WO2022113161A1 - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board - Google Patents

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

Info

Publication number
WO2022113161A1
WO2022113161A1 PCT/JP2020/043605 JP2020043605W WO2022113161A1 WO 2022113161 A1 WO2022113161 A1 WO 2022113161A1 JP 2020043605 W JP2020043605 W JP 2020043605W WO 2022113161 A1 WO2022113161 A1 WO 2022113161A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
meth
photosensitive
photosensitive resin
mass
Prior art date
Application number
PCT/JP2020/043605
Other languages
French (fr)
Japanese (ja)
Inventor
志歩 田中
Original Assignee
昭和電工マテリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to PCT/JP2020/043605 priority Critical patent/WO2022113161A1/en
Priority to PCT/JP2021/042092 priority patent/WO2022113829A1/en
Priority to KR1020237019362A priority patent/KR20230109152A/en
Priority to CN202210896651.8A priority patent/CN115167077A/en
Priority to JP2022562370A priority patent/JP7425982B2/en
Priority to CN202180007845.1A priority patent/CN114902137A/en
Priority to TW110142698A priority patent/TW202227577A/en
Publication of WO2022113161A1 publication Critical patent/WO2022113161A1/en
Priority to JP2023179342A priority patent/JP2024008940A/en

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.
  • a photosensitive resin composition is used as a resist material used for an etching treatment or a plating treatment, and a layer formed on a support film using the photosensitive resin composition (hereinafter, “photosensitive”).
  • Photosensitive elements with also referred to as "layers" are widely used.
  • the printed wiring board is manufactured by the following procedure, for example, using the above-mentioned photosensitive element. That is, first, the photosensitive layer of the photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. Next, the photosensitive layer is exposed via a mask film or the like to form a photocurable portion. At this time, the support film is peeled off before or after the exposure. Then, the region other than the light-cured portion of the photosensitive layer is removed with a developing solution to form a resist pattern. Next, using the resist pattern as a resist, an etching treatment or a plating treatment 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 characteristics in the etching treatment or the plating treatment, excellent adhesion to the circuit forming substrate, and excellent resolution in forming the resist pattern.
  • Patent Document 1 discloses a photosensitive resin composition having excellent sensitivity and resolution by using a specific sensitizing dye.
  • Patent Document 2 discloses a photosensitive resin composition having excellent sensitivity and resolution by using a specific alkali-soluble polymer and a compound having an ethylenic double bond.
  • the photosensitive layer When laminating the photosensitive layer of the photosensitive element on the circuit forming substrate, if the photosensitive layer has low followability to the circuit forming substrate, a fine void is generated between the photosensitive layer and the circuit forming substrate. , May affect the formation of conductor patterns. Therefore, the photosensitive layer is required to have excellent followability to the circuit forming substrate.
  • the present disclosure discloses a photosensitive resin composition capable of forming a photosensitive layer having excellent followability to a circuit forming substrate, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a printed wiring board. It is an object of the present invention to provide the manufacturing method of.
  • the photosensitive resin composition according to the present disclosure contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the binder polymer is a structural unit derived from a polymerizable monomer having a carboxy group (a structural unit ().
  • A1 a structural unit (a2) derived from styrene or a styrene derivative, a structural unit (a3) derived from an alkyl (meth) acrylic rate having an alkyl group having 1 to 3 carbon atoms, and 4 to 4 carbon atoms. It has a structural unit (a4) derived from an alkyl (meth) methacrylate having 12 alkyl groups.
  • the photosensitive element according to the present disclosure includes a support and a photosensitive layer formed on the support, and the photosensitive layer contains the above-mentioned photosensitive resin composition.
  • the method for forming a resist pattern according to the present disclosure includes a step of forming a photosensitive layer on a substrate by using the above-mentioned photosensitive resin composition or a photosensitive element, and irradiation of at least a part of the photosensitive layer with active light.
  • the process includes a step of forming a photo-cured portion and a step of removing at least a part of the unphoto-cured portion of the photosensitive layer from the substrate.
  • the method for manufacturing a printed wiring board according to the present disclosure includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern.
  • a photosensitive resin composition capable of forming a photosensitive layer having excellent followability to a circuit forming substrate, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and printing.
  • a method for manufacturing a wiring board can be provided.
  • the term "process” is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.
  • the term "layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view.
  • the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • (meth) acrylic acid means at least one of “acrylic acid” and the corresponding “methacrylic acid”, and the same applies to other similar expressions such as (meth) acrylate.
  • the “solid content” is a non-volatile substance excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatile when the resin composition is dried. It shows the components that remain without leaving, and also includes liquid, water candy-like, and wax-like substances at room temperature around 25 ° C.
  • the photosensitive resin composition according to the present embodiment contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the binder polymer is a structural unit derived from a polymerizable monomer having a carboxy group.
  • A1 a structural unit (a2) derived from styrene or a styrene derivative, a structural unit (a3) derived from an alkyl (meth) acrylic rate having an alkyl group having 1 to 3 carbon atoms, and 4 carbon atoms. It has a structural unit (a4) derived from an alkyl (meth) methacrylate having up to 12 alkyl groups.
  • the component (A) component includes a structural unit (a1) having a carboxy group, a structural unit (a2) derived from styrene or a styrene derivative, and an alkyl (meth) having an alkyl group having 1 to 3 carbon atoms.
  • the binder polymer has a structural unit (a1) from the viewpoint of alkali developability.
  • the polymerizable monomer having a carboxy group include (meth) acrylic acid, ⁇ -bromoacrylic acid, ⁇ -chloroacrylic acid, ⁇ -furyl (meth) acrylic acid, ⁇ -styryl (meth) acrylic acid, and the like.
  • Maleic acid monoesters such as maleic acid, maleic acid anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, silicic acid, ⁇ -cyanosilicic acid, itaconic acid, crotonic acid, and propioleic acid Can be mentioned.
  • the polymerizable monomer having a carboxy group may be (meth) acrylic acid or methacrylic acid from the viewpoint of further improving the alkali developability.
  • the content of the structural unit (a1) is 10 to 30% by mass, 15 to 28% by mass, or 20 based on the total amount of the component (A) from the viewpoint of improving the alkali developability and the followability in a well-balanced manner. It may be up to 26% by mass.
  • the content of the structural unit (a1) is 10% by mass or more, the alkali developability tends to be improved, and when the content is 30% by mass or less, the followability tends to be excellent.
  • the binder polymer has a structural unit (a2) from the viewpoint of resolution.
  • the styrene derivative is a polymerizable compound in which a hydrogen atom in the ⁇ -position or aromatic ring of styrene such as vinyltoluene and ⁇ -methylstyrene is substituted.
  • the content of the structural unit (a2) in the component (A) is 10 to 50% by mass and 12 to 45 based on the total amount of the component (A). It may be% by mass, or 14 to 44% by mass.
  • the binder polymer has a structural unit (a3) from the viewpoint of resolution.
  • alkyl (meth) acrylic rate having an alkyl group having 1 to 3 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
  • the content of the structural unit (a3) in the component (A) is 5 to 70% by mass and 12 to 65 based on the total amount of the component (A) from the viewpoint of improving the alkali developability and the followability in a well-balanced manner. It may be% by mass, or 15 to 64% by mass.
  • the content of the structural unit (a3) is 5% by mass or more, the alkali developability tends to be improved, and when the content is 70% by mass or less, the followability tends to be excellent.
  • the binder polymer has a structural unit (a4) from the viewpoint of followability.
  • the alkyl group having 4 to 12 carbon atoms may be a linear or branched alkyl group.
  • Examples of the alkyl (meth) methacrylate having an alkyl group having 4 to 12 carbon atoms include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and octyl (meth) acrylate.
  • 2-Ethylhexyl (meth) acrylate nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.
  • the content of the structural unit (a4) in the component (A) is 0.5 to 30% by mass, 0, based on the total amount of the component (A). It may be 8 to 25% by mass, or 1 to 22% by mass.
  • the component (A) may further have a structural unit (a5) other than the structural units (a1) to (a4).
  • a structural unit (a5) examples include benzyl (meth) acrylate or a derivative thereof, acrylamide such as diacetoneacrylamide, and an ether compound of vinyl alcohol such as vinyl-n-butyl ether.
  • the acid value of the component (A) is 100 mgKOH / g or more, 110 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g or more from the viewpoint of further improving the balance between developability, resolution and followability. May be good.
  • the acid value of the component (A) may be 180 mgKOH / g or less, 170 mgKOH / g or less, 165 mgKOH / g or less, or 160 mgKOH / g or less from the viewpoint of further improving the followability of the photosensitive layer.
  • the weight average molecular weight (Mw) of the component (A) may be 60,000 or less, 56,000 or less, 54,000 or less, or 52,000 or less in terms of further excellent developability.
  • the Mw of the component (A) may be 10,000 or more, 15,000 or more, 20,000 or more, or 25,000 or more in terms of further excellent adhesion.
  • the degree of dispersion (weight average molecular weight / number average molecular weight) of the component (A) may be 3.0 or less, 2.8 or less, or 2.5 or less in terms of further excellent resolution and adhesion. The resolution tends to improve as the degree of dispersion decreases.
  • the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC) and are converted values using standard polystyrene as a standard sample.
  • the glass transition temperature (Tg) of the component (A) may be 80 to 130 ° C., 85 to 125 ° C., or 90 to 120 ° C. from the viewpoint of further improving the followability.
  • the component (A) one type can be used alone or two or more types can be used in combination.
  • the component (A) includes, for example, two or more kinds of binder polymers composed of different polymerizable monomers, two or more kinds of binder polymers having different Mw, and different dispersities. Two or more kinds of binder polymers can be mentioned.
  • the content of the component (A) is 30 to 80 parts by mass, 40 to 75 parts by mass, 50 to 70 parts by mass, or 50 to 60 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It may be a department. When the content of the component (A) is within this range, the strength of the light-cured portion of the photosensitive layer becomes better.
  • Component (B) photopolymerizable compound
  • the component (B) is not particularly limited as long as it has at least one ethylenically unsaturated bond and is photopolymerizable.
  • the ethylenically unsaturated bond is not particularly limited as long as photopolymerization is possible. Examples of the ethylenically unsaturated bond include ⁇ , ⁇ -unsaturated carbonyl groups such as (meth) acryloyl group.
  • Examples of the photopolymerizable compound having an ⁇ , ⁇ -unsaturated carbonyl group include ⁇ , ⁇ -unsaturated carboxylic acid ester of a polyhydric alcohol, bisphenol type (meth) acrylate, and ⁇ , ⁇ -unmodified of a glycidyl group-containing compound.
  • Examples include saturated carboxylic acid adducts, (meth) acrylates with urethane bonds, nonylphenoxypolyethyleneoxyacrylates, and (meth) acrylic acid alkyl esters.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester of the polyhydric alcohol include polyethylene glycol di (meth) acrylate having an ethylene group number of 2 to 14, and polypropylene glycol di (meth) acrylate having a propylene group number of 2 to 14. Meta) acrylate, polyethylene / polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) having 2 to 14 ethylene groups and 2 to 14 propylene groups.
  • EO modification means having a block structure of ethylene oxide (EO) group
  • PO modification means having a block structure of propylene oxide (PO) group.
  • the component (B) may contain a polyalkylene glycol di (meth) acrylate from the viewpoint of improving the flexibility of the resist pattern.
  • the polyalkylene glycol di (meth) acrylate may have at least one of an EO group and a PO group, and may have both an EO group and a PO group.
  • the EO group and the PO group may be continuously present in a block or randomly.
  • the PO group may be either an oxy-n-propylene group or an oxyisopropylene group.
  • the secondary carbon of the propylene group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.
  • polyalkylene glycol di (meth) acrylate examples include, for example, FA-023M (manufactured by Showa Denko Materials Co., Ltd.), FA-024M (manufactured by Showa Denko Materials Co., Ltd.), and NK ester HEMA-9P (new). Nakamura Chemical Industry Co., Ltd.).
  • the component (B) may contain (meth) acrylate having a urethane bond from the viewpoint of improving the flexibility of the resist pattern.
  • the (meth) acrylate having a urethane bond include a (meth) acrylic monomer having an OH group at the ⁇ -position and a diisocyanate (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexa).
  • Examples thereof include addition reactants with methylene diisocyanate), tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO and PO-modified urethane di (meth) acrylate.
  • Examples of commercially available products of EO-modified urethane di (meth) acrylate include “UA-11” and “UA-21EB” (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • Examples of commercially available products of EO and PO-modified urethane di (meth) acrylate include “UA-13” (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
  • the component (B) may contain dipentaerythritol or a (meth) acrylate compound having a skeleton derived from pentaerythritol from the viewpoint of easily forming a thick-film resist pattern and improving resolution and adhesion in a well-balanced manner.
  • the (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol preferably has four or more (meth) acryloyl groups, and is preferably dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate. May be.
  • the component (B) may contain a bisphenol type (meth) acrylate, or may contain a bisphenol A type (meth) acrylate among the bisphenol type (meth) acrylates. ..
  • the bisphenol A type (meth) acrylate include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy)).
  • 2,2-bis (4-((meth) acryloxipolyethoxy) phenyl) propane is preferable from the viewpoint of further improving the resolution and putter forming property.
  • nonylphenoxypolyethyleneoxyacrylate examples include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, and nonylphenoxynonaethyleneoxy.
  • examples thereof include acrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.
  • the content of the component (B) is preferably 20 to 60 parts by mass, more preferably 30 to 55 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is more preferably 35 to 50 parts by mass.
  • the content of the component (B) is in this range, the light sensitivity and the coating film property become better in addition to the resolution and adhesion of the photosensitive resin composition and the resist hem generation property.
  • the component (C) is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators. From the viewpoint of improving pattern formation, those that generate free radicals by active light, for example, acylphosphine oxide type, oxime ester type, aromatic ketone type, quinone type, alkylphenone type, imidazole type, aclysine type, phenylglycine. Examples thereof include photopolymerization initiators such as radicals and quinones.
  • the component (C) may contain an acridine-based photopolymerization initiator, a phenylglycine-based photopolymerization initiator, or an imidazole-based photopolymerization initiator in terms of improving sensitivity and resolution in a well-balanced manner, and may contain an acridine-based photopolymerization initiator. Is preferably included.
  • the component (C) one type can be used alone or two or more types can be used in combination.
  • acridin-based photopolymerization initiator examples include 9-phenylacridines, 9- (p-methylphenyl) acridins, 9- (m-methylphenyl) acridins, 9- (p-chlorophenyl) acridins, and 9- (m-).
  • Chlorophenyl) acridines 9-aminoacridines, 9-dimethylaminoacridines, 9-diethylaminoacridines, 9-pentylaminoacridines, 1,2-bis (9-acridinyl) ethane, 1,4-bis (9-acridinyl) butane, 1,6-bis (9-acridinyl) hexane, 1,8-bis (9-acridinyl) octane, 1,10-bis (9-acridinyl) decane, 1,12-bis (9-acridinyl) dodecane, 1, Bis (9) such as 14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) hexadecane, 1,18-bis (9-acridinyl) octadecane, 1,20-bis (9-acridinyl) icosane, etc.
  • phenylglycine-based photopolymerization initiator examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • imidazole-based photopolymerization initiator examples include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxy).
  • the content of the component (C) is 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, and 0.4 to 3 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). , Or 0.5 to 2 parts by mass.
  • the content of the component (C) is 0.1 parts by mass or more, the light sensitivity, resolution and adhesion tend to be improved, and when the content is 10 parts by mass or less, the resist pattern forming property tends to be better.
  • the photosensitive resin composition according to the present embodiment may further contain a sensitizer having absorption at 340 to 430 nm as the component (D).
  • a sensitizer having absorption at 340 to 430 nm as the component (D).
  • the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stylben compounds, triazine compounds and thiophene compounds. , Naphthalimide compounds, and triarylamine compounds.
  • the sensitizer may contain at least one selected from the group consisting of pyrazoline compounds, anthracene compounds, coumarin compounds, and triarylamine compounds from the viewpoint of sensitivity and adhesion, and may contain pyrazoline compounds, anthracene compounds, and coumarin compounds. It may contain at least one selected from the group consisting of.
  • Examples of the pyrazoline compound include 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline and 1-phenyl-3- (4-tert-butylstyryl) -5- (4-). Examples thereof include tert-butylphenyl) pyrazoline and 1-phenyl-3-biphenyl-5- (4-tert-butylphenyl) pyrazoline.
