WO2023238299A1 - Alkali-soluble resin, photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board - Google Patents

Alkali-soluble resin, photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board Download PDF

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Publication number
WO2023238299A1
WO2023238299A1 PCT/JP2022/023189 JP2022023189W WO2023238299A1 WO 2023238299 A1 WO2023238299 A1 WO 2023238299A1 JP 2022023189 W JP2022023189 W JP 2022023189W WO 2023238299 A1 WO2023238299 A1 WO 2023238299A1
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Prior art keywords
resin composition
photosensitive
alkali
meth
photosensitive resin
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PCT/JP2022/023189
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French (fr)
Japanese (ja)
Inventor
基彰 油井
琢 澤木
健宏 木下
夏木 戸田
俊昌 名越
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株式会社レゾナック
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Application filed by 株式会社レゾナック filed Critical 株式会社レゾナック
Priority to JP2024526131A priority Critical patent/JPWO2023238299A1/ja
Priority to PCT/JP2022/023189 priority patent/WO2023238299A1/en
Priority to CN202280086725.XA priority patent/CN118475880A/en
Priority to TW112120665A priority patent/TW202406943A/en
Publication of WO2023238299A1 publication Critical patent/WO2023238299A1/en

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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
    • 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

Definitions

  • the present disclosure relates to an alkali-soluble resin, 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 layers formed using the photosensitive resin compositions on support films are widely used.
  • Photosensitive elements comprising a photosensitive layer (also referred to as a “photosensitive layer”) are widely used.
  • a printed wiring board is manufactured using the photosensitive element described above, for example, by the following procedure. 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. Thereafter, areas other than the photocured portions of the photosensitive layer are removed using a developer to form a resist pattern. Next, using the resist pattern as a resist, etching or plating is performed to form a conductor pattern, and finally the photocured portion (resist pattern) of the photosensitive layer is peeled off (removed).
  • the photosensitive layer is required to have excellent properties in etching or plating, as well as excellent adhesion with circuit forming substrates and excellent resolution in resist pattern formation (e.g. , see Patent Document 1).
  • aqueous stripping solutions have come to be used to strip resist patterns instead of conventionally used amine stripping solutions (for example, Patent Document 2 reference.).
  • the photosensitive resin composition not only has high developability in the unexposed area and forms a resist pattern with excellent resolution and adhesion, but also has the ability to peel off the photocured area in order to peel and remove the resist pattern. It is required to be excellent in gender.
  • the present disclosure relates to an alkali-soluble resin used in a photosensitive resin composition having excellent developability, resolution, adhesion, and peelability, a photosensitive resin composition and a photosensitive element containing the alkali-soluble resin, and a photosensitive element using the same.
  • An object of the present invention is to provide a method for forming a resist pattern and a method for manufacturing a printed wiring board.
  • the content of the structural units derived from the acrylic acid is 18 to 25% by mass based on the total mass of the structural units derived from the polymerizable monomers constituting the alkali-soluble resin. 1].
  • the content of the structural units derived from acrylic acid is 18 to 25% by mass based on the total mass of the structural units derived from the polymerizable monomers constituting the alkali-soluble resin. 9].
  • the alkali-soluble resin according to [9] or [10] above which has a weight average molecular weight of 10,000 to 80,000.
  • the alkali-soluble resin according to any one of [9] to [11] above which has an acid value of 100 to 200 mgKOH/g.
  • 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 [8] above.
  • [14] Forming a photosensitive layer on the substrate using the photosensitive resin composition according to any one of [1] to [8] above or the photosensitive element according to [13] above, The method includes the steps of: irradiating at least a portion of the photosensitive layer with actinic rays 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 forming a resist pattern.
  • a method for manufacturing a printed wiring board comprising the step of etching or plating a substrate on which a resist pattern is formed by the resist pattern forming method described in [14] above to form a conductor pattern.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a photosensitive element.
  • the term "process” is used not only to refer to an independent process, but also to include any process that achieves the intended effect even if it cannot be clearly distinguished from other processes. It will be done.
  • the term “layer” includes a structure having a shape formed on the entire surface as well as a structure having a shape formed in a part of the layer.
  • a numerical range indicated using “ ⁇ ” indicates a range that includes the numerical values written before and after " ⁇ " as the minimum and maximum values, respectively.
  • the upper limit or lower limit of the numerical range of one step may be replaced with the upper limit or lower limit of the numerical range of another step.
  • the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples.
  • the alkali-soluble resin according to the present embodiment has a structural unit derived from acrylic acid, a structural unit derived from styrene or a styrene derivative, and a structural unit derived from a (meth)acrylate compound having an alicyclic structure.
  • a coating film with a thickness of about 5 ⁇ m is formed by spin coating a varnish obtained by dissolving a resin in an arbitrary solvent onto a substrate such as a silicon wafer. This is immersed in any one of a TMAH aqueous solution, a metal hydroxide aqueous solution, a metal carbonate aqueous solution, or an organic amine aqueous solution at 20 to 25°C. As a result, when the coating can be uniformly dissolved, the resin can be considered to be soluble in an alkaline aqueous solution.
  • the alkali-soluble resin according to the present embodiment can be used as a binder polymer of a photosensitive resin composition, and improves the developability, resolution, adhesion, and releasability of the photosensitive layer formed from the photosensitive resin composition. can be improved.
  • the alkali-soluble resin according to the present embodiment can be produced, for example, by radical polymerizing polymerizable monomers containing acrylic acid, styrene or a styrene derivative, and (meth)acrylate having an alicyclic structure. can.
  • the alkali-soluble resin has a structural unit derived from acrylic acid
  • the alkali developability of the photosensitive resin composition can be improved, and the removability of the resist pattern can be improved.
  • Acrylic acid and methacrylic acid may be used together, but if the content of structural units derived from methacrylic acid is increased, the releasability tends to decrease.
  • the alkali-soluble resin has a structural unit derived from styrene or a styrene derivative (hereinafter also referred to as "styrenic structural unit"), the resolution and adhesion of the photosensitive resin composition are improved, and the amount of resist streaks generated is reduced. can be reduced.
  • styrene derivatives include vinyltoluene, ⁇ -methylstyrene, p-methylstyrene, and p-ethylstyrene.
  • the content of styrene structural units is based on the total mass of structural units derived from the polymerizable monomers constituting the binder polymer. may be 55% by mass or more, 60% by mass or more, or 64% by mass or more. From the viewpoint that the development time is appropriately shortened and development residues are less likely to occur, the content of the styrene structural unit may be 84% by mass or less, 80% by mass or less, or 78% by mass or less.
  • the alkali-soluble resin has 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. Can be mentioned.
  • the content of the structural units derived from the (meth)acrylate compound having an alicyclic structure is based on the total mass (100% by 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 resin composition, it may be 0.5% by mass or more, 0.8% by mass or more, or 1% by mass or more, and it improves the developability of the photosensitive resin composition. From the viewpoint of further improvement, the content may be 20% by mass or less, 18% by mass or less, or 16% by mass or less.
  • the weight average molecular weight (Mw) of the alkali-soluble resin may be 10,000 to 80,000, 15,000 to 70,000, 20,000 to 60,000, 23,000 to 50,000, or 25,000 to 45,000.
  • Mw is 80,000 or less, resolution and developability tend to improve, and when Mw is 10,000 or more, the flexibility of the cured film improves, making it difficult for the resist pattern to chip or peel. There is a tendency.
  • the dispersity (Mw/Mn) of the alkali-soluble resin may be 1.0 to 3.0, 1.0 to 2.5, or 1.0 to 2.3. As the degree of dispersion decreases, resolution tends to improve.
  • the photosensitive resin composition according to the present embodiment includes (A) a binder polymer (hereinafter sometimes referred to as “component (A)”), (B) a photopolymerizable compound (hereinafter referred to as “component (B)”). ), (C) a photopolymerization initiator (hereinafter sometimes referred to as “(C) component”), and (D) a sensitizer (hereinafter sometimes referred to as "(D) component”). ).
  • component (A) a binder polymer
  • component (B) a photopolymerizable compound
  • component (C) component) a photopolymerizable compound
  • (C) component) a photopolymerization initiator
  • (D) component” a sensitizer
  • component (A) is 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass, Alternatively, it may be 50 parts by mass or more, and from the viewpoint of further improving sensitivity and resolution, it may be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less.
  • Component (B) Photopolymerizable compound
  • the photosensitive resin composition contains one or more of the (B) components.
  • Component (B) may be any compound that polymerizes when exposed to light, and may be, for example, a compound having an ethylenically unsaturated bond.
  • Component (B) may include a polyfunctional monomer having two or more reactive groups that react with radicals.
  • Component (B) may contain a bisphenol A type (meth)acrylate compound from the viewpoint of further improving alkali developability, resolution, and removability after curing.
  • Component (B) is 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane(2,2-bis(4-((meth) (acryloxypentaethoxy)phenyl)propane, etc.).
  • 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane a compound having 10 or more oxyethylene groups may be used, and a compound having less than 10 oxyethylene groups may be used.
  • a compound having 10 or more oxyethylene groups and a compound having less than 10 oxyethylene groups may be used together.
  • Component (B) may include a compound having three or more (meth)acryloyl groups from the viewpoint of improving sensitivity and adhesion.
  • 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.
  • photopolymerizable compounds include nonylphenoxypolyethylene oxyacrylate, phthalic acid compounds, (meth)acrylic acid alkyl esters, and photopolymerizable compounds having at least one cationically polymerizable cyclic ether group in the molecule (oxetane compounds). etc.).
  • the other photopolymerizable compound is at least one selected from the group consisting of nonylphenoxy polyethylene oxyacrylate and phthalic acid compounds, from the viewpoint of further improving resolution, adhesion, resist shape, and peelability after curing. It's good.
  • component (B) contains other photopolymerizable compounds
  • the content of the other photopolymerizable compounds is determined from the viewpoint of further suitably improving resolution, adhesion, resist shape, and removability after curing.
  • ) may be 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 25% by weight or less, or 20% by weight or less, based on the total amount of the components.
  • the content of the compound having a total of 2 to 40 EO groups and/or PO groups is 2 to 15% by mass, 4 to 12% by mass, based on the total amount of component (B), from the viewpoint of further improving adhesion and resolution. % or 5 to 8% by mass.
  • the content of the hexaarylbiimidazole compound is 90% by mass or more, 95% by mass or more, or 99% by mass based on the total amount of component (C) from the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film. % or more.
  • Component (C) may consist only of a hexaarylbiimidazole compound.
  • the content of component (D) is 0.01 to 5 parts by mass, 0.01 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B). It may be 1 part by mass, or 0.01 to 0.2 part by mass.
  • the photosensitive resin composition further contains (E) Component: Polymerization Inhibitor from the viewpoint of suppressing polymerization in unexposed areas during resist pattern formation and further improving resolution. Good too.
  • the polymerization inhibitor may be, for example, 4-tert-butylcatechol, 2,2,6,6-tetramethylpiperidinooxyl free radical, or the like.
  • component (E) is 0.001 to 0.10 parts by mass, 0.005 to 0.08 parts by mass, or 0. It may be .01 to 0.05 parts by weight.
  • the photosensitive resin composition may further contain one or more components other than the components mentioned above.
  • Other ingredients 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, photochromic agent, thermal coloring inhibitor, plasticizer (p-toluenesulfonamide, etc.), pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion agent, leveling agent, peeling agent Examples include accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and the like.
  • the content of other components may be 0.005 parts by mass or more, or 0.01 parts by mass or more, and 20 parts by mass or less, based on 100 parts by mass of the total amount of components (A) and (B). It's okay
  • the photosensitive resin composition may further contain one or more organic solvents from the viewpoint of adjusting 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% by mass or more and 70% by mass or less based on the total amount of the photosensitive resin composition.
  • the photosensitive resin composition can be suitably used for forming a resist pattern, and can be particularly suitably used for the method for manufacturing a wiring board described below.
  • the photosensitive element of this embodiment includes a support and a photosensitive layer formed on the support, and the photosensitive layer contains the above-described photosensitive resin composition.
  • the photosensitive layer may be laminated onto the 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. As shown in FIG. 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 a protective layer provided as necessary. 4 and other layers.
  • 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 polyolefin film such as a polyethylene film, a polypropylene film, etc. .
  • the support 2 and the protective layer 4 may each be a film of a hydrocarbon polymer other than polyolefin. Films of hydrocarbon-based polymers comprising polyolefins 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 polymer film.
  • the type of polymer film constituting the protective layer 4 may be the same as or different from the type of polymer film constituting the support 2.
  • These polymer films are, for example, a polyethylene terephthalate film such as the PS series (for example, PS-25) manufactured by Teijin Ltd., a polyethylene film such as NF-15 manufactured by Tamapoly Co., Ltd., or a polyethylene film such as NF-15 manufactured by Oji Paper Co., Ltd.
  • a polypropylene film such as Alphan MA-410, E-200C) or manufactured by Shin-Etsu Film Co., Ltd.
  • 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 when exposing through the support 2. From the viewpoint of suitable exposure to light, the thickness may be 100 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less.
  • the thickness of the protective layer 4 is 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 laminating the photosensitive layer 3 and support 2 on the substrate while peeling off the protective layer 4. From the viewpoint of improving productivity, the thickness may be 100 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less.
  • the photosensitive layer 3 is made of the photosensitive resin composition described above.
  • the thickness of the photosensitive layer 3 after drying is 1 ⁇ m or more from the viewpoint of facilitating coating and improving productivity. Alternatively, it may be 5 ⁇ m or more, and from the viewpoint of further improving adhesion and resolution, it may be 100 ⁇ m or less, 50 ⁇ m or less, or 40 ⁇ m or less.
  • the photosensitive element 1 can be obtained, for example, as follows. First, a photosensitive layer 3 is formed on a support 2. The photosensitive layer 3 can be formed, for example, by coating a photosensitive resin composition containing an organic solvent to form a coating layer, and drying this coating layer. Next, a protective layer 4 is formed on the surface of the photosensitive layer 3 opposite to 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, and bar coating.
  • the coating layer is dried so that the amount of organic solvent remaining in the photosensitive layer 3 is, for example, 2% by mass or less. be exposed.
  • 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 absorption layer, and a gas barrier layer.
  • 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.
  • the photosensitive element roll the photosensitive element 1 is preferably wound so that the support 2 is on the outside.
  • the winding core is made of, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, or the like.
  • the end face of the photosensitive element roll may be provided with an end face separator from the viewpoint of end face protection, and may be provided with a moisture-proof end face separator 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 for forming a resist pattern, and can be particularly suitably used for a method for manufacturing a printed wiring board, which will be described later.
  • the method for forming a resist pattern of the present embodiment includes a step of forming a photosensitive layer on a substrate using the photosensitive resin composition or the photosensitive element (photosensitive layer forming step); a step of irradiating at least a portion (predetermined portion) with actinic rays to form a photocured portion (exposure step); and a step of removing at least a portion of the non-photocured portion from the substrate (development step). , and may include other steps as necessary.
  • the resist pattern can be said to be a pattern of a photocured product of a 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 photosensitive layer forming step is preferably carried out under reduced pressure from the viewpoint of adhesion and trackability.
  • 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 approximately 0.1 to 1.0 MPa (approximately 1 to 10 kgf/cm 2 ), but these conditions are appropriately selected as necessary. Note that if the photosensitive layer is heated to 70 to 130° C., it is not necessary to preheat the substrate, but it is also possible to preheat the substrate in order to further improve adhesion and followability.
  • the exposure step at least a portion of the photosensitive layer formed on the substrate is irradiated with actinic rays, so that the portion irradiated with the actinic rays is photocured and a latent image is formed.
  • actinic rays can be irradiated through the support, but if the support is light-shielding, After removing the support, the photosensitive layer is irradiated with actinic rays.
  • Examples of the exposure method include a method (mask exposure method) of irradiating actinic rays imagewise through a negative or positive mask pattern called artwork.
