WO2024135574A1 - 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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Publication number
WO2024135574A1
WO2024135574A1 PCT/JP2023/045139 JP2023045139W WO2024135574A1 WO 2024135574 A1 WO2024135574 A1 WO 2024135574A1 JP 2023045139 W JP2023045139 W JP 2023045139W WO 2024135574 A1 WO2024135574 A1 WO 2024135574A1
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Prior art keywords
resin composition
resist pattern
photosensitive resin
mass
photosensitive
Prior art date
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Ceased
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PCT/JP2023/045139
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English (en)
French (fr)
Japanese (ja)
Inventor
夏木 戸田
謙介 吉原
哲也 加藤
陽介 賀口
祐作 渡邉
博史 小野
琢 澤木
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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 CN202380037165.3A priority Critical patent/CN120344918A/zh
Priority to EP23906936.2A priority patent/EP4607280A4/en
Priority to KR1020257017834A priority patent/KR20250095734A/ko
Priority to JP2024566023A priority patent/JPWO2024135574A1/ja
Publication of WO2024135574A1 publication Critical patent/WO2024135574A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/20—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene

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 layer formed on a support film using the photosensitive resin composition (hereinafter also referred to as a "photosensitive layer”) are widely used as resist materials for etching, plating, and the like.
  • Printed wiring boards are manufactured using the above-mentioned photosensitive element, for example, in the following manner. That is, first, the photosensitive layer of the photosensitive element is laminated onto a circuit-forming substrate such as a copper-clad laminate. Next, the photosensitive layer is exposed to light through a mask film or the like to form a photocured portion. At this time, the support film is peeled off before or after exposure. After that, the areas of the photosensitive layer other than the photocured portion are removed with a developer to form a resist pattern. Next, the resist pattern is used as a resist to perform an etching process or a plating process to form a conductor pattern, and finally the photocured portion of the photosensitive layer (resist pattern) is peeled off (removed).
  • the photosensitive layer is required to have excellent characteristics in etching or plating processes, as well as excellent adhesion to the circuit-forming substrate and excellent resolution in forming the resist pattern (see, for example, Patent Documents 1 and 2).
  • photosensitive resin compositions are required to form resist patterns with high adhesion to smooth substrates with a surface roughness (Ra) of 200 nm or less.
  • Ra surface roughness
  • photosensitive resin compositions with excellent adhesion tend to require long development times for the photosensitive layer and long peeling times for the resist pattern. From the perspective of improving productivity, it is desirable for photosensitive resin compositions to have shorter development and peeling times.
  • the present disclosure aims to provide a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board that are excellent in developability, adhesion, and peelability.
  • the present inventors have discovered a photosensitive resin composition that uses a binder polymer having a specific composition and has an absorbance within a specific range, thereby making it possible to form a resist pattern that has excellent adhesion to a smooth substrate, and that can shorten the development time of the photosensitive layer and the peeling time of the resist pattern.
  • 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 containing 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 a structural unit derived from styrene or a styrene derivative, and the photosensitive resin composition has an absorbance of 0.0030 to 0.0120 for light with a wavelength of 365 nm per 1 ⁇ m of thickness.
  • the sensitizer comprises a pyrazoline compound or a dialkylaminobenzophenone 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 [5] above.
  • a method for forming a resist pattern comprising the steps of: forming a photosensitive layer on a substrate having a surface roughness of 200 nm or less using the photosensitive resin composition described in any one of [1] to [5] above or the photosensitive element described in [6] above; irradiating at least a part of the photosensitive layer with actinic radiation 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 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 [7] above to form a conductor pattern.
  • the present disclosure provides a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board that are excellent in developability, adhesion, and peelability.
  • 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 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 comprises (A) a binder polymer (hereinafter, sometimes referred to as “component (A)”), (B) a photopolymerizable compound (hereinafter, sometimes referred to as “component (B)”), and (C) a photopolymerization initiator (hereinafter, sometimes referred to as “component (C)”), and (D) a sensitizer (hereinafter, sometimes referred to as “component (D)”).
