WO2012101908A1 - 感光性樹脂組成物、感光性エレメント、レジストパターンの製造方法及びプリント配線板の製造方法 - Google Patents

感光性樹脂組成物、感光性エレメント、レジストパターンの製造方法及びプリント配線板の製造方法 Download PDF

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WO2012101908A1
WO2012101908A1 PCT/JP2011/078350 JP2011078350W WO2012101908A1 WO 2012101908 A1 WO2012101908 A1 WO 2012101908A1 JP 2011078350 W JP2011078350 W JP 2011078350W WO 2012101908 A1 WO2012101908 A1 WO 2012101908A1
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group
resin composition
photosensitive resin
mass
meth
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PCT/JP2011/078350
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English (en)
French (fr)
Japanese (ja)
Inventor
宮坂　昌宏
昌樹 遠藤
昌孝 櫛田
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日立化成工業株式会社
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Priority to CN2011800659901A priority Critical patent/CN103339568A/zh
Priority to KR1020137019317A priority patent/KR20140005929A/ko
Priority to JP2012554634A priority patent/JPWO2012101908A1/ja
Publication of WO2012101908A1 publication Critical patent/WO2012101908A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive element, a method for producing a resist pattern, and a method for producing a printed wiring board.
  • photosensitive resin compositions and photosensitive elements (laminates) having a support film and a photosensitive resin composition layer are widely used as resist materials used for etching and plating processes. It has been.
  • the printed wiring board is manufactured as follows, for example. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on the circuit forming substrate. Next, after peeling off and removing the support film, the exposed portion is cured by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays. Then, the resist pattern which consists of hardened
  • the manufacturing method of the printed wiring board by the etching process is a method of peeling the resist after forming the circuit by etching away the conductor layer of the circuit forming substrate not covered with the resist pattern.
  • the method for producing a printed wiring board by plating is to perform a plating process such as copper and solder on a conductor layer of a circuit forming substrate not covered with a resist pattern, and then remove the resist pattern. In this method, the coated metal surface is soft-etched.
  • a method of exposing via a photomask using a mercury lamp as a light source has been used, but in recent years, pattern digital data called DLP (Digital Light Processing) or LDI (Laser Direct Imaging) is used.
  • DLP Digital Light Processing
  • LDI Laser Direct Imaging
  • a direct drawing exposure method is used in which an image is directly drawn on a photosensitive resin composition layer. This direct drawing exposure method has been introduced for manufacturing a high-density package substrate because it has better alignment accuracy than a photomask-based exposure method and can provide a high-definition pattern.
  • the width between circuits is narrow, it is also important that the resist shape is excellent. If the cross-sectional shape of the resist is trapezoidal or inverted trapezoidal, or if the resist is skirted, it may cause a short circuit or disconnection in the circuit formed by the subsequent etching process or plating process. Is preferably rectangular and without skirting.
  • the photosensitive resin composition is required to have excellent peel characteristics after curing. That is, the resist stripping time is shortened to improve the production efficiency of the stripping process, and the resist stripping piece size is reduced to prevent the stripping of the stripping pieces on the circuit board, thereby reducing the production yield. Will improve.
  • the conventional photosensitive resin composition is required to be further improved particularly in terms of resolution, adhesion and resist shape.
  • it has been a problem to improve resolution and adhesion in units of 1 ⁇ m.
  • the present invention provides a photosensitive resin composition that is excellent in all of sensitivity, resolution, adhesion, resist shape, and peeling property after curing, a photosensitive element using the same, a method for producing a resist pattern, and printed wiring. It aims at providing the manufacturing method of a board.
  • the present invention includes the following aspects.
  • the first aspect of the present invention comprises (A) component: binder polymer, (B) component: a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group, (C) component: a photopolymerization initiator, (D) component: a photosensitive resin composition containing a sensitizing dye and satisfying at least one of the following conditions (1) and (2).
  • the sensitizing dye contains at least one compound selected from the group consisting of a pyrazoline compound, an anthracene compound, and a triarylamine compound.
  • the binder polymer includes a structural unit derived from at least one selected from the group consisting of (meth) acrylic acid benzyl ester and (meth) acrylic acid benzyl ester derivatives.
  • the sensitivity, resolution, adhesion, appropriate development time, resist shape and release properties after curing are all good, and a photosensitive resin composition having particularly excellent resolution and adhesion is provided. .
  • the photopolymerization initiator preferably contains a 2,4,5-triarylimidazole dimer. Thereby, sensitivity, resolution, and adhesiveness can be improved.
  • the second aspect of the present invention is a photosensitive element having a support and a photosensitive resin composition layer formed on the support and being a coating film of the photosensitive resin composition.
  • a step of forming a photosensitive resin composition layer which is a coating film of the photosensitive resin composition, on a substrate, and active in at least a part of the photosensitive resin composition layer. Irradiating light to expose the part of the region to form a cured part; removing the region other than the cured part of the photosensitive resin composition layer from the substrate; Forming a resist pattern made of a cured product of the photosensitive resin composition.
  • the wavelength of the actinic ray to be irradiated is preferably in the range of 340 nm to 420 nm.
  • a fourth aspect of the present invention is a method for manufacturing a printed wiring board including a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern. Thereby, a printed wiring board can be manufactured with a high yield.
  • the photosensitive resin composition which is excellent in all of sensitivity, resolution, adhesiveness, a resist shape, and the peeling characteristic after hardening, and the photosensitive element using this, the manufacturing method of a resist pattern, and a print A method for manufacturing a wiring board can be provided.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acryloyl group means acryloyl group or methacryloyl group.
  • the (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene chain
  • the (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene chain.
  • EO-modified means a compound having a (poly) oxyethylene chain
  • PO-modified means a compound having a (poly) oxypropylene chain
  • PO-modified means a compound having both a (poly) oxyethylene chain and a (poly) oxypropylene chain
  • BO-modified means a compound having a (poly) oxybutylene chain
  • EO / BO-modified means a compound having both a (poly) oxyethylene chain and a (poly) oxybutylene chain. It means that.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. It is.
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
  • the photosensitive resin composition of the present invention comprises (A) component: a binder polymer, (B) component: a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group, and (C) component: a photopolymerization initiator. And (D) component: a sensitizing dye, and satisfying at least one of the following conditions (1) and (2).
  • the sensitizing dye contains at least one compound selected from the group consisting of a pyrazoline compound, an anthracene compound, and a triarylamine compound.
  • the binder polymer includes a structural unit derived from at least one selected from the group consisting of (meth) acrylic acid benzyl ester and (meth) acrylic acid benzyl ester derivatives.
  • an example of the embodiment of the present invention includes (A) component: binder polymer, (B) component: polymerizable compound having an ethylenically unsaturated bond and oxybutylene group, and (C) component: photopolymerization initiator. (D) component: a sensitizing dye containing at least one compound selected from the group consisting of a pyrazoline compound, an anthracene compound and a triarylamine compound (hereinafter also referred to as “specific sensitizing dye”). It is an adhesive resin composition.