  • Examples of the anthracene compound include 9,10-dibutoxyanthracene and 9,10-diphenylanthracene.
  • Examples of the coumarin compound include 3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), and 2,3,6,7-tetrahydro-. Examples thereof include 9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] kilolysine-11-one.
  • the content of the component (D) is 0.01 to 10% by mass and 0.05 to 5 based on the total solid content of the photosensitive resin composition. It may be% by mass, or 0.1 to 3% by mass.
  • the content of the component (D) is 0.01% by mass or more, the sensitivity and resolution are further improved, and when it is 10% by mass or less, the resist shape is suppressed from becoming an inverted trapezoid. , Adhesion is further improved. From the viewpoint of the balance between resolution and adhesion, the content of the component (D) is 0.005 to 0.5 parts by mass, 0.008 with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be up to 0.2 parts by mass or 0.01 to 0.1 parts by mass.
  • the photosensitive resin composition according to the present embodiment may further contain a heat stabilizer as the component (E).
  • a heat stabilizer as the component (E).
  • the component (E) include quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol (hindered phenol derivatives), and 2,2,6,6-tetramethylpiperidine.
  • examples thereof include aminoxyl derivatives such as -1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, and hindered amine derivatives such as tetramethylpiperidylmethacrylate.
  • the aminoxyl derivative as the component (E)
  • the content of the component (E) may be 0.005 to 10 parts by mass, 0.01 to 8 parts by mass, or 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A). ..
  • the content of the component (E) is 0.005 to 20 parts by mass, 0.01 to 5 parts by mass, or 0.02 to 1 part by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It may be a department.
  • the content is 0.005 part by mass or more, the resolution and the ability to suppress the resist hem generation amount tend to be more excellent, and when the content is 20 parts by mass or less, the sensitivity tends to be more excellent.
  • the photosensitive resin composition according to the present embodiment contains, if necessary, a dye, a photocoloring agent, a heat coloring inhibitor, a plasticizer, a pigment, a filler, a defoaming agent, a flame retardant, an adhesion imparting agent, and leveling.
  • Additives such as agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, and polymerization inhibitors may be further contained. These additives may be used alone or in combination of two or more.
  • Examples of the dye include malachite green, Victoria pure blue, brilliant green, and methyl violet.
  • Examples of the photocoloring agent include tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline.
  • Examples of the plasticizer include p-toluenesulfonamide.
  • the content of the additive is 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass, respectively, with respect to 100 parts by mass of the total amount of the component (A) and the component (B). There may be.
  • the photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, if necessary. Therefore, it can be prepared as a solution having a solid content of about 30 to 60% by mass.
  • a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, if necessary. Therefore, it can be prepared as a solution having a solid content of about 30 to 60% by mass.
  • the photosensitive element of the present embodiment includes a support and a photosensitive layer formed on the support, and the photosensitive layer includes the above-mentioned photosensitive resin composition.
  • the photosensitive layer may be laminated on the substrate and then exposed without peeling the support (support film).
  • the photosensitive element 1 according to the present embodiment has a support 2 and a photosensitive layer 3 derived from the photosensitive resin composition formed on the support 2, as shown in FIG. 1 as a schematic cross-sectional view of an example thereof. And other layers such as the protective layer 4 provided as needed.
  • polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalate (PEN), and polyolefin films such as polypropylene and polyethylene.
  • PET film may be used because it is easily available and has excellent handleability (particularly, heat resistance, heat shrinkage rate, breaking strength) in the manufacturing process.
  • the haze of the support may be 0.01-1.0% or 0.01-0.5%. When the haze is 0.01% or more, the support itself tends to be easy to manufacture, and when it is 1.0% or less, there is a tendency to reduce the minute defects that may occur in the resist pattern. "Haze” means cloudiness.
  • the haze in the present disclosure refers to a value measured using a commercially available turbidity meter (turbidity meter) in accordance with the method specified in JIS K7105. The haze can be measured with a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • the thickness of the support may be 1 to 100 ⁇ m, 5 to 60 ⁇ m, 10 to 50 ⁇ m, 10 to 40 ⁇ m, 10 to 30 ⁇ m, or 10 to 25 ⁇ m.
  • the thickness of the support is 1 ⁇ m or more, it tends to be possible to prevent the support from being torn when the support is peeled off. Further, when the thickness of the support is 100 ⁇ m or less, it is possible to prevent the resolution from being lowered when exposed through the support.
  • the photosensitive element may be further provided with a protective layer, if necessary.
  • a protective layer a film may be used in which the adhesive force between the photosensitive layer and the protective layer is smaller than the adhesive force between the photosensitive layer and the support, and a low fisheye film may be used. You may use it. Specifically, for example, those that can be used as the above-mentioned support can be mentioned. From the viewpoint of peelability from the photosensitive layer, a polyethylene film may be used.
  • the thickness of the protective layer varies depending on the application, but may be about 1 to 100 ⁇ m.
  • the photosensitive element can be manufactured, for example, as follows. That is, a solution (coating liquid) of the photosensitive resin composition is applied onto the support to form a coating layer, and the coating layer is formed by drying the solution. Next, by covering the surface of the photosensitive layer opposite to the support with a protective layer, the support, the photosensitive layer formed on the support, and the protective layer laminated on the photosensitive layer are provided. A photosensitive element is obtained.
  • the coating liquid can be applied onto the support by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating and the like.
  • Drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it may be carried out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of residual solvent in the photosensitive layer may be 2% by mass or less from the viewpoint of preventing the diffusion of the solvent in a later step.
  • the thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on the intended use, but the thickness after drying may be 1 to 100 ⁇ m, 1 to 50 ⁇ m, or 5 to 40 ⁇ m. When the thickness is 1 ⁇ m or more, industrial coating is facilitated and productivity is improved. Further, when the thickness is 100 ⁇ m or less, the adhesion and the resolution are improved.
  • the form of the photosensitive element is not particularly limited.
  • it may be in the form of a sheet, or may be in the form of a roll wound around a winding core.
  • the support film When winding in a roll shape, the support film may be wound so as to be on the outside.
  • the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
  • An end face separator may be installed on the end face of the roll-shaped photosensitive element from the viewpoint of end face protection, or a moisture-proof end face separator may be installed from the viewpoint of edge fusion resistance.
  • the photosensitive element may be wrapped in a black sheet having low moisture permeability and packaged.
  • the photosensitive element can be suitably used, for example, in a method for forming a resist pattern, which will be described later. Above all, from the viewpoint of resolution, it is suitable for application to a manufacturing method for forming a conductor pattern by an etching process.
  • the method for forming the resist pattern of the present embodiment is as follows: (i) a step of forming a photosensitive layer on a substrate by using the photosensitive resin composition or the photosensitive element (photosensitive layer forming step). ii) A step (exposure step) of irradiating at least a part (predetermined part) of the photosensitive layer with active light to form a photocurable portion, and (iii) at least a part of the unphotocured portion from the substrate. It may be configured to include a step (development step) for removing the above-mentioned light, and if necessary, other steps.
  • the resist pattern can be said to be a photocured product pattern of the photosensitive resin composition, and can also be said to be 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 resin composition may be applied and dried, or after the protective layer is removed from the photosensitive element, the photosensitive layer of the photosensitive element is formed. It may be crimped to the above substrate while heating.
  • a photosensitive element it is composed of a substrate, a photosensitive layer, and a support, and a laminated body in which these are laminated in order can be obtained.
  • the substrate is not particularly limited, but usually, a circuit forming substrate provided with an insulating layer and a conductor layer formed on the insulating layer, or a die pad (lead frame substrate) such as an alloy substrate is used.
  • the photosensitive layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability.
  • the photosensitive layer and / or the substrate may be heated at a temperature of 70 to 130 ° C. during crimping.
  • the crimping may be performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm 2 ), but these conditions are appropriately selected as necessary. If the photosensitive layer is heated to 70 to 130 ° C., it is not necessary to preheat the substrate in advance, but the substrate can be preheated in order to further improve the adhesion and the followability.
  • (Ii) exposure step In the exposure step, by irradiating at least a part of the photosensitive layer formed on the substrate with the active light beam, the portion irradiated with the active light ray is photocured to form a latent image.
  • the active light can be irradiated through the support if the support is transparent to the active light, but if the support is light-shielding. Irradiates the photosensitive layer with active light rays after removing the support.
  • Examples of the exposure method include a method of irradiating an image with active light rays via a negative or positive mask pattern called artwork (mask exposure method). Further, a method of irradiating an active ray in an image shape by a projection exposure method may be adopted. Further, a method of irradiating an active ray in an image shape 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
  • a known light source can be used, and for example, a carbon arc lamp, a mercury steam arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid-state laser such as a YAG laser, a semiconductor laser and the like can be used. Those that effectively radiate ultraviolet rays and visible light are used.
  • a resist pattern is formed on the substrate by removing at least a part of the unphotocured portion (other than the photocured portion) of the photosensitive layer from the substrate.
  • a support is present on the photosensitive layer, the support is removed, and then the region other than the photocured portion (which can be said to be an unexposed portion) is removed (developed).
  • development methods wet development and dry development, and wet development is widely used.
  • developer In the case of wet development, develop by a known development method using a developer corresponding to the photosensitive resin composition.
  • the developing method include a dip method, a paddle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like, and a high-pressure spray method may be used from the viewpoint of improving resolution. .. Development may be performed by combining these two or more methods.
  • the composition of the developer is appropriately selected according to the composition of the photosensitive resin composition.
  • the developing solution include an alkaline aqueous solution and an organic solvent developing solution.
  • an alkaline aqueous solution may be used as the developer.
  • the base of the alkaline aqueous solution include alkali hydroxides such as hydroxides of lithium, sodium or potassium; alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates; potassium phosphates, sodium phosphates and the like.
  • Alkaline metal phosphates Alkaline metal phosphates; Alkaline metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borosand, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl- 1,3-Propanediol, 1,3-diaminopropanol-2, morpholine and the like are used.
  • 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 0.
  • a dilute solution of 1 to 5 mass% sodium tetraborate or the like 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 according to the alkaline developability of the photosensitive layer.
  • a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution.
  • 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. Examples include monobutyl ether.
  • organic solvent used in the organic solvent developer examples include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone.
  • water may be added to these organic solvents so as to be in the range of 1 to 20% by mass to prepare an organic solvent developer.
  • heating at about 60 to 250 ° C. or exposure of about 0.2 to 10 J / cm 2 is performed as necessary. May include a step of further curing the resist pattern.
  • the method for manufacturing a printed wiring board of the present embodiment includes a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern to form a conductor pattern, and if necessary, a resist. It may be configured to include other steps such as a pattern removing step.
  • the conductor layer provided on the substrate is plated using the resist pattern formed on the substrate as a mask.
  • the resist may be removed by removing the resist pattern described later, and the conductor layer covered with the resist may be further etched to form the conductor pattern.
  • the method of the plating treatment may be an electrolytic plating treatment, an electroless plating treatment, or an electroless plating treatment.
  • the conductor layer provided on the substrate is removed by etching using the resist pattern formed on the substrate as a mask to form the conductor pattern.
  • the etching treatment method is appropriately selected according to the conductor layer to be removed.
  • the etching solution include a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
  • the resist pattern on the substrate may be removed after the etching treatment or the plating treatment.
  • the resist pattern can be removed, for example, with a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step.
  • a stronger alkaline aqueous solution for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution, or the like is used.
  • a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form the conductor pattern.
  • the etching treatment method at this time is appropriately selected according to 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 the present embodiment can be applied not only to the manufacture of a single-layer printed wiring board but also to the manufacture of a multilayer printed wiring board, and also to the manufacture of a printed wiring board having a small-diameter through hole. It is possible.
  • Binder polymer Methacrylic acid (MAA), styrene (ST), methyl methacrylate (MMA), butyl methacrylate (BMA), butyl acrylate (BA), as polymerizable monomers for synthesizing the binder polymers used in Examples and Comparative Examples.
  • MAA Methacrylic acid
  • ST styrene
  • MMA methyl methacrylate
  • BMA butyl methacrylate
  • BA butyl acrylate
  • BZMA benzyl methacrylate
  • the above solution a was added dropwise to the mixed solution in the flask over 4 hours, and then the mixture was stirred at 80 ° C. for 2 hours. Then, the above solution b was added dropwise to the solution in the flask, and the mixture was stirred at 80 ° C. for 2 hours. Further, the solution in the flask was heated to 95 ° C. over 1 hour while stirring was continued, and then the solution c was added dropwise over 10 minutes and stirred at 95 ° C. for 2 hours to carry out the reaction. After cooling the reaction solution to 50 ° C., methanol was added to obtain a solution of the binder polymer (A-1). The non-volatile content (solid content) of the binder polymer (A-1) was 47.7% by mass.
  • Binder Polymers (A-2) to (A-16) The binder polymer (A-2) was obtained in the same manner as in obtaining the solution of the binder polymer (A-1), except that the polymerizable monomer was used in the mass ratio shown in Table 1 or Table 2. )-(A-16) was obtained.
  • Weight average molecular weight 120 mg of the binder polymer solution was collected and dissolved in 5 mL of tetrahydrofuran to prepare a sample for Mw measurement. Mw was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions of GPC are shown below.
  • Glass-transition temperature The glass transition temperature (Tg) of the binder polymer was calculated from the Fox formula.
  • Photosensitive resin composition The components (A), (B) and (C) of the blending amount (parts by mass) shown in Table 3 or Table 4 are mixed with 5 parts by mass of methanol, 10 parts by mass of toluene and 11 parts by mass of acetone as solvents. As a result, the photosensitive resin compositions of Examples and Comparative Examples were prepared, respectively.
  • the blending amount of the binder polymer shown in Tables 3 and 4 is the mass of the non-volatile component (solid content amount).
  • a solution of the photosensitive resin composition is applied onto a polyethylene terephthalate (PET) film (Teijin Film Solution Co., Ltd., trade name "G2J") (support) having a thickness of 16 ⁇ m, and hot air convection drying at 75 ° C and 125 ° C.
  • PET polyethylene terephthalate
  • G2J trade name
  • the film was sequentially dried in a vessel to form a photosensitive layer having a thickness of 25 ⁇ m after drying.
  • a polypropylene film (Tamapoli Co., Ltd., product name "NF-13”) (protective layer) is laminated on this photosensitive layer, and the support, the photosensitive layer, and the protective layer are laminated in this order. Obtained.
  • the copper surface of the copper-clad laminate was etched to prepare a substrate having eight round holes having a diameter of 200 ⁇ m and a depth of 11 ⁇ m.
  • the substrate was heated to 80 ° C., and the photosensitive element was laminated on the substrate.
  • Lamination was performed using a heat roll at 110 ° C. at a crimping pressure of 0.3 MPa and a roll speed of 1.5 m / min on the substrate while removing the protective layer. In this way, a laminated body in which the substrate, the photosensitive layer, and the support were laminated in this order was obtained.
  • the round hole portion was observed from directly above the laminate using an optical microscope (Keyence Corporation, VK-8500), and the diameter of bubbles generated between the round hole of the substrate and the photosensitive layer was measured. The smaller the diameter of the bubble, the better the followability.
  • the photosensitive resin composition containing the binder polymer having a specific structure can form a photosensitive layer having excellent followability.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