  • the binder polymer has a structural unit derived from acrylic acid and a structural unit derived from styrene or a styrene derivative.
  • the photosensitive resin composition has a thickness of 1 ⁇ m.
  • the absorbance of the photosensitive resin composition for light having a wavelength of 365 nm per 1 ⁇ m of thickness is 0.0030 to 0.0120. It means the absorbance for light having a wavelength of 365 nm per 1 ⁇ m of layer thickness.
  • the photosensitive resin composition of this embodiment contains the above components (A) to (D) as essential components, and has an absorbance of 0.0030 to 0.0120 for light with a wavelength of 365 nm per 1 ⁇ m of thickness, making it possible to form a resist pattern with a good resist shape and to obtain good resolution and adhesion.
  • Each component that the photosensitive resin composition may contain is described in detail below.
  • the photosensitive resin composition according to this embodiment contains a binder polymer having a specific structure as the component (A), and thus the developability, resolution, adhesion, and releasability of a photosensitive layer formed from the photosensitive resin composition can be improved.
  • Component (A) can be produced by radical polymerization of a polymerizable monomer containing acrylic acid and styrene or a styrene derivative.
  • the (A) component has structural units derived from acrylic acid, which improves the alkaline developability of the photosensitive resin composition and the peelability of the resist pattern.
  • Acrylic acid and methacrylic acid may be used in combination, but increasing the content of structural units derived from methacrylic acid tends to decrease the peelability.
  • the content of structural units derived from acrylic acid in component (A) is preferably 15% by mass or more, and may be 16% by mass or more, 17% by mass or more, 18% by mass or more, or 20% by mass or more, based on the total mass of structural units derived from polymerizable monomers constituting the binder polymer (100% by mass), from the viewpoint of further shortening the development time.
  • the content of structural units derived from acrylic acid is preferably 26% by mass or less, and may be 25% by mass or less, 24% by mass or less, or 23% by mass or less, from the viewpoint of further improving adhesion.
  • the content of structural units derived from acrylic acid may be 15 to 26% by mass, 16 to 25% by mass, 17 to 24% by mass, 18 to 24% by mass, or 20 to 23% by mass, from the viewpoint of improving developability and adhesion in a well-balanced manner.
  • the (A) component has a structural unit derived from styrene or a styrene derivative (hereinafter also referred to as a "styrene-based structural unit"), which can improve the resolution and adhesion of the photosensitive resin composition.
  • styrene-based structural unit a structural unit derived from styrene or a styrene derivative
  • examples of styrene derivatives include vinyl toluene, ⁇ -methyl styrene, p-methyl styrene, and p-ethyl styrene.
  • the content of the styrene-based structural units in component (A) may be 50% by mass or more, 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 further improving adhesion.
  • the content of the styrene-based structural units may be 85% by mass or less, 84% by mass or less, 83% by mass or less, or 80% by mass or less, from the viewpoint of further shortening the peeling time. From the viewpoint of improving adhesion and peeling in a balanced manner, the content of the styrene-based structural units may be 50 to 85% by mass, 55 to 84% by mass, 60 to 83% by mass, or 65 to 80% by mass.
  • Component (A) may further have a structural unit derived from a (meth)acrylate compound having an alicyclic structure.
  • a structural unit derived from a (meth)acrylate compound having an alicyclic structure By having a structural unit derived from a (meth)acrylate compound having an alicyclic structure, the resolution and adhesion of the photosensitive resin composition can be improved.
  • (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 structural units derived from the (meth)acrylate compound having an alicyclic structure may be 1% by mass or more, 2% by mass or more, or 4% by mass or more, based on the total mass of the structural units derived from the polymerizable monomers constituting the binder polymer (100% by mass), from the viewpoint of further improving the resolution and adhesion of the photosensitive resin composition, and may be 15% by mass or less, 10% by mass or less, or 8% by mass or less, from the viewpoint of further improving the developability of the photosensitive resin composition.
