TWI691792B - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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TWI691792B
TWI691792B TW108117792A TW108117792A TWI691792B TW I691792 B TWI691792 B TW I691792B TW 108117792 A TW108117792 A TW 108117792A TW 108117792 A TW108117792 A TW 108117792A TW I691792 B TWI691792 B TW I691792B
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epoxy resin
mass
resin composition
parts
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TW201937290A (en
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布施好章
吉野利純
小島正幸
大崎真也
佐藤邦明
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日商日立化成股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Epoxy Resins (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本發明是關於一種感光性樹脂組成物，其含有：(A)含有酸改質乙烯基之環氧樹脂；(B)醯基氧化膦系光聚合起始劑；(C)添加劑，該(C)添加劑是選自(C1)烷基胺基苯衍生物、(C2)吡唑啉系敏化劑或蒽系敏化劑、(C3)光聚合起始劑、(C4)抗氧化劑及(C5)含有氫硫基之化合物中的至少一種，該(C3)光聚合起始劑是選自咪唑系光聚合起始劑、吖啶系光聚合起始劑及二茂鈦系光聚合起始劑中的至少一種，該(C4)抗氧化劑是選自受阻酚系抗氧化劑、醌系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑及磷系抗氧化劑中的至少一種；及，(D)光聚合性化合物。The present invention relates to a photosensitive resin composition, which contains: (A) an epoxy resin containing an acid-modified vinyl group; (B) an acylphosphine oxide-based photopolymerization initiator; (C) an additive, the (C ) The additive is selected from (C1) alkylaminobenzene derivatives, (C2) pyrazoline-based sensitizer or anthracene-based sensitizer, (C3) photopolymerization initiator, (C4) antioxidant and (C5 ) At least one compound containing a hydrogen sulfide group, the (C3) photopolymerization initiator is selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators and titanocene-based photopolymerization initiators At least one of the (C4) antioxidants is at least one selected from hindered phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants; and, (D) light Polymerizable compound.

Description

感光性樹脂組成物Photosensitive resin composition

本發明有關一種感光性樹脂組成物、使用該感光性樹脂組成物而成之感光性元件、永久遮罩阻劑層、及具備該永久遮罩阻劑層之印刷電路板。The present invention relates to a photosensitive resin composition, a photosensitive element formed using the photosensitive resin composition, a permanent mask resist layer, and a printed circuit board provided with the permanent mask resist layer.

在印刷電路板製造之領域中，已在進行將永久遮罩阻劑層(permanent mask resist)形成於印刷電路板上的技術。永久遮罩阻劑層，其具有下述作用：在使用印刷電路板時，防止導體層腐蝕、保持導體層間的電絕緣性。近年來，永久遮罩阻劑層變得亦具有作為阻焊膜(solder resist film)之作用，該作用是在透過焊料將半導體元件進行覆晶(flip chip)安裝、打線接合(wire bonding)等之步驟中，防止焊料附著於印刷電路板的導體層的不要的部份。In the field of printed circuit board manufacturing, technology for forming a permanent mask resist layer on a printed circuit board has been carried out. The permanent masking resist layer has the following functions: when the printed circuit board is used, the conductor layer is prevented from corroding and the electrical insulation between the conductor layers is maintained. In recent years, the permanent mask resist layer has also been used as a solder resist film (solder resist film), which is used for solder chip mounting of semiconductor devices (flip chip), wire bonding (wire bonding), etc. In this step, solder is prevented from attaching to unnecessary parts of the conductor layer of the printed circuit board.

以往，印刷電路板之製造中的永久遮罩阻劑層，是以採用熱硬化性樹脂組成物之網版印刷、或採用感光性樹脂組成物之照相法所製作而成。例如，在採用FC(Flip Chip，覆晶)、TAB(Tape Automated Bonding，捲帶式自動接合)、及COF(Chip On Film，晶粒軟膜接合)之類的安裝方式而成的撓性電路板中，除了IC晶片、電子零件、LCD(Liquid Crystal Display)面板、及連接電路圖案部分以外，是將熱硬化性樹脂糊進行網版印刷並且熱硬化而形成永久遮罩阻劑層(例如，專利文獻1)。Conventionally, the permanent mask resist layer in the manufacture of printed circuit boards has been manufactured by screen printing using a thermosetting resin composition or photographic method using a photosensitive resin composition. For example, in the flexible circuit board that adopts mounting methods such as FC (Flip Chip), TAB (Tape Automated Bonding), and COF (Chip On Film). In addition to IC chips, electronic parts, LCD (Liquid Crystal Display) panels, and connection circuit pattern parts, thermosetting resin paste is screen printed and thermally cured to form a permanent mask resist layer (for example, patent Literature 1).

又，在電子零件所搭載之BGA(Ball Grid Array，球柵陣列封裝)、CSP(Chip Size Package，晶片尺寸封裝)等半導體封裝基板中，為了下述理由：(1)透過焊料將半導體元件覆晶安裝於半導體封裝基板上、(2)將半導體元件與半導體封裝基板進行打線接合、或(3)將半導體封裝基板以焊料接合於母板，而必須去除該接合部分的永久遮罩阻劑層。因此，此永久遮罩阻劑層之形成是採用照相法，該照相法是將感光性樹脂組成物塗佈乾燥後，選擇性地照射紫外線等活性光線而使其硬化，將未照射部分以顯影液去除而形成圖像。照相法由於其作業性良好而適合於大量生產，因此在電子材料業界中被廣泛地應用於感光性樹脂組成物的圖像形成(例如，專利文獻2～4)。 [先前技術文獻] (專利文獻)In addition, in semiconductor packaging substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) mounted on electronic components, for the following reasons: (1) covering the semiconductor element with solder The crystal is mounted on the semiconductor package substrate, (2) the semiconductor element and the semiconductor package substrate are wire bonded, or (3) the semiconductor package substrate is soldered to the motherboard, and the permanent mask resist layer of the bonded portion must be removed . Therefore, this permanent mask resist layer is formed by a photographic method. After the photosensitive resin composition is applied and dried, it is selectively irradiated with ultraviolet rays and other active rays to harden it, and the unirradiated portion is developed The liquid is removed to form an image. The photographic method is suitable for mass production because of its good workability, and therefore it is widely used in image formation of photosensitive resin compositions in the electronic material industry (for example, Patent Documents 2 to 4). [Prior Technical Literature] (Patent Literature)

專利文獻1：日本特開2003-198105號公報 專利文獻2：日本特開平11-240930號公報 專利文獻3：日本特開2010-235739號公報 專利文獻4：日本特開2011-133851號公報Patent Document 1: Japanese Patent Laid-Open No. 2003-198105 Patent Document 2: Japanese Patent Laid-Open No. 11-240930 Patent Document 3: Japanese Patent Laid-Open No. 2010-235739 Patent Document 4: Japanese Patent Laid-Open No. 2011-133851

[發明所欲解決之問題] 然而，採用如專利文獻2～4中所記載般的添加了顏料、填料等而成的感光性樹脂組成物時，會有下述情形：顏料、填料等妨礙紫外線穿透、或是吸收了紫外線，當欲形成20～40μm以上之較厚的永久遮罩阻劑層時，會有底部的感光性樹脂組成物無法充分進行光硬化的情形，結果在顯影後產生底部被挖空而成之底切(undercut)。 若為了提升底部的光硬化性而增加紫外線照射的曝光量，則會有下述問題：光繞射及光暈變大，圖案剖面的中間部(中心部)及最深部(底部)的線寬相對於表面部(上部)的線寬而言變大，以致產生阻劑層形狀惡化、或解析度下降的問題。又，亦有下述問題：由於氧抑制造成阻劑深度方向之從表面至3μm左右的區域光硬化不足，以致阻劑層上部缺損、阻劑層形狀惡化。因此，目前尚不存在一種感光性樹脂組成物，該感光性樹脂組成物在形成20～40μm以上之較厚的永久遮罩阻劑層時，底部光硬化性良好而解析度優異。[Problems to be solved by the invention] However, when a photosensitive resin composition containing pigments, fillers, etc. as described in Patent Documents 2 to 4 is used, there may be cases where pigments, fillers, etc. hinder the penetration of ultraviolet rays or absorb ultraviolet rays When a thick permanent mask resist layer of 20-40 μm or more is to be formed, the photosensitive resin composition at the bottom may not be sufficiently photocured, and as a result, the bottom is hollowed out after development Undercut. If the exposure amount of ultraviolet irradiation is increased in order to improve the photohardenability of the bottom, there will be the following problems: light diffraction and halo increase, the line width of the middle part (center part) and the deepest part (bottom part) of the pattern cross section The line width of the surface portion (upper portion) becomes larger, so that the shape of the resist layer is deteriorated or the resolution is lowered. In addition, there is also a problem that due to oxygen suppression, the area from the surface of the resist depth to about 3 μm in the depth direction of the resist is insufficiently photocured, so that the upper part of the resist layer is damaged and the shape of the resist layer is deteriorated. Therefore, at present, there is no photosensitive resin composition which has good photocurability at the bottom and excellent resolution when a thick permanent mask resist layer of 20 to 40 μm or more is formed.

進而，近年來，隨著電子機器的小型化、高性能化，永久遮罩阻劑層之孔徑大小和孔間的間隔間距也有微細化的傾向。例如，採用了下述高精細度的圖案：孔徑大小為100μm且孔間的間隔間距為100μm、或者孔徑大小為80μm且孔間的間隔間距為80μm。因此，正尋求一種永久遮罩阻劑層，該永久遮罩阻劑層例如在覆晶安裝中的解析度提升，並且從焊料充填性的觀點而言阻劑層形狀的安定性亦優異。Furthermore, in recent years, with the miniaturization and high performance of electronic devices, the pore size of the permanent mask resist layer and the pitch between pores also tend to be finer. For example, the following high-precision pattern is adopted: the pore size is 100 μm and the interval between holes is 100 μm, or the pore size is 80 μm and the interval between holes is 80 μm. Therefore, a permanent mask resist layer is sought. The resolution of the permanent mask resist layer is improved, for example, in flip-chip mounting, and the shape stability of the resist layer is also excellent from the viewpoint of solder fillability.