The photosensitive resin composition according to the present disclosure contains a binder polymer, a photopolymerizable compound, and a photoinitiator. The binder polymer has: a structural unit (a1) derived from a polymerizable monomer having a carboxy group; a structural unit (a2) derived from styrene or a styrene derivative; a structural unit (a3) derived from an alkyl(meth)acrylate that has an alkyl group having 1-3 carbon atoms; and a structural unit (a4) derived from an alkyl(meth)methacrylate that has an alkyl group having 4-12 carbon atoms.

Description

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Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
　本開示は、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 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, a photosensitive resin composition is used as a resist material used for an etching treatment or a plating treatment, and a layer formed on a support film using the photosensitive resin composition (hereinafter, “photosensitive”). Photosensitive elements with (also referred to as "layers") 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。 The printed wiring board is manufactured by the following procedure, for example, using the above-mentioned photosensitive element. That is, first, the photosensitive layer of the photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. Next, the photosensitive layer is exposed via a mask film or the like to form a photocurable portion. At this time, the support film is peeled off before or after the exposure. Then, the region other than the light-cured portion of the photosensitive layer is removed with a developing solution to form a resist pattern. Next, using the resist pattern as a resist, an etching treatment or a plating treatment 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。 In recent years, as the density of printed wiring boards has increased and the conductor pattern has become finer, the contact area between the circuit board and the photosensitive layer, which is a resist, has become smaller. Therefore, the photosensitive layer is required to have excellent characteristics in the etching treatment or the plating treatment, excellent adhesion to the circuit forming substrate, and excellent resolution in forming the resist pattern.
　例えば、特許文献１には、特定の増感色素を用いることで、感度及び解像度に優れた感光性樹脂組成物が開示されている。また、特許文献２には、特定のアルカリ可溶性高分子及びエチレン性二重結合を有する化合物を用いることで、感度及び解像度に優れた感光性樹脂組成物が開示されている。 For example, Patent Document 1 discloses a photosensitive resin composition having excellent sensitivity and resolution by using a specific sensitizing dye. Further, Patent Document 2 discloses a photosensitive resin composition having excellent sensitivity and resolution by using a specific alkali-soluble polymer and a compound having an ethylenic double bond.
特開２００９－００３１７７号公報Japanese Unexamined Patent Publication No. 2009-003177 特開２０１３－０６１５５６号公報Japanese Unexamined Patent Publication No. 2013-061556
　感光性エレメントの感光層を回路形成用基板上にラミネートする際に、感光層の回路形成用基板に対する追従性が低いと、感光層と回路形成用基板との間に微細な空隙が生じてしまい、導体パターンの形成に影響を与えることがある。そのため、感光層には、回路形成用基板に対して優れた追従性を有することが求められる。 When laminating the photosensitive layer of the photosensitive element on the circuit forming substrate, if the photosensitive layer has low followability to the circuit forming substrate, a fine void is generated between the photosensitive layer and the circuit forming substrate. , May affect the formation of conductor patterns. Therefore, the photosensitive layer is required to have excellent followability to the circuit forming substrate.
　本開示は、回路形成用基板に対する追従性に優れる感光層を形成することができる感光性樹脂組成物、該感光性樹脂組成物を用いた感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法を提供することを目的とする。 The present disclosure discloses a photosensitive resin composition capable of forming a photosensitive layer having excellent followability to a circuit forming substrate, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a printed wiring board. It is an object of the present invention to provide the manufacturing method of.
　本開示に係る感光性樹脂組成物は、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、を含有し、バインダーポリマーが、カルボキシ基を有する重合性単量体に由来する構造単位（ａ１）と、スチレン又はスチレン誘導体に由来する構造単位（ａ２）と、炭素数が１～３のアルキル基を有するアルキル（メタ）アクリルレートに由来する構造単位（ａ３）と、炭素数が４～１２のアルキル基を有するアルキル（メタ）メタクリレートに由来する構造単位（ａ４）とを有する。 The photosensitive resin composition according to the present disclosure contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the binder polymer is a structural unit derived from a polymerizable monomer having a carboxy group (a structural unit (). A1), a structural unit (a2) derived from styrene or a styrene derivative, a structural unit (a3) derived from an alkyl (meth) acrylic rate having an alkyl group having 1 to 3 carbon atoms, and 4 to 4 carbon atoms. It has a structural unit (a4) derived from an alkyl (meth) methacrylate having 12 alkyl groups.
　本開示に係る感光性エレメントは、支持体と、該支持体上に形成された感光層とを備え、感光層が上述の感光性樹脂組成物を含む。 The photosensitive element according to the present disclosure includes a support and a photosensitive layer formed on the support, and the photosensitive layer contains the above-mentioned photosensitive resin composition.
　本開示に係るレジストパターンの形成方法は、基板上に、上述の感光性樹脂組成物又は感光性エレメントを用いて、感光層を形成する工程と、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、上記基板から、感光層の未光硬化部の少なくとも一部を除去する工程と、を備える。 The method for forming a resist pattern according to the present disclosure includes a step of forming a photosensitive layer on a substrate by using the above-mentioned photosensitive resin composition or a photosensitive element, and irradiation of at least a part of the photosensitive layer with active light. The process includes a step of forming a photo-cured portion and a step of removing at least a part of the unphoto-cured portion of the photosensitive layer from the substrate.
　本開示に係る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。 The method for manufacturing a printed wiring board according to the present disclosure includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern.
　本開示によれば、回路形成用基板に対する追従性に優れる感光層を形成することができる感光性樹脂組成物、該感光性樹脂組成物を用いた感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法を提供することができる。 According to the present disclosure, a photosensitive resin composition capable of forming a photosensitive layer having excellent followability to a circuit forming substrate, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and printing. A method for manufacturing a wiring board 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。It is a schematic cross-sectional view which shows one Embodiment of a photosensitive element.
　以下、本開示について、詳細に説明する。ただし、本開示は以下の実施形態に限定されるものではない。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。本明細書において、「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。 Hereinafter, this disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. Is done. In the present specification, the term "layer" includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view.
　本明細書において、「～」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。また、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。本明細書において組成物中の各成分の量について言及する場合、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。 In the present specification, the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. Further, in the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. When referring to the amount of each component in the composition in the present specification, if a plurality of substances corresponding to each component are present in the composition, the plurality of substances present in the composition are not specified unless otherwise specified. Means the total amount of.
　本明細書において、「（メタ）アクリル酸」とは、「アクリル酸」及びそれに対応する「メタクリル酸」の少なくとも一方を意味し、（メタ）アクリレート等の他の類似表現についても同様である。本明細書において、「固形分」とは、感光性樹脂組成物に含まれる水、溶媒等の揮発する物質を除いた不揮発分のことであり、該樹脂組成物を乾燥させた際に、揮発せずに残る成分を示し、また２５℃付近の室温で液状、水飴状、及びワックス状のものも含む。 In the present specification, "(meth) acrylic acid" means at least one of "acrylic acid" and the corresponding "methacrylic acid", and the same applies to other similar expressions such as (meth) acrylate. In the present specification, the "solid content" is a non-volatile substance excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatile when the resin composition is dried. It shows the components that remain without leaving, and also includes liquid, water candy-like, and wax-like substances at room temperature around 25 ° C.
［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、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、を含有し、バインダーポリマーが、カルボキシ基を有する重合性単量体に由来する構造単位（ａ１）と、スチレン又はスチレン誘導体に由来する構造単位（ａ２）と、炭素数が１～３のアルキル基を有するアルキル（メタ）アクリルレートに由来する構造単位（ａ３）と、炭素数が４～１２のアルキル基を有するアルキル（メタ）メタクリレートに由来する構造単位（ａ４）とを有する。以下、本実施形態における感光性樹脂組成物で用いられる各成分について詳細に説明する。 [Photosensitive resin composition]
The photosensitive resin composition according to the present embodiment contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the binder polymer is a structural unit derived from a polymerizable monomer having a carboxy group. (A1), a structural unit (a2) derived from styrene or a styrene derivative, a structural unit (a3) derived from an alkyl (meth) acrylic rate having an alkyl group having 1 to 3 carbon atoms, and 4 carbon atoms. It has a structural unit (a4) derived from an alkyl (meth) methacrylate having up to 12 alkyl groups. Hereinafter, each component used in the photosensitive resin composition in the present embodiment will be described in detail.
（（Ａ）成分：バインダーポリマー）
　本実施形態に係る（Ａ）成分は、カルボキシ基を有する構造単位（ａ１）と、スチレン又はスチレン誘導体に由来する構造単位（ａ２）と、炭素数が１～３のアルキル基を有するアルキル（メタ）アクリルレートに由来する構造単位（ａ３）と、炭素数が４～１２のアルキル基を有するアルキル（メタ）メタクリレートに由来する構造単位（ａ４）とを有するバインダーポリマーを含む。 ((A) component: binder polymer)
The component (A) according to the present embodiment includes a structural unit (a1) having a carboxy group, a structural unit (a2) derived from styrene or a styrene derivative, and an alkyl (meth) having an alkyl group having 1 to 3 carbon atoms. ) A binder polymer having a structural unit (a3) derived from an acrylic rate and a structural unit (a4) derived from an alkyl (meth) methacrylate having an alkyl group having 4 to 12 carbon atoms.
　バインダーポリマーは、アルカリ現像性の見地から、構造単位（ａ１）を有する。カルボキシ基を有する重合性単量体としては、例えば、（メタ）アクリル酸、α－ブロモアクリル酸、α－クロルアクリル酸、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、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル等のマレイン酸モノエステル、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。アルカリ現像性をより向上する点から、カルボキシ基を有する重合性単量体は、（メタ）アクリル酸であってもよく、メタクリル酸であってもよい。 The binder polymer has a structural unit (a1) from the viewpoint of alkali developability. Examples of the polymerizable monomer having a carboxy group include (meth) acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, and the like. Maleic acid monoesters such as maleic acid, maleic acid anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, silicic acid, α-cyanosilicic acid, itaconic acid, crotonic acid, and propioleic acid Can be mentioned. The polymerizable monomer having a carboxy group may be (meth) acrylic acid or methacrylic acid from the viewpoint of further improving the alkali developability.
　アルカリ現像性と追従性とをバランスよく向上させる点から、構造単位（ａ１）の含有量は、（Ａ）成分の全体量を基準として、１０～３０質量％、１５～２８質量％、又は２０～２６質量％であってもよい。構造単位（ａ１）の含有量が１０質量％以上ではアルカリ現像性が向上する傾向があり、３０質量％以下では追従性に優れる傾向がある。 The content of the structural unit (a1) is 10 to 30% by mass, 15 to 28% by mass, or 20 based on the total amount of the component (A) from the viewpoint of improving the alkali developability and the followability in a well-balanced manner. It may be up to 26% by mass. When the content of the structural unit (a1) is 10% by mass or more, the alkali developability tends to be improved, and when the content is 30% by mass or less, the followability tends to be excellent.
　バインダーポリマーは、解像性の見地から、構造単位（ａ２）を有する。スチレン誘導体は、ビニルトルエン、α－メチルスチレン等のスチレンのα位又は芳香環における水素原子が置換された重合可能な化合物である。 The binder polymer has a structural unit (a2) from the viewpoint of resolution. The styrene derivative is a polymerizable compound in which a hydrogen atom in the α-position or aromatic ring of styrene such as vinyltoluene and α-methylstyrene is substituted.
　アルカリ現像性と追従性とをバランスよく向上させる点から、（Ａ）成分における構造単位（ａ２）の含有量は、（Ａ）成分の全体量を基準として、１０～５０質量％、１２～４５質量％、又は１４～４４質量％であってもよい。 From the viewpoint of improving the alkaline developability and the followability in a well-balanced manner, the content of the structural unit (a2) in the component (A) is 10 to 50% by mass and 12 to 45 based on the total amount of the component (A). It may be% by mass, or 14 to 44% by mass.
　バインダーポリマーは、解像性の見地から、構造単位（ａ３）を有する。炭素数が１～３のアルキル基を有するアルキル（メタ）アクリルレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、及びプロピル（メタ）アクリレートが挙げられる。 The binder polymer has a structural unit (a3) from the viewpoint of resolution. Examples of the alkyl (meth) acrylic rate having an alkyl group having 1 to 3 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
　アルカリ現像性と追従性とをバランスよく向上させる点から、（Ａ）成分における構造単位（ａ３）の含有量は、（Ａ）成分の全体量を基準として、５～７０質量％、１２～６５質量％、又は１５～６４質量％であってもよい。構造単位（ａ３）の含有量が５質量％以上ではアルカリ現像性が向上する傾向があり、７０質量％以下では追従性に優れる傾向がある。 The content of the structural unit (a3) in the component (A) is 5 to 70% by mass and 12 to 65 based on the total amount of the component (A) from the viewpoint of improving the alkali developability and the followability in a well-balanced manner. It may be% by mass, or 15 to 64% by mass. When the content of the structural unit (a3) is 5% by mass or more, the alkali developability tends to be improved, and when the content is 70% by mass or less, the followability tends to be excellent.
　バインダーポリマーは、追従性の見地から、構造単位（ａ４）を有する。炭素数が４～１２のアルキル基は、直鎖状又は分岐状のアルキル基であってもよい。炭素数が４～１２のアルキル基を有するアルキル（メタ）メタクリレートとしては、例えば、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、及びドデシル（メタ）アクリレートが挙げられる。 The binder polymer has a structural unit (a4) from the viewpoint of followability. The alkyl group having 4 to 12 carbon atoms may be a linear or branched alkyl group. Examples of the alkyl (meth) methacrylate having an alkyl group having 4 to 12 carbon atoms include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and octyl (meth) acrylate. , 2-Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.
　アルカリ現像性と追従性とをバランスよく向上させる点から、（Ａ）成分における構造単位（ａ４）の含有量は、（Ａ）成分の全体量を基準として、０．５～３０質量％、０．８～２５質量％、又は１～２２質量％であってもよい。 From the viewpoint of improving the alkaline developability and the followability in a well-balanced manner, the content of the structural unit (a4) in the component (A) is 0.5 to 30% by mass, 0, based on the total amount of the component (A). It may be 8 to 25% by mass, or 1 to 22% by mass.
　（Ａ）成分は、構造単位（ａ１）～（ａ４）以外の構造単位（ａ５）を更に有してもよい。構造単位（ａ５）を導入するための重合性単量体としては、例えば、（メタ）アクリル酸ベンジル又はその誘導体、ジアセトンアクリルアミド等のアクリルアミド、ビニル－ｎ－ブチルエーテル等のビニルアルコールのエーテル化合物、アクリロニトリル、（メタ）アクリル酸シクロアルキルエステル、（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）アクリル酸イソボルニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸ジシクロペンタニル、（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、（メタ）アクリル酸ジシクロペンテニルオキシエチル、（メタ）アクリル酸ジシクロペンタニルオキシエチル、（メタ）アクリル酸イソボルニルオキシエチル、（メタ）アクリル酸シクロヘキシルオキシエチル、（メタ）アクリル酸アダマンチルオキシエチル、（メタ）アクリル酸ジシクロペンテニルオキシプロピルオキシエチル、（メタ）アクリル酸ジシクロペンタニルオキシプロピルオキシエチル、（メタ）アクリル酸ジシクロペンテニルオキシプロピルオキシエチル、及び（メタ）アクリル酸アダマンチルオキシプロピルオキシエチルが挙げられる。これらは１種単独で又は２種類以上を任意に組み合わせて用いることができる。 The component (A) may further have a structural unit (a5) other than the structural units (a1) to (a4). Examples of the polymerizable monomer for introducing the structural unit (a5) include benzyl (meth) acrylate or a derivative thereof, acrylamide such as diacetoneacrylamide, and an ether compound of vinyl alcohol such as vinyl-n-butyl ether. Acrylonitrile, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid dicyclopentanyl , (Meta) dimethylaminoethyl acrylate, (meth) diethylaminoethyl acrylate, (meth) glycidyl acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (Meta) acrylate, (meth) dicyclopentenyloxyethyl acrylate, (meth) dicyclopentanyloxyethyl acrylate, (meth) isobornyloxyethyl acrylate, (meth) cyclohexyloxyethyl acrylate, (meth) ) Adamanthyloxyethyl acrylate, (meth) dicyclopentenyloxypropyloxyethyl acrylate, (meth) dicyclopentanyloxypropyloxyethyl acrylate, (meth) dicyclopentenyloxypropyloxyethyl acrylate, and (meth) ) Adamantyloxypropyloxyethyl acrylate can be mentioned. These can be used alone or in any combination of two or more.