  • binder polymer comprising a constituent unit derived from at least one selected from the group consisting of (A) component: (meth) acrylic acid benzyl ester and (meth) acrylic acid benzyl ester derivative. (Hereinafter also referred to as “specific binder polymer”), (B) component: a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group, (C) component: a photopolymerization initiator, and (D) component: A photosensitive resin composition containing a sensitizing dye.
  • the photosensitive resin composition includes a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group, and a combination of at least one of a specific sensitizing dye and a specific binder polymer, sensitivity, resolution, It is excellent in all of adhesiveness, appropriate development time, resist shape, and peeling property after curing, and exhibits an effect peculiar to the present application, in particular, excellent in resolution and adhesiveness.
  • the photosensitive resin composition preferably contains a combination of a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group, a specific sensitizing dye, and a specific binder polymer.
  • a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group is combined with at least one compound selected from the group consisting of a pyrazoline compound, an anthracene compound and a triarylamine compound as a sensitizing dye. Therefore, compared with the case of using a general dialkylaminobenzophenone compound as a sensitizing dye, it is excellent in all of sensitivity, resolution, adhesion, appropriate development time, resist shape and release characteristics after curing, Excellent resolution and adhesion.
  • a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group
  • a (meth) acrylic acid benzyl ester and a (meth) acrylic acid benzyl ester derivative as a binder polymer.
  • a styrene-acrylic copolymer that does not contain a structural unit derived from a (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative by combining a binder polymer containing a structural unit.
  • it is excellent in all of sensitivity, resolution, adhesiveness, appropriate development time, resist shape and release characteristics after curing, and particularly excellent in resolution and adhesiveness.
  • the photosensitive resin composition can further improve sensitivity, resolution, and adhesion by including 2,4,5-triarylimidazole dimer as a photopolymerization initiator. This may be because, for example, the amount of exposure light absorbed is increased by the sensitizing dye, and the polymerization efficiency is further improved by interaction with the photopolymerization initiator.
  • the photosensitive resin composition is at least one of a polymerizable compound having an ethylenically unsaturated bond and an oxybutylene group (hereinafter also referred to as “specific polymerizable compound”) as the component (B). Including species.
  • the oxybutylene group is preferably a group represented by the following general formula (1). In the formula (1), n represents an integer of 1 to 30.
  • the specific polymerizable compound is not particularly limited as long as it is a compound having at least one ethylenically unsaturated bond and at least one oxybutylene group. From the viewpoint of resolution, adhesion and developability, a compound having two ethylenically unsaturated bonds and at least one partial structure represented by the general formula (1) is preferable, and two ethylenically unsaturated bonds And at least one of the partial structure represented by the general formula (1) and at least one of an oxyethylene group and an oxypropylene group, and the two ethylenically unsaturated bonds at both ends. More preferably, it is a compound which has. Specific examples include compounds represented by any of the following general formulas (2) to (5).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • XO each independently represents an oxyethylene group or an oxypropylene group.
  • BO represents an oxybutylene group represented by the general formula (1).
  • a and b represent the number of constituent units composed of an oxyethylene group or an oxypropylene group, and each represents an integer of 0 to 20, and a + b represents an integer of 0 to 40.
  • p and q represent the number of constituent units composed of an oxybutylene group, and each independently represents an integer of 1 to 30.
  • the bonding position of XO and BO is not limited to the above structure, and a structure in which an oxyethylene group or oxypropylene group is bonded to the benzene ring side and an oxybutylene group is bonded to the (meth) acrylic acid residue side. It may be.
  • a compound in which a + b is 1 to 12 and p + q is 1 to 8 is preferable from the viewpoint of resolution, adhesion, and developability, and a + b is 1 to 10. More preferred are compounds wherein p + q is 1-6, more preferred are dimethacrylate compounds wherein a + b is 1-10, p + q is 1-6 and XO is an oxyethylene group, and a + b is 2 Particularly preferred are dimethacrylate compounds wherein ⁇ 8, p + q is 2 ⁇ 4, and XO is an oxyethylene group.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • XO represents an oxyethylene group or an oxypropylene group.
  • BO represents an oxybutylene group represented by the general formula (1).
  • c and d represent the number of constituent units composed of an oxyethylene group or an oxypropylene group, and each represents an integer from 0 to 20 and c + d from 0 to 40.
  • r represents the content of structural units composed of oxybutylene groups and represents an integer of 1 to 30.
  • a compound in which c + d is 4 to 20 and r is 2 to 12 is preferable from the viewpoint of resolution, adhesion, and developability, and c + d is 8 to 16. More preferred are compounds wherein r is 4 to 10, more preferred are dimethacrylate compounds wherein c + d is 8 to 16, r is 4 to 10 and XO is an oxyethylene group, and c + d is 10 Particularly preferred are dimethacrylate compounds in which r is 14 and r is 4 to 8 and XO is an oxyethylene group.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • XO represents an oxyethylene group or an oxypropylene group.
  • BO represents an oxybutylene group represented by the general formula (1).
  • e represents the number of structural units composed of oxyethylene or oxypropylene groups, and represents an integer of 1 to 20.
  • s and t represent the number of constituent units composed of an oxybutylene group, and each independently represents an integer of 1 to 30.
  • a compound in which e is 4 to 20 and s + t is 2 to 12 is preferable from the viewpoint of resolution, adhesion, and developability, and e is 8 to 16. More preferred are compounds wherein s + t is 4 to 10, more preferred are dimethacrylate compounds wherein e is 8 to 16, s + t is 4 to 10, and XO is an oxyethylene group, and e is 10 Particularly preferred are dimethacrylate compounds wherein ⁇ 14, s + t is 4 ⁇ 8 and XO is an oxyethylene group.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • XO represents an oxyethylene group or an oxypropylene group.
  • BO represents an oxybutylene group represented by the general formula (1).
  • f and g represent the number of constituent units composed of oxyethylene or oxypropylene groups, and each independently represents an integer of 0 to 20.
  • p and q represent the number of constituent units composed of an oxybutylene group, and each independently represents an integer of 1 to 30.
  • Z represents a divalent linking group.
  • Examples of the divalent linking group represented by Z include, for example, an alkylene group having 4 to 10 carbon atoms, a residue derived from tolylene diisocyanate, a residue derived from 4,4'-diphenylmethane diisocyanate, and an isophorone diisocyanate. Residues, residues derived from hydrogenated 4,4′-diphenylmethane diisocyanate, and the like can be mentioned.
  • a residue derived from tolylene diisocyanate means a divalent group obtained by removing two urethane residues from a diurethane compound produced from tolylene diisocyanate, specifically, a hydrogen atom from an aromatic ring of toluene. It is a tolylene group formed by removing two. The same applies to other residues.
  • the divalent linking group represented by Z is preferably an alkylene group having 4 to 8 carbon atoms from the viewpoint of resolution and adhesion.