本發明之目的在於提供一種感光性樹脂組成物，該感光性樹脂組成物是有鑑於此種問題而完成，其在導通孔(Via)開口部之底部的硬化性優異，因此不會發生底部被挖空而成之底切、及阻劑層上部之缺損，而且因為不會有紫外線照射的曝光量增加的情形，所以能形成一種圖案，其圖案剖面的中間部(中心部)及最深部(底部)的線寬相對於表面部的線寬而言不會變大，亦即圖案輪廓直線性良好，且阻劑層形狀優異、解析度優異，本發明之目的亦在於提供一種使用該感光性樹脂組成物而成的感光性元件、永久遮罩阻劑層、及具備該永久遮罩阻劑層之印刷電路板。 又，本發明提供一種感光性元件、永久遮罩阻劑層、及具備該永久遮罩阻劑層之印刷電路板，藉由採用本發明之感光性樹脂組成物，而能形成一種圖案，該圖案的孔徑大小和孔間的間隔間距伴隨近年來的電子機器小型化及高性能化而微細化，且形成穩定性優異。 [解決問題之技術手段]An object of the present invention is to provide a photosensitive resin composition which is completed in view of such a problem, and has excellent curability at the bottom of the opening of the via (Via), so that no bottom The undercut made by hollowing out, and the defect of the upper part of the resist layer, and because there is no increase in the exposure amount of ultraviolet radiation, a pattern can be formed, the middle part (center part) and the deepest part of the pattern cross section (Bottom) The line width does not become larger than the line width of the surface, that is, the pattern outline has good linearity, and the shape of the resist layer is excellent, and the resolution is excellent. The purpose of the present invention is also to provide a method for using the sensitivity A photosensitive element made of a resin composition, a permanent mask resist layer, and a printed circuit board provided with the permanent mask resist layer. Furthermore, the present invention provides a photosensitive element, a permanent mask resist layer, and a printed circuit board provided with the permanent mask resist layer. By using the photosensitive resin composition of the present invention, a pattern can be formed. The pore size of the pattern and the pitch between the holes have been miniaturized with the recent miniaturization and high performance of electronic devices, and the formation stability is excellent. [Technical means to solve the problem]

本發明人為了解決前述問題而反覆專心研究，結果發現可藉由下述發明解決。亦即本發明提供下述感光性樹脂組成物、感光性元件、永久遮罩阻劑層、及印刷電路板。In order to solve the aforementioned problems, the present inventors have repeatedly studied and found that they can be solved by the following invention. That is, the present invention provides the following photosensitive resin composition, photosensitive element, permanent mask resist layer, and printed circuit board.

[1] 一種感光性樹脂組成物，其含有：(A)含有酸改質乙烯基之環氧樹脂；(B)醯基氧化膦(acylphosphine oxide)系光聚合起始劑；(C)添加劑，該(C)添加劑是選自(C1)烷基胺基苯衍生物、(C2)吡唑啉系敏化劑或蒽系敏化劑、(C3)光聚合起始劑、(C4)抗氧化劑及(C5)含有氫硫基之化合物中的至少一種，該(C3)光聚合起始劑是選自咪唑系光聚合起始劑、吖啶系光聚合起始劑及二茂鈦系光聚合起始劑中的至少一種，該(C4)抗氧化劑是選自受阻酚系抗氧化劑、醌系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑及磷系抗氧化劑中的至少一種；及，(D)光聚合性化合物。 [2] 一種感光性元件，其具備：支撐體；及，感光層，該感光層是將上述[1]所述之感光性樹脂組成物使用於該支撐體上而成。 [3] 一種永久遮罩阻劑層，其由上述[1]所述之感光性樹脂組成物所形成。 [4] 一種印刷電路板，其具備上述[3]所述之永久遮罩阻劑層。 [發明之功效][1] A photosensitive resin composition comprising: (A) an epoxy resin containing an acid-modified vinyl group; (B) an acylphosphine oxide-based photopolymerization initiator; (C) an additive, The (C) additive is selected from (C1) alkylaminobenzene derivatives, (C2) pyrazoline sensitizer or anthracene sensitizer, (C3) photopolymerization initiator, (C4) antioxidant And (C5) at least one compound containing a hydrogen sulfide group, the (C3) photopolymerization initiator is selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators and titanocene-based photopolymerization At least one of the initiators, the (C4) antioxidant is at least one selected from hindered phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants; and, ( D) Photopolymerizable compound. [2] A photosensitive element comprising: a support; and a photosensitive layer obtained by using the photosensitive resin composition described in [1] above on the support. [3] A permanent mask resist layer formed of the photosensitive resin composition described in [1] above. [4] A printed circuit board including the permanent mask resist layer described in [3] above. [Efficacy of invention]

根據本發明，可獲得一種感光性樹脂組成物，其能形成一種圖案，該圖案不會發生底部被挖空而成之底切、及阻劑層上部之缺損，圖案輪廓直線性良好，阻劑層形狀優異、解析度優異，根據本發明亦可獲得一種感光性元件、永久遮罩阻劑層、及具備該永久遮罩阻劑層之印刷電路板，其能形成一種圖案，該圖案的孔徑大小和孔間的間隔間距微細化且形成穩定性優異。According to the present invention, a photosensitive resin composition can be obtained which can form a pattern without undercuts made by hollowing out the bottom and defects on the upper part of the resist layer, the pattern outline has good linearity, and the resist The layer shape is excellent and the resolution is excellent. According to the present invention, a photosensitive element, a permanent mask resist layer, and a printed circuit board provided with the permanent mask resist layer can also be obtained, which can form a pattern with an aperture of the pattern The size and the pitch between the holes are miniaturized and the formation stability is excellent.

[感光性樹脂組成物] 本發明中之實施形態(以下，有時稱為「本實施形態」)的感光性樹脂組成物，是一種感光性樹脂組成物，其含有：(A)含有酸改質乙烯基之環氧樹脂(以下，有時稱為「(A)成分」)；(B)醯基氧化膦系光聚合起始劑(以下，有時稱為「(B)成分」)；(C)添加劑(以下，有時稱為「(C)成分」)，該(C)添加劑是選自(C1)烷基胺基苯衍生物(以下，有時稱為「(C1)成分」)、(C2)吡唑啉系敏化劑或蒽系敏化劑(以下，有時稱為「(C2)成分」)、(C3)光聚合起始劑(以下，有時稱為「(C3)成分」)、(C4)抗氧化劑(以下，有時稱為「(C4)成分」)及(C5)含有氫硫基之化合物(以下，有時稱為「(C5)成分」)中的至少一種，該(C3)光聚合起始劑是選自咪唑系光聚合起始劑、吖啶系光聚合起始劑及二茂鈦系光聚合起始劑中的至少一種，該(C4)抗氧化劑是選自受阻酚系抗氧化劑、醌系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑及磷系抗氧化劑中的至少一種；及，(D)光聚合性化合物(以下，有時稱為「(D)成分」)。 以下，針對各成分進行說明。[Photosensitive resin composition] The photosensitive resin composition of an embodiment of the present invention (hereinafter, sometimes referred to as "this embodiment") is a photosensitive resin composition, which contains: (A) an epoxy resin containing an acid-modified vinyl group (Hereinafter, sometimes referred to as "(A) component"); (B) acetylphosphine oxide-based photopolymerization initiator (hereinafter, sometimes referred to as "(B) component"); (C) additives (hereinafter, Sometimes referred to as "(C) component"), the (C) additive is selected from (C1) alkylaminobenzene derivatives (hereinafter, sometimes referred to as "(C1) component"), (C2) pyrazole Porphyrin sensitizer or anthracene sensitizer (hereinafter, sometimes referred to as "(C2) component"), (C3) photopolymerization initiator (hereinafter, sometimes referred to as "(C3) component"), ( C4) At least one of antioxidants (hereinafter, sometimes referred to as "(C4) component") and (C5) compounds containing hydrogen sulfide groups (hereinafter, sometimes referred to as "(C5) component"), the (C3 ) The photopolymerization initiator is at least one selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators and titanocene-based photopolymerization initiators. The (C4) antioxidant is selected from hindered At least one of a phenol-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant; and, (D) a photopolymerizable compound (hereinafter, sometimes referred to as "(D) component "). Hereinafter, each component will be described.

＜(A)含有酸改質乙烯基之環氧樹脂＞ 本實施形態的感光性樹脂組成物，其包含了含有酸改質乙烯基之環氧樹脂作為(A)成分。 (A)含有酸改質乙烯基之環氧樹脂，只要是將環氧樹脂以含有乙烯基之有機酸進行改質而成者即可，並無特別限制，較佳是環氧樹脂(a’)，其為使環氧樹脂(a)與含有乙烯基之單羧酸(b)反應而獲得，進而較佳是環氧樹脂(a’’)，其為進而使該環氧樹脂(a’)與含有飽和基或不飽和基之多元酸酐(polybasic acid anhydride)(c)反應而獲得。<(A) Epoxy resin containing acid modified vinyl> The photosensitive resin composition of this embodiment contains an epoxy resin containing an acid-modified vinyl group as the (A) component. (A) The epoxy resin containing an acid-modified vinyl group is not particularly limited as long as the epoxy resin is modified with an organic acid containing a vinyl group, and is preferably an epoxy resin (a' ), which is obtained by reacting an epoxy resin (a) with a monocarboxylic acid (b) containing a vinyl group, further preferably an epoxy resin (a''), which is further used to make the epoxy resin (a' ) Obtained by reacting with polybasic acid anhydride (c) containing saturated or unsaturated groups.

作為環氧樹脂(a)，較佳是選自具有下述通式(I)～(V)所示的結構單元之環氧樹脂中的至少一種。針對具有各通式所示之結構單元之環氧樹脂，進行說明。The epoxy resin (a) is preferably at least one selected from epoxy resins having structural units represented by the following general formulas (I) to (V). The epoxy resin having the structural unit represented by each general formula will be described.

〔具有如通式(I)所示的結構單元之酚醛清漆型環氧樹脂〕 首先，作為環氧樹脂(a)，可較佳地列舉具有下述通式(I)所示的結構單元之酚醛清漆型環氧樹脂，而作為具有此種結構單元之環氧樹脂，可較佳地列舉例如下述通式(I’)所示的酚醛清漆型環氧樹脂。[Novolac-type epoxy resin having a structural unit represented by the general formula (I)] First, as the epoxy resin (a), a novolac-type epoxy resin having a structural unit represented by the following general formula (I) can be preferably cited, and as the epoxy resin having such a structural unit, it can be compared Preferably, for example, a novolak type epoxy resin represented by the following general formula (I′).