  • a method of irradiating actinic rays imagewise using a projection exposure method may be adopted.
  • a method of irradiating actinic rays imagewise by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be adopted.
  • LDI Laser Direct Imaging
  • DLP Digital Light Processing
  • known light sources can be used, such as 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, semiconductor lasers, etc.
  • gas lasers such as argon lasers
  • solid state lasers such as YAG lasers
  • semiconductor lasers etc.
  • a material that effectively emits ultraviolet rays and visible light is used.
  • development is performed by a known development method using a developer compatible with the photosensitive resin composition.
  • the developing method include methods using a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like.
  • a high-pressure spray method may be used as a developing method. Development may be performed by combining two or more of these methods.
  • Examples of the organic solvent used in the alkaline aqueous solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol.
  • Monobutyl ether is mentioned.
  • organic solvent used in the organic solvent developer examples 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 an amount in the range of 1 to 20% by mass to form an organic solvent developer.
  • the method for forming a resist pattern in this embodiment after removing the uncured portion in the development step, heating at about 60 to 250°C or exposure to about 0.2 to 10 J/cm 2 is performed as necessary.
  • the method may also include a step of further curing the resist pattern.
  • the method for manufacturing a printed wiring board of this embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the above-described method for forming a resist pattern.
  • the method may also include other steps such as a pattern removal step.
  • plating is performed on the conductor layer provided on the substrate using a resist pattern formed on the substrate as a mask.
  • a conductor pattern may be formed by removing the resist by removing a resist pattern, which will be described later, and further etching the conductor layer covered with this resist.
  • the plating method may be electrolytic plating, electroless plating, or electroless plating.
  • a conductor layer provided on the substrate is etched away using a resist pattern formed on the substrate as a mask to form a conductor pattern.
  • the etching method is appropriately selected depending on the conductor layer to be removed.
  • the etching solution include a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
  • the resist pattern on the substrate may be removed.
  • the resist pattern can be removed, for example, using an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used in the above-mentioned developing step.
  • an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used in the above-mentioned developing step.
  • the strongly alkaline aqueous solution for example, a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 10% by mass aqueous potassium hydroxide solution, etc. are used.
  • the conductor layer covered with the resist is further etched by an etching process to form a conductor pattern, thereby making it possible to manufacture a desired printed wiring board.
  • the etching method at this time is appropriately selected depending on the conductor layer to be removed. For example, the above-mentioned etching solution can be applied.
  • the method for manufacturing a printed wiring board according to this embodiment is applicable not only to the manufacturing of single-layer printed wiring boards but also to the manufacturing of multilayer printed wiring boards, and also to the manufacturing of printed wiring boards having small-diameter through holes. It is possible.
  • Alkali-soluble resin As a polymerizable monomer, a compound having a homopolymer Tg shown below was prepared.
  • AA Acrylic acid (Tg: 106°C)
  • MAA methacrylic acid (Tg: 228°C)
  • ST Styrene (Tg: 100°C)
  • TCDMA dicyclopentanyl methacrylate (Tg: 175°C)
  • BZMA Benzyl methacrylate (Tg: 54°C)
  • IBOA Isobornyl acrylate (Tg: 94°C)
  • HEMA Hydroxyethyl methacrylate (Tg: 55°C)
  • 2-EHA 2-ethylhexyl acrylate (Tg: -70°C)
  • Solution (a) was prepared by dissolving 4.4 g of AIBN in 26.3 g of propylene glycol monomethyl ether.
  • Example 2 A solution of binder polymer (A-2) was obtained under the same conditions as in Example 1, except that the amount of AIBN in solution (a) was changed to 5.5 g.
  • Example 3 A solution of binder polymer (A-3) was obtained under the same conditions as in Example 1, except that the amount of AIBN in solution (a) was changed to 11.9 g.
  • Binder polymers (A-4) to (A-8) were prepared under the same conditions as binder polymer (A-2) except that the amount of polymerizable monomer in mixture (x) was changed to the mass ratio shown in Table 1. A solution of was obtained.
  • Binder polymer (A-2) was prepared under the same conditions as binder polymer (A-2) except that the type and amount of the polymerizable monomer in mixture (x) were changed to the polymerizable monomers and mass ratio shown in Table 1. Solutions of 9) to (A-13) were obtained.
  • Binder polymer (A-2) was prepared under the same conditions as binder polymer (A-2) except that the type and amount of the polymerizable monomer in mixture (x) were changed to the polymerizable monomers and mass ratio shown in Table 1. Solutions of 14) to (A-16) were obtained.
  • 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.)
  • THF Tetrahydrofuran
  • the Tg of the binder polymer was calculated from the Fox equation.
  • the acid value of the binder polymer was measured by neutralization titration method according to JIS K6901:2008 5.3.2.
  • a photosensitive resin composition was prepared by mixing each component in the amount (parts by mass) shown in Table 2 with respect to the solid content of the binder polymer solution of 56 parts by mass. Details of each component shown in Table 2 are as follows.
  • a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "QS-69") with a thickness of 16 ⁇ m was prepared as a support. After coating the photosensitive resin composition on the support, it was sequentially dried in a hot air convection dryer at 80° C. and 120° C. to form a photosensitive layer having a thickness of 25 ⁇ m after drying.
  • a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-15”) was laminated as a protective layer on this photosensitive layer to obtain a photosensitive element in which the support, the photosensitive layer, and the protective layer were laminated in this order.
  • a copper-clad laminate (manufactured by Showa Denko Materials Co., Ltd., product name "MCL-E-679"), which is a glass epoxy material with copper foil (thickness: 35 ⁇ m) laminated on both sides, was washed with water, pickled, and washed with water. , dried with air flow.
  • the surface-treated copper-clad laminate was heated to 80° C., and while the protective layer was peeled off, a photosensitive element was laminated so that the photosensitive layer was in contact with the copper surface. Thereby, a laminate in which the copper-clad laminate, the photosensitive layer, and the support were laminated in this order was obtained.
  • Lamination was performed using a heat roll at 110° C. at a pressure of 0.4 MPa and a roll speed of 1.05 m/min.
  • the above laminate was cut into 5 cm square pieces 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 using a 1% by mass aqueous sodium carbonate solution at 30°C at a pressure of 0.15 MPa, and the unexposed area of 1 mm or more was removed. The shortest time during which this could be visually confirmed was defined as the shortest development time.
  • a full cone type nozzle was used. The distance between the test piece and the tip of the nozzle was 6 cm, and the test piece was arranged so that the center of the test piece and the center of the nozzle coincided. It means that the shorter the minimum development time (unit: seconds), the better the developability.
  • a Hitachi 41 step step tablet was placed on the support of the test piece, and a direct writing exposure machine (manufactured by Via Mechanics Co., Ltd., trade name "DE-1UH") using a blue-violet laser diode with a wavelength of 405 nm as a light source was used. Then, the photosensitive layer was exposed through the support at an exposure amount (irradiation energy amount) such that the number of steps remaining after development of the Hitachi 41-step step tablet was 18 steps. The photosensitivity was evaluated based on the exposure amount (unit: mJ/cm 2 ) at this time. The smaller the exposure amount, the higher the photosensitivity.
  • the support was peeled from the laminate to expose the photosensitive layer, and unexposed areas were removed by spraying a 1% by mass aqueous sodium carbonate solution at 30°C for 60 seconds.
  • adhesion is evaluated by the minimum value of the line width in the resist pattern in which the space portions (unexposed portions) are removed without any residue and the line portions (exposed portions) are formed without meandering or chipping. did. It means that the smaller this value is, the better the adhesion is. A case where the adhesion is 10 ⁇ m or less is considered to be a pass.
  • the support was peeled from the laminate to expose the photosensitive layer, and unexposed areas were removed by spraying a 1% by mass aqueous sodium carbonate solution at 30°C for 60 seconds.
  • the resolution was evaluated by the minimum value of the space width in the resist pattern in which the space portions (unexposed portions) were removed without any residue and the line portions (exposed portions) were formed without meandering or chipping. . The smaller this number is, the better the resolution is. A case where the resolution is 12 ⁇ m or less is considered a pass.

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Abstract

A photosensitive resin composition according to one embodiment of the present disclosure contains a binder polymer, a photopolymerizable compound, a photopolymerization initiation agent, and a sensitization agent, wherein the binder polymer includes an alkali-soluble resin having a structural unit derived from acrylic acid, a structural unit derived from styrene or a styrene derivative, and a structural unit derived from a (meth)acrylate compound having an alicyclic structure.

Description

アルカリ可溶性樹脂、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Alkali-soluble resin, photosensitive resin composition, photosensitive element, resist pattern forming method, and printed wiring board manufacturing method
　本開示は、アルカリ可溶性樹脂、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に関する。 The present disclosure relates to an alkali-soluble resin, a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.
　プリント配線板の製造分野においては、エッチング処理又はめっき処理等に用いられるレジスト材料として、感光性樹脂組成物、及び、支持フィルム上に感光性樹脂組成物を用いて形成された層（以下、「感光層」ともいう）を備える感光性エレメントが広く用いられている。 In the field of manufacturing printed wiring boards, photosensitive resin compositions and layers formed using the photosensitive resin compositions on support films (hereinafter referred to as " Photosensitive elements comprising a photosensitive layer (also referred to as a "photosensitive layer") are widely used.
　プリント配線板は、上記感光性エレメントを用いて、例えば、以下の手順で製造されている。すなわち、まず、感光性エレメントの感光層を銅張積層板等の回路形成用基板上にラミネートする。次に、マスクフィルム等を介して感光層を露光し、光硬化部を形成する。このとき、露光前又は露光後に支持フィルムを剥離する。その後、感光層の光硬化部以外の領域を現像液で除去し、レジストパターンを形成する。次に、レジストパターンをレジストとして、エッチング処理又はめっき処理を施して導体パターンを形成させ、最終的に感光層の光硬化部（レジストパターン）を剥離（除去）する。 A printed wiring board is manufactured using the photosensitive element described above, for example, by the following procedure. 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. Thereafter, areas other than the photocured portions of the photosensitive layer are removed using a developer to form a resist pattern. Next, using the resist pattern as a resist, etching or plating is performed to form a conductor pattern, and finally the photocured portion (resist pattern) of the photosensitive layer is peeled off (removed).
　近年、プリント配線板の高密度化に伴い、導体パターンの微細化が進むにつれて、回路形成用基板とレジストである感光層との接触面積が小さくなっている。そのため、感光層には、エッチング処理又はめっき処理における優れた特性が要求されると共に、回路形成用基板との優れた密着性、及び、レジストパターンの形成における優れた解像度が要求されている（例えば、特許文献１参照。）。また、環境への影響の観点から、レジストパターンの剥離には、従来、用いられていたアミン系剥離液に替えて、水溶液系剥離液が用いられるようになってきている（例えば、特許文献２参照。）。 In recent years, as the density of printed wiring boards has increased and conductor patterns have become finer, the contact area between the circuit-forming substrate and the photosensitive layer, which is a resist, has become smaller. Therefore, the photosensitive layer is required to have excellent properties in etching or plating, as well as excellent adhesion with circuit forming substrates and excellent resolution in resist pattern formation (e.g. , see Patent Document 1). Furthermore, from the perspective of environmental impact, aqueous stripping solutions have come to be used to strip resist patterns instead of conventionally used amine stripping solutions (for example, Patent Document 2 reference.).
特開２００９－００３１７７号公報Japanese Patent Application Publication No. 2009-003177 特開２０１３－０６１５５６号公報JP2013-061556A
　感光性樹脂組成物には、未露光部の現像性が高く、優れた解像性及び密着性を有するレジストパターンを形成するだけでなく、レジストパターンを剥離除去するために、光硬化部の剥離性に優れることが求められる。 The photosensitive resin composition not only has high developability in the unexposed area and forms a resist pattern with excellent resolution and adhesion, but also has the ability to peel off the photocured area in order to peel and remove the resist pattern. It is required to be excellent in gender.
　本開示は、現像性、解像性、密着性、及び剥離性に優れる感光性樹脂組成物に用いられるアルカリ可溶性樹脂、該アルカリ可溶性樹脂を含む感光性樹脂組成物及び感光性エレメント、並びにそれらを用いた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を提供することを目的とする。 The present disclosure relates to an alkali-soluble resin used in a photosensitive resin composition having excellent developability, resolution, adhesion, and peelability, a photosensitive resin composition and a photosensitive element containing the alkali-soluble resin, and a photosensitive element using the same. An object of the present invention is to provide a method for forming a resist pattern and a method for manufacturing a printed wiring board.
　上記目的を達成するために、本開示の一態様は、以下のアルカリ可溶性樹脂、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に関する。
［１］バインダーポリマーと、光重合性化合物と、光重合開始剤と、増感剤と、を含有する感光性樹脂組成物であって、前記バインダーポリマーが、アクリル酸に由来する構造単位と、スチレン又はスチレン誘導体に由来する構造単位と、脂環構造を有する（メタ）アクリレート化合物に由来する構造単位と、を有するアルカリ可溶性樹脂を含む、感光性樹脂組成物。
［２］前記アクリル酸に由来する構造単位の含有量が、前記アルカリ可溶性樹脂を構成する重合性単量体に由来する構造単位の全質量を基準として、１８～２５質量％である、上記［１］に記載の感光性樹脂組成物。
［３］前記アルカリ可溶性樹脂の重量平均分子量が、１００００～８００００である、上記［１］又は［２］に記載の感光性樹脂組成物。
［４］前記アルカリ可溶性樹脂の酸価が、１００～２００ｍｇＫＯＨ／ｇである、上記［１］～［３］のいずれかに記載の感光性樹脂組成物。
［５］前記増感剤が、アントラセン化合物を含む、上記［１］～［４］のいずれかに記載の感光性樹脂組成物。
［６］前記光重合性化合物が、オキシエチレン基の数が１０以上である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンを含む、上記［１］～［５］のいずれかに記載の感光性樹脂組成物。
［７］前記光重合性化合物が、オキシエチレン基の数が１０未満である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンを含む、上記［１］～［６］のいずれかに記載の感光性樹脂組成物。
［８］前記光重合性化合物が、オキシエチレン基の数が１０以上である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンと、オキシエチレン基の数が１０未満である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンとを含む、上記［１］～［５］のいずれかに記載の感光性樹脂組成物。
［９］アクリル酸に由来する構造単位と、スチレン又はスチレン誘導体に由来する構造単位と、脂環構造を有する（メタ）アクリレート化合物に由来する構造単位と、を有する、アルカリ可溶性樹脂。
［１０］前記アクリル酸に由来する構造単位の含有量が、前記アルカリ可溶性樹脂を構成する重合性単量体に由来する構造単位の全質量を基準として、１８～２５質量％である、上記［９］に記載のアルカリ可溶性樹脂。
［１１］重量平均分子量が１００００～８００００である、上記［９］又は［１０］に記載のアルカリ可溶性樹脂。
［１２］酸価が１００～２００ｍｇＫＯＨ／ｇである、上記［９］～［１１］のいずれかに記載のアルカリ可溶性樹脂。
［１３］支持体と、該支持体上に上記［１］～［８］のいずれかに記載の感光性樹脂組成物を用いて形成された感光層と、を備える感光性エレメント。
［１４］基板上に、上記［１］～［８］のいずれかに記載の感光性樹脂組成物又は上記［１３］に記載の感光性エレメントを用いて、感光層を形成する工程と、前記感光層の少なくとも一部に活性光線を照射して、光硬化部を形成する工程と、前記基板から、前記感光層の未光硬化部を除去して、レジストパターンを形成する工程と、を備える、レジストパターンの形成方法。
［１５］上記［１４］に記載のレジストパターンの形成方法によりレジストパターンが形成された基板をエッチング処理又はめっき処理して、導体パターンを形成する工程を備える、プリント配線板の製造方法。
［１６］前記エッチング処理又はめっき処理の後に、前記レジストパターンを除去する工程を更に備える、上記［１５］に記載のプリント配線板の製造方法。 In order to achieve the above object, one embodiment of the present disclosure relates to the following alkali-soluble resin, photosensitive resin composition, photosensitive element, resist pattern forming method, and printed wiring board manufacturing method.