  • a compound in which f + g is 4 to 20 and p + q is 2 to 12 is preferable, and f + g is 8 to 16. More preferred are compounds wherein p + q is 4 to 10, more preferred are dimethacrylate compounds wherein f + g is 8 to 16, p + q is 4 to 10, and XO is an oxyethylene group, and f + g is 10 Particularly preferred is a dimethacrylate compound having ⁇ 14, p + q of 4 to 8, and XO being an oxyethylene group.
  • the total content of the structural unit consisting of the oxybutylene group represented by the general formula (1) in the compound represented by any one of the general formula (2) to the general formula (5) is determined from the viewpoint of resolution and adhesion.
  • Each independently is preferably an integer of 1 to 30, more preferably an integer of 1 to 25, still more preferably an integer of 1 to 20, and particularly preferably 1 to 8.
  • the total number of repeating oxyethylene groups and oxypropylene groups is each independently an integer of 0 to 40. , Preferably an integer of 1 to 30, more preferably an integer of 4 to 20, and particularly preferably an integer of 5 to 15. When the total number of the contents is 40 or less, more excellent resolution, adhesion, and resist shape tend to be obtained.
  • the total number of repeating oxyethylene groups and oxypropylene groups is 1 to 20, preferably 5 to 15.
  • the specific polymerizable compound is preferably at least one compound represented by any one of the general formulas (2) to (5) from the viewpoints of resolution and adhesion. ), More preferably at least one compound represented by any one of general formula (3) and general formula (5), represented by any one of general formula (2) and general formula (5). More preferably, it is at least one compound.
  • the content of the specific polymerizable compound in the component (B) is not particularly limited, but from the viewpoint of improving the development time, resolution, adhesion, resist shape, and release properties after curing in a balanced manner, the total mass of the component (B)
  • the content is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 25% by mass to 40% by mass.
  • the component (B) may further contain at least one other polymerizable compound not having the partial structure represented by the general formula (1) in addition to the specific polymerizable compound.
  • Other polymerizable compounds are not particularly limited as long as they do not have the partial structure represented by the general formula (1) in the molecule and have at least one ethylenically unsaturated bond.
  • Examples of compounds having two ethylenically unsaturated bonds in the molecule include bisphenol A di (meth) acrylate compounds, hydrogenated bisphenol A di (meth) acrylate compounds, and di (meth) acrylates having urethane bonds in the molecule.
  • Examples include compounds, polyalkylene glycol di (meth) acrylate compounds having both (poly) oxyethylene chains and (poly) oxypropylene chains in the molecule, and trimethylolpropane di (meth) acrylate.
  • the other polymerizable compound preferably contains at least one bisphenol A-based di (meth) acrylate compound from the viewpoint of improving the resolution and peeling properties after curing.
  • the bisphenol A-based di (meth) acrylate compound include compounds represented by the following general formula (6).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group.
  • m 1 , m 2 , n 1, and n 2 each represent an integer that is a content number, m 1 + m 2 is 1 to 40, and n 1 + n 2 is 0 to 20.
  • the order of bonding of the oxyethylene group and the oxypropylene group is not limited to the general formula (6), and the oxyethylene group and the oxypropylene group may be interchanged.
  • m 1 + m 2 is preferably 4 to 30.
  • N 1 + n 2 is preferably 0 to 16.
  • m 1 + m 2 is 2 to 10 and n 1 + n 2 is 0 It is preferable to use a compound in combination with a compound in which m 1 + m 2 is 20 to 40 and n 1 + n 2 is 0 to 6.
  • m 1 + m 2 is 2 to 8 and n 1 + n 2 is 0
  • the content of the bisphenol A-based di (meth) acrylate compound in the component (B) is not particularly limited, but is preferably 10% by mass to 80% by mass, and preferably 30% by mass to the total mass of the component (B). More preferably, it is 70 mass%.
  • the component (B) is a poly having both (poly) oxyethylene chains and (poly) oxypropylene chains in the molecule. It is preferable to include at least one of alkylene glycol di (meth) acrylate.
  • polyalkylene glycol di (meth) acrylate As the polyalkylene glycol di (meth) acrylate, (poly) oxyethylene chain and (poly) oxypropylene chain ((poly) oxy-n-propylene chain or (poly) Those having both oxyisopropylene chains) are preferred.
  • the polyalkylene glycol di (meth) acrylate further includes a (poly) oxy-n-pentylene chain, a (poly) oxyhexylene chain, and structural isomers thereof, which are represented by the general formula (1). It may have a (poly) oxyalkylene chain having about 4 to 6 carbon atoms other than the partial structure to be formed.
  • the (poly) oxyethylene chain and the (poly) oxypropylene chain may be continuously present in blocks or randomly.
  • the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.
  • polyalkylene glycol di (meth) acrylate a compound represented by the following general formula (7), a compound represented by the general formula (8) or a compound represented by the general formula (9) is particularly preferable. These can be used alone or in combination of two or more.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group.
  • m 3 , m 4 , m 5 and m 6 represent the number of structural units composed of oxyethylene groups
  • n 3 , n 4 , n 5 and n 6 represent the number of structural units composed of oxypropylene groups
  • the total number of repeating oxyethylene groups m 3 + m 4 , m 5 and m 6 are each independently an integer of 1 to 30, and the total number of repeating oxypropylene groups n 3 , n 4 + n 5 and n 6 are each independently 1 to It is an integer of 30.
  • the total number of repeating oxyethylene groups m 3 + m 4 , m 5 and m 6 is an integer of 1 to 30. , Preferably an integer of 1 to 10, more preferably an integer of 4 to 9, and particularly preferably an integer of 5 to 8. When the total content is 30 or less, better resolution, adhesion, and resist shape tend to be obtained.
  • the total number of repeating oxypropylene groups n 3 , n 4 + n 5 and n 6 is an integer of 1 to 30, preferably an integer of 5 to 20, more preferably an integer of 8 to 16, Preferably, it is an integer of 10 to 14.
  • the total number of the contents is 30 or less, better resolution can be obtained and generation of sludge tends to be suppressed.
  • the content of the polyalkylene glycol di (meth) acrylate in the component (B) is not particularly limited, but is preferably 5% by mass to 50% by mass in the total mass of the component (B), and 10% by mass to 40%. More preferably, it is mass%.
  • the component (B) may contain at least one compound having one ethylenically unsaturated bond in the molecule.
  • the compound having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters.
  • nonylphenoxypolyethyleneoxyacrylate and a phthalic acid-based compound from the viewpoint of improving the resolution, adhesion, resist shape, and release property after curing in a well-balanced manner.
  • nonylphenoxypolyethyleneoxyacrylate examples include nonylphenoxytriethyleneoxyacrylate, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethylene Examples include oxyacrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, nonylphenoxyundecaethyleneoxyacrylate, and the like. These can be used alone or in any combination of two or more.
  • phthalic acid compounds examples include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxyethyl-o- Phthalate, and ⁇ -hydroxypropyl- ⁇ ′-(meth) acryloyloxyethyl-o-phthalate, among others, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′-(meth) acryloyloxyethyl-o- Phthalate is preferred.
