WO2021029039A1 - 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

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Publication number
WO2021029039A1
WO2021029039A1 PCT/JP2019/031950 JP2019031950W WO2021029039A1 WO 2021029039 A1 WO2021029039 A1 WO 2021029039A1 JP 2019031950 W JP2019031950 W JP 2019031950W WO 2021029039 A1 WO2021029039 A1 WO 2021029039A1
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Prior art keywords
resin composition
meth
photosensitive
photosensitive resin
mass
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PCT/JP2019/031950
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French (fr)
Japanese (ja)
Inventor
みゆき 室町
絵美子 海老原
満明 渡辺
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昭和電工マテリアルズ株式会社
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Priority to JP2021539767A priority Critical patent/JP7327485B2/en
Priority to PCT/JP2019/031950 priority patent/WO2021029039A1/en
Priority to CN201980099117.0A priority patent/CN114222766A/en
Publication of WO2021029039A1 publication Critical patent/WO2021029039A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—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
    • 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 and a layer formed on a support film using the photosensitive resin composition (hereinafter, "" A photosensitive element having a “photosensitive layer”) is 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 through 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 photocurable 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 photocurable 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 resin composition is required not only to form a resist pattern having high developability in the unexposed portion and having excellent resolution, but also to peel off the resist pattern in order to peel off the photocured portion. Is required to be excellent.
  • the present disclosure provides a photosensitive resin composition having an excellent balance of developability, resolution and peeling characteristics, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.
  • the purpose is.
  • the photosensitive resin composition according to the present disclosure contains a binder polymer having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator, and the acid value of the binder polymer is determined. It is 165 to 195 mgKOH / g, and the photopolymerizable compound contains a (meth) acrylate having a phthalic acid skeleton.
  • the binder polymer may have 41 to 64% by mass of structural units derived from styrene or a styrene derivative.
  • the weight average molecular weight of the binder polymer may be 5000 to 37000.
  • the content of the (meth) acrylate having a phthalic acid skeleton may be 1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.
  • the said photopolymerization initiator may contain an acridine-based photopolymerization initiator.
  • 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 irradiating a predetermined portion of the photosensitive layer with active light.
  • a step of forming a photocurable portion and a step of removing at least a part of the photosensitive layer other than the photocurable portion from the substrate are provided.
  • 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.
  • the method for manufacturing a printed wiring board may further include a step of removing the photocurable portion after the etching treatment or the plating treatment.
  • a photosensitive resin composition having an excellent balance of developability, resolution and peeling characteristics, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board are described. Can be provided.
  • 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 content 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 vaporization, and also includes those that are liquid, candy-like, and wax-like at room temperature around 25 ° C.
  • the photosensitive resin composition according to the present embodiment contains a binder polymer having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator.
  • the acid value of the binder polymer is 165 to 195 mgKOH / g, and the photopolymerizable compound contains a phthalate compound.
  • the binder polymer (A) (hereinafter, also referred to as “component (A)”) has a structural unit derived from styrene or a styrene derivative, thereby improving the peeling property of the photosensitive layer formed from the photosensitive resin composition. be able to.
  • the component (A) can be produced, for example, by radically polymerizing a polymerizable monomer containing styrene or a styrene derivative.
  • the styrene derivative is a polymerizable compound in which the hydrogen atom in the ⁇ -position or aromatic ring of styrene such as vinyltoluene and ⁇ -methylstyrene is substituted.
  • the content of the structural unit derived from styrene or the styrene derivative in the component (A) is 41 to 64% by mass, 41 to 60% by mass, 42 to 55% by mass, or 43 based on the total amount of the component (A). It may be up to 50% by mass. When this content is 41% by mass or more, the resolution tends to be further improved, and when it is 64% by mass or less, it is possible to suppress the peeling piece from becoming large during development, and the time required for peeling tends to be long. is there.
  • the component (A) may have a carboxy group from the viewpoint of alkali developability.
  • the component (A) having a carboxy group can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxy group and a polymerizable monomer containing styrene or a styrene derivative.
  • Examples of 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, ⁇ -cyanosilic acid, itaconic acid, crotonic acid, and propiolic 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 derived from the polymerizable monomer having a carboxy group is 10 to 50% by mass based on the total amount of the component (A) from the viewpoint of improving the alkali developability and the alkali resistance in a well-balanced manner. , 15-40% by mass, or 20-35% by mass. When this content is 10% by mass or more, the alkali developability tends to be improved, and when it is 50% by mass or less, the alkali resistance tends to be excellent.
  • the component (A) further includes a structural unit derived from a polymerizable monomer other than styrene or a styrene derivative and a polymerizable monomer having a carboxy group (hereinafter, also referred to as “(other polymerizable monomer”)).
  • Other polymerizable monomers include, for example, acrylamides such as diacetoneacrylamide, ethers of vinyl alcohols such as acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid alkyl esters, and (meth) acrylic acid alkyl esters.
  • Acrylic acid benzyl ester (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-tri Fluoroethyl (meth) acrylate and 2,2,3,3-tetrafluoropropyl (meth) acrylate can be mentioned.
  • Other polymerizable monomers may be used alone or in combination of two or more. Can be done.
  • the component (A) may have a structural unit derived from the (meth) acrylic acid alkyl ester from the viewpoint of improving the plasticity.
  • the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid pentyl.
  • Esters (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl Examples thereof include esters, (meth) acrylic acid undecyl esters, and (meth) acrylic acid dodecyl esters.
  • the acid value of the component (A) is 165 to 195 mgKOH / g, and 170 to 195 mgKOH / g, 175 to 193 mgKOH / g, or 180 to 190 mgKOH / g from the viewpoint of further improving the balance between developability, resolution and peeling characteristics. It may be g.
  • the weight average molecular weight (Mw) of the component (A) may be 5000 to 37000, 8000 to 36000, 10000 to 35000, or 15000 to 33000.
  • Mw of the component (A) is 5000 or more, the developer resistance of the photocurable portion tends to be excellent, and when it is 37,000 or less, the development time of the unexposed portion tends to be suppressed from becoming long.
  • the component (A) may have a dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0 or 1.0 to 2.0. The resolution tends to improve as the degree of dispersion decreases.
