may be electrolytic plating or electroless plating, or may be electroless plating.
  • the resist pattern on the substrate is removed.
  • the resist pattern can be removed, for example, by using an inorganic alkaline stripper or an organic alkaline stripper.
  • inorganic alkaline stripper include a 1-10% by mass aqueous solution of sodium hydroxide and a 1-10% by mass aqueous solution of potassium hydroxide.
  • organic alkaline stripper include an amine-based stripper such as ethanolamine, ethylenediamine, or diethylenetriamine, and an aqueous solution of tetramethylammonium hydroxide. From the viewpoint of the removability of the thick-film resist pattern, an organic alkaline stripper may also be used.
  • Methods for removing the resist pattern include, for example, the immersion method and the spray method, which may be used alone or in combination.
  • the conductor layer covered by the resist can be etched by etching to form a conductor pattern, thereby producing the desired printed wiring board.
  • the method of etching in this case is appropriately selected depending on the conductor layer to be removed.
  • the etching solution described above can be used.
  • the method for manufacturing a wiring board according to this embodiment can be applied to the manufacture of not only single-layer wiring boards, but also multi-layer wiring boards, and can also be applied to the manufacture of wiring boards with small-diameter through holes.
  • Each photosensitive resin composition was prepared by mixing the components shown in Table 1 in the amounts (parts by mass) shown in the table.
  • the amounts (parts by mass) of components other than the solvent shown in Table 1 are the masses of non-volatile matters (solid contents). Details of each component shown in Table 1 are as follows.
  • Component (A)) A-1 Ethylene glycol monomethyl ether/toluene solution (solid content: 47% by mass) of a copolymer of methacrylic acid/methyl methacrylate/styrene/benzyl methacrylate (mass ratio: 27/5/45/23, Mw: 47000, acid value: 176.1 mg KOH/g, Tg: 107° C.)
  • Component (B)) b1-1: Dicyclopentanyl acrylate (manufactured by Resonac Corporation, product name "FA-513AS”) b1-2: Dicyclopentanyl methacrylate (manufactured by Resonac Corporation, product name "FA-513M”) b1-3: Isobornyl acrylate (Osaka Organic Chemical Industry Ltd.) b2-1: 70% solution of 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (average 10 mol adduct of ethylene oxide) in propylene glyco
  • a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "FB-40") having a thickness of 16 ⁇ m was prepared as a support.
  • the photosensitive resin composition was applied onto the support and then dried in hot air convection dryers at 80° C. and 120° C. in sequence to form a photosensitive layer having a thickness of 40 ⁇ m after drying.
  • a polyethylene film (manufactured by Tamapoly Corporation, product name "NF-15”) was laminated onto the photosensitive layer as a protective layer to obtain a photosensitive element in which the support, photosensitive layer, and protective layer were laminated in that order.
  • a copper-clad laminate (manufactured by Resonac Corporation, product name "MCL-E-67") comprising a glass epoxy material and copper foil (thickness: 16 ⁇ m) arranged on both sides thereof was pickled and washed with water, and then dried with an air flow.
  • the copper-clad laminate was heated to 80°C, and then, while peeling off the protective layer, a photosensitive element was laminated onto the copper-clad laminate so that the photosensitive layer was in contact with the copper surface, thereby obtaining a laminate L1 comprising the copper-clad laminate, the photosensitive layer, and the support in that order.
  • the lamination was performed using a heat roll at 110°C, with a pressure of 0.4 MPa and a roll speed of 1.0 m/min.
  • the laminate L1 was cut into a square shape (5 cm x 5 cm), and the support was peeled off to obtain a test piece.
  • the unexposed photosensitive layer in the test piece was spray-developed at a pressure of 0.18 MPa using a 1% by mass aqueous solution of sodium carbonate at 30°C, and the shortest time at which it was possible to visually confirm that 1 mm or more of the unexposed photosensitive layer had been removed was defined as the minimum development time (MD).