  • ⁇ -Chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (manufactured by Hitachi Chemical Co., Ltd., product name). These can be used alone or in combination of two or more.
  • the content is not particularly limited, but the resolution, adhesion, resist shape, and release characteristics after curing are balanced.
  • the total mass of the component (B) is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, and 5% by mass to 20% by mass. More preferably it is.
  • (B) component can contain at least 1 sort (s) of the compound which has 3 or more of ethylenically unsaturated bonds in a molecule
  • numerator As a compound having three or more ethylenically unsaturated bonds in the molecule, for example, a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid has 2 to 14 ethylene groups.
  • the component (B) is represented by any one of the general formulas (2) to (5) in which the content in the component (B) is 5% by mass to 50% by mass from the viewpoint of resolution and adhesion.
  • the content of the specific polymerizable compound represented by (5) and the component (B) is 10
  • Binder polymer The photosensitive resin composition contains at least one binder polymer.
  • a commonly used binder polymer can be used without any particular limitation. Among them, a binder polymer having a structural unit derived from at least one of (meth) acrylic acid benzyl ester and (meth) acrylic acid benzyl ester derivative is preferable, and a structural unit derived from (meth) acrylic acid, and (meth) acrylic acid
  • a binder polymer having a structural unit derived from at least one of benzyl ester and a (meth) acrylic acid benzyl ester derivative is more preferable, a structural unit derived from (meth) acrylic acid, and a structural unit derived from styrene or a styrene derivative; More preferred are binder polymers having a structural unit derived from a (meth) acrylic acid benzyl ester or a (meth) acrylic acid benzyl ester derivative and a structural unit
  • Examples of other polymerizable monomers other than (meth) acrylic acid, (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative that can constitute the binder polymer include, for example, styrene, vinyltoluene, ⁇ -methyl Polymerizable styrene derivatives having a substituent on the ⁇ -position or aromatic ring such as styrene; acrylamide such as diacetone acrylamide; esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether; alkyl (meth) acrylate Ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid furfuryl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid isobornyl ester, (meth) acrylic acid adamantyl ester, (meta Acu Dicyclopentanyl ester of lauric acid,
  • the binder polymer may contain a structural unit derived from (meth) acrylic acid alkyl ester from the viewpoint of improving alkali developability and peelability.
  • the content is preferably 1% by mass to 50% by mass based on the total mass of the molecule, and 2% by mass to The content is more preferably 30% by mass, and further preferably 3% by mass to 20% by mass.
  • the content is 1% by mass or more, it is possible to suppress the peeling piece from becoming large, and the peeling time tends to be long.
  • there exists a tendency for sufficient resolution and adhesiveness to be acquired as this content is 50 mass% or less.
  • Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (10).
  • R 10 represents a hydrogen atom or a methyl group
  • R 11 represents an alkyl group having 1 to 12 carbon atoms.
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R 11 in the general formula (10) 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. Decyl group, undecyl group, dodecyl group, and structural isomers thereof. From the viewpoint of further improving the peeling characteristics, the alkyl group preferably has 6 or less carbon atoms, and more preferably has 4 or less carbon atoms.
  • Examples of the monomer represented by the general formula (10) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) ) Acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) ) Acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, and the like. These may be used alone or in any combination of two or more.
  • the binder polymer is at least one of a structural unit derived from styrene or a derivative thereof, and a structural unit derived from benzyl (meth) acrylate or a benzyl derivative (meth) acrylate, from the viewpoint of improving resolution and adhesion. It is preferable to contain.
  • the content is not particularly limited, but is 5% by mass to 80% by mass based on the total mass of the binder polymer molecule. It is preferably 15% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, particularly preferably 30% by mass to 55% by mass, and 35% by mass. It is very preferable to be ⁇ 50 mass%. When this content is 10% by mass or more, better adhesion tends to be obtained, and when this content is 80% by mass or less, it is possible to suppress the peeling piece from becoming large, and the peeling time is long. There is a tendency that it can be suppressed.
  • the content of the structural unit derived from benzyl (meth) acrylate or a derivative thereof in the binder polymer is not particularly limited, but is preferably 5% by mass to 80% by mass based on the total mass of the binder polymer molecule. % To 75% by mass, more preferably 20% to 70% by mass, further preferably 20% to 65% by mass, and 20% to 40% by mass. Is particularly preferred. There exists a tendency for a more favorable resolution to be obtained as this content rate is 5 mass% or more. Moreover, there exists a tendency which can suppress that a peeling piece becomes large as this content rate is 80 mass% or less, and can suppress that peeling time becomes long.
  • the acid value of the binder polymer is not particularly limited, but is preferably 100 mgKOH / g to 250 mgKOH / g, more preferably 120 mgKOH / g to 230 mgKOH / g, and further preferably 130 mgKOH / g to 220 mgKOH / g. 140 mg KOH / g to 210 mg KOH / g is particularly preferable.
  • this acid value is 100 mgKOH / g or more, there is a tendency that it is possible to suppress an increase in development time. Moreover, there exists a tendency for the developing solution resistance (adhesion) of the hardened
  • the binder polymer includes at least one structural unit derived from benzyl (meth) acrylate or a derivative thereof, at least one structural unit derived from (meth) acrylic acid, and a structural unit derived from styrene or a derivative thereof. And at least one structural unit derived from a (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 6 carbon atoms. More preferable embodiments of the binder polymer are derived from at least one structural unit derived from benzyl (meth) acrylate or a derivative thereof, at least one structural unit derived from (meth) acrylic acid, and styrene or a derivative thereof.
  • (meth) acrylic acid in a binder polymer molecule having at least one structural unit derived from (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 6 carbon atoms.
  • the content of structural units derived from benzyl or a derivative thereof is 20% by mass to 70% by mass.
  • Further preferred embodiments of the binder polymer are derived from at least one structural unit derived from benzyl (meth) acrylate or a derivative thereof, at least one structural unit derived from (meth) acrylic acid, and styrene or a derivative thereof.
  • (meth) acrylic acid in a binder polymer molecule having at least one structural unit derived from (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 6 carbon atoms.
  • the content of structural units derived from benzyl or a derivative thereof is 20% by mass to 65% by mass
  • the content of structural units derived from styrene or a derivative thereof is 30% by mass to 55% by mass
  • the content of structural units derived from (meth) acrylic acid alkyl ester containing 6 alkyl groups is 2% by mass to 30% by mass.
  • the acid value is 130mgKOH / g ⁇ 220mgKOH / g.
  • the weight average molecular weight (Mw) of the binder polymer is not particularly limited. When measured by gel permeation chromatography (GPC) (converted with a calibration curve using standard polystyrene), the weight average molecular weight (Mw) is preferably 10,000 to 100,000, more preferably 20,000 to 80,000. More preferably, it is 25000-70000. When the weight average molecular weight (Mw) is 10,000 or more, the developer resistance (adhesiveness) of the cured product of the photosensitive resin composition tends to be better. Moreover, there exists a tendency which can suppress that developing time becomes long as it is 100000 or less.