[1] A photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photoinitiator, and a sensitizer, wherein the binder polymer contains a structural unit derived from acrylic acid, A photosensitive resin composition comprising an alkali-soluble resin having a structural unit derived from styrene or a styrene derivative and a structural unit derived from a (meth)acrylate compound having an alicyclic structure.
[2] The content of the structural units derived from the acrylic acid is 18 to 25% by mass based on the total mass of the structural units derived from the polymerizable monomers constituting the alkali-soluble resin. 1]. The photosensitive resin composition described in [1].
[3] The photosensitive resin composition according to [1] or [2] above, wherein the alkali-soluble resin has a weight average molecular weight of 10,000 to 80,000.
[4] The photosensitive resin composition according to any one of [1] to [3] above, wherein the alkali-soluble resin has an acid value of 100 to 200 mgKOH/g.
[5] The photosensitive resin composition according to any one of [1] to [4] above, wherein the sensitizer contains an anthracene compound.
[6] The above [1] to [5], wherein the photopolymerizable compound contains 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane having 10 or more oxyethylene groups. ] The photosensitive resin composition according to any one of the above.
[7] The above-mentioned [1] to [6], wherein the photopolymerizable compound contains 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane having less than 10 oxyethylene groups. ] The photosensitive resin composition according to any one of the above.
[8] The photopolymerizable compound is 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane having 10 or more oxyethylene groups and less than 10 oxyethylene groups. The photosensitive resin composition according to any one of [1] to [5] above, comprising 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane.
[9] An alkali-soluble resin having a structural unit derived from acrylic acid, a structural unit derived from styrene or a styrene derivative, and a structural unit derived from a (meth)acrylate compound having an alicyclic structure.
[10] The content of the structural units derived from acrylic acid is 18 to 25% by mass based on the total mass of the structural units derived from the polymerizable monomers constituting the alkali-soluble resin. 9].
[11] The alkali-soluble resin according to [9] or [10] above, which has a weight average molecular weight of 10,000 to 80,000.
[12] The alkali-soluble resin according to any one of [9] to [11] above, which has an acid value of 100 to 200 mgKOH/g.
[13] 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 [8] above.
[14] Forming a photosensitive layer on the substrate using the photosensitive resin composition according to any one of [1] to [8] above or the photosensitive element according to [13] above, The method includes the steps of: irradiating at least a portion of the photosensitive layer with actinic rays 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 forming a resist pattern.
[15] A method for manufacturing a printed wiring board, comprising the step of etching or plating a substrate on which a resist pattern is formed by the resist pattern forming method described in [14] above to form a conductor pattern.
[16] The method for manufacturing a printed wiring board according to [15] above, further comprising a step of removing the resist pattern after the etching treatment or the plating treatment.
　本開示によれば、現像性、解像性、密着性、及び剥離性に優れる感光性樹脂組成物に用いられるアルカリ可溶性樹脂、該アルカリ可溶性樹脂を含む感光性樹脂組成物及び感光性エレメント、並びにそれらを用いた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を提供することができる。 According to the present disclosure, an alkali-soluble resin used in a photosensitive resin composition having excellent developability, resolution, adhesion, and removability, a photosensitive resin composition and a photosensitive element containing the alkali-soluble resin, and A method of forming a resist pattern and a method of manufacturing a printed wiring board using the same can be provided.
感光性エレメントの一実施形態を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing one embodiment of a photosensitive element.
　以下、本開示を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。 Hereinafter, modes for carrying out the present disclosure will be described in detail. However, the present invention is not limited to the following embodiments.
　本明細書において、「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。「層」との語は、平面図として観察したときに、全面に形成されている形状の構造に加え、一部に形成されている形状の構造も包含される。「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 In this specification, the term "process" is used not only to refer to an independent process, but also to include any process that achieves the intended effect even if it cannot be clearly distinguished from other processes. It will be done. When observed as a plan view, the term "layer" includes a structure having a shape formed on the entire surface as well as a structure having a shape formed in a part of the layer. A numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range of one step may be replaced with the upper limit or lower limit of the numerical range of another step. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples.
　本明細書において、「（メタ）アクリレート」とは、「アクリレート」及びそれに対応する「メタクリレート」の少なくとも一方を意味する。（メタ）アクリロイル等の他の類似表現についても同様である。 In this specification, "(meth)acrylate" means at least one of "acrylate" and "methacrylate" corresponding thereto. The same applies to other similar expressions such as (meth)acryloyl.
　本明細書において、感光性樹脂組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。本明細書において、「固形分」とは、感光性樹脂組成物において、揮発する物質（水、溶剤等）を除いた不揮発分を指す。すなわち、「固形分」とは、後述する感光性樹脂組成物の乾燥において揮発せずに残る溶剤以外の成分を指し、室温（２５℃）で液状、水飴状又はワックス状の成分も含む。 In the present specification, if there are multiple substances corresponding to each component in the composition, the amount of each component in the photosensitive resin composition refers to the amount of each component present in the composition, unless otherwise specified. means the total amount of substance. As used herein, "solid content" refers to nonvolatile content excluding volatile substances (water, solvent, etc.) in the photosensitive resin composition. That is, the "solid content" refers to components other than the solvent that remain without being volatilized during drying of the photosensitive resin composition described below, and also includes components that are liquid, starch syrup, or wax-like at room temperature (25° C.).
［アルカリ可溶性樹脂］
　本実施形態に係るアルカリ可溶性樹脂は、アクリル酸に由来する構造単位と、スチレン又はスチレン誘導体に由来する構造単位と、脂環構造を有する（メタ）アクリレート化合物に由来する構造単位とを有する。 [Alkali-soluble resin]
The alkali-soluble resin according to the present embodiment has a structural unit derived from acrylic acid, a structural unit derived from styrene or a styrene derivative, and a structural unit derived from a (meth)acrylate compound having an alicyclic structure.
　アルカリ可溶性樹脂とは、アルカリ性水溶液に可溶な樹脂である。アルカリ性水溶液とは、例えば、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液、金属水酸化物水溶液、金属炭酸塩水溶液、及び有機アミン水溶液が挙げられる。樹脂がアルカリ性水溶液に可溶であることは、例えば、以下のようにして確認することができる。 An alkali-soluble resin is a resin that is soluble in an alkaline aqueous solution. Examples of the alkaline aqueous solution include a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, a metal carbonate aqueous solution, and an organic amine aqueous solution. Whether the resin is soluble in an alkaline aqueous solution can be confirmed, for example, as follows.
　樹脂を任意の溶剤に溶解して得られたワニスを、シリコンウェハ等の基板上にスピン塗布して形成することにより厚さ５μｍ程度の塗膜とする。これをＴＭＡＨ水溶液、金属水酸化物水溶液、金属炭酸塩水溶液、又は有機アミン水溶液のいずれかに２０～２５℃において、浸漬する。この結果、塗膜が均一に溶解し得るとき、その樹脂はアルカリ性水溶液に可溶であると見なすことができる。 A coating film with a thickness of about 5 μm is formed by spin coating a varnish obtained by dissolving a resin in an arbitrary solvent onto a substrate such as a silicon wafer. This is immersed in any one of a TMAH aqueous solution, a metal hydroxide aqueous solution, a metal carbonate aqueous solution, or an organic amine aqueous solution at 20 to 25°C. As a result, when the coating can be uniformly dissolved, the resin can be considered to be soluble in an alkaline aqueous solution.
　本実施形態に係るアルカリ可溶性樹脂は、感光性樹脂組成物のバインダーポリマーとして用いることができ、感光性樹脂組成物から形成される感光層の現像性、解像性、密着性、及び剥離性を向上することができる。 The alkali-soluble resin according to the present embodiment can be used as a binder polymer of a photosensitive resin composition, and improves the developability, resolution, adhesion, and releasability of the photosensitive layer formed from the photosensitive resin composition. can be improved.
　本実施形態に係るアルカリ可溶性樹脂は、例えば、アクリル酸と、スチレン又はスチレン誘導体と、脂環構造を有する（メタ）アクリレートと、を含む重合性単量体をラジカル重合させることにより製造することができる。 The alkali-soluble resin according to the present embodiment can be produced, for example, by radical polymerizing polymerizable monomers containing acrylic acid, styrene or a styrene derivative, and (meth)acrylate having an alicyclic structure. can.
　アルカリ可溶性樹脂がアクリル酸由来の構造単位を有することで、感光性樹脂組成物のアルカリ現像性を向上する共に、レジストパターンの剥離性を向上することができる。アクリル酸とメタクリル酸とを併用してもよいが、メタクリル酸由来の構造単位の含有量を増えると、剥離性が低下し易くなる。 When the alkali-soluble resin has a structural unit derived from acrylic acid, the alkali developability of the photosensitive resin composition can be improved, and the removability of the resist pattern can be improved. Acrylic acid and methacrylic acid may be used together, but if the content of structural units derived from methacrylic acid is increased, the releasability tends to decrease.
　アルカリ現像性とアルカリ耐性とをバランスよく向上させる点から、アクリル酸に由来する構造単位の含有量は、アルカリ可溶性樹脂を構成する重合性単量体に由来する構造単位の全質量を基準（１００質量％）として、１５～２５質量％、１８～２４質量％、１９～２４質量％、又は１９～２３質量％であってもよい。この含有量が１５質量％以上ではアルカリ現像性が向上する傾向があり、２５質量％以下ではアルカリ耐性に優れる傾向がある。 In order to improve alkaline developability and alkali resistance in a well-balanced manner, the content of structural units derived from acrylic acid is based on the total mass of structural units derived from polymerizable monomers constituting the alkali-soluble resin (100 (mass%) may be 15 to 25 mass%, 18 to 24 mass%, 19 to 24 mass%, or 19 to 23 mass%. When this content is 15% by mass or more, alkali developability tends to improve, and when this content is 25% by mass or less, alkali resistance tends to be excellent.
　アルカリ可溶性樹脂がスチレン又はスチレン誘導体に由来する構造単位（以下、「スチレン系構造単位」ともいう）を有することで、感光性樹脂組成物の解像性及び密着性を向上すると共にレジストすそ発生量を低減することができる。スチレン誘導体としては、例えば、ビニルトルエン、α－メチルスチレン、ｐ－メチルスチレン、及びｐ－エチルスチレンが挙げられる。 Since the alkali-soluble resin has a structural unit derived from styrene or a styrene derivative (hereinafter also referred to as "styrenic structural unit"), the resolution and adhesion of the photosensitive resin composition are improved, and the amount of resist streaks generated is reduced. can be reduced. Examples of styrene derivatives include vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene.
　解像性及び密着性を向上すると共にレジストすそ発生量を低減する観点から、スチレン系構造単位の含有量は、バインターポリマーを構成する重合性単量体に由来する構造単位の全質量を基準として、５５質量％以上、６０質量％以上、又は６４質量％以上であってよい。現像時間が適度に短くなり、現像残りが発生し難くなる観点から、スチレン系構造単位の含有量は、８４質量％以下、８０質量％以下、又は７８質量％以下であってよい。 From the perspective of improving resolution and adhesion as well as reducing the amount of resist fringing, the content of styrene structural units is based on the total mass of structural units derived from the polymerizable monomers constituting the binder polymer. may be 55% by mass or more, 60% by mass or more, or 64% by mass or more. From the viewpoint that the development time is appropriately shortened and development residues are less likely to occur, the content of the styrene structural unit may be 84% by mass or less, 80% by mass or less, or 78% by mass or less.
　アルカリ可溶性樹脂が、脂環構造を有する（メタ）アクリレート化合物に由来する構造単位を有することで、感光性樹脂組成物の解像性及び密着性が向上することができる。脂環構造を有する（メタ）アクリレートとしては、例えば、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、シクロペンタニル（メタ）アクリレート、及びジシクロペンタニル（メタ）アクリレートが挙げられる。 When the alkali-soluble resin has 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. Examples of (meth)acrylates having an alicyclic structure include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, cyclopentanyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Can be mentioned.
　脂環構造を有する（メタ）アクリレート化合物に由来する構造単位の含有量は、バインターポリマーを構成する重合性単量体に由来する構造単位の全質量を基準（１００質量％）として、感光性樹脂組成物の解像性及び密着性をより向上する観点から、０．５質量％以上、０．８質量％以上、又は１質量％以上であってよく、感光性樹脂組成物の現像性をより向上する観点から、２０質量％以下、１８質量％以下、又は１６質量％以下であってよい。 The content of the structural units derived from the (meth)acrylate compound having an alicyclic structure is based on the total mass (100% by 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 resin composition, it may be 0.5% by mass or more, 0.8% by mass or more, or 1% by mass or more, and it improves the developability of the photosensitive resin composition. From the viewpoint of further improvement, the content may be 20% by mass or less, 18% by mass or less, or 16% by mass or less.
　アルカリ可溶性樹脂は、上記以外の重合性単量体（以下、「他の単量体」ともいう。）に由来する構造単位を更に含んでよい。他の単量体としては、例えば、メタクリル酸、２－エチルヘキシル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸ベンジル又はその誘導体、（メタ）アクリル酸フルフリル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸グリシジル、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、β－フリル（メタ）アクリル酸、β－スチリル（メタ）アクリル酸、マレイン酸、マレイン酸無水物、マレイン酸モノアルキルエステル、フマール酸、ケイ皮酸、α－シアノケイ皮酸、イタコン酸、クロトン酸、及びプロピオール酸が挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いることができる。 The alkali-soluble resin may further include a structural unit derived from a polymerizable monomer other than the above (hereinafter also referred to as "other monomer"). Other monomers include, for example, methacrylic acid, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, benzyl (meth)acrylate or its derivatives, furfuryl (meth)acrylate, (meth)acrylic acid Tetrahydrofurfuryl, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3- Tetrafluoropropyl (meth)acrylate, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, fumaric acid, cinnamic acid, α-cyanosilicon Mention may be made of cortic acid, itaconic acid, crotonic acid, and propiolic acid. These can be used alone or in combination of two or more.
　アルカリ可溶性樹脂の重量平均分子量（Ｍｗ）は、１００００～８００００、１５０００～７００００、２００００～６００００、２３０００～５００００、又は２５０００～４５０００であってよい。Ｍｗが８００００以下であると、解像性及び現像性が向上する傾向にあり、Ｍｗが１００００以上であると、硬化膜の可とう性が向上し、レジストパターンの欠け、剥がれが発生し難くなる傾向にある。アルカリ可溶性樹脂の分散度（Ｍｗ／Ｍｎ）は、１．０～３．０、１．０～２．５、又は１．０～２．３であってよい。分散度が小さくなると、解像性が向上する傾向にある。 The weight average molecular weight (Mw) of the alkali-soluble resin may be 10,000 to 80,000, 15,000 to 70,000, 20,000 to 60,000, 23,000 to 50,000, or 25,000 to 45,000. When Mw is 80,000 or less, resolution and developability tend to improve, and when Mw is 10,000 or more, the flexibility of the cured film improves, making it difficult for the resist pattern to chip or peel. There is a tendency. The dispersity (Mw/Mn) of the alkali-soluble resin may be 1.0 to 3.0, 1.0 to 2.5, or 1.0 to 2.3. As the degree of dispersion decreases, resolution tends to improve.
　重量平均分子量及び分散度は、例えば、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により標準ポリスチレンの検量線を用いて測定することができる。より具体的には実施例に記載の条件で測定することができる。 The weight average molecular weight and dispersity can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. More specifically, it can be measured under the conditions described in Examples.