  • Component (A) may further contain structural units derived from polymerizable monomers 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 derivatives 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 acid monoalkyl
  • the weight average molecular weight (Mw) of component (A) may be 10,000 to 60,000, 15,000 to 55,000, 20,000 to 50,000, or 23,000 to 45,000. When Mw is 60,000 or less, the resolution and developability tend to be improved, and when Mw is 10,000 or more, chipping and peeling of the resist pattern tend to be less likely to occur.
  • the dispersity (Mw/Mn) of component (A) may be 1.0 to 3.0, 1.0 to 2.5, or 1.0 to 2.3. When the dispersity is smaller, the resolution tends to be improved.
  • 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.
  • GPC gel permeation chromatography
  • the acid value of component (A) may be 140 to 200 mgKOH/g, 150 to 190 mgKOH/g, 160 to 180 mgKOH/g, or 165 to 175 mgKOH/g from the viewpoint of achieving both developability and releasability.
  • the acid value of component (A) can be adjusted by a 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 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, 45 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, 65 parts by mass or less, or 60 parts by mass or less, from the viewpoint of further improving sensitivity and resolution.
  • the component (B) component is not particularly limited as long as it has at least one ethylenically unsaturated bond and is a photopolymerizable compound.
  • the component (B) is preferably a compound having alkali developability, resolution, and post-curing property. From the viewpoint of improving the release properties, it is preferable that the adhesive contains at least one type of bisphenol type (meth)acrylate, and among the bisphenol type (meth)acrylates, it is more preferable that the adhesive contains bisphenol A type (meth)acrylate.
  • bisphenol A type (meth)acrylates 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.
  • 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane is preferred from the viewpoint of further improving resolution and release properties.
  • 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.
  • bisphenol A type (meth)acrylates include, for example, BPE-200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) as 2,2-bis(4-((meth)acryloxydipropoxy)phenyl)propane, BP-2EM (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) as ethoxylated bisphenol A dimethacrylate, and BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) and FA-321M (trade name, manufactured by Showa Denko Materials Co., Ltd.) as 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane. These bisphenol A type (meth)acrylates may be used alone or in combination of two or more types.
  • the content of the bisphenol type (meth)acrylate may be 40 to 98 mass%, 50 to 97 mass%, 60 to 95 mass%, or 70 to 90 mass% based on the total amount of the (B) component. If the content is 40 mass% or more, the resolution, adhesion, and suppression of the occurrence of resist tails will be better, and if it is 98 mass% or less, the development time will be appropriately short and the occurrence of undeveloped portions will be more unlikely.
  • the (B) component other than the bisphenol type (meth)acrylate may further include at least one polyalkylene glycol di(meth)acrylate having at least one of a (poly)oxyethylene chain and a (poly)oxypropylene chain in the molecule, from the viewpoint of improving the flexibility of the cured product (cured film), and may further include a polyalkylene glycol di(meth)acrylate having both a (poly)oxyethylene chain and a (poly)oxypropylene chain in the molecule.
  • the total number of oxyethylene groups (EO groups) and/or oxypropylene groups (PO groups) in the polyalkylene glycol di(meth)acrylate may be 2 to 40, 4 to 30, or 6 to 20, from the viewpoint of further improving adhesion and resolution.
  • polyalkylene glycol di(meth)acrylates examples include FA-023M (trade name, manufactured by Showa Denko Materials Co., Ltd.), FA-024M (trade name, manufactured by Showa Denko Materials Co., Ltd.), and NK Ester HEMA-9P (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These may be used alone or in combination of two or more types.
  • the content of polyalkylene glycol di(meth)acrylate may be 2 to 40 mass%, 3 to 30 mass%, or 5 to 20 mass% based on the total amount of component (B).
  • component (B) may also be used as component (B).
  • component (B) may contain at least one selected from nonylphenoxy polyethyleneoxy acrylate and phthalic acid compounds.
  • the content thereof may be 5 to 50 mass%, 5 to 40 mass%, or 10 to 30 mass% based on the total amount of component (B).
  • 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, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate, and ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate.
  • ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (product name, manufactured by Showa Denko Materials Co., Ltd.).
  • component (B) may contain a (meth)acrylic acid polyol ester.
  • the (meth)acrylic acid polyol ester include trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, trimethylolpropane polybutoxy tri(meth)acrylate, trimethylolpropane polyethoxy polypropoxy tri(meth)acrylate, trimethylolethane polyethoxy tri(meth)acrylate, trimethylolethane polypropoxy tri(meth)acrylate, trimethylolethane polybutoxy tri(meth)acrylate, trimethylolethane polyethoxy tri(meth)acrylate, trimethylolethane polybutoxy tri(meth)acrylate, trimethylolethane polyethoxy tri(meth)acrylate, trimethylolethane polybutoxy tri(meth)acrylate, trimethylolethane polyethoxy tri(meth)acrylate,
  • the content of component (B) is preferably 20 to 60 parts by mass, more preferably 30 to 55 parts by mass, and even more preferably 35 to 50 parts by mass, relative to 100 parts by mass of the total amount of components (A) and (B).
  • the photosensitive resin composition has better photosensitivity and coating properties in addition to better resolution and adhesion.
  • component (C) Photopolymerization initiator
  • the component (C) is not particularly limited as long as it is a component that can polymerize the 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; 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-trimethylbenzoyl
  • 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.
  • component (C) By adjusting the content of component (C) so that the absorbance of the photosensitive resin composition for light with a wavelength of 365 nm per 1 ⁇ m of thickness is 0.0030 or more, deterioration of resolution can be suppressed, and by adjusting the absorbance of the photosensitive resin composition for light with a wavelength of 365 nm per 1 ⁇ m of thickness is 0.0120 or less, resolution and adhesion can be improved.
  • 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 a pyrazoline compound or a dialkylaminobenzophenone compound from the viewpoint of further improving resolution and adhesion.
  • pyrazoline compounds include 1-(4-methoxyphenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1,5-bis-(4-methoxyphenyl)-3-(4-methoxystyryl)-pyrazoline, 1-(4-isopropylphenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1,5-bis-(4-isopropylphenyl)-3-(4- isopropylstyryl)-pyrazoline, 1-(4-methoxyphenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4
  • dialkylaminobenzophenone compounds examples include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.
  • component (D) By adjusting the content of component (D) so that the absorbance of the photosensitive resin composition for light with a wavelength of 365 nm per 1 ⁇ m of thickness is 0.0030 or more, deterioration of resolution can be suppressed, and by adjusting the absorbance of the photosensitive resin composition for light with a wavelength of 365 nm per 1 ⁇ m of thickness is 0.0120 or less, resolution and adhesion can be improved.
  • the content of the (D) component may be 1.60 parts by mass or less, 1.50 parts by mass or less, 1.40 parts by mass or less, or 1.35 parts by mass or less, per 100 parts by mass of the (C) component, from the viewpoint of further improving adhesion.
  • the content of the (D) component may be 0.15 to 1.60 parts by mass, 0.20 to 1.50 parts by mass, 0.25 to 1.40 parts by mass, or 0.30 to 1.35 parts by mass, per 100 parts by mass of the (C) component, from the viewpoint of improving developability, adhesion, and peelability in a balanced manner.
  • the content of component (D) may be 0.01 to 0.10 parts by mass, 0.01 to 0.09 parts by mass, or 0.01 to 0.08 parts by mass per 100 parts by mass of the total amount of components (A) and (B).
  • the photosensitive resin composition may further contain a polymerization inhibitor as component (E) from the viewpoint of suppressing polymerization in unexposed areas during resist pattern formation and further improving resolution.
  • a polymerization inhibitor examples include 4-tert-butylcatechol and 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl.
  • 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.), tribromophenyl sulfone, photocoloring agents, 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 or 0.01 parts by mass or more, or may be 20 parts by mass or less, relative to 100 parts by mass of the total amount of the components (A) and
  • the photosensitive resin composition may contain an organic solvent to improve the handling properties of the photosensitive resin 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, propylene glycol monomethyl ether, and mixed solvents thereof.