  • a full cone type nozzle was used for the spray development. The distance between the test piece and the tip of the nozzle was 6 cm, and the test piece was positioned so that the center of the test piece and the center of the nozzle coincided. The shorter the minimum development time (unit: second), the better the developability.
  • a Hitachi 41-step step tablet was placed on the support of laminate L1, and the photosensitive layer was exposed through the support using a direct imaging exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name "FDi-Ms") with a blue-violet laser diode with a wavelength of 405 nm as a light source, at an exposure amount (amount of irradiation energy) that resulted in 15 remaining steps on the Hitachi 41-step step tablet.
  • the sensitivity (photosensitivity) was evaluated based on the exposure amount (unit: mJ/ cm2 ) at this time. A smaller exposure amount means higher sensitivity.
  • the support was peeled off from the laminate L1 to expose the photosensitive layer, and the unexposed areas were removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30°C for twice the minimum development time.
  • the space areas (unexposed areas) were removed without residue, and the line areas (exposed areas) were formed without meandering or chipping.
  • Resolution was evaluated based on the minimum space width (unit: ⁇ m) in the resist pattern, and adhesion was evaluated based on the minimum line width (unit: ⁇ m) in the resist pattern. For both resolution and adhesion, the smaller the numerical value, the better the result.
  • the support was peeled off from the laminate L2 to expose the photosensitive layer, and the unexposed areas were removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30°C for twice the minimum development time.
  • the formed via pattern (via hole pattern) was observed under an optical microscope, and the round hole resolution was evaluated based on the value of the smallest via pattern diameter among those that were completely removed (opened) cleanly among the via patterns arranged in a lattice pattern. The smaller this value, the better the round hole resolution.
  • a glass chrome type phototool (having a planar pattern of 45 mm ⁇ 60 mm) was used as a negative for evaluating a peel test on the support of the laminate L1, and exposure was performed on the photosensitive layer through the support using a direct imaging exposure machine (FDi-Ms) with an exposure amount such that the number of remaining steps of a Hitachi 41-step step tablet was 15.
  • FDi-Ms direct imaging exposure machine
  • the support was peeled off from the laminate L1 to expose the photosensitive layer, and a 1% by mass aqueous solution of sodium carbonate was sprayed at 30°C for twice the minimum development time to remove the unexposed areas, yielding a substrate on which a cured film had been formed.
  • This substrate was left at room temperature for 3 hours, and then immersed in an amine-based stripping solution (aqueous solution of 6% by volume R-100S + 2% by volume R-101, manufactured by Mitsubishi Gas Chemical Co., Inc.) heated to 50°C and stirred at a speed of 400 rpm.
  • the time from the start of stirring until the cured film was completely removed from the substrate was taken as the stripping time (unit: seconds). A shorter stripping time means better strippability.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

Une composition de résine photosensible selon la présente invention contient un polymère liant, un composé photopolymérisable, un initiateur de photopolymérisation et un sensibilisateur. Le composé photopolymérisable contient un (méth)acrylate monofonctionnel ayant un squelette bicyclo. La quantité contenue du (méth)acrylate monofonctionnel ayant un squelette bicyclo est inférieure à 5,0 parties en masse par rapport à 100 parties en masse de la quantité totale du polymère liant et du composé photopolymérisable.
PCT/JP2024/032544 2023-09-29 2024-09-11 Composition de résine photosensible, élément photosensible, procédé de formation de motif de résine photorésine et procédé de fabrication de substrat de câblage Pending WO2025070065A1 (fr)

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Citations (1)

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Publication number Priority date Publication date Assignee Title
JP2006308701A (ja) * 2005-04-26 2006-11-09 Fuji Photo Film Co Ltd パターン形成材料、並びにパターン形成装置及びパターン形成方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006308701A (ja) * 2005-04-26 2006-11-09 Fuji Photo Film Co Ltd パターン形成材料、並びにパターン形成装置及びパターン形成方法

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