　アルカリ可溶性樹脂の酸価は、現像性と剥離性とを両立する観点から、１４０～２００ｍｇＫＯＨ／ｇ、１５０～１９０ｍｇＫＯＨ／ｇ、又は１６０～１８０ｍｇＫＯＨ／ｇであってよい。アルカリ可溶性樹脂の酸価が１４０ｍｇＫＯＨ／ｇ以上であることで、現像時間が長くなることを充分に抑制でき、２００ｍｇＫＯＨ／ｇ以下であることで、感光性樹脂組成物の硬化物の耐現像液性（密着性）を向上し易くなる。アルカリ可溶性樹脂の酸価は、アクリル酸に由来する構造単位により調整できる。アルカリ可溶性樹脂の酸価は、ＪＩＳ　Ｋ６９０１：２００８　５．３．２に従い、測定することができる。 The acid value of the alkali-soluble resin may be 140 to 200 mgKOH/g, 150 to 190 mgKOH/g, or 160 to 180 mgKOH/g from the viewpoint of achieving both developability and peelability. When the acid value of the alkali-soluble resin is 140 mgKOH/g or more, it is possible to sufficiently suppress the development time from increasing, and when it is 200 mgKOH/g or less, the developer resistance of the cured product of the photosensitive resin composition is improved. (adhesion) becomes easier to improve. The acid value of the alkali-soluble resin can be adjusted by the structural unit derived from acrylic acid. The acid value of the alkali-soluble resin can be measured according to JIS K6901:2008 5.3.2.
　アルカリ可溶性樹脂のガラス転移温度（Ｔｇ）は、８０～１２０℃、９０～１１５℃、又は９５～１１０℃であってよい。アルカリ可溶性樹脂のＴｇが８０℃以上であると、感光性樹脂組成物から形成される感光層のラミネート性を向上し易くなり、１１５℃以下であると、感光性樹脂組成物の密着性、解像性、及び保存安定性を向上し易くなる。アルカリ可溶性樹脂のＴｇは、Ｆｏｘの式に従って求められる値であり、アルカリ可溶性樹脂を構成する各重合性単量体の質量、該各重合性単量体のホモポリマーのＴｇから算出することができる。 The glass transition temperature (Tg) of the alkali-soluble resin may be 80 to 120°C, 90 to 115°C, or 95 to 110°C. If the Tg of the alkali-soluble resin is 80°C or higher, the lamination properties of the photosensitive layer formed from the photosensitive resin composition will be easily improved, and if it is 115°C or lower, the adhesion and dissolution of the photosensitive resin composition will be improved. It becomes easier to improve image quality and storage stability. The Tg of the alkali-soluble resin is a value determined according to the Fox formula, and can be calculated from the mass of each polymerizable monomer constituting the alkali-soluble resin and the Tg of the homopolymer of each polymerizable monomer. .
［感光性樹脂組成物］
　本実施形態に係る感光性樹脂組成物は、（Ａ）バインダーポリマー（以下、「（Ａ）成分」という場合がある。）、（Ｂ）光重合性化合物（以下、「（Ｂ）成分」という場合がある。）と、（Ｃ）光重合開始剤（以下、「（Ｃ）成分」という場合がある。）と、（Ｄ）増感剤（以下、「（Ｄ）成分」という場合がある。）を含有する。以下、感光性樹脂組成物が含有し得る各成分について詳述する。 [Photosensitive resin composition]
The photosensitive resin composition according to the present embodiment includes (A) a binder polymer (hereinafter sometimes referred to as "component (A)"), (B) a photopolymerizable compound (hereinafter referred to as "component (B)"). ), (C) a photopolymerization initiator (hereinafter sometimes referred to as "(C) component"), and (D) a sensitizer (hereinafter sometimes referred to as "(D) component"). ). Each component that the photosensitive resin composition may contain will be described in detail below.
（Ａ）成分：バインダーポリマー
　（Ａ）成分は、本実施形態に係るアルカリ可溶性樹脂を含む。感光性樹脂組成物が、特定の構造を有するアルカリ可溶性樹脂を含有することで、露光部の現像時のアルカリ耐性が向上し、優れた解像性及び密着性を有するレジストパターンを形成することできる。該レジストパターンは、強アルカリ性水溶液によって、剥離することができる。（Ａ）成分は、１種の樹脂のみで構成されてもよく、２種以上の樹脂を含んで構成されてもよい。 (A) Component: Binder polymer The (A) component contains the alkali-soluble resin according to the present embodiment. When the photosensitive resin composition contains an alkali-soluble resin having a specific structure, the alkali resistance of the exposed area during development is improved, and a resist pattern with excellent resolution and adhesion can be formed. . The resist pattern can be removed with a strong alkaline aqueous solution. Component (A) may be composed of only one type of resin, or may be composed of two or more types of resin.
　（Ａ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、フィルムの成形性に優れる観点から、２０質量部以上、３０質量部以上、４０質量部、又は５０質量部以上であってよく、感度及び解像度が更に向上する観点から、８０質量部以下、７０質量部以下、又は６０質量部以下であってよい。 The content of component (A) is 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass, Alternatively, it may be 50 parts by mass or more, and from the viewpoint of further improving sensitivity and resolution, it may be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less.
（Ｂ）成分：光重合性化合物
　感光性樹脂組成物は、（Ｂ）成分の１種又は２種以上を含んでいる。（Ｂ）成分は、光により重合する化合物であればよく、例えば、エチレン性不飽和結合を有する化合物であってよい。（Ｂ）成分は、ラジカルにより反応する反応基を２以上有する多官能モノマーを含んでもよい。（Ｂ）成分は、アルカリ現像性、解像度、及び、硬化後の剥離性を更に向上させる観点から、ビスフェノールＡ型（メタ）アクリレート化合物を含んでもよい。 (B) Component: Photopolymerizable compound The photosensitive resin composition contains one or more of the (B) components. Component (B) may be any compound that polymerizes when exposed to light, and may be, for example, a compound having an ethylenically unsaturated bond. Component (B) may include a polyfunctional monomer having two or more reactive groups that react with radicals. Component (B) may contain a bisphenol A type (meth)acrylate compound from the viewpoint of further improving alkali developability, resolution, and removability after curing.
　ビスフェノールＡ型（メタ）アクリレート化合物としては、２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパン（２，２－ビス（４－（（メタ）アクリロキシペンタエトキシ）フェニル）プロパン等）、２，２－ビス（４－（（メタ）アクリロキシポリプロポキシ）フェニル）プロパン、２，２－ビス（４－（（メタ）アクリロキシポリブトキシ）フェニル）プロパン、及び２，２－ビス（４－（（メタ）アクリロキシポリエトキシポリプロポキシ）フェニル）プロパンが挙げられる。（Ｂ）成分は、解像度及び剥離性を更に向上させる観点から、２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパン（２，２－ビス（４－（（メタ）アクリロキシペンタエトキシ）フェニル）プロパン等）を含んでもよい。２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンとしては、オキシエチレン基の数が１０以上である化合物を用いてもよく、オキシエチレン基の数が１０未満である化合物を用いてもよく、オキシエチレン基の数が１０以上である化合物と、オキシエチレン基の数が１０未満である化合物とを併用してもよい。 Bisphenol A type (meth)acrylate compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane(2,2-bis(4-((meth)acryloxypentaethoxy)phenyl) ) propane etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2, Examples include 2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane. Component (B) is 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane(2,2-bis(4-((meth) (acryloxypentaethoxy)phenyl)propane, etc.). As 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, a compound having 10 or more oxyethylene groups may be used, and a compound having less than 10 oxyethylene groups may be used. A compound having 10 or more oxyethylene groups and a compound having less than 10 oxyethylene groups may be used together.
　ビスフェノールＡ型（メタ）アクリレート化合物の含有量は、レジストの解像度が更に向上する観点から、（Ｂ）成分の全量を基準として、２０質量％以上又は４０質量％以上であってよく、１００質量％以下、９５質量％以下、又は９０質量％以下であってよい。 From the viewpoint of further improving the resolution of the resist, the content of the bisphenol A type (meth)acrylate compound may be 20% by mass or more or 40% by mass or more, and 100% by mass, based on the total amount of component (B). The content may be 95% by mass or less, or 90% by mass or less.
　（Ｂ）成分は、解像度及び可とう性を更に好適に向上させる観点から、多価アルコールにα，β－不飽和カルボン酸を反応させて得られるα，β－不飽和エステル化合物を含んでもよい。α，β－不飽和エステル化合物としては、例えば、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ＥＯ変性ポリプロピレングリコール等のポリアルキレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＥＯ・ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、及びテトラメチロールメタンテトラ（メタ）アクリレートが挙げられる。 Component (B) may contain an α,β-unsaturated ester compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid from the viewpoint of further improving resolution and flexibility. . Examples of α,β-unsaturated ester compounds include polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, EO-modified polypropylene glycol, trimethylolpropane di(meth)acrylate, etc. ) 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 Examples include tri(meth)acrylate and tetramethylolmethanetetra(meth)acrylate.
　（Ｂ）成分は、感度及び密着性の向上の観点から、３つ以上の（メタ）アクリロイル基を有する化合物を含んでもよい。３つ以上の（メタ）アクリロイル基を有する化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＥＯ・ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性ペンタエリスリトールテトラ（メタ）アクリレート、ＥＯ変性ジトリメチロールプロパンテトラ（メタ）アクリレート、及びＥＯ変性ジペンタエリスリトールヘキサ（メタ）アクリレートが挙げられる。 Component (B) may include a compound having three or more (meth)acryloyl groups from the viewpoint of improving sensitivity and adhesion. Examples of 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. Examples include 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.
　α，β－不飽和エステル化合物の含有量は、（Ｂ）成分の全量を基準として、可とう性が向上する観点から、２０質量％以上又は３０質量％以上であってよく、解像度が更に向上する観点から、７０質量％以下又は６０質量％以下であってよい。 The content of the α,β-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 improving flexibility, which further improves resolution. From the viewpoint of this, it may be 70% by mass or less or 60% by mass or less.
　感光性樹脂組成物は、（Ｂ）成分として、ビスフェノールＡ系（メタ）アクリレート化合物及びα，β－不飽和エステル化合物以外のその他の光重合性化合物を含んでいてもよい。 The photosensitive resin composition may contain, as component (B), a photopolymerizable compound other than the bisphenol A-based (meth)acrylate compound and the α,β-unsaturated ester compound.
　その他の光重合性化合物としては、ノニルフェノキシポリエチレンオキシアクリレート、フタル酸系化合物、（メタ）アクリル酸アルキルエステル、分子内に少なくとも１つのカチオン重合可能な環状エーテル基を有する光重合性化合物（オキセタン化合物等）などが挙げられる。その他の光重合性化合物は、解像度、密着性、レジスト形状及び硬化後の剥離性を更に好適に向上させる観点から、ノニルフェノキシポリエチレンオキシアクリレート及びフタル酸系化合物からなる群より選ばれる少なくとも１種であってよい。 Other photopolymerizable compounds include nonylphenoxypolyethylene oxyacrylate, phthalic acid compounds, (meth)acrylic acid alkyl esters, and photopolymerizable compounds having at least one cationically polymerizable cyclic ether group in the molecule (oxetane compounds). etc.). The other photopolymerizable compound is at least one selected from the group consisting of nonylphenoxy polyethylene oxyacrylate and phthalic acid compounds, from the viewpoint of further improving resolution, adhesion, resist shape, and peelability after curing. It's good.
　ノニルフェノキシポリエチレンオキシアクリレートとしては、例えば、ノニルフェノキシトリエチレンオキシアクリレート、ノニルフェノキシテトラエチレンオキシアクリレート、ノニルフェノキシペンタエチレンオキシアクリレート、ノニルフェノキシヘキサエチレンオキシアクリレート、ノニルフェノキシヘプタエチレンオキシアクリレート、ノニルフェノキシオクタエチレンオキシアクリレート、ノニルフェノキシノナエチレンオキシアクリレート、ノニルフェノキシデカエチレンオキシアクリレート、及びノニルフェノキシウンデカエチレンオキシアクリレートが挙げられる。 Examples of nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytriethyleneoxyacrylate, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, and nonylphenoxyoctaethyleneoxyacrylate. acrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.
　フタル酸系化合物としては、例えば、γ－クロロ－β－ヒドロキシプロピル－β’－（メタ）アクリロイルオキシエチル－ｏ－フタレート（別名：３－クロロ－２－ヒドロキシプロピル－２－（メタ）アクリロイルオキシエチルフタレート）、β－ヒドロキシエチル－β’－（メタ）アクリロイルオキシエチル－ｏ－フタレート、及びβ－ヒドロキシプロピル－β’－（メタ）アクリロイルオキシエチル－ｏ－フタレートが挙げられる。 Examples of phthalic acid compounds include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate (also known as 3-chloro-2-hydroxypropyl-2-(meth)acryloyloxy ethyl phthalate), β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate.
　（Ｂ）成分がその他の光重合性化合物を含む場合、その他の光重合性化合物の含有量は、解像度、密着性、レジスト形状及び硬化後の剥離性を更に好適に向上させる観点から、（Ｂ）成分の全量を基準として、１質量％以上、３質量％以上、又は５質量％以上であってよく、３０質量％以下、２５質量％以下、又は２０質量％以下であってよい。 When component (B) contains other photopolymerizable compounds, the content of the other photopolymerizable compounds is determined from the viewpoint of further suitably improving resolution, adhesion, resist shape, and removability after curing. ) may be 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 25% by weight or less, or 20% by weight or less, based on the total amount of the components.
　（Ｂ）成分は、上述した化合物の中でも、密着性及び解像度をより向上させる観点から、分子内にオキシエチレン基（ＥＯ基）及び／又はオキシプロピレン基（ＰＯ基）を合計２～４０有する化合物を含んでもよい。ＥＯ基及び／又はＰＯ基の合計数は、密着性及び解像度を更に向上させる観点から、２～４０、又は、２～３０であってよい。 Among the above-mentioned compounds, component (B) is a compound having a total of 2 to 40 oxyethylene groups (EO groups) and/or oxypropylene groups (PO groups) in the molecule, from the viewpoint of further improving adhesion and resolution. May include. The total number of EO groups and/or PO groups may be 2 to 40 or 2 to 30 from the viewpoint of further improving adhesion and resolution.
　ＥＯ基及び／又はＰＯ基を合計２～４０有する化合物の含有量は、（Ｂ）成分の全量を基準として、密着性及び解像度を更に向上させる観点から、２～１５質量％、４～１２質量％、又は、５～８質量％であってよい。 The content of the compound having a total of 2 to 40 EO groups and/or PO groups is 2 to 15% by mass, 4 to 12% by mass, based on the total amount of component (B), from the viewpoint of further improving adhesion and resolution. % or 5 to 8% by mass.
　（Ｂ）成分の含有量は、感光性樹脂組成物の固形分全量を基準として、感度及び解像度が更に向上する観点から、３質量％以上、１０質量％以上、又は２５質量％以上であってよく、フィルムの成形性に優れる観点から、７０質量％以下、６０質量％以下、又は５０質量％以下であってよい。 The content of component (B) is 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 viewpoint of further improving sensitivity and resolution. From the viewpoint of excellent film formability, the content may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.
（Ｃ）成分：光重合開始剤
　感光性樹脂組成物は、（Ｃ）成分の１種又は２種以上を含んでいる。（Ｃ）成分としては、（Ｂ）成分を重合させることができる成分であれば、特に限定されず、通常用いられる光重合開始剤から適宜選択することができる。 (C) Component: Photopolymerization initiator The photosensitive resin composition contains one or more of the (C) components. 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.