  • the components (A) to (D) may be dissolved in an organic solvent to form a solution with a solid content of about 30 to 60 mass% (hereinafter referred to as the "coating liquid").
  • the solid content refers to the remaining components after removing the volatile components from the solution of the photosensitive resin composition.
  • the photosensitive resin composition of this embodiment has an absorbance of 0.0030 to 0.0120 for light of a wavelength of 365 nm per 1 ⁇ m of thickness.
  • the absorbance When the absorbance is 0.0030 or more, the decrease in resolution can be suppressed. Furthermore, when the absorbance is 0.0120 or less, the resolution and adhesion are improved. From the viewpoint of further suppressing the decrease in resolution, the absorbance may be 0.0040 or more, 0.0050 or more, 0.0055 or more, or 0.0060 or more, and from the viewpoint of further improving the resolution and adhesion, the absorbance may be 0.0115 or less, 0.0110 or less, 0.0100 or less, or 0.0095 or less.
  • the absorbance of the photosensitive resin composition can be adjusted as appropriate by adjusting the types and contents of the above-mentioned components (A) to (D) and other components.
  • the absorbance of the photosensitive resin composition can be measured by forming a photosensitive layer by forming a film from the photosensitive resin composition, and measuring the absorbance of this photosensitive layer for light with a wavelength of 365 nm using, for example, an ultraviolet-visible spectrophotometer such as a U-3310 spectrophotometer (manufactured by Hitachi High-Tech Science Corporation).
  • the absorbance per 1 ⁇ m of thickness of the photosensitive resin composition can be calculated by dividing the absorbance measured for the photosensitive layer by the thickness of the photosensitive layer (unit: ⁇ m).
  • the photosensitive element of the present embodiment includes a support and a photosensitive layer formed on the support, and the photosensitive layer contains the above-mentioned photosensitive resin composition.
  • the photosensitive layer may be laminated on a substrate and then exposed to light without peeling off the support (support film).
  • 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
  • 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 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more from the viewpoint of facilitating coating and improving productivity, and may be 100 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 35 ⁇ m or less, or 30 ⁇ m or less from the viewpoint of further improving adhesion and resolution.
  • the photosensitive layer in the photosensitive element is a layer formed using the photosensitive resin composition, and therefore may have an absorbance of 0.0030 to 0.0120 for light with a wavelength of 365 nm per 1 ⁇ m of thickness.
  • the absorbance When the absorbance is 0.0030 or more, the decrease in resolution can be suppressed. Furthermore, when the absorbance is 0.0120 or less, the resolution and adhesion are improved. From the viewpoint of further suppressing the decrease in resolution, the absorbance may be 0.0040 or more, 0.0050 or more, 0.0055 or more, or 0.0060 or more, and from the viewpoint of further improving the resolution and adhesion, it may be 0.0115 or less, 0.0110 or less, 0.0100 or less, or 0.0095 or less.
  • the method for measuring the absorbance of the photosensitive layer is as described above.
  • 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 having a surface roughness of 200 nm or less 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.
  • a developer suitable for the photosensitive resin composition is used and development is carried out by a known development method.
  • development methods include the dip method, paddle method, spray method, brushing, scrubbing, and rocking immersion. From the viewpoint of improving resolution, a high-pressure spray method may be used as a development method. Development may be carried out 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 mass 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 of the present embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern has been formed 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.
  • 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 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 aqueous solution that can be used are a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution, etc.
  • 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.
  • AA acrylic acid
  • ST styrene
  • TCDMA dicyclopentanyl methacrylate
  • a solution of binder polymer (A-4) was obtained under the same conditions as in (A-3), except that the amount of Perbutyl O in the mixture (x) was changed to 11.5 g.
  • MAA methacrylic acid
  • ST 283.0 g of styrene
  • TCDMA dicyclopentanyl methacrylate
  • the binder polymer solution was dissolved in tetrahydrofuran (THF) to prepare a 0.2 mass% THF solution.