　（Ａ）成分の酸価は、現像性、解像性及び追従性のバランスをより向上する点から、１００ｍｇＫＯＨ／ｇ以上、１１０ｍｇＫＯＨ／ｇ以上、１２０ｍｇＫＯＨ／ｇ以上、又は１３０ｍｇＫＯＨ／ｇ以上であってもよい。（Ａ）成分の酸価は、感光層の追従性をより向上させる点からは、１８０ｍｇＫＯＨ／ｇ以下、１７０ｍｇＫＯＨ／ｇ以下、１６５ｍｇＫＯＨ／ｇ以下、又は１６０ｍｇＫＯＨ／ｇ以下であってもよい。 The acid value of the component (A) is 100 mgKOH / g or more, 110 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g or more from the viewpoint of further improving the balance between developability, resolution and followability. May be good. The acid value of the component (A) may be 180 mgKOH / g or less, 170 mgKOH / g or less, 165 mgKOH / g or less, or 160 mgKOH / g or less from the viewpoint of further improving the followability of the photosensitive layer.
　（Ａ）成分の重量平均分子量（Ｍｗ）は、現像性に更に優れる点では、６００００以下、５６０００以下、５４０００以下、又は５２０００以下であってもよい。（Ａ）成分のＭｗは、密着性に更に優れる点では、１００００以上、１５０００以上、２００００以上、又は２５０００以上であってもよい。（Ａ）成分の分散度（重量平均分子量／数平均分子量）は、解像度及び密着性に更に優れる点では、３．０以下、２．８以下、又は２．５以下であってもよい。分散度が小さくなると解像度が向上する傾向にある。重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定され、標準ポリスチレンを標準試料として換算した値である。 The weight average molecular weight (Mw) of the component (A) may be 60,000 or less, 56,000 or less, 54,000 or less, or 52,000 or less in terms of further excellent developability. The Mw of the component (A) may be 10,000 or more, 15,000 or more, 20,000 or more, or 25,000 or more in terms of further excellent adhesion. The degree of dispersion (weight average molecular weight / number average molecular weight) of the component (A) may be 3.0 or less, 2.8 or less, or 2.5 or less in terms of further excellent resolution and adhesion. The resolution tends to improve as the degree of dispersion decreases. The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC) and are converted values using standard polystyrene as a standard sample.
　（Ａ）成分のガラス転移温度（Ｔｇ）は、追従性をより向上する点から、８０～１３０℃、８５～１２５℃、又は９０～１２０℃であってもよい。 The glass transition temperature (Tg) of the component (A) may be 80 to 130 ° C., 85 to 125 ° C., or 90 to 120 ° C. from the viewpoint of further improving the followability.
　（Ａ）成分は、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。２種以上を組み合わせて使用する場合の（Ａ）成分としては、例えば、異なる重合性単量体からなる２種以上のバインダーポリマー、異なるＭｗの２種以上のバインダーポリマー、及び、異なる分散度の２種以上のバインダーポリマーが挙げられる。 As the component (A), one type can be used alone or two or more types can be used in combination. When two or more kinds are used in combination, the component (A) includes, for example, two or more kinds of binder polymers composed of different polymerizable monomers, two or more kinds of binder polymers having different Mw, and different dispersities. Two or more kinds of binder polymers can be mentioned.
　（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、３０～８０質量部、４０～７５質量部、５０～７０質量部、又は５０～６０質量部であってもよい。（Ａ）成分の含有量がこの範囲内であると、感光層の光硬化部の強度がより良好となる。 The content of the component (A) is 30 to 80 parts by mass, 40 to 75 parts by mass, 50 to 70 parts by mass, or 50 to 60 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It may be a department. When the content of the component (A) is within this range, the strength of the light-cured portion of the photosensitive layer becomes better.
（（Ｂ）成分：光重合性化合物）
　（Ｂ）成分としては、エチレン性不飽和結合の少なくとも１つを有し、光重合可能な化合物であれば特に限定されない。エチレン性不飽和結合は、光重合が可能であれば特に限定されない。エチレン性不飽和結合としては、例えば、（メタ）アクリロイル基等のα，β－不飽和カルボニル基が挙げられる。 (Component (B): photopolymerizable compound)
The component (B) is not particularly limited as long as it has at least one ethylenically unsaturated bond and is photopolymerizable. The ethylenically unsaturated bond is not particularly limited as long as photopolymerization is possible. Examples of the ethylenically unsaturated bond include α, β-unsaturated carbonyl groups such as (meth) acryloyl group.
　α，β－不飽和カルボニル基を有する光重合性化合物としては、例えば、多価アルコールのα，β－不飽和カルボン酸エステル、ビスフェノール型（メタ）アクリレート、グリシジル基含有化合物のα，β－不飽和カルボン酸付加物、ウレタン結合を有する（メタ）アクリレート、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（メタ）アクリル酸アルキルエステルが挙げられる。 Examples of the photopolymerizable compound having an α, β-unsaturated carbonyl group include α, β-unsaturated carboxylic acid ester of a polyhydric alcohol, bisphenol type (meth) acrylate, and α, β-unmodified of a glycidyl group-containing compound. Examples include saturated carboxylic acid adducts, (meth) acrylates with urethane bonds, nonylphenoxypolyethyleneoxyacrylates, and (meth) acrylic acid alkyl esters.
　多価アルコールのα，β－不飽和カルボン酸エステルとしては、例えば、エチレン基の数が２～１４であるポリエチレングリコールジ（メタ）アクリレート、プロピレン基の数が２～１４であるポリプロピレングリコールジ（メタ）アクリレート、エチレン基の数が２～１４でありプロピレン基の数が２～１４であるポリエチレン・ポリプロピレングリコールジ（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、テトラメチロールメタンテトラ（メタ）アクリレート、及びジペンタエリスリトール又はペンタエリスリトール由来の骨格を有する（メタ）アクリレート化合物が挙げられる。「ＥＯ変性」とはエチレンオキサイド（ＥＯ）基のブロック構造を有するものであることを意味し、「ＰＯ変性」とはプロピレンオキサイド（ＰＯ）基のブロック構造を有するものであることを意味する。 Examples of the α, β-unsaturated carboxylic acid ester of the polyhydric alcohol include polyethylene glycol di (meth) acrylate having an ethylene group number of 2 to 14, and polypropylene glycol di (meth) acrylate having a propylene group number of 2 to 14. Meta) acrylate, polyethylene / polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) having 2 to 14 ethylene groups and 2 to 14 propylene groups. Acrylic, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra Examples thereof include (meth) acrylates and (meth) acrylate compounds having a skeleton derived from dipentaerythritol or pentaerythritol. "EO modification" means having a block structure of ethylene oxide (EO) group, and "PO modification" means having a block structure of propylene oxide (PO) group.
　（Ｂ）成分は、レジストパターンの柔軟性を向上する観点から、ポリアルキレングリコールジ（メタ）アクリレートを含んでもよい。ポリアルキレングリコールジ（メタ）アクリレートは、ＥＯ基及びＰＯ基の少なくとも一方を有してもよく、ＥＯ基及びＰＯ基の双方を有してもよい。ＥＯ基及びＰＯ基の双方を有するポリアルキレングリコールジ（メタ）アクリレートにおいて、ＥＯ基及びＰＯ基は、それぞれ連続してブロック的に存在しても、ランダムに存在してもよい。また、ＰＯ基は、オキシ－ｎ－プロピレン基又はオキシイソプロピレン基のいずれであってもよい。なお、（ポリ）オキシイソプロピレン基において、プロピレン基の２級炭素が酸素原子に結合していてもよく、１級炭素が酸素原子に結合していてもよい。 The component (B) may contain a polyalkylene glycol di (meth) acrylate from the viewpoint of improving the flexibility of the resist pattern. The polyalkylene glycol di (meth) acrylate may have at least one of an EO group and a PO group, and may have both an EO group and a PO group. In the polyalkylene glycol di (meth) acrylate having both EO group and PO group, the EO group and the PO group may be continuously present in a block or randomly. Further, the PO group may be either an oxy-n-propylene group or an oxyisopropylene group. In the (poly) oxyisopropylene group, the secondary carbon of the propylene group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.
　ポリアルキレングリコールジ（メタ）アクリレートの市販品としては、例えば、ＦＡ－０２３Ｍ（昭和電工マテリアルズ株式会社製）、ＦＡ－０２４Ｍ（昭和電工マテリアルズ株式会社製）、及びＮＫエステルＨＥＭＡ－９Ｐ（新中村化学工業株式会社製）が挙げられる。 Commercially available products of polyalkylene glycol di (meth) acrylate include, for example, FA-023M (manufactured by Showa Denko Materials Co., Ltd.), FA-024M (manufactured by Showa Denko Materials Co., Ltd.), and NK ester HEMA-9P (new). Nakamura Chemical Industry Co., Ltd.).
　（Ｂ）成分は、レジストパターンの柔軟性を向上する観点から、ウレタン結合を有する（メタ）アクリレートを含んでもよい。ウレタン結合を有する（メタ）アクリレートとしては、例えば、β位にＯＨ基を有する（メタ）アクリルモノマーとジイソシアネート（イソホロンジイソシアネート、２，６－トルエンジイソシアネート、２，４－トルエンジイソシアネート、１，６－ヘキサメチレンジイソシアネート等）との付加反応物、トリス（（メタ）アクリロキシテトラエチレングリコールイソシアネート）ヘキサメチレンイソシアヌレート、ＥＯ変性ウレタンジ（メタ）アクリレート、及びＥＯ，ＰＯ変性ウレタンジ（メタ）アクリレートが挙げられる。 The component (B) may contain (meth) acrylate having a urethane bond from the viewpoint of improving the flexibility of the resist pattern. Examples of the (meth) acrylate having a urethane bond include a (meth) acrylic monomer having an OH group at the β-position and a diisocyanate (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexa). Examples thereof include addition reactants with methylene diisocyanate), tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO and PO-modified urethane di (meth) acrylate.
　ＥＯ変性ウレタンジ（メタ）アクリレートの市販品としては、例えば、「ＵＡ－１１」及び「ＵＡ－２１ＥＢ」（新中村化学工業株式会社製）が挙げられる。ＥＯ，ＰＯ変性ウレタンジ（メタ）アクリレートの市販品としては、例えば、「ＵＡ－１３」（新中村化学工業株式会社製）が挙げられる。 Examples of commercially available products of EO-modified urethane di (meth) acrylate include "UA-11" and "UA-21EB" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Examples of commercially available products of EO and PO-modified urethane di (meth) acrylate include "UA-13" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
　（Ｂ）成分は、厚膜のレジストパターンが形成し易く、解像度及び密着性をバランスよく向上させる観点から、ジペンタエリスリトール又はペンタエリスリトール由来の骨格を有する（メタ）アクリレート化合物を含んでもよい。ジペンタエリスリトール又はペンタエリスリトール由来の骨格を有する（メタ）アクリレート化合物は、（メタ）アクリロイル基を４つ以上有することが好ましく、ジペンタエリスリトールペンタ（メタ）アクリレート、又はジペンタエリスリトールヘキサ（メタ）アクリレートであってもよい。 The component (B) may contain dipentaerythritol or a (meth) acrylate compound having a skeleton derived from pentaerythritol from the viewpoint of easily forming a thick-film resist pattern and improving resolution and adhesion in a well-balanced manner. The (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol preferably has four or more (meth) acryloyl groups, and is preferably dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate. May be.
　解像度及び硬化後の剥離特性をより向上させる観点から、（Ｂ）成分は、ビスフェノール型（メタ）アクリレートを含んでもよく、ビスフェノール型（メタ）アクリレートの中でもビスフェノールＡ型（メタ）アクリレートを含んでもよい。ビスフェノールＡ型（メタ）アクリレートとしては、例えば、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。中でも、解像度及びパター形成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）プロパンが好ましい。 From the viewpoint of further improving the resolution and the peeling property after curing, the component (B) may contain a bisphenol type (meth) acrylate, or may contain a bisphenol A type (meth) acrylate among the bisphenol type (meth) acrylates. .. Examples of the bisphenol A type (meth) acrylate include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy)). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane. Be done. Of these, 2,2-bis (4-((meth) acryloxipolyethoxy) phenyl) propane is preferable from the viewpoint of further improving the resolution and putter forming property.
　商業的に入手可能なものとしては、例えば、２，２－ビス（４－（（メタ）アクリロキシジプロポキシ）フェニル）プロパンは、ＢＰＥ－２００（新中村化学工業株式会社）、２，２－ビス（４－（メタクリロキシペンタエトキシ）フェニル）プロパンは、ＢＰＥ－５００（新中村化学工業株式会社）、ＦＡ－３２１Ｍ（昭和電工マテリアルズ株式会社）等が挙げられる。 Commercially available products include, for example, 2,2-bis (4-((meth) acryloxidipropoxy) phenyl) propane, BPE-200 (Shin Nakamura Chemical Industry Co., Ltd.), 2,2-. Examples of bis (4- (methacryloxypentethoxy) phenyl) propane include BPE-500 (Shin Nakamura Chemical Industry Co., Ltd.) and FA-321M (Showa Denko Materials Co., Ltd.).
　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 the nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, and nonylphenoxynonaethyleneoxy. Examples thereof include acrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.
　（Ｂ）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、２０～６０質量部とすることが好ましく、３０～５５質量部とすることがより好ましく、３５～５０質量部とすることが更に好ましい。（Ｂ）成分の含有量がこの範囲であると、感光性樹脂組成物の解像度及び密着性、レジストすそ発生性に加えて、光感度及び塗膜性がより良好となる。 The content of the component (B) is preferably 20 to 60 parts by mass, more preferably 30 to 55 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is more preferably 35 to 50 parts by mass. When the content of the component (B) is in this range, the light sensitivity and the coating film property become better in addition to the resolution and adhesion of the photosensitive resin composition and the resist hem generation property.
（（Ｃ）成分：光重合開始剤）
　（Ｃ）成分としては、（Ｂ）成分を重合させることができるものであれば、特に制限は無く、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。パターン形成性を向上させる観点から、活性光線により遊離ラジカルを生成するもの、例えば、アシルホスフィンオキサイド系、オキシムエステル系、芳香族ケトン系、キノン系、アルキルフェノン系、イミダゾール系、アクリジン系、フェニルグリシン系、クマリン系等の光重合開始剤が挙げられる。 (Component (C): Photopolymerization Initiator)
The component (C) is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators. From the viewpoint of improving pattern formation, those that generate free radicals by active light, for example, acylphosphine oxide type, oxime ester type, aromatic ketone type, quinone type, alkylphenone type, imidazole type, aclysine type, phenylglycine. Examples thereof include photopolymerization initiators such as radicals and quinones.
　（Ｃ）成分は、感度及び解像度をバランスよく向上する点で、アクリジン系光重合開始剤、フェニルグリシン系光重合開始剤、又はイミダゾール系光重合開始剤を含んでもよく、アクリジン系光重合開始剤を含むことが好ましい。（Ｃ）成分は、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 component (C) may contain an acridine-based photopolymerization initiator, a phenylglycine-based photopolymerization initiator, or an imidazole-based photopolymerization initiator in terms of improving sensitivity and resolution in a well-balanced manner, and may contain an acridine-based photopolymerization initiator. Is preferably included. As the component (C), one type can be used alone or two or more types can be used in combination.
　アクリジン系光重合開始剤としては、例えば、９－フェニルアクリジン、９－（ｐ－メチルフェニル）アクリジン、９－（ｍ－メチルフェニル）アクリジン、９－（ｐ－クロロフェニル）アクリジン、９－（ｍ－クロロフェニル）アクリジン、９－アミノアクリジン、９－ジメチルアミノアクリジン、９－ジエチルアミノアクリジン、９－ペンチルアミノアクリジン、１，２－ビス（９－アクリジニル）エタン、１，４－ビス（９－アクリジニル）ブタン、１，６－ビス（９－アクリジニル）ヘキサン、１，８－ビス（９－アクリジニル）オクタン、１，１０－ビス（９－アクリジニル）デカン、１，１２－ビス（９－アクリジニル）ドデカン、１，１４－ビス（９－アクリジニル）テトラデカン、１，１６－ビス（９－アクリジニル）ヘキサデカン、１，１８－ビス（９－アクリジニル）オクタデカン、１，２０－ビス（９－アクリジニル）エイコサン等のビス（９－アクリジニル）アルカン、１，３－ビス（９－アクリジニル）－２－オキサプロパン、１，３－ビス（９－アクリジニル）－２－チアプロパン、及び１，５－ビス（９－アクリジニル）－３－チアペンタンが挙げられる。 Examples of the acridin-based photopolymerization initiator include 9-phenylacridines, 9- (p-methylphenyl) acridins, 9- (m-methylphenyl) acridins, 9- (p-chlorophenyl) acridins, and 9- (m-). Chlorophenyl) acridines, 9-aminoacridines, 9-dimethylaminoacridines, 9-diethylaminoacridines, 9-pentylaminoacridines, 1,2-bis (9-acridinyl) ethane, 1,4-bis (9-acridinyl) butane, 1,6-bis (9-acridinyl) hexane, 1,8-bis (9-acridinyl) octane, 1,10-bis (9-acridinyl) decane, 1,12-bis (9-acridinyl) dodecane, 1, Bis (9) such as 14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) hexadecane, 1,18-bis (9-acridinyl) octadecane, 1,20-bis (9-acridinyl) icosane, etc. -Acridinyl) alkane, 1,3-bis (9-acridinyl) -2-oxapropane, 1,3-bis (9-acridinyl) -2-thiapropane, and 1,5-bis (9-acridinyl) -3- Chiapentane can be mentioned.
　フェニルグリシン系光重合開始剤としては、例えば、Ｎ－フェニルグリシン、Ｎ－メチル－Ｎ－フェニルグリシン、及びＮ－エチル－Ｎ－フェニルグリシンが挙げられる。 Examples of the phenylglycine-based photopolymerization initiator include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
　イミダゾール系光重合開始剤としては、例えば、２－（ｏ－クロロフェニル）－４，５－ジフェニルビイミダゾール、２，２’，５－トリス－（ｏ－クロロフェニル）－４－（３，４－ジメトキシフェニル）－４’，５’－ジフェニルビイミダゾール、２，４－ビス－（ｏ－クロロフェニル）－５－（３，４－ジメトキシフェニル）－ジフェニルビイミダゾール、２，４，５－トリス－（ｏ－クロロフェニル）－ジフェニルビイミダゾール、２－（ｏ－クロロフェニル）－ビス－４，５－（３，４－ジメトキシフェニル）－ビイミダゾール、２，２’－ビス－（２－フルオロフェニル）－４，４’，５，５’－テトラキス－（３－メトキシフェニル）－ビイミダゾール、２，２’－ビス－（２，３－ジフルオロメチルフェニル）－４，４’，５，５’－テトラキス－（３－メトキシフェニル）－ビイミダゾール、２，２’－ビス－（２，４－ジフルオロフェニル）－４，４’，５，５’－テトラキス－（３－メトキシフェニル）－ビイミダゾール、及び２，２’－ビス－（２，５－ジフルオロフェニル）－４，４’，５，５’－テトラキス－（３－メトキシフェニル）－ビイミダゾールが挙げられる。 Examples of the imidazole-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxy). Phenyl) -4', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris-(o) -Chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4, 4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-tetrakis- ( 3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, and 2, Examples thereof include 2'-bis- (2,5-difluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole.
　（Ｃ）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、０．１～１０質量部、０．２～５質量部、０．４～３質量部、又は０．５～２質量部であってもよい。（Ｃ）成分の含有量が０．１質量部以上では、光感度、解像度及び密着性が向上する傾向があり、１０質量部以下では、レジストパターン形成性により優れる傾向がある。 The content of the component (C) is 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, and 0.4 to 3 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). , Or 0.5 to 2 parts by mass. When the content of the component (C) is 0.1 parts by mass or more, the light sensitivity, resolution and adhesion tend to be improved, and when the content is 10 parts by mass or less, the resist pattern forming property tends to be better.
（（Ｄ）成分：増感剤）
　本実施形態に係る感光性樹脂組成物は、（Ｄ）成分として３４０～４３０ｎｍに吸収を有する増感剤を更に含有してよい。これにより、感光性樹脂組成物の光感度が更に良好となる。増感剤としては、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、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、及びトリアリールアミン化合物が挙げられる。増感剤は、感度及び密着性の観点から、ピラゾリン化合物、アントラセン化合物、クマリン化合物、及びトリアリールアミン化合物からなる群より選ばれる少なくとも１種を含んでよく、ピラゾリン化合物、アントラセン化合物、及びクマリン化合物からなる群より選ばれる少なくとも１種を含んでよい。 ((D) component: sensitizer)