　（Ｃ）成分としては、例えば、ヘキサアリールビイミダゾール化合物；ベンゾフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、４－（２－ヒドロキシエトキシ）フェニル－２－（ヒドロキシ－２－プロピル）ケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパノン－１等の芳香族ケトン化合物；アルキルアントラキノン等のキノン化合物；ベンゾインアルキルエーテル等のベンゾインエーテル化合物；ベンゾイン、アルキルベンゾイン等のベンゾイン化合物；ベンジルジメチルケタール等のベンジル誘導体；及びビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，６－ジメチルベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、（２，４，６－トリメチルベンゾイル）エトキシフェニルフォスフィンオキサイド等のフォスフィンオキサイド化合物が挙げられる。 Component (C) includes, for example, a hexaarylbiimidazole compound; 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, 2-methyl- Aromatic ketone compounds such as 1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; quinone compounds such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; Benzyl derivatives such as benzyl dimethyl ketal; and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, ( Examples include phosphine oxide compounds such as 2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide.
　（Ｃ）成分は、ポリエチレンフィルムへの光増感剤の浸透を更に抑制できる観点から、ヘキサアリールビイミダゾール化合物を含んでよい。ヘキサアリールビイミダゾール化合物におけるアリール基は、フェニル基等であってよい。ヘキサアリールビイミダゾール化合物におけるアリール基に結合する水素原子は、ハロゲン原子（塩素原子等）により置換されていてもよい。 Component (C) may contain a hexaarylbiimidazole compound from the viewpoint of further 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, etc.).
　ヘキサアリールビイミダゾール化合物は、２，４，５－トリアリールイミダゾール二量体であってよい。２，４，５－トリアリールイミダゾール二量体としては、例えば、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ビス－（ｍ－メトキシフェニル）イミダゾール二量体、及び２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体が挙げられる。ヘキサアリールビイミダゾール化合物は、ポリエチレンフィルムへの光増感剤の浸透を更に抑制できる観点から、好ましくは２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体であり、より好ましくは２，２－ビス（ｏ－クロロフェニル）－４，５－４’，５’－テトラフェニル－１，２’ビイミダゾールである。 The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-( Examples include 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, more preferably a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, from the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film. , 2-bis(o-chlorophenyl)-4,5-4',5'-tetraphenyl-1,2'biimidazole.
　ヘキサアリールビイミダゾール化合物の含有量は、ポリエチレンフィルムへの光増感剤の浸透を更に抑制できる観点から、（Ｃ）成分の全量を基準として、９０質量％以上、９５質量％以上、又は９９質量％以上であってよい。（Ｃ）成分は、ヘキサアリールビイミダゾール化合物のみからなっていてよい。 The content of the hexaarylbiimidazole compound is 90% by mass or more, 95% by mass or more, or 99% by mass based on the total amount of component (C) from the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film. % or more. Component (C) may consist only of a hexaarylbiimidazole compound.
　（Ｃ）成分の含有量は、感度及び密着性が更に向上する観点から、感光性樹脂組成物の固形分全量を基準として、０．１質量％以上、０．５質量％以上、又は１質量％以上であってよく、２０質量％以下、１０質量％以下、又は５質量％以下であってよい。 From the viewpoint of further improving sensitivity and adhesion, the content of component (C) is 0.1% by mass or more, 0.5% by mass or more, or 1% by mass based on the total solid content of the photosensitive resin composition. % or more, and may be 20% by mass or less, 10% by mass or less, or 5% by mass or less.
（Ｄ）成分：増感剤
　感光性樹脂組成物は、（Ｄ）成分の１種又は２種以上を含んでいる。本実施形態に係る感光性樹脂組成物は、（Ｄ）成分を含有することにより、露光に用いる活性光線の吸収波長を有効に利用することができる。 (D) Component: Sensitizer The photosensitive resin composition contains one or more of the (D) components. By containing the component (D), the photosensitive resin composition according to the present embodiment can effectively utilize the absorption wavelength of actinic rays used for exposure.
　（Ｄ）成分としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物、及びアミノアクリジン化合物が挙げられる。（Ｄ）成分は、解像度をより向上する観点からピラゾリン化合物又はアントラセン化合物を含んでもよく、アントラセン化合物を含むことが好ましい。 Component (D) includes, for example, a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone compound, a thioxanthone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound, a stilbene compound, and a triazine. compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. Component (D) may contain a pyrazoline compound or an anthracene compound from the viewpoint of further improving resolution, and preferably contains an anthracene compound.
　ピラゾリン化合物としては、例えば、１－（４－メトキシフェニル）－３－スチリル－５－フェニル－ピラゾリン、１－フェニル－３－（４－メトキシスチリル）－５－（４－メトキシフェニル）－ピラゾリン、１，５－ビス－（４－メトキシフェニル）－３－（４－メトキシスチリル）－ピラゾリン、１－（４－イソプロピルフェニル）－３－スチリル－５－フェニル－ピラゾリン、１－フェニル－３－（４－イソプロピルスチリル）－５－（４－イソプロピルフェニル）－ピラゾリン、１，５－ビス－（４－イソプロピルフェニル）－３－（４－イソプロピルスチリル）－ピラゾリン、１－（４－メトキシフェニル）－３－（４－ｔｅｒｔ－ブチル－スチリル）－５－（４－ｔｅｒｔ－ブチル－フェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（４－メトキシスチリル）－５－（４－メトキシフェニル）－ピラゾリン、１－（４－イソプロピル－フェニル）－３－（４－ｔｅｒｔ－ブチル－スチリル）－５－（４－ｔｅｒｔ－ブチル－フェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（４－イソプロピル－スチリル）－５－（４－イソプロピル－フェニル）－ピラゾリン、１－（４－メトキシフェニル）－３－（４－イソプロピルスチリル）－５－（４－イソプロピルフェニル）－ピラゾリン、１－（４－イソプロピル－フェニル）－３－（４－メトキシスチリル）－５－（４－メトキシフェニル）－ピラゾリン、１－フェニル－３－（３，５－ジメトキシスチリル）－５－（３，５－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（３，４－ジメトキシスチリル）－５－（３，４－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，６－ジメトキシスチリル）－５－（２，６－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，５－ジメトキシスチリル）－５－（２，５－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，３－ジメトキシスチリル）－５－（２，３－ジメトキシフェニル）－ピラゾリン、１－フェニル－３－（２，４－ジメトキシスチリル）－５－（２，４－ジメトキシフェニル）－ピラゾリン、１－（４－メトキシフェニル）－３－（３，５－ジメトキシスチリル）－５－（３，５－ジメトキシフェニル）－ピラゾリン、１－（４－メトキシフェニル）－３－（３，４－ジメトキシスチリル）－５－（３，４－ジメトキシフェニル）－ピラゾリン、１－（４－メトキシフェニル）－３－（２，６－ジメトキシスチリル）－５－（２，６－ジメトキシフェニル）－ピラゾリン、１－（４－メトキシフェニル）－３－（２，５－ジメトキシスチリル）－５－（２，５－ジメトキシフェニル）－ピラゾリン、１－（４－メトキシフェニル）－３－（２，３－ジメトキシスチリル）－５－（２，３－ジメトキシフェニル）－ピラゾリン、１－（４－メトキシフェニル）－３－（２，４－ジメトキシスチリル）－５－（２，４－ジメトキシフェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（３，５－ジメトキシスチリル）－５－（３，５－ジメトキシフェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（３，４－ジメトキシスチリル）－５－（３，４－ジメトキシフェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（２，６－ジメトキシスチリル）－５－（２，６－ジメトキシフェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（２，５－ジメトキシスチリル）－５－（２，５－ジメトキシフェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（２，３－ジメトキシスチリル）－５－（２，３－ジメトキシフェニル）－ピラゾリン、１－（４－ｔｅｒｔ－ブチル－フェニル）－３－（２，４－ジメトキシスチリル）－５－（２，４－ジメトキシフェニル）－ピラゾリン、１－（４－イソプロピル－フェニル）－３－（３，５－ジメトキシスチリル）－５－（３，５－ジメトキシフェニル）－ピラゾリン、１－（４－イソプロピル－フェニル）－３－（３，４－ジメトキシスチリル）－５－（３，４－ジメトキシフェニル）－ピラゾリン、１－（４－イソプロピル－フェニル）－３－（２，６－ジメトキシスチリル）－５－（２，６－ジメトキシフェニル）－ピラゾリン、１－（４－イソプロピル－フェニル）－３－（２，５－ジメトキシスチリル）－５－（２，５－ジメトキシフェニル）－ピラゾリン、１－（４－イソプロピル－フェニル）－３－（２，３－ジメトキシスチリル）－５－（２，３－ジメトキシフェニル）－ピラゾリン、及び１－（４－イソプロピル－フェニル）－３－（２，４－ジメトキシスチリル）－５－（２，４－ジメトキシフェニル）－ピラゾリンが挙げられる。 Examples of the pyrazoline compound 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-tert-butyl-phenyl)-3-(4-methoxystyryl)-5-( 4-Methoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-tert -butyl-phenyl)-3-(4-isopropyl-styryl)-5-(4-isopropyl-phenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(4-isopropylstyryl)-5-(4 -isopropylphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl) )-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-( 2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1 -Phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxy phenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-( 3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl) )-pyrazoline, 1-(4-methoxyphenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2 ,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl) -Pyrazoline, 1-(4-tert-butyl-phenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl) -3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,6-dimethoxystyryl)-5- (2,6-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-( 4-tert-butyl-phenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2, 4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl) -Pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-( 2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxy phenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, and 1-(4-isopropyl-phenyl)- 3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline is mentioned.
　アントラセン化合物としては、例えば、９，１０－ジメトキシアントラセン、９，１０－ジエトキシアントラセン、９，１０－ジプロポキシアントラセン、９，１０－ジブトキシアントラセン、及び９，１０－ジペントキシアントラセンが挙げられる。 Examples of anthracene compounds include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene. .
　（Ｄ）成分の含有量は、光感度及び解像性を向上させる観点から、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、０．０１～５質量部、０．０１～１質量部、又は０．０１～０．２質量部であってもよい。 From the viewpoint of improving photosensitivity and resolution, the content of component (D) is 0.01 to 5 parts by mass, 0.01 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B). It may be 1 part by mass, or 0.01 to 0.2 part by mass.
（Ｅ）成分：重合禁止剤
　感光性樹脂組成物は、レジストパターン形成時の未露光部における重合を抑制し、解像度を更に向上させる観点から、（Ｅ）成分：重合禁止剤を更に含有してもよい。重合禁止剤は、例えば、４－ｔｅｒｔ－ブチルカテコール、２，２，６，６－テトラメチルピペリジノオキシルフリーラジカル等であってよい。 (E) Component: Polymerization Inhibitor The photosensitive resin composition further contains (E) Component: Polymerization Inhibitor from the viewpoint of suppressing polymerization in unexposed areas during resist pattern formation and further improving resolution. Good too. The polymerization inhibitor may be, for example, 4-tert-butylcatechol, 2,2,6,6-tetramethylpiperidinooxyl free radical, or the like.
　（Ｅ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、０．００１～０．１０質量部、０．００５～０．０８質量部、又は、０．０１～０．０５質量部であってよい。 The content of component (E) is 0.001 to 0.10 parts by mass, 0.005 to 0.08 parts by mass, or 0. It may be .01 to 0.05 parts by weight.
　感光性樹脂組成物は、上述した成分以外のその他の成分の１種又は２種以上を更に含有してもよい。その他の成分としては、水素供与体（ビス［４－（ジメチルアミノ）フェニル］メタン、ビス［４－（ジエチルアミノ）フェニル］メタン、ロイコクリスタルバイオレット、Ｎ－フェニルグリシン等）、染料（マラカイトグリーン等）、トリブロモフェニルスルホン、光発色剤、熱発色防止剤、可塑剤（ｐ－トルエンスルホンアミド等）、顔料、充填剤、消泡剤、難燃剤、安定剤、密着性付与剤、レベリング剤、剥離促進剤、酸化防止剤、香料、イメージング剤、熱架橋剤などが挙げられる。その他の成分の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、０．００５質量部以上又は０．０１質量部以上であってよく、２０質量部以下であってもよい。 The photosensitive resin composition may further contain one or more components other than the components mentioned above. Other ingredients 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, photochromic agent, thermal coloring inhibitor, plasticizer (p-toluenesulfonamide, etc.), pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion agent, leveling agent, peeling agent Examples include accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and the like. The content of other components may be 0.005 parts by mass or more, or 0.01 parts by mass or more, and 20 parts by mass or less, based on 100 parts by mass of the total amount of components (A) and (B). It's okay.
　感光性樹脂組成物は、粘度を調整する観点から、有機溶剤の１種又は２種以上を更に含有してもよい。有機溶剤としては、例えば、メタノール、エタノール、アセトン、メチルエチルケトン、メチルセロソルブ、エチルセロソルブ、トルエン、Ｎ，Ｎ－ジメチルホルムアミド、及びプロピレングリコールモノメチルエーテルが挙げられる。有機溶剤の含有量は、感光性樹脂組成物の全量を基準として、４０質量％以上であってよく、７０質量％以下であってよい。 The photosensitive resin composition may further contain one or more organic solvents from the viewpoint of adjusting the viscosity. Examples of 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% by mass or more and 70% by mass or less based on the total amount of the photosensitive resin composition.
　感光性樹脂組成物は、レジストパターンの形成に好適に用いることができ、後述する配線基板の製造方法に特に好適に用いることができる。 The photosensitive resin composition can be suitably used for forming a resist pattern, and can be particularly suitably used for the method for manufacturing a wiring board described below.
［感光性エレメント］
　本実施形態の感光性エレメントは、支持体と、該支持体上に形成されたと感光層とを備え、感光層は上述の感光性樹脂組成物を含む。本実施形態に係る感光性エレメントを用いる場合には、感光層を基板上にラミネートした後、支持体（支持フィルム）を剥離することなく露光してもよい。図１は、一実施形態に係る感光性エレメントの模式断面図である。図１に示すように、感光性エレメント１は、支持体２と、支持体２上に形成された上記感光性樹脂組成物に由来する感光層３とを備え、必要に応じて設けられる保護層４等のその他の層を備えて構成される。 [Photosensitive element]
The photosensitive element of this embodiment includes a support and a photosensitive layer formed on the support, and the photosensitive layer contains the above-described photosensitive resin composition. When using the photosensitive element according to this embodiment, the photosensitive layer may be laminated onto the 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. As shown in FIG. 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 a protective layer provided as necessary. 4 and other layers.
　支持体２及び保護層４は、それぞれ、耐熱性及び耐溶剤性を有するポリマーフィルムであってよく、例えば、ポリエチレンテレフタレートフィルム等のポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム等のポリオレフィンフィルムなどであってよい。支持体２及び保護層４は、それぞれ、ポリオレフィン以外の炭化水素系ポリマーのフィルムであってよい。ポリオレフィンを含む炭化水素系ポリマーのフィルムは、低密度であってよく、例えば１．０１４ｇ／ｃｍ３以下の密度を有していてよい。支持体２及び保護層４は、それぞれ、当該低密度の炭化水素系ポリマーフィルムを延伸してなる延伸フィルムであってもよい。保護層４を構成するポリマーフィルムの種類は、支持体２を構成するポリマーフィルムの種類と同じであっても異なっていてもよい。 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 polyolefin film such as a polyethylene film, a polypropylene film, etc. . The support 2 and the protective layer 4 may each be a film of a hydrocarbon polymer other than polyolefin. Films of hydrocarbon-based polymers comprising polyolefins 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 polymer film. The type of polymer film constituting the protective layer 4 may be the same as or different from the type of polymer film constituting the support 2.
　これらのポリマーフィルムは、それぞれ、例えば、帝人株式会社製のＰＳシリーズ（例えばＰＳ－２５）等のポリエチレンテレフタレートフィルム、タマポリ株式会社製のＮＦ－１５等のポリエチレンフィルム、又は、王子製紙株式会社製（例えば、アルファンＭＡ－４１０、Ｅ－２００Ｃ）、信越フィルム株式会社製等のポリプロピレンフィルムとして購入可能である。 These polymer films are, for example, a polyethylene terephthalate film such as the PS series (for example, PS-25) manufactured by Teijin Ltd., a polyethylene film such as NF-15 manufactured by Tamapoly Co., Ltd., or a polyethylene film such as NF-15 manufactured by Oji Paper Co., Ltd. For example, it can be purchased as a polypropylene film such as Alphan MA-410, E-200C) or manufactured by Shin-Etsu Film Co., Ltd.