  • Mw was measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene. The GPC conditions are shown below.
  • Measuring device Showdex (registered trademark) GPC-101 (manufactured by Showa Denko K.K.)
  • Detector Differential refractometer Showdex RI-71S (manufactured by Showa Denko K.K.)
  • the acid value of the binder polymer was measured by neutralization titration method in accordance with JIS K6901:2008 5.3.2.
  • the photosensitive resin composition of the example was prepared by mixing each component in the amount (parts by mass) shown in Table 2 with respect to the binder polymer solution having a solid content of 57 parts by mass.
  • the photosensitive resin composition of the comparative example was prepared by mixing the respective components in the amounts (parts by mass). Details of each component shown in Tables 2 and 3 are as follows.
  • B-1 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (manufactured by Showa Denko Materials Co., Ltd., product name "FA-321M", number of EO groups: 10 (average value))
  • B-2 Ethoxylated bisphenol A dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "BP-2EM", number of EO groups: 2.6 (average value))
  • B-3 PO-EO-PO modified dimethacrylate (manufactured by Showa Denko Materials Co., Ltd., product name "FA-024M”), number of EO groups: 6 (average value), number of PO groups: 12 (average value) ))
  • C Photopolymerization initiator
  • C-1 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (manufactured
  • a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "FS-31") having a thickness of 16 ⁇ m was prepared as a support.
  • the photosensitive resin composition was applied onto the support and then dried for 10 minutes in a hot air convection dryer at 90° C. to form a photosensitive layer having a thickness of 25 ⁇ m after drying.
  • a polyethylene film (manufactured by Tamapoly Corporation, product name "NF-15A”) was laminated as a protective layer on the photosensitive layer to obtain a photosensitive element in which the support, photosensitive layer, and protective layer were laminated in this order.
  • a photosensitive element was laminated (laminated) on the surface of a slide glass (manufactured by Matsunami Glass Industry Co., Ltd., white slide glass cut No. 1 S1126).
  • the lamination was performed by using a heat roll at 110 ° C. with a pressure of 0.4 MPa and a roll speed of 1.0 m / min so that the photosensitive layer of the photosensitive element was in contact with the surface of the slide glass while peeling off the protective layer. After the photosensitive layer was laminated on the slide glass, the support was peeled off.
  • the absorbance and light transmittance of the photosensitive layer were measured using a U-3310 spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd.) under the measurement conditions of wavelength range: 330 to 700 nm, scan speed: 300 nm / min, scan interval: 0.50 nm, and slit width: 2 nm.
  • the baseline measurement was performed using untreated slide glass as the reference and sample.
  • the slide glass on which the photosensitive layer was laminated was placed on the sample side holder, and the untreated slide glass was placed on the reference side holder to perform the measurement. From the obtained absorption spectrum, the absorbance and light transmittance at the exposure wavelength (365 nm) were recorded and used as the absorbance and light transmittance of the photosensitive layer.
  • the absorbance of the photosensitive layer was divided by the thickness of the photosensitive layer to obtain the absorbance per 1 ⁇ m of thickness.
  • a substrate (Ra: 150 nm) in which electroless copper plating was applied onto Ajinomoto Buildup Film (registered trademark) ABF (Ajinomoto Fine-Techno Co., Ltd., product name "GL-102") was heated to 80°C, and a photosensitive element was laminated (laminated) onto the copper surface of the substrate.
  • 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, so that the photosensitive layer of the photosensitive element was in contact with the copper surface of the copper substrate while peeling off the protective layer. This resulted in a laminate in which the substrate, photosensitive layer, and support were laminated in this order.
  • the obtained laminate was used as a test piece for the test shown below.
  • the support was peeled off from the test piece to expose the photosensitive layer, and a 1% by mass aqueous solution of sodium carbonate at 30° C. was sprayed onto the exposed surface. The time required for the photosensitive layer to be completely removed was measured and taken as the minimum development time.