  • the weight average molecular weight and the number average molecular weight in the present specification are values measured by gel permeation chromatography (GPC) and converted using standard polystyrene as a standard sample.
  • 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 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 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) described later. It may be 60 parts by mass. When the content of the component (A) is within this range, the strength of the photocurable portion of the photosensitive layer becomes better.
  • the (B) photopolymerizable compound (hereinafter, also referred to as “component (B)”) contains a (meth) acrylate having a phthalic acid skeleton to improve the resolution of the resist pattern and the peeling characteristics after curing in a well-balanced manner. be able to.
  • Examples of the (meth) acrylate having a phthalate skeleton include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate and ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxy.
  • Ethyl-o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate can be mentioned.
  • ⁇ -Chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (Hitachi Kasei Co., Ltd.).
  • the content of the (meth) acrylate having a phthalic acid skeleton is 1 to 30 parts by mass, 2 to 25 parts by mass, 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Alternatively, it may be 8 to 15 parts by mass. When the content of the (meth) acrylate having a phthalic acid skeleton is within this range, the peeling property becomes better.
  • the component (B) may further contain a photopolymerizable compound (hereinafter, also referred to as “another photopolymerizable compound”) other than the (meth) acrylate having a phthalic acid skeleton.
  • a photopolymerizable compound hereinafter, also referred to as “another photopolymerizable compound”
  • another photopolymerizable compound a compound having an ethylenically unsaturated bond can be used.
  • Other photopolymerizable compounds may be used alone or in combination of two or more.
  • the ethylenically unsaturated bond is not particularly limited as long as photopolymerization is possible.
  • the ethylenically unsaturated bond include ⁇ , ⁇ -unsaturated carbonyl groups such as (meth) acryloyl group.
  • the photopolymerizable compound having an ⁇ , ⁇ -unsaturated carbonyl group include ⁇ , ⁇ -unsaturated carboxylic acid ester of polyhydric alcohol, bisphenol type (meth) acrylate, and ⁇ , ⁇ -unmodified compound containing a glycidyl group.
  • 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-modified trimethylolpropane tri (meth) acrylate PO-modified trimethylolpropane tri (meth) acrylate
  • EO PO-modified trimethylolpropane tri (meth) acrylate
  • PO PO-modified trimethylolpropane tri (meth) acrylate
  • tetramethylolmethanetri (meth) acrylate tetramethylolmethanetetra
  • examples include (meth) acrylates and (meth) acrylate compounds having a skeleton derived from dipentaerythritol or pentaerythritol.
  • EO modification means that it has a block structure of ethylene oxide (EO) group
  • PO modification means that it has 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 blocks 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 Hitachi Kasei Co., Ltd.), FA-024M (manufactured by Hitachi Kasei Co., Ltd.), and NK Ester HEMA-9P (Shin-Nakamura Chemical Industry Co., Ltd.). Made by the company).
  • the component (B) may contain a (meth) acrylate having a urethane bond from the viewpoint of improving the flexibility of the resist pattern.
  • a (meth) acrylate having a urethane bond examples 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) acryloxitetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO and PO-modified urethane di (meth) acrylate.
  • Examples of commercially available EO-modified urethane di (meth) acrylate products 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. It may be.
  • the component (B) may contain a bisphenol type (meth) acrylate, and 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) acryloxipolyethoxy) 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 (C) photopolymerization initiator (hereinafter, also referred to as “component (C)”) is not particularly limited as long as the component (B) can be polymerized, and the photopolymerization initiator that is usually used is used. It can be selected as appropriate. 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, acridine type, phenylglycine Examples thereof include photopolymerization initiators such as radicals and coumarins.
  • 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.
  • 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.
  • one type can be used alone or two or more types can be used in combination.
  • acrydin-based photopolymerization initiator examples include 9-phenylacrine, 9- (p-methylphenyl) acrydin, 9- (m-methylphenyl) acrydin, 9- (p-chlorophenyl) acrydin, and 9- (m-).
  • Chlorophenyl) acrydin 9-aminoacrine, 9-dimethylaminoacrine, 9-diethylaminoacrine, 9-pentylaminoacrine, 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 components (A) and (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 includes dyes, photocolorants, thermal color inhibitors, plasticizers, pigments, fillers, defoaming agents, flame retardants, adhesion imparting agents, and leveling, if necessary.
  • 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.
  • dyes include malachite green, Victoria pure blue, brilliant green, and methyl violet.
  • photocoloring agent include tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline.
  • 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 components (A) and (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 for a schematic cross-sectional view of an example thereof. And other layers such as a 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 is excellent in 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 suppress a decrease in resolution when exposure is performed through the support.
  • the photosensitive element may further include 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 fish eye 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 formed. 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, and bar coating.
  • 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 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 it 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 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.
  • the photosensitive element can be suitably used, for example, in a resist pattern forming method described later. Above all, from the viewpoint of resolution, it is suitable for application to a manufacturing method for forming a conductor pattern by plating.
  • the method for forming the resist pattern of the present embodiment includes (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), and ii) At least a part (predetermined part) of the photosensitive layer is irradiated with active light to form a photocurable portion (exposure step), and (iii) at least a part other than the photocurable portion from the substrate.
  • a step (development step) for removing the above-mentioned light is provided, and other steps may be included if necessary.
  • the resist pattern can be said to be a photocured product pattern of the photosensitive resin composition and also 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 is used, a laminate composed of a substrate, a photosensitive layer, and a support, and these are laminated in this order can be obtained.
  • the substrate is not particularly limited, but usually a circuit-forming substrate having 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 active light, the portion irradiated with the active light 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 of active light rays through 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, 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, or the like. Those that effectively emit ultraviolet rays and visible light are used.
  • a resist pattern is formed on the substrate by removing at least a part of the photosensitive layer other than the photocurable portion 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.
  • wet development it is developed 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 developing solution 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.
  • 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 carbonates or bicarbonates of lithium, sodium, potassium or ammonium; potassium phosphate, sodium phosphate and the like.
  • Alkali metal phosphates Alkali 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.
  • Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, a dilute solution of 0.1 to 5% by mass sodium hydroxide, 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 coated 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 resist pattern formed on the substrate is used as a mask, and the conductor layer provided on the substrate is etched and removed to form the conductor pattern.
  • the method of etching is appropriately selected according to the conductor layer to be removed.
  • the etching solution include a cupric chloride solution, a ferric chloride solution, an alkali 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 by, for example, using 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 mass% sodium hydroxide aqueous solution, a 1 to 10 mass% potassium hydroxide aqueous solution, or the like is used.
  • a desired printed wiring board can be manufactured by further etching the conductor layer coated 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 production of a single-layer printed wiring board but also to the production of a multilayer printed wiring board, and also to the production of a printed wiring board having a small diameter through hole or the like. It is possible.
  • Solution a was prepared by mixing 24 g of methacrylic acid, 26 g of methyl methacrylate, 35 g of styrene, 0.02 g of 4-methoxyphenol, and 0.7 g of azobisisobutyronitrile. 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.
  • 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 continuing stirring, 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) and (A-3) The binder polymer (A-2) and (A-2) and (in the same manner as in obtaining a solution of the binder polymer (A-1), except that the polymerizable monomer was used in the mass ratio shown in the table 1 are used. A solution of A-3) was obtained.
  • Weight average molecular weight 120 mg of the binder polymer solution was collected and dissolved in 5 mL of THF 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.
  • Photosensitive resin composition The photosensitive resin compositions of Examples and Comparative Examples were prepared by mixing each component in the blending amount (part by mass) shown in Table 2 with a solvent (methanol, toluene, acetone).
  • the blending amount of the binder polymer shown in Table 2 is the mass of the non-volatile component (solid content).
  • 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 container 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.
  • Hitachi 41-step step tablet with a concentration range of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm x 187 mm, and a step size of 3 mm x 12 mm as a negative mask on the support of the laminate. (Made by Hitachi Kasei Co., Ltd.) was placed. Next, the photosensitive layer was exposed with a predetermined amount of energy using a DLP exposure machine (manufactured by Hitachi Via Mechanics, Ltd., trade name “DE-1UH”) having a wavelength of 405 nm using a semiconductor laser as a light source.
  • a DLP exposure machine manufactured by Hitachi Via Mechanics, Ltd., trade name “DE-1UH”
  • the support was peeled off, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed for twice the shortest development time (the shortest time for removing the unexposed portion) to remove the unexposed portion (development). processing).
  • the amount of energy (mJ / cm 2 ) at which the number of steps of the photocurable film step tablet formed on the substrate was 15.0 was determined, and the light sensitivity of the photosensitive resin composition was evaluated. The smaller this value is, the higher the light sensitivity is.
  • the resolution is evaluated by the value of the smallest space width among the resist patterns formed in which the space portion (unexposed portion) is cleanly removed and the line portion (exposed portion) does not meander or chip. did. The smaller this value is, the better the resolution and adhesion are.
  • the photosensitive layer of the laminate was exposed using a drawing pattern forming a cured film of 40 mm ⁇ 50 mm. After the exposure, the support was peeled off, and a development process similar to the evaluation of light sensitivity was performed to prepare a test piece having a cured film of 40 mm ⁇ 50 mm formed on the substrate.
  • the test piece After leaving the test piece at room temperature for 24 hours, the test piece was immersed in a 3.0 mass% sodium hydroxide aqueous solution at 50 ° C., and the time (seconds) until the cured film was completely peeled off from the substrate was measured. In addition, the size of the peeled piece was visually observed. The shorter the peeling time and the smaller the peeling piece size, the better the peeling characteristics.

Abstract

A photosensitive resin composition according to the present invention comprises a binder polymer having a structural unit derived from styrene or a styrene derivative, one or more photopolymerizable compounds, and a photopolymerization initiator, wherein the binder polymer has an acid value of 165-195 mgKOH/g and the photopolymerizable compounds include a (meth)acrylate having a phthalic acid skeleton.

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等に用いられるレジスト材料として、感光性樹脂組成物、及び、支持フィルム上に感光性樹脂組成物を用いて形成された層（以下、「感光層」ともいう）を備える感光性エレメントが広く用いられている。 In the field of manufacturing printed wiring boards, as a resist material used for etching treatment or plating treatment, a photosensitive resin composition and a layer formed on a support film using the photosensitive resin composition (hereinafter, "" A photosensitive element having a "photosensitive layer") is 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 through 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 photocurable 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 photocurable 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JP-A-2009-0031777 特開２０１３－０６１５５６号公報Japanese Unexamined Patent Publication No. 2013-061556
　生産効率の向上のために、各プロセスの短縮、短時間化が要求されている。例えば剥離時間の短縮が、解像度等の要求と同時に要求されている。感光性樹脂組成物には、未露光部の現像性が高く、優れた解像度を有するレジストパターンを形成することが求められるだけでなく、レジストパターンを剥離除去するために、光硬化部の剥離特性に優れることが求められる。 In order to improve production efficiency, shortening and shortening of each process are required. For example, shortening of peeling time is required at the same time as demand for resolution and the like. The photosensitive resin composition is required not only to form a resist pattern having high developability in the unexposed portion and having excellent resolution, but also to peel off the resist pattern in order to peel off the photocured portion. Is required to be excellent.
　本開示は、現像性、解像度及び剥離特性のバランスに優れ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 provides a photosensitive resin composition having an excellent balance of developability, resolution and peeling characteristics, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board. The purpose is.
　本開示に係る感光性樹脂組成物は、スチレン又はスチレン誘導体に由来する構造単位を有する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、上記バインダーポリマーの酸価が、１６５～１９５ｍｇＫＯＨ／ｇであり、上記光重合性化合物が、フタル酸骨格を有する（メタ）アクリレートを含む。 The photosensitive resin composition according to the present disclosure contains a binder polymer having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator, and the acid value of the binder polymer is determined. It is 165 to 195 mgKOH / g, and the photopolymerizable compound contains a (meth) acrylate having a phthalic acid skeleton.
　上記バインダーポリマーは、スチレン又はスチレン誘導体に由来する構造単位を４１～６４質量％有してよい。上記バインダーポリマーの重量平均分子量は、５０００～３７０００であってよい。 The binder polymer may have 41 to 64% by mass of structural units derived from styrene or a styrene derivative. The weight average molecular weight of the binder polymer may be 5000 to 37000.
　上記フタル酸骨格を有する（メタ）アクリレートの含有量は、バインダーポリマー及び光重合性化合物の総量１００質量部に対して、１～３０質量部であってよい。また、上記光重合開始剤は、アクリジン系光重合開始剤を含んでよい。 The content of the (meth) acrylate having a phthalic acid skeleton may be 1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. Moreover, the said photopolymerization initiator may contain an acridine-based photopolymerization initiator.
　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と、上記基板から、感光層の光硬化部以外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 irradiating a predetermined portion of the photosensitive layer with active light. A step of forming a photocurable portion and a step of removing at least a part of the photosensitive layer other than the photocurable portion from the substrate are provided.
　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。上記プリント配線板の製造方法は、エッチング処理又はめっき処理の後に、上記光硬化部を除去する工程を更に備えてよい。 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. The method for manufacturing a printed wiring board may further include a step of removing the photocurable portion after the etching treatment or the plating treatment.
　本開示によれば、現像性、解像度及び剥離特性のバランスに優れ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 having an excellent balance of developability, resolution and peeling characteristics, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board are described. 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。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。 The present disclosure will be described in detail below. 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.
　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。 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.
　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, the "solid content" is a non-volatile content 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 vaporization, and also includes those that are liquid, candy-like, and wax-like 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、スチレン又はスチレン誘導体に由来する構造単位を有する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。上記バインダーポリマーの酸価は、１６５～１９５ｍｇＫＯＨ／ｇであり、上記光重合性化合物は、フタル酸系化合物を含む。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 having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator. The acid value of the binder polymer is 165 to 195 mgKOH / g, and the photopolymerizable compound contains a phthalate compound. Hereinafter, each component used in the photosensitive resin composition in the present embodiment will be described in detail.
（（Ａ）バインダーポリマー）
　（Ａ）バインダーポリマー（以下、「（Ａ）成分」ともいう）は、スチレン又はスチレン誘導体に由来する構造単位を有することで、感光性樹脂組成物から形成される感光層の剥離特性を向上することができる。（Ａ）成分は、例えば、スチレン又はスチレン誘導体を含む重合性単量体をラジカル重合させることにより製造することができる。 ((A) Binder polymer)
The binder polymer (A) (hereinafter, also referred to as “component (A)”) has a structural unit derived from styrene or a styrene derivative, thereby improving the peeling property of the photosensitive layer formed from the photosensitive resin composition. be able to. The component (A) can be produced, for example, by radically polymerizing a polymerizable monomer containing styrene or a styrene derivative.
　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。（Ａ）成分におけるスチレン又はスチレン誘導体に由来する構造単位の含有量は、（Ａ）成分の全体量を基準として、４１～６４質量％、４１～６０質量％、４２～５５質量％、又は４３～５０質量％であってもよい。この含有量が４１質量％以上では、解像度がより向上する傾向があり、６４質量％以下では、現像時に剥離片が大きくなることを抑制でき、剥離に要する時間の長時間化が抑えられる傾向がある。 The styrene derivative is a polymerizable compound in which the hydrogen atom in the α-position or aromatic ring of styrene such as vinyltoluene and α-methylstyrene is substituted. The content of the structural unit derived from styrene or the styrene derivative in the component (A) is 41 to 64% by mass, 41 to 60% by mass, 42 to 55% by mass, or 43 based on the total amount of the component (A). It may be up to 50% by mass. When this content is 41% by mass or more, the resolution tends to be further improved, and when it is 64% by mass or less, it is possible to suppress the peeling piece from becoming large during development, and the time required for peeling tends to be long. is there.
　（Ａ）成分は、アルカリ現像性の見地から、カルボキシ基を有してもよい。カルボキシ基を有する（Ａ）成分は、例えば、カルボキシ基を有する重合性単量体と、スチレン又はスチレン誘導体を含む重合性単量体とをラジカル重合させることにより製造することができる。 The component (A) may have a carboxy group from the viewpoint of alkali developability. The component (A) having a carboxy group can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxy group and a polymerizable monomer containing styrene or a styrene derivative.
　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。 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-cyanosilic acid, itaconic acid, crotonic acid, and propiolic 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.
　アルカリ現像性とアルカリ耐性とをバランスよく向上させる点から、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の含有量は、（Ａ）成分の全体量を基準として、１０～５０質量％、１５～４０質量％、又は２０～３５質量％であってもよい。この含有量が１０質量％以上ではアルカリ現像性が向上する傾向があり、５０質量％以下ではアルカリ耐性に優れる傾向がある。 The content of the structural unit derived from the polymerizable monomer having a carboxy group is 10 to 50% by mass based on the total amount of the component (A) from the viewpoint of improving the alkali developability and the alkali resistance in a well-balanced manner. , 15-40% by mass, or 20-35% by mass. When this content is 10% by mass or more, the alkali developability tends to be improved, and when it is 50% by mass or less, the alkali resistance tends to be excellent.
　（Ａ）成分は、スチレン又はスチレン誘導体及びカルボキシ基を有する重合性単量体以外の重合性単量体（以下、「（他の重合性単量体」ともいう）に由来する構造単位を更に有してもよい。他の重合性単量体としては、例えば、ジアセトンアクリルアミド等のアクリルアミド、アクリロニトリル、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類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸ベンジルエステル、（メタ）アクリル酸テトラヒドロフルフリルエステル、（メタ）アクリル酸ジメチルアミノエチルエステル、（メタ）アクリル酸ジエチルアミノエチルエステル、（メタ）アクリル酸グリシジルエステル、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、が挙げられる。他の重合性単量体は、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 (A) further includes a structural unit derived from a polymerizable monomer other than styrene or a styrene derivative and a polymerizable monomer having a carboxy group (hereinafter, also referred to as “(other polymerizable monomer”)). Other polymerizable monomers include, for example, acrylamides such as diacetoneacrylamide, ethers of vinyl alcohols such as acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid alkyl esters, and (meth) acrylic acid alkyl esters. ) Acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-tri Fluoroethyl (meth) acrylate and 2,2,3,3-tetrafluoropropyl (meth) acrylate can be mentioned. Other polymerizable monomers may be used alone or in combination of two or more. Can be done.
　（Ａ）成分は、可塑性を向上する点から、（メタ）アクリル酸アルキルエステルに由来する構造単位を有してもよい。（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸プロピルエステル、（メタ）アクリル酸ブチルエステル、（メタ）アクリル酸ペンチルエステル、（メタ）アクリル酸ヘキシルエステル、（メタ）アクリル酸ヘプチルエステル、（メタ）アクリル酸オクチルエステル、（メタ）アクリル酸２－エチルヘキシルエステル、（メタ）アクリル酸ノニルエステル、（メタ）アクリル酸デシルエステル、（メタ）アクリル酸ウンデシルエステル、及び（メタ）アクリル酸ドデシルエステルが挙げられる。 The component (A) may have a structural unit derived from the (meth) acrylic acid alkyl ester from the viewpoint of improving the plasticity. Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid pentyl. Esters, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl Examples thereof include esters, (meth) acrylic acid undecyl esters, and (meth) acrylic acid dodecyl esters.
　（Ａ）成分の酸価は、１６５～１９５ｍｇＫＯＨ／ｇであり、現像性、解像度及び剥離特性のバランスをより向上する点から、１７０～１９５ｍｇＫＯＨ／ｇ、１７５～１９３ｍｇＫＯＨ／ｇ、又は１８０～１９０ｍｇＫＯＨ／ｇであってもよい。 The acid value of the component (A) is 165 to 195 mgKOH / g, and 170 to 195 mgKOH / g, 175 to 193 mgKOH / g, or 180 to 190 mgKOH / g from the viewpoint of further improving the balance between developability, resolution and peeling characteristics. It may be g.
　（Ａ）成分の重量平均分子量（Ｍｗ）は、５０００～３７０００、８０００～３６０００、１００００～３５０００、又は１５０００～３３０００であってもよい。（Ａ）成分のＭｗが５０００以上では、光硬化部の耐現像液性が優れる傾向にあり、３７０００以下では、未露光部の現像時間が長くなるのを抑えられる傾向にある。（Ａ）成分は、分散度（重量平均分子量／数平均分子量）が１．０～３．０、又は１．０～２．０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。 The weight average molecular weight (Mw) of the component (A) may be 5000 to 37000, 8000 to 36000, 10000 to 35000, or 15000 to 33000. When the Mw of the component (A) is 5000 or more, the developer resistance of the photocurable portion tends to be excellent, and when it is 37,000 or less, the development time of the unexposed portion tends to be suppressed from becoming long. The component (A) may have a dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0 or 1.0 to 2.0. The resolution tends to improve as the degree of dispersion decreases.
　本明細書におけ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 and the number average molecular weight in the present specification are values measured by gel permeation chromatography (GPC) and converted using standard polystyrene as a standard sample.
　（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 binder polymers can be mentioned.
　（Ａ）成分の含有量は、（Ａ）成分及び後述する（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 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) described later. It may be 60 parts by mass. When the content of the component (A) is within this range, the strength of the photocurable portion of the photosensitive layer becomes better.
（（Ｂ）光重合性化合物）
　（Ｂ）光重合性化合物（以下、「（Ｂ）成分」ともいう）は、フタル酸骨格を有する（メタ）アクリレートを含むことで、レジストパターンの解像度及び硬化後の剥離特性をバランスよく向上させることができる。 ((B) Photopolymerizable compound)
The (B) photopolymerizable compound (hereinafter, also referred to as “component (B)”) contains a (meth) acrylate having a phthalic acid skeleton to improve the resolution of the resist pattern and the peeling characteristics after curing in a well-balanced manner. be able to.
　フタル酸骨格を有する（メタ）アクリレートとしては、例えば、γ－クロロ－β－ヒドロキシプロピル－β’－（メタ）アクリロイルオキシエチル－ｏ－フタレート、β－ヒドロキシエチル－β’－（メタ）アクリロイルオキシエチル－ｏ－フタレート、及びβ－ヒドロキシプロピル－β’－（メタ）アクリロイルオキシエチル－ｏ－フタレートが挙げられる。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－フタレートは、ＦＡ－ＭＥＣＨ（日立化成株式会社）として商業的に入手可能である。 Examples of the (meth) acrylate having a phthalate skeleton include γ-chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate and β-hydroxyethyl-β'-(meth) acryloyloxy. Ethyl-o-phthalate and β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate can be mentioned. γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (Hitachi Kasei Co., Ltd.).
　フタル酸骨格を有する（メタ）アクリレートの含有量は、（Ａ）成分及び（Ｂ）成分の総量１００質量部に対して、１～３０質量部、２～２５質量部、５～２０質量部、又は８～１５質量部であってもよい。フタル酸骨格を有する（メタ）アクリレートの含有量がこの範囲内であると、剥離特性がより良好となる。 The content of the (meth) acrylate having a phthalic acid skeleton is 1 to 30 parts by mass, 2 to 25 parts by mass, 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Alternatively, it may be 8 to 15 parts by mass. When the content of the (meth) acrylate having a phthalic acid skeleton is within this range, the peeling property becomes better.
　（Ｂ）成分は、フタル酸骨格を有する（メタ）アクリレート以外の光重合性化合物（以下、「他の光重合性化合物」ともいう）を更に含んでよい。他の光重合性化合物としては、エチレン性不飽和結合を有する化合物を用いることができる。他の光重合性化合物は、１種を単独で又は２種以上を組み合わせて用いてもよい。 The component (B) may further contain a photopolymerizable compound (hereinafter, also referred to as “another photopolymerizable compound”) other than the (meth) acrylate having a phthalic acid skeleton. As the other photopolymerizable compound, a compound having an ethylenically unsaturated bond can be used. Other photopolymerizable compounds may be used alone or in combination of two or more.
　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。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。 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. Examples of the photopolymerizable compound having an α, β-unsaturated carbonyl group include α, β-unsaturated carboxylic acid ester of polyhydric alcohol, bisphenol type (meth) acrylate, and α, β-unmodified compound containing a glycidyl group. 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. Acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra Examples include (meth) acrylates and (meth) acrylate compounds having a skeleton derived from dipentaerythritol or pentaerythritol. "EO modification" means that it has a block structure of ethylene oxide (EO) group, and "PO modification" means that it has 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 an EO group and a PO group, the EO group and the PO group may be continuously present in blocks 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（日立化成株式会社製）、ＦＡ－０２４Ｍ（日立化成株式会社製）、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 Hitachi Kasei Co., Ltd.), FA-024M (manufactured by Hitachi Kasei Co., Ltd.), and NK Ester HEMA-9P (Shin-Nakamura Chemical Industry Co., Ltd.). Made by the company).
　（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 a (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) acryloxitetraethylene 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 EO-modified urethane di (meth) acrylate products 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. It 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, and 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) acryloxipolyethoxy) 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（日立化成株式会社）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- (methacryloxypentaethoxy) phenyl) propane include BPE-500 (Shin Nakamura Chemical Industry Co., Ltd.) and FA-321M (Hitachi Kasei 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 nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, and nonylphenoxynonaethyleneoxy. Examples thereof include acrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.
（（Ｃ）光重合開始剤）
　（Ｃ）光重合開始剤（以下、「（Ｃ）成分」ともいう）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。 ((C) Photopolymerization Initiator)
The (C) photopolymerization initiator (hereinafter, also referred to as “component (C)”) is not particularly limited as long as the component (B) can be polymerized, and the photopolymerization initiator that is usually used is used. It can be selected as appropriate. 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, acridine type, phenylglycine Examples thereof include photopolymerization initiators such as radicals and coumarins.
　（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. 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 acrydin-based photopolymerization initiator include 9-phenylacrine, 9- (p-methylphenyl) acrydin, 9- (m-methylphenyl) acrydin, 9- (p-chlorophenyl) acrydin, and 9- (m-). Chlorophenyl) acrydin, 9-aminoacrine, 9-dimethylaminoacrine, 9-diethylaminoacrine, 9-pentylaminoacrine, 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'-diphenylbimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o) -Chlorophenyl) -diphenylbimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -bimidazole, 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 components (A) and (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.
（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 includes dyes, photocolorants, thermal color inhibitors, plasticizers, pigments, fillers, defoaming agents, flame retardants, adhesion imparting agents, and leveling, if necessary. 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 dyes 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 components (A) and (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 for a schematic cross-sectional view of an example thereof. And other layers such as a 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 is excellent in 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 suppress a decrease in resolution when exposure is performed 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 further include 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 fish eye 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 formed. 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, and bar coating.
　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 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、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 it 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又は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 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.
　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、めっき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 resist pattern forming method described later. Above all, from the viewpoint of resolution, it is suitable for application to a manufacturing method for forming a conductor pattern by plating.
［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光硬化部以外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 includes (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), and ii) At least a part (predetermined part) of the photosensitive layer is irradiated with active light to form a photocurable portion (exposure step), and (iii) at least a part other than the photocurable portion from the substrate. A step (development step) for removing the above-mentioned light is provided, and other steps may be included if necessary. The resist pattern can be said to be a photocured product pattern of the photosensitive resin composition and also 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 of 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, a laminate composed of a substrate, a photosensitive layer, and a support, and these are laminated in this order can be obtained. The substrate is not particularly limited, but usually a circuit-forming substrate having 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 active light, the portion irradiated with the active light 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 of active light rays through 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, 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, or the like. Those that effectively emit 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 photosensitive layer other than the photocurable portion 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, it is developed 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 developing solution 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 carbonates or bicarbonates of lithium, sodium, potassium or ammonium; potassium phosphate, sodium phosphate and the like. Alkali metal phosphates; Alkali 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。 Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, a dilute solution of 0.1 to 5% by mass sodium hydroxide, 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－ブチロラクトン等が挙げられる。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 coated 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、過酸化水素系エッチング液等が挙げられる。 On the other hand, in the etching process, the resist pattern formed on the substrate is used as a mask, and the conductor layer provided on the substrate is etched and removed to form the conductor pattern. The method of etching 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 alkali 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。この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 by, for example, using 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 mass% sodium hydroxide aqueous solution, a 1 to 10 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 coated 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 production of a single-layer printed wiring board but also to the production of a multilayer printed wiring board, and also to the production of a printed wiring board having a small diameter through hole or the like. 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（Ａ－１））
　メタクリル酸２４ｇ、メタクリル酸メチル２６ｇ、スチレン３５ｇ、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))
Solution a was prepared by mixing 24 g of methacrylic acid, 26 g of methyl methacrylate, 35 g of styrene, 0.02 g of 4-methoxyphenol, and 0.7 g of azobisisobutyronitrile. 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、メタクリル酸５ｇ、及びスチレン１０ｇ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。 48 g of propylene glycol monomethyl ether, 40 g of toluene, 5 g of methacrylic acid, and 10 g of styrene are put into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, and nitrogen gas is blown into the flask. While stirring at 80 ° C. for 30 minutes, a mixed solution was obtained.
　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 continuing stirring, 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）及び（Ａ－３））
　重合性単量体を表１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）及び（Ａ－３）の溶液を得た。 (Binder polymers (A-2) and (A-3))
The binder polymer (A-2) and (A-2) and (in the same manner as in obtaining a solution of the binder polymer (A-1), except that the polymerizable monomer was used in the mass ratio shown in the table 1 are used. A solution of A-3) 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ＴＨＦ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 THF 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－Ｒ４２０、Ｇｅｌｐａｃｋ　ＧＬ－Ｒ４３０及びＧｅｌｐａｃｋ　ＧＬ－Ｒ４４０（日立化成株式会社製、カラム仕様：１０．７ｍｍφ×３００ｍｍ）
溶離液：テトラヒドロフラン（以下、「ＴＨＦ」ともいう）
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－３３００型ＲＩ（株式会社日立製作所製） (GPC condition)
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Columns: Gelpack GL-R420, Gelpack GL-R430 and Gelpack GL-R440 (manufactured by Hitachi Kasei Co., Ltd., column specifications: 10.7 mmφ x 300 mm)
Eluent: tetrahydrofuran (hereinafter also referred to as "THF")
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-3300 type RI (manufactured by Hitachi, Ltd.)
（酸価）
　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)
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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［感光性樹脂組成物］
　表２に示す配合量（質量部）の各成分と、溶剤（メタノール、トルエン、アセトン）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２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 photosensitive resin compositions of Examples and Comparative Examples were prepared by mixing each component in the blending amount (part by mass) shown in Table 2 with a solvent (methanol, toluene, acetone). The blending amount of the binder polymer shown in Table 2 is the mass of the non-volatile component (solid content).
　表２に示す各成分の詳細は、以下のとおりである。
（（Ｂ）光重合性化合物）
ＦＡ－３２１Ｍ：２，２－ビス（４－（メタクリロキシペンタエトキシ）フェニル）プロパン（日立化成株式会社）
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）
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）
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（日立化成株式会社）
（（Ｃ）光重合開始剤）
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）
Ｎ－ＰＧ：Ｎ－フェニルグリシン（常州強力電子新材料株式会社）
（光発色剤）
ＬＣＶ：ロイコクリスタルバイオレット（山田化学工業株式会社）
ＴＰＳ：トリブロモフェニルスルホン（常州強力電子新材料株式会社）
（密着付与剤）
ＳＦ－８０８Ｈ：カルボキシベンゾトリアゾール、５－アミノ－１Ｈ－テトラゾール及びメトキシプロパノールの混合物（サンワ化成株式会社）
（染料）
ＭＫＧ：マラカイトグリーン（大阪有機化学工業株式会社） Details of each component shown in Table 2 are as follows.
((B) Photopolymerizable compound)
FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (Hitachi Kasei Co., Ltd.)
M2200: Ethoxylated bisphenol A dimethacrylate (EO average 20 mol denaturation) (manufactured by Miwon)
BPE-200: Ethoxylated bisphenol A dimethacrylate (EO average 4 mol denaturation) (Shin Nakamura Chemical Industry Co., Ltd.)
FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (Hitachi Kasei Co., Ltd.)
((C) Photopolymerization Initiator)
9-PA: 9-Phenyl Acridine (Joshu Strong Electronics New Materials Co., Ltd.)
N-PG: N-Phenylglycine (Joshu Strong Electronics New Materials Co., Ltd.)
(Photo color former)
LCV: Leuco Crystal Violet (Yamada Chemical Co., Ltd.)
TPS: Tribromophenyl sulfone (Joshu Strong Electronics New Materials Co., Ltd.)
(Adhesion imparting agent)
SF-808H: Mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (Sanwa Kasei Co., Ltd.)
(dye)
MKG: Malachite Green (Osaka Organic Chemical Industry 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 container 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.
（積層体）
　銅箔（厚み：３５μｍ）をガラス繊維強化エポキシ樹脂層の両面に積層した銅張積層板（日立化成株式会社製、商品名「ＭＣＬ－Ｅ－６７」）を水洗、酸洗及び水洗後、空気流で乾燥した。次いで、銅張積層板を８０℃に加温し、感光性エレメントを銅張積層板の銅表面に積層した。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０．４ＭＰａの圧着圧力、１．０ｍ／分のロール速度で行った。こうして、銅張積層板と感光層と支持体とがこの順に積層された積層体を得た。 (Laminate)
A copper-clad laminate (manufactured by Hitachi Kasei Co., Ltd., trade name "MCL-E-67") in which copper foil (thickness: 35 μm) is laminated on both sides of a glass fiber reinforced epoxy resin layer is washed with water, pickled and washed with water, and then air. It was dried in the stream. Next, the copper-clad laminate was heated to 80 ° C., and the photosensitive element was laminated on the copper surface of the copper-clad laminate. Lamination was carried out using a heat roll at 110 ° C. at a crimping pressure of 0.4 MPa and a roll speed of 1.0 m / min on the substrate while removing the protective layer. In this way, a laminate in which the copper-clad laminate, the photosensitive layer, and the support were laminated in this order was obtained.
（光感度）
　積層体の支持体上に、ネガマスクとして濃度領域０．００～２．００、濃度ステップ０．０５、タブレットの大きさ２０ｍｍ×１８７ｍｍ、各ステップの大きさが３ｍｍ×１２ｍｍである日立４１段ステップタブレット（日立化成株式会社製）を載置した。次いで、半導体レーザを光源とした波長４０５ｎｍのＤＬＰ露光機（日立ビアメカニクス株式会社製、商品名「ＤＥ－１ＵＨ」）を用いて、所定のエネルギー量で感光層を露光した。 (Light sensitivity)
Hitachi 41-step step tablet with a concentration range of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm x 187 mm, and a step size of 3 mm x 12 mm as a negative mask on the support of the laminate. (Made by Hitachi Kasei Co., Ltd.) was placed. Next, the photosensitive layer was exposed with a predetermined amount of energy using a DLP exposure machine (manufactured by Hitachi Via Mechanics, Ltd., trade name “DE-1UH”) having a wavelength of 405 nm using a semiconductor laser as a light source.
　露光後、支持体を剥離し、３０℃の１質量％炭酸ナトリウム水溶液を最短現像時間（未露光部分が除去される最短時間）の２倍の時間でスプレーし、未露光部分を除去した（現像処理）。現像処理後、基板上に形成された光硬化膜のステップタブレットの段数が１５．０段となるエネルギー量（ｍＪ／ｃｍ２）を求め、感光性樹脂組成物の光感度を評価した。この数値が小さいほど、光感度が高いことを示す。 After the exposure, the support was peeled off, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed for twice the shortest development time (the shortest time for removing the unexposed portion) to remove the unexposed portion (development). processing). After the development treatment, the amount of energy (mJ / cm 2 ) at which the number of steps of the photocurable film step tablet formed on the substrate was 15.0 was determined, and the light sensitivity of the photosensitive resin composition was evaluated. The smaller this value is, the higher the light sensitivity is.