　支持体２の厚さは、支持体２を感光層３から剥離する際の支持体２の破損を抑制できる観点から、１μｍ以上又は５μｍ以上であってよく、支持体２を介して露光する場合にも好適に露光できる観点から、１００μｍ以下、５０μｍ以下、又は３０μｍ以下であってよい。 The thickness of the support 2 may be 1 μm or more or 5 μm or more from the viewpoint of suppressing damage to the support 2 when peeling the support 2 from the photosensitive layer 3, and when exposing through the support 2. From the viewpoint of suitable exposure to light, the thickness may be 100 μm or less, 50 μm or less, or 30 μm or less.
　保護層４の厚さは、保護層４を剥がしながら感光層３及び支持体２を基板上にラミネートする際、保護層４の破損を抑制できる観点から、１μｍ以上、５μｍ以上、又は１５μｍ以上であってよく、生産性が向上する観点から、１００μｍ以下、５０μｍ以下、又は３０μｍ以下であってよい。 The thickness of the protective layer 4 is 1 μm or more, 5 μm or more, or 15 μm or more, from the viewpoint of suppressing damage to the protective layer 4 when laminating the photosensitive layer 3 and support 2 on the substrate while peeling off the protective layer 4. From the viewpoint of improving productivity, the thickness may be 100 μm or less, 50 μm or less, or 30 μm or less.
　感光層３は、上述した感光性樹脂組成物からなっている。感光層３の乾燥後（感光性樹脂組成物が有機溶剤を含有する場合は有機溶剤を揮発させた後）の厚さは、塗工が容易になり、生産性が向上する観点から、１μｍ以上又は５μｍ以上であってよく、密着性及び解像度が更に向上する観点から、１００μｍ以下、５０μｍ以下、又は４０μｍ以下であってよい。 The photosensitive layer 3 is made of the photosensitive resin composition described above. The thickness of the photosensitive layer 3 after drying (after volatilizing the organic solvent if the photosensitive resin composition contains an organic solvent) is 1 μm or more from the viewpoint of facilitating coating and improving productivity. Alternatively, it may be 5 μm or more, and from the viewpoint of further improving adhesion and resolution, it may be 100 μm or less, 50 μm or less, or 40 μm or less.
　感光性エレメント１は、例えば、以下のようにして得ることができる。まず、支持体２上に感光層３を形成する。感光層３は、例えば、有機溶剤を含有する感光性樹脂組成物を塗布して塗布層を形成し、この塗布層を乾燥することにより形成できる。次いで、感光層３の支持体２と反対側の面上に保護層４を形成する。 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 coating a photosensitive resin composition containing an organic solvent to form a coating layer, and drying this coating layer. Next, a protective layer 4 is formed on the surface of the photosensitive layer 3 opposite to the support 2.
　塗布層は、例えば、ロールコート、コンマコート、グラビアコート、エアーナイフコート、ダイコート、バーコート等の公知の方法により形成される。塗布層の乾燥は、感光層３中に残存する有機溶剤の量が例えば２質量％以下となるように行われ、具体的には、例えば、７０～１５０℃にて、５～３０分間程度行われる。 The coating layer is formed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, and bar coating. The coating layer is dried so that the amount of organic solvent remaining in the photosensitive layer 3 is, for example, 2% by mass or less. be exposed.
　感光性エレメントは、他の一実施形態において、保護層を備えていなくてもよく、クッション層、接着層、光吸収層、ガスバリア層等のその他の層を更に備えていてもよい。 In another embodiment, 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 absorption layer, and a gas barrier layer.
　感光性エレメント１は、例えば、シート状であってよく、巻芯にロール状に巻き取られた感光性エレメントロールの形態であってもよい。感光性エレメントロールにおいては、感光性エレメント１は、好ましくは、支持体２が外側になるように巻き取られている。巻芯は、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、アクリロニトリル－ブタジエン－スチレン共重合体等で形成されている。感光性エレメントロールの端面には、端面保護の観点から、端面セパレータが設けられていてよく、耐エッジフュージョンの観点から、防湿端面セパレータが設けられていてよい。感光性エレメント１は、例えば、透湿性の小さいブラックシートで包装されていてよい。 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 so that the support 2 is on the outside. The winding core is made of, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, or the like. The end face of the photosensitive element roll may be provided with an end face separator from the viewpoint of end face protection, and may be provided with a moisture-proof end face separator from the viewpoint of edge fusion resistance. The photosensitive element 1 may be wrapped, for example, in a black sheet with low moisture permeability.
　感光性エレメント１は、レジストパターンの形成に好適に用いることができ、後述するプリント配線基板の製造方法に特に好適に用いることができる。 The photosensitive element 1 can be suitably used for forming a resist pattern, and can be particularly suitably used for a method for manufacturing a printed wiring board, which will be described later.
［レジストパターンの形成方法］
　本実施形態のレジストパターンの形成方法は、基板上に、上記感光性樹脂組成物、又は、上記感光性エレメントを用いて、感光層を形成する工程（感光層形成工程）と、上記感光層の少なくとも一部（所定部分）に活性光線を照射して、光硬化部を形成する工程（露光工程）と、上記基板上から上記未光硬化部の少なくとも一部を除去する工程（現像工程）と、を備え、必要に応じてその他の工程を含んで構成されてもよい。レジストパターンとは、感光性樹脂組成物の光硬化物パターンともいえ、レリーフパターンともいえる。レジストパターンの形成方法は、レジストパターン付き基板の製造方法ともいえる。 [Method of forming resist pattern]
The method for forming a resist pattern of the present embodiment includes a step of forming a photosensitive layer on a substrate using the photosensitive resin composition or the photosensitive element (photosensitive layer forming step); a step of irradiating at least a portion (predetermined portion) with actinic rays to form a photocured portion (exposure step); and a step of removing at least a portion of the non-photocured portion from the substrate (development step). , and may include other steps as necessary. The resist pattern can be said to be a pattern of a photocured product of a 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.
（感光層形成工程）
　基板上に感光層を形成する方法としては、例えば、上記感光性樹脂組成物を塗布及び乾燥してもよく、又は、上記感光性エレメントから保護層を除去した後、感光性エレメントの感光層を加熱しながら上記基板に圧着してもよい。感光性エレメントを用いた場合、基板と感光層と支持体とからなり、これらが順に積層された積層体が得られる。上記基板としては特に制限されないが、通常、絶縁層と絶縁層上に形成された導体層とを備えた回路形成用基板、又は合金基材等のダイパッド（リードフレーム用基材）が用いられる。 (Photosensitive layer forming process)
As a method for forming the photosensitive layer on the substrate, for example, the photosensitive resin composition may be applied and dried, or the photosensitive layer of the photosensitive element may be formed after removing the protective layer from the photosensitive element. It may be pressed onto the substrate while being heated. When a photosensitive element is used, a laminate consisting of a substrate, a photosensitive layer, and a support is obtained, which are laminated in this order. Although the above-mentioned substrate is not particularly limited, a circuit forming substrate including an insulating layer and a conductor layer formed on the insulating layer, or a die pad (lead frame base material) such as an alloy base material is used.
　感光性エレメントを用いた場合、感光層形成工程は、密着性及び追従性の見地から、減圧下で行うことが好ましい。圧着の際の感光層及び／又は基板の加熱は、７０～１３０℃の温度で行ってもよい。圧着は、０．１～１．０ＭＰａ程度（１～１０ｋｇｆ／ｃｍ２程度）の圧力で行ってもよいが、これらの条件は必要に応じて適宜選択される。なお、感光層を７０～１３０℃に加熱すれば、予め基板を予熱処理することは必要ではないが、密着性及び追従性を更に向上させるために、基板の予熱処理を行うこともできる。 When a photosensitive element is used, the photosensitive layer forming step is preferably carried out under reduced pressure from the viewpoint of adhesion and trackability. 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 approximately 0.1 to 1.0 MPa (approximately 1 to 10 kgf/cm 2 ), but these conditions are appropriately selected as necessary. Note that if the photosensitive layer is heated to 70 to 130° C., it is not necessary to preheat the substrate, but it is also possible to preheat the substrate in order to further improve adhesion and followability.
（露光工程）
　露光工程においては、基板上に形成された感光層の少なくとも一部に活性光線を照射することで、活性光線が照射された部分が光硬化して、潜像が形成される。この際、感光層上に支持体が存在する場合、その支持体が活性光線に対して透過性であれば、支持体を通して活性光線を照射することができるが、支持体が遮光性の場合には、支持体を除去した後に感光層に活性光線を照射する。 (Exposure process)
In the exposure step, at least a portion of the photosensitive layer formed on the substrate is irradiated with actinic rays, so that the portion irradiated with the actinic rays is photocured and a latent image is formed. At this time, if a support is present on the photosensitive layer, if the support is transparent to actinic rays, the actinic rays can be irradiated through the support, but if the support is light-shielding, After removing the support, the photosensitive layer is irradiated with actinic rays.
　露光方法としては、アートワークと呼ばれるネガ又はポジマスクパターンを介して活性光線を画像状に照射する方法（マスク露光法）が挙げられる。また、投影露光法により活性光線を画像状に照射する方法を採用してもよい。また、ＬＤＩ（Ｌａｓｅｒ　Ｄｉｒｅｃｔ　Ｉｍａｇｉｎｇ）露光法、ＤＬＰ（Ｄｉｇｉｔａｌ　Ｌｉｇｈｔ　Ｐｒｏｃｅｓｓｉｎｇ）露光法等の直接描画露光法により活性光線を画像状に照射する方法を採用してもよい。 Examples of the exposure method include a method (mask exposure method) of irradiating actinic rays imagewise through a negative or positive mask pattern called artwork. Alternatively, a method of irradiating actinic rays imagewise using a projection exposure method may be adopted. Alternatively, a method of irradiating actinic rays imagewise by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be adopted.
　活性光線の光源としては、公知の光源を用いることができ、例えば、カーボンアーク灯、水銀蒸気アーク灯、高圧水銀灯、キセノンランプ、アルゴンレーザ等のガスレーザ、ＹＡＧレーザ等の固体レーザ、半導体レーザ等の紫外線、可視光を有効に放射するものが用いられる。 As the active light source, known light sources can be used, such as 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, semiconductor lasers, etc. A material that effectively emits ultraviolet rays and visible light is used.
（現像工程）
　現像工程においては、上記感光層の未光硬化部（光硬化部以外）の少なくとも一部が基板上から除去されることで、レジストパターンが基板上に形成される。 (Developing process)
In the development step, at least a portion of the unphotocured portion (other than the photocured portion) of the photosensitive layer is removed from the substrate, thereby forming a resist pattern on the substrate.
　感光層上に支持体が存在している場合には、支持体を除去してから、上記光硬化部以外の領域（未露光部分ともいえる）の除去（現像）を行う。現像方法には、ウェット現像とドライ現像とがあるが、ウェット現像が広く用いられている。 If a support is present on the photosensitive layer, the support is removed and then the area other than the photocured area (which can also be called an unexposed area) is removed (developed). Development methods include wet development and dry development, and wet development is widely used.
　ウェット現像による場合、感光性樹脂組成物に対応した現像液を用いて、公知の現像方法により現像する。現像方法としては、ディップ方式、パドル方式、スプレー方式、ブラッシング、スラッピング、スクラッビング、揺動浸漬等を用いた方法が挙げられる。解像度を向上する観点からは、現像方法として高圧スプレー方式を用いてもよい。これら２種以上の方法を組み合わせて現像を行ってもよい。 In the case of wet development, development is performed by a known development method using a developer compatible with the photosensitive resin composition. Examples of the developing method include methods using a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, a high-pressure spray method may be used as a developing method. Development may be performed by combining two or more of these methods.
　現像液の構成は上記感光性樹脂組成物の構成に応じて適宜選択される。現像液としては、例えば、アルカリ性水溶液及び有機溶剤現像液が挙げられる。 The composition of the developer is appropriately selected depending on the composition of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution and an organic solvent developer.
　安全且つ安定であり、操作性が良好である見地から、現像液として、アルカリ性水溶液を用いてもよい。アルカリ性水溶液の塩基としては、リチウム、ナトリウム又はカリウムの水酸化物等の水酸化アルカリ；リチウム、ナトリウム、カリウム又はアンモニウムの炭酸塩又は重炭酸塩等の炭酸アルカリ；リン酸カリウム、リン酸ナトリウム等のアルカリ金属リン酸塩；ピロリン酸ナトリウム、ピロリン酸カリウム等のアルカリ金属ピロリン酸塩；ホウ砂、メタケイ酸ナトリウム、水酸化テトラメチルアンモニウム、エタノールアミン、エチレンジアミン、ジエチレントリアミン、２－アミノ－２－ヒドロキシメチル－１，３－プロパンジオール、１，３－ジアミノプロパノール－２、モルホリンなどが用いられる。 An alkaline aqueous solution may be used as the developer from the viewpoint of safety, stability, and good operability. Bases for alkaline aqueous solutions include alkali hydroxides such as hydroxides of lithium, sodium or potassium; alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; potassium phosphates, sodium phosphates, etc. Alkali metal phosphates; 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, morpholine, etc. are used.
　現像に用いるアルカリ性水溶液としては、０．１～５質量％炭酸ナトリウムの希薄溶液、０．１～５質量％炭酸カリウムの希薄溶液、０．１～５質量％水酸化ナトリウムの希薄溶液、０．１～５質量％四ホウ酸ナトリウムの希薄溶液等を用いることができる。アルカリ性水溶液のｐＨは、９～１１の範囲としてもよく、その温度は、感光層のアルカリ現像性に合わせて調節できる。アルカリ性水溶液中には、例えば、表面活性剤、消泡剤、現像を促進させるための少量の有機溶剤等を混入させてもよい。 The alkaline aqueous solution used for development includes a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, and a dilute solution of 0.1 to 5% by mass of sodium hydroxide. A dilute solution of 1 to 5% by mass sodium tetraborate, etc. can be used. The pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature can be adjusted depending on the alkaline developability of the photosensitive layer. For example, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, etc. may be mixed into the alkaline aqueous solution.
　アルカリ性水溶液に用いられる有機溶剤としては、例えば、アセトン、酢酸エチル、炭素数１～４のアルコキシ基をもつアルコキシエタノール、エチルアルコール、イソプロピルアルコール、ブチルアルコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、及びジエチレングリコールモノブチルエーテルが挙げられる。 Examples of the organic solvent used in the alkaline aqueous solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Monobutyl ether is mentioned.
　有機溶剤現像液に用いられる有機溶剤としては、例えば、１，１，１－トリクロロエタン、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、シクロヘキサノン、メチルイソブチルケトン、及びγ－ブチロラクトンが挙げられる。これらの有機溶剤には、引火防止のため、１～２０質量％の範囲となるように水を添加して有機溶剤現像液としてもよい。 Examples of the organic solvent used in the organic solvent developer include 1,1,1-trichloroethane, N-methyl-2-pyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. . In order to prevent ignition, water may be added to these organic solvents in an amount in the range of 1 to 20% by mass to form an organic solvent developer.
　本実施形態におけるレジストパターンの形成方法においては、現像工程において未硬化部分を除去した後、必要に応じて６０～２５０℃程度での加熱又は０．２～１０Ｊ／ｃｍ２程度の露光を行うことにより、レジストパターンを更に硬化する工程を含んでもよい。 In the method for forming a resist pattern in this embodiment, after removing the uncured portion in the development step, heating at about 60 to 250°C or exposure to about 0.2 to 10 J/cm 2 is performed as necessary. The method may also include a step of further curing the resist pattern.