  • GPC gel permeation chromatography
  • the dispersity (Mw / Mn) of the binder polymer is not particularly limited, but is preferably 1.0 to 3.0, and more preferably 1.0 to 2.5. When the degree of dispersion is 3.0 or less, the adhesion and resolution tend to be better.
  • the binder polymer may have, in the molecule, a characteristic group that has photosensitivity to light having a wavelength in the range of 350 nm to 440 nm, if necessary.
  • binder polymer As the binder polymer as the component (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination.
  • a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymer components (including different monomer units as copolymer components), two or more types of different weight average molecular weights
  • the binder polymer include two or more types of binder polymers having different degrees of dispersion.
  • a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.
  • the content of component (A) is preferably 30 parts by mass to 70 parts by mass, and preferably 35 parts by mass to 65 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B). More preferred is 40 to 60 parts by mass.
  • the film formability to become more favorable that this content is 30 mass parts or more.
  • a sensitivity and a resolution to become more favorable that it is 70 mass parts or less.
  • the photosensitive resin composition includes at least one specific polymerizable compound represented by any one of the general formulas (2) to (5) as the component (B), and (A ) At least one structural unit derived from benzyl (meth) acrylate or a derivative thereof as a component, at least one structural unit derived from (meth) acrylic acid, or at least one structural unit derived from styrene or a derivative thereof.
  • binder polymer having at least one structural unit derived from a (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 6 carbon atoms, wherein the content of (A) component is (A) component and The total amount of component (B) is preferably 30 to 70 parts by mass with respect to 100 parts by mass.
  • a more preferred embodiment of the photosensitive resin composition is a specific polymerization represented by any one of the general formula (2), the general formula (3) and the general formula (5) as the component (B) from the viewpoint of resolution and adhesion.
  • at least one structural unit derived from benzyl (meth) acrylate or a derivative thereof as component (A) at least one structural unit derived from (meth) acrylic acid, styrene or the like (Meth) acrylic acid in the molecule having at least one structural unit derived from a derivative and at least one structural unit derived from a (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 6 carbon atoms
  • the content of the structural unit derived from benzyl (meth) acrylate or a derivative thereof in the molecule is 20% by mass to 65% by mass.
  • the content of the structural unit derived from the derivative is 30% by mass to 55% by mass, and the content of the structural unit derived from the (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 6 carbon atoms is 2% by mass.
  • a binder polymer having an acid value of 130 mgKOH / g to 220 mgKOH / g, and the content of component (A) is 100 parts by mass of the total amount of component (A) and component (B) On the other hand, it is 40 to 60 parts by mass.
  • Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator.
  • the photopolymerization initiator include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 Aromatic ketone compounds such as morpholino-propan-1-one, quinone compounds such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- 2,4,5-triarylimidazole dimer compounds such as (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 9-pheny
  • the photopolymerization initiator as component (C) preferably contains at least one 2,4,5-triarylimidazole dimer from the viewpoint of improving sensitivity and adhesion, and 2- (o-chlorophenyl). ) -4,5-diphenylimidazole dimer is more preferable.
  • the 2,4,5-triarylimidazole dimer may have a symmetric structure or an asymmetric structure.
  • the content of component (C) is preferably 0.1 to 10 parts by weight, and preferably 1 to 7 parts by weight with respect to 100 parts by weight as the total of component (A) and component (B). More preferred is 2 to 6 parts by mass, still more preferred is 3 to 5 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. Moreover, there exists a tendency for a more favorable resist shape to be obtained as it is 10 mass parts or less.
  • the component (C) in the present invention contains at least one 2,4,5-triarylimidazole dimer in an amount of 0.1 parts by mass to 100 parts by mass of the total amount of the components (A) and (B). It is preferable to contain 10 parts by mass, and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is 1 part by mass to 7 parts by mass with respect to 100 parts by mass as the total of component (A) and component (B). It is more preferable to include a part.
  • Sensitizing dye The photosensitive resin composition contains at least one sensitizing dye.
  • sensitizing dyes include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, Examples include a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound. These can be used alone or in combination of two or more.
  • the sensitizing dye as component (D) is at least one selected from the group consisting of pyrazoline compounds, anthracene compounds, coumarin compounds, triarylamine compounds, thioxanthone compounds, and aminoacridine compounds. It is preferable to include a species, and it is more preferable to include at least one selected from the group consisting of a pyrazoline compound, an anthracene compound, and a triarylamine compound.
  • the pyrazolines are preferably pyrazoline compounds represented by any one of the following general formula (11) and general formula (12).
  • R 3 to R 5 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or Indicates a halogen atom.
  • x1, y1 and z1 each independently represent an integer of 0 to 5, and the sum of x1, y1 and z1 is 1 to 6.
  • a plurality of R 3 to R 5 may be the same as or different from each other.
  • R 3 to R 5 is a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched chain group having 1 to 10 carbon atoms. It is preferably an alkoxy group, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched alkoxy group having 1 to 3 carbon atoms, and an isopropyl group More preferably, it is a methoxy group or an ethoxy group.
  • pyrazoline compound represented by the general formula (11) examples include 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4- tert-butyl-styryl) -5- (4-tert-butyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- ( 3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1 -Phenyl-3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2
  • R 6 to R 8 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, A halogen atom or a phenyl group is shown.
  • x2, y2 and z2 each independently represent an integer of 0 to 5, and the sum of x2, y2 and z2 is 1 to 6.
  • a plurality of R 6 to R 8 may be the same as or different from each other.
  • R 6 to R 8 is a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched chain group having 1 to 10 carbon atoms. It is preferably an alkoxy group or a phenyl group, and is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a phenyl group.
  • R 6 to R 8 is a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched chain group having 1 to 10 carbon atoms. It is preferably an alkoxy group or a phenyl group, and is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a phenyl group.
  • a tert-butyl group an isopropyl group, a meth
  • Examples of the pyrazoline compound represented by the general formula (12) include 1-phenyl-3,5-bis (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3,5-bis (4-methoxy-). Phenyl) -pyrazoline, 1-phenyl-3- (4-methoxy-phenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-phenyl) -5 -(4-methoxy-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropyl-phenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert- Butyl-phenyl) -5- (4-isopropyl-phenyl) -pyrazoline, 1-phenyl-3- (4-methoxy-phenyl) -5- (4-isopropy
  • the anthracene compound is preferably an anthracene compound represented by the following general formula (13).
  • R 9 and R 10 are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxyalkyl having 2 to 12 carbon atoms.
  • R 11 to R 18 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a halogen atom, a cyano group, a carboxy group, or a phenyl group. , A phenoxy group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a benzoyl group.
  • the linear or branched alkyl group having 1 to 20 carbon atoms or the linear or branched alkoxyalkyl group having 2 to 12 carbon atoms may be substituted with a hydroxyl group.
