WO2025115078A1 - 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 - Google Patents

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 Download PDF

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WO2025115078A1
WO2025115078A1 PCT/JP2023/042403 JP2023042403W WO2025115078A1 WO 2025115078 A1 WO2025115078 A1 WO 2025115078A1 JP 2023042403 W JP2023042403 W JP 2023042403W WO 2025115078 A1 WO2025115078 A1 WO 2025115078A1
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Prior art keywords
mass
resin composition
photosensitive
photosensitive resin
resist pattern
Prior art date
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PCT/JP2023/042403
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English (en)
French (fr)
Japanese (ja)
Inventor
夏木 戸田
琢 澤木
謙介 吉原
陽介 賀口
博史 小野
祐作 渡邉
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Resonac Corp
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Resonac Corp
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Application filed by Resonac Corp filed Critical Resonac Corp
Priority to PCT/JP2023/042403 priority Critical patent/WO2025115078A1/ja
Priority to JP2025561100A priority patent/JPWO2025115821A1/ja
Priority to CN202480011248.XA priority patent/CN120641826A/zh
Priority to KR1020257026946A priority patent/KR20250133781A/ko
Priority to PCT/JP2024/041692 priority patent/WO2025115821A1/ja
Priority to EP24897506.2A priority patent/EP4692935A1/en
Priority to TW113145511A priority patent/TW202530869A/zh
Publication of WO2025115078A1 publication Critical patent/WO2025115078A1/ja
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/20—Exposure; Apparatus 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
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists
    • 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
    • H05K3/108—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 by semi-additive methods; masks 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
    • H05K3/10—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
    • H05K3/181—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 by electroless plating
    • H05K3/182—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 by electroless plating characterised by the patterning method
    • H05K3/184—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 by electroless plating characterised by the patterning method using masks

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 printed wiring board.
  • photosensitive resin compositions and photosensitive elements comprising a support and a layer formed on the support using the photosensitive resin composition (hereinafter also referred to as the "photosensitive layer") are widely used as resist materials used in etching or plating processes.
  • Printed wiring boards are manufactured, for example, using the above-mentioned photosensitive element in the following procedure.
  • the photosensitive layer of the photosensitive element is laminated onto a circuit-forming substrate such as a copper-clad laminate.
  • a predetermined portion of the photosensitive layer is exposed to light through a photomask to form a photocured portion.
  • the support is peeled off before or after exposure.
  • areas of the photosensitive layer other than the photocured portion are removed with a developer to form a resist pattern on the substrate.
  • the resist pattern is used as a resist to perform an etching process or a plating process to form a conductor pattern on the substrate, and finally the resist is peeled off and removed.
  • the present disclosure aims to provide a photosensitive resin composition and photosensitive element that are excellent in sensitivity, developability, and adhesion, as well as a method for forming a resist pattern and a method for manufacturing a printed wiring board using the same.
  • one aspect of the present disclosure relates to the following photosensitive resin composition, photosensitive element, method for forming a resist pattern, and method for producing a printed wiring board.
  • a photosensitive resin composition comprising a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a sensitizer, wherein the binder polymer has a structural unit derived from acrylic acid, and the sensitizer contains an anthracene compound.
  • the anthracene compound includes at least one selected from the group consisting of an anthracene compound having an aryl group and an anthracene compound having an alkoxy group.
  • a method for forming a resist pattern comprising: a step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of [1] to [3] above or the photosensitive element according to [4] above; a step of irradiating at least a part of the photosensitive layer with actinic radiation to form a photocured portion; and a step of removing an unphotocured portion of the photosensitive layer from the substrate to form a resist pattern.
  • a method for producing a printed 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 the above-mentioned [5] to form a conductor pattern.
  • the present disclosure provides a photosensitive resin composition and photosensitive element that are excellent in sensitivity, developability, and adhesion, as well as a method for forming a resist pattern and a method for manufacturing a printed wiring board using the same.
  • 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 with the upper or lower limit of a numerical range of another stage.
  • the upper or lower limit of the numerical range may be replaced with the values shown in the examples.
  • (meth)acrylate means at least one of "acrylate” and its corresponding “methacrylate”. The same applies to other similar expressions such as (meth)acryloyl.