The photosensitive resin composition according to the present embodiment may further contain a sensitizer having absorption at 340 to 430 nm as the component (D). As a result, the light sensitivity of the photosensitive resin composition becomes even better. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stylben compounds, triazine compounds and thiophene compounds. , Naphthalimide compounds, and triarylamine compounds. The sensitizer may contain at least one selected from the group consisting of pyrazoline compounds, anthracene compounds, coumarin compounds, and triarylamine compounds from the viewpoint of sensitivity and adhesion, and may contain pyrazoline compounds, anthracene compounds, and coumarin compounds. It may contain at least one selected from the group consisting of.
　ピラゾリン化合物としては、例えば、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－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、及び１－フェニル－３－ビフェニル－５－（４－ｔｅｒｔ－ブチルフェニル）ピラゾリンが挙げられる。アントラセン化合物としては、例えば、９，１０－ジブトキシアントラセン及び９，１０－ジフェニルアントラセンが挙げられる。クマリン化合物としては、例えば、３－ベンゾイル－７－ジエチルアミノクマリン、７－ジエチルアミノ－４－メチルクマリン、３，３’－カルボニルビス（７－ジエチルアミノクマリン）、及び２，３，６，７－テトラヒドロ－９－メチル－１Ｈ，５Ｈ，１１Ｈ－［１］ベンゾピラノ［６，７，８－ｉｊ］キロリジン－１１－オンが挙げられる。 Examples of the pyrazoline compound include 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline and 1-phenyl-3- (4-tert-butylstyryl) -5- (4-). Examples thereof include tert-butylphenyl) pyrazoline and 1-phenyl-3-biphenyl-5- (4-tert-butylphenyl) pyrazoline. Examples of the anthracene compound include 9,10-dibutoxyanthracene and 9,10-diphenylanthracene. Examples of the coumarin compound include 3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), and 2,3,6,7-tetrahydro-. Examples thereof include 9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] kilolysine-11-one.
　感光性樹脂組成物が（Ｄ）成分を含有する場合、（Ｄ）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、０．０１～１０質量％、０．０５～５質量％、又は０．１～３質量％であってもよい。（Ｄ）成分の含有量が、０．０１質量％以上であることで、感度及び解像性がより向上し、１０質量％以下であることで、レジスト形状が逆台形になることを抑制し、密着性がより向上する。解像度及び密着性のバランスの観点から、（Ｄ）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、０．００５～０．５質量部、０．００８～０．２質量部、又は０．０１～０．１質量部であってもよい。 When the photosensitive resin composition contains the component (D), the content of the component (D) is 0.01 to 10% by mass and 0.05 to 5 based on the total solid content of the photosensitive resin composition. It may be% by mass, or 0.1 to 3% by mass. When the content of the component (D) is 0.01% by mass or more, the sensitivity and resolution are further improved, and when it is 10% by mass or less, the resist shape is suppressed from becoming an inverted trapezoid. , Adhesion is further improved. From the viewpoint of the balance between resolution and adhesion, the content of the component (D) is 0.005 to 0.5 parts by mass, 0.008 with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be up to 0.2 parts by mass or 0.01 to 0.1 parts by mass.
（（Ｅ）成分：熱安定剤）
　本実施形態に係る感光性樹脂組成物は、（Ｅ）成分として熱安定剤を更に含有してよい。（Ｅ）成分としては、例えば、ベンゾキノン、ハイドロキノン等のキノン誘導体、４－メトキシフェノール、４－ｔ－ブチルカテコール等のフェノール誘導体（ヒンダードフェノール誘導体）、２，２，６，６－テトラメチルピペリジン－１－オキシル、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－１－オキシル等のアミノキシル誘導体、テトラメチルピペリジルメタクリレート等のヒンダードアミン誘導体が挙げられる。中でも（Ｅ）成分としてアミノキシル誘導体を用いることで、感光性樹脂組成物が良好な感度を有しつつ、形成されるレジストパターンの解像性及び密着性をより向上させることができる。 ((E) component: heat stabilizer)
The photosensitive resin composition according to the present embodiment may further contain a heat stabilizer as the component (E). Examples of the component (E) include quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol (hindered phenol derivatives), and 2,2,6,6-tetramethylpiperidine. Examples thereof include aminoxyl derivatives such as -1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, and hindered amine derivatives such as tetramethylpiperidylmethacrylate. Above all, by using the aminoxyl derivative as the component (E), it is possible to further improve the resolution and adhesion of the resist pattern to be formed while the photosensitive resin composition has good sensitivity.
　（Ｅ）成分の含有量は、（Ａ）成分の総量１００質量部に対して０．００５～１０質量部、０．０１～８質量部、又は０．０１～５質量部であってもよい。（Ｅ）成分の含有量が０．００５質量部以上であることで、解像性及び密着性がより優れる傾向があり、１０質量部以下であることで、感度がより優れる傾向がある。（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、０．００５～２０質量部、０．０１～５質量部、又は０．０２～１質量部であってもよい。この含有量が０．００５質量部以上であることで、解像性及びレジストすそ発生量の抑制性がより優れる傾向があり、２０質量部以下であることで、感度がより優れる傾向がある。 The content of the component (E) may be 0.005 to 10 parts by mass, 0.01 to 8 parts by mass, or 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A). .. When the content of the component (E) is 0.005 parts by mass or more, the resolution and adhesion tend to be more excellent, and when the content is 10 parts by mass or less, the sensitivity tends to be more excellent. The content of the component (E) is 0.005 to 20 parts by mass, 0.01 to 5 parts by mass, or 0.02 to 1 part by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It may be a department. When the content is 0.005 part by mass or more, the resolution and the ability to suppress the resist hem generation amount tend to be more excellent, and when the content is 20 parts by mass or less, the sensitivity tends to be more excellent.
（その他の成分）
　本実施形態に係る感光性樹脂組成物には、必要に応じて、染料、光発色剤、熱発色防止剤、可塑剤、顔料、充填剤、消泡剤、難燃剤、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、重合禁止剤等の添加剤を更に含有してもよい。これらの添加剤は、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。 (Other ingredients)
The photosensitive resin composition according to the present embodiment contains, if necessary, a dye, a photocoloring agent, a heat coloring inhibitor, a plasticizer, a pigment, a filler, a defoaming agent, a flame retardant, an adhesion imparting agent, and leveling. Additives such as agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, and polymerization inhibitors may be further contained. These additives may be used alone or in combination of two or more.
　染料としては、例えば、マラカイトグリーン、ビクトリアピュアブルー、ブリリアントグリーン、及びメチルバイオレットが挙げられる。光発色剤としては、例えば、トリブロモフェニルスルホン、ロイコクリスタルバイオレット、ジフェニルアミン、ベンジルアミン、トリフェニルアミン、ジエチルアニリン、及びｏ－クロロアニリンが挙げられる。可塑剤としては、例えば、ｐ－トルエンスルホンアミドが挙げられる。 Examples of the dye include malachite green, Victoria pure blue, brilliant green, and methyl violet. Examples of the photocoloring agent include tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline. Examples of the plasticizer include p-toluenesulfonamide.
　添加剤の含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対してそれぞれ０．０１～１０質量部、０．０５～５質量部、又は０．１～３質量部であってもよい。 The content of the additive is 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass, respectively, with respect to 100 parts by mass of the total amount of the component (A) and the component (B). There may be.
　感光性樹脂組成物は、必要に応じて、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、プロピレングリコールモノメチルエーテル等の溶剤又はこれらの混合溶剤に溶解して、固形分が３０～６０質量％程度の溶液として調製することができる。 The photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, if necessary. Therefore, it can be prepared as a solution having a solid content of about 30 to 60% by mass.
［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。本実施形態の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。本実施形態に係る感光性エレメント１は、図１にその一例の模式断面図を示すように、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 the present embodiment includes a support and a photosensitive layer formed on the support, and the photosensitive layer includes the above-mentioned photosensitive resin composition. When the photosensitive element of the present embodiment is used, the photosensitive layer may be laminated on the substrate and then exposed without peeling the support (support film). The photosensitive element 1 according to the present embodiment has a support 2 and a photosensitive layer 3 derived from the photosensitive resin composition formed on the support 2, as shown in FIG. 1 as a schematic cross-sectional view of an example thereof. And other layers such as the protective layer 4 provided as needed.
（支持体）
　支持体しては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレン－２，６－ナフタレート（ＰＥＮ）等のポリエステルフィルム、及びポリプロピレン、ポリエチレン等のポリオレフィンフィルムが挙げられる。中でも、入手し易く、且つ、製造工程におけるハンドリング性（特に、耐熱性、熱収縮率、破断強度）に優れる点で、ＰＥＴフィルムであってもよい。 (Support)
Examples of the support include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalate (PEN), and polyolefin films such as polypropylene and polyethylene. Among them, a PET film may be used because it is easily available and has excellent handleability (particularly, heat resistance, heat shrinkage rate, breaking strength) in the manufacturing process.
　支持体のヘーズは、０．０１～１．０％又は０．０１～０．５％であってもよい。ヘーズが０．０１％以上であると、支持体自体を製造し易くなる傾向があり、１．０％以下であると、レジストパターンに発生し得る微小欠損を低減する傾向がある。「ヘーズ」とは、曇り度を意味する。本開示におけるヘーズは、ＪＩＳ　Ｋ　７１０５に規定される方法に準拠して、市販の曇り度計（濁度計）を用いて測定された値をいう。ヘーズは、例えば、ＮＤＨ－５０００（日本電色工業（株）製）等の市販の濁度計で測定が可能である。 The haze of the support may be 0.01-1.0% or 0.01-0.5%. When the haze is 0.01% or more, the support itself tends to be easy to manufacture, and when it is 1.0% or less, there is a tendency to reduce the minute defects that may occur in the resist pattern. "Haze" means cloudiness. The haze in the present disclosure refers to a value measured using a commercially available turbidity meter (turbidity meter) in accordance with the method specified in JIS K7105. The haze can be measured with a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
　支持体の厚みは、１～１００μｍ、５～６０μｍ、１０～５０μｍ、１０～４０μｍ、１０～３０μｍ、又は１０～２５μｍであってもよい。支持体の厚みが１μｍ以上であることで、支持体を剥離する際に支持体が破れることを抑制できる傾向がある。また、支持体の厚みが１００μｍ以下であることで、支持体を通して露光する場合に解像性が低下することを抑制することができる。 The thickness of the support may be 1 to 100 μm, 5 to 60 μm, 10 to 50 μm, 10 to 40 μm, 10 to 30 μm, or 10 to 25 μm. When the thickness of the support is 1 μm or more, it tends to be possible to prevent the support from being torn when the support is peeled off. Further, when the thickness of the support is 100 μm or less, it is possible to prevent the resolution from being lowered when exposed through the support.
（保護層）
　感光性エレメントは、必要に応じて保護層を更に備えてもよい。保護層としては、感光層と支持体との間の接着力よりも、感光層と保護層との間の接着力が小さくなるようなフィルムを用いてもよく、また、低フィッシュアイのフィルムを用いてもよい。具体的には、例えば、上述する支持体として用いることができるものが挙げられる。感光層からの剥離性の見地から、ポリエチレンフィルムであってもよい。保護層の厚さは、用途により異なるが、１～１００μｍ程度であってもよい。 (Protective layer)
The photosensitive element may be further provided with a protective layer, if necessary. As the protective layer, a film may be used in which the adhesive force between the photosensitive layer and the protective layer is smaller than the adhesive force between the photosensitive layer and the support, and a low fisheye film may be used. You may use it. Specifically, for example, those that can be used as the above-mentioned support can be mentioned. From the viewpoint of peelability from the photosensitive layer, a polyethylene film may be used. The thickness of the protective layer varies depending on the application, but may be about 1 to 100 μm.
　感光性エレメントは、例えば、以下のようにして製造することができる。すなわち、支持体上に、感光性樹脂組成物の溶液（塗布液）を塗布して塗布層を形成し、これを乾燥することで感光層を形成する。次いで、感光層の支持体とは反対側の面を保護層で被覆することにより、支持体と、該支持体上に形成された感光層と、該感光層上に積層された保護層とを備える、感光性エレメントが得られる。 The photosensitive element can be manufactured, for example, as follows. That is, a solution (coating liquid) of the photosensitive resin composition is applied onto the support to form a coating layer, and the coating layer is formed by drying the solution. Next, by covering the surface of the photosensitive layer opposite to the support with a protective layer, the support, the photosensitive layer formed on the support, and the protective layer laminated on the photosensitive layer are provided. A photosensitive element is obtained.
　塗布液の支持体上への塗布は、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行うことができる。 The coating liquid can be applied onto the support by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating and the like.
　塗布層の乾燥は、塗布層から有機溶剤の少なくとも一部を除去することができれば特に制限はない。例えば、７０～１５０℃にて、５～３０分間程度行ってもよい。乾燥後、感光層中の残存溶剤量は、後の工程での溶剤の拡散を防止する観点から、２質量％以下であってもよい。 Drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it may be carried out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of residual solvent in the photosensitive layer may be 2% by mass or less from the viewpoint of preventing the diffusion of the solvent in a later step.
　感光性エレメントにおける感光層の厚みは、用途により適宜選択することができるが、乾燥後の厚みで１～１００μｍ、１～５０μｍ、又は５～４０μｍであってもよい。厚さが１μｍ以上であることで、工業的な塗工が容易になり、生産性が向上する。また、厚みが１００μｍ以下であることで、密着性及び解像度が向上する。 The thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on the intended use, but the thickness after drying may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm. When the thickness is 1 μm or more, industrial coating is facilitated and productivity is improved. Further, when the thickness is 100 μm or less, the adhesion and the resolution are improved.
　感光性エレメントの形態は特に制限されない。例えば、シート状であってもよく、巻芯にロール状に巻き取った形状であってもよい。ロール状に巻き取る場合、支持フィルムが外側になるように巻き取ってもよい。巻芯としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ＡＢＳ樹脂（アクリロニトリル－ブタジエン－スチレン共重合体）等のプラスチックが挙げられる。 The form of the photosensitive element is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a winding core. When winding in a roll shape, the support film may be wound so as to be on the outside. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
　ロール状の感光性エレメントの端面には、端面保護の点から端面セパレータを設置してもよく、耐エッジフュージョンの点から防湿端面セパレータを設置してもよい。感光性エレメントは、透湿性の小さいブラックシートに包んで包装してもよい。 An end face separator may be installed on the end face of the roll-shaped photosensitive element from the viewpoint of end face protection, or a moisture-proof end face separator may be installed from the viewpoint of edge fusion resistance. The photosensitive element may be wrapped in a black sheet having low moisture permeability and packaged.
　感光性エレメントは、例えば、後述するレジストパターンの形成方法に好適に用いることができる。中でも、解像性の観点で、エッチング処理によって導体パターンを形成する製造方法への応用に適している。 The photosensitive element can be suitably used, for example, in a method for forming a resist pattern, which will be described later. Above all, from the viewpoint of resolution, it is suitable for application to a manufacturing method for forming a conductor pattern by an etching process.
［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、（ｉ）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、（ｉｉ）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、（ｉｉｉ）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 the resist pattern of the present embodiment is as follows: (i) a step of forming a photosensitive layer on a substrate by using the photosensitive resin composition or the photosensitive element (photosensitive layer forming step). ii) A step (exposure step) of irradiating at least a part (predetermined part) of the photosensitive layer with active light to form a photocurable portion, and (iii) at least a part of the unphotocured portion from the substrate. It may be configured to include a step (development step) for removing the above-mentioned light, and if necessary, other steps. The resist pattern can be said to be a photocured product pattern of the photosensitive resin composition, and can also be said to be 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.
（（ｉ）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。 ((I) Photosensitive layer forming step)
As a method for forming the photosensitive layer on the substrate, for example, the photosensitive resin composition may be applied and dried, or after the protective layer is removed from the photosensitive element, the photosensitive layer of the photosensitive element is formed. It may be crimped to the above substrate while heating. When a photosensitive element is used, it is composed of a substrate, a photosensitive layer, and a support, and a laminated body in which these are laminated in order can be obtained. The substrate is not particularly limited, but usually, a circuit forming substrate provided with an insulating layer and a conductor layer formed on the insulating layer, or a die pad (lead frame substrate) such as an alloy substrate 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 performed under reduced pressure from the viewpoint of adhesion and followability. The photosensitive layer and / or the substrate may be heated at a temperature of 70 to 130 ° C. during crimping. The crimping may be performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm 2 ), but these conditions are appropriately selected as necessary. If the photosensitive layer is heated to 70 to 130 ° C., it is not necessary to preheat the substrate in advance, but the substrate can be preheated in order to further improve the adhesion and the followability.