  • the cycloalkyl group having 5 to 12 carbon atoms or the cycloalkyl ether group having 5 to 12 carbon atoms may be substituted with a hydroxyl group.
  • the phenyl group, benzyl group, benzoyl group and alkanoyl group in R 9 and R 10 may have a substituent.
  • substituents include an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • the at least 1 sort (s) chosen from the group which consists of can be mentioned.
  • R 9 and R 10 are preferably each independently an alkyl group having 1 to 20 carbon atoms from the viewpoint of resolution and adhesion, An alkyl group is more preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is still more preferred.
  • Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • R 9 and R 10 may be the same or different, but are preferably the same from the viewpoint of resolution and adhesion. Specific examples include combinations of ethyl groups, combinations of propyl groups, combinations of butyl groups, and the like.
  • R 11 to R 18 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms from the viewpoints of resolution and adhesion.
  • an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxy group is preferable.
  • R 11 to R 18 are each independently a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, It is preferably a heptenyl group, an ethoxycarbonyl group, a hydroxyethoxycarbonyl group, or a phenoxy group.
  • R 11 to R 18 in the general formula (13) from the viewpoint of resolution and adhesion, all of them are hydrogen atoms; any one of them is a methyl group, an ethyl group, a propyl group, a butyl group , A pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an ethoxycarbonyl group, a hydroxyethoxycarbonyl group, or a phenoxy group, and everything else is a hydrogen atom; Any two of them are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, ethoxycarbonyl, hydroxyethoxycarbonyl Group, or phenoxy
  • R 9 and R 10 are alkyl groups having 1 to 4 carbon atoms and R 11 to R 18 are hydrogen atoms from the viewpoint of resolution and adhesion. Particularly preferred.
  • Specific examples of the compound represented by the general formula (13) preferably include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.
  • the triarylamine compound is preferably a triarylamine compound represented by the following general formula (14).
  • R 19 , R 20 and R 21 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched chain having 1 to 4 carbon atoms.
  • h, i, and j represent integers of 0 to 5 selected so that the value of h + i + j is 1 or more.
  • h 2 or more
  • a plurality of R 19 may be the same or different.
  • i is 2 or more
  • a plurality of R 20 may be the same or different.
  • j is 2 or more
  • a plurality of R 21 may be the same or different.
  • R 19 is a linear or branched alkyl group having 1 to 10 carbon atoms and i and j are 0 from the viewpoints of resolution and adhesion.
  • H is preferably 1
  • R 19 is a linear or branched alkyl group having 1 to 4 carbon atoms, i and j are 0, and h is preferably 1.
  • the content of the component (D) is not particularly limited, but is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 0.05 parts by mass More preferably, it is ⁇ 5 parts by mass, and further preferably 0.1-3 parts by mass. There exists a tendency for a more favorable sensitivity and resolution to be obtained as this content is 0.01 mass part or more. Moreover, there exists a tendency for a more favorable resist shape to be obtained as it is 10 mass parts or less.
  • the sensitizing dye as the component (D) is composed of at least one selected from the group consisting of a pyrazoline compound, an anthracene compound and a triarylamine compound from the viewpoints of resolution and adhesiveness, as the component (A) and the component (B). It is preferable to contain 0.01 to 10 parts by mass with respect to 100 parts by mass in total.
  • at least one selected from the group consisting of triarylamine compounds represented by the general formula (14) is 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass as a total of the components (A) and (B). It is more preferable to include a part.
  • the photosensitive resin composition comprises at least one specific polymerizable compound represented by any one of the general formulas (2) to (5) as the component (B), and (D ) At least one selected from the group consisting of a pyrazoline compound, an anthracene compound and a triarylamine compound as a component, 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight as a total of the component (A) and the component (B) It is preferable to include.
  • a more preferred embodiment of the photosensitive resin composition is a specific polymerization represented by any one of the general formula (2), the general formula (3) and the general formula (5) as the component (B) from the viewpoint of resolution and adhesion. And at least one kind of an organic compound and a pyrazoline compound represented by the general formula (11) or the general formula (12) as a component (D), an anthracene compound represented by the general formula (13), and a general formula (14) And at least one selected from the group consisting of triarylamine compounds is contained in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass as the total of component (A) and component (B).
  • the photosensitive resin composition preferably further contains at least one of component (E): amine compound.
  • component (E): amine compound examples include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leuco crystal violet. These can be used individually by 1 type or in combination of 2 or more types.
  • the content is not particularly limited, but 0.01 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is preferably from 10 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, and particularly preferably from 0.1 to 2 parts by mass.
  • this content is 0.01 parts by mass or more, better sensitivity tends to be obtained, and when it is 10 parts by mass or less, excessive (E) component is prevented from being precipitated as foreign matter after film formation. it can.
  • the said photosensitive resin composition can contain other components other than the above as needed.
  • Other components include photopolymerizable compounds (such as oxetane compounds) having at least one cationically polymerizable cyclic ether group in the molecule, cationic polymerization initiators, dyes such as malachite green, and photochromic colors such as tribromophenylsulfone.
  • the said photosensitive resin composition can contain a solvent as needed. It does not restrict
  • the content of the solvent is appropriately selected according to the purpose.
  • the photosensitive resin composition can be made into a solution having a solid content of about 30% by mass to 60% by mass. In addition, solid content is the total amount of the non-volatile component in the photosensitive resin composition.
  • the said photosensitive resin composition can be used for formation of the photosensitive resin composition layer as follows, for example.
  • the coating solution is applied onto the surface of a support such as a support film or a metal plate, which will be described later, and dried to form a photosensitive resin composition layer, which is a coating film of the photosensitive resin composition, on the support.
  • a support such as a support film or a metal plate, which will be described later
  • a photosensitive resin composition layer which is a coating film of the photosensitive resin composition, on the support.
  • the metal plate include iron alloys such as copper, copper alloys, nickel, chromium, iron, and stainless steel, preferably copper, copper alloys, iron alloys, and the like.
  • the thickness of the formed photosensitive resin composition layer varies depending on its use, but is preferably about 1 ⁇ m to 100 ⁇ m after drying.
  • the surface (surface) opposite to the surface facing the support of the photosensitive resin composition layer may be covered with a protective film.
  • the protective film include polymer films such as polyethylene and polypropylene.
  • a photosensitive element 10 of the present invention has a support 2 and a photosensitive resin composition layer 4 that is a coating film of the photosensitive resin composition formed on the support. And it has other layers, such as the protective film 6 provided as needed.
  • the support 2 for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.
  • the thickness of the support (hereinafter also referred to as “polymer film”) is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, and even more preferably 5 ⁇ m to 30 ⁇ m. It can suppress that a polymer film tears at the time of application
  • the photosensitive element 10 may further include a protective film 6 that covers a surface (surface) opposite to the surface facing the support 2 of the photosensitive resin composition layer 4 as necessary.