  • 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”).
  • the (A) component has a structural unit derived from acrylic acid, and the (D) component contains an anthracene compound.
  • the photosensitive resin composition according to the present embodiment is excellent in sensitivity, developability, and adhesion by using such a specific binder polymer and a specific sensitizer in combination, and can be suitably used for a direct imaging exposure method.
  • each component that may be contained in the photosensitive resin composition will be described in detail.
  • Component (A) Binder Polymer
  • the photosensitive resin composition contains one or more types of component (A).
  • Component (A) has a structural unit derived from acrylic acid (hereinafter, sometimes referred to as "first structural unit”).
  • Component (A) can be produced by radical polymerization of a polymerizable monomer containing acrylic acid.
  • the photosensitive resin composition according to this embodiment contains a binder polymer having a first structural unit as component (A), which can improve the sensitivity, developability, and adhesion of the photosensitive layer formed from the photosensitive resin composition.
  • Acrylic acid has a lower glass transition temperature and is softer than methacrylic acid. The inventors have found that by using acrylic acid as a polymerizable monomer, the glass transition temperature of the resulting binder polymer can be lowered, and that by using such a binder polymer, the developability can be improved, as well as the sensitivity and adhesion can be improved.
  • the content of the first structural unit in component (A) may be 15% by mass or more, 18% by mass or more, 19% by mass or more, or 20% by mass or more, based on the total mass of the structural units derived from the polymerizable monomers constituting the binder polymer, from the viewpoints of sensitivity, developability, and adhesion, and may be 27% by mass or less, 26% by mass or less, 25% by mass or less, or 24% by mass or less, based on the viewpoint of alkali resistance.
  • the content of the first structural unit in component (A) may be 15% by mass to 27% by mass, 18% by mass to 26% by mass, 19% by mass to 25% by mass, or 20% by mass to 24% by mass, based on the total mass of the structural units derived from the polymerizable monomers constituting the binder polymer.
  • the (A) component may have a structural unit derived from styrene or a styrene derivative (hereinafter sometimes referred to as the "second structural unit") from the viewpoint of improving the resolution and adhesion of the photosensitive resin composition and reducing the amount of resist tail generation.
  • styrene derivatives include vinyl toluene, ⁇ -methyl styrene, p-methyl styrene, and p-ethyl styrene.
  • the content of the second structural unit in component (A) may be 55% by mass or more, 60% by mass or more, or 65% by mass or more, based on the total mass of the structural units derived from the polymerizable monomers constituting the binder polymer, from the viewpoint of improving resolution and adhesion and reducing the amount of resist tail generation, and may be 84% by mass or less, 80% by mass or less, 78% by mass or less, or 75% by mass or less, from the viewpoint of appropriately shortening the development time and reducing the occurrence of undeveloped portions.
  • component (A) may have a structural unit derived from a (meth)acrylate compound having an alicyclic structure (hereinafter, sometimes referred to as a "third structural unit").
  • (meth)acrylates having an alicyclic structure include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, cyclopentanyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.
  • the content of the third structural unit in component (A) may be 0.5 mass% or more, 0.8 mass% or more, 1.0 mass% or more, 2.0 mass% or more, 3.0 mass% or more, or 4.0 mass% or more, based on the total mass of the structural units derived from the polymerizable monomers constituting the binder polymer, from the viewpoint of further improving the resolution and adhesion of the photosensitive resin composition, and may be 20 mass% or less, 18 mass% or less, 16 mass% or less, 14 mass% or less, or 12 mass% or less, from the viewpoint of further improving the developability of the photosensitive resin composition.
  • Component (A) may further have a structural unit derived from a polymerizable monomer other than those mentioned above (hereinafter also referred to as "other monomers").
  • other monomers include methacrylic acid, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, benzyl (meth)acrylate or a derivative thereof, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, ⁇ -furyl (meth)acrylic acid, ⁇ -styryl (meth)acrylic acid, maleic acid, maleic anhydride, maleic
  • the weight average molecular weight (Mw) of component (A) may be 20,000 or more, 25,000 or more, 30,000 or more, or 35,000 or more, and may be 80,000 or less, 70,000 or less, 60,000 or less, or 50,000 or less.