（（ｉｉ）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。 ((Ii) exposure step)
In the exposure step, by irradiating at least a part of the photosensitive layer formed on the substrate with the active light beam, the portion irradiated with the active light ray is photocured to form a latent image. At this time, when the support is present on the photosensitive layer, the active light can be irradiated through the support if the support is transparent to the active light, but if the support is light-shielding. Irradiates the photosensitive layer with active light rays after removing the support.
　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 of irradiating an image with active light rays via a negative or positive mask pattern called artwork (mask exposure method). Further, a method of irradiating an active ray in an image shape by a projection exposure method may be adopted. Further, a method of irradiating an active ray in an image shape 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 light source of the active light, a known light source can be used, and for example, a carbon arc lamp, a mercury steam arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid-state laser such as a YAG laser, a semiconductor laser and the like can be used. Those that effectively radiate ultraviolet rays and visible light are used.
（（ｉｉｉ）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。 ((Iii) development process)
In the developing step, a resist pattern is formed on the substrate by removing at least a part of the unphotocured portion (other than the photocured portion) of the photosensitive layer from 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 region other than the photocured portion (which can be said to be an unexposed portion) is removed (developed). There are two types of development methods, 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、解像性向上の観点からは、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, develop by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a dip method, a paddle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like, and a high-pressure spray method may be used from the viewpoint of improving resolution. .. Development may be performed by combining these two or more 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 according to the composition of the photosensitive resin composition. Examples of the developing solution include an alkaline aqueous solution and an organic solvent developing solution.
　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。 From the viewpoint of being safe, stable, and having good operability, an alkaline aqueous solution may be used as the developer. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as hydroxides of lithium, sodium or potassium; alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates; potassium phosphates, sodium phosphates and the like. Alkaline metal phosphates; Alkaline metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borosand, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl- 1,3-Propanediol, 1,3-diaminopropanol-2, morpholine and the like 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 0. A dilute solution of 1 to 5 mass% sodium tetraborate or the like 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 according to the alkaline developability of the photosensitive layer. For example, a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in 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. Examples include monobutyl ether.
　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-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. In order to prevent ignition, water may be added to these organic solvents so as to be in the range of 1 to 20% by mass to prepare 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 of forming a resist pattern in the present embodiment, after removing the uncured portion in the developing step, heating at about 60 to 250 ° C. or exposure of about 0.2 to 10 J / cm 2 is performed as necessary. May 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 the present embodiment includes a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern to form a conductor pattern, and if necessary, a resist. It may be configured to include other steps such as a pattern removing 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, the conductor layer provided on the substrate is plated using the resist pattern formed on the substrate as a mask. After the plating treatment, the resist may be removed by removing the resist pattern described later, and the conductor layer covered with the resist may be further etched to form the conductor pattern. The method of the plating treatment may be an electrolytic plating treatment, an electroless plating treatment, or an electroless plating treatment.
　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, the conductor layer provided on the substrate is removed by etching using the resist pattern formed on the substrate as a mask to form the conductor pattern. The etching treatment method is appropriately selected according to 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。 The resist pattern on the substrate may be removed after the etching treatment or the plating treatment. The resist pattern can be removed, for example, with a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As the strongly alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution, or the like is 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 the plating treatment, a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form the conductor pattern. The etching treatment method at this time is appropriately selected according to 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 the present embodiment can be applied not only to the manufacture of a single-layer printed wiring board but also to the manufacture of a multilayer printed wiring board, and also to the manufacture of a printed wiring board having a small-diameter through hole. It is possible.
　以下、実施例及び比較例に基づいて本実施態様の目的及び利点をより具体的に説明するが、本実施態様は以下の実施例に限定されるものではない。 Hereinafter, the purpose and advantages of this embodiment will be described more specifically based on Examples and Comparative Examples, but this embodiment is not limited to the following examples.
［バインダーポリマー］
　実施例及び比較例で用いるバインダーポリマーを合成するための重合性単量体として、メタクリル酸（ＭＡＡ）、スチレン（ＳＴ）、メチルメタクリレート（ＭＭＡ）、ブチルメタクリレート（ＢＭＡ）、ブチルアクリレート（ＢＡ）、２－エチルヘキシルアクリレート（ＥＨＡ）、及びベンジルメタクリレート（ＢＺＭＡ）を準備した。 [Binder polymer]
Methacrylic acid (MAA), styrene (ST), methyl methacrylate (MMA), butyl methacrylate (BMA), butyl acrylate (BA), as polymerizable monomers for synthesizing the binder polymers used in Examples and Comparative Examples. 2-Ethylhexyl acrylate (EHA) and benzyl methacrylate (BZMA) were prepared.
（バインダーポリマー（Ａ－１））
　メタクリル酸（ＭＡＡ）２５．５ｇ、スチレン（ＳＴ）５２．９ｇ、メチルメタクリレート（ＭＭＡ）９．９ｇ、ブチルアクリレート（ＢＡ）３．２ｇ、ベンジルメタクリレート（ＢＺＭＡ）２３．５ｇ、４－メトキシフェノール０．０２ｇ、及びアゾビスイソブチロニトリル０．７ｇを混合して、溶液ａを調製した。また、プロピレングリコールモノメチルエーテル９ｇ、トルエン７．６ｇ、及びアゾビスイソブチロニトリル０．１４ｇを混合して、溶液ｂを調製した。さらに、プロピレングリコールモノメチルエーテル４．５ｇ、トルエン７．６ｇ、及びアゾビスイソブチロニトリル０．５ｇを混合して、溶液ｃを調製した。 (Binder polymer (A-1))
Methacrylic acid (MAA) 25.5 g, styrene (ST) 52.9 g, methyl methacrylate (MMA) 9.9 g, butyl acrylate (BA) 3.2 g, benzyl methacrylate (BZMA) 23.5 g, 4-methoxyphenol 0. 02 g and 0.7 g of azobisisobutyronitrile were mixed to prepare a solution a. Further, 9 g of propylene glycol monomethyl ether, 7.6 g of toluene, and 0.14 g of azobisisobutyronitrile were mixed to prepare a solution b. Further, 4.5 g of propylene glycol monomethyl ether, 7.6 g of toluene, and 0.5 g of azobisisobutyronitrile were mixed to prepare a solution c.
　撹拌機、還流冷却器、温度計、滴下ロート及び窒素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４８ｇ、トルエン４０ｇを投入し、フラスコ内に窒素ガスを吹き込みながら８０℃で３０分間撹拌して混合液を得た。 Put 48 g of propylene glycol monomethyl ether and 40 g of toluene into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, and stir at 80 ° C. for 30 minutes while blowing nitrogen gas into the flask. To obtain a mixed solution.
　フラスコ内の混合液に上記溶液ａを４時間かけて滴下した後、８０℃で２時間撹拌した。次いで、フラスコ内の溶液に上記溶液ｂを滴下し、８０℃で２時間撹拌した。更に、撹拌を続けたまま、フラスコ内の溶液を１時間かけて９５℃まで昇温させた後、上記溶液ｃを１０分間かけて滴下して９５℃で２時間撹拌して反応を行った。反応液を５０℃まで冷却した後、メタノールを添加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４７．７質量％であった。 The above solution a was added dropwise to the mixed solution in the flask over 4 hours, and then the mixture was stirred at 80 ° C. for 2 hours. Then, the above solution b was added dropwise to the solution in the flask, and the mixture was stirred at 80 ° C. for 2 hours. Further, the solution in the flask was heated to 95 ° C. over 1 hour while stirring was continued, and then the solution c was added dropwise over 10 minutes and stirred at 95 ° C. for 2 hours to carry out the reaction. After cooling the reaction solution to 50 ° C., methanol was added to obtain a solution of the binder polymer (A-1). The non-volatile content (solid content) of the binder polymer (A-1) was 47.7% by mass.
（バインダーポリマー（Ａ－２）～（Ａ－１６））
　重合性単量体を表１又は表２に示す材料を同表に示す質量比で用いた以外は、バインダーポリマー（Ａ－１）の溶液を得るのと同様にして、バインダーポリマー（Ａ－２）～（Ａ－１６）の溶液を得た。 (Binder Polymers (A-2) to (A-16))
The binder polymer (A-2) was obtained in the same manner as in obtaining the solution of the binder polymer (A-1), except that the polymerizable monomer was used in the mass ratio shown in Table 1 or Table 2. )-(A-16) was obtained.
（重量平均分子量）
　バインダーポリマー溶液を１２０ｍｇ採取し、５ｍＬのテトラヒドロフランに溶解して、Ｍｗ測定用の試料を調製した。Ｍｗは、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ）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。 (Weight average molecular weight)
120 mg of the binder polymer solution was collected and dissolved in 5 mL of tetrahydrofuran to prepare a sample for Mw measurement. Mw was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions of GPC are shown below.
（ＧＰＣ条件）
ポンプ：日立　Ｌ－６０００型（株式会社日立製作所製）
カラム：Ｇｅｌｐａｃｋ　ＧＬ－Ｒ４４０、Ｇｅｌｐａｃｋ　ＧＬ－Ｒ４５０及びＧｅｌｐａｃｋ　ＧＬ－Ｒ４４０Ｍ（昭和電工マテリアルズ・テクノサービス株式会社製、カラム仕様：１０．７ｍｍφ×３００ｍｍ）
溶離液：テトラヒドロフラン
測定温度：４０℃
注入量：２００μＬ
圧力：４９Ｋｇｆ／ｃｍ２（４．８ＭＰａ）
流量：２．０５ｍＬ／分
検出器：日立　Ｌ－２４９０型ＲＩ（株式会社日立製作所製） (GPC condition)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R440, Gelpack GL-R450 and Gelpack GL-R440M (manufactured by Showa Denko Materials Techno Service Co., Ltd., column specifications: 10.7 mmφ x 300 mm)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49 Kgf / cm 2 (4.8 MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-2490 type RI (manufactured by Hitachi, Ltd.)
（酸価）
　酸価は、ＪＩＳ　Ｋ００７０に基づいた中和滴定法により測定した。バインダーポリマー約１ｇに混合溶剤（質量比：トルエン／メタノール＝７０／３０）を加えて溶解した溶液に、指示薬としてフェノールフタレイン溶液を適量添加し、０．１Ｎの水酸化カリウム水溶液で滴定を行うことで、バインダーポリマーの酸価を測定した。 (Acid value)
The acid value was measured by a neutralization titration method based on JIS K0070. An appropriate amount of a phenolphthalein solution is added as an indicator to a solution prepared by adding a mixed solvent (mass ratio: toluene / methanol = 70/30) to about 1 g of the binder polymer, and titration is performed with a 0.1 N potassium hydroxide aqueous solution. Therefore, the acid value of the binder polymer was measured.
（ガラス転移温度）
　バインダーポリマーのガラス転移温度（Ｔｇ）は、Ｆｏｘの式から算出した。 (Glass-transition temperature)
The glass transition temperature (Tg) of the binder polymer was calculated from the Fox formula.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［感光性樹脂組成物］
　表３又は表４に示す配合量（質量部）の（Ａ）、（Ｂ）及び（Ｃ）成分と、溶剤であるメタノール５質量部、トルエン１０質量部、及びアセトン１１質量部とを混合することにより、実施例及び比較例の感光性樹脂組成物をそれぞれ調製した。表３及び４に示すバインダーポリマーの配合量は、不揮発分の質量（固形分量）である。 [Photosensitive resin composition]
The components (A), (B) and (C) of the blending amount (parts by mass) shown in Table 3 or Table 4 are mixed with 5 parts by mass of methanol, 10 parts by mass of toluene and 11 parts by mass of acetone as solvents. As a result, the photosensitive resin compositions of Examples and Comparative Examples were prepared, respectively. The blending amount of the binder polymer shown in Tables 3 and 4 is the mass of the non-volatile component (solid content amount).
　表３及び４に示す各成分の詳細は、以下のとおりである。
（（Ｂ）成分：光重合性化合物）
Ｂ－１：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）
Ｂ－２：ＦＡ－ＭＥＣＨ　γ－クロロ－β－ヒドロキシプロピル－β’－メタクリロイルオキシエチル－ｏ－フタレート（昭和電工マテリアルズ株式会社）
Ｂ－３：Ｍ２２００　エトキシ化ビスフェノールＡジメタクリレート（ＥＯ平均２０ｍｏｌ変性）（Ｍｉｗｏｎ社製）
Ｂ－４：ＢＰＥ－２００　エトキシ化ビスフェノールＡジメタクリレート（ＥＯ平均４ｍｏｌ変性）（新中村化学工業株式会社）
Ｂ－５：ＳＲ４５４　ＥＯ変性トリメチロールプロパンアクリレート（巴工業株式会社）
Ｂ－６：ＦＡ－１３７Ｍ　ＥＯ変性トリメチロールプロパンアクリレート（昭和電工マテリアルズ株式会社）
Ｂ－７：ＤＰＥＡ－１２　ＥＯ基を有するジペンタエリスリトール（メタ）アクリレート（日本化薬株式会社）
（（Ｃ）成分：光重合開始剤）
Ｃ－１：９－ＰＡ　９－フェニルアクリジン（常州強力電子新材料株式会社）
Ｃ－２：Ｎ－ＰＧ　Ｎ－フェニルグリシン（常州強力電子新材料株式会社） Details of each component shown in Tables 3 and 4 are as follows.
(Component (B): photopolymerizable compound)
B-1: FA-321M 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane (Showa Denko Materials Co., Ltd.)
B-2: FA-MECH γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (Showa Denko Materials Co., Ltd.)
B-3: M2200 ethoxylated bisphenol A dimethacrylate (EO average 20 mol denaturation) (manufactured by Miwon)
B-4: BPE-200 ethoxylated bisphenol A dimethacrylate (EO average 4 mol denaturation) (Shin Nakamura Chemical Industry Co., Ltd.)
B-5: SR454 EO-modified trimethylolpropane acrylate (Tomoe Kogyo Co., Ltd.)
B-6: FA-137M EO-modified trimethylolpropane acrylate (Showa Denko Materials Co., Ltd.)
B-7: Dipentaerythritol (meth) acrylate having a DPEA-12 EO group (Nippon Kayaku Co., Ltd.)
(Component (C): Photopolymerization Initiator)
C-1: 9-PA 9-Phenyl Acridine (Changzhou Strong Electronics New Materials Co., Ltd.)
C-2: N-PG N-Phenylglycine (Changzhou Strong Electronics New Materials Co., Ltd.)
［感光性エレメント］
　感光性樹脂組成物の溶液を、厚み１６μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（帝人フィルムソリューション株式会社、商品名「Ｇ２Ｊ」）（支持体）上に塗布し、７５℃及び１２５℃の熱風対流式乾燥器で順次乾燥して、乾燥後の厚みが２５μｍの感光層を形成した。この感光層上にポリプロピレンフィルム（タマポリ株式会社、製品名「ＮＦ－１３」）（保護層）を貼り合わせ、支持体と、感光層と、保護層とがこの順に積層された感光性エレメントをそれぞれ得た。 [Photosensitive element]
A solution of the photosensitive resin composition is applied onto a polyethylene terephthalate (PET) film (Teijin Film Solution Co., Ltd., trade name "G2J") (support) having a thickness of 16 μm, and hot air convection drying at 75 ° C and 125 ° C. The film was sequentially dried in a vessel to form a photosensitive layer having a thickness of 25 μm after drying. A polypropylene film (Tamapoli Co., Ltd., product name "NF-13") (protective layer) is laminated on this photosensitive layer, and the support, the photosensitive layer, and the protective layer are laminated in this order. Obtained.
（追従性）
　銅張積層板の銅表面をエッチングして、直径２００μｍ及び深さ１１μｍの丸穴を８箇所に形成した基板を作製した。次いで、基板を８０℃に加温し、感光性エレメントを基板に積層した。積層は、１１０℃のヒートロールを用いて、保護層を除去しながら、基板の０．３ＭＰａの圧着圧力、１．５ｍ／分のロール速度で行った。こうして、基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。光学顕微鏡（キーエンス株式会社、ＶＫ－８５００）を用いて積層体の真上から丸穴部を観察して、基板の丸穴と感光層との間に発生する気泡の直径を測定した。気泡の直径が小さいほど、追従性に優れることを意味する。 (Followability)
The copper surface of the copper-clad laminate was etched to prepare a substrate having eight round holes having a diameter of 200 μm and a depth of 11 μm. Next, the substrate was heated to 80 ° C., and the photosensitive element was laminated on the substrate. Lamination was performed using a heat roll at 110 ° C. at a crimping pressure of 0.3 MPa and a roll speed of 1.5 m / min on the substrate while removing the protective layer. In this way, a laminated body in which the substrate, the photosensitive layer, and the support were laminated in this order was obtained. The round hole portion was observed from directly above the laminate using an optical microscope (Keyence Corporation, VK-8500), and the diameter of bubbles generated between the round hole of the substrate and the photosensitive layer was measured. The smaller the diameter of the bubble, the better the followability.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１～４から明らかなように、特定の構造を有するバインダーポリマーを含有する感光性樹脂組成物は、追従性に優れる感光層を形成できる。 As is clear from Tables 1 to 4, the photosensitive resin composition containing the binder polymer having a specific structure can form a photosensitive layer having excellent followability.
　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 (9)