  • the protective film 6 preferably has a smaller adhesive strength to the photosensitive resin composition layer than the adhesive strength of the support to the photosensitive resin composition layer, and is preferably a low fish eye film.
  • fish eye means that a material constituting a protective film is melted by heat, kneaded, extruded, biaxially stretched, a film is produced by a casting method, etc., and foreign materials, undissolved materials, oxidative deterioration of the material. This means that an object or the like is taken into the film. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
  • a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester 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.
  • the protective film may be the same as the above support.
  • the thickness of the protective film is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, still more preferably 5 ⁇ m to 30 ⁇ m, and particularly preferably 15 ⁇ m to 30 ⁇ m.
  • the protective film can be prevented from being broken when the photosensitive resin composition layer and the support film are laminated on the substrate while peeling off the protective film.
  • productivity improves by being 100 micrometers or less.
  • the photosensitive element of this invention can be manufactured as follows, for example.
  • coating liquid a solvent
  • It can be manufactured by a manufacturing method including a process and other processes as necessary.
  • Application of the coating solution onto the support can be performed by a known method such as a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater, spray coater or the like.
  • 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 can be 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 composition 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 composition layer in the photosensitive element can be appropriately selected depending on the application, but the thickness after drying is preferably 1 ⁇ m to 200 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to It is especially preferable that it is 50 micrometers. When this thickness is 1 ⁇ m or more, industrial coating becomes easy and productivity is improved. In the case of 200 ⁇ m or less, the effects of the present invention are sufficiently obtained, the photosensitivity is high, and the photocurability at the bottom of the resist tends to be excellent.
  • the thickness in the photosensitive resin composition layer is preferably 1 ⁇ m to 40 ⁇ m, and more preferably 5 ⁇ m to 35 ⁇ m.
  • the photosensitive element of the present invention may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer, if necessary.
  • an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer, if necessary.
  • these intermediate layers for example, the intermediate layers described in JP-A-2006-098982 can be applied to the present invention.
  • the form of the photosensitive element of the present invention 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 core include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and plastics such as ABS (acrylonitrile-butadiene-styrene copolymer).
  • an end face separator from the standpoint of protecting the end face 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.
  • a packaging method it is preferable to wrap and package in a black sheet with low moisture permeability.
  • the photosensitive element of the present invention can be suitably used, for example, for a resist pattern manufacturing method described later.
  • a photosensitive resin composition layer which is a coating film of the photosensitive resin composition, is formed on a circuit forming substrate (hereinafter sometimes referred to as “substrate”).
  • a photosensitive resin composition layer forming step and (ii) an exposure step of irradiating at least a partial region of the photosensitive resin composition layer with an actinic ray to form a cured portion in the partial region; (Iii) removing a region other than the cured portion of the photosensitive resin composition layer from the substrate to form a resist pattern made of a cured product of the photosensitive resin composition on the substrate.
  • other steps are included as necessary.
  • Photosensitive resin composition layer forming step In the photosensitive resin composition layer forming step, a photosensitive resin composition layer derived from the photosensitive resin composition is formed on a substrate.
  • the substrate usually includes an insulating layer and a conductor layer formed on the insulating layer.
  • substrate which the photosensitive resin composition layer touches becomes a conductor layer normally. There is no restriction
  • the photosensitive resin composition of the photosensitive element is removed after removing the protective film. This can be done by pressing the layer to the substrate while heating. Thereby, the laminated body provided with a board
  • This photosensitive resin composition layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Heating at the time of pressure bonding is preferably performed 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 ), but these conditions are appropriately selected as necessary. If the photosensitive resin composition layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the substrate is pre-heated in order to further improve adhesion and followability. You can also.
  • Exposure step In the exposure step, at least a part of the photosensitive resin composition layer formed on the substrate is irradiated with active light, and the exposed portion irradiated with the active light is photocured to form a latent image. It is formed.
  • the support existing on the photosensitive resin composition layer is transmissive to actinic rays, it can be irradiated with actinic rays through the support, but the support is light-shielding. For this, the photosensitive resin composition layer is irradiated with actinic rays after the support is removed.
  • Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method).
  • a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.
  • LDI Laser Direct Imaging
  • DLP Digital Light Processing
  • active light sources include 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, semiconductor lasers, and gallium nitride.
  • gas lasers such as argon lasers
  • solid state lasers such as YAG lasers
  • semiconductor lasers and gallium nitride.
  • a laser that effectively emits ultraviolet rays such as a blue-violet laser is used.
  • the wavelength of the actinic ray is not particularly limited, but is preferably in the range of 340 nm to 420 nm, and more preferably in the range of 390 nm to 420 nm, from the viewpoint of obtaining the effects of the present invention more reliably. .
  • development step In the development step, an uncured portion of the photosensitive resin composition layer is removed from the substrate by development, whereby a resist pattern made of a cured product obtained by photocuring the photosensitive resin composition layer. (Photocured portion) is formed on the substrate. When a support film is present on the photosensitive resin composition layer, the support film is removed, and then removal (development) of unexposed portions other than the exposed portions is performed. Development methods include wet development and dry development.
  • 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 dip method, a battle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like. From the viewpoint of improving the resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.
  • the configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. Specifically, 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 alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate.
  • 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 used for development is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating 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, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3- Examples include 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. Is mentioned. These are used alone or in combination of two or more.
  • the concentration of the organic solvent in the aqueous developer is usually preferably 2 to 90% by mass, and the temperature can be adjusted according to the 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 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone. These organic solvents are preferably added with water in the range of 1% by mass to 20% by mass in order to prevent ignition.
  • the resist pattern may be further cured and used.
  • the method for producing a printed wiring board of the present invention includes a step of forming a conductor pattern by etching or plating a circuit forming substrate on which a photocured portion (resist pattern) is formed by the method for producing a resist pattern, Other steps such as a photocured portion removing step may be included as necessary.
  • the photosensitive element is particularly suitable for the production of a printed wiring board by a method including a plating process, and particularly suitable for use in a semi-additive method (SAP).
  • SAP semi-additive method
  • the photosensitive element according to this embodiment is particularly suitable for use in SAP.
  • the conductor layer of the circuit forming substrate not covered with the resist pattern is removed by etching to form a conductor pattern.
  • Etching method is appropriately selected according to the conductor layer to be removed.
  • a cupric chloride solution a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution can be mentioned. It is desirable to use a ferric chloride solution from the viewpoint of good etch factor. .
  • the plating process copper and solder are plated on the conductor layer of the circuit forming substrate that is not covered with the resist pattern, using the resist pattern formed on the substrate as a mask. After the plating process, the resist pattern is removed, and the conductor layer covered with the resist pattern is etched to form a conductor pattern.
  • the plating treatment method may be electrolytic plating treatment or electroless plating treatment.
  • Plating treatment includes copper plating such as copper sulfate plating, copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate plating, 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 by, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step.
  • a 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.
  • 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.
  • Examples of the resist pattern peeling method include an immersion method and a spray method, and these may be used alone or in combination.