  • the Mw of component (A) may be 20,000 to 80,000, 25,000 to 70,000, 30,000 to 60,000, or 35,000 to 50,000.
  • Mw is 80,000 or less, the resolution and developability tend to be further improved, and when Mw is 20,000 or more, the flexibility of the cured film is improved, and chipping and peeling of the resist pattern tend to be less likely to occur.
  • Mw can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, it can be measured under the conditions described in the examples.
  • GPC gel permeation chromatography
  • the acid value of component (A) may be 140 mgKOH/g or more, 150 mgKOH/g or more, 160 mgKOH/g or more, or 170 mgKOH/g or more, and may be 200 mgKOH/g or less, 190 mgKOH/g or less, 185 mgKOH/g or less, or 180 mgKOH/g or less. From the viewpoint of achieving both developability and peelability, the acid value of component (A) may be 140 to 200 mgKOH/g, 150 to 190 mgKOH/g, 160 to 185 mgKOH/g, or 170 to 180 mgKOH/g.
  • the acid value of component (A) is 140 mgKOH/g or more, it is possible to more sufficiently prevent the development time from becoming long, and when the acid value is 200 mgKOH/g or less, it is easier to improve the developer resistance (adhesion) of the cured product of the photosensitive resin composition.
  • the acid value of component (A) can be adjusted by the structural unit derived from acrylic acid.
  • the acid value of component (A) can be measured in accordance with JIS K6901:2008 5.3.2.
  • the glass transition temperature (Tg) of the (A) component may be 80°C or higher, 90°C or higher, 95°C or higher, or 100°C or higher, or 113°C or lower, 112°C or lower, 111°C or lower, or 110°C or lower.
  • the Tg of the (A) component may be 80°C to 113°C, 90°C to 112°C, 95°C to 111°C, or 100°C to 110°C.
  • the Tg of the (A) component is a value calculated according to the Fox formula, and can be calculated from the mass of each polymerizable monomer constituting the (A) component and the Tg of the homopolymer of each polymerizable monomer.
  • the content of the (A) component may be 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more, relative to 100 parts by mass of the total amount of the (A) component and the (B) component, from the viewpoint of excellent formability of the film, and may be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, from the viewpoint of further improving sensitivity and resolution.
  • the photosensitive resin composition contains one or more of the components (B).
  • the component (B) may be any compound that is polymerizable by light, and may be, for example, a compound having an ethylenically unsaturated bond.
  • the component (B) may contain a polyfunctional monomer having two or more reactive groups that react with radicals.
  • the component (B) may contain a bisphenol A type (meth)acrylate compound from the viewpoints of developability, resolution, and peelability after curing.
  • bisphenol A type (meth)acrylate compounds examples include 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.
  • component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane.
  • 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane a compound having 10 or more oxyethylene groups may be used, or a compound having less than 10 oxyethylene groups may be used, or a compound having 10 or more oxyethylene groups may be used in combination with a compound having less than 10 oxyethylene groups.
  • 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane for example, 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane can be mentioned.
  • the content of the bisphenol A type (meth)acrylate compound may be 20% by mass or more, 40% by mass or more, 60% by mass or more, or 80% by mass or more, and may be 100% by mass or less, or 95% by mass or less, based on the total amount of the (B) component.
  • the content of the compound having 10 or more oxyethylene groups may be 20% by mass or more, 40% by mass or more, 60% by mass or more, or 70% by mass or more, and may be 100% by mass or less, 95% by mass or less, or 90% by mass or less, based on the total amount of the (B) component.
  • component (B) may contain an ⁇ , ⁇ -unsaturated ester compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • ⁇ , ⁇ -unsaturated ester compounds include polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and EO-modified polypropylene glycol, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO-PO-modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and tetramethylolmethane tetra(meth)acrylate.
  • component (B) may contain a compound having three or more (meth)acryloyl groups.
  • compounds having three or more (meth)acryloyl groups 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, and EO-modified dipentaerythritol hexa(meth)acrylate.
  • the content of the ⁇ , ⁇ -unsaturated ester compound may be 20% by mass or more or 30% by mass or more based on the total amount of component (B) from the viewpoint of flexibility, and may be 70% by mass or less or 60% by mass or less from the viewpoint of resolution.