Figure 02_image001
Figure 02_image001

通式(I)中，R11 表示氫原子或甲基，Y1 表示縮水甘油基。 具有通式(I)所示的結構單元之酚醛清漆型環氧樹脂中，通式(I)所示的結構單元的含量，較佳是70質量%以上，更佳是90質量%以上，進而更佳是95質量%以上。 又，通式(I’)中，R11’ 表示氫原子或甲基，Y1’ 表示氫原子或縮水甘油基，並且氫原子與縮水甘油基之莫耳比，較佳是0：100～30：70，更佳是0：100～10：90，進而更佳是0：100。由氫原子與縮水甘油基之莫耳比可知，至少一個Y1’ 是表示縮水甘油基。通式(I’)中，n1表示1以上之整數。又，複數的R11’ 可為相同亦可為不同；複數的Y1’ 可為相同亦可為不同。In the general formula (I), R 11 represents a hydrogen atom or a methyl group, and Y 1 represents a glycidyl group. In the novolak type epoxy resin having the structural unit represented by the general formula (I), the content of the structural unit represented by the general formula (I) is preferably 70% by mass or more, more preferably 90% by mass or more, and More preferably, it is 95% by mass or more. Furthermore, in the general formula (I'), R 11' represents a hydrogen atom or a methyl group, Y 1'represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0: 100 to 30:70, preferably 0:100 to 10:90, and more preferably 0:100. A hydrogen atom and the apparent molar ratio of glycidyl group, at least one of Y 1 'is a glycidyl group. In the general formula (I'), n1 represents an integer of 1 or more. Moreover, the plural R 11' may be the same or different; the plural Y 1'may be the same or different.

如上所述，n1為1以上之整數，較佳是10～200，更佳是30～150，進而更佳是30～100。n1在上述範圍內時，有下述傾向：可獲得阻劑層形狀、解析度、耐熱性、密著性及電絕緣性之平衡更加優異的阻劑圖案。As described above, n1 is an integer of 1 or more, preferably 10 to 200, more preferably 30 to 150, and still more preferably 30 to 100. When n1 is within the above range, there is a tendency that a resist pattern with a more excellent balance of the shape, resolution, heat resistance, adhesion, and electrical insulation of the resist layer can be obtained.

作為通式(I’)所示的酚醛清漆型環氧樹脂，可較佳地列舉例如：苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等。此等酚醛清漆型環氧樹脂，例如，可藉由以公知的方法，使苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂等苯酚樹脂，與環氧氯丙烷(epichlorohydrin)等環氧鹵素丙烷反應而獲得。Examples of the novolak-type epoxy resins represented by the general formula (I') include phenol novolak-type epoxy resins and cresol novolak-type epoxy resins. These novolac-type epoxy resins can be obtained, for example, by reacting phenol resins such as phenol novolak resin and cresol novolak resin with epoxy halogen propane such as epichlorohydrin (epichlorohydrin) by a known method. .

作為通式(I’)所示的酚醛清漆型環氧樹脂，可在商業上取得的有例如：YDCN-701、YDCN-702、YDCN-703、YDCN-704、YDCN-704L、YDPN-638、YDPN-602(以上為NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.製造，商品名)；DEN-431、DEN-439(以上為The Dow Chemical Company製造，商品名)；EOCN-120、EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027、BREN(以上為Nippon Kayaku Co., Ltd.製造，商品名)；EPN-1138、EPN-1235、EPN-1299(以上為BASF Japan Ltd.製造，商品名)；N-730、N-770、N-865、N-665、N-673、VH-4150、VH-4240(以上為DIC Corporation製造，商品名)等。As the novolac epoxy resin represented by the general formula (I'), commercially available are, for example: YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (above is manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD., trade name); DEN-431, DEN-439 (above is manufactured by The Dow Chemical Company, trade name); EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (above are manufactured by Nippon Kayaku Co., Ltd., trade name); EPN-1138, EPN-1235, EPN-1299 (above It is manufactured by BASF Japan Ltd., trade name); N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (the above is a trade name manufactured by DIC Corporation), etc.

〔具有如通式(II)所示的結構單元之環氧樹脂〕 作為環氧樹脂(a)，可較佳地列舉具有下述通式(II)所示的結構單元之環氧樹脂，而作為具有此種結構單元之環氧樹脂，可較佳地列舉例如：下述通式(II’)所示的雙酚A型環氧樹脂及雙酚F型環氧樹脂。[Epoxy resin having structural unit represented by general formula (II)] As the epoxy resin (a), an epoxy resin having a structural unit represented by the following general formula (II) can be preferably exemplified, and as the epoxy resin having such a structural unit, an epoxy resin can be preferably exemplified: Bisphenol A type epoxy resin and bisphenol F type epoxy resin represented by the following general formula (II').

Figure 02_image003
Figure 02_image003

通式(II)中，R12 表示氫原子或甲基，Y2 表示縮水甘油基。 具有通式(II)所示的結構單元之環氧樹脂中，通式(II)所示的結構單元的含量，較佳是70質量%以上，更佳是90質量%以上，進而更佳是95質量%以上。 又，通式(II’)中，R12’ 表示氫原子或甲基，Y2’ 表示氫原子或縮水甘油基，並且氫原子與縮水甘油基之莫耳比，較佳是0：100～30：70，更佳是0：100～10：90，進而更佳是0：100。由氫原子與縮水甘油基之莫耳比可知，至少一個Y2’ 是表示縮水甘油基。通式(II’)中，n2表示1以上之整數。又，複數的R12’ 可為相同亦可為不同，而n2為2以上時，複數的Y2’ 可為相同亦可為不同。In the general formula (II), R 12 represents a hydrogen atom or a methyl group, and Y 2 represents a glycidyl group. In the epoxy resin having the structural unit represented by the general formula (II), the content of the structural unit represented by the general formula (II) is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Furthermore, in the general formula (II'), R 12' represents a hydrogen atom or a methyl group, Y 2'represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0: 100 to 30:70, preferably 0:100 to 10:90, and more preferably 0:100. A hydrogen atom and the apparent molar ratio of glycidyl group, at least one Y 2 'is a glycidyl group. In the general formula (II'), n2 represents an integer of 1 or more. Moreover, the plural R 12' may be the same or different, and when n2 is 2 or more, the plural Y 2'may be the same or different.

如上所述，n2為1以上之整數，較佳是10～100，更佳是10～80，進而更佳是15～60。n2在上述範圍內時，有下述傾向：可獲得阻劑層形狀、解析度、密著性、耐熱性及電絕緣性之平衡更加優異的阻劑圖案。As described above, n2 is an integer of 1 or more, preferably 10 to 100, more preferably 10 to 80, and still more preferably 15 to 60. When n2 is within the above range, there is a tendency that a resist pattern with a more excellent balance of the shape, resolution, adhesion, heat resistance, and electrical insulation of the resist layer can be obtained.

由通式(II’)所示且Y2’ 為縮水甘油基之雙酚A型環氧樹脂或雙酚F型環氧樹脂，例如，可藉由使下述通式(VII)所示的雙酚A型環氧樹脂或雙酚F型環氧樹脂的羥基與環氧氯丙烷等環氧鹵素丙烷反應而獲得。The bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (II′) and Y 2′ is a glycidyl group, for example, by using the following general formula (VII) The hydroxy group of bisphenol A type epoxy resin or bisphenol F type epoxy resin is reacted with epoxy halogen propane such as epichlorohydrin.

Figure 02_image005
Figure 02_image005

通式(VII)中，R12 及n2與上述相同。In the general formula (VII), R 12 and n2 are the same as described above.

考慮到獲得阻劑層形狀、解析度、塗膜強度、耐熱性、絕緣可靠性、耐熱衝擊性及解析度的平衡更加優異的阻劑圖案時，環氧鹵素丙烷的使用量較佳是：相對於通式(VII)所示的環氧樹脂中的羥基1莫耳而言設為2～10莫耳。In consideration of obtaining a resist pattern with a more excellent balance of the shape, resolution, coating film strength, heat resistance, insulation reliability, thermal shock resistance, and resolution of the resist layer, the amount of epoxy halogen propane used is preferably: The hydroxyl group in the epoxy resin represented by the general formula (VII) is 1 to 10 moles.

從與上述相同的觀點而言，較佳是：在通式(VII)所示的環氧樹脂與環氧鹵素丙烷反應時，使用鹼性催化劑。作為鹼性催化劑，可較佳地列舉例如：鹼土族金屬氫氧化物、鹼金屬碳酸鹽、鹼金屬氫氧化物等，從催化劑活性的觀點而言，進而較佳是氫氧化鈉、氫氧化鉀、氫氧化鈣等鹼金屬氫氧化物。又，其使用量較佳是：相對於通式(VII)所示的環氧樹脂中的羥基1莫耳而言為0.9～2莫耳。From the same viewpoint as above, it is preferable to use an alkaline catalyst when the epoxy resin represented by the general formula (VII) reacts with epoxyhalopropane. Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. From the viewpoint of catalyst activity, sodium hydroxide and potassium hydroxide are more preferred. , Calcium hydroxide and other alkali metal hydroxides. In addition, the usage amount thereof is preferably 0.9 to 2 moles relative to 1 mole of hydroxyl groups in the epoxy resin represented by the general formula (VII).

在通式(VII)所示的環氧樹脂與環氧鹵素丙烷之反應中，從更加提升反應速率的觀點而言，較佳是使用例如下述作為有機溶媒：甲醇、乙醇等醇類；甲基賽珞蘇、乙基賽珞蘇等賽珞蘇(cellosolve)類；四氫呋喃(tetrahydrofuran)、二口咢烷(dioxane)等醚類；二甲基甲醯胺、二甲基乙醯胺、二甲基亞碸等極性有機溶劑等。可從此等有機溶劑中，單獨使用一種，或將二種以上組合使用，從調整極性的觀點而言，較佳是將二種以上組合使用。In the reaction of the epoxy resin represented by the general formula (VII) and the epoxy halogen propane, from the viewpoint of further increasing the reaction rate, it is preferable to use, for example, the following as an organic solvent: alcohols such as methanol and ethanol; Cellosolve such as kisailuosu, ethyl siluosu, etc.; ethers such as tetrahydrofuran, dioxane; dimethylformamide, dimethylacetamide, bis Polar organic solvents such as methyl sulfite. From these organic solvents, one type may be used alone, or two or more types may be used in combination. From the viewpoint of polarity adjustment, it is preferable to use two or more types in combination.