［プリント配線板の製造方法］
　本実施形態のプリント配線板の製造方法は、上記レジストパターンの形成方法によって、レジストパターンが形成された基板をエッチング処理又はめっき処理して導体パターンを形成する工程を含み、必要に応じて、レジストパターン除去工程等のその他の工程を含んで構成されてもよい。 [Manufacturing method of printed wiring board]
The method for manufacturing a printed wiring board of this embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the above-described method for forming a resist pattern. The method may also include other steps such as a pattern removal step.
　めっき処理では、基板上に形成されたレジストパターンをマスクとして、基板上に設けられた導体層にめっき処理が行われる。めっき処理の後、後述するレジストパターンの除去によりレジストを除去し、更にこのレジストによって被覆されていた導体層をエッチングして、導体パターンを形成してもよい。めっき処理の方法としては、電解めっき処理であっても、無電解めっき処理であってもよいが、無電解めっき処理であってもよい。 In the plating process, plating is performed on the conductor layer provided on the substrate using a resist pattern formed on the substrate as a mask. After the plating process, a conductor pattern may be formed by removing the resist by removing a resist pattern, which will be described later, and further etching the conductor layer covered with this resist. The plating method may be electrolytic plating, electroless plating, or electroless plating.
　一方、エッチング処理では、基板上に形成されたレジストパターンをマスクとして、基板上に設けられた導体層をエッチング除去し、導体パターンを形成する。エッチング処理の方法は、除去すべき導体層に応じて適宜選択される。エッチング液としては、例えば、塩化第二銅溶液、塩化第二鉄溶液、アルカリエッチング溶液、及び過酸化水素系エッチング液が挙げられる。 On the other hand, in the etching process, a conductor layer provided on the substrate is etched away using a resist pattern formed on the substrate as a mask to form a conductor pattern. The etching method is appropriately selected depending on the conductor layer to be removed. Examples of the etching solution include a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
　エッチング処理又はめっき処理の後、基板上のレジストパターンは除去してもよい。レジストパターンの除去は、例えば、上記現像工程に用いたアルカリ性水溶液よりも更に強アルカリ性の水溶液により剥離することができる。強アルカリ性の水溶液としては、例えば、１～１０質量％水酸化ナトリウム水溶液、１～１０質量％水酸化カリウム水溶液等が用いられる。 After the etching process or the plating process, the resist pattern on the substrate may be removed. The resist pattern can be removed, for example, using an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used in the above-mentioned developing step. As the strongly alkaline aqueous solution, for example, a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 10% by mass aqueous potassium hydroxide solution, etc. are used.
　めっき処理を施してからレジストパターンを除去した場合、更にエッチング処理によってレジストで被覆されていた導体層をエッチングし、導体パターンを形成することで所望のプリント配線板を製造することができる。この際のエッチング処理の方法は、除去すべき導体層に応じて適宜選択される。例えば、上述のエッチング液を適用することができる。 When the resist pattern is removed after plating, the conductor layer covered with the resist is further etched by an etching process to form a conductor pattern, thereby making it possible to manufacture a desired printed wiring board. The etching method at this time is appropriately selected depending on the conductor layer to be removed. For example, the above-mentioned etching solution can be applied.
　本実施形態に係るプリント配線板の製造方法は、単層プリント配線板のみならず、多層プリント配線板の製造にも適用可能であり、また小径スルーホールを有するプリント配線板等の製造にも適用可能である。 The method for manufacturing a printed wiring board according to this embodiment is applicable not only to the manufacturing of single-layer printed wiring boards but also to the manufacturing of multilayer printed wiring boards, and also to the manufacturing of printed wiring boards having small-diameter through holes. It is possible.
　以下、実施例により本開示を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present disclosure will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
［アルカリ可溶性樹脂］
　重合性単量体として、以下に示すホモポリマーのＴｇを有する化合物を準備した。
ＡＡ：アクリル酸（Ｔｇ：１０６℃）
ＭＡＡ：メタクリル酸（Ｔｇ：２２８℃）
ＳＴ：スチレン（Ｔｇ：１００℃）
ＴＣＤＭＡ：ジシクロペンタニルメタクリレート（Ｔｇ：１７５℃）
ＢＺＭＡ：ベンジルメタクリレート（Ｔｇ：５４℃）
ＩＢＯＡ：イソボルニルアクリレート（Ｔｇ：９４℃）
ＨＥＭＡ：ヒドロキシエチルメタクリレート（Ｔｇ：５５℃）
２－ＥＨＡ：２－エチルヘキシルアクリレート（Ｔｇ：－７０℃） [Alkali-soluble resin]
As a polymerizable monomer, a compound having a homopolymer Tg shown below was prepared.
AA: Acrylic acid (Tg: 106°C)
MAA: methacrylic acid (Tg: 228°C)
ST: Styrene (Tg: 100°C)
TCDMA: dicyclopentanyl methacrylate (Tg: 175°C)
BZMA: Benzyl methacrylate (Tg: 54°C)
IBOA: Isobornyl acrylate (Tg: 94°C)
HEMA: Hydroxyethyl methacrylate (Tg: 55°C)
2-EHA: 2-ethylhexyl acrylate (Tg: -70°C)
（実施例１）
　重合性単量体であるアクリル酸（ＡＡ）１００．４ｇ、スチレン（ＳＴ）３０８．９ｇ、及びジシクロペンタニルメタクリレート（ＴＣＤＭＡ）２９．７ｇ（ＡＡ／ＳＴ／ＴＯＤＭＡの質量比＝２２．９／７０．３／６．８）と、熱ラジカル重合開始剤であるアゾビスイソブチロニトリル（ＡＩＢＮ）２．２ｇと、溶剤であるプロピレングリコールモノメチルエーテル１２９．５ｇとを混合し、混合物（ｘ）を調製した。４．４ｇのＡＩＢＮを２６．３ｇのプロピレングリコールモノメチルエーテルに溶解して溶液（ａ）を調製した。 (Example 1)
Polymerizable monomers acrylic acid (AA) 100.4 g, styrene (ST) 308.9 g, and dicyclopentanyl methacrylate (TCDMA) 29.7 g (mass ratio of AA/ST/TODMA = 22.9/ 70.3/6.8), 2.2 g of azobisisobutyronitrile (AIBN), a thermal radical polymerization initiator, and 129.5 g of propylene glycol monomethyl ether, a solvent, to form a mixture (x). was prepared. Solution (a) was prepared by dissolving 4.4 g of AIBN in 26.3 g of propylene glycol monomethyl ether.
　攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテル４５．６ｇ及びトルエン１７５．１ｇを加え、窒素雰囲気下でガス置換しながら攪拌し、８０℃に昇温した。次いで、混合物（ｘ）を２時間かけてフラスコ内に滴下した。滴下終了後、８０℃で２時間攪拌した後、溶液（ａ）を加えて、更に３時間攪拌した。次いで攪拌を続けたまま、フラスコ内の溶液を２０分かけて１００℃まで昇温させた後、１００℃で２時間攪拌した。次いで、プロピレングリコールモノメチルエーテル９３．７ｇ及びトルエン７４．３ｇを加え、攪拌しながら室温まで冷却してバインダーポリマー（Ａ－１）の溶液を得た。バインダーポリマー（Ａ－１）の不揮発分（固形分）は４４．３質量％であった。 45.6 g of propylene glycol monomethyl ether and 175.1 g of toluene were added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing the gas under a nitrogen atmosphere, and the temperature was raised to 80°C. It was warm. Then, mixture (x) was added dropwise into the flask over 2 hours. After the dropwise addition was completed, the mixture was stirred at 80° C. for 2 hours, and then solution (a) was added and stirred for an additional 3 hours. Next, while stirring was continued, the temperature of the solution in the flask was raised to 100°C over 20 minutes, and then stirred at 100°C for 2 hours. Next, 93.7 g of propylene glycol monomethyl ether and 74.3 g of toluene were added, and the mixture was cooled to room temperature while stirring to obtain a solution of binder polymer (A-1). The nonvolatile content (solid content) of the binder polymer (A-1) was 44.3% by mass.
（実施例２）
　溶液（ａ）のＡＩＢＮの量を５．５ｇに変更した以外は、実施例１と同様の条件で、バインダーポリマー（Ａ－２）の溶液を得た。 (Example 2)
A solution of binder polymer (A-2) was obtained under the same conditions as in Example 1, except that the amount of AIBN in solution (a) was changed to 5.5 g.
（実施例３）
　溶液（ａ）のＡＩＢＮの量を１１．９ｇに変更した以外は、実施例１と同様の条件で、バインダーポリマー（Ａ－３）の溶液を得た。 (Example 3)
A solution of binder polymer (A-3) was obtained under the same conditions as in Example 1, except that the amount of AIBN in solution (a) was changed to 11.9 g.
（実施例４～８）
　混合物（ｘ）の重合性単量体の量を表１に示す質量比に変更した以外はバインダーポリマー（Ａ－２）と同様の条件で、バインダーポリマー（Ａ－４）～（Ａ－８）の溶液を得た。 (Examples 4 to 8)
Binder polymers (A-4) to (A-8) were prepared under the same conditions as binder polymer (A-2) except that the amount of polymerizable monomer in mixture (x) was changed to the mass ratio shown in Table 1. A solution of was obtained.
（実施例９～１３）
　混合物（ｘ）の重合性単量体の種類及び量を表１に示す重合性単量体及び質量比に変更した以外はバインダーポリマー（Ａ－２）と同様の条件で、バインダーポリマー（Ａ－９）～（Ａ－１３）の溶液を得た。 (Examples 9 to 13)
Binder polymer (A-2) was prepared under the same conditions as binder polymer (A-2) except that the type and amount of the polymerizable monomer in mixture (x) were changed to the polymerizable monomers and mass ratio shown in Table 1. Solutions of 9) to (A-13) were obtained.
（比較例１～３）
　混合物（ｘ）の重合性単量体の種類及び量を表１に示す重合性単量体及び質量比に変更した以外はバインダーポリマー（Ａ－２）と同様の条件で、バインダーポリマー（Ａ－１４）～（Ａ－１６）の溶液を得た。 (Comparative Examples 1 to 3)
Binder polymer (A-2) was prepared under the same conditions as binder polymer (A-2) except that the type and amount of the polymerizable monomer in mixture (x) were changed to the polymerizable monomers and mass ratio shown in Table 1. Solutions of 14) to (A-16) were obtained.
（重量平均分子量）
　Ｍｗ測定用の試料として、ポリマー溶液をテトラヒドロフラン（ＴＨＦ）に溶解して、０．２質量％ＴＨＦ溶液を調製した。Ｍｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によって測定し、標準ポリスチレンの検量線を用いて換算することにより導出した。ＧＰＣの条件を以下に示す。
　測定装置：ショウデックス（登録商標）ＧＰＣ－１０１（昭和電工株式会社製）
　検出器：示差屈折計　ショウデックス　ＲＩ‐７１Ｓ（昭和電工株式会社製）
　カラム：ショウデックス　ＬＦ‐８０４＋ＬＦ‐８０４（昭和電工株式会社製）
　カラム温度：４０℃
　溶離液：テトラヒドロフラン（ＴＨＦ）
　流速：１ｍＬ／分 (Weight average molecular weight)
As a sample for Mw measurement, a polymer solution was dissolved in tetrahydrofuran (THF) to prepare a 0.2% by mass THF solution. Mw was determined by gel permeation chromatography (GPC) and calculated using a standard polystyrene calibration curve. The conditions for GPC 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.)
Column: Showdex LF-804+LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40℃
Eluent: Tetrahydrofuran (THF)
Flow rate: 1mL/min
（ガラス転移温度）
　バインダーポリマーのＴｇは、Ｆｏｘの式から算出した。 (Glass-transition temperature)
The Tg of the binder polymer was calculated from the Fox equation.
（酸価）
　ＪＩＳ　Ｋ６９０１：２００８　５．３．２に従い、中和滴定法によりバインダーポリマーの酸価を測定した。 (Acid value)
The acid value of the binder polymer was measured by neutralization titration method according to JIS K6901:2008 5.3.2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［感光性樹脂組成物］
　バインダーポリマー溶液の固形分量が５６質量部に対して、表２に示す配合量（質量部）の各成分を混合することにより、感光性樹脂組成物を調製した。表２に示す各成分の詳細については、以下のとおりである。 [Photosensitive resin composition]
A photosensitive resin composition was prepared by mixing each component in the amount (parts by mass) shown in Table 2 with respect to the solid content of the binder polymer solution of 56 parts by mass. Details of each component shown in Table 2 are as follows.
（光重合性化合物）
ＦＡ－３２１Ｍ：２，２－ビス（４－（メタクリロキシペンタエトキシ）フェニル）プロパン（昭和電工マテリアルズ株式会社製）
ＢＰ－２ＥＭ：２，２－ビス（４－（メタクリロキシジエトキシ）フェニル）プロパン（共栄社化学株式会社製）
ＦＡ－０２４Ｍ：ＥＯＰＯ変性ジメタクリレート（昭和電工マテリアルズ株式会社製）
（光重合開始剤）
Ｂ－ＣＩＭ：２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール（Ｈａｍｐｆｏｒｄ社製）
（増感剤）
ＤＢＡ：９，１０－ジブトキシアントラセン（川崎化成工業株式会社製）
（重合禁止剤）
ＴＥＭＰＯ：２，２，６，６－テトラメチルピペリジノオキシルフリーラジカル（株式会社ＡＤＥＫＡ製）
ＴＢＣ：４－ｔｅｒｔ－ブチルカテコール（ＤＩＣ株式会社製、商品名「ＤＩＣ－ＴＢＣ」）
（密着付与剤）
ＳＦ－８０８Ｈ：カルボキシベンゾトリアゾール、５－アミノ－１Ｈ－テトラゾール及びメトキシプロパノールの混合物（サンワ化成株式会社製）
（光発色剤）
ＬＣＶ：ロイコクリスタルバイオレット（山田化学工業株式会社製）
（染料）
ＭＫＧ：マラカイトグリーン（大阪有機化学工業株式会社製） (Photopolymerizable compound)
FA-321M: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (manufactured by Showa Denko Materials Co., Ltd.)
BP-2EM: 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (manufactured by Kyoeisha Chemical Co., Ltd.)
FA-024M: EOPO modified dimethacrylate (manufactured by Showa Denko Materials Co., Ltd.)
(Photopolymerization initiator)
B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (manufactured by Hampford)
(sensitizer)
DBA: 9,10-dibutoxyanthracene (manufactured by Kawasaki Chemical Industries, Ltd.)
(Polymerization inhibitor)
TEMPO: 2,2,6,6-tetramethylpiperidinooxyl free radical (manufactured by ADEKA Co., Ltd.)
TBC: 4-tert-butylcatechol (manufactured by DIC Corporation, product name "DIC-TBC")
(Adhesion agent)
SF-808H: mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (manufactured by Sanwa Kasei Co., Ltd.)
(photocoloring agent)
LCV: Leuco Crystal Violet (manufactured by Yamada Chemical Industry Co., Ltd.)
(dye)
MKG: Malachite Green (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［感光性エレメント］
　支持体として厚さ１６μｍのポリエチレンテレフタレートフィルム（東レ株式会社製、商品名「ＱＳ－６９」）を用意した。支持体上に、感光性樹脂組成物を塗布した後、８０℃及び１２０℃の熱風対流式乾燥器で順次乾燥して、乾燥後の厚さが２５μｍの感光層を形成した。この感光層上に保護層としてポリエチレンフィルム（タマポリ株式会社製、商品名「ＮＦ－１５」）を貼り合わせ、支持体と感光層と保護層とが順に積層された感光性エレメントを得た。 [Photosensitive element]
A polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "QS-69") with a thickness of 16 μm was prepared as a support. After coating the photosensitive resin composition on the support, it was sequentially dried in a hot air convection dryer at 80° C. and 120° C. to form a photosensitive layer having a thickness of 25 μm after drying. A polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-15") was laminated as a protective layer on this photosensitive layer to obtain a photosensitive element in which the support, the photosensitive layer, and the protective layer were laminated in this order.