  • a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment 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 manufactured by 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. It can also be applied to manufacturing.
  • Binder polymer> [Synthesis of Binder Polymer (A-1)] A polymerizable monomer (monomer) of 150 g of methacrylic acid, 125 g of benzyl methacrylate, 25 g of methyl methacrylate and 200 g of styrene (mass ratio 30/25/5/40), and 9.0 g of azobisisobutyronitrile. The solution obtained by mixing was designated as “Solution a”.
  • Solution b A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of methyl cellosolve and 40 g of toluene was designated as “Solution b”.
  • the solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring.
  • the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. 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 (A-1) solution.
  • the binder polymer (A-1) had a non-volatile content (solid content) of 47.8% by mass, a weight average molecular weight of 30,000, and an acid value of 196 mgKOH / g.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
  • Binder Polymers (A-2) to (A-3) As the polymerizable monomer (monomer), the binder polymer (A-2) was obtained in the same manner as in the case of obtaining a solution of the binder polymer (A-1) except that the materials shown in Table 1 were used in the mass ratio shown in the same table. ) To (A-3) were obtained. The acid value and weight average molecular weight of the obtained binder polymer are shown in Table 1.
  • ⁇ (B) component polymerizable compound>
  • the polymerizable compound shown below was prepared as the polymerizable compound having an ethylenically unsaturated bond.
  • Polymerizable compound (B-1): EOBO-modified bisphenol A methacrylate represented by the general formula (2) (the total number of repeating oxyethylene groups (average value of a + b) is 2 mol, the total number of repeating oxybutylene groups represented by the general formula (1) (p + q (Average value) is 2 mol, R 1 , R 2 methyl group)
  • Polymerizable compound (B-2): EOBO-modified bisphenol A methacrylate represented by the general formula (2) (repeating total number of oxyethylene groups (average value of a + b) is 8 mol, repeating total number of oxybutylene groups represented by the general formula (1) (p + q (Average value) is 2 mol, R 1 , R 2 methyl group)
  • -DBA (trade name, manufactured by Kawasaki Chemical Industry Co., Ltd.): 9,10-dibutoxyanthracene / PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline / J205 (manufactured by Nippon Distillation Co., Ltd., trade name): Triphenylamine derivative represented by the following formula (15)
  • Examples 1 to 12 Comparative Examples 1 to 5> Using the compounds prepared above, each component was mixed so as to have the composition shown in Table 2 below, and solution-like photosensitive resin compositions according to Examples 1 to 12 and Comparative Examples 1 to 5 were prepared. .
  • the unit of the numerical values in Table 2 is parts by mass, and “-” indicates no compounding.
  • Photosensitive element Each of the photosensitive resin compositions obtained above was uniformly applied onto a polyethylene terephthalate film (product name “HTF-01” manufactured by Teijin Limited) with a thickness of 16 ⁇ m, and hot air convection at 70 ° C. and 110 ° C. It dried with the type
  • a protective film manufactured by Tamapoly Co., Ltd., product name “NF-15” is bonded onto the photosensitive resin composition layer, and a polyethylene terephthalate film (supporting film), the photosensitive resin composition layer, a protective film, Each of the photosensitive elements laminated in order was obtained.
  • the copper surface of a copper-clad laminate (product name: MCL-E-679F, manufactured by Hitachi Chemical Co., Ltd.) consisting of a glass epoxy material and copper foil (thickness 16 ⁇ m) formed on both sides is treated with a CZ treatment solution. (MEC Co., Ltd.) After heating the roughened copper substrate (hereinafter also simply referred to as “substrate”) to 80 ° C., the photosensitive elements according to Examples 1 to 12 and Comparative Examples 1 to 5 were placed on the copper surface of the substrate. Was laminated. Lamination was performed under the conditions of a temperature of 120 ° C.
  • substrate was obtained.
  • the photosensitive resin composition layer was exposed, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 24 seconds to remove unexposed portions.
  • a resist pattern (cured film) made of a cured product of the photosensitive resin composition was formed on the copper surface of the substrate.
  • the sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining steps of the step tablet obtained as a cured film. The sensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps, the better the sensitivity. The results are shown in Table 4.
  • the space part (unexposed part) is removed neatly, and the line part (exposed part) has the smallest line width / space width value among the resist patterns formed without meandering or chipping. Resolution and adhesion were evaluated. A smaller value means better resolution and adhesion. The results are shown in Table 4.
  • the obtained resist shape (cross-sectional shape of the resist pattern) was observed using a Hitachi scanning electron microscope S-500A, and the shape was evaluated. The results are shown in Table 4.
  • the resist shape is trapezoidal or inverted trapezoidal, or when there is a skirting or cracking of the resist, there is a tendency that a short circuit or disconnection is likely to occur in a circuit formed by the subsequent etching process or plating process. Therefore, it is desirable that the resist shape is rectangular (rectangular) and that there is no bottoming or cracking of the resist.
  • the term “crack” means that a line portion (exposed portion) of the resist pattern is cracked or cracked, or accompanying this, the line portion is chipped or broken.
  • the photosensitive resin compositions of Examples 1 to 12 all had good sensitivity, resolution, adhesion, resist shape, and release characteristics after curing.
  • the photosensitive resin compositions of Comparative Examples 1 to 5 were inferior to those of Examples in terms of resolution, adhesion, or resist shape.

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WO2014141969A1 (ja) * 2013-03-12 2014-09-18 日産化学工業株式会社 めっきレジスト用樹脂組成物およびそれを用いた基板の製造方法
JP2014182282A (ja) * 2013-03-19 2014-09-29 Hitachi Chemical Co Ltd 感光性樹脂組成物、感光性エレメント、レジストパターン付き基板の製造方法及びプリント配線板の製造方法
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JP2013061556A (ja) * 2011-09-14 2013-04-04 Asahi Kasei E-Materials Corp 感光性樹脂組成物
JP2013083785A (ja) * 2011-10-07 2013-05-09 Asahi Kasei E-Materials Corp 感光性樹脂組成物及び感光性樹脂積層体
JPWO2014141969A1 (ja) * 2013-03-12 2017-02-16 日産化学工業株式会社 めっきレジスト用樹脂組成物およびそれを用いた基板の製造方法
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JP2020064318A (ja) * 2017-03-01 2020-04-23 旭化成株式会社 感光性樹脂組成物
CN110446976B (zh) * 2017-03-01 2023-03-24 旭化成株式会社 感光性树脂组合物
KR20200086743A (ko) 2018-01-18 2020-07-17 아사히 가세이 가부시키가이샤 감광성 수지 적층체 및 그 제조 방법
KR20220061260A (ko) 2018-01-18 2022-05-12 아사히 가세이 가부시키가이샤 감광성 수지 적층체 및 그 제조 방법
KR20230131250A (ko) 2021-03-05 2023-09-12 아사히 가세이 가부시키가이샤 감광성 수지 적층체 및 그 제조 방법

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