又，反應溫度較佳是20～120℃，更佳是50～120℃，反應時間較佳是0.5～10小時。反應溫度和反應時間在上述範圍內時，較不易使反應變慢，且較不易產生副反應產物。In addition, the reaction temperature is preferably 20 to 120°C, more preferably 50 to 120°C, and the reaction time is preferably 0.5 to 10 hours. When the reaction temperature and reaction time are within the above ranges, it is less likely to slow down the reaction, and it is less likely to produce side reaction products.

上述反應後，較佳是：在加熱減壓下，藉由蒸餾將未反應之環氧鹵素丙烷、有機溶媒等餾除，而獲得通式(II’)所示的環氧樹脂。 又，從獲得純度更高的環氧樹脂的觀點而言，可將所得之環氧樹脂再次溶解於有機溶媒中，添加上述鹼金屬氫氧化物等鹼性催化劑而進行反應。此時，從提高反應速率的觀點而言，較佳是：在相對於環氧樹脂而言為0.1～3質量%的範圍內，使用四級銨鹽、冠醚(crown ether)等相間轉移催化劑(phase transfer catalyst)。此時，可藉由過濾或水洗等方式將反應結束後所生成之鹽等去除，進而在加熱減壓下將有機溶媒等餾除，藉此獲得高純度之環氧樹脂。After the above reaction, it is preferable to distill off unreacted epoxyhalopropane, an organic solvent, or the like by distillation under heating and reduced pressure to obtain an epoxy resin represented by the general formula (II'). In addition, from the viewpoint of obtaining a higher-purity epoxy resin, the obtained epoxy resin can be dissolved in an organic solvent again, and an alkaline catalyst such as the above-mentioned alkali metal hydroxide can be added to carry out the reaction. In this case, from the viewpoint of increasing the reaction rate, it is preferable to use an interphase transfer catalyst such as a quaternary ammonium salt or a crown ether in the range of 0.1 to 3% by mass relative to the epoxy resin. (phase transfer catalyst). At this time, the salts and the like generated after the reaction can be removed by filtration or water washing, etc., and then the organic solvent and the like can be distilled off under heating and reduced pressure, thereby obtaining a high-purity epoxy resin.

作為通式(II’)所示的雙酚A型環氧樹脂或雙酚F型環氧樹脂，可在商業上取得的有例如：Epikote807、815、825、827、828、834、1001、1004、1007及1009(以上為Mitsubishi Chemical Corporation製造，商品名)；DER-330、DER-301、DER-361(以上為The Dow Chemical Company製造，商品名)；YD-8125、YDF-170、YDF-175S、YDF-2001、YDF-2004、YDF-8170(以上為NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD. 製造，商品名)等。As the bisphenol A epoxy resin or bisphenol F epoxy resin represented by the general formula (II'), commercially available are, for example: Epikote807, 815, 825, 827, 828, 834, 1001, 1004 , 1007 and 1009 (above are manufactured by Mitsubishi Chemical Corporation, trade name); DER-330, DER-301, DER-361 (above are manufactured by The Dow Chemical Company, trade name); YD-8125, YDF-170, YDF- 175S, YDF-2001, YDF-2004, YDF-8170 (above are manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD., trade name), etc.

〔具有如通式(III)所示的結構單元之環氧樹脂〕 作為環氧樹脂(a)，可較佳地列舉具有下述通式(III)所示的結構單元之環氧樹脂，而作為具有此種結構單元之環氧樹脂，可較佳地列舉例如下述通式(III’)所示的三酚甲烷型環氧樹脂。[Epoxy resin having structural unit represented by general formula (III)] As the epoxy resin (a), an epoxy resin having a structural unit represented by the following general formula (III) can be preferably exemplified, and as the epoxy resin having such a structural unit, the following can be preferably exemplified: The triphenol methane type epoxy resin represented by the general formula (III').

Figure 02_image007
Figure 02_image007

通式(III)及(III’)中，Y3 表示氫原子或縮水甘油基，並且氫原子與縮水甘油基之莫耳比，較佳是0：100～30：70。由氫原子與縮水甘油基之莫耳比可知，至少一個Y3 是表示縮水甘油基。通式(III’)中，n3表示1以上之整數。又，複數的Y3 可為相同亦可為不同。In the general formulae (III) and (III'), Y 3 represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0:100 to 30:70. It can be seen from the molar ratio of hydrogen atoms to glycidyl groups that at least one Y 3 represents a glycidyl group. In the general formula (III'), n3 represents an integer of 1 or more. In addition, plural Y 3 may be the same or different.

如上所述，n3為1以上之整數，較佳是10～100，更佳是15～80，進而更佳是15～70。n3在上述範圍內時，可獲得阻劑層形狀、解析度、耐熱性、密著性及電絕緣性之平衡更加優異的阻劑圖案。As described above, n3 is an integer of 1 or more, preferably 10 to 100, more preferably 15 to 80, and still more preferably 15 to 70. When n3 is within the above range, a resist pattern with a more excellent balance of the shape, resolution, heat resistance, adhesion, and electrical insulation of the resist layer can be obtained.

具有通式(III)所示的結構單元之環氧樹脂中，通式(III)所示的結構單元的含量，較佳是70質量%以上，更佳是90質量%以上，進而更佳是95質量%以上。In the epoxy resin having the structural unit represented by the general formula (III), the content of the structural unit represented by the general formula (III) is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

作為通式(III’)所示的三酚甲烷型環氧樹脂，可在商業上取得的有例如：FAE-2500、EPPN-501H、EPPN-502H(以上為Nippon Kayaku Co., Ltd.製造，商品名)。As the triphenol methane epoxy resin represented by the general formula (III'), commercially available are, for example: FAE-2500, EPPN-501H, EPPN-502H (above manufactured by Nippon Kayaku Co., Ltd., Product name).

〔具有如通式(IV)所示的結構單元之雙酚酚醛清漆型環氧樹脂〕 作為環氧樹脂(a)，可較佳地列舉具有下述通式(IV)所示的結構單元之雙酚酚醛清漆型環氧樹脂。[Bisphenol novolac epoxy resin having a structural unit represented by general formula (IV)] As the epoxy resin (a), a bisphenol novolac-type epoxy resin having a structural unit represented by the following general formula (IV) is preferably exemplified.

Figure 02_image009
Figure 02_image009

通式(IV)中，R13 表示氫原子、烷基、芳基、芳烷基、磺基或三鹵甲基，Y4 表示氫原子或縮水甘油基。至少一個Y4 是表示縮水甘油基，複數的R13 可為相同亦可為不同。In the general formula (IV), R 13 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfo group, or a trihalomethyl group, and Y 4 represents a hydrogen atom or a glycidyl group. At least one Y 4 represents a glycidyl group, and plural R 13 may be the same or different.

R13 的烷基的碳數，較佳是1～20，更佳是1～12，進而更佳是1～3。又，烷基可為直鏈，亦可為支鏈，且亦可為經鹵素原子、烷基、芳基、芳烷基、胺基、醯胺基、烷氧基等所置換之烷基。 作為烷基，可較佳地列舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、戊基、二級戊基、異戊基、新戊基等；其中，較佳是甲基。 作為芳基，可列舉：苯基、聯苯基、萘基、蒽基、菲基等，較佳是成環碳數6～20之芳基，更佳是成環碳數6～14之芳基。又，芳基亦可為經鹵素原子、烷基、芳基、芳烷基、胺基、醯胺基、烷氧基等所置換之芳基。 作為芳烷基，只要是上述烷基的其中一個氫原子經上述芳基所置換而成之芳烷基即可，並無特別限制，可列舉例如：苄基、苯乙基、苯丙基、萘甲基等。又，亦可為經鹵素原子、烷基、芳基、芳烷基、胺基、醯胺基、烷氧基等所置換之芳烷基。The carbon number of the alkyl group of R 13 is preferably from 1 to 20, more preferably from 1 to 12, and even more preferably from 1 to 3. In addition, the alkyl group may be linear or branched, and may also be an alkyl group substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amine group, an amide group, an alkoxy group, or the like. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, secondary pentyl and isopropyl. Amyl, neopentyl and the like; among them, methyl is preferred. Examples of the aryl group include phenyl, biphenyl, naphthyl, anthracenyl, and phenanthrenyl groups, preferably aryl groups having 6 to 20 ring-forming carbon atoms, and more preferably aryl groups having 6 to 14 ring-forming carbon atoms. base. In addition, the aryl group may be an aryl group substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amine group, an amide group, an alkoxy group, or the like. The aralkyl group is not particularly limited as long as it is an aralkyl group in which one of the hydrogen atoms of the alkyl group is replaced by the aryl group, and examples include benzyl, phenethyl, and phenylpropyl. Naphthylmethyl and so on. In addition, it may be an aralkyl group substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amine group, an amide group, an alkoxy group, or the like.

具有通式(IV)所示的結構單元之環氧樹脂中，通式(IV)所示的結構單元的含量，較佳是70質量%以上，更佳是90質量%以上，進而更佳是95質量%以上。 該結構單元的含量在上述範圍內時，可獲得阻劑層形狀、解析度、耐熱性、密著性及電絕緣性之平衡更加優異的阻劑圖案。In the epoxy resin having the structural unit represented by the general formula (IV), the content of the structural unit represented by the general formula (IV) is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. When the content of the structural unit is within the above range, a resist pattern with a more excellent balance of the shape, resolution, heat resistance, adhesion, and electrical insulation of the resist layer can be obtained.

〔具有如通式(V)所示的結構單元之雙酚酚醛清漆型環氧樹脂〕 作為環氧樹脂(a)，可較佳地列舉下述具有通式(V)所示的結構單元之雙酚酚醛清漆型環氧樹脂。[Bisphenol novolac epoxy resin having a structural unit represented by general formula (V)] As the epoxy resin (a), a bisphenol novolac-type epoxy resin having a structural unit represented by the following general formula (V) can be preferably exemplified.