  • the photosensitive resin composition may contain, as component (B), a photopolymerizable compound other than the bisphenol A (meth)acrylate compound and the ⁇ , ⁇ -unsaturated ester compound.
  • photopolymerizable compounds include, for example, nonylphenoxy polyethyleneoxy acrylate, 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 compound may be at least one selected from the group consisting of nonylphenoxy polyethyleneoxy acrylate and phthalic acid compounds.
  • nonylphenoxy polyethyleneoxyacrylates include nonylphenoxy triethyleneoxyacrylate, nonylphenoxy tetraethyleneoxyacrylate, nonylphenoxy pentaethyleneoxyacrylate, nonylphenoxy hexaethyleneoxyacrylate, nonylphenoxy heptaethyleneoxyacrylate, nonylphenoxy octaethyleneoxyacrylate, nonylphenoxy nonaethyleneoxyacrylate, nonylphenoxy decaethyleneoxyacrylate, and nonylphenoxy undecaethyleneoxyacrylate.
  • 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
  • component (B) contains other photopolymerizable compounds
  • the content of the other photopolymerizable compounds may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on the total amount of component (B), from the viewpoints of resolution, adhesion, resist shape, and releasability after curing.
  • component (B) may contain, among the above-mentioned compounds, a compound having a total of 2 to 40 oxyethylene groups (EO groups) and/or oxypropylene groups (PO groups) in the molecule. From the viewpoints of adhesion and resolution, the total number of EO groups and/or PO groups may be 2 to 40 or 2 to 30.
  • EO groups oxyethylene groups
  • PO groups oxypropylene groups
  • the content of the compound having a total of 2 to 40 EO groups and/or PO groups may be 2 to 15 mass%, 4 to 12 mass%, or 5 to 8 mass%, based on the total amount of component (B), from the viewpoints of adhesion and resolution.
  • 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.
  • Component (C) Photopolymerization Initiator
  • the photosensitive resin composition contains one or more types 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
  • the (C) component may contain a hexaarylbiimidazole compound from the viewpoint of suppressing the penetration of the photosensitizer into the polyethylene film.
  • 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 (chlorine atom or the like).
  • 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 hexaarylbiimidazole compound is preferably a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, and more preferably 2,2-bis(o-chlorophenyl)-4,5-4',5'-tetraphenyl-1,2'biimidazole.
  • the content of the hexaarylbiimidazole compound may be 90% by mass or more, 95% by mass or more, or 99% by mass or more based on the total amount of component (C).
  • Component (C) may consist solely of the hexaarylbiimidazole compound.
  • the content of component (C) may be 0.1 mass% or more, 0.5 mass% or more, or 1.0 mass% or more, based on the total solid content of the photosensitive resin composition, and may be 20 mass% or less, 10 mass% or less, or 5 mass% or less.
  • Component (D) Sensitizer
  • the photosensitive resin composition contains one or more types of component (D).
  • the component (D) contains an anthracene compound.
  • the photosensitive resin composition according to this embodiment contains an anthracene compound as component (D), which can improve the sensitivity and adhesion of the photosensitive layer formed from the photosensitive resin composition.
  • the photosensitive resin composition according to this embodiment uses a binder polymer having a structural unit derived from acrylic acid in combination with an anthracene compound, which can provide a synergistic effect of improving adhesion.
  • the anthracene compound may have a substituent bonded to the anthracene ring, or may have a substituent bonded to at least one of the carbon atoms at positions 1 to 10 (e.g., positions 9 and 10) of the anthracene ring.
  • substituents examples include alkyl groups (non-cyclic alkyl groups having 1 to 20 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, etc.), aryl groups, vinyl groups, hydroxy groups, carboxy groups, carboxylate groups, aldehyde groups, alkoxy groups, carbonyl groups, alkoxycarbonyl groups, alkanoyl groups (alkanoyl groups having 2 to 12 carbon atoms, etc.), oxycarbonyl groups, carbonyloxy groups, amino groups, epoxy groups, furyl groups, cyano groups, halogeno groups (fluoro groups, chloro groups, bromo groups, etc.), nitro groups, acetyl groups, sulfonyl groups, and sulfonamide groups.