［積層体］
　銅箔（厚さ：３５μｍ）を両面に積層したガラスエポキシ材である銅張積層板（昭和電工マテリアルズ株式会社製、商品名「ＭＣＬ－Ｅ－６７９」）を、水洗、酸洗及び水洗後、空気流で乾燥した。表面処理された銅張積層板を８０℃に加温し、保護層を剥離しながら、感光層が銅表面に接するように、感光性エレメントをラミネートした。これにより、銅張積層板と感光層と支持体とがこの順に積層された積層体を得た。ラミネートは、１１０℃のヒートロールを用いて、０．４ＭＰａの圧着圧力、１．０５ｍ／分のロール速度で行った。 [Laminated body]
A copper-clad laminate (manufactured by Showa Denko Materials Co., Ltd., product name "MCL-E-679"), which is a glass epoxy material with copper foil (thickness: 35 μm) laminated on both sides, was washed with water, pickled, and washed with water. , dried with air flow. The surface-treated copper-clad laminate was heated to 80° C., and while the protective layer was peeled off, a photosensitive element was laminated so that the photosensitive layer was in contact with the copper surface. Thereby, a laminate in which the copper-clad laminate, the photosensitive layer, and the support were laminated in this order was obtained. Lamination was performed using a heat roll at 110° C. at a pressure of 0.4 MPa and a roll speed of 1.05 m/min.
［評価］
　得られた積層体を以下に示す評価の試験片として用いた。評価結果を表３に示す。 [evaluation]
The obtained laminate was used as a test piece for the evaluation shown below. The evaluation results are shown in Table 3.
（最小現像時間）
　上記積層体を５ｃｍ四方に切断し、最小現像時間測定用の試験片を得た。試験片から支持体を剥離した後、３０℃の１質量％炭酸ナトリウム水溶液を用いて、露光していない感光層を０．１５ＭＰａの圧力でスプレー現像し、１ｍｍ以上の未露光部が除去されたことを目視で確認できる最短の時間を、最短現像時間とした。ノズルは、フルコーンタイプを使用した。上記試験片とノズル先端との距離は６ｃｍであり、試験片の中心とノズルの中心が一致するように配置した。最小現像時間（単位：秒）が短いほど、現像性が良好であることを意味する。 (Minimum development time)
The above laminate was cut into 5 cm square pieces 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 using a 1% by mass aqueous sodium carbonate solution at 30°C at a pressure of 0.15 MPa, and the unexposed area of 1 mm or more was removed. The shortest time during which this could be visually confirmed was defined as the shortest development time. A full cone type nozzle was used. The distance between the test piece and the tip of the nozzle was 6 cm, and the test piece was arranged so that the center of the test piece and the center of the nozzle coincided. It means that the shorter the minimum development time (unit: seconds), the better the developability.
（感度）
　試験片の支持体上に、日立４１段ステップタブレットを載置し、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名「ＤＥ－１ＵＨ」）を用いて、日立４１段ステップタブレットの現像後の残存ステップ段数が１８段となる露光量（照射エネルギー量）で、支持体を介して感光層を露光した。このときの露光量（単位：ｍＪ／ｃｍ２）により光感度を評価した。露光量が少ないほど、光感度が高いことを意味する。 (sensitivity)
A Hitachi 41 step step tablet was placed on the support of the test piece, and a direct writing exposure machine (manufactured by Via Mechanics Co., Ltd., trade name "DE-1UH") using a blue-violet laser diode with a wavelength of 405 nm as a light source was used. Then, the photosensitive layer was exposed through the support at an exposure amount (irradiation energy amount) such that the number of steps remaining after development of the Hitachi 41-step step tablet was 18 steps. The photosensitivity was evaluated based on the exposure amount (unit: mJ/cm 2 ) at this time. The smaller the exposure amount, the higher the photosensitivity.
（密着性）
　ライン幅（Ｌ）／スペース幅（Ｓ）（以下、「Ｌ／Ｓ」と記す。）がｘ／３ｘ（ｘ＝１～２０（１μｍ間隔で変化））（単位：μｍ）である描画パターンを用いて、日立４１段ステップタブレットの残存段数が１７段となるエネルギー量で、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名「ＤＥ－１ＵＨ」）により、上記積層体の感光層に対して露光（描画）を行った。 (Adhesion)
A drawing pattern whose line width (L)/space width (S) (hereinafter referred to as "L/S") is x/3x (x = 1 to 20 (varies in 1 μm intervals)) (unit: μm). A direct writing exposure machine (manufactured by Via Mechanics Co., Ltd., product name "DE-1UH") that uses a blue-violet laser diode with a wavelength of 405 nm as a light source has an energy amount that makes the remaining number of steps of the Hitachi 41-step step tablet 17. The photosensitive layer of the laminate was exposed (drawn) using the following steps.
　露光後、積層体から支持体を剥離し、感光層を露出させ、１質量％炭酸ナトリウム水溶液を３０℃にて６０秒間スプレーすることにより、未露光部分を除去した。現像後、スペース部分（未露光部分）が残渣なく除去され、且つライン部分（露光部分）が蛇行及び欠けを生じることなく形成されたレジストパターンにおけるライン幅のうちの最小値により、密着性を評価した。この数値が小さいほど密着性が良好であることを意味する。密着性が１０μｍ以下である場合を合格とする。 After exposure, the support was peeled from the laminate to expose the photosensitive layer, and unexposed areas were removed by spraying a 1% by mass aqueous sodium carbonate solution at 30°C for 60 seconds. After development, adhesion is evaluated by the minimum value of the line width in the resist pattern in which the space portions (unexposed portions) are removed without any residue and the line portions (exposed portions) are formed without meandering or chipping. did. It means that the smaller this value is, the better the adhesion is. A case where the adhesion is 10 μm or less is considered to be a pass.
（解像度）
　Ｌ／Ｓがｘ／ｘ（ｘ＝１～２０（１μｍ間隔で変化））（単位：μｍ）である描画パターンを用いて、日立４１段ステップタブレットの残存段数が１７段となるエネルギー量で、波長４０５ｎｍの青紫色レーザダイオードを光源とする直描露光機（ビアメカニクス株式会社製、商品名「ＤＥ－１ＵＨ」）により、上記積層体の感光層に対して露光（描画）を行った。 (resolution)
Using a drawing pattern in which L/S is x/x (x = 1 to 20 (changes in 1 μm intervals)) (unit: μm), the amount of energy is such that the number of remaining steps of the Hitachi 41-step step tablet is 17 steps, The photosensitive layer of the laminate was exposed to light (drawing) using a direct drawing exposure machine (manufactured by Via Mechanics Co., Ltd., trade name "DE-1UH") using a blue-violet laser diode with a wavelength of 405 nm as a light source.
　露光後、積層体から支持体を剥離し、感光層を露出させ、１質量％炭酸ナトリウム水溶液を３０℃にて６０秒間スプレーすることにより、未露光部分を除去した。現像後、スペース部分（未露光部分）が残渣なく除去され、且つライン部分（露光部分）が蛇行及び欠けを生じることなく形成されたレジストパターンにおけるスペース幅のうちの最小値により、解像度を評価した。この数値が小さいほど解像度が良好であることを意味する。解像度が１２μｍ以下である場合を合格とする。 After exposure, the support was peeled from the laminate to expose the photosensitive layer, and unexposed areas were removed by spraying a 1% by mass aqueous sodium carbonate solution at 30°C for 60 seconds. After development, the resolution was evaluated by the minimum value of the space width in the resist pattern in which the space portions (unexposed portions) were removed without any residue and the line portions (exposed portions) were formed without meandering or chipping. . The smaller this number is, the better the resolution is. A case where the resolution is 12 μm or less is considered a pass.
（剥離性）
　前記評価用積層基板上に、剥離性評価用として４５ｍｍ×６５ｍｍの長方形の硬化膜を形成するマスクデータを使用して露光した。次いで上記光感度の評価と同様の条件で現像処理を行って、未露光部を除去した。その後、容量４００ｍＬのビーカーに５０℃、３．０質量％ＮａＯＨ水溶液（剥離液）３００ｍＬを準備した。剥離液を長さ３０ｍｍの攪拌子を用いて２００回転／分（ｒｐｍ）で攪拌しながら、現像後の基板を剥離液に浸漬し、硬化膜が基板から離れるまでの時間を計測した。硬化膜が基板から離れるまでの時間が早いほど、剥離時間が短く剥離性が良好であるといえる。 (Releasability)
The multilayer substrate for evaluation was exposed to light using mask data for forming a rectangular cured film of 45 mm x 65 mm for peelability evaluation. Next, development was performed under the same conditions as in the above photosensitivity evaluation to remove unexposed areas. Thereafter, 300 mL of a 3.0% by mass NaOH aqueous solution (stripping solution) at 50° C. was prepared in a 400 mL beaker. While stirring the stripping solution at 200 revolutions per minute (rpm) using a stirrer with a length of 30 mm, the developed substrate was immersed in the stripping solution, and the time until the cured film separated from the substrate was measured. It can be said that the faster the cured film separates from the substrate, the shorter the peeling time and the better the peelability.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　１…感光性エレメント、２…支持体、３…感光層、４…保護層。 1... Photosensitive element, 2... Support, 3... Photosensitive layer, 4... Protective layer.

Claims (16)

  1. 　バインダーポリマーと、光重合性化合物と、光重合開始剤と、増感剤と、を含有する感光性樹脂組成物であって、
    　前記バインダーポリマーが、アクリル酸に由来する構造単位と、スチレン又はスチレン誘導体に由来する構造単位と、脂環構造を有する（メタ）アクリレート化合物に由来する構造単位と、を有するアルカリ可溶性樹脂を含む、感光性樹脂組成物。     A photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a sensitizer,
    The binder polymer includes an alkali-soluble resin having a structural unit derived from acrylic acid, a structural unit derived from styrene or a styrene derivative, and a structural unit derived from a (meth)acrylate compound having an alicyclic structure. Photosensitive resin composition.
  2. 　前記アクリル酸に由来する構造単位の含有量が、前記アルカリ可溶性樹脂を構成する重合性単量体に由来する構造単位の全質量を基準として、１５～２５質量％である、請求項１に記載の感光性樹脂組成物。 According to claim 1, the content of the structural units derived from acrylic acid is 15 to 25% by mass based on the total mass of the structural units derived from the polymerizable monomers constituting the alkali-soluble resin. photosensitive resin composition.
  3. 　前記アルカリ可溶性樹脂の重量平均分子量が、１００００～８００００である、請求項１又は２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin has a weight average molecular weight of 10,000 to 80,000.
  4. 　前記アルカリ可溶性樹脂の酸価が、１４０～２００ｍｇＫＯＨ／ｇである、請求項１～３のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin has an acid value of 140 to 200 mgKOH/g.
  5. 　前記増感剤が、アントラセン化合物を含む、請求項１～４のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the sensitizer contains an anthracene compound.
  6. 　前記光重合性化合物が、オキシエチレン基の数が１０以上である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンを含む、請求項１～５のいずれか一項に記載の感光性樹脂組成物。 Any one of claims 1 to 5, wherein the photopolymerizable compound contains 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane having 10 or more oxyethylene groups. The photosensitive resin composition described in .
  7. 　前記光重合性化合物が、オキシエチレン基の数が１０未満である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンを含む、請求項１～６のいずれか一項に記載の感光性樹脂組成物。 Any one of claims 1 to 6, wherein the photopolymerizable compound comprises 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane having less than 10 oxyethylene groups. The photosensitive resin composition described in .
  8. 　前記光重合性化合物が、オキシエチレン基の数が１０以上である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンと、オキシエチレン基の数が１０未満である２，２－ビス（４－（（メタ）アクリロキシポリエトキシ）フェニル）プロパンとを含む、請求項１～５のいずれか一項に記載の感光性樹脂組成物。 The photopolymerizable compound is 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane in which the number of oxyethylene groups is 10 or more, and 2 in which the number of oxyethylene groups is less than 10. , 2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, the photosensitive resin composition according to any one of claims 1 to 5.
  9. 　アクリル酸に由来する構造単位と、スチレン又はスチレン誘導体に由来する構造単位と、脂環構造を有する（メタ）アクリレート化合物に由来する構造単位と、を有する、アルカリ可溶性樹脂。 An alkali-soluble resin having a structural unit derived from acrylic acid, a structural unit derived from styrene or a styrene derivative, and a structural unit derived from a (meth)acrylate compound having an alicyclic structure.
  10. 　前記アクリル酸に由来する構造単位の含有量が、前記アルカリ可溶性樹脂を構成する重合性単量体に由来する構造単位の全質量を基準として、１５～２５質量％である、請求項９に記載のアルカリ可溶性樹脂。 According to claim 9, the content of the structural units derived from the acrylic acid is 15 to 25% by mass based on the total mass of the structural units derived from the polymerizable monomers constituting the alkali-soluble resin. alkaline soluble resin.
  11. 　重量平均分子量が１００００～８００００である、請求項９又は１０に記載のアルカリ可溶性樹脂。 The alkali-soluble resin according to claim 9 or 10, which has a weight average molecular weight of 10,000 to 80,000.
  12. 　酸価が１４０～２００ｍｇＫＯＨ／ｇである、請求項９～１１のいずれか一項項に記載のアルカリ可溶性樹脂。 The alkali-soluble resin according to any one of claims 9 to 11, which has an acid value of 140 to 200 mgKOH/g.
  13. 　支持体と、該支持体上に請求項１～８のいずれか一項に記載の感光性樹脂組成物を用いて形成された感光層と、を備える感光性エレメント。 A photosensitive element comprising a support and a photosensitive layer formed on the support using the photosensitive resin composition according to any one of claims 1 to 8.
  14. 　基板上に、請求項１～８のいずれか一項に記載の感光性樹脂組成物又は請求項１３に記載の感光性エレメントを用いて、感光層を形成する工程と、
    　前記感光層の少なくとも一部に活性光線を照射して、光硬化部を形成する工程と、
    　前記基板から、前記感光層の未光硬化部を除去して、レジストパターンを形成する工程と、
    を備える、レジストパターンの形成方法。     forming a photosensitive layer on the substrate using the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive element according to claim 13;
    irradiating at least a portion of the photosensitive layer with actinic rays to form a photocured portion;
    removing an unphotocured portion of the photosensitive layer from the substrate to form a resist pattern;
    A method for forming a resist pattern, comprising:
  15. 　請求項１４に記載のレジストパターンの形成方法によりレジストパターンが形成された基板をエッチング処理又はめっき処理して、導体パターンを形成する工程を備える、プリント配線板の製造方法。 A method for manufacturing a printed wiring board, comprising the step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 14 to form a conductor pattern.
  16. 　前記エッチング処理又はめっき処理の後に、前記レジストパターンを除去する工程を更に備える、請求項１５に記載のプリント配線板の製造方法。 The method for manufacturing a printed wiring board according to claim 15, further comprising a step of removing the resist pattern after the etching treatment or the plating treatment.
PCT/JP2022/023189 2022-06-08 2022-06-08 Alkali-soluble resin, photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board WO2023238299A1 (en)

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WO2022030053A1 (en) * 2020-08-07 2022-02-10 昭和電工マテリアルズ株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
WO2022054599A1 (en) * 2020-09-14 2022-03-17 富士フイルム株式会社 Photosensitive transfer material, method for producing resin pattern, etching method, and method for manufacturing electronic device

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WO2022030053A1 (en) * 2020-08-07 2022-02-10 昭和電工マテリアルズ株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
WO2022054599A1 (en) * 2020-09-14 2022-03-17 富士フイルム株式会社 Photosensitive transfer material, method for producing resin pattern, etching method, and method for manufacturing electronic device

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