Figure 02_image011
Figure 02_image011

通式(V)中，R14 表示氫原子、烷基、芳基、芳烷基、磺基或三鹵甲基，Y5 表示氫原子或縮水甘油基。至少一個Y5 是表示縮水甘油基，複數的R14 可為相同亦可為不同。又，作為R14 的烷基、芳基、芳烷基，可例示與R13 所述者相同的基，且其較佳的態樣亦相同。In the general formula (V), R 14 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfo group, or a trihalomethyl group, and Y 5 represents a hydrogen atom or a glycidyl group. At least one Y 5 represents a glycidyl group, and plural R 14 may be the same or different. And, R 14 is alkyl group, aryl group, aralkyl group, and R can be exemplified by the same group 13, and the preferred aspects are also the same.

具有通式(V)所示的結構單元之環氧樹脂中，通式(V)所示的結構單元的含量，較佳是70質量%以上，更佳是90質量%以上，進而更佳是95質量%以上。上述範圍內時，可獲得阻劑層形狀、解析度、耐熱性、密著性及電絕緣性之平衡更加優異的阻劑圖案。In the epoxy resin having the structural unit represented by the general formula (V), the content of the structural unit represented by the general formula (V) is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Within the above range, a resist pattern with a more excellent balance of the shape, resolution, heat resistance, adhesion, and electrical insulation of the resist layer can be obtained.

通式(V)中，R14 為氫原子且Y5 為縮水甘油基者，商業上可取得EXA-7376系列(DIC Corporation製造，商品名)；又，R14 為甲基且Y5 為縮水甘油基者，商業上可取得EPON SU8系列(Mitsubishi Chemical Corporation製造，商品名)。In the general formula (V), where R 14 is a hydrogen atom and Y 5 is a glycidyl group, EXA-7376 series (manufactured by DIC Corporation, trade name) are commercially available; in addition, R 14 is a methyl group and Y 5 is a glycidyl group The glyceryl group is commercially available as EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, trade name).

具有通式(IV)及(V)所示的結構單元之雙酚酚醛清漆型環氧樹脂，例如，可藉由使下述通式(VIII)及(IX)分別所示之雙酚酚醛清漆型樹脂的羥基與環氧氯丙烷等環氧鹵素丙烷反應而獲得。The bisphenol novolak-type epoxy resin having the structural units represented by general formulas (IV) and (V) can be obtained, for example, by using bisphenol novolaks represented by the following general formulas (VIII) and (IX) The hydroxyl group of the type resin is obtained by reacting epoxy halogen propane such as epichlorohydrin.

Figure 02_image013
Figure 02_image013

通式(VIII)中，R13 與上述通式(IV)中的R13 相同，通式(IX)中，R14 與上述通式(V)中的R14 相同。In the general formula (VIII), R 13 the same as in the general formula (IV), the R 13, in formula (IX), R 14 is the same as the above-described formula (V) in R 14.

此等具有通式(VIII)及(IX)所示的構造單元之雙酚酚醛清漆樹脂，較佳是：例如，可在磺酸(該磺酸在分子構造內具有碳數1～4之烷基)存在下，使雙酚化合物與醛化合物或酮化合物進行反應而獲得。These bisphenol novolak resins having the structural units represented by the general formulas (VIII) and (IX) are preferably, for example, sulfonic acid (the sulfonic acid has a C 1-4 alkane in the molecular structure It is obtained by reacting a bisphenol compound with an aldehyde compound or a ketone compound in the presence of a radical).

此處，作為雙酚化合物，只要是具有2個羥苯基之化合物即可，並無特別限制，可較佳地列舉例如：雙酚A、雙酚AP、雙酚AF、雙酚B、雙酚BP、雙酚C、雙酚E、雙酚F、雙酚G、雙酚M、雙酚S、雙酚P、雙酚TMC、雙酚Z等；更佳是雙酚A及雙酚F。Here, the bisphenol compound is not particularly limited as long as it has two hydroxyphenyl compounds, and preferably includes, for example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, and bisphenol Phenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, bisphenol Z, etc.; more preferably bisphenol A and bisphenol F .

作為與上述雙酚化合物反應之醛化合物，可較佳地列舉：甲醛、乙醛、苯甲醛、4-甲基苯甲醛、3,4-二甲基苯甲醛、聯苯甲醛、萘甲醛等；作為酮化合物，可較佳地列舉：二苯甲酮、芴酮(fluorenone)、茚酮(indanone)等。其中，較佳是甲醛。Examples of the aldehyde compound that reacts with the bisphenol compound include formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, bibenzaldehyde, and naphthalene formaldehyde. Examples of the ketone compound include benzophenone, fluorenone, and indanone. Among them, formaldehyde is preferred.

作為磺酸(該磺酸在分子構造內具有碳數1～4之烷基)，可較佳地列舉：甲磺酸、乙磺酸、丙磺酸、丁磺酸等烷基磺酸；及，在烷基部分具有氟原子之全氟烷基磺酸等。As the sulfonic acid (the sulfonic acid has an alkyl group having 1 to 4 carbon atoms in the molecular structure), preferably, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, etc.; and , Perfluoroalkyl sulfonic acid with a fluorine atom in the alkyl portion.

具有通式(IV)及(V)所示的結構單元之雙酚酚醛清漆型環氧樹脂，更具體而言，較佳是如以下進行而獲得。 將上述雙酚化合物和醛化合物或酮化合物裝入反應容器內，在惰性氣體氣氛下，一面攪拌，一面以維持在20～200℃的範圍內之方式，連續或間斷地添加磺酸，使雙酚化合物與醛化合物或酮化合物反應，而獲得粗雙酚酚醛清漆樹脂。繼而，將該粗雙酚酚醛清漆樹脂，以非水溶性有機溶媒進行萃取，而作成雙酚酚醛清漆樹脂溶液，並將此雙酚酚醛清漆樹脂溶液進行水洗、中和，進而將該非水溶性有機溶媒餾除，而獲得雙酚酚醛清漆型環氧樹脂。The bisphenol novolak-type epoxy resin having the structural units represented by the general formulas (IV) and (V) is more specifically obtained as follows. The above-mentioned bisphenol compound and aldehyde compound or ketone compound are charged into a reaction vessel, and while stirring under an inert gas atmosphere, sulfonic acid is continuously or intermittently added in such a way as to maintain a range of 20 to 200°C to The phenol compound reacts with the aldehyde compound or ketone compound to obtain a crude bisphenol novolak resin. Then, the crude bisphenol novolak resin is extracted with a water-insoluble organic solvent to prepare a bisphenol novolak resin solution, and the bisphenol novolak resin solution is washed with water and neutralized, and then the water-insoluble organic resin The solvent was distilled off to obtain a bisphenol novolak-type epoxy resin.

此處，作為非水溶性有機溶媒，從使萃取、水洗及中和作業效率提升的觀點而言，較佳是沸點為100～130℃之非水溶性有機溶媒。作為非水溶性有機溶媒，可較佳地列舉例如：丁醇、戊醇、甲氧基乙醇、乙氧基乙醇、二乙二醇、甲基異丁酮等，其中，更佳是丁醇、甲氧基乙醇、甲基異丁酮，進而更佳是甲基異丁酮。Here, as the water-insoluble organic solvent, from the viewpoint of improving the efficiency of extraction, water washing, and neutralization, a water-insoluble organic solvent having a boiling point of 100 to 130° C. is preferred. Examples of the water-insoluble organic solvent include butanol, pentanol, methoxyethanol, ethoxyethanol, diethylene glycol, and methyl isobutyl ketone. Among them, butanol, Methoxyethanol, methyl isobutyl ketone, and more preferably methyl isobutyl ketone.

上述水洗是進行至粗雙酚酚醛清漆樹脂溶液為pH3～7為止，較佳是進行至pH5～7為止，可視需要而使用氫氧化鈉、碳酸鈉、氨、三伸乙四胺等鹼性物質進行中和。 上述餾除，例如，較佳是藉由在溫度170～200℃，壓力3kPa以下的條件下進行加熱減壓蒸餾，獲得純度較高的雙酚酚醛清漆樹脂。The above water washing is performed until the crude bisphenol novolak resin solution is at a pH of 3 to 7, preferably at a pH of 5 to 7, and an alkaline substance such as sodium hydroxide, sodium carbonate, ammonia, triethylenetetramine can be used as necessary Neutralize. For the above-mentioned distillation, for example, it is preferable to obtain bisphenol novolak resin with high purity by heating and vacuum distillation under the conditions of a temperature of 170 to 200° C. and a pressure of 3 kPa or less.

作為環氧樹脂(a)，從製程允差(process tolerance)優異且同時可提升耐溶劑性的觀點而言，較佳是：具有通式(I)所示的結構單元之酚醛清漆型環氧樹脂、具有通式(II)所示的結構單元之環氧樹脂、具有通式(IV)所示的結構單元之雙酚酚醛清漆型環氧樹脂，更佳是：通式(I’)所示之酚醛清漆型環氧樹脂、通式(II’)所示之雙酚A型環氧樹脂或雙酚F型環氧樹脂、及具有通式(IV)所示的結構單元之雙酚酚醛清漆A型環氧樹脂或雙酚酚醛清漆F型環氧樹脂。 又，從可更加減少薄膜基板的彎曲且同時可更加提升耐熱衝擊性的觀點而言，較佳是：將具有通式(IV)所示的結構單元之環氧樹脂，與具有通式(V)所示的結構單元之環氧樹脂合併使用。As the epoxy resin (a), from the viewpoint of being excellent in process tolerance and improving solvent resistance at the same time, it is preferably: a novolac epoxy resin having a structural unit represented by the general formula (I) The resin, the epoxy resin having the structural unit represented by the general formula (II), and the bisphenol novolac epoxy resin having the structural unit represented by the general formula (IV) are more preferably: Novolac epoxy resin shown, bisphenol A epoxy resin or bisphenol F epoxy resin represented by general formula (II'), and bisphenol novolac having structural unit represented by general formula (IV) Varnish A epoxy resin or bisphenol novolac F epoxy resin. In addition, from the viewpoint that the bending of the thin film substrate can be further reduced and the thermal shock resistance can be further improved, it is preferable that the epoxy resin having the structural unit represented by the general formula (IV) and the general formula (V ) The epoxy resins of the structural units shown are used in combination.