  • alkyl groups non-cyclic alkyl groups having 1 to 20 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, etc.
  • aryl groups vinyl groups, hydroxy groups, carboxy
  • anthracene compounds include 1-methylanthracene, 2-methylanthracene, 9-methylanthracene, 2-ethylanthracene, 2-butylanthracene, 9-vinylanthracene, 9-phenylanthracene, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthraldehyde, 9,10-dimethylanthracene, 9,10-dimethoxyanthracene, and 9,10-diethane.
  • the anthracene compound may have at least one substituent selected from the group consisting of an aryl group, an alkoxy group, and a halogeno group.
  • aryl group examples include a phenyl group, an aralkyl group, a benzoyl group, and a styryl group.
  • aralkyl group examples include a benzyl group and a phenethyl group.
  • An anthracene compound having an aryl group may have an aryl group bonded to at least one of the carbon atoms at the 9th and 10th positions of the anthracene ring.
  • anthracene compound having an aryl group examples include 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, and 9-(4-bromophenyl)-10-phenylanthracene.
  • the alkoxy group may be an unsubstituted alkoxy group or a substituted alkoxy group.
  • An example of a substituted alkoxy group is a hydroxyalkoxy group.
  • the number of carbon atoms in the alkoxy group may be 1 or more, 2 or more, 3 or more, or 4 or more, and may be 10 or less, 8 or less, 6 or less, or 5 or less.
  • the number of carbon atoms in the alkoxy group may be 1 to 10 or 2 to 8.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
  • An anthracene compound having an alkoxy group may have an alkoxy group bonded to at least one of the carbon atoms at the 9th and 10th positions of the anthracene ring.
  • Examples of an anthracene compound having an alkoxy group include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene.
  • Component (D) may further contain a sensitizer other than an anthracene compound, as long as it does not interfere with the effects of the present disclosure.
  • the content of the (D) component may be 0.15 parts by mass or more, 0.20 parts by mass or more, 0.30 parts by mass or more, 0.40 parts by mass or more, 0.50 parts by mass or more, 0.55 parts by mass or more, or 0.60 parts by mass or more, relative to 100 parts by mass of the total amount of the (A) component and the (B) component, and may be 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, 1.0 parts by mass or less, 0.9 parts by mass or less, or 0.8 parts by mass or less.
  • the content of the (D) component may be 0.15 parts by mass to 5.0 parts by mass, 0.20 parts by mass to 4.0 parts by mass, 0.30 parts by mass to 3.0 parts by mass, 0.40 parts by mass to 2.0 parts by mass, 0.50 parts by mass to 1.0 parts by mass, 0.55 parts by mass to 0.9 parts by mass, or 0.60 parts by mass to 0.8 parts by mass, relative to 100 parts by mass of the total amount of the (A) component and the (B) component.
  • the content of the (D) component may be 2.0 parts by mass or more, 3.0 parts by mass or more, 5.0 parts by mass or more, 8.0 parts by mass or more, 10.0 parts by mass or more, or 10.5 parts by mass or more, and may be 16.0 parts by mass or less, 15.0 parts by mass or less, 14.0 parts by mass or less, 13.0 parts by mass or less, 12.5 parts by mass or less, or 12.0 parts by mass or less, based on 100 parts by mass of the total amount of the (C) component, based on the viewpoints of sensitivity and adhesion.
  • the content of the (D) component may be 2.0 parts by mass to 16.0 parts by mass, 3.0 parts by mass to 15.0 parts by mass, 5.0 parts by mass to 14.0 parts by mass, 8.0 parts by mass to 13.0 parts by mass, 10.0 parts by mass to 12.5 parts by mass, or 10.5 parts by mass to 12.0 parts by mass, based on 100 parts by mass of the total amount of the (C) component, based on the viewpoints of sensitivity and adhesion.
  • the content of component (E) may be 0.001 to 0.10 parts by mass, 0.005 to 0.08 parts by mass, or 0.01 to 0.06 parts by mass per 100 parts by mass of the total amount of components (A) and (B).