  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、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、カルボキシ基を有する重合性単量体に由来する構造単位（ａ１）と、スチレン又はスチレン誘導体に由来する構造単位（ａ２）と、炭素数が１～３のアルキル基を有するアルキル（メタ）アクリルレートに由来する構造単位（ａ３）と、炭素数が４～１２のアルキル基を有するアルキル（メタ）メタクリレートに由来する構造単位（ａ４）とを有する、感光性樹脂組成物。     A photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
    The binder polymer has a structural unit (a1) derived from a polymerizable monomer having a carboxy group, a structural unit (a2) derived from styrene or a styrene derivative, and an alkyl having 1 to 3 carbon atoms. A photosensitive resin composition having a structural unit (a3) derived from (meth) acrylic rate and a structural unit (a4) derived from alkyl (meth) methacrylate having an alkyl group having 4 to 12 carbon atoms.
  2. 　前記バインダーポリマーの酸価が、１００ｍｇＫＯＨ／ｇ以上１８０ｍｇＫＯＨ／ｇ以下である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the acid value of the binder polymer is 100 mgKOH / g or more and 180 mgKOH / g or less.
  3. 　前記バインダーポリマーの重量平均分子量が、１００００以上６００００以下である、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 binder polymer has a weight average molecular weight of 10,000 or more and 60,000 or less.
  4. 　前記構造単位（ａ４）の含有量が、前記バインダーポリマーの全体量を基準として、０．５～３０質量％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 content of the structural unit (a4) is 0.5 to 30% by mass based on the total amount of the binder polymer.
  5. 　前記光重合開始剤が、アクリジン系光重合開始剤を含む、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 photopolymerization initiator contains an acridine-based photopolymerization initiator.
  6. 　支持体と、該支持体上に形成された感光層と、を備え、
    　前記感光層が、請求項１～５のいずれか一項に記載の感光性樹脂組成物を含む、感光性エレメント。     A support and a photosensitive layer formed on the support are provided.
    A photosensitive element in which the photosensitive layer contains the photosensitive resin composition according to any one of claims 1 to 5.
  7. 　基板上に、請求項１～５のいずれか一項に記載の感光性樹脂組成物又は請求項６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の少なくとも一部を除去する工程と、
    を備える、レジストパターンの形成方法。     A step of forming a photosensitive layer on a substrate by using the photosensitive resin composition according to any one of claims 1 to 5 or the photosensitive element according to claim 6.
    A step of irradiating at least a part of the photosensitive layer with active light to form a photocurable portion, and
    A step of removing at least a part of the unlightened portion of the photosensitive layer from the substrate,
    A method of forming a resist pattern.
  8. 　請求項７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 a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 7.
  9. 　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８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 8, further comprising a step of removing the resist pattern after the etching treatment or the plating treatment.
PCT/JP2020/043605 2020-11-24 2020-11-24 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board WO2022113161A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
PCT/JP2020/043605 WO2022113161A1 (en) 2020-11-24 2020-11-24 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
PCT/JP2021/042092 WO2022113829A1 (en) 2020-11-24 2021-11-16 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board
KR1020237019362A KR20230109152A (en) 2020-11-24 2021-11-16 Photosensitive resin composition, photosensitive element, method for forming a resist pattern, and method for manufacturing a printed wiring board
CN202210896651.8A CN115167077A (en) 2020-11-24 2021-11-16 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
JP2022562370A JP7425982B2 (en) 2020-11-24 2021-11-16 Photosensitive resin composition, photosensitive element, resist pattern forming method, and printed wiring board manufacturing method
CN202180007845.1A CN114902137A (en) 2020-11-24 2021-11-16 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
TW110142698A TW202227577A (en) 2020-11-24 2021-11-17 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board
JP2023179342A JP2024008940A (en) 2020-11-24 2023-10-18 Photosensitive resin composition, photosensitive element, formation method of resist pattern, and manufacturing method of printed wiring board