(含有乙烯基之單羧酸(b)) 作為與上述環氧樹脂(a)反應之含有乙烯基之單羧酸(b)，可較佳地列舉例如：丙烯酸；丙烯酸的二聚物、甲基丙烯酸、β-呋喃甲基丙烯酸、β-苯乙烯基丙烯酸、桂皮酸、巴豆酸、α-氰基桂皮酸等丙烯酸衍生物；半酯化合物，該半酯化合物是含有羥基之丙烯酸酯與二元酸酐之反應生成物；半酯化合物，該半酯化合物是含有乙烯基之單縮水甘油醚或含有乙烯基之單縮水甘油酯與二元酸酐之反應生成物等。(Vinyl-containing monocarboxylic acid (b)) Examples of the vinyl-containing monocarboxylic acid (b) that reacts with the epoxy resin (a) include, for example, acrylic acid; acrylic acid dimer, methacrylic acid, β-furan methacrylic acid, and β- Acrylic acid derivatives such as styryl acrylic acid, cinnamic acid, crotonic acid, α-cyano cinnamic acid; half-ester compounds, which are the reaction products of hydroxyl-containing acrylates and dibasic acid anhydrides; half-ester compounds, the The half ester compound is a reaction product of a monoglycidyl ether containing a vinyl group or a monoglycidyl ester containing a vinyl group and a dibasic acid anhydride.

半酯化合物，是藉由使含有羥基之丙烯酸酯、含有乙烯基之單縮水甘油醚或含有乙烯基之單縮水甘油酯，與二元酸酐以等莫耳比進行反應而獲得。此等含有乙烯基之單羧酸(b)可單獨使用一種，或將二種以上組合使用。The half-ester compound is obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride at an equal molar ratio. These vinyl-containing monocarboxylic acids (b) may be used alone or in combination of two or more.

作為合成上述半酯化合物(亦即含有乙烯基之單羧酸(b)之一例)所用的含有羥基之丙烯酸酯、含有乙烯基之單縮水甘油醚、含有乙烯基之單縮水甘油酯，可較佳地列舉例如：(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、聚乙二醇單(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、乙烯基縮水甘油醚、(甲基)丙烯酸縮水甘油酯等。As hydroxyl-containing acrylates, vinyl-containing monoglycidyl ethers, and vinyl-containing monoglycidyl esters used in the synthesis of the above-mentioned half-ester compounds (that is, examples of vinyl-containing monocarboxylic acids (b)), it can be compared Good examples include: hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, trimethylolpropane di (Meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, vinyl glycidyl ether, glycidyl (meth)acrylate, etc.

作為合成上述半酯化合物所用之二元酸酐，可使用含有飽和基之二元酸酐、含有不飽和基之二元酸酐。作為二元酸酐的具體例，可較佳地列舉：琥珀酸酐、馬來酸酐、四氫酞酸酐、酞酸酐、甲基四氫酞酸酐、乙基四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、乙基六氫酞酸酐、伊康酸酐(itaconic anhydride)等。As the dibasic acid anhydride used in the synthesis of the above-mentioned half-ester compound, a dibasic acid anhydride containing a saturated group and a dibasic acid anhydride containing an unsaturated group can be used. As specific examples of the dibasic acid anhydride, preferably succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc.

在上述之環氧樹脂(a)與含有乙烯基之單羧酸(b)之反應中，較佳是：相對於環氧樹脂(a)的環氧基1當量，以含有乙烯基之單羧酸(b)為0.6～1.05當量之比例進行反應；更佳是以0.8～1.0當量之比例進行反應；進而更佳是以0.9～1.0當量之比例進行反應。藉由以此種比例進行反應，可提升光聚合性，亦即感光性會更加優異。In the reaction of the above-mentioned epoxy resin (a) and vinyl group-containing monocarboxylic acid (b), it is preferred that the vinyl group-containing monocarboxylic acid is equivalent to 1 equivalent of the epoxy group of the epoxy resin (a) The acid (b) is reacted at a ratio of 0.6 to 1.05 equivalents; more preferably at a ratio of 0.8 to 1.0 equivalents; further preferably at a ratio of 0.9 to 1.0 equivalents. By carrying out the reaction in such a ratio, the photopolymerizability can be improved, that is, the photosensitivity can be more excellent.

環氧樹脂(a)與含有乙烯基之單羧酸(b)之反應，可將環氧樹脂(a)與含有乙烯基之單羧酸(b)溶解於有機溶劑而進行。 作為有機溶劑，可較佳地列舉例如：甲乙酮、環己酮等酮類；甲苯、二甲苯、四甲苯等芳香族烴類；甲基賽珞蘇、丁基賽珞蘇、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二丙二醇單***、二丙二醇二***、三乙二醇單***等二醇醚類；乙酸乙酯、乙酸丁酯、丁基賽珞蘇乙酸酯、卡必醇乙酸酯等酯類；辛烷、癸烷等脂肪族烴類；石油醚、石腦油(petroleum naphtha)、氫化石腦油、溶劑石腦油等石油系溶劑等。The reaction of the epoxy resin (a) and the vinyl-containing monocarboxylic acid (b) can be carried out by dissolving the epoxy resin (a) and the vinyl-containing monocarboxylic acid (b) in an organic solvent. As the organic solvent, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetratoluene; methylcellulose, butylcellulose, methylcarbitol , Butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl cellulose acetate , Carbitol acetate and other esters; octane, decane and other aliphatic hydrocarbons; petroleum ether, naphtha (petroleum naphtha), hydrogenated naphtha, solvent naphtha and other petroleum-based solvents.

進而，為了促進反應，較佳是使用催化劑。作為催化劑，可較佳地列舉例如：三乙胺、苄甲胺、甲基三乙基氯化銨、苄基三甲基氯化銨、苄基三甲基溴化銨、苄基三甲基碘化銨、三苯基膦等。催化劑的使用量，相對於環氧樹脂(a)與含有乙烯基之單羧酸(b)的合計100質量份，較佳是0.1～10質量份。設為上述使用量時，會促進環氧樹脂(a)與含有乙烯基之單羧酸(b)之反應，因此較佳。Furthermore, in order to promote the reaction, it is preferable to use a catalyst. As the catalyst, preferably, for example, triethylamine, benzylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethyl Ammonium iodide, triphenylphosphine, etc. The use amount of the catalyst is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total of the epoxy resin (a) and the vinyl-containing monocarboxylic acid (b). When it is set to the above-mentioned usage amount, the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) is accelerated, which is preferable.

基於防止反應中之聚合之目的，較佳是使用聚合抑制劑。作為聚合抑制劑，可較佳地列舉例如：氫醌(hydroquinone)、甲基氫醌、氫醌單甲醚、兒茶酚(catechol)、五倍子酚(pyrogallol)等。聚合抑制劑的使用量，相對於環氧樹脂(a)與含有乙烯基之單羧酸(b)的合計100質量份，較佳是0.01～1質量份。設為上述使用量時，會提升組成物的貯藏穩定性(shelf life)，因此較佳。又，反應溫度，較佳是60～150℃，更佳是80～120℃。For the purpose of preventing polymerization during the reaction, it is preferred to use a polymerization inhibitor. Examples of the polymerization inhibitor include, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like. The use amount of the polymerization inhibitor is preferably 0.01 to 1 part by mass relative to 100 parts by mass of the total of the epoxy resin (a) and the vinyl-containing monocarboxylic acid (b). When it is set to the above-mentioned usage amount, the shelf life of the composition is improved, which is preferable. The reaction temperature is preferably 60 to 150°C, and more preferably 80 to 120°C.

又，可視需要而將含有乙烯基之單羧酸(b)與下述化合物合併使用：對羥基苯乙醇等酚系化合物；偏苯三甲酸酐(trimellitic anhydride)、均苯四酸酐(pyromellitic anhydride)、二苯甲酮四羧酸酐(benzophenonetetracarboxylic anhydride)、聯苯基四羧酸酐等多元酸酐。In addition, if necessary, vinyl-containing monocarboxylic acid (b) may be used in combination with the following compounds: phenolic compounds such as p-hydroxyphenyl ethanol; trimellitic anhydride, pyromellitic anhydride, Polyanhydrides such as benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic anhydride.

發明人推測，如此進行而獲得之環氧樹脂(a’)，是具有由環氧樹脂(a)之環氧基與含有乙烯基之單羧酸(b)之羧基之間的加成反應所形成之羥基的環氧樹脂。The inventor speculates that the epoxy resin (a') obtained in this way has an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl-containing monocarboxylic acid (b) The epoxy resin formed by the hydroxyl group.

(多元酸酐(c)) 作為(A)含有酸改質乙烯基之環氧樹脂，亦可較佳地列舉：環氧樹脂(a’’)，其為藉由使多元酸酐(c)與上述環氧樹脂(a’)反應而獲得。發明人推測，該環氧樹脂(a’’)，是環氧樹脂(a’)中之羥基(亦包含環氧樹脂(a)中原本就存在之羥基)與多元酸酐(c)之酸酐基進行半酯化而成。(Polyanhydride (c)) As (A) an epoxy resin containing an acid-modified vinyl group, preferably, an epoxy resin (a''), which is obtained by combining a polybasic acid anhydride (c) with the above epoxy resin (a') Obtained by reaction. The inventor speculates that the epoxy resin (a'') is the hydroxyl group in the epoxy resin (a') (including the hydroxyl group originally present in the epoxy resin (a)) and the anhydride group of the polyacid anhydride (c) By half esterification.

作為多元酸酐(c)，可較佳地使用：含有飽和基之多元酸酐、含有不飽和基之多元酸酐。作為多元酸酐(c)的具體例，可較佳地列舉：琥珀酸酐、馬來酸酐、四氫酞酸酐、酞酸酐、甲基四氫酞酸酐、乙基四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、乙基六氫酞酸酐、伊康酸酐等。As the polybasic acid anhydride (c), polybasic acid anhydrides containing saturated groups and polybasic acid anhydrides containing unsaturated groups can be preferably used. Specific examples of the polybasic acid anhydride (c) include preferably succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc.

在環氧樹脂(a’)與多元酸酐(c)之反應中，相對於環氧樹脂(a’)中的羥基1當量，使多元酸酐(c)0.1～1.0當量進行反應，可藉此調整含有酸改質乙烯基之環氧樹脂的酸價。In the reaction of epoxy resin (a') and polybasic acid anhydride (c), 0.1 to 1.0 equivalent of polybasic acid anhydride (c) is reacted with respect to 1 equivalent of hydroxyl group in epoxy resin (a'), which can be adjusted accordingly Acid value of epoxy resin containing acid modified vinyl.