  • the photosensitive resin composition may further contain one or more other components other than the above-mentioned components.
  • the other components include hydrogen donors (bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet, N-phenylglycine, etc.), dyes (malachite green, etc.), photocoloring agents (tribromophenylsulfone, leuco crystal violet, etc.), thermal coloring inhibitors, plasticizers (p-toluenesulfonamide, etc.), pigments, fillers, defoamers, flame retardants, stabilizers, adhesion agents, leveling agents, peeling promoters, antioxidants, fragrances, imaging agents, and thermal crosslinking agents.
  • the content of the other components may be 0.005 parts by mass or more, 0.01 parts by mass or more, or 20 parts by mass or less, based on 100 parts by mass of the total amount of the components
  • the photosensitive resin composition may further contain one or more organic solvents in order to adjust the viscosity.
  • organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether.
  • the content of the organic solvent may be 40 mass% or more and 70 mass% or less based on the total amount of the photosensitive resin composition.
  • the photosensitive resin composition can be suitably used to form resist patterns, and is particularly suitable for use in the method for manufacturing wiring boards described below.
  • the photosensitive element according to the present embodiment includes a support and a photosensitive layer formed on the support using the photosensitive resin composition.
  • the photosensitive layer may be laminated on a substrate and then exposed without peeling off the support.
  • Figure 1 is a schematic cross-sectional view of a photosensitive element according to one embodiment. As shown in Figure 1, the photosensitive element 1 includes a support 2 and a photosensitive layer 3 derived from the photosensitive resin composition formed on the support 2, and is configured to include 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., etc.
  • PS series e.g. PS-25
  • NF-15 manufactured by Tamapoly Co., Ltd.
  • polypropylene films manufactured by Oji Paper Co., Ltd. e.g. Alphan MA-410, E-200C
  • Shin-Etsu Film Co., Ltd. etc.
  • 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 formed using the photosensitive resin composition described above.
  • the thickness of the photosensitive layer 3 after drying may be 1 ⁇ m or more or 5 ⁇ m or more from the viewpoint of facilitating coating and improving productivity, and may be 100 ⁇ m or less, 50 ⁇ m or less, or 40 ⁇ m or less from the viewpoint of further improving adhesion and resolution.
  • 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 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 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 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 unphotocured part of the photosensitive layer 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 heating and pressing the photosensitive layer of the photosensitive element onto the substrate.
  • the photosensitive element When the photosensitive element is used, a laminate is obtained in which the substrate, the photosensitive layer, and the support are laminated in this order.
  • 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 photosensitive layer forming step may be performed 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 performed 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 direct imaging exposure methods such as LDI (Laser Direct Imaging) exposure and DLP (Digital Light Processing) exposure, which irradiate an image with active light rays, a method of irradiating an image with active light rays through a negative or positive mask pattern called artwork (mask exposure method), and a method of irradiating an image with active light rays by projection exposure.
  • direct imaging exposure methods such as LDI (Laser Direct Imaging) exposure and DLP (Digital Light Processing) exposure
  • LDI Laser Direct Imaging
  • DLP Digital Light Processing
  • the photosensitive resin composition and photosensitive element according to this embodiment have high sensitivity and excellent developability and adhesion, even when the direct imaging exposure method is adopted.
  • 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.
  • a support is present on the photosensitive layer, the support is removed before removing (developing) the areas other than the photocured areas (also known as the unexposed areas).
  • developer the areas other than the photocured areas
  • wet development wet development and dry development, with wet development being the most widely used.
  • development may be performed by a known developing method using a developer that is compatible with the photosensitive resin composition.
  • the developing method include a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, and rocking immersion.
  • a high-pressure spray method may be used as a developing 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, for example, 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 having an alkoxy group with 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 printed wiring board according to 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-described resist pattern forming method, and may include other steps, such as a resist pattern removal step, as necessary.
  • 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.
  • etching process a resist pattern formed on a substrate is used as a mask to etch away the conductive layer provided on the substrate, forming a conductive pattern.
  • the method of etching is appropriately selected depending on the conductive layer to be removed.
  • etching solutions include cupric chloride solutions, ferric chloride solutions, alkaline etching solutions, and hydrogen peroxide-based etching solutions.