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2020/043605 WO2022113161A1 (en) 2020-11-24 2020-11-24 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board

Publications (1)

Publication Number Publication Date
WO2022113161A1 true WO2022113161A1 (en) 2022-06-02

Family

ID=81754092

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/JP2020/043605 WO2022113161A1 (en) 2020-11-24 2020-11-24 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
PCT/JP2021/042092 WO2022113829A1 (en) 2020-11-24 2021-11-16 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/042092 WO2022113829A1 (en) 2020-11-24 2021-11-16 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board

Country Status (5)

Country Link
JP (2) JP7425982B2 (en)
KR (1) KR20230109152A (en)
CN (2) CN114902137A (en)
TW (1) TW202227577A (en)
WO (2) WO2022113161A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024210041A1 (en) * 2023-04-03 2024-10-10 株式会社レゾナック Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing circuit board

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03236956A (en) * 1989-05-17 1991-10-22 Asahi Chem Ind Co Ltd Photo-setting resin laminate and manufacture of printed wiring board using the same
JP2010020264A (en) * 2007-08-09 2010-01-28 Nichigo Morton Co Ltd Solder resist film, resist pattern forming method and luminescent device
WO2013141286A1 (en) * 2012-03-23 2013-09-26 日立化成株式会社 Photosensitive resin composition, method for manufacturing processed glass substrate using same, and touch panel and method for manufacturing same
JP2017129736A (en) * 2016-01-20 2017-07-27 互応化学工業株式会社 Photosensitive resin composition, dry film, printed wiring board and production method of photosensitive resin composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4924230B2 (en) 2007-06-21 2012-04-25 日立化成工業株式会社 Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method
JP4935833B2 (en) 2009-01-23 2012-05-23 日立化成工業株式会社 Photosensitive resin composition, photosensitive element using the same, method for forming partition of image display device, and method for manufacturing image display device
JP2010249884A (en) 2009-04-10 2010-11-04 Dupont Mrc Dryfilm Ltd Photopolymerizable resin composition and photosensitive film using the same
JP5777461B2 (en) 2011-09-14 2015-09-09 旭化成イーマテリアルズ株式会社 Photosensitive resin composition
CN108241259B (en) 2018-01-24 2021-08-10 杭州福斯特电子材料有限公司 Resist composition with good hole masking function and capable of directly depicting, exposing and imaging
CN111965939B (en) * 2020-08-11 2023-06-20 杭州福斯特电子材料有限公司 Photosensitive resin composition and dry film resist thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03236956A (en) * 1989-05-17 1991-10-22 Asahi Chem Ind Co Ltd Photo-setting resin laminate and manufacture of printed wiring board using the same
JP2010020264A (en) * 2007-08-09 2010-01-28 Nichigo Morton Co Ltd Solder resist film, resist pattern forming method and luminescent device
WO2013141286A1 (en) * 2012-03-23 2013-09-26 日立化成株式会社 Photosensitive resin composition, method for manufacturing processed glass substrate using same, and touch panel and method for manufacturing same
JP2017129736A (en) * 2016-01-20 2017-07-27 互応化学工業株式会社 Photosensitive resin composition, dry film, printed wiring board and production method of photosensitive resin composition

Also Published As

Publication number Publication date
WO2022113829A1 (en) 2022-06-02
JPWO2022113829A1 (en) 2022-06-02
CN115167077A (en) 2022-10-11
JP2024008940A (en) 2024-01-19
TW202227577A (en) 2022-07-16
JP7425982B2 (en) 2024-02-01
KR20230109152A (en) 2023-07-19
CN114902137A (en) 2022-08-12

Similar Documents

Publication Publication Date Title
JP5626428B2 (en) Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method
JP5327310B2 (en) Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method
US20160170299A1 (en) Photosensitive resin composition for projection exposure, photosensitive element, method for forming resist pattern, process for producing printed wiring board and process for producing lead frame
JPWO2008078483A1 (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
WO2009154194A1 (en) Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board
JP2009003000A (en) Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, method for manufacturing printed wiring board and method for removing photocured product
JP2009042720A (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and method for manufacturing printed circuit board
JP6690532B2 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
JP5600903B2 (en) Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method
WO2022113829A1 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board
JP5532551B2 (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
JP2024003098A (en) Photosensitive resin film, resist pattern forming method, and wiring pattern forming method
JP7507862B2 (en) Alkali-soluble resin, photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for forming wiring pattern
JP2022136596A (en) Photosensitive resin film, photosensitive element, and method of manufacturing laminate
JP7327485B2 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
WO2022201432A1 (en) Photosensitive resin film, resist pattern forming method, and method for forming wiring pattern
WO2023050062A1 (en) Polymer, photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for forming wiring pattern
WO2024135501A1 (en) Photosensitive element and method for forming resist pattern
JP2010197831A (en) Photosensitive resin composition and photosensitive element using the composition, method for forming resist pattern and method for manufacturing printed wiring board
JP2010039459A (en) Photosensitive resin composition, and photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board using the same
JP2010060891A (en) Photosensitive resin composition, photosensitive element using the same, method for forming resist pattern and method for manufacturing printed wiring board
JP2013122488A (en) Photosensitive resin composition, and photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board using the composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20963426

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20963426

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP