WO2014148273A1 - Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for manufacturing printed wiring board - Google Patents

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

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Publication number
WO2014148273A1
WO2014148273A1 PCT/JP2014/055866 JP2014055866W WO2014148273A1 WO 2014148273 A1 WO2014148273 A1 WO 2014148273A1 JP 2014055866 W JP2014055866 W JP 2014055866W WO 2014148273 A1 WO2014148273 A1 WO 2014148273A1
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mass
photosensitive resin
component
meth
resin composition
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PCT/JP2014/055866
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French (fr)
Japanese (ja)
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徹文 藤井
昌孝 櫛田
充 石
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日立化成株式会社
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033Non-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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers
    • C09D125/02Homopolymers or copolymers of hydrocarbons
    • C09D125/04Homopolymers or copolymers of styrene
    • C09D125/06Polystyrene
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings
    • H05K3/285Permanent coating compositions
    • H05K3/287Photosensitive compositions
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01Dielectrics
    • H05K2201/0137Materials
    • H05K2201/0145Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus 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
    • H05K3/06Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061Etching masks
    • H05K3/064Photoresists

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive element, a method for manufacturing a substrate with a resist pattern, and a method for manufacturing a printed wiring board.
  • Photosensitive elements having the following are widely used.
  • a printed wiring board is formed by laminating the photosensitive element on a circuit-forming substrate, exposing the photosensitive resin layer in a pattern, and then removing the unexposed portion with a developer to form a resist pattern, followed by an etching process. Alternatively, after the plating process is performed to form a circuit on the substrate, the cured portion that is the exposed portion is removed from the substrate and removed.
  • an alkaline developer such as an aqueous solution of sodium carbonate or an aqueous solution of sodium hydrogen carbonate is mainly used from the viewpoint of environment and safety.
  • the unexposed portion of the photosensitive resin layer is removed from the substrate by the development pressure with these developers and the spray pressure of water washing. Therefore, the photosensitive resin composition is required to be capable of forming a cured film (resist pattern) having excellent tent reliability (tenting property) that is not damaged by the spray pressure of development and washing after exposure. . Further, it is necessary to improve the adhesion so that the cured film does not peel from the substrate due to the spray pressure of development and washing with water.
  • a laser direct imaging (LDI) method has been adopted as a method for directly drawing a pattern produced by CAD (computer-aided design) without using a mask and using laser light.
  • CAD computer-aided design
  • the resist material used in the LDI method which is required to be used with a smaller exposure amount, requires alkali resistance at a low exposure amount and a low degree of cure. Often used.
  • a compound having a rigid skeleton deteriorates the tenting property, a resist having high throughput, high resolution and high tenting property by the LDI method has not been developed so far.
  • the present invention has an object to provide a photosensitive resin composition that can form a resist pattern even at a low exposure amount and is excellent in tent reliability, resolution, and adhesion of a formed cured film. To do. Moreover, it aims at providing the manufacturing method of the photosensitive element using the said photosensitive resin composition, the board
  • component a binder polymer
  • component a photopolymerizable compound
  • component a photopolymerization initiator
  • component a compound having (poly) ethylene oxide [— (C 2 H 4 O) n —: n is 1 or more] as a structural unit
  • the content of the structural unit in the total solid content of the polymer is 10% by mass to 60% by mass
  • the content of the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] relative to the total solid content of the component (A) and the component (B) is 25% by
  • ⁇ 3> a support film; A photosensitive resin layer that is a coating film of the photosensitive resin composition according to ⁇ 1> or ⁇ 2>, provided on the support film; A photosensitive element.
  • ⁇ 5> A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to ⁇ 4>.
  • the present invention it is possible to form a resist pattern even at a low exposure amount, and it is possible to provide a photosensitive resin composition excellent in tent reliability, resolution, and adhesion of a formed cured film. It becomes. Moreover, it becomes possible to provide the photosensitive element using the said photosensitive resin composition, the manufacturing method of a board
  • (meth) acrylic acid means at least one of “acrylic acid” and “methacrylic acid”
  • (meth) acrylate means at least one of “acrylate” and “methacrylate” corresponding thereto.
  • (meth) acryloxy means at least one of “acryloxy” and “methacryloxy”.
  • (poly) ethylene oxide” or “(poly) oxyethylene” means at least one kind of polyoxyethylene group in which an oxyethylene group and two or more ethylene groups are connected by an ether bond
  • Propylene oxide” or “(poly) oxypropylene” means at least one polyoxypropylene group in which an oxypropylene group and two or more propylene groups are linked by an ether bond.
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • laminate indicates that the layers are stacked, and two or more layers may be bonded, or two or more layers may be detachable.
  • the photosensitive resin composition of the present embodiment comprises (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: (poly). And a compound having ethylene oxide [— (C 2 H 4 O) n —: n is 1 or more] as a structural unit (hereinafter sometimes referred to as “(poly) ethylene oxide compound”).
  • Component (A) a structural unit derived from at least one selected from the group consisting of (A1) styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative (hereinafter referred to as “structural unit”)
  • the content of the structural unit (A1) in the total solid content of the binder polymer is 10% by mass to 60% by mass.
  • the content of the structural unit of the (poly) ethylene oxide [— (C 2 H 4 O) n —] relative to the total solid content of the component (A) and the component (B) is 25% by mass or more. is there.
  • the component (D): (poly) ethylene oxide compound may also serve as the component (A), the component (B) or the component (C), and as components other than the components (A) to (C) It may be contained.
  • the said photosensitive resin composition may further contain another component as needed.
  • a resist pattern can be formed even at a low exposure amount.
  • the photosensitive resin composition can be formed and has excellent tent reliability, resolution and adhesion of the cured film to be formed. Below, each component is demonstrated in detail.
  • the photosensitive resin composition contains at least one binder polymer as the component (A).
  • the binder polymer has a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and has a binder polymer solid content.
  • the content of the structural unit (A1) in the total amount is 10% by mass to 60% by mass.
  • At least one of the binder polymers has a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative.
  • a structural unit derived from at least one selected from styrene and styrene derivatives it is preferable to have a structural unit derived from at least one selected from styrene and styrene derivatives.
  • the content of the structural unit (A1) in the binder polymer is 10% by mass to 60% by mass in the total solid content of the binder polymer from the viewpoint of improving both adhesion and peeling properties.
  • the lower limit of the content rate of (A1) is 13 mass% or more, It is more preferable that it is 15 mass%, It is still more preferable that it is 17 mass% or more.
  • the upper limit of the content of (A1) is more preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and 25% by mass or less. It is particularly preferred. When the content is 10% by mass or more, the adhesion tends to be improved.
  • the peeling piece refers to a piece generated when peeling a resist pattern composed of a cured product of the photosensitive resin composition.
  • styrene derivative examples include polymerizable styrene derivatives substituted at the ⁇ -position or aromatic ring, such as ⁇ -methylstyrene, vinyltoluene, and p-chlorostyrene.
  • benzyl (meth) acrylate derivatives include 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4-t-butylbenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, Examples include 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, and 4-chlorobenzyl (meth) acrylate.
  • At least one of the (A) binder polymer may be referred to as a structural unit derived from (A2) alkyl (meth) acrylate (the alkyl group has 1 to 20 carbon atoms) (hereinafter referred to as “structural unit (A2)”). It is preferable to have The alkyl group in the alkyl (meth) acrylate may be linear or branched. Examples of the alkyl (meth) acrylate include compounds represented by the following general formula (I).
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group having 1 to 20 carbon atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 4 in the general formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, undecyl group, dodecyl group and structural isomers thereof.
  • the alkyl group having 1 to 20 carbon atoms represented by R 4 may have a substituent. Examples of the substituent include a hydroxyl group, an epoxy group, and a halogen atom. When the alkyl group having 1 to 20 carbon atoms represented by R 4 has a substituent, the number of substituents and the substitution position are not particularly limited.
  • the alkyl group in the alkyl (meth) acrylate preferably has 1 to 20 carbon atoms, more preferably 5 to 20 carbon atoms from the viewpoint of further improving tenting properties, and the number of carbon atoms. More preferably, it is 8-14.
  • Examples of the compound represented by the general formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
  • the content of the structural unit (A2) in the total mass of the binder polymer is 1% by mass to 70% by mass from the viewpoint of adhesion, resolution, and developability. It is preferably 30% by mass to 65% by mass, and more preferably 45% by mass to 60% by mass.
  • the content is 1% by mass or more, the tenting property of the cured film is further improved, and when the content is 70% by mass or less, the resolution and adhesion are further improved.
  • At least one of the binder polymers preferably has a carboxy group from the viewpoint of alkali developability.
  • the binder polymer containing a carboxy group can be produced, for example, by radical polymerization using a polymerizable monomer having a carboxy group.
  • structural unit (A3) a structural unit derived from a polymerizable monomer having a carboxy group.
  • 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 ( (Meth) acrylic acid derivatives; maleic acid; maleic acid derivatives such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc. (Meth) acrylic acid is preferable, and methacrylic acid is more preferable.
  • the content of the structural unit (A3) is 12% by mass to 50% by mass in the total mass of the binder polymer from the viewpoint of the balance between alkali developability and developer resistance.
  • the content is more preferably 15% by mass to 35% by mass, and further preferably 15% by mass to 30% by mass.
  • the binder polymer may contain other structural units other than the above (A1) to (A3).
  • the other structural unit may be a structural unit derived from the following polymerizable monomer.
  • the polymerizable monomer include acrylamides such as diacetone acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; and organic acid derivatives such as maleic anhydride. These can be used alone or in combination of two or more.
  • the content of other structural units in the total mass of the binder polymer is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoints of adhesion, resolution, and developability. It is more preferable not to contain (0.5 mass% or less). That is, the content of the total amount of the structural units (A1), (A2), and (A3) in the total solid content of the binder polymer is preferably 90% by mass or more, and preferably 95% by mass or more. More preferably, it is more preferably 99.5% by mass or more.
  • a binder polymer is obtained by polymerizing the monomer corresponding to each structural unit.
  • the polymerization method include radical polymerization.
  • each structural unit may be randomly contained in the copolymer such as a so-called random copolymer, or some specific unit such as a block copolymer. It may be a copolymer in which structural units exist in a localized manner.
  • Each structural unit may be a single type or a plurality of types.
  • a binder polymer having the structural units (A1), (A2) and (A3) may be used, or at least of the binder polymer having the structural unit (A1) and the structural units (A2) and (A3). You may use together the binder polymer which has one side.
  • the binder polymer having the structural unit (A1) may further have at least one of the structural units (A2) and (A3).
  • binder polymer that does not have any of the structural units (A1), (A2), and (A3) may be used in combination.
  • binder polymers are not particularly limited as long as they are soluble in an alkaline aqueous solution and can form a film.
  • acrylic resins (however, those not including the structural unit (A1), (A2) or (A3)), epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins are listed. It is done. Of these, acrylic resins are preferred from the viewpoint of alkali developability. These can be used alone or in combination of two or more.
  • the content of the structural unit (A1) in the total amount of binder polymer solids is 10% by mass to 60% by mass.
  • the lower limit of the content rate of (A1) is 13 mass% or more, It is more preferable that it is 15 mass%, It is still more preferable that it is 17 mass% or more.
  • the upper limit of the content of (A1) is more preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and 25% by mass or less. It is particularly preferred.
  • the content of the other binder polymer in the total amount of the binder polymer solid content is preferably 10% by mass or less, and more preferably 5% by mass or less. It is more preferable that other binder polymers are not substantially contained (0.5% by mass or less), and it is particularly preferable that other binder polymers are not contained.
  • the weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 30,000 to 200,000, from the viewpoint of the balance between developer resistance and alkali developability. More preferably, it is from 1,000 to 100,000.
  • the weight average molecular weight in this specification is a value measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene, and the measurement conditions are the same as in the examples.
  • the acid value of the binder polymer is preferably 120 mgKOH / g to 200 mgKOH / g, and more preferably 150 mgKOH / g to 170 mgKOH / g.
  • the binder polymer as component (A) can be used singly or in combination of two or more.
  • a binder polymer in the case of using two or more types in combination two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion, etc. Is mentioned.
  • the degree of dispersion of the binder polymer is obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).
  • the content of the binder polymer as component (A) is preferably 30 parts by mass to 80 parts by mass, and 40 parts by mass to 75 parts by mass with respect to 100 parts by mass of the total solid content of components (A) and (B). More preferably, it is more preferably 50 parts by mass to 70 parts by mass. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.
  • the photosensitive resin composition contains at least one photopolymerizable compound as the component (B).
  • the photopolymerizable compound as component (B) is not particularly limited, and can be appropriately selected from commonly used photopolymerizable compounds.
  • Examples of the photopolymerizable compound include compounds having a photopolymerizable unsaturated double bond.
  • examples of the photopolymerizable compound include polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polyethylene polypropylene glycol di (meth) acrylate; trimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) Bisphenol A-based (meth) acrylate compounds such as propane and 2,2-bis (4-((meth) acryloxypolyethyleneoxypolypropyleneoxy) phenyl) propane; ⁇ -chloro- ⁇ -hydro Xylpropyl- ⁇ '-(meth) acryloyloxyethylene-o-phthalate,
  • the photopolymerizable compound includes at least one selected from the group consisting of bisphenol A (meth) acrylate compounds and polyalkylene glycol poly (meth) acrylates. It is more preferable to use at least one bisphenol A-based (meth) acrylate compound and at least one polyalkylene glycol poly (meth) acrylate in combination, and 2,2-bis (4-((meth) acryloxy) More preferably, at least one of polyethyleneoxy) phenyl) propane and at least one of polyethylene glycol poly (meth) acrylate are used in combination.
  • Examples of 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethyleneoxy) phenyl) propane, 2,2- And bis (4-((meth) acryloxypentaethyleneoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethyleneoxy) phenyl) propane, and the like.
  • 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane commercially available ones include, for example, EO-modified bisphenol A dimethacrylate (of oxyethylene groups in one molecule).
  • the average value of the total number of structural units is 2.6) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “BPE-100”), EO-modified bisphenol A dimethacrylate (total number of structural units of oxyethylene groups in one molecule) (Average value of 10) ((product name “BPE-500” manufactured by Shin-Nakamura Chemical Co., Ltd.) or (product name “FA-321M” manufactured by Hitachi Chemical Co., Ltd.))), EO-modified bisphenol A dimethacrylate (product name “FA-321M”)
  • the average value of the total number of structural units of oxyethylene groups in one molecule is 30) (made by Shin-Nakamura Chemical Co., Ltd., product name “B
  • the component (B) it is preferable to include at least one compound having two or more photopolymerizable unsaturated double bonds in one molecule.
  • the content of the compound having two or more photopolymerizable unsaturated double bonds in one molecule in the total solid content of component (B) is: 75% by mass or more is preferable.
  • the content of the compound having two or more photopolymerizable unsaturated double bonds in one molecule is 75% by mass or more, so that tenting properties, resolution, and There is a tendency for adhesion to improve.
  • the content of the component (B): photopolymerizable compound in the photosensitive resin composition is 20 parts by mass to 70 parts by mass in 100 parts by mass of the total solid content of the component (A) and the component (B). preferable.
  • the content of the component (B) is preferably 20 parts by mass or more, and 25 parts by mass in 100 parts by mass of the solid content of the component (A) and the component (B). Part or more is more preferable, and 30 parts by mass or more is still more preferable.
  • the content of component (B) is 70 parts by mass or less in 100 parts by mass of the total solid content of component (A) and component (B).
  • 60 parts by mass or less is more preferable, 55 parts by mass or less is more preferable, and 50 parts by mass or less is particularly preferable.
  • the said photosensitive resin composition contains at least 1 sort (s) of a photoinitiator as (C) component.
  • a photoinitiator There is no restriction
  • the component (C) preferably contains an acridine compound having one or two acridinyl groups in one molecule. That is, the component (C) is composed of an acridine compound having two acridinyl groups (hereinafter also referred to as “(C1) compound”) and an acridine compound having one acridinyl group (hereinafter also referred to as “(C2) compound”). It is preferable that at least one compound selected from the group consisting of:
  • Examples of the (C1) compound include acridine compounds represented by the following general formula (II).
  • R 3 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. From the viewpoint of more reliably obtaining the effect exhibited by the photosensitive resin composition, R 3 is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 14 carbon atoms.
  • Examples of the compound represented by the general formula (II) include 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4-di (9-acridinyl). Butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di (9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9-acridinyl) dodecane, 14-di (9-acridinyl) tetradecane, 1,16-di (9-acridinyl) hexadecane, 1,18-di (9-
  • an acridine compound in which R 3 in the formula (II) is a heptylene group (for example, product name “N-1717” manufactured by ADEKA Corporation) ) Is preferably included.
  • the content of the compound (C1) is from the viewpoint of sensitivity, resolution, and adhesion, and the components (A) and (B)
  • the total solid content of 100 parts by mass is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, and 1 part by mass to 5 parts by mass. More preferred is 1 to 3 parts by mass. There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.
  • Examples of the (C2) compound include acridine compounds represented by the following general formula (III).
  • R 4 represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms.
  • m represents an integer of 0 to 5. When m is 2 or more, the plurality of R 4 may be the same or different.
  • Examples of the acridine compound represented by the general formula (III) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p-chlorophenyl) acridine, Examples include 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine and 9-pentylaminoacridine. These are used individually by 1 type or in combination of 2 or more types.
  • the content of the (C2) compound is (A) and (B) from the viewpoint of sensitivity, resolution and adhesion.
  • the amount is preferably from 0.1 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, more preferably from 1 to 5 parts by weight, based on 100 parts by weight of the total solid content of the components. More preferred is 1 to 3 parts by mass. There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.
  • the photosensitive resin composition may contain a photopolymerization initiator other than the compound (C1) and the compound (C2) as the component (C).
  • photopolymerization initiators other than the (C1) compound and the (C2) compound include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4 ′.
  • Aromatic ketone compounds such as 2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2 -Phenylanthraquinone, 2,3-diphenylanthraquinone, Quinone compounds such as chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl1,4-naphthoquinone, 2,
  • the 2,4,5-triarylimidazole dimer is a symmetric compound in which the aryl group substituents of the two 2,4,5-triarylimidazoles constituting the dimer are the same. They may be different or asymmetrical compounds.
  • the content is (A) from the viewpoint of sensitivity and internal photocurability. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the total solid content of the component and component (B), and More preferably, it is 2 to 5 parts by mass.
  • the content of the component (C) is 0.01 parts by mass to 20 parts with respect to 100 parts by mass of the total solid content of the components (A) and (B) from the viewpoints of sensitivity, adhesion, and internal photocurability.
  • the mass is preferably 0.05 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and still more preferably 0.1 parts by mass to 5 parts by mass.
  • the photosensitive resin composition contains at least one compound having (poly) ethylene oxide [— (C 2 H 4 O) n —: n is 1 or more] as a structural unit as the component (D).
  • the (poly) ethylene oxide compound as component (D) may be used alone or in combination of two or more.
  • Component (D): The (poly) ethylene oxide compound may also serve as component (A), component (B) or component (C), and is contained as a component other than components (A) to (C). May be.
  • the (poly) ethylene oxide compound also serves as the component (A): binder polymer
  • examples include those containing structural units derived from (poly) ethylene oxide mono (meth) acrylate or derivatives thereof.
  • the (poly) ethylene oxide compound also serves as the component (B): photopolymerizable compound, for example, 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane, polyethylene glycol poly ( And (meth) acrylate.
  • the proportion of the (poly) ethylene oxide [— (C 2 H 4 O) n —] structural unit in one molecule is preferably 60% by mass or more. More preferably, it is 70 to 90% by mass.
  • trimethylolpropane polyethylene ether tri (meth) acrylate, pentaerythritol propane polyethylene ether tetra (meth) acrylate and the like are preferable. More preferably, trimethylolpropane polyethylene ether tri (meth) acrylate, pentaerythritol propane polyethylene ether tetra (meth) acrylate, etc., which is a structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] Is a compound having a proportion (EO content) in a molecule of 70% by mass to 90% by mass.
  • the photosensitive resin composition using this compound further improves the resolution and tenting properties of the cured film.
  • the content of the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] with respect to the total solid content of the component (A) and the component (B) is 25% by mass or more, It is preferably 25% by mass to 40% by mass.
  • the content of the (poly) ethylene oxide compound is 25% by mass to 35% by mass in the total solid content of the photosensitive resin composition. More preferably, the content is 25% by mass to 30% by mass.
  • the photosensitive resin composition of the present embodiment if necessary, a dye such as malachite green, Victoria pure blue, brilliant green, methyl violet; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, Photochromic agent such as o-chloroaniline; Thermochromic inhibitor; Plasticizer such as p-toluenesulfonamide; Pigment; Filler; Antifoaming agent; Flame retardant; Adhesion imparting agent; Leveling agent; Other additives such as an inhibitor, a polymerization inhibitor, a fragrance, an imaging agent, and a thermal crosslinking agent may be further included.
  • a dye such as malachite green, Victoria pure blue, brilliant green, methyl violet; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline
  • Photochromic agent such as o-chloroaniline
  • Thermochromic inhibitor Plasticizer such as
  • the content can be appropriately selected according to the purpose and the like.
  • it can be contained in an amount of about 0.01 to 20 parts by mass per 100 parts by mass of the total solid content of the component (A) and the component (B). These can be used individually by 1 type or in combination of 2 or more types.
  • the photosensitive resin composition may further contain at least one organic solvent.
  • Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. These may be used alone or in combination of two or more. Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a solid content of about 30% by mass to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”).
  • the photosensitive resin composition can be used for forming a photosensitive resin layer of a photosensitive element described later. That is, another embodiment of the present invention is the use of the photosensitive resin composition for a photosensitive element. Moreover, the said photosensitive resin composition can be used for the manufacturing method of the board
  • the photosensitive element of this invention has a support film and the photosensitive resin layer which is a coating film of the said photosensitive resin composition provided on the said support film.
  • the said photosensitive element may have other layers, such as a protective film, as needed.
  • FIG. 1 shows an embodiment of the photosensitive element of the present invention.
  • the support film 2, the photosensitive resin layer 4 which is the coating film of the said photosensitive resin composition, and the protective film 6 are laminated
  • the photosensitive element 10 can be obtained as follows, for example. On the support film 2, the coating liquid which is the said photosensitive resin composition containing an organic solvent is apply
  • stacked on the photosensitive resin layer 4 is obtained.
  • the photosensitive element 10 does not necessarily include the protective film 6.
  • a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.
  • the thickness of the support film 2 is preferably 1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, and still more preferably 1 ⁇ m to 30 ⁇ m.
  • the support film 2 can be prevented from being broken when the support film 2 is peeled from the photosensitive resin layer 4.
  • the fall of the resolution when exposing the photosensitive resin layer 4 through the support film 2 is suppressed because it is 100 micrometers or less.
  • the protective film 6 preferably has a smaller adhesive force to the photosensitive resin layer 4 than the adhesive force of the support film 2 to the photosensitive resin layer 4.
  • a low fisheye film is preferred.
  • fish eye means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
  • the protective film 6 a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.
  • polyester such as polyethylene terephthalate, polypropylene, and polyethylene
  • examples of commercially available products include polypropylene films such as Alfan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as PS series such as PS-25 manufactured by Teijin Limited. It is done.
  • the protective film 6 may be the same as the support film 2.
  • the thickness of the protective film 6 is preferably 1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, and even more preferably 1 ⁇ m to 30 ⁇ m.
  • the protective film 6 can be prevented from being broken when the photosensitive resin layer 4 and the support film 2 are laminated on the substrate while peeling off the protective film 6.
  • it is 100 ⁇ m or less, it is excellent in handleability and inexpensiveness.
  • the photosensitive element of this embodiment can be manufactured as follows, for example.
  • Coating solution prepared by dissolving at least (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) photopolymerization initiator, and (D) component: (poly) ethylene oxide compound in the organic solvent.
  • Application of the coating solution onto the support film 2 can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater.
  • the 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 is preferably performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
  • the thickness of the photosensitive resin layer 4 in the photosensitive element 10 can be appropriately selected depending on the intended use.
  • the thickness after drying is preferably 1 ⁇ m to 200 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to 50 ⁇ m. More preferably.
  • the thickness is 1 ⁇ m or more, industrial coating becomes easy.
  • the thickness is 200 ⁇ m or less, the sensitivity and the photocurability of the resist bottom tend to be sufficiently obtained.
  • the photosensitive element 10 may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
  • an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
  • the intermediate layers described in JP-A-2006-098982 can also be applied in the present invention.
  • the form of the obtained photosensitive element 10 is not particularly limited.
  • it may be in the form of a sheet, or may be in the form of a roll wound around a core.
  • the material of the core include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and plastics such as ABS resin (acrylonitrile-butadiene-styrene copolymer).
  • end face protection it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance.
  • As a packaging method it is preferable to wrap and package in a black sheet with low moisture permeability.
  • the photosensitive element 10 can be suitably used, for example, in a method for manufacturing a substrate with a resist pattern described later.
  • a resist pattern can be formed on a substrate using the photosensitive resin composition.
  • the method for manufacturing a substrate with a resist pattern according to this embodiment includes (i) a lamination step of laminating a photosensitive resin layer formed using the photosensitive resin composition on the substrate, and (ii) the photosensitive resin layer. An exposure step of irradiating at least a part of the region with actinic rays to cure the region; and (iii) removing an unexposed portion other than the region of the photosensitive resin layer from the substrate. And a developing step for forming a resist pattern composed of a cured product of the photosensitive resin composition.
  • substrate with a resist pattern may have another process further as needed.
  • the photosensitive resin layer formed using the photosensitive resin composition is laminated
  • a substrate circuit forming substrate
  • the photosensitive resin layer 4 is laminated on the substrate after the protective film 6 is removed and then the photosensitive resin layer 4 of the photosensitive element 10. This is performed by pressure-bonding to the substrate while heating. Thereby, the laminated body provided with the board
  • This lamination operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability.
  • the photosensitive resin layer and / or the substrate is preferably heated at a temperature of 70 ° C. to 130 ° C.
  • the pressure bonding is preferably performed at a pressure of about 0.1 MPa to 1.0 MPa (about 1 kgf / cm 2 to 10 kgf / cm 2 ). These conditions are appropriately selected as necessary. Note that if the photosensitive resin layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance. be able to.
  • (Ii) Exposure Step In the exposure step, at least a part of the photosensitive resin layer 4 formed on the substrate as described above is irradiated with actinic rays, so that the exposed portion irradiated with actinic rays is light. Curing forms a latent image. Examples of the actinic ray irradiation include a method of irradiating actinic rays in an image form through a negative or positive mask pattern.
  • the support film 2 existing on the photosensitive resin layer 4 is transparent to the active light, the active light can be irradiated through the support film 2, and the support film 2 can be applied to the active light.
  • the photosensitive resin layer 4 is irradiated with actinic rays after the support film 2 is removed.
  • the light source of actinic light is not particularly limited, and conventionally known light sources such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid state lasers such as YAG lasers, A semiconductor laser, a gallium nitride blue-violet laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, a laser direct drawing exposure method may be used.
  • the photosensitive resin composition of the present embodiment can be suitably used for a direct drawing exposure method. That is, one preferred embodiment of the present invention is an application of the photosensitive resin composition to a direct drawing exposure method.
  • development step the uncured portion of the photosensitive resin layer 4 is removed from the circuit-forming substrate by development, so that the photosensitive resin layer 4 is a cured product obtained by photocuring. A pattern is formed on the substrate.
  • development methods include wet development and dry development, and wet development is widely used.
  • development is performed by a known development method using a developer corresponding to the photosensitive resin composition.
  • the developing method include a method using a dipping method, a battle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, a high-pressure spray method is suitable. You may develop by combining these 2 or more types of methods.
  • the constitution of the developer is appropriately selected according to the constitution of the photosensitive resin composition.
  • alkaline aqueous solution aqueous developer, organic solvent developer and the like can be mentioned.
  • An alkaline aqueous solution is safe and stable when used as a developer, and has good operability.
  • Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like.
  • Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1% by mass to 5% by mass of sodium tetraborate is preferred.
  • the pH of the alkaline aqueous solution is preferably in the range of 9-11.
  • the temperature of the alkaline aqueous solution is adjusted according to the alkali developability of the photosensitive resin layer.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
  • the aqueous developer is, for example, a developer composed of water or an alkaline aqueous solution and one or more organic solvents.
  • the base of the alkaline aqueous solution in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 , 3-propanediol, 1,3-diaminopropanol-2, morpholine and the like.
  • the pH of the aqueous developer is preferably as low as possible within the range where development is sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.
  • Organic solvents used in the aqueous developer 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, diethylene glycol monobutyl ether Etc. These are used individually by 1 type or in combination of 2 or more types.
  • the concentration of the organic solvent in the aqueous developer is preferably 2% by mass to 90% by mass.
  • the temperature can be adjusted according to alkali developability.
  • a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.
  • organic solvent developer examples include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone. It is preferable to add water to these organic solvents in an amount of 1 to 20% by mass in order to prevent ignition.
  • organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone. It is preferable to add water to these organic solvents in an amount of 1 to 20% by mass in order to prevent ignition.
  • the resist pattern is further formed by performing heating at about 60 ° C. to 250 ° C. or exposure at about 0.2 J / cm 2 to 10 J / cm 2 as necessary. You may further include the process to harden
  • the method for producing a printed wiring board of the present invention includes a step of etching or plating a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern.
  • a conductor pattern is formed by etching or plating.
  • the manufacturing method of a printed wiring board may include other processes, such as a resist removal process, as needed. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.
  • the conductor layer of the circuit forming substrate not covered with the resist is removed by etching to form a conductor pattern.
  • the etching method is appropriately selected according to the conductor layer to be removed.
  • Etching solutions include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, etc. Among these, ferric chloride solution is used from the viewpoint of good etch factor. It is preferable.
  • the plating process copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the resist, using the resist pattern formed on the substrate as a mask. After the plating process, the cured resist is removed, and the conductor layer covered with the resist is etched to form a conductor pattern.
  • the method of plating treatment may be electrolytic plating treatment or electroless plating treatment.
  • plating treatment examples include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, Examples thereof include gold plating such as soft gold plating.
  • the resist pattern on the substrate is removed.
  • the resist pattern can be removed using, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step.
  • a stronger alkaline aqueous solution for example, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution, or the like is used.
  • a 1% by mass to 10% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is preferably used, and a 1% by mass to 5% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is more preferably used.
  • a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by etching to form a conductor pattern.
  • the etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.
  • the printed wiring board manufacturing method of the present invention can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. .
  • FIG. 2 is a diagram showing a conventional method for manufacturing a multilayer printed wiring board.
  • a multilayer printed wiring board 100A shown in FIG. 2F has a wiring pattern on the surface and inside.
  • the multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating material, a metal foil, and the like, and appropriately forming a wiring pattern by an etching method, a semi-additive method, or the like.
  • an interlayer insulating layer 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 2A).
  • the interlayer insulating layer 103 may be printed with a thermosetting composition using a screen printer or a roll coater, or a film made of the thermosetting composition is prepared in advance, and this film is printed using a laminator. It can also be attached to the surface of the wiring board.
  • an opening 104 is formed using a YAG laser or a carbon dioxide gas laser at a portion that needs to be electrically connected to the outside, and smear (residue) around the opening 104 is removed by a desmear process (FIG. 2B). )reference).
  • a seed layer 105 is formed by an electroless plating method (see FIG. 2C).
  • a photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a resist pattern 106 (see FIG. 2D).
  • a wiring pattern 107 is formed by electrolytic plating, the resist pattern 106 is removed by a stripping solution, and then the seed layer 105 is removed by etching (see FIG. 2E).
  • the multilayer printed wiring board 100A can be manufactured (see FIG. 2F).
  • the photosensitive resin composition of the present embodiment can be suitably used for the production of a printed wiring board. That is, one of the preferred embodiments of the present invention is application of the photosensitive resin composition to the production of a printed wiring board.
  • “Solution a-1” was dropped into the above mixed solution in the flask over 4 hours, and the solution in the flask was kept at 80 ° C. for 2 hours while stirring. Next, a solution obtained by further dissolving 1 g of azobisisobutyronitrile in 100 g of “solution a-1” was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 minutes. Keep warm for hours. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a binder polymer solution as component (A-1).
  • Acetone was added to this binder polymer solution to prepare a non-volatile component (solid content) of 50% by mass.
  • the weight average molecular weight of the binder polymer was 55000.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the weight average molecular weight was 100,000.
  • FA-321M EO-modified bisphenol A dimethacrylate (the average value of the total number of structural units of oxyethylene groups in one molecule is 10) (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D). BPE-100: EO-modified bisphenol A dimethacrylate (the average value of the total number of structural units of oxyethylene groups in one molecule is 2.6). Corresponds to component (B) and also applies to component (D).
  • FA-137M trimethylolpropane polyethylene oxide trimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.) Corresponds to component (B) and also applies to component (D).
  • A-TMPT-3EO Modified trimethylolpropane triacrylate (average of the total number of structural units of oxyethylene groups in one molecule is 3).
  • UA-HCY-19 Urethane reaction product of hexamethylene diisocyanate trimer and polyethylene oxide methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).
  • PDE-400 Polyethylene glycol # 400 dimethacrylate (manufactured by NOF Corporation, product name, average value of the total number of structural units of oxyethylene group is 9).
  • FA-314A Nonylphenoxy polyethylene glycol acrylate (average value of the total number of structural units of oxyethylene group is 4) (product name, manufactured by Hitachi Chemical Co., Ltd.) Corresponds to component (B) and also applies to component (D).
  • M-114 Nonylphenoxypolyethylene glycol acrylate (average value of the total number of structural units of oxyethylene group is 8). Corresponds to component (B) and also applies to component (D).
  • FA-MECH (2-hydroxy-3-chloro) propyl-2-methacryloyloxyethyl phthalate. Corresponds to component (B).
  • UA-13 Urethane reaction product of hexamethylene diisocyanate and polypropylene oxide (poly) ethylene oxide methacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
  • FA-023M Polypropylene oxide, polyethylene oxide dimethacrylate (dipolymethacrylate of (poly) ethylene oxide- (poly) propylene oxide- (poly) ethylene oxide block copolymer) (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
  • FA-024M polypropylene oxide polyethylene oxide dimethacrylate (dimethacrylate of (poly) propylene oxide- (poly) ethylene oxide- (poly) propylene oxide block copolymer) (product name, manufactured by Hitachi Chemical Co., Ltd.) Corresponds to component (B) and also applies to component (D).
  • APG-400 Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Corresponds to component (B).
  • N-1717 1,7-di (9-acridinyl) heptane (product name, manufactured by ADEKA Corporation).
  • 9-PA 9-phenylacridine (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name).
  • component (C) 9-phenylacridine (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name).
  • the “structural unit (A1) content” is at least one selected from the group consisting of styrene or a styrene derivative and benzyl (meth) acrylate or benzyl (meth) acrylate derivative in the binder polymer. It represents the content (% by mass) of the derived structural unit. “Styrene content” represents the content (% by mass) of structural units derived from at least one selected from the group consisting of styrene and styrene derivatives in the total solid mass of the photosensitive resin composition.
  • “BzMA content” is the content of structural units derived from at least one selected from the group consisting of benzyl (meth) acrylate and benzyl (meth) acrylate derivatives in the total solid mass of the photosensitive resin composition. (% By mass).
  • the “EO content” in the upper column of Table 3 and Table 4 represents the content (% by mass) of the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] in each component.
  • the “EO content” in the bottom left column is the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n ⁇ ] relative to the total solid mass of the components (A) and (B). The content (mass%) of is expressed.
  • photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 14 were each applied onto a polyethylene terephthalate film (trade name “G2-16” manufactured by Teijin Limited) having a thickness of 16 ⁇ m, and hot air at 100 ° C. It dried for 10 minutes with the convection type dryer, and formed the photosensitive resin layer whose film thickness after drying is 30 micrometers.
  • a protective film (trade name “NF-13”, manufactured by Tamapoly Co., Ltd.) is laminated on the photosensitive resin layer by roll pressurization, so that a polyethylene terephthalate film (support film), the photosensitive resin layer, and the protective film are protected.
  • Photosensitive elements according to Examples 1 to 11 and Comparative Examples 1 to 14 in which films were laminated in this order were obtained.
  • the laminated substrates for evaluation were respectively prepared by laminating (lamination). Lamination is performed at a speed of 1.5 m / min so that the photosensitive resin layer of each photosensitive element adheres to each copper surface of the substrate while removing the protective film using a 110 ° C. heat roll. It was. Moreover, the heat roll pressure at the time of lamination was 0.4 MPa.
  • the obtained multilayer substrate for evaluation was allowed to cool, and when the temperature reached 23 ° C., a phototool having a step tablet was brought into close contact with the polyethylene terephthalate film (support film) on the surface of the multilayer substrate for evaluation.
  • a 41 step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm ⁇ 187 mm, and a size of each step of 3 mm ⁇ 12 mm was used.
  • the photosensitive resin layer was exposed through a phototool having such a step tablet and a polyethylene terephthalate film. The exposure was performed at an exposure amount of 20 mJ / cm 2 using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor excitation solid laser as a light source.
  • the polyethylene terephthalate film was peeled off from the evaluation laminate substrate to expose the photosensitive resin layer.
  • the exposed photosensitive resin layer was sprayed (developed) with a 1.0% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds to remove unexposed portions.
  • the cured film which consists of hardened
  • the exposure was performed at an exposure amount of 20 mJ / cm 2 using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor excitation solid laser as a light source.
  • the tent reliability was evaluated using a hole breakage number measuring substrate 40 as shown in FIG. 3 manufactured as follows.
  • a copper-clad laminate (trade name MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.) is connected with 3 independent round holes 41 and 3 round holes each with a diameter of 4 mm to 6 mm.
  • the three continuous holes 42 whose intervals were gradually shortened were each produced by a die cutting machine.
  • the burr generated when the round hole 41 and the triple hole 42 were produced was removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was used as the substrate 40 for measuring the number of broken holes. .
  • the obtained substrate for measuring the number of broken holes was heated to 80 ° C., and the protective film was peeled off from the photosensitive element obtained above so that the photosensitive resin layer faced the copper surface.
  • 11 and Comparative Examples 1 to 14 were laminated under the conditions of 120 ° C. and 0.4 MPa, respectively, to produce laminated substrates for tent reliability evaluation.
  • the laminated substrate for tent reliability evaluation is cooled, and when the temperature of the laminated substrate for tent reliability evaluation reaches 23 ° C., a semiconductor-excited solid laser is used as the light source for the polyethylene terephthalate film (support film) surface.
  • the exposure was performed at an exposure amount of 20 mJ / cm 2 using an exposure apparatus (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.).
  • the film was left at room temperature (25 ° C.) for 15 minutes, and then the polyethylene terephthalate film was peeled off from the laminated substrate for tent reliability evaluation, and developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds. After development, the number of broken holes in the three holes was measured, and the deformed tent breaking rate was calculated as the number of broken holes with respect to the number of all three holes, and the tent reliability (%) was evaluated. The higher this number, the higher the tent reliability. The results are shown in Tables 5 and 6.

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Abstract

This photosensitive resin composition contains a binder polymer (component (A)), a photopolymerizable compound (component (B)), a photopolymerization initiator (component (C)), and a compound that has a (poly)ethylene oxide as a structural unit (component (D)). The binder polymer (component (A)) has (A1) a structural unit which is derived from at least one substance that is selected from the group consisting of styrene, styrene derivatives, benzyl (meth)acrylate and benzyl (meth)acrylate derivatives, and the content of the structural unit in the total solid content of the binder polymer is 10-60% by mass. In addition, the content of the (poly)ethylene oxide structural unit relative to the total solid content of the component (A) and the component (B) is 25% by mass or more.

Description

感光性樹脂組成物、感光性エレメント、レジストパターン付き基板の製造方法及びプリント配線板の製造方法Photosensitive resin composition, photosensitive element, method for manufacturing substrate with resist pattern, and method for manufacturing printed wiring board
 本発明は、感光性樹脂組成物、感光性エレメント、レジストパターン付き基板の製造方法及びプリント配線板の製造方法に関する。 The present invention relates to a photosensitive resin composition, a photosensitive element, a method for manufacturing a substrate with a resist pattern, and a method for manufacturing a printed wiring board.
 従来、プリント配線板の製造分野において、エッチング処理、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、及び感光性樹脂組成物を用いて得られる感光性樹脂層と支持体と保護フィルムとを有する感光性エレメントが広く用いられている。 Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition as a resist material used for etching treatment, plating treatment, and the like, and a photosensitive resin layer, a support, and a protective film obtained using the photosensitive resin composition, Photosensitive elements having the following are widely used.
 プリント配線板は、上記感光性エレメントを回路形成用基板上にラミネートし、前記感光性樹脂層をパターン状に露光した後、未露光部を現像液で除去してレジストパターンを形成し、エッチング処理又はめっき処理を施して基板上に回路を形成した後、露光部である硬化部分を基板上から剥離して除去する方法によって製造されている。 A printed wiring board is formed by laminating the photosensitive element on a circuit-forming substrate, exposing the photosensitive resin layer in a pattern, and then removing the unexposed portion with a developer to form a resist pattern, followed by an etching process. Alternatively, after the plating process is performed to form a circuit on the substrate, the cured portion that is the exposed portion is removed from the substrate and removed.
 上記現像液としては、環境性及び安全性の見地から、炭酸ナトリウム水溶液、炭酸水素ナトリウム水溶液等のアルカリ現像液が主流となっている。感光性樹脂層の未露光部分は、これら現像液による現像及び水洗のスプレー圧により、基板から除去される。したがって、感光性樹脂組成物には、露光後、現像及び水洗のスプレー圧によって破損しない、優れたテント信頼性(テンティング性)を有する硬化膜(レジストパターン)を形成可能であることが求められる。また、硬化膜が現像及び水洗のスプレー圧によって基板から剥離しないよう、密着性を高める必要がある。 As the developer, an alkaline developer such as an aqueous solution of sodium carbonate or an aqueous solution of sodium hydrogen carbonate is mainly used from the viewpoint of environment and safety. The unexposed portion of the photosensitive resin layer is removed from the substrate by the development pressure with these developers and the spray pressure of water washing. Therefore, the photosensitive resin composition is required to be capable of forming a cured film (resist pattern) having excellent tent reliability (tenting property) that is not damaged by the spray pressure of development and washing after exposure. . Further, it is necessary to improve the adhesion so that the cured film does not peel from the substrate due to the spray pressure of development and washing with water.
 優れたテント信頼性を有するためには感光性樹脂組成物から形成される硬化膜の柔軟性を高めることが効果的である。しかし、硬化膜の柔軟性を高めると、硬化膜の耐アルカリ性が低下し、解像性が低下する問題がある。 In order to have excellent tent reliability, it is effective to increase the flexibility of the cured film formed from the photosensitive resin composition. However, when the flexibility of the cured film is increased, there is a problem that the alkali resistance of the cured film is lowered and the resolution is lowered.
 特に、最近ではマスクを必要とせず、CAD(computer-aided design)で作製したパターンをレーザー光により直接描画する方法として、LDI(laser direct imaging)方式が採用されている。しかしながら、スループットの観点から、より少ない露光量での使用が求められるLDI方式に用いられるレジスト材料には、低露光量及び低硬化度での耐アルカリ性が要求されるため、剛直な骨格の化合物が使用されることが多い。しかしながら、剛直な骨格の化合物はテンティング性を低下させるため、LDI方式で高スループット、高解像度及び高テンティング性を併せ持つレジストはこれまで開発されなかった。例えば、特開2006-234995号公報、特開2007-122028号公報、国際公開第2008/078483号公報、特開2009-69465号公報、及び国際公開第2010/103918号公報に記載の感光性樹脂組成物を用いた場合でも、改善の余地があった。 In particular, recently, a laser direct imaging (LDI) method has been adopted as a method for directly drawing a pattern produced by CAD (computer-aided design) without using a mask and using laser light. However, from the viewpoint of throughput, the resist material used in the LDI method, which is required to be used with a smaller exposure amount, requires alkali resistance at a low exposure amount and a low degree of cure. Often used. However, since a compound having a rigid skeleton deteriorates the tenting property, a resist having high throughput, high resolution and high tenting property by the LDI method has not been developed so far. For example, the photosensitive resins described in JP-A-2006-234995, JP-A-2007-122028, WO2008 / 078483, JP-A-2009-69465, and WO2010 / 103918. Even when the composition was used, there was room for improvement.
 そこで本発明は、低露光量でもレジストパターンを形成することが可能であり、形成される硬化膜のテント信頼性、解像性及び密着性に優れる感光性樹脂組成物を提供することを目的とする。また、上記感光性樹脂組成物を用いた感光性エレメント、レジストパターン付き基板の製造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。 Therefore, the present invention has an object to provide a photosensitive resin composition that can form a resist pattern even at a low exposure amount and is excellent in tent reliability, resolution, and adhesion of a formed cured film. To do. Moreover, it aims at providing the manufacturing method of the photosensitive element using the said photosensitive resin composition, the board | substrate with a resist pattern, and a printed wiring board.
 前記課題を解決するための具体的手段は以下の通りである。
<1> (A)成分:バインダーポリマーと、
 (B)成分:光重合性化合物と、
 (C)成分:光重合開始剤と、
 (D)成分:(ポリ)エチレンオキサイド〔-(CO)-:nは1以上〕を構造単位として有する化合物と、を含有し、
 前記(A)成分:バインダーポリマーが、(A1)スチレン、スチレン誘導体、ベンジル(メタ)アクリレート及びベンジル(メタ)アクリレート誘導体からなる群より選択される少なくとも1種に由来する構造単位を有し、バインダーポリマーの固形分総量における前記構造単位の含有率が10質量%~60質量%であり、
 前記(A)成分と前記(B)成分の固形分総量に対する、前記(ポリ)エチレンオキサイド〔-(CO)-〕の構造単位の含有率が、25質量%以上である、感光性樹脂組成物。
Specific means for solving the above problems are as follows.
<1> (A) component: a binder polymer,
(B) component: a photopolymerizable compound;
(C) component: a photopolymerization initiator,
(D) component: a compound having (poly) ethylene oxide [— (C 2 H 4 O) n —: n is 1 or more] as a structural unit,
Component (A): The binder polymer has a structural unit derived from at least one selected from the group consisting of (A1) styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and a binder The content of the structural unit in the total solid content of the polymer is 10% by mass to 60% by mass,
The content of the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] relative to the total solid content of the component (A) and the component (B) is 25% by mass or more. Photosensitive resin composition.
<2> 前記(A)バインダーポリマーが、(A2)(メタ)アクリル酸アルキル(アルキル基の炭素数が1~20)に由来する構造単位を含有する、前記<1>に記載の感光性樹脂組成物。 <2> The photosensitive resin according to <1>, wherein the (A) binder polymer contains a structural unit derived from (A2) alkyl (meth) acrylate (the alkyl group has 1 to 20 carbon atoms). Composition.
<3> 支持フィルムと、
 前記支持フィルム上に設けられる、前記<1>又は<2>に記載の感光性樹脂組成物の塗膜である感光性樹脂層と、
 を有する感光性エレメント。
<3> a support film;
A photosensitive resin layer that is a coating film of the photosensitive resin composition according to <1> or <2>, provided on the support film;
A photosensitive element.
<4> 前記<1>又は<2>に記載の感光性樹脂組成物を用いて形成された感光性樹脂層を基板上に積層する積層工程と、
 前記感光性樹脂層の少なくとも一部の領域に活性光線を照射して、前記領域を硬化させる露光工程と、
 前記感光性樹脂層の前記領域以外の未露光部分を前記基板上から除去することにより、前記基板上に、前記感光性樹脂組成物の硬化物で構成されるレジストパターンを形成する現像工程と、
 を有するレジストパターン付き基板の製造方法。
<4> A laminating step of laminating a photosensitive resin layer formed using the photosensitive resin composition according to <1> or <2> on a substrate;
An exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to cure the region;
A developing step of forming a resist pattern composed of a cured product of the photosensitive resin composition on the substrate by removing an unexposed portion other than the region of the photosensitive resin layer from the substrate,
The manufacturing method of the board | substrate with a resist pattern which has this.
<5> 前記<4>に記載の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又はめっきする工程を含む、プリント配線板の製造方法。 <5> A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to <4>.
 本発明によれば、低露光量でもレジストパターンを形成することが可能であり、形成される硬化膜のテント信頼性、解像性及び密着性に優れる感光性樹脂組成物を提供することが可能となる。また、上記感光性樹脂組成物を用いた感光性エレメント、レジストパターン付き基板の製造方法及びプリント配線板の製造方法を提供することが可能となる。 According to the present invention, it is possible to form a resist pattern even at a low exposure amount, and it is possible to provide a photosensitive resin composition excellent in tent reliability, resolution, and adhesion of a formed cured film. It becomes. Moreover, it becomes possible to provide the photosensitive element using the said photosensitive resin composition, the manufacturing method of a board | substrate with a resist pattern, and the manufacturing method of a printed wiring board.
本発明の感光性エレメントの一実施形態を示す端面図である。It is an end view which shows one Embodiment of the photosensitive element of this invention. 本発明の感光性エレメントの仕様箇所を例示する工程図である。It is process drawing which illustrates the specification location of the photosensitive element of this invention. テント信頼性の評価に用いる穴破れ数測定用基板の上面図である。It is a top view of the hole tearing number measuring substrate used for evaluation of tent reliability.
 以下、必要に応じて図面を参照しつつ、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。なお、図面中、同一要素には同一符号を付すこととし、重複する説明は省略する。また、図面の寸法比率は図示の比率に限られるものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.
 本明細書における「(メタ)アクリル酸」とは「アクリル酸」及び「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」とは「アクリレート」及びそれに対応する「メタクリレート」の少なくとも一方を意味し、「(メタ)アクリロキシ」とは「アクリロキシ」及び「メタクリロキシ」の少なくとも一方を意味する。
 また「(ポリ)エチレンオキサイド」又は「(ポリ)オキシエチレン」とは、オキシエチレン基及び2以上のエチレン基がエーテル結合で連結したポリオキシエチレン基の少なくとも1種を意味し、また「(ポリ)プロピレンオキサイド」又は「(ポリ)オキシプロピレン」とは、オキシプロピレン基及び2以上のプロピレン基がエーテル結合で連結したポリオキシプロピレン基の少なくとも1種を意味する。
In this specification, “(meth) acrylic acid” means at least one of “acrylic acid” and “methacrylic acid”, and “(meth) acrylate” means at least one of “acrylate” and “methacrylate” corresponding thereto. And “(meth) acryloxy” means at least one of “acryloxy” and “methacryloxy”.
Further, “(poly) ethylene oxide” or “(poly) oxyethylene” means at least one kind of polyoxyethylene group in which an oxyethylene group and two or more ethylene groups are connected by an ether bond, and “(poly) ") Propylene oxide" or "(poly) oxypropylene" means at least one polyoxypropylene group in which an oxypropylene group and two or more propylene groups are linked by an ether bond.
 本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。また「~」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。更に組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。また、「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が脱着可能であってもよい。 In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . A numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Further, the term “lamination” indicates that the layers are stacked, and two or more layers may be bonded, or two or more layers may be detachable.
<感光性樹脂組成物>
 本実施形態の感光性樹脂組成物は、(A)成分:バインダーポリマーと、(B)成分:光重合性化合物と、(C)成分:光重合開始剤と、(D)成分:(ポリ)エチレンオキサイド〔-(CO)-:nは1以上〕を構造単位として有する化合物(以降「(ポリ)エチレンオキサイド化合物」と称する場合がある)と、を含有する。前記(A)成分:バインダーポリマーが、(A1)スチレン、スチレン誘導体、ベンジル(メタ)アクリレート及びベンジル(メタ)アクリレート誘導体からなる群より選択される少なくとも1種に由来する構造単位(以降「構造単位(A1)」と称する場合がある。)を有し、バインダーポリマーの固形分総量における前記構造単位(A1)の含有率は、10質量%~60質量%である。そして、前記(A)成分と前記(B)成分の固形分総量に対する、前記(ポリ)エチレンオキサイド〔-(CO)-〕の構造単位の含有率が、25質量%以上である。
<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment comprises (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: (poly). And a compound having ethylene oxide [— (C 2 H 4 O) n —: n is 1 or more] as a structural unit (hereinafter sometimes referred to as “(poly) ethylene oxide compound”). Component (A): a structural unit derived from at least one selected from the group consisting of (A1) styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative (hereinafter referred to as “structural unit”) The content of the structural unit (A1) in the total solid content of the binder polymer is 10% by mass to 60% by mass. The content of the structural unit of the (poly) ethylene oxide [— (C 2 H 4 O) n —] relative to the total solid content of the component (A) and the component (B) is 25% by mass or more. is there.
 ここで、(D)成分:(ポリ)エチレンオキサイド化合物は、上記(A)成分、(B)成分又は(C)成分を兼ねていてもよく、(A)~(C)成分以外の成分として含有されていてもよい。前記感光性樹脂組成物は、必要に応じてその他の成分を更に含んでもよい。 Here, the component (D): (poly) ethylene oxide compound may also serve as the component (A), the component (B) or the component (C), and as components other than the components (A) to (C) It may be contained. The said photosensitive resin composition may further contain another component as needed.
 構造単位(A1)を10質量%~60質量%含有するバインダーポリマーを用い、且つ(ポリ)エチレンオキサイドの構造単位の含有率を25質量%以上に調整することで、低露光量でもレジストパターンを形成することが可能であり、形成される硬化膜のテント信頼性、解像性及び密着性に優れる感光性樹脂組成物とすることができる。
 以下では、各成分について詳細に説明する。
By using a binder polymer containing 10% by mass to 60% by mass of the structural unit (A1) and adjusting the content of the structural units of (poly) ethylene oxide to 25% by mass or more, a resist pattern can be formed even at a low exposure amount. The photosensitive resin composition can be formed and has excellent tent reliability, resolution and adhesion of the cured film to be formed.
Below, each component is demonstrated in detail.
〔(A)成分:バインダーポリマー〕
 感光性樹脂組成物は、(A)成分としてバインダーポリマー少なくとも1種を含有する。そして、前記バインダーポリマーは、スチレン、スチレン誘導体、ベンジル(メタ)アクリレート及びベンジル(メタ)アクリレート誘導体からなる群より選択される少なくとも1種に由来する構造単位(A1)を有し、バインダーポリマー固形分総量における構造単位(A1)の含有率は、10質量%~60質量%である。バインダーポリマー固形分総量における構造単位(A1)を特定量含むことにより、バインダーポリマーの柔軟性を維持しながら、硬化物としたときの密着性に優れる。
[(A) component: binder polymer]
The photosensitive resin composition contains at least one binder polymer as the component (A). The binder polymer has a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and has a binder polymer solid content. The content of the structural unit (A1) in the total amount is 10% by mass to 60% by mass. By including the specific amount of the structural unit (A1) in the total amount of the binder polymer solid content, the adhesiveness when cured is excellent while maintaining the flexibility of the binder polymer.
・構造単位(A1)
 バインダーポリマーの少なくとも1種は、スチレン、スチレン誘導体、ベンジル(メタ)アクリレート及びベンジル(メタ)アクリレート誘導体からなる群より選択される少なくとも1種に由来する構造単位(A1)を有する。中でも、スチレン及びスチレン誘導体から選択される少なくとも1種に由来する構造単位を有することが好ましい。
・ Structural unit (A1)
At least one of the binder polymers has a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative. Among these, it is preferable to have a structural unit derived from at least one selected from styrene and styrene derivatives.
 バインダーポリマーにおける構造単位(A1)の含有率は、密着性及び剥離特性を共に良好にする見地から、バインダーポリマーの固形分総量中、10質量%~60質量%である。中でも、(A1)の含有率の下限値は、13質量%以上であることが好ましく、15質量%であることがより好ましく、17質量%以上であることが更に好ましい。(A1)の含有率の上限値は、50質量%以下であることがより好ましく、40質量%以下であることがより好ましく、30質量%以下であることが更に好ましく、25質量%以下であることが特に好ましい。この含有率が10質量%以上であると、密着性が向上する傾向があり、60質量%以下であると、剥離片が大きくなることを抑制し、剥離時間が長くなることを抑制でき、テンティング性が向上する傾向がある。剥離片とは、感光性樹脂組成物の硬化物で構成されるレジストパターンを剥離する際に発生する破片をいう。 The content of the structural unit (A1) in the binder polymer is 10% by mass to 60% by mass in the total solid content of the binder polymer from the viewpoint of improving both adhesion and peeling properties. Especially, it is preferable that the lower limit of the content rate of (A1) is 13 mass% or more, It is more preferable that it is 15 mass%, It is still more preferable that it is 17 mass% or more. The upper limit of the content of (A1) is more preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and 25% by mass or less. It is particularly preferred. When the content is 10% by mass or more, the adhesion tends to be improved. When the content is 60% by mass or less, the peeling piece can be prevented from becoming large, and the peeling time can be prevented from becoming long. Tending to be improved. The peeling piece refers to a piece generated when peeling a resist pattern composed of a cured product of the photosensitive resin composition.
 スチレン誘導体の具体例としては、α-メチルスチレン、ビニルトルエン、p-クロロスチレン等のα-位又は芳香族環において置換されている重合可能なスチレン誘導体を挙げることができる。
 ベンジル(メタ)アクリレート誘導体の具体例としては、4-メチルベンジル(メタ)アクリレート、4-エチルベンジル(メタ)アクリレート、4-t-ブチルベンジル(メタ)アクリレート、4-メトキシベンジル(メタ)アクリレート、4-エトキシベンジル(メタ)アクリレート、4-ヒドロキシベンジル(メタ)アクリレート及び4-クロロベンジル(メタ)アクリレートが挙げられる。
Specific examples of the styrene derivative include polymerizable styrene derivatives substituted at the α-position or aromatic ring, such as α-methylstyrene, vinyltoluene, and p-chlorostyrene.
Specific examples of benzyl (meth) acrylate derivatives include 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4-t-butylbenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, Examples include 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, and 4-chlorobenzyl (meth) acrylate.
・構造単位(A2)
 前記(A)バインダーポリマーの少なくとも1種は、(A2)(メタ)アクリル酸アルキル(アルキル基の炭素数が1~20)に由来する構造単位(以降「構造単位(A2)」と称する場合がある)を有することが好ましい。(メタ)アクリル酸アルキルにおけるアルキル基は、直鎖状又は分岐状のいずれであってもよい。(メタ)アクリル酸アルキルとしては、下記一般式(I)で表される化合物が挙げられる。
・ Structural unit (A2)
At least one of the (A) binder polymer may be referred to as a structural unit derived from (A2) alkyl (meth) acrylate (the alkyl group has 1 to 20 carbon atoms) (hereinafter referred to as “structural unit (A2)”). It is preferable to have The alkyl group in the alkyl (meth) acrylate may be linear or branched. Examples of the alkyl (meth) acrylate include compounds represented by the following general formula (I).
 CH=C(R)-COOR       (I) CH 2 = C (R 3 ) -COOR 4 (I)
 一般式(I)中、Rは水素原子又はメチル基を示し、Rは炭素数1~20のアルキル基を示す。 In general formula (I), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkyl group having 1 to 20 carbon atoms.
 一般式(I)中のRで示される炭素数1~20のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基及びこれらの構造異性体が挙げられる。Rで示される炭素数1~20のアルキル基は、置換基を有していてもよい。前記置換基としては、水酸基、エポキシ基、ハロゲン原子等を挙げることができる。Rで示される炭素数1~20のアルキル基が置換基を有する場合、置換基の数及び置換位置は特に制限されない。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R 4 in the general formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, undecyl group, dodecyl group and structural isomers thereof. The alkyl group having 1 to 20 carbon atoms represented by R 4 may have a substituent. Examples of the substituent include a hydroxyl group, an epoxy group, and a halogen atom. When the alkyl group having 1 to 20 carbon atoms represented by R 4 has a substituent, the number of substituents and the substitution position are not particularly limited.
 前記(メタ)アクリル酸アルキルにおけるアルキル基は、炭素数が1~20であることが好ましく、テンティング性をより向上させる観点から、炭素数が5~20であることがより好ましく、炭素数が8~14であることが更に好ましい。 The alkyl group in the alkyl (meth) acrylate preferably has 1 to 20 carbon atoms, more preferably 5 to 20 carbon atoms from the viewpoint of further improving tenting properties, and the number of carbon atoms. More preferably, it is 8-14.
 一般式(I)で表される化合物としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル等が挙げられる。これらは1種単独で、又は2種以上を組み合わせて用いることができる。 Examples of the compound represented by the general formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
 バインダーポリマーが構造単位(A2)を含む場合、バインダーポリマー総質量中における構造単位(A2)の含有率は、密着性、解像性及び現像性の観点から、1質量%~70質量%であることが好ましく、30質量%~65質量%であることがより好ましく、45質量%~60質量%であることが更に好ましい。この含有率を1質量%以上とすることで硬化膜のテンティング性がより向上し、70質量%以下とすることで解像性及び密着性が更に向上する。 When the binder polymer includes the structural unit (A2), the content of the structural unit (A2) in the total mass of the binder polymer is 1% by mass to 70% by mass from the viewpoint of adhesion, resolution, and developability. It is preferably 30% by mass to 65% by mass, and more preferably 45% by mass to 60% by mass. When the content is 1% by mass or more, the tenting property of the cured film is further improved, and when the content is 70% by mass or less, the resolution and adhesion are further improved.
・構造単位(A3)
 バインダーポリマーの少なくとも1種は、アルカリ現像性の見地から、カルボキシ基を有することが好ましい。カルボキシ基を含むバインダーポリマーは、例えば、カルボキシ基を有する重合性単量体を用いてラジカル重合させることにより製造することができる。以降、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を「構造単位(A3)」と称する場合がある。カルボキシ基を有する重合性単量体としては、(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)アクリル酸等の(メタ)アクリル酸誘導体;マレイン酸;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誘導体;フマル酸、ケイ皮酸、α-シアノケイ皮酸、イタコン酸、クロトン酸、プロピオール酸等が挙げられ、(メタ)アクリル酸が好ましく、メタクリル酸がより好ましい。
・ Structural unit (A3)
At least one of the binder polymers preferably has a carboxy group from the viewpoint of alkali developability. The binder polymer containing a carboxy group can be produced, for example, by radical polymerization using a polymerizable monomer having a carboxy group. Hereinafter, a structural unit derived from a polymerizable monomer having a carboxy group may be referred to as “structural unit (A3)”. 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 ( (Meth) acrylic acid derivatives; maleic acid; maleic acid derivatives such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc. (Meth) acrylic acid is preferable, and methacrylic acid is more preferable.
 バインダーポリマーが構造単位(A3)を含む場合、アルカリ現像性と現像液耐性のバランスの見地から、バインダーポリマーの総質量中、構造単位(A3)の含有率は12質量%~50質量%であることが好ましく、アルカリ現像性により優れる点から、15質量%~35質量%であることがより好ましく、15質量%~30質量%が更に好ましい。 When the binder polymer contains the structural unit (A3), the content of the structural unit (A3) is 12% by mass to 50% by mass in the total mass of the binder polymer from the viewpoint of the balance between alkali developability and developer resistance. In view of superior alkali developability, the content is more preferably 15% by mass to 35% by mass, and further preferably 15% by mass to 30% by mass.
・その他の構造単位
 バインダーポリマーは、上記(A1)~(A3)以外のその他の構造単位を含んでいてもよい。その他の構造単位は、次のような重合性単量体に由来する構造単位であってもよい。上記重合性単量体としては、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化合物;マレイン酸無水物等の有機酸誘導体などが挙げられる。これらは1種単独で、又は2種以上を組み合わせて用いることができる。
Other structural units The binder polymer may contain other structural units other than the above (A1) to (A3). The other structural unit may be a structural unit derived from the following polymerizable monomer. Examples of the polymerizable monomer include acrylamides such as diacetone acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; and organic acid derivatives such as maleic anhydride. These can be used alone or in combination of two or more.
 バインダーポリマー総質量中におけるその他の構造単位の含有率は、密着性、解像性及び現像性の観点から、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、実質含有しない(0.5質量%以下である)ことが更に好ましい。
 つまり、バインダーポリマーの固形分総質量中における、構造単位(A1)、(A2)及び(A3)の総量の含有率は、90質量%以上であることが好ましく、95質量%以上であることがより好ましく、99.5質量%以上であることが更に好ましい。
The content of other structural units in the total mass of the binder polymer is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoints of adhesion, resolution, and developability. It is more preferable not to contain (0.5 mass% or less).
That is, the content of the total amount of the structural units (A1), (A2), and (A3) in the total solid content of the binder polymer is preferably 90% by mass or more, and preferably 95% by mass or more. More preferably, it is more preferably 99.5% by mass or more.
・バインダーポリマー
 バインダーポリマーは、それぞれの構造単位に対応する単量体を重合させることにより得られる。重合方法としては、ラジカル重合を挙げることができる。
 このようにして得られる共重合体において各構造単位は、いわゆるランダム共重合体のように共重合体中にランダムに含まれていてもよく、或いはブロック共重合体のように一部の特定の構造単位が局在して存在する共重合体であってもよい。そして、それぞれの構造単位は、単一種であっても複数種であってもよい。
-Binder polymer A binder polymer is obtained by polymerizing the monomer corresponding to each structural unit. Examples of the polymerization method include radical polymerization.
In the copolymer thus obtained, each structural unit may be randomly contained in the copolymer such as a so-called random copolymer, or some specific unit such as a block copolymer. It may be a copolymer in which structural units exist in a localized manner. Each structural unit may be a single type or a plurality of types.
 バインダーポリマーとしては、構造単位(A1)、(A2)及び(A3)を有するバインダーポリマーを用いてもよいし、構造単位(A1)を有するバインダーポリマーと構造単位(A2)及び(A3)の少なくとも一方を有するバインダーポリマーとを併用してもよい。構造単位(A1)を有するバインダーポリマーは、構造単位(A2)及び(A3)の少なくとも一方を更に有していてもよい。 As the binder polymer, a binder polymer having the structural units (A1), (A2) and (A3) may be used, or at least of the binder polymer having the structural unit (A1) and the structural units (A2) and (A3). You may use together the binder polymer which has one side. The binder polymer having the structural unit (A1) may further have at least one of the structural units (A2) and (A3).
 更に、構造単位(A1)、(A2)及び(A3)のいずれも有しない他のバインダーポリマーを併用してもよい。他のバインダーポリマーとしては、アルカリ水溶液に可溶で皮膜形成可能なものであれば特に制限はない。例えば、アクリル系樹脂(但し、構造単位(A1)、(A2)又は(A3)を含まないもの)、エポキシ系樹脂、アミド系樹脂、アミドエポキシ系樹脂、アルキド系樹脂、及びフェノール系樹脂が挙げられる。中でも、アルカリ現像性の観点から、アクリル系樹脂が好ましい。これらは1種単独で、又は2種以上を組み合わせて用いることができる。 Furthermore, another binder polymer that does not have any of the structural units (A1), (A2), and (A3) may be used in combination. Other binder polymers are not particularly limited as long as they are soluble in an alkaline aqueous solution and can form a film. For example, acrylic resins (however, those not including the structural unit (A1), (A2) or (A3)), epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins are listed. It is done. Of these, acrylic resins are preferred from the viewpoint of alkali developability. These can be used alone or in combination of two or more.
 他のバインダーポリマーを用いる場合でも、バインダーポリマー固形分総量における構造単位(A1)の含有率は、10質量%~60質量%である。中でも、(A1)の含有率の下限値は、13質量%以上であることが好ましく、15質量%であることがより好ましく、17質量%以上であることが更に好ましい。(A1)の含有率の上限値は、50質量%以下であることがより好ましく、40質量%以下であることがより好ましく、30質量%以下であることが更に好ましく、25質量%以下であることが特に好ましい。 Even when other binder polymer is used, the content of the structural unit (A1) in the total amount of binder polymer solids is 10% by mass to 60% by mass. Especially, it is preferable that the lower limit of the content rate of (A1) is 13 mass% or more, It is more preferable that it is 15 mass%, It is still more preferable that it is 17 mass% or more. The upper limit of the content of (A1) is more preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and 25% by mass or less. It is particularly preferred.
 また、他のバインダーポリマーを用いる場合、バインダーポリマー固形分総量における他のバインダーポリマーの含有率は10質量%以下であることが好ましく、5質量%以下であることがより好ましい。他のバインダーポリマーは実質含有しない(0.5質量%以下)ことが更に好ましく、他のバインダーポリマーは含有しないことが特に好ましい。 When using another binder polymer, the content of the other binder polymer in the total amount of the binder polymer solid content is preferably 10% by mass or less, and more preferably 5% by mass or less. It is more preferable that other binder polymers are not substantially contained (0.5% by mass or less), and it is particularly preferable that other binder polymers are not contained.
 バインダーポリマーの重量平均分子量は、耐現像液性及びアルカリ現像性のバランスの見地から、20,000~300,000であることが好ましく、30,000~200,000であることがより好ましく、40,000~100,000であることが更に好ましい。
 なお、本明細書における重量平均分子量は、ゲルパーミエーションクロマトグラフィー法により測定され、標準ポリスチレンを用いて作成した検量線により換算された値であり、測定条件は実施例と同一である。
The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 30,000 to 200,000, from the viewpoint of the balance between developer resistance and alkali developability. More preferably, it is from 1,000 to 100,000.
In addition, the weight average molecular weight in this specification is a value measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene, and the measurement conditions are the same as in the examples.
 バインダーポリマーの酸価は、120mgKOH/g~200mgKOH/gであることが好ましく、150mgKOH/g~170mgKOH/gであることがより好ましい。 The acid value of the binder polymer is preferably 120 mgKOH / g to 200 mgKOH / g, and more preferably 150 mgKOH / g to 170 mgKOH / g.
 (A)成分であるバインダーポリマーは、1種単独で、又は2種以上を組み合わせて用いることができる。2種類以上を組み合わせて用いる場合のバインダーポリマーとしては、異なる共重合成分からなる2種類以上のバインダーポリマー、異なる重量平均分子量の2種類以上のバインダーポリマー、異なる分散度の2種類以上のバインダーポリマー等が挙げられる。なお、バインダーポリマーの分散度とは、重量平均分子量(Mw)を数平均分子量(Mn)で除して得られる。 The binder polymer as component (A) can be used singly or in combination of two or more. As a binder polymer in the case of using two or more types in combination, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion, etc. Is mentioned. The degree of dispersion of the binder polymer is obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).
 (A)成分であるバインダーポリマーの含有量は、(A)成分及び(B)成分の固形分総量100質量部に対して30質量部~80質量部とすることが好ましく、40質量部~75質量部とすることがより好ましく、50質量部~70質量部とすることが更に好ましい。(A)成分の含有量がこの範囲であると、感光性樹脂組成物の塗膜性及び光硬化物の強度がより良好となる。 The content of the binder polymer as component (A) is preferably 30 parts by mass to 80 parts by mass, and 40 parts by mass to 75 parts by mass with respect to 100 parts by mass of the total solid content of components (A) and (B). More preferably, it is more preferably 50 parts by mass to 70 parts by mass. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.
〔(B)成分:光重合性化合物〕
 前記感光性樹脂組成物は、(B)成分として光重合性化合物の少なくとも1種を含む。(B)成分である光重合性化合物は、特に制限されず、通常用いられる光重合性化合物から適宜選択して用いることができる。光重合性化合物として、光重合可能な不飽和二重結合を有する化合物を挙げることができる。
[(B) component: photopolymerizable compound]
The photosensitive resin composition contains at least one photopolymerizable compound as the component (B). The photopolymerizable compound as component (B) is not particularly limited, and can be appropriately selected from commonly used photopolymerizable compounds. Examples of the photopolymerizable compound include compounds having a photopolymerizable unsaturated double bond.
 具体的に、光重合性化合物としては、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ポリエチレンポリプロピレングリコールジ(メタ)アクリレート等のポリアルキレングリコールジ(メタ)アクリレート;トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の多官能(メタ)アクリレート;2,2-ビス(4-((メタ)アクリロキシポリエチレンオキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシポリエチレンオキシポリプロピレンオキシ)フェニル)プロパン等のビスフェノールA系(メタ)アクリレート化合物;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レン-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レン-o-フタレート、β-ヒドロキシプロピル-β’-(メタ)アクリロイルオキシエチレン-o-フタレート等のフタル酸誘導体;(メタ)アクリル酸アルキル;などが挙げられる。 Specifically, examples of the photopolymerizable compound include polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polyethylene polypropylene glycol di (meth) acrylate; trimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) Bisphenol A-based (meth) acrylate compounds such as propane and 2,2-bis (4-((meth) acryloxypolyethyleneoxypolypropyleneoxy) phenyl) propane; γ-chloro-β-hydro Xylpropyl-β '-(meth) acryloyloxyethylene-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethylene-o-phthalate, β-hydroxypropyl-β '-(meth) acryloyloxyethylene- phthalic acid derivatives such as o-phthalate; alkyl (meth) acrylate; and the like.
 これらの中でも、密着性及び解像性の観点から、光重合性化合物としては、ビスフェノールA系(メタ)アクリレート化合物及びポリアルキレングリコールポリ(メタ)アクリレートからなる群より選ばれる少なくとも1種を含むことが好ましく、ビスフェノールA系(メタ)アクリレート化合物の少なくとも1種及びポリアルキレングリコールポリ(メタ)アクリレートの少なくとも1種を併用することがより好ましく、2,2-ビス(4-((メタ)アクリロキシポリエチレンオキシ)フェニル)プロパンの少なくとも1種及びポリエチレングリコールポリ(メタ)アクリレートの少なくとも1種を併用することが更に好ましい。 Among these, from the viewpoint of adhesion and resolution, the photopolymerizable compound includes at least one selected from the group consisting of bisphenol A (meth) acrylate compounds and polyalkylene glycol poly (meth) acrylates. It is more preferable to use at least one bisphenol A-based (meth) acrylate compound and at least one polyalkylene glycol poly (meth) acrylate in combination, and 2,2-bis (4-((meth) acryloxy) More preferably, at least one of polyethyleneoxy) phenyl) propane and at least one of polyethylene glycol poly (meth) acrylate are used in combination.
 2,2-ビス(4-((メタ)アクリロキシポリエチレンオキシ)フェニル)プロパンとしては、例えば、2,2-ビス(4-((メタ)アクリロキシジエチレンオキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシペンタエチレンオキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシペンタデカエチレンオキシ)フェニル)プロパン等が挙げられる。 Examples of 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethyleneoxy) phenyl) propane, 2,2- And bis (4-((meth) acryloxypentaethyleneoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethyleneoxy) phenyl) propane, and the like.
 2,2-ビス(4-((メタ)アクリロキシポリエチレンオキシ)フェニル)プロパンの中でも、商業的に入手可能なものとして、例えば、EO変性ビスフェノールA系ジメタクリレート(一分子中のオキシエチレン基の構造単位の総数の平均値が2.6)(新中村化学工業株式会社製、製品名「BPE-100」)、EO変性ビスフェノールA系ジメタクリレート(一分子中のオキシエチレン基の構造単位の総数の平均値が10)((新中村化学工業株式会社製、製品名「BPE-500」)又は(日立化成株式会社製、製品名「FA-321M」))、EO変性ビスフェノールA系ジメタクリレート(一分子中のオキシエチレン基の構造単位の総数の平均値が30)(新中村化学工業株式会社製、製品名「BPE-1300」)等が挙げられる。これらは1種を単独で又は2種以上を組み合わせて用いることができる。 Among 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane, commercially available ones include, for example, EO-modified bisphenol A dimethacrylate (of oxyethylene groups in one molecule). The average value of the total number of structural units is 2.6) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “BPE-100”), EO-modified bisphenol A dimethacrylate (total number of structural units of oxyethylene groups in one molecule) (Average value of 10) ((product name “BPE-500” manufactured by Shin-Nakamura Chemical Co., Ltd.) or (product name “FA-321M” manufactured by Hitachi Chemical Co., Ltd.))), EO-modified bisphenol A dimethacrylate (product name “FA-321M”) The average value of the total number of structural units of oxyethylene groups in one molecule is 30) (made by Shin-Nakamura Chemical Co., Ltd., product name “BPE-1300”) It is. These can be used individually by 1 type or in combination of 2 or more types.
 (B)成分としては、光重合可能な不飽和二重結合を1分子中に2以上有する化合物を少なくとも1種含むことが好ましい。(B)成分である光重合性化合物を複数組み合わせて使用する場合、(B)成分の固形分総量中、光重合可能な不飽和二重結合を1分子中に2以上有する化合物の含有率は、75質量%以上であることが好ましい。(B)成分の固形分総量中、光重合可能な不飽和二重結合を1分子中に2以上有する化合物の含有率が75質量%以上であることで、テンティング性、解像性、及び密着性が向上する傾向がある。 As the component (B), it is preferable to include at least one compound having two or more photopolymerizable unsaturated double bonds in one molecule. When a plurality of photopolymerizable compounds as component (B) are used in combination, the content of the compound having two or more photopolymerizable unsaturated double bonds in one molecule in the total solid content of component (B) is: 75% by mass or more is preferable. In the total solid content of the component (B), the content of the compound having two or more photopolymerizable unsaturated double bonds in one molecule is 75% by mass or more, so that tenting properties, resolution, and There is a tendency for adhesion to improve.
 前記感光性樹脂組成物における(B)成分:光重合性化合物の含有量は、(A)成分及び(B)成分の固形分総量100質量部中に20質量部~70質量部とすることが好ましい。テント信頼性及び解像性をより向上する点で、(B)成分の含有量は(A)成分及び(B)成分の固形分総量100質量部中に、20質量部以上が好ましく、25質量部以上がより好ましく、30質量部以上が更に好ましい。フィルム性を付与する点及び硬化後のレジスト形状に優れる点で、(B)成分の含有量は、(A)成分及び(B)成分の固形分総量100質量部中に、70質量部以下が好ましく、60質量部以下がより好ましく、55質量部以下が更に好ましく、50質量部以下が特に好ましい。 The content of the component (B): photopolymerizable compound in the photosensitive resin composition is 20 parts by mass to 70 parts by mass in 100 parts by mass of the total solid content of the component (A) and the component (B). preferable. In terms of further improving the tent reliability and resolution, the content of the component (B) is preferably 20 parts by mass or more, and 25 parts by mass in 100 parts by mass of the solid content of the component (A) and the component (B). Part or more is more preferable, and 30 parts by mass or more is still more preferable. In terms of imparting film properties and excellent resist shape after curing, the content of component (B) is 70 parts by mass or less in 100 parts by mass of the total solid content of component (A) and component (B). Preferably, 60 parts by mass or less is more preferable, 55 parts by mass or less is more preferable, and 50 parts by mass or less is particularly preferable.
〔(C)成分:光重合開始剤〕
 前記感光性樹脂組成物は、(C)成分として光重合開始剤の少なくとも1種を含む。光重合開始剤としては特に制限なく、通常用いられる光重合開始剤から適宜選択して用いることができる。中でも(C)成分は一分子中にアクリジニル基を1つ又は2つ有するアクリジン化合物を含むことが好ましい。すなわち、(C)成分は、アクリジニル基を2つ有するアクリジン化合物(以下、「(C1)化合物」ともいう)及びアクリジニル基を1つ有するアクリジン化合物(以下、「(C2)化合物」ともいう)からなる群より選ばれる化合物のうち少なくとも1種を含むことが好ましい。
[(C) component: photopolymerization initiator]
The said photosensitive resin composition contains at least 1 sort (s) of a photoinitiator as (C) component. There is no restriction | limiting in particular as a photoinitiator, It can select from the photoinitiator used normally, and can use it suitably. Among these, the component (C) preferably contains an acridine compound having one or two acridinyl groups in one molecule. That is, the component (C) is composed of an acridine compound having two acridinyl groups (hereinafter also referred to as “(C1) compound”) and an acridine compound having one acridinyl group (hereinafter also referred to as “(C2) compound”). It is preferable that at least one compound selected from the group consisting of:
 (C1)化合物としては、例えば、下記一般式(II)で表されるアクリジン化合物が挙げられる。 Examples of the (C1) compound include acridine compounds represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
 式(II)中、Rは炭素数2~20のアルキレン基、炭素数2~20のオキサジアルキレン基又は炭素数2~20のチオジアルキレン基を示す。感光性樹脂組成物の奏する効果をより確実に得る観点から、Rは炭素数2~20のアルキレン基であることが好ましく、炭素数4~14のアルキレン基であることがより好ましい。 In the formula (II), R 3 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. From the viewpoint of more reliably obtaining the effect exhibited by the photosensitive resin composition, R 3 is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 14 carbon atoms.
 上記一般式(II)で表される化合物としては、例えば、1,2-ジ(9-アクリジニル)エタン、1,3-ジ(9-アクリジニル)プロパン、1,4-ジ(9-アクリジニル)ブタン、1,5-ジ(9-アクリジニル)ペンタン、1,6-ジ(9-アクリジニル)ヘキサン、1,7-ジ(9-アクリジニル)ヘプタン、1,8-ジ(9-アクリジニル)オクタン、1,9-ジ(9-アクリジニル)ノナン、1,10-ジ(9-アクリジニル)デカン、1,11-ジ(9-アクリジニル)ウンデカン、1,12-ジ(9-アクリジニル)ドデカン、1,14-ジ(9-アクリジニル)テトラデカン、1,16-ジ(9-アクリジニル)ヘキサデカン、1,18-ジ(9-アクリジニル)オクタデカン、1,20-ジ(9-アクリジニル)エイコサン等のジ(9-アクリジニル)アルカン;1,3-ジ(9-アクリジニル)-2-オキサプロパン、1,5-ジ(9-アクリジニル)-3-オキサペンタン等のジ(9-アクリジニル)オキサアルカン;1,3-ジ(9-アクリジニル)-2-チアプロパン、1,5-ジ(9-アクリジニル)-3-チアペンタン等のジ(9-アクリジニル)チオアルカン;などが挙げられる。これらは1種単独で又は2種以上を組み合わせて使用される。 Examples of the compound represented by the general formula (II) include 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4-di (9-acridinyl). Butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di (9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9-acridinyl) dodecane, 14-di (9-acridinyl) tetradecane, 1,16-di (9-acridinyl) hexadecane, 1,18-di (9-acridinyl) octadecane, 1,20-di (9-acridinyl) Di (9-acridinyl) alkanes such as Kosan; Di (9-acridinyl) such as 1,3-di (9-acridinyl) -2-oxapropane and 1,5-di (9-acridinyl) -3-oxapentane Oxaalkanes; di (9-acridinyl) thioalkanes such as 1,3-di (9-acridinyl) -2-thiapropane and 1,5-di (9-acridinyl) -3-thiapentane; These are used individually by 1 type or in combination of 2 or more types.
 光感度及び解像性をより良好にする見地から、(C1)化合物として、式(II)中のRがヘプチレン基であるアクリジン化合物(例えば、株式会社ADEKA製、製品名「N-1717」)を含むことが好ましい。 From the standpoint of improving photosensitivity and resolution, as the (C1) compound, an acridine compound in which R 3 in the formula (II) is a heptylene group (for example, product name “N-1717” manufactured by ADEKA Corporation) ) Is preferably included.
 感光性樹脂組成物が、光重合開始剤として(C1)化合物を含む場合、(C1)化合物の含有量は、感度、解像性及び密着性の見地から、(A)成分及び(B)成分の固形分総量100質量部に対して0.1質量部~10質量部であることが好ましく、0.5質量部~5質量部であることがより好ましく、1質量部~5質量部であることが更に好ましく、1質量部~3質量部であることが特に好ましい。この含有量が0.1質量部以上であるとより良好な感度、解像性又は密着性が得られる傾向がある。10質量部以下であるとより良好なレジスト形状を得られる傾向がある。 When the photosensitive resin composition contains the compound (C1) as a photopolymerization initiator, the content of the compound (C1) is from the viewpoint of sensitivity, resolution, and adhesion, and the components (A) and (B) The total solid content of 100 parts by mass is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, and 1 part by mass to 5 parts by mass. More preferred is 1 to 3 parts by mass. There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.
 (C2)化合物としては、例えば、下記一般式(III)で表されるアクリジン化合物が挙げられる。 Examples of the (C2) compound include acridine compounds represented by the following general formula (III).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
 式(III)中、Rはハロゲン原子、アミノ基、カルボキシル基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数1~6のアルキルアミノ基を示す。mは0~5の整数を示す。mが2以上の場合、複数のRは同一であっても異なっていてもよい。 In formula (III), R 4 represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms. m represents an integer of 0 to 5. When m is 2 or more, the plurality of R 4 may be the same or different.
 一般式(III)で表されるアクリジン化合物としては、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及び9-ペンチルアミノアクリジンが挙げられる。これらは1種単独で又は2種以上を組み合わせて使用される。 Examples of the acridine compound represented by the general formula (III) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p-chlorophenyl) acridine, Examples include 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine and 9-pentylaminoacridine. These are used individually by 1 type or in combination of 2 or more types.
 前記感光性樹脂組成物が、光重合開始剤として(C2)化合物を含む場合、(C2)化合物の含有量は、感度、解像性及び密着性の見地から、(A)成分及び(B)成分の固形分総量100質量部に対して0.1質量部~10質量部であることが好ましく、0.5質量部~5質量部であることがより好ましく、1質量部~5質量部であることが更に好ましく、1質量部~3質量部であることが特に好ましい。この含有量が0.1質量部以上であるとより良好な感度、解像性又は密着性が得られる傾向がある。10質量部以下であるとより良好なレジスト形状を得られる傾向がある。 When the photosensitive resin composition contains the (C2) compound as a photopolymerization initiator, the content of the (C2) compound is (A) and (B) from the viewpoint of sensitivity, resolution and adhesion. The amount is preferably from 0.1 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, more preferably from 1 to 5 parts by weight, based on 100 parts by weight of the total solid content of the components. More preferred is 1 to 3 parts by mass. There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.
 前記感光性樹脂組成物は、(C)成分として、前記(C1)化合物及び(C2)化合物以外の光重合開始剤を含んでいてもよい。 The photosensitive resin composition may contain a photopolymerization initiator other than the compound (C1) and the compound (C2) as the component (C).
 (C1)化合物及び(C2)化合物以外の光重合開始剤としては、ベンゾフェノン、N,N’-テトラメチル-4,4’-ジアミノベンゾフェノン(ミヒラーケトン)、N,N’-テトラエチル-4,4’-ジアミノベンゾフェノン、4-メトキシ-4’-ジメチルアミノベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-プロパノン-1等の芳香族ケトン化合物;2-エチルアントラキノン、フェナントレンキノン、2-t-ブチルアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン、2,3-ベンズアントラキノン、2-フェニルアントラキノン、2,3-ジフェニルアントラキノン、1-クロロアントラキノン、2-メチルアントラキノン、1,4-ナフトキノン、9,10-フェナンタラキノン、2-メチル1,4-ナフトキノン、2,3-ジメチルアントラキノン等のキノン化合物;ベンゾインメチルエーテル、ベンゾインエチルエーテル及びベンゾインフェニルエーテル等のベンゾインエーテル化合物、ベンゾイン、メチルベンゾイン、エチルベンゾイン等のベンゾイン化合物;2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ジ(メトキシフェニル)イミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、2-(p-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体等の2,4,5-トリアリールイミダゾール二量体;ベンジルジメチルケタール等のベンジル誘導体;9,10-ジメトキシアントラセン、9,10-ジエトキシアントラセン、9,10-ジプロポキシアントラセン、9,10-ジブトキシアントラセン、9,10-ジペントキシアントラセン等の置換アントラセン化合物;クマリン化合物;オキサゾール化合物;ピラゾリン化合物;トリアリールアミン化合物;などが挙げられる。
 これらは、1種単独で又は2種以上を組み合わせて使用される。また、ジエチルチオキサントンとジメチルアミノ安息香酸との組み合わせのように、チオキサントン化合物と3級アミン化合物とを組み合わせて光重合開始剤としてもよい。
Examples of photopolymerization initiators other than the (C1) compound and the (C2) compound include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4 ′. -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl Aromatic ketone compounds such as 2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2 -Phenylanthraquinone, 2,3-diphenylanthraquinone, Quinone compounds such as chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether And benzoin ether compounds such as benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) ) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer; benzyl derivatives such as benzyldimethyl ketal; 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9 , 10-dipropoxyanthracene, 9,10-dibutoxyanthracene, substituted anthracene compounds such as 9,10-dipentoxyanthracene; coumarin compounds; oxazole compounds; pyrazoline compounds; triarylamine compounds;
These are used individually by 1 type or in combination of 2 or more types. Moreover, it is good also as a photoinitiator combining a thioxanthone compound and a tertiary amine compound like the combination of diethyl thioxanthone and a dimethylamino benzoic acid.
 なお、前記2,4,5-トリアリールイミダゾール二量体は、二量体を構成する2つの2,4,5-トリアリールイミダゾールのアリール基の置換基が、同一であり対称な化合物であってもよいし、互いに相違して非対称な化合物であってもよい。 The 2,4,5-triarylimidazole dimer is a symmetric compound in which the aryl group substituents of the two 2,4,5-triarylimidazoles constituting the dimer are the same. They may be different or asymmetrical compounds.
 感光性樹脂組成物が、(C)成分として(C1)化合物及び(C2)化合物以外の光重合開始剤を含む場合、その含有量は、感度及び内部の光硬化性の観点から、(A)成分及び(B)成分の固形分総量100質量部に対して、0.01質量部~10質量部であることが好ましく、0.1質量部~7質量部であることがより好ましく、0.2質量部~5質量部であることが更に好ましい。 When the photosensitive resin composition contains a photopolymerization initiator other than the (C1) compound and the (C2) compound as the component (C), the content is (A) from the viewpoint of sensitivity and internal photocurability. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the total solid content of the component and component (B), and More preferably, it is 2 to 5 parts by mass.
 (C)成分の含有量は、感度、密着性及び内部の光硬化性の観点から、(A)成分及び(B)成分の固形分総量100質量部に対して、0.01質量部~20質量部であることが好ましく、0.05質量部~10質量部であることがより好ましく、0.1質量部~5質量部であることが更に好ましい。 The content of the component (C) is 0.01 parts by mass to 20 parts with respect to 100 parts by mass of the total solid content of the components (A) and (B) from the viewpoints of sensitivity, adhesion, and internal photocurability. The mass is preferably 0.05 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and still more preferably 0.1 parts by mass to 5 parts by mass.
〔(D)成分:(ポリ)エチレンオキサイド化合物〕
 前記感光性樹脂組成物は、(D)成分として(ポリ)エチレンオキサイド〔-(CO)-:nは1以上〕を構造単位として有する化合物の少なくとも1種を含む。(D)成分である(ポリ)エチレンオキサイド化合物は、1種単独で、又は2種以上を組み合わせて用いてもよい。(D)成分:(ポリ)エチレンオキサイド化合物は、上記(A)成分、(B)成分又は(C)成分を兼ねていてもよく、(A)~(C)成分以外の成分として含有されていてもよい。
[(D) component: (poly) ethylene oxide compound]
The photosensitive resin composition contains at least one compound having (poly) ethylene oxide [— (C 2 H 4 O) n —: n is 1 or more] as a structural unit as the component (D). The (poly) ethylene oxide compound as component (D) may be used alone or in combination of two or more. Component (D): The (poly) ethylene oxide compound may also serve as component (A), component (B) or component (C), and is contained as a component other than components (A) to (C). May be.
 (ポリ)エチレンオキサイド化合物が、(A)成分:バインダーポリマーを兼ねている場合、例えば、(ポリ)エチレンオキサイドモノ(メタ)アクリレート又はその誘導体に由来する構造単位を含むものが挙げられる。
 (ポリ)エチレンオキサイド化合物が、(B)成分:光重合性化合物を兼ねている場合、例えば、2,2-ビス(4-((メタ)アクリロキシポリエチレンオキシ)フェニル)プロパン、ポリエチレングリコールポリ(メタ)アクリレート等が挙げられる。
In the case where the (poly) ethylene oxide compound also serves as the component (A): binder polymer, examples include those containing structural units derived from (poly) ethylene oxide mono (meth) acrylate or derivatives thereof.
When the (poly) ethylene oxide compound also serves as the component (B): photopolymerizable compound, for example, 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane, polyethylene glycol poly ( And (meth) acrylate.
 (ポリ)エチレンオキサイド化合物は、一分子中、(ポリ)エチレンオキサイド〔-(CO)-〕構造単位の占める割合(EO含有率)が60質量%以上であることが好ましく、70質量%~90質量%であることがより好ましい。 In the (poly) ethylene oxide compound, the proportion of the (poly) ethylene oxide [— (C 2 H 4 O) n —] structural unit in one molecule (EO content) is preferably 60% by mass or more. More preferably, it is 70 to 90% by mass.
 (ポリ)エチレンオキサイド化合物としては、トリメチロールプロパンポリエチレンエーテルトリ(メタ)アクリレート、ペンタエリスリトールプロパンポリエチレンエーテルテトラ(メタ)アクリレート等が好ましい。より好ましくは、トリメチロールプロパンポリエチレンエーテルトリ(メタ)アクリレート、ペンタエリスリトールプロパンポリエチレンエーテルテトラ(メタ)アクリレート等であって、(ポリ)エチレンオキサイド〔-(CO)-〕の構造単位の一分子中に占める割合(EO含有率)が70質量%~90質量%の化合物である。この化合物を用いた感光性樹脂組成物は、解像性と硬化膜のテンティング性がより向上する。 As the (poly) ethylene oxide compound, trimethylolpropane polyethylene ether tri (meth) acrylate, pentaerythritol propane polyethylene ether tetra (meth) acrylate and the like are preferable. More preferably, trimethylolpropane polyethylene ether tri (meth) acrylate, pentaerythritol propane polyethylene ether tetra (meth) acrylate, etc., which is a structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] Is a compound having a proportion (EO content) in a molecule of 70% by mass to 90% by mass. The photosensitive resin composition using this compound further improves the resolution and tenting properties of the cured film.
 前記(A)成分と前記(B)成分の固形分総量に対する、前記(ポリ)エチレンオキサイド〔-(CO)-〕の構造単位の含有率は、25質量%以上であり、25質量%~40質量%であることが好ましい。(ポリ)エチレンオキサイド化合物の含有率を25質量%以上とすることで硬化膜が柔軟になり、優れたテンティング性を有する。また、40質量%以下とすることで、剥離時間が短くなる。
 より解像性に優れ、且つ剥離時間が短くなる観点からは、(ポリ)エチレンオキサイド化合物の含有率は、感光性樹脂組成物の固形分総量中、25質量%~35質量%であることがより好ましく、25質量%~30質量%であることが更に好ましい。
The content of the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] with respect to the total solid content of the component (A) and the component (B) is 25% by mass or more, It is preferably 25% by mass to 40% by mass. By setting the content of the (poly) ethylene oxide compound to 25% by mass or more, the cured film becomes flexible and has excellent tenting properties. Moreover, peeling time becomes short by setting it as 40 mass% or less.
From the viewpoint of more excellent resolution and shortening of the peeling time, the content of the (poly) ethylene oxide compound is 25% by mass to 35% by mass in the total solid content of the photosensitive resin composition. More preferably, the content is 25% by mass to 30% by mass.
〔その他の成分〕
 また、本実施形態の感光性樹脂組成物は、必要に応じて、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、メチルバイオレット等の染料;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、o-クロロアニリン等の光発色剤;熱発色防止剤;p-トルエンスルホンアミド等の可塑剤;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;重合禁止剤;香料;イメージング剤;熱架橋剤などのその他の添加剤を更に含んでいてもよい。
[Other ingredients]
In addition, the photosensitive resin composition of the present embodiment, if necessary, a dye such as malachite green, Victoria pure blue, brilliant green, methyl violet; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, Photochromic agent such as o-chloroaniline; Thermochromic inhibitor; Plasticizer such as p-toluenesulfonamide; Pigment; Filler; Antifoaming agent; Flame retardant; Adhesion imparting agent; Leveling agent; Other additives such as an inhibitor, a polymerization inhibitor, a fragrance, an imaging agent, and a thermal crosslinking agent may be further included.
 前記感光性樹脂組成物がその他の添加剤を含む場合、その含有量は目的等に応じて適宜選択できる。例えば(A)成分及び(B)成分の固形分総量100質量部に対して各々0.01質量部~20質量部程度含有することができる。これらは、1種単独で又は2種以上を組み合わせて用いることができる。 When the photosensitive resin composition contains other additives, the content can be appropriately selected according to the purpose and the like. For example, it can be contained in an amount of about 0.01 to 20 parts by mass per 100 parts by mass of the total solid content of the component (A) and the component (B). These can be used individually by 1 type or in combination of 2 or more types.
 また、感光性樹脂組成物は、有機溶剤の少なくとも1種を更に含んでいてもよい。有機溶剤としては、メタノール、エタノール等のアルコール溶剤;アセトン、メチルエチルケトン等のケトン溶剤;メチルセロソルブ、エチルセロソルブ、プロピレングリコールモノメチルエーテル等のグリコールエーテル溶剤;トルエン等の芳香族炭化水素溶剤;N,N-ジメチルホルムアミド等の非プロトン性極性溶剤;などが挙げられる。これらは1種単独でも、2種以上を組み合わせて用いてもよい。
 前記感光性樹脂組成物に含まれる有機溶剤の含有量は目的等に応じて適宜選択することができる。例えば、固形分が30質量%~60質量%程度となる溶液(以下、有機溶剤を含む感光性樹脂組成物を「塗布液」ともいう)として用いることができる。
Moreover, the photosensitive resin composition may further contain at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. These may be used alone or in combination of two or more.
Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a solid content of about 30% by mass to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”).
 前記感光性樹脂組成物は、後述する感光性エレメントの感光性樹脂層の形成に使用できる。すなわち本発明の別の実施形態は、前記感光性樹脂組成物の感光性エレメントへの使用である。また、前記感光性樹脂組成物は、後述するレジストパターン付き基板の製造方法及びプリント配線板の製造方法に使用できる。 The photosensitive resin composition can be used for forming a photosensitive resin layer of a photosensitive element described later. That is, another embodiment of the present invention is the use of the photosensitive resin composition for a photosensitive element. Moreover, the said photosensitive resin composition can be used for the manufacturing method of the board | substrate with a resist pattern mentioned later and the manufacturing method of a printed wiring board.
<感光性エレメント>
 本発明の感光性エレメントは、支持フィルムと、前記支持フィルム上に設けられる前記感光性樹脂組成物の塗膜である感光性樹脂層とを有する。前記感光性エレメントは、必要に応じて保護フィルム等のその他の層を有していてもよい。
<Photosensitive element>
The photosensitive element of this invention has a support film and the photosensitive resin layer which is a coating film of the said photosensitive resin composition provided on the said support film. The said photosensitive element may have other layers, such as a protective film, as needed.
 図1に、本発明の感光性エレメントの一実施形態を示す。図1に示す感光性エレメント10では、支持フィルム2、前記感光性樹脂組成物の塗膜である感光性樹脂層4、保護フィルム6がこの順に積層されている。感光性エレメント10は、例えば、以下のようにして得ることができる。支持フィルム2上に、有機溶剤を含む前記感光性樹脂組成物である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性樹脂層4を形成する。次いで、感光性樹脂層4の支持フィルム2とは反対側の表面を保護フィルム6で被覆することにより、支持フィルム2と、該支持フィルム2上に積層された感光性樹脂層4と、該感光性樹脂層4上に積層された保護フィルム6とを備える、本実施形態の感光性エレメント10が得られる。感光性エレメント10は、保護フィルム6は必ずしも備えなくてもよい。 FIG. 1 shows an embodiment of the photosensitive element of the present invention. In the photosensitive element 10 shown in FIG. 1, the support film 2, the photosensitive resin layer 4 which is the coating film of the said photosensitive resin composition, and the protective film 6 are laminated | stacked in this order. The photosensitive element 10 can be obtained as follows, for example. On the support film 2, the coating liquid which is the said photosensitive resin composition containing an organic solvent is apply | coated, an application layer is formed, and the photosensitive resin layer 4 is formed by drying this. Next, the surface of the photosensitive resin layer 4 opposite to the supporting film 2 is covered with a protective film 6, thereby supporting the supporting film 2, the photosensitive resin layer 4 laminated on the supporting film 2, and the photosensitive film. The photosensitive element 10 of this embodiment provided with the protective film 6 laminated | stacked on the photosensitive resin layer 4 is obtained. The photosensitive element 10 does not necessarily include the protective film 6.
 支持フィルム2としては、ポリエチレンテレフタレート等のポリエステル、ポリプロピレン、ポリエチレンなどの耐熱性及び耐溶剤性を有する重合体フィルムを用いることができる。 As the support film 2, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.
 支持フィルム2(重合体フィルム)の厚みは、1μm~100μmであることが好ましく、1μm~50μmであることがより好ましく、1μm~30μmであることが更に好ましい。支持フィルム2の厚みが1μm以上であることで、支持フィルム2を感光性樹脂層4から剥離する際に支持フィルム2が破れることを抑制できる。また100μm以下であることで、支持フィルム2を介して感光性樹脂層4を露光するときの解像度の低下が抑制される。 The thickness of the support film 2 (polymer film) is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 1 μm to 30 μm. When the thickness of the support film 2 is 1 μm or more, the support film 2 can be prevented from being broken when the support film 2 is peeled from the photosensitive resin layer 4. Moreover, the fall of the resolution when exposing the photosensitive resin layer 4 through the support film 2 is suppressed because it is 100 micrometers or less.
 保護フィルム6としては、感光性樹脂層4に対する接着力が、支持フィルム2の感光性樹脂層4に対する接着力よりも小さいものが好ましい。また低フィッシュアイのフィルムが好ましい。ここで、「フィッシュアイ」とは、材料を熱溶融し、混練、押し出し、2軸延伸、キャスティング法等によりフィルムを製造する際に、材料の異物、未溶解物、酸化劣化物等がフィルム中に取り込まれたものを意味する。すなわち、「低フィッシュアイ」とは、フィルム中の上記異物等が少ないことを意味する。 The protective film 6 preferably has a smaller adhesive force to the photosensitive resin layer 4 than the adhesive force of the support film 2 to the photosensitive resin layer 4. A low fisheye film is preferred. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
 具体的に、保護フィルム6としては、ポリエチレンテレフタレート等のポリエステル、ポリプロピレン、ポリエチレンなどの耐熱性及び耐溶剤性を有する重合体フィルムを用いることができる。市販のものとしては、王子製紙株式会社製アルファンMA-410、E-200C、信越フィルム株式会社製等のポリプロピレンフィルム、帝人株式会社製PS-25等のPSシリーズなどのポリエチレンテレフタレートフィルムなどが挙げられる。なお、保護フィルム6は支持フィルム2と同一のものでもよい。 Specifically, as the protective film 6, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. Examples of commercially available products include polypropylene films such as Alfan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as PS series such as PS-25 manufactured by Teijin Limited. It is done. The protective film 6 may be the same as the support film 2.
 保護フィルム6の厚みは1μm~100μmであることが好ましく、1μm~50μmであることがより好ましく、1μm~30μmであることが更に好ましい。保護フィルム6の厚みが1μm以上であると、保護フィルム6を剥がしながら、感光性樹脂層4及び支持フィルム2を基板上にラミネートする際、保護フィルム6が破れることを抑制できる。100μm以下であると、取扱い性と廉価性に優れる。 The thickness of the protective film 6 is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and even more preferably 1 μm to 30 μm. When the thickness of the protective film 6 is 1 μm or more, the protective film 6 can be prevented from being broken when the photosensitive resin layer 4 and the support film 2 are laminated on the substrate while peeling off the protective film 6. When it is 100 μm or less, it is excellent in handleability and inexpensiveness.
 本実施形態の感光性エレメントは、具体的には例えば以下のようにして製造することができる。少なくとも、(A)成分:バインダーポリマー、(B)成分:光重合性化合物、及び(C)光重合開始剤、及び(D)成分:(ポリ)エチレンオキサイド化合物を前記有機溶剤に溶解した塗布液を準備する工程と、前記塗布液を支持フィルム2上に塗布して塗布層を形成する工程と、前記塗布層を乾燥して感光性樹脂層を形成する工程と、を含む製造方法で製造することができる。 Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. Coating solution prepared by dissolving at least (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) photopolymerization initiator, and (D) component: (poly) ethylene oxide compound in the organic solvent. And a step of forming a coating layer by applying the coating liquid on the support film 2 and a step of forming a photosensitive resin layer by drying the coating layer. be able to.
 前記塗布液の支持フィルム2上への塗布は、ロールコータ、コンマコータ、グラビアコータ、エアーナイフコータ、ダイコータ、バーコータ等の公知の方法により行うことができる。 Application of the coating solution onto the support film 2 can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater.
 前記塗布層の乾燥は、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分~30分間程度行うことが好ましい。乾燥後、感光性樹脂層中の残存有機溶剤量は、後の工程での有機溶剤の拡散を防止する観点から、2質量%以下とすることが好ましい。 The 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 is preferably performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
 感光性エレメント10における感光性樹脂層4の厚みは、用途により適宜選択することができ、乾燥後の厚みで1μm~200μmであることが好ましく、5μm~100μmであることがより好ましく、10μm~50μmであることが更に好ましい。この厚みが1μm以上であることで、工業的な塗工が容易になり、200μm以下の場合には、感度及びレジスト底部の光硬化性が充分に得られる傾向がある。 The thickness of the photosensitive resin layer 4 in the photosensitive element 10 can be appropriately selected depending on the intended use. The thickness after drying is preferably 1 μm to 200 μm, more preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm. More preferably. When the thickness is 1 μm or more, industrial coating becomes easy. When the thickness is 200 μm or less, the sensitivity and the photocurability of the resist bottom tend to be sufficiently obtained.
 感光性エレメント10は、更にクッション層、接着層、光吸収層、ガスバリア層等の中間層などを有していてもよい。これらの中間層としては、特開2006-098982号公報等に記載の中間層を本発明においても適用することができる。 The photosensitive element 10 may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, the intermediate layers described in JP-A-2006-098982 can also be applied in the present invention.
 得られた感光性エレメント10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、又は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2が外側になるように巻き取ることが好ましい。巻芯の材質としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ABS樹脂(アクリロニトリル-ブタジエン-スチレン共重合体)等のプラスチックなどが挙げられる。このようにして得られたロール状の感光性エレメントロールの端面には、端面保護の見地から端面セパレータを設置することが好ましく、耐エッジフュージョンの見地から防湿端面セパレータを設置することが好ましい。梱包方法としては、透湿性の小さいブラックシートに包んで包装することが好ましい。 The form of the obtained photosensitive element 10 is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When winding in roll form, it is preferable to wind up so that the support film 2 may become an outer side. Examples of the material of the core include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and plastics such as ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.
 感光性エレメント10は、例えば、後述するレジストパターン付き基板の製造方法に好適に用いることができる。 The photosensitive element 10 can be suitably used, for example, in a method for manufacturing a substrate with a resist pattern described later.
<レジストパターン付き基板の製造方法>
 前記感光性樹脂組成物を用いて、基板上にレジストパターンを形成することができる。本実施形態のレジストパターン付き基板の製造方法は、(i)前記感光性樹脂組成物を用いて形成された感光性樹脂層を基板上に積層する積層工程と、(ii)前記感光性樹脂層の少なくとも一部の領域に活性光線を照射して、前記領域を硬化させる露光工程と、(iii)感光性樹脂層の前記領域以外の未露光部分を基板上から除去することにより、基板上に、感光性樹脂組成物の硬化物で構成されるレジストパターンを形成する現像工程と、を有する。前記レジストパターン付き基板の製造方法は必要に応じて更にその他の工程を有していてもよい。
<Method for manufacturing substrate with resist pattern>
A resist pattern can be formed on a substrate using the photosensitive resin composition. The method for manufacturing a substrate with a resist pattern according to this embodiment includes (i) a lamination step of laminating a photosensitive resin layer formed using the photosensitive resin composition on the substrate, and (ii) the photosensitive resin layer. An exposure step of irradiating at least a part of the region with actinic rays to cure the region; and (iii) removing an unexposed portion other than the region of the photosensitive resin layer from the substrate. And a developing step for forming a resist pattern composed of a cured product of the photosensitive resin composition. The manufacturing method of the said board | substrate with a resist pattern may have another process further as needed.
(i)積層工程
 まず、感光性樹脂組成物を用いて形成される感光性樹脂層を基板上に積層する。基板としては、絶縁層と該絶縁層上に形成された導体層とを備えた基板(回路形成用基板)を用いることができる。
(I) Lamination process First, the photosensitive resin layer formed using the photosensitive resin composition is laminated | stacked on a board | substrate. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.
 感光性樹脂層の基板上への積層は、例えば、前記感光性エレメント10が保護フィルム6を有している場合には、保護フィルム6を除去した後、感光性エレメント10の感光性樹脂層4を加熱しながら上記基板に圧着することにより行われる。これにより、基板と感光性樹脂層4と支持フィルム2とをこの順に備える積層体が得られる。 For example, when the photosensitive element 10 has the protective film 6, the photosensitive resin layer 4 is laminated on the substrate after the protective film 6 is removed and then the photosensitive resin layer 4 of the photosensitive element 10. This is performed by pressure-bonding to the substrate while heating. Thereby, the laminated body provided with the board | substrate, the photosensitive resin layer 4, and the support film 2 in this order is obtained.
 この積層作業は、密着性及び追従性の見地から、減圧下で圧着させることが好ましい。圧着の際、感光性樹脂層及び/又は基板は、70℃~130℃の温度で加熱されることが好ましい。また圧着は、0.1MPa~1.0MPa程度(1kgf/cm~10kgf/cm程度)の圧力で行うことが好ましい。これらの条件は必要に応じて適宜選択される。なお、感光性樹脂層を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、回路形成用基板の予熱処理を行うことで密着性及び追従性を更に向上させることができる。 This lamination operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability. During the pressure bonding, the photosensitive resin layer and / or the substrate is preferably heated at a temperature of 70 ° C. to 130 ° C. The pressure bonding is preferably performed at a pressure of about 0.1 MPa to 1.0 MPa (about 1 kgf / cm 2 to 10 kgf / cm 2 ). These conditions are appropriately selected as necessary. Note that if the photosensitive resin layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance. be able to.
(ii)露光工程
 露光工程では、上記のようにして基板上に形成された感光性樹脂層4の少なくとも一部の領域に活性光線を照射することで、活性光線が照射された露光部が光硬化して、潜像が形成される。活性光線の照射としては、例えば、ネガ又はポジマスクパターンを通して画像状に活性光線を照射する方法が挙げられる。この際、感光性樹脂層4上に存在する支持フィルム2が活性光線に対して透明である場合には、支持フィルム2を通して活性光線を照射することができ、支持フィルム2が活性光線に対して遮光性を示す場合には、支持フィルム2を除去した後に感光性樹脂層4に活性光線を照射する。
(Ii) Exposure Step In the exposure step, at least a part of the photosensitive resin layer 4 formed on the substrate as described above is irradiated with actinic rays, so that the exposed portion irradiated with actinic rays is light. Curing forms a latent image. Examples of the actinic ray irradiation include a method of irradiating actinic rays in an image form through a negative or positive mask pattern. At this time, when the support film 2 existing on the photosensitive resin layer 4 is transparent to the active light, the active light can be irradiated through the support film 2, and the support film 2 can be applied to the active light. When light-shielding properties are exhibited, the photosensitive resin layer 4 is irradiated with actinic rays after the support film 2 is removed.
 活性光線の光源としては特に制限されず、従来公知の光源、例えばカーボンアーク灯、水銀蒸気アーク灯、超高圧水銀灯、高圧水銀灯、キセノンランプ、アルゴンレーザー等のガスレーザー、YAGレーザー等の固体レーザー、半導体レーザー及び窒化ガリウム系青紫色レーザー等の紫外線、可視光などを有効に放射するものが用いられる。またレーザー直接描画露光法を用いてもよい。 The light source of actinic light is not particularly limited, and conventionally known light sources such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid state lasers such as YAG lasers, A semiconductor laser, a gallium nitride blue-violet laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, a laser direct drawing exposure method may be used.
 本実施形態の感光性樹脂組成物は、直接描画露光方法に好適に使用することができる。即ち、本発明の好適な実施形態の一つは、前記感光性樹脂組成物の直接描画露光法への応用である。 The photosensitive resin composition of the present embodiment can be suitably used for a direct drawing exposure method. That is, one preferred embodiment of the present invention is an application of the photosensitive resin composition to a direct drawing exposure method.
(iii)現像工程
 現像工程においては、上記感光性樹脂層4の未硬化部分が回路形成用基板上から現像により除去されることで、上記感光性樹脂層4が光硬化した硬化物であるレジストパターンが基板上に形成される。感光性樹脂層4上に支持フィルム2が存在している場合には、支持フィルム2を除去してから、未露光部分の除去(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り、ウェット現像が広く用いられている。
(Iii) Development Step In the development step, the uncured portion of the photosensitive resin layer 4 is removed from the circuit-forming substrate by development, so that the photosensitive resin layer 4 is a cured product obtained by photocuring. A pattern is formed on the substrate. When the support film 2 exists on the photosensitive resin layer 4, the support film 2 is removed, and then the unexposed portion is removed (development). Development methods include wet development and dry development, and wet development is widely used.
 ウェット現像による場合、感光性樹脂組成物に対応した現像液を用いて、公知の現像方法により現像する。現像方法としては、ディップ方式、パトル方式、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、高圧スプレー方式が適している。これら2種以上の方法を組み合わせて現像を行ってもよい。 In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dipping method, a battle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, a high-pressure spray method is suitable. You may develop by combining these 2 or more types of methods.
 現像液の構成は、前記感光性樹脂組成物の構成に応じて適宜選択される。例えば、アルカリ性水溶液、水系現像液、有機溶剤系現像液等が挙げられる。 The constitution of the developer is appropriately selected according to the constitution of the photosensitive resin composition. For example, alkaline aqueous solution, aqueous developer, organic solvent developer and the like can be mentioned.
 アルカリ性水溶液は、現像液として用いられる場合、安全且つ安定であり、操作性が良好である。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;などが用いられる。 An alkaline aqueous solution is safe and stable when used as a developer, and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate;
 現像に用いるアルカリ性水溶液としては、0.1質量%~5質量%炭酸ナトリウムの希薄溶液、0.1質量%~5質量%炭酸カリウムの希薄溶液、0.1質量%~5質量%水酸化ナトリウムの希薄溶液、0.1質量%~5質量%四ホウ酸ナトリウムの希薄溶液等が好ましい。アルカリ性水溶液のpHは9~11の範囲とすることが好ましい。また、アルカリ性水溶液の温度は、感光性樹脂層のアルカリ現像性に合わせて調節される。アルカリ性水溶液中には、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% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1% by mass to 5% by mass of sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature of the alkaline aqueous solution is adjusted according to the alkali developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
 前記水系現像液は、例えば、水又はアルカリ性水溶液と1種以上の有機溶剤とからなる現像液である。ここで、アルカリ性水溶液の塩基としては、先に述べた物質以外に、例えば、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、モルホリン等が挙げられる。水系現像液のpHは、現像が充分に行われる範囲でできるだけ小さくすることが好ましく、pH8~12とすることが好ましく、pH9~10とすることがより好ましい。 The aqueous developer is, for example, a developer composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 , 3-propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the aqueous developer is preferably as low as possible within the range where development is sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.
 水系現像液に用いる有機溶剤としては、アセトン、酢酸エチル、炭素原子数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、ジエチレングリコールモノブチルエーテル等が挙げられる。これらは、1種単独で又は2種類以上を組み合わせて使用される。水系現像液における有機溶剤の濃度は、通常、2質量%~90質量%とすることが好ましい。またその温度は、アルカリ現像性に合わせて調整することができる。水系現像液中には、界面活性剤、消泡剤等を少量混入することもできる。 Organic solvents used in the aqueous developer 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, diethylene glycol monobutyl ether Etc. These are used individually by 1 type or in combination of 2 or more types. In general, the concentration of the organic solvent in the aqueous developer is preferably 2% by mass to 90% by mass. Moreover, the temperature can be adjusted according to alkali developability. A small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.
 有機溶剤系現像液としては、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、γ-ブチロラクトン等の有機溶剤が挙げられる。これらの有機溶剤には、引火防止のため、1~20質量%の範囲で水を添加することが好ましい。 Examples of the organic solvent developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It is preferable to add water to these organic solvents in an amount of 1 to 20% by mass in order to prevent ignition.
 前記現像工程においては、未露光部分を除去した後、必要に応じて60℃~250℃程度の加熱又は0.2J/cm~10J/cm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更に含んでもよい。 In the development step, after removing the unexposed portion, the resist pattern is further formed by performing heating at about 60 ° C. to 250 ° C. or exposure at about 0.2 J / cm 2 to 10 J / cm 2 as necessary. You may further include the process to harden | cure.
<プリント配線板の製造方法>
 本発明のプリント配線板の製造方法は、前記レジストパターン付き基板の製造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又はめっきする工程を含む。エッチング又はめっきにより導体パターンが形成される。プリント配線板の製造方法は、必要に応じてレジスト除去工程等のその他の工程を含んでいてもよい。基板のエッチング処理又はめっき処理は、形成されたレジストパターンをマスクとして、基板の導体層等に対して行われる。
<Method for manufacturing printed wiring board>
The method for producing a printed wiring board of the present invention includes a step of etching or plating a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern. A conductor pattern is formed by etching or plating. The manufacturing method of a printed wiring board may include other processes, such as a resist removal process, as needed. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.
 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、レジストによって被覆されていない回路形成用基板の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、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、過酸化水素エッチング液等が挙げられ、これらの中では、エッチファクタが良好な点から塩化第二鉄溶液を用いることが好ましい。 In the etching process, using the resist pattern formed on the substrate as a mask, the conductor layer of the circuit forming substrate not covered with the resist is removed by etching to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Etching solutions include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, etc. Among these, ferric chloride solution is used from the viewpoint of good etch factor. It is preferable.
 一方、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、レジストによって被覆されていない回路形成用基板の導体層上に、銅、はんだ等をめっきする。めっき処理の後、硬化レジストを除去し、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する。めっき処理の方法は、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。めっき処理としては、例えば、硫酸銅めっき、ピロリン酸銅めっき等の銅めっき、ハイスローはんだめっき等のはんだめっき、ワット浴(硫酸ニッケル-塩化ニッケル)めっき、スルファミン酸ニッケル等のニッケルめっき、ハード金メッキ、ソフト金メッキ等の金メッキなどが挙げられる。 On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the resist, using the resist pattern formed on the substrate as a mask. After the plating process, the cured resist is removed, and the conductor layer covered with the resist is etched to form a conductor pattern. The method of plating treatment may be electrolytic plating treatment or electroless plating treatment. Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, Examples thereof include gold plating such as soft gold plating.
 上記エッチング処理及びめっき処理の後、基板上のレジストパターンは除去される。レジストパターンの除去は、例えば、前記現像工程に用いたアルカリ性水溶液より更に強アルカリ性の水溶液を用いて行うことができる。この強アルカリ性の水溶液としては、例えば、1質量%~10質量%水酸化ナトリウム水溶液、1質量%~10質量%水酸化カリウム水溶液等が用いられる。なかでも、1質量%~10質量%水酸化ナトリウム水溶液又は水酸化カリウム水溶液を用いることが好ましく、1質量%~5質量%水酸化ナトリウム水溶液又は水酸化カリウム水溶液を用いることがより好ましい。 After the etching process and the plating process, the resist pattern on the substrate is removed. The resist pattern can be removed using, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As the strong alkaline aqueous solution, for example, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution, or the like is used. Of these, a 1% by mass to 10% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is preferably used, and a 1% by mass to 5% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is more preferably 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。エッチング処理の方法は、除去すべき導体層に応じて適宜選択される。例えば、上述のエッチング液を適用することができる。 When the resist pattern is removed after plating, a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by etching to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.
 本発明の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 printed wiring board manufacturing method of the present invention can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. .
 図2は、従来の多層プリント配線基板の製造方法を示す図である。図2(f)に示す多層プリント配線基板100Aは表面及び内部に配線パターンを有する。多層プリント配線基板100Aは、銅張積層体、層間絶縁材及び金属箔等を積層し、そしてエッチング法、セミアディティブ法等によって配線パターンを適宜形成することによって得られる。 FIG. 2 is a diagram showing a conventional method for manufacturing a multilayer printed wiring board. A multilayer printed wiring board 100A shown in FIG. 2F has a wiring pattern on the surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating material, a metal foil, and the like, and appropriately forming a wiring pattern by an etching method, a semi-additive method, or the like.
 まず、表面に配線パターン102を有する銅張積層体101の両面に層間絶縁層103を形成する(図2(a)参照)。層間絶縁層103は、熱硬化性組成物をスクリーン印刷機又はロールコータを用いて印刷してもよいし、熱硬化性組成物からなるフィルムを予め準備し、ラミネーターを用いて、このフィルムをプリント配線基板の表面に貼り付けることもできる。次いで、外部と電気的に接続することが必要な箇所を、YAGレーザー又は炭酸ガスレーザーを用いて開口104を形成し、開口104周辺のスミア(残渣)をデスミア処理により除去する(図2(b)参照)。次いで、無電解めっき法によりシード層105を形成する(図2(c)参照)。上記シード層105上に感光性樹脂組成物をラミネートし、所定の箇所を露光、現像処理してレジストパターン106を形成する(図2(d)参照)。次いで、電解めっき法により配線パターン107を形成し、剥離液によりレジストパターン106を除去した後、上記シード層105をエッチングにより除去する(図2(e)参照)。以上を繰り返し行い、最表面にソルダーレジスト108を形成することで多層プリント配線基板100Aを作製することができる(図2(f)参照)。 First, an interlayer insulating layer 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 2A). The interlayer insulating layer 103 may be printed with a thermosetting composition using a screen printer or a roll coater, or a film made of the thermosetting composition is prepared in advance, and this film is printed using a laminator. It can also be attached to the surface of the wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser at a portion that needs to be electrically connected to the outside, and smear (residue) around the opening 104 is removed by a desmear process (FIG. 2B). )reference). Next, a seed layer 105 is formed by an electroless plating method (see FIG. 2C). A photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a resist pattern 106 (see FIG. 2D). Next, a wiring pattern 107 is formed by electrolytic plating, the resist pattern 106 is removed by a stripping solution, and then the seed layer 105 is removed by etching (see FIG. 2E). By repeating the above and forming the solder resist 108 on the outermost surface, the multilayer printed wiring board 100A can be manufactured (see FIG. 2F).
 本実施形態の感光性樹脂組成物は、プリント配線板の製造に好適に使用することができる。即ち、本発明の好適な実施形態の一つは、前記感光性樹脂組成物のプリント配線板の製造への応用である。 The photosensitive resin composition of the present embodiment can be suitably used for the production of a printed wiring board. That is, one of the preferred embodiments of the present invention is application of the photosensitive resin composition to the production of a printed wiring board.
 なお、日本出願2013-057222の開示はその全体が参照により本明細書に取り込まれる。
 本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
The entire disclosure of Japanese application 2013-057222 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.
 以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。尚、特に断りのない限り、「部」及び「%」は質量基準である。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
[(A)成分:バインダーポリマー][(P-1)の合成方法](溶液a-1の調製)
 表1に示す重合性単量体(共重合単量体、モノマー)の混合液に、ラジカル反応開始剤であるアゾビスイソブチロニトリル2.0gを溶解して、「溶液a-1」を調製した。
[Component (A): Binder Polymer] [Synthesis Method of (P-1)] (Preparation of Solution a-1)
Dissolve 2.0 g of azobisisobutyronitrile, which is a radical reaction initiator, in a mixed solution of polymerizable monomers (copolymerization monomers, monomers) shown in Table 1 to obtain “Solution a-1”. Prepared.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
(ラジカル重合反応)
 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、有機溶剤であるメチルセロソルブ240g及びトルエン160gの混合液(質量比3:2)400gを投入した。フラスコ内に窒素ガスを吹き込みながら、上記混合液を撹拌しつつ加熱して80℃まで昇温させた。
(Radical polymerization reaction)
Into a flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 400 g of a mixed solution of 240 g of methyl cellosolve and 160 g of toluene (mass ratio 3: 2) was charged. While the nitrogen gas was blown into the flask, the mixture was heated while stirring to raise the temperature to 80 ° C.
 フラスコ内の上記混合液に、「溶液a-1」を4時間かけて滴下した後、フラスコ内の溶液を撹拌しながら80℃にて2時間保温した。次いで、フラスコ内の溶液に、「溶液a-1」100gにアゾビスイソブチロニトリル1gを更に溶解した溶液を10分間かけて滴下した後、フラスコ内の溶液を撹拌しながら80℃にて3時間保温した。更に、フラスコ内の溶液を30分間かけて90℃まで昇温させ、90℃にて2時間保温した後、冷却することにより、(A-1)成分であるバインダーポリマー溶液を得た。 “Solution a-1” was dropped into the above mixed solution in the flask over 4 hours, and the solution in the flask was kept at 80 ° C. for 2 hours while stirring. Next, a solution obtained by further dissolving 1 g of azobisisobutyronitrile in 100 g of “solution a-1” was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 minutes. Keep warm for hours. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a binder polymer solution as component (A-1).
 このバインダーポリマー溶液にアセトンを加えて、不揮発成分(固形分)が50質量%になるように調製した。バインダーポリマーの重量平均分子量は55000であった。なお、重量平均分子量は、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の条件は、以下に示すとおりである。 Acetone was added to this binder polymer solution to prepare a non-volatile component (solid content) of 50% by mass. The weight average molecular weight of the binder polymer was 55000. The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions for GPC are as follows.
-GPC条件-
 ポンプ:日立 L-6000型(株式会社日立製作所製)
 カラム:以下の計3本
 Gelpack GL-R420
 Gelpack GL-R430
 Gelpack GL-R440
  (以上、日立化成株式会社製、商品名)
 溶離液:テトラヒドロフラン
 測定温度:25℃
 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 conditions-
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Column: The following three total Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440
(The above is a product name manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)
[(P-2)の合成方法](溶液a-2の調製)
 表2に示す重合性単量体(共重合単量体、モノマー)の混合液に、ラジカル反応開始剤であるアゾビスイソブチロニトリル1.0gを溶解して、「溶液a-2」を調製した。
[Synthesis Method of (P-2)] (Preparation of Solution a-2)
Dissolve 1.0 g of azobisisobutyronitrile, which is a radical reaction initiator, in a mixed solution of polymerizable monomers (copolymerization monomer, monomer) shown in Table 2 to obtain “solution a-2”. Prepared.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 その後、(A-1)成分と同様にラジカル重合反応を行った。重量平均分子量は100,000であった。 Thereafter, a radical polymerization reaction was carried out in the same manner as the component (A-1). The weight average molecular weight was 100,000.
[感光性樹脂組成物の調製]
 上記で得られたバインダーポリマーの溶液に、(B)成分及び(C)成分、アセトン8g、トルエン8g、メタノール8gを下記表3又は表4に示す配合量(g)で配合することにより、実施例1~11及び比較例1~14の感光性樹脂組成物の溶液をそれぞれ調製した。なお、表3及び表4に示すバインダーポリマーの配合量は、不揮発成分の質量(固形分量)である。
[Preparation of photosensitive resin composition]
Implemented by blending the component (B) and component (C), acetone 8 g, toluene 8 g, and methanol 8 g in the binder polymer solution obtained above in the blending amounts (g) shown in Table 3 or 4 below. Solutions of the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 14 were prepared. In addition, the compounding quantity of the binder polymer shown in Table 3 and Table 4 is the mass (solid content) of a non-volatile component.
Figure JPOXMLDOC01-appb-T000005
 
Figure JPOXMLDOC01-appb-T000005
 
[規則26に基づく補充 17.04.2014] 
Figure WO-DOC-TABLE-4
 
[Supplement under rule 26 17.04.2014]
Figure WO-DOC-TABLE-4
 表3及び表4に示す材料の詳細は以下の通りである。
 ・P-1:上記で調製したバインダーポリマー:メタクリル酸/メタクリル酸メチル/スチレン(25/50/25(質量比))の共重合体、重量平均分子量55000、酸価163mgKOH/g、固形分50質量%メチルセロソルブ/トルエン=6/4(質量比)溶液。構造単位(A1)、(A2)及び(A3)を含む。
Details of the materials shown in Tables 3 and 4 are as follows.
P-1: Binder polymer prepared above: copolymer of methacrylic acid / methyl methacrylate / styrene (25/50/25 (mass ratio)), weight average molecular weight 55000, acid value 163 mg KOH / g, solid content 50 Mass% methyl cellosolve / toluene = 6/4 (mass ratio) solution. Including structural units (A1), (A2) and (A3).
 ・P-2:上記で調製したバインダーポリマー:メタクリル酸/メタクリル酸メチル/アクリル酸オクチル(25/50/25(質量比))の共重合体、重量平均分子量100000、酸価163mgKOH/g、固形分50質量%メチルセロソルブ/トルエン=6/4(質量比)溶液。構造単位(A2)及び(A3)を含む。 P-2: Binder polymer prepared above: copolymer of methacrylic acid / methyl methacrylate / octyl acrylate (25/50/25 (mass ratio)), weight average molecular weight 100,000, acid value 163 mg KOH / g, solid 50% by weight methyl cellosolve / toluene = 6/4 (mass ratio) solution. Including structural units (A2) and (A3).
 ・P-3:メタクリル酸/メタクリル酸ベンジル/メタクリル酸メチル/スチレン(30/25/5/40(質量比))の共重合体、重量平均分子量30000、酸価196mgKOH/g、固形分50質量%メチルセロソルブ/トルエン=6/4(質量比)溶液。構造単位(A1)、(A2)及び(A3)を含む。 P-3: A copolymer of methacrylic acid / benzyl methacrylate / methyl methacrylate / styrene (30/25/5/40 (mass ratio)), weight average molecular weight 30000, acid value 196 mgKOH / g, solid content 50 mass % Methyl cellosolve / toluene = 6/4 (mass ratio) solution. Including structural units (A1), (A2) and (A3).
 ・FA-321M:EO変性ビスフェノールA系ジメタクリレート(一分子中のオキシエチレン基の構造単位の総数の平均値が10)(日立化成株式会社製、製品名)。(B)成分に該当し、かつ(D)成分にも該当。
 ・BPE-100:EO変性ビスフェノールA系ジメタクリレート(一分子中のオキシエチレン基の構造単位の総数の平均値が2.6)。(B)成分に該当し、かつ(D)成分にも該当。
 ・FA-137M:トリメチロールプロパンポリエチレンオキサイドトリメタクリレート(日立化成株式会社製、製品名)。(B)成分に該当し、かつ(D)成分にも該当。
 ・A-TMPT-3EO:変性トリメチロールプロパントリアクリレート(一分子中のオキシエチレン基の構造単位の総数の平均値が3)。(B)成分に該当し、かつ(D)成分にも該当。
 ・UA-HCY-19:ヘキサメチレンジイソシアネートトリマーとポリエチレンオキサイドメタクリレートのウレタン反応物(新中村化学工業株式会社製、製品名)。(B)成分に該当し、かつ(D)成分にも該当。
 ・PDE-400:ポリエチレングリコール#400ジメタクリレート(日油株式会社製、製品名、オキシエチレン基の構造単位の総数の平均値が9)。(B)成分に該当し、かつ(D)成分にも該当。
FA-321M: EO-modified bisphenol A dimethacrylate (the average value of the total number of structural units of oxyethylene groups in one molecule is 10) (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
BPE-100: EO-modified bisphenol A dimethacrylate (the average value of the total number of structural units of oxyethylene groups in one molecule is 2.6). Corresponds to component (B) and also applies to component (D).
FA-137M: trimethylolpropane polyethylene oxide trimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.) Corresponds to component (B) and also applies to component (D).
A-TMPT-3EO: Modified trimethylolpropane triacrylate (average of the total number of structural units of oxyethylene groups in one molecule is 3). Corresponds to component (B) and also applies to component (D).
UA-HCY-19: Urethane reaction product of hexamethylene diisocyanate trimer and polyethylene oxide methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Corresponds to component (B) and also applies to component (D).
PDE-400: Polyethylene glycol # 400 dimethacrylate (manufactured by NOF Corporation, product name, average value of the total number of structural units of oxyethylene group is 9). Corresponds to component (B) and also applies to component (D).
 ・FA-314A:ノニルフェノキシポリエチレングリコールアクリレート(オキシエチレン基の構造単位の総数の平均値が4)(日立化成株式会社製、製品名)。(B)成分に該当し、かつ(D)成分にも該当。
 ・M-114:ノニルフェノキシポリエチレングリコールアクリレート(オキシエチレン基の構造単位の総数の平均値が8)。(B)成分に該当し、かつ(D)成分にも該当。
 ・FA-MECH:(2-ヒドロキシ-3-クロロ)プロピル-2-メタクリロイルオキシエチルフタレート。(B)成分に該当。
 ・UA-13:ヘキサメチレンジイソシアネートとポリプロピレンオキサイド(ポリ)エチレンオキサイドメタクリレートのウレタン反応物(日立化成株式会社製、製品名)。(B)成分に該当し、かつ(D)成分にも該当。
FA-314A: Nonylphenoxy polyethylene glycol acrylate (average value of the total number of structural units of oxyethylene group is 4) (product name, manufactured by Hitachi Chemical Co., Ltd.) Corresponds to component (B) and also applies to component (D).
M-114: Nonylphenoxypolyethylene glycol acrylate (average value of the total number of structural units of oxyethylene group is 8). Corresponds to component (B) and also applies to component (D).
FA-MECH: (2-hydroxy-3-chloro) propyl-2-methacryloyloxyethyl phthalate. Corresponds to component (B).
UA-13: Urethane reaction product of hexamethylene diisocyanate and polypropylene oxide (poly) ethylene oxide methacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
 ・FA-023M:ポリプロピレンオキサイドポリエチレンオキサイドジメタクリレート((ポリ)エチレンオキサイド-(ポリ)プロピレンオキサイド-(ポリ)エチレンオキサイド ブロック共重合体のジメタクリレート)(日立化成株式会社製、製品名)。(B)成分に該当し、かつ(D)成分にも該当。
 ・FA-024M:ポリプロピレンオキサイドポリエチレンオキサイドジメタクリレート((ポリ)プロピレンオキサイド-(ポリ)エチレンオキサイド-(ポリ)プロピレンオキサイドブロック共重合体のジメタクリレート)(日立化成株式会社製、製品名)。(B)成分に該当し、かつ(D)成分にも該当。
 ・APG-400:ポリプロピレングリコールジアクリレート(新中村化学工業株式会社製、製品名)。(B)成分に該当。
FA-023M: Polypropylene oxide, polyethylene oxide dimethacrylate (dipolymethacrylate of (poly) ethylene oxide- (poly) propylene oxide- (poly) ethylene oxide block copolymer) (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
FA-024M: polypropylene oxide polyethylene oxide dimethacrylate (dimethacrylate of (poly) propylene oxide- (poly) ethylene oxide- (poly) propylene oxide block copolymer) (product name, manufactured by Hitachi Chemical Co., Ltd.) Corresponds to component (B) and also applies to component (D).
APG-400: Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Corresponds to component (B).
 ・N-1717:1,7-ジ(9-アクリジニル)ヘプタン(株式会社ADEKA製、製品名)。(C)成分に該当。
 ・9-PA:9-フェニルアクリジン(新日鉄住金化学株式会社製、製品名)。(C)成分に該当。
N-1717: 1,7-di (9-acridinyl) heptane (product name, manufactured by ADEKA Corporation). Corresponds to component (C).
9-PA: 9-phenylacridine (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name). Corresponds to component (C).
 ・LCV:ロイコクリスタルバイオレット(山田化学株式会社製、製品名)
 ・MKG:マラカイトグリーン(大阪有機化学工業株式会社製、製品名)
LCV: Leuco Crystal Violet (product name, manufactured by Yamada Chemical Co., Ltd.)
・ MKG: Malachite Green (Osaka Organic Chemical Co., Ltd., product name)
 表3及び表4において「構造単位(A1)含有率」は、バインダーポリマー中の、スチレン若しくはスチレン誘導体及びベンジル(メタ)アクリレート若しくはベンジル(メタ)アクリレート誘導体からなる群より選択される少なくとも1種に由来する構造単位の含有率(質量%)を表す。「スチレン含有率」は、感光性樹脂組成物の固形分総質量中の、スチレン及びスチレン誘導体からなる群より選択される少なくとも1種に由来する構造単位の含有率(質量%)を表す。「BzMA含有率」は、感光性樹脂組成物の固形分総質量中の、ベンジル(メタ)アクリレート及びベンジル(メタ)アクリレート誘導体からなる群より選択される少なくとも1種に由来する構造単位の含有率(質量%)を表す。 In Tables 3 and 4, the “structural unit (A1) content” is at least one selected from the group consisting of styrene or a styrene derivative and benzyl (meth) acrylate or benzyl (meth) acrylate derivative in the binder polymer. It represents the content (% by mass) of the derived structural unit. “Styrene content” represents the content (% by mass) of structural units derived from at least one selected from the group consisting of styrene and styrene derivatives in the total solid mass of the photosensitive resin composition. “BzMA content” is the content of structural units derived from at least one selected from the group consisting of benzyl (meth) acrylate and benzyl (meth) acrylate derivatives in the total solid mass of the photosensitive resin composition. (% By mass).
 また、表3及び表4の上欄の「EO含有率」は、各成分中の(ポリ)エチレンオキサイド〔-(CO)-〕の構造単位の含有率(質量%)を表す。そして、左最下欄の「EO含有率」は、(A)成分と(B)成分の固形分総質量に対する、(ポリ)エチレンオキサイド〔-(CO)-〕の構造単位の含有率(質量%)を表す。 The “EO content” in the upper column of Table 3 and Table 4 represents the content (% by mass) of the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] in each component. To express. The “EO content” in the bottom left column is the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n −] relative to the total solid mass of the components (A) and (B). The content (mass%) of is expressed.
〔感光性エレメントの作製〕
 実施例1~11及び比較例1~14の感光性樹脂組成物を、それぞれ厚さ16μmのポリエチレンテレフタレートフィルム(帝人株式会社製、商品名「G2-16」)上に塗布し、100℃の熱風対流式乾燥器で10分間乾燥して、乾燥後の膜厚が30μmである感光性樹脂層を形成した。この感光性樹脂層上に保護フィルム(タマポリ株式会社製、商品名「NF-13」)をロール加圧にて積層することにより、ポリエチレンテレフタレートフィルム(支持フィルム)と、感光性樹脂層と、保護フィルムとがこの順に積層された実施例1~11及び比較例1~14にかかる感光性エレメントをそれぞれ得た。
[Production of photosensitive element]
The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 14 were each applied onto a polyethylene terephthalate film (trade name “G2-16” manufactured by Teijin Limited) having a thickness of 16 μm, and hot air at 100 ° C. It dried for 10 minutes with the convection type dryer, and formed the photosensitive resin layer whose film thickness after drying is 30 micrometers. A protective film (trade name “NF-13”, manufactured by Tamapoly Co., Ltd.) is laminated on the photosensitive resin layer by roll pressurization, so that a polyethylene terephthalate film (support film), the photosensitive resin layer, and the protective film are protected. Photosensitive elements according to Examples 1 to 11 and Comparative Examples 1 to 14 in which films were laminated in this order were obtained.
〔評価用積層基板の作製〕
 続いて、ガラスエポキシ材と、その両面に形成された銅箔(厚さ35μm)とからなる1.6mm厚の銅張積層板(日立化成株式会社製、商品名「MCL-E-67」)の銅表面を、#600相当のブラシを持つ研磨機(三啓株式会社製)を用いて研磨し、水洗後、空気流で乾燥させた。この銅張積層板(以下、「基板」という。)を加熱して80℃に昇温させた後、実施例1~11及び比較例1~14にかかる感光性エレメントを基板の両側の銅表面にラミネート(積層)して、評価用積層基板をそれぞれ作製した。ラミネートは、110℃のヒートロールを用いて、保護フィルムを除去しながら、各感光性エレメントの感光性樹脂層が基板の各銅表面に密着するようにして、1.5m/分の速度で行った。また、ラミネート時のヒートロール圧力を0.4MPaとした。
[Preparation of laminated substrate for evaluation]
Subsequently, a 1.6 mm thick copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MCL-E-67”) composed of a glass epoxy material and copper foil (thickness 35 μm) formed on both sides thereof. The copper surface was polished using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air stream. After heating this copper clad laminate (hereinafter referred to as “substrate”) to 80 ° C., the photosensitive elements according to Examples 1 to 11 and Comparative Examples 1 to 14 were placed on the copper surfaces on both sides of the substrate. The laminated substrates for evaluation were respectively prepared by laminating (lamination). Lamination is performed at a speed of 1.5 m / min so that the photosensitive resin layer of each photosensitive element adheres to each copper surface of the substrate while removing the protective film using a 110 ° C. heat roll. It was. Moreover, the heat roll pressure at the time of lamination was 0.4 MPa.
〔感度の評価〕
 得られた評価用積層基板を放冷し、23℃になった時点で、評価用積層基板の表面のポリエチレンテレフタレートフィルム(支持フィルム)に、ステップタブレットを有するフォトツールを密着させた。ステップタブレットとしては、濃度領域が0.00~2.00、濃度ステップが0.05、タブレットの大きさが20mm×187mm、各ステップの大きさが3mm×12mmである41段ステップタブレットを用いた。このようなステップタブレットを有するフォトツール及びポリエチレンテレフタレートフィルムを介して、感光性樹脂層に対して露光を行った。露光は、半導体励起固体レーザーを光源とする露光機(日本オルボテック株式会社製、商品名「Paragon-9000m」)を用いて、20mJ/cmの露光量で行った。
[Evaluation of sensitivity]
The obtained multilayer substrate for evaluation was allowed to cool, and when the temperature reached 23 ° C., a phototool having a step tablet was brought into close contact with the polyethylene terephthalate film (support film) on the surface of the multilayer substrate for evaluation. As the step tablet, a 41 step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and a size of each step of 3 mm × 12 mm was used. . The photosensitive resin layer was exposed through a phototool having such a step tablet and a polyethylene terephthalate film. The exposure was performed at an exposure amount of 20 mJ / cm 2 using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor excitation solid laser as a light source.
 露光後、評価用積層基板からポリエチレンテレフタレートフィルムを剥離し、感光性樹脂層を露出させた。露出した感光性樹脂層に対し、1.0質量%炭酸ナトリウム水溶液を30℃にて50秒間スプレー(現像処理)することにより、未露光部分を除去した。このようにして、評価用積層基板の銅表面に、感光性樹脂組成物の硬化物からなる硬化膜を形成した。得られた硬化膜のステップタブレットの段数を測定することにより、実施例1~11及び比較例1~14の感光性樹脂組成物及びそれらから得られた感光性エレメントの感度(光感度)を評価した。このステップタブレットの段数が高いほど、感度が高いことを意味する。結果を表5及び6に示す。 After the exposure, the polyethylene terephthalate film was peeled off from the evaluation laminate substrate to expose the photosensitive resin layer. The exposed photosensitive resin layer was sprayed (developed) with a 1.0% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds to remove unexposed portions. Thus, the cured film which consists of hardened | cured material of the photosensitive resin composition was formed in the copper surface of the laminated substrate for evaluation. By measuring the number of steps of the step tablet of the obtained cured film, the sensitivity (photosensitivity) of the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 14 and the photosensitive elements obtained therefrom was evaluated. did. The higher the number of steps of the step tablet, the higher the sensitivity. The results are shown in Tables 5 and 6.
〔密着性及び解像度の評価〕
 前記評価用積層基板上に密着性評価用として、ライン幅/スペース幅がn/3n(単位:μm、n=5μm~30μmで5μm間隔)の評価用パターンと、解像度評価用として、ライン幅/スペース幅が3n/n(単位:μm、n=5μm~30μmで5μm間隔)の評価用パターンとを有するフォトツールデータを使用した。露光は、半導体励起固体レーザーを光源とする露光機(日本オルボテック株式会社製、商品名「Paragon-9000m」)を用いて、20mJ/cmの露光量で行った。次いで上記光感度の評価と同様の条件で現像処理を行って、未露光部を除去した。密着性は現像処理によって硬化膜が残存しているライン幅の最も小さい値(単位:μm)により評価した。また解像性は現像処理によって光硬化されていない部分をきれいに除去することができたライン幅間のスペース幅の最も小さい値(単位:μm)により評価した。密着性及び解像度の評価は共に数値が小さいほど良好な値である。結果を表5及び6に示す。
[Evaluation of adhesion and resolution]
An evaluation pattern having a line width / space width of n / 3n (unit: μm, n = 5 μm to 30 μm with an interval of 5 μm) and a line width / Photo tool data having an evaluation pattern having a space width of 3 n / n (unit: μm, n = 5 μm to 30 μm and 5 μm interval) was used. The exposure was performed at an exposure amount of 20 mJ / cm 2 using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor excitation solid laser as a light source. Subsequently, development processing was performed under the same conditions as in the evaluation of the photosensitivity to remove unexposed portions. The adhesion was evaluated by the smallest value (unit: μm) of the line width in which the cured film remained by the development process. Further, the resolution was evaluated by the smallest value (unit: μm) of the space width between the line widths where the portion not photocured by the development treatment could be removed cleanly. The evaluation of adhesion and resolution is better as the numerical value is smaller. The results are shown in Tables 5 and 6.
〔テント信頼性〕
 テント信頼性は、図3に示すような穴破れ数測定用基板40を以下のようにして作製し、これを用いて評価した。銅張積層板(日立化成株式会社製商品名MCL-E-67)に、直径4mm~6mmの穴径で、それぞれ3つの独立した丸穴41及び3つの丸穴が連結し、かつ丸穴の間隔が徐々に短くなる3連穴42を型抜き機によりそれぞれ作製した。丸穴41及び3連穴42を作製した際に生じたバリを#600相当のブラシをもつ研磨機(三啓株式会社製)を使用して取り除き、これを穴破れ数測定用基板40とした。
[Tent reliability]
The tent reliability was evaluated using a hole breakage number measuring substrate 40 as shown in FIG. 3 manufactured as follows. A copper-clad laminate (trade name MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.) is connected with 3 independent round holes 41 and 3 round holes each with a diameter of 4 mm to 6 mm. The three continuous holes 42 whose intervals were gradually shortened were each produced by a die cutting machine. The burr generated when the round hole 41 and the triple hole 42 were produced was removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was used as the substrate 40 for measuring the number of broken holes. .
 得られた穴破れ数測定用基板を80℃に加温し、上記で得られた感光性エレメントから保護フィルムを剥がして、感光性樹脂層がその銅表面に対向するように、実施例1~11及び比較例1~14にかかる感光性エレメントを120℃、0.4MPaの条件で、それぞれラミネートして、テント信頼性評価用積層基板をそれぞれ作製した。 The obtained substrate for measuring the number of broken holes was heated to 80 ° C., and the protective film was peeled off from the photosensitive element obtained above so that the photosensitive resin layer faced the copper surface. 11 and Comparative Examples 1 to 14 were laminated under the conditions of 120 ° C. and 0.4 MPa, respectively, to produce laminated substrates for tent reliability evaluation.
 ラミネート後、テント信頼性評価用積層基板を冷却し、テント信頼性評価用積層基板の温度が23℃になった時点で、ポリエチレンテレフタレートフィルム(支持フィルム)面に対して、半導体励起固体レーザーを光源とする露光機(日本オルボテック株式会社製、商品名「Paragon-9000m」)を用いて、20mJ/cmの露光量で行った。 After lamination, the laminated substrate for tent reliability evaluation is cooled, and when the temperature of the laminated substrate for tent reliability evaluation reaches 23 ° C., a semiconductor-excited solid laser is used as the light source for the polyethylene terephthalate film (support film) surface. The exposure was performed at an exposure amount of 20 mJ / cm 2 using an exposure apparatus (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.).
 露光後、室温(25℃)で15分間放置し、続いてテント信頼性評価用積層基板からポリエチレンテレフタレートフィルムを剥がし、30℃で1質量%炭酸ナトリウム水溶液を50秒間スプレーすることにより現像した。現像後、3連穴の穴破れ数を測定し、全3連穴数に対する穴破れ数として異形テント破れ率を算出し、テント信頼性(%)を評価した。この数値が高いほど、テント信頼性が高いことを意味する。結果を表5及び表6に示す。 After the exposure, the film was left at room temperature (25 ° C.) for 15 minutes, and then the polyethylene terephthalate film was peeled off from the laminated substrate for tent reliability evaluation, and developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds. After development, the number of broken holes in the three holes was measured, and the deformed tent breaking rate was calculated as the number of broken holes with respect to the number of all three holes, and the tent reliability (%) was evaluated. The higher this number, the higher the tent reliability. The results are shown in Tables 5 and 6.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 表5及び表6から、本発明の感光性樹脂組成物を用いた実施例1~11にかかる感光性エレメントを用いた場合は、いずれにおいても比較例1~14にかかる感光性エレメントを用いた場合と比較し、良好な密着性、解像性及び優れたテント信頼性を示した。比較例にかかる感光性エレメントに関しては、光感度は実施例にかかる感光性エレメントと同等であったが、密着、解像性又はテント信頼性が劣っていた。 From Tables 5 and 6, when the photosensitive elements according to Examples 1 to 11 using the photosensitive resin composition of the present invention were used, the photosensitive elements according to Comparative Examples 1 to 14 were used in both cases. Compared to the case, it showed good adhesion, resolution and excellent tent reliability. Regarding the photosensitive element according to the comparative example, the photosensitivity was the same as that of the photosensitive element according to the example, but the adhesion, resolution, or tent reliability was inferior.

Claims (5)

  1.  (A)成分:バインダーポリマーと、
     (B)成分:光重合性化合物と、
     (C)成分:光重合開始剤と、
     (D)成分:(ポリ)エチレンオキサイド〔-(CO)-:nは1以上〕を構造単位として有する化合物と、を含有し、
     前記(A)成分:バインダーポリマーが、(A1)スチレン、スチレン誘導体、ベンジル(メタ)アクリレート及びベンジル(メタ)アクリレート誘導体からなる群より選択される少なくとも1種に由来する構造単位を有し、バインダーポリマーの固形分総量における前記構造単位の含有率が10質量%~60質量%であり、
     前記(A)成分と前記(B)成分の固形分総量に対する、前記(ポリ)エチレンオキサイド〔-(CO)-〕の構造単位の含有率が、25質量%以上である、感光性樹脂組成物。
    (A) component: binder polymer,
    (B) component: a photopolymerizable compound;
    (C) component: a photopolymerization initiator,
    (D) component: a compound having (poly) ethylene oxide [— (C 2 H 4 O) n —: n is 1 or more] as a structural unit,
    Component (A): The binder polymer has a structural unit derived from at least one selected from the group consisting of (A1) styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and a binder The content of the structural unit in the total solid content of the polymer is 10% by mass to 60% by mass,
    The content of the structural unit of (poly) ethylene oxide [— (C 2 H 4 O) n —] relative to the total solid content of the component (A) and the component (B) is 25% by mass or more. Photosensitive resin composition.
  2.  前記(A)バインダーポリマーが、(A2)(メタ)アクリル酸アルキル(アルキル基の炭素数が1~20)に由来する構造単位を含有する、請求項1に記載の感光性樹脂組成物。 2. The photosensitive resin composition according to claim 1, wherein the (A) binder polymer contains a structural unit derived from (A2) alkyl (meth) acrylate (the alkyl group has 1 to 20 carbon atoms).
  3.  支持フィルムと、
     前記支持フィルム上に設けられる、請求項1又は請求項2に記載の感光性樹脂組成物の塗膜である感光性樹脂層と、
     を有する感光性エレメント。
    A support film;
    A photosensitive resin layer that is a coating film of the photosensitive resin composition according to claim 1 or 2 provided on the support film;
    A photosensitive element.
  4.  請求項1又は請求項2に記載の感光性樹脂組成物を用いて形成された感光性樹脂層を基板上に積層する積層工程と、
     前記感光性樹脂層の少なくとも一部の領域に活性光線を照射して、前記領域を硬化させる露光工程と、
     前記感光性樹脂層の前記領域以外の未露光部分を前記基板上から除去することにより、前記基板上に、前記感光性樹脂組成物の硬化物で構成されるレジストパターンを形成する現像工程と、
     を有するレジストパターン付き基板の製造方法。
    A laminating step of laminating a photosensitive resin layer formed using the photosensitive resin composition according to claim 1 or 2 on a substrate;
    An exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to cure the region;
    A developing step of forming a resist pattern composed of a cured product of the photosensitive resin composition on the substrate by removing an unexposed portion other than the region of the photosensitive resin layer from the substrate,
    The manufacturing method of the board | substrate with a resist pattern which has this.
  5.  請求項4に記載の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又はめっきする工程を含む、プリント配線板の製造方法。 A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to claim 4.
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