（解像度）
　積層体の支持体上に、解像度評価用ネガとしてガラスクロムタイプのフォトツール（解像度ネガ：ライン幅／スペース幅がｘ／ｘ（ｘ：１～３０、単位：μｍ）の配線パターンを有するもの）を使用し、日立４１段ステップタブレットの現像後の残存ステップ段数が１７．０となるエネルギー量で露光を行った。露光後、光感度の評価と同様に、感光層の現像処理を行った。 (resolution)
A glass chrome type photo tool as a negative for resolution evaluation on the support of the laminate (resolution negative: having a wiring pattern with a line width / space width of x / x (x: 1 to 30, unit: μm)) The exposure was performed with an amount of energy such that the number of remaining step steps after development of the Hitachi 41-step step tablet was 17.0. After the exposure, the photosensitive layer was developed in the same manner as in the evaluation of the light sensitivity.
　現像処理後、スペース部分（未露光部分）がきれいに除去され、かつライン部分（露光部分）が蛇行又は欠けを生じることなく形成されたレジストパターンのうち、最も小さいスペース幅の値により、解像度を評価した。この数値が小さいほど、解像度及び密着性が良好であることを意味する。 After the development process, the resolution is evaluated by the value of the smallest space width among the resist patterns formed in which the space portion (unexposed portion) is cleanly removed and the line portion (exposed portion) does not meander or chip. did. The smaller this value is, the better the resolution and adhesion are.
（剥離特性）
　４０ｍｍ×５０ｍｍの硬化膜を形成する描画パターンを用いて、積層体の感光層に対して露光を行った。露光後、支持体を剥離し、光感度の評価と同様の現像処理を行うことにより、基板上に４０ｍｍ×５０ｍｍの硬化膜が形成された試験片を作製した。 (Peeling characteristics)
The photosensitive layer of the laminate was exposed using a drawing pattern forming a cured film of 40 mm × 50 mm. After the exposure, the support was peeled off, and a development process similar to the evaluation of light sensitivity was performed to prepare a test piece having a cured film of 40 mm × 50 mm formed on the substrate.
　試験片を室温で一昼夜放置した後、５０℃の３．０質量％水酸化ナトリウム水溶液に試験片を浸漬し、硬化膜が基板から完全に剥離するまでの時間（秒）を計測した。また、剥離片のサイズを目視で観察した。剥離時間が短く、剥離片サイズが小さいほど剥離特性が良好であることを意味する。 After leaving the test piece at room temperature for 24 hours, the test piece was immersed in a 3.0 mass% sodium hydroxide aqueous solution at 50 ° C., and the time (seconds) until the cured film was completely peeled off from the substrate was measured. In addition, the size of the peeled piece was visually observed. The shorter the peeling time and the smaller the peeling piece size, the better the peeling characteristics.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　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. 　スチレン又はスチレン誘導体に由来する構造単位を有する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、
    　前記バインダーポリマーの酸価が、１６５～１９５ｍｇＫＯＨ／ｇであり、
    　前記光重合性化合物が、フタル酸骨格を有する（メタ）アクリレートを含む、感光性樹脂組成物。     It contains a binder polymer having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator.
    The acid value of the binder polymer is 165 to 195 mgKOH / g.
    A photosensitive resin composition in which the photopolymerizable compound contains a (meth) acrylate having a phthalic acid skeleton.
  2. 　前記バインダーポリマーが、前記スチレン又はスチレン誘導体に由来する構造単位を４１～６４質量％有する、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 binder polymer has 41 to 64% by mass of structural units derived from the styrene or the styrene derivative.
  3. 　前記バインダーポリマーの重量平均分子量が、５０００～３７０００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 5000 to 37000.
  4. 　前記フタル酸骨格を有する（メタ）アクリレートの含有量が、前記バインダーポリマー及び前記光重合性化合物の総量１００質量部に対して、１～３０質量部である、請求項１～３のいずれか一項に記載の感光性樹脂組成物。 Any one of claims 1 to 3, wherein the content of the (meth) acrylate having a phthalic acid skeleton is 1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. The photosensitive resin composition according to the section.
  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と、
    　前記基板から、前記感光層の前記光硬化部以外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 a predetermined portion of the photosensitive layer with active light to form a photocurable portion, and
    A step of removing at least a part of the photosensitive layer other than the photocurable portion 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、前記光硬化部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 photocurable portion after the etching treatment or the plating treatment.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006154556A (en) * 2004-11-30 2006-06-15 Fuji Photo Film Co Ltd Pattern forming material, and pattern forming apparatus and pattern forming method
JP2013092675A (en) * 2011-10-26 2013-05-16 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, method of forming resist pattern, and method of making printed wiring board
WO2013125429A1 (en) * 2012-02-20 2013-08-29 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
JP2014182305A (en) * 2013-03-19 2014-09-29 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, method for manufacturing substrate with resist pattern, and method for manufacturing printed wiring board
WO2015156292A1 (en) * 2014-04-10 2015-10-15 日立化成株式会社 Photosensitive resin composition, photosensitive element, and method for manufacturing processed glass substrate
WO2016017596A1 (en) * 2014-07-28 2016-02-04 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for producing resist pattern and method for manufacturing printed wiring board
JP2017181663A (en) * 2016-03-29 2017-10-05 日立化成株式会社 Photosensitive resin composition
JP2018084591A (en) * 2015-03-23 2018-05-31 日立化成株式会社 Photosensitive resin composition, photosensitive element, mask material for sand blast, and method for processing the surface of target material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006154556A (en) * 2004-11-30 2006-06-15 Fuji Photo Film Co Ltd Pattern forming material, and pattern forming apparatus and pattern forming method
JP2013092675A (en) * 2011-10-26 2013-05-16 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, method of forming resist pattern, and method of making printed wiring board
WO2013125429A1 (en) * 2012-02-20 2013-08-29 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
JP2014182305A (en) * 2013-03-19 2014-09-29 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, method for manufacturing substrate with resist pattern, and method for manufacturing printed wiring board
WO2015156292A1 (en) * 2014-04-10 2015-10-15 日立化成株式会社 Photosensitive resin composition, photosensitive element, and method for manufacturing processed glass substrate
WO2016017596A1 (en) * 2014-07-28 2016-02-04 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for producing resist pattern and method for manufacturing printed wiring board
JP2018084591A (en) * 2015-03-23 2018-05-31 日立化成株式会社 Photosensitive resin composition, photosensitive element, mask material for sand blast, and method for processing the surface of target material
JP2017181663A (en) * 2016-03-29 2017-10-05 日立化成株式会社 Photosensitive resin composition

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