  • the resist pattern on the substrate may be removed.
  • the resist pattern can be removed, for example, by stripping with an aqueous solution that is more strongly alkaline than the aqueous solution used in the development process.
  • the strongly alkaline aqueous solution that can be used include a 1 to 10% by mass aqueous solution of sodium hydroxide and a 1 to 10% by mass aqueous solution of potassium hydroxide.
  • 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 printed wiring board according to this embodiment can be applied to the manufacture of not only single-layer printed wiring boards, but also multi-layer printed wiring boards, and can also be applied to the manufacture of printed wiring boards with small-diameter through holes.
  • Measuring device Showdex (registered trademark) GPC-101 (manufactured by Resonac Co., Ltd.)
  • Detector Differential refractometer Shodex RI-71S (manufactured by Resonac Co., Ltd.)
  • the Tg of the binder polymer was calculated from the Fox formula.
  • the acid value of the binder polymer was measured by neutralization titration method in accordance with JIS K6901:2008 5.3.2.
  • a photosensitive resin composition was prepared by mixing each component in the blending amount (parts by mass) shown in Table 2 with respect to a binder polymer solution having a solid content of 57.0 parts by mass. Details of each component shown in Table 2 are as follows.
  • a photosensitive element A polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "QS-69”) having a thickness of 16 ⁇ m was prepared as a support. A photosensitive resin composition was applied onto the support, and then dried in a hot air convection dryer at 80° C. and 120° C. in sequence to form a photosensitive layer having a thickness of 25 ⁇ m after drying. A polyethylene film (manufactured by Tamapoly Corporation, product name "NF-15”) was laminated onto this photosensitive layer as a protective layer, to obtain a photosensitive element in which the support, photosensitive layer, and protective layer were laminated in this order.
  • a copper-clad laminate (manufactured by Resonac Corporation, product name "MCL-E-679"), which is a glass epoxy material with copper foil (thickness: 35 ⁇ m) laminated on both sides, was surface-treated by washing with water, pickling, and washing with water, and then dried with an air flow.
  • the surface-treated copper-clad laminate was heated to 80°C, and 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. This resulted in a laminate in which the copper-clad laminate, the photosensitive layer, and the support were laminated in this order.
  • the lamination was performed using a heat roll at 110°C, with a pressure of 0.4 MPa and a roll speed of 1.05 m/min.
  • the laminate was allowed to cool to 23°C.
  • a phototool having a step tablet was attached to the support on the surface of the laminate.
  • As the step tablet a 41-step step tablet was used, with a density range of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm x 187 mm, and each step size of 3 mm x 12 mm.
  • the photosensitive layer was exposed through the phototool having the step tablet and the support. The exposure was performed at an exposure dose of 100 mJ/ cm2 using a direct imaging exposure machine (FDi-Ms) with a blue-violet laser diode having a wavelength of 405 nm as a light source.
  • FDi-Ms direct imaging exposure machine
  • the support was peeled off from the laminate to expose the photosensitive layer.
  • a 1% by weight aqueous solution of sodium carbonate at 30°C was sprayed onto the exposed photosensitive layer for 50 seconds to remove the unexposed areas.
  • a cured film formed from the cured product of the photosensitive resin composition was formed on the copper-clad laminate of the laminate.
  • the number of steps on the step tablet of this cured film was visually confirmed to determine the sensitivity. The higher the number of steps on the step tablet, the higher the sensitivity.
  • the laminate was cut into 5 cm squares to obtain test pieces for measuring the minimum development time. After peeling off the support from the test piece, the unexposed photosensitive layer was spray-developed at a pressure of 0.15 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 an unexposed portion of 1 mm or more had been removed was defined as the minimum development time (unit: seconds).
  • a full cone type nozzle was used for 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, the better the developability.
  • the support was peeled off from the laminate 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 50 seconds.
  • the space areas unexposed areas
  • the line areas were formed without meandering or chipping.
  • Adhesion was evaluated based on the minimum line width (unit: ⁇ m) in the resist pattern. The smaller this value, the better the adhesion.

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PCT/JP2023/042403 2023-11-27 2023-11-27 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 Pending WO2025115078A1 (ja)

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