  • a glass chrome type phototool (resolution negative: having a wiring pattern with a line width/space width of 3x/x (x: 1 to 10, unit: ⁇ m), adhesion negative: having a wiring pattern with a line width/space width of x/3x (x: 1 to 18, unit: ⁇ m)) was used as a negative for evaluating resolution and adhesion, and the photosensitive layer was exposed with a predetermined amount of energy using a projection exposure apparatus (manufactured by Ushio Inc., product name "UX-2240-SM-XJ01") with an ultra-high pressure mercury lamp (365 nm) as a light source. After exposure, the support was peeled off to expose the photosensitive layer, and a 1% by mass aqueous solution of sodium carbonate at 30° C. was sprayed for a time twice the minimum development time to remove the unexposed portion (development treatment).
  • the space areas (unexposed areas) were completely removed, and the line areas (exposed areas) were formed without any warping, meandering, or chipping.
  • the smallest line width/space width value among the resist patterns was used to evaluate the resolution and adhesion.
  • a glass chrome type phototool (having a planar pattern of 50 mm x 40 mm) was used as a negative for evaluating the peel test on the support of the test piece, and the photosensitive layer was exposed to the above-mentioned predetermined energy amount using a projection exposure apparatus (manufactured by Ushio Inc., product name "UX-2240-SM-XJ01") with an ultra-high pressure mercury lamp (365 nm) as a light source.
  • Ushio Inc. product name "UX-2240-SM-XJ01”
  • UX-2240-SM-XJ01 ultra-high pressure mercury lamp
  • the substrate was immersed in an amine-based stripping solution (15% by volume R-100S + 8% by volume R-101 aqueous solution, manufactured by Mitsubishi Gas Chemical Co., Ltd.) heated to 50°C. The time until the photosensitive layer was completely removed was measured and used as the stripping time.
  • an amine-based stripping solution (15% by volume R-100S + 8% by volume R-101 aqueous solution, manufactured by Mitsubishi Gas Chemical Co., Ltd.

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PCT/JP2023/045139 2022-12-23 2023-12-15 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 Ceased WO2024135574A1 (ja)

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CN202380037165.3A CN120344918A (zh) 2022-12-23 2023-12-15 感光性树脂组合物、感光性元件、抗蚀剂图案的形成方法及印刷线路板的制造方法
EP23906936.2A EP4607280A4 (en) 2022-12-23 2023-12-15 PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT, RESERVE PATTERN FORMATION METHOD, AND PRINTED CIRCUIT BOARD PRODUCTION METHOD
KR1020257017834A KR20250095734A (ko) 2022-12-23 2023-12-15 감광성 수지 조성물, 감광성 엘리먼트, 레지스트 패턴의 형성 방법, 및 프린트 배선판의 제조 방법
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5746239A (en) * 1980-09-05 1982-03-16 Konishiroku Photo Ind Co Ltd Photosensitive printing plate
JP2009003177A (ja) 2007-06-21 2009-01-08 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
JP2013195712A (ja) 2012-03-19 2013-09-30 Hitachi Chemical Co Ltd 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
WO2021187549A1 (ja) * 2020-03-19 2021-09-23 富士フイルム株式会社 転写フィルム、感光性材料、パターン形成方法、回路基板の製造方法、タッチパネルの製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018040933A (ja) * 2016-09-07 2018-03-15 日立化成株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの製造方法、及びプリント配線板の製造方法
WO2022030053A1 (ja) * 2020-08-07 2022-02-10 昭和電工マテリアルズ株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5746239A (en) * 1980-09-05 1982-03-16 Konishiroku Photo Ind Co Ltd Photosensitive printing plate
JP2009003177A (ja) 2007-06-21 2009-01-08 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
JP2013195712A (ja) 2012-03-19 2013-09-30 Hitachi Chemical Co Ltd 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
WO2021187549A1 (ja) * 2020-03-19 2021-09-23 富士フイルム株式会社 転写フィルム、感光性材料、パターン形成方法、回路基板の製造方法、タッチパネルの製造方法

Non-Patent Citations (1)

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Title
See also references of EP4607280A4

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