(A)含有酸改質乙烯基之環氧樹脂的酸價，較佳是30～150mgKOH/g，更佳是40～120mgKOH/g，進而更佳是50～100mgKOH/g。酸價為30mgKOH/g以上時，感光性樹脂組成物於稀鹼溶液中的溶解性較不易下降，酸價為150mgKOH/g以下時，硬化膜的電特性較不易下降。(A) The acid value of the epoxy resin containing acid-modified vinyl is preferably 30 to 150 mgKOH/g, more preferably 40 to 120 mgKOH/g, and still more preferably 50 to 100 mgKOH/g. When the acid value is 30 mgKOH/g or more, the solubility of the photosensitive resin composition in the dilute alkaline solution is less likely to decrease, and when the acid value is 150 mgKOH/g or less, the electrical characteristics of the cured film are less likely to decrease.

環氧樹脂(a’)與多元酸酐(c)之反應溫度，較佳是60～120℃。The reaction temperature of the epoxy resin (a') and the polybasic acid anhydride (c) is preferably 60 to 120°C.

又，亦可視需要而部分地合併使用例如氫化雙酚A型環氧樹脂來作為環氧樹脂(a)。進而，亦可部分地合併使用苯乙烯-馬來酸酐共聚物的(甲基)丙烯酸羥乙酯改質物等苯乙烯-馬來酸系樹脂來作為(A)含有酸改質乙烯基之環氧樹脂。Furthermore, if necessary, for example, a hydrogenated bisphenol A type epoxy resin may be used in combination as the epoxy resin (a). Furthermore, styrene-maleic acid-based resins such as styrene-maleic anhydride copolymer-modified hydroxyethyl (meth)acrylate modified products may also be used in combination as (A) acid-modified vinyl-containing epoxy Resin.

(A)含有酸改質乙烯基之環氧樹脂的重量平均分子量，較佳是3000～30000，更佳是4000～25000，進而更佳是5000～18000。(A)成分的重量平均分子量為上述範圍內時，可獲得阻劑層形狀、解析度、耐熱性、密著性及電絕緣性之平衡更加優異的阻劑圖案。此處，重量平均分子量是藉由以四氫呋喃為溶媒之膠體滲透層析法(gel permeation chromatography，GPC)進行測定，再以聚苯乙烯所換算之重量平均分子量。更具體而言，例如，可用下述GPC測定裝置及測定條件進行測定，並將使用標準聚苯乙烯的檢量線(calibration curve)而換算之值，作為重量平均分子量。又，檢量線的製作，是使用5樣本套組(「PStQuick MP-H」及「PStQuick B」，TOSOH CORPORATION製造)作為標準聚苯乙烯。 (GPC測定裝置) GPC測定裝置：高速GPC裝置「HCL-8320GPC」，偵檢器為示差折射計(differential refractometer)，TOSOH CORPORATION製造。 管柱：TSKgel SuperMultipore HZ-H(管柱長度：15cm，管柱內徑：4.6mm)，TOSOH CORPORATION製造。 (測定條件) 溶媒：四氫呋喃(THF) 測定溫度：40℃ 流量：0.35ml/分鐘 試料濃度：10mg/THF5ml 注入量：20μl(A) The weight average molecular weight of the epoxy resin containing an acid-modified vinyl group is preferably 3,000 to 30,000, more preferably 4,000 to 25,000, and still more preferably 5,000 to 18,000. (A) When the weight-average molecular weight of the component is within the above range, a resist pattern with a more excellent balance of the shape, resolution, heat resistance, adhesion, and electrical insulation of the resist layer can be obtained. Here, the weight average molecular weight is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and the weight average molecular weight is converted to polystyrene. More specifically, for example, the measurement can be performed using the following GPC measurement device and measurement conditions, and the value converted using the calibration curve of standard polystyrene is used as the weight average molecular weight. In addition, the calibration line was produced by using a 5-sample set ("PStQuick MP-H" and "PStQuick B", manufactured by TOSOH CORPORATION) as standard polystyrene. (GPC measuring device) GPC measuring device: High-speed GPC device "HCL-8320GPC", the detector is a differential refractometer, manufactured by TOSOH CORPORATION. Column: TSKgel SuperMultipore HZ-H (length of column: 15 cm, inner diameter of column: 4.6 mm), manufactured by TOSOH CORPORATION. (Measurement conditions) Solvent: Tetrahydrofuran (THF) Measuring temperature: 40℃ Flow rate: 0.35ml/min Sample concentration: 10mg/THF5ml Injection volume: 20μl

作為(A)含有酸改質乙烯基之環氧樹脂，較佳是：環氧樹脂(a’)，其為將具有通式(I)所示的結構單元且較佳是如通式(I’)所示的酚醛清漆型環氧樹脂、或具有通式(II)所示的結構單元且較佳是如通式(II’)所示的雙酚A型環氧樹脂和雙酚F型環氧樹脂作為環氧樹脂(a)，與含有乙烯基之單羧酸(b)反應而獲得；以及，環氧樹脂(a’’)，其為使該環氧樹脂(a’)與含有飽和基或不飽和基之多元酸酐(c)反應而獲得；更佳是環氧樹脂(a’’)。As (A) an epoxy resin containing an acid-modified vinyl group, preferably: an epoxy resin (a'), which has a structural unit represented by the general formula (I) and is preferably as the general formula (I Novolac-type epoxy resin represented by'), or having a structural unit represented by general formula (II) and preferably a bisphenol A epoxy resin and bisphenol F type represented by general formula (II') The epoxy resin is obtained as an epoxy resin (a) by reacting with a vinyl-containing monocarboxylic acid (b); and, an epoxy resin (a''), which contains the epoxy resin (a′) and The polyacid anhydride (c) of a saturated group or an unsaturated group is obtained by reaction; more preferably, it is an epoxy resin (a'').

此等環氧樹脂(a’)及(a’’)可單獨使用一種，或將二種以上組合使用，較佳是將複數種組合使用。作為該組合，較佳是下述二種的組合：從通式(I’)所示的酚醛清漆型環氧樹脂所得之環氧樹脂(a’)或(a’’)，與從通式(II’)所示的雙酚A型環氧樹脂及雙酚F型環氧樹脂所得之環氧樹脂(a’)或(a’’)；更佳是下述二種的組合：從通式(I’)所示的酚醛清漆型環氧樹脂所得之環氧樹脂(a’’)，與從通式(II’)所示的雙酚A型環氧樹脂及雙酚F型環氧樹脂所得之環氧樹脂(a’’)。 從通式(I’)所示的酚醛清漆型環氧樹脂所得之環氧樹脂(a’)或(a’’)，與從通式(II’)所示的雙酚A型環氧樹脂及雙酚F型環氧樹脂所得之環氧樹脂(a’)或(a’’)，兩者的質量混合比，較佳是95：5～30：70，更佳是90：10～40：60，進而更佳是80：20～45：55。These epoxy resins (a') and (a'') may be used singly or in combination of two or more kinds, and it is preferable to use a combination of plural kinds. As this combination, the following two combinations are preferred: an epoxy resin (a') or (a'') obtained from a novolak-type epoxy resin represented by the general formula (I′), and a general formula (II') epoxy resin (a') or (a'') obtained from the bisphenol A epoxy resin and the bisphenol F epoxy resin; more preferably a combination of the following two types: The epoxy resin (a'') obtained from the novolak epoxy resin represented by formula (I'), and the bisphenol A epoxy resin and bisphenol F epoxy represented by general formula (II') The epoxy resin (a'') obtained from the resin. The epoxy resin (a') or (a'') obtained from the novolak epoxy resin represented by the general formula (I'), and the bisphenol A epoxy resin represented by the general formula (II') And the epoxy resin (a') or (a'') obtained from the bisphenol F type epoxy resin, the mass mixing ratio of the two is preferably 95:5-30:70, more preferably 90:10-40 : 60, and more preferably 80:20 to 45:55.

又，當使用後述之(C5)含有氫硫基之化合物作為(C)成分時，環氧樹脂(a’)及(a’’)較佳是下述二種的組合：從具有通式(IV)所示的結構單元之雙酚酚醛清漆型環氧樹脂所得之環氧樹脂(a’)或(a’’)，與從通式(II’)所示的雙酚A型環氧樹脂及雙酚F型環氧樹脂所得之環氧樹脂(a’)或(a’’)；更佳是下述二種的組合：從具有通式(IV)所示的結構單元之雙酚酚醛清漆A型環氧樹脂或雙酚F型環氧樹脂所得之環氧樹脂(a’’)，與從通式(II’)所示的雙酚A型環氧樹脂及雙酚F型環氧樹脂所得之環氧樹脂(a’’)。 從具有通式(IV)所示的結構單元之雙酚酚醛清漆型環氧樹脂所得之環氧樹脂(a’)或(a’’)，與從通式(II’)所示的雙酚A型環氧樹脂及雙酚F型環氧樹脂所得之環氧樹脂(a’)或(a’’)，兩者的質量混合比，較佳是90：10～30：70，更佳是80：20～40：60，進而更佳是70：30～50：50。In addition, when (C5) a hydrogen sulfide group-containing compound described later is used as the (C) component, the epoxy resins (a') and (a'') are preferably a combination of the following two: IV) The epoxy resin (a') or (a'') obtained from the bisphenol novolak type epoxy resin of the structural unit shown in the structural unit, and the bisphenol A type epoxy resin represented by the general formula (II') Epoxy resin (a') or (a'') obtained from bisphenol F-type epoxy resin; more preferably a combination of the following two: from a bisphenol novolac having a structural unit represented by the general formula (IV) Epoxy resin (a'') obtained from varnish A type epoxy resin or bisphenol F type epoxy resin, and bisphenol A type epoxy resin and bisphenol F type epoxy resin represented by general formula (II') The epoxy resin (a'') obtained from the resin. An epoxy resin (a') or (a'') obtained from a bisphenol novolak-type epoxy resin having a structural unit represented by the general formula (IV), and a bisphenol represented by the general formula (II') The epoxy resin (a') or (a'') obtained from the A-type epoxy resin and the bisphenol F-type epoxy resin, the mass mixing ratio of the two is preferably 90:10-30:70, more preferably 80:20 to 40:60, more preferably 70:30 to 50:50.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(A)成分的含量較佳是20～80質量份，更佳是30～75質量份，進而更佳是40～75質量份。(A)成分的含量在上述範圍內時，可獲得耐熱性、電特性、及耐化學性更加優異的塗膜。此處，本實施形態中之固形成分總量，是指(A)～(F)成分所含之固形成分的合計量。例如，本實施形態的感光性樹脂組成物包含(A)～(D)成分時，(A)～(D)成分所含之固形成分的合計量為固形成分總量；又，本實施形態的感光性樹脂組成物包含(A)～(E)成分時，(A)～(E)成分所含之固形成分的合計量為固形成分總量；又，本實施形態的感光性樹脂組成物包含(A)～(F)成分時，(A)～(F)成分所含之固形成分的合計量為固形成分總量。When the total solid content in the photosensitive resin composition is set to 100 parts by mass, the content of (A) component is preferably 20 to 80 parts by mass, more preferably 30 to 75 parts by mass, and still more preferably 40 to 75 Quality parts. (A) When the content of the component is within the above range, a coating film having more excellent heat resistance, electrical characteristics, and chemical resistance can be obtained. Here, the total amount of solid content in this embodiment means the total amount of solid content contained in the components (A) to (F). For example, when the photosensitive resin composition of this embodiment includes the components (A) to (D), the total amount of solid components contained in the components (A) to (D) is the total amount of solid components; When the photosensitive resin composition contains the components (A) to (E), the total amount of solid components contained in the components (A) to (E) is the total amount of solid components; and the photosensitive resin composition of the present embodiment includes In the case of components (A) to (F), the total amount of solid components contained in the components (A) to (F) is the total amount of solid components.

＜(B)醯基氧化膦系光聚合起始劑＞ 本實施形態的感光性樹脂組成物，含有醯基氧化膦系光聚合起始劑作為(B)成分。 (B)醯基氧化膦系光聚合起始劑，只要是具有醯基氧化膦基(=P(=O)-C(=O)-基)之光聚合起始劑即可，並無特別限制，可較佳地列舉例如：(2,6-二甲氧基苄醯基)-2,4,6-三甲基苄醯基戊基氧化膦、雙(2,4,6-三甲基苄醯基)-苯基氧化膦、2,4,6-三甲基苄醯基二苯基氧化膦、2,4,6-三甲基苄醯基苯基次膦酸乙酯、(2,5-二羥苯基)二苯基氧化膦、(對羥苯基)二苯基氧化膦、雙(對羥苯基)苯基氧化膦、及參(對羥苯基)氧化膦等，可單獨使用一種，或將二種以上組合使用。＜(B) Acylphosphine oxide photopolymerization initiator＞ The photosensitive resin composition of this embodiment contains a phosphine oxide photopolymerization initiator as a component (B). (B) Acrylate-based phosphine oxide-based photopolymerization initiator, as long as it is a photopolymerization initiator having an acyl-based phosphine oxide group (=P(=O)-C(=O)- group), there is no special The limitation can be preferably exemplified by: (2,6-dimethoxybenzyl acetyl)-2,4,6-trimethyl benzyl pentyl phosphine oxide, bis(2,4,6-trimethyl (Benzylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzylphenylphosphinate, ( 2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, ginseng (p-hydroxyphenyl)phosphine oxide, etc. , One kind can be used alone, or two or more kinds can be used in combination.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(B)醯基氧化膦系光聚合起始劑的含量較佳是0.2～15質量份。(B)成分的含量為0.2質量份以上時，曝光部較不易在顯影中溶出，15質量份以下時，耐熱性則較不易下降。又，從相同理由而言，(B)光聚合起始劑的含量，較佳是0.2～10質量份，更佳是0.2～5質量份，特佳是0.5～5質量份，極佳是0.5～3質量份。When the total amount of solid content in the photosensitive resin composition is 100 parts by mass, the content of (B) amide phosphine oxide-based photopolymerization initiator is preferably 0.2 to 15 parts by mass. (B) When the content of the component is 0.2 parts by mass or more, the exposed portion is less likely to be eluted during development, and when it is 15 parts by mass or less, the heat resistance is less likely to decrease. For the same reason, the content of (B) photopolymerization initiator is preferably 0.2 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, particularly preferably 0.5 to 5 parts by mass, and very preferably 0.5 ~3 parts by mass.

又，可將N,N-二甲胺基苯甲酸乙酯、N,N-二甲胺基苯甲酸異戊酯、4-二甲胺基苯甲酸戊酯、三乙胺、三乙醇胺等三級胺類等光聚合起始助劑單獨使用一種，或將二種以上組合使用。In addition, triethylamine N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. One type of photopolymerization initiation aids such as grade amines are used alone, or two or more types are used in combination.

＜(C)添加劑＞ 本實施形態的感光性樹脂組成物，含有選自下述化合物中的至少一種作為(C)成分：(C1)烷基胺基苯衍生物、(C2)吡唑啉系敏化劑或蒽系敏化劑、(C3)光聚合起始劑、(C4)抗氧化劑及(C5)含有氫硫基之化合物，該(C3)光聚合起始劑是選自咪唑系光聚合起始劑、吖啶系光聚合起始劑及二茂鈦系光聚合起始劑中的至少一種，該(C4)抗氧化劑是選自受阻酚系抗氧化劑、醌系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑及磷系抗氧化劑中的至少一種。藉由將此等添加劑與(B)醯基氧化膦系光聚合起始劑合併使用，可獲得一種感光性樹脂組成物，其能形成圖案輪廓直線性良好、阻劑層形狀優異、解析度優異的圖案。＜(C) Additives＞ The photosensitive resin composition of this embodiment contains at least one selected from the following compounds as (C) component: (C1) alkylaminobenzene derivative, (C2) pyrazoline-based sensitizer or anthracene-based Sensitizer, (C3) photopolymerization initiator, (C4) antioxidant and (C5) compound containing hydrogen sulfide group, the (C3) photopolymerization initiator is selected from imidazole series photopolymerization initiator, acridine At least one of a pyridine-based photopolymerization initiator and a titanocene-based photopolymerization initiator, the (C4) antioxidant is selected from hindered phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur-based antioxidants At least one of an oxidant and a phosphorus-based antioxidant. By using these additives in combination with (B) acetylphosphine oxide-based photopolymerization initiator, a photosensitive resin composition can be obtained, which can form a pattern with good contour linearity, excellent resist layer shape, and excellent resolution picture of.

〔(C1)烷基胺基苯衍生物〕 (C1)烷基胺基苯衍生物，只要是在苯環上具有烷基胺基即可，並無特別限制，其能作為氫供應體而有效地發揮功能，更加提升感光性樹脂組成物的感光性及經時穩定性。此處，氫供應體代表一種化合物，其能供應氫原子給因上述光聚合起始劑之曝光處理所產生的自由基。本實施形態中，從形成圖案輪廓直線性良好、阻劑層形狀優異、解析度優異的圖案的觀點而言，上述(B)醯基氧化膦系光聚合起始劑與作為氫供應體之(C1)烷基胺基苯衍生物的組合特別有效。[(C1) Alkylaminobenzene derivatives] (C1) The alkylaminobenzene derivative is not particularly limited as long as it has an alkylamine group on the benzene ring, and it can effectively function as a hydrogen supplier to further enhance the photosensitive resin composition Sensitivity and stability over time. Here, the hydrogen donor represents a compound that can supply hydrogen atoms to free radicals generated by the exposure treatment of the above photopolymerization initiator. In the present embodiment, from the viewpoint of forming a pattern with good pattern outline linearity, excellent resist layer shape, and excellent resolution, the (B) acetylphosphine oxide-based photopolymerization initiator and the hydrogen donor ( C1) The combination of alkylaminobenzene derivatives is particularly effective.

作為(C1)烷基胺基苯衍生物，可較佳地列舉例如苯甘胺酸衍生物、胺基苯甲酸衍生物、胺基苯甲酸酯衍生物等。 作為苯甘胺酸衍生物，可較佳地列舉：N-苯甘胺酸、N,N-二苯甘胺酸、N-萘甘胺酸等。 作為胺基苯甲酸衍生物，可較佳地列舉：2-甲胺基苯甲酸、2-乙基胺基苯甲酸等。又，作為胺基苯甲酸酯衍生物，可較佳地列舉：N,N-二甲胺基苯甲酸乙酯、N,N-二乙胺基苯甲酸乙酯、N,N-二甲胺基苯甲酸異戊酯、N,N-二乙胺基苯甲酸異戊酯等。Examples of (C1) alkylaminobenzene derivatives include phenylglycine derivatives, aminobenzoic acid derivatives, and aminobenzoate derivatives. Phenylglycine derivatives can preferably be exemplified by N-phenylglycine, N,N-diphenylglycine, N-naphthylglycine, and the like. Examples of the aminobenzoic acid derivatives include 2-methylaminobenzoic acid and 2-ethylaminobenzoic acid. Further, as the amino benzoate derivative, preferably, ethyl N,N-dimethylaminobenzoate, ethyl N,N-diethylaminobenzoate, N,N-dimethyl Isoamyl aminobenzoate, isoamyl N,N-diethylaminobenzoate, etc.

本實施形態中，亦可使用具有烷基胺基之芳香族胺化合物。作為其具體例，可較佳地列舉例如：烷基碳數為8～14之二烷基二苯胺、辛基化二苯胺、4,4’-雙(α,α-二甲基苯甲基)二苯胺、N-苯基-N’-異丙基-對伸苯二胺、N-苯基-N’-(1,3-二甲基丁基)-對伸苯二胺、及N-苯基-N’-(3-甲基丙烯醯氧基-2-羥丙基)-對伸苯二胺等。 此等(C1)烷基胺基苯衍生物之中，較佳是N-苯甘胺酸、2-甲胺基苯甲酸、及N,N-二乙胺基苯甲酸乙酯。In this embodiment, an aromatic amine compound having an alkylamine group can also be used. Specific examples thereof include preferably dialkyldiphenylamines having an alkyl carbon number of 8 to 14, octylated diphenylamines, and 4,4'-bis(α,α-dimethylbenzyl). ) Diphenylamine, N-phenyl-N'-isopropyl-p-phenylene diamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylene diamine, and N -Phenyl-N'-(3-methacryloxy-2-hydroxypropyl)-p-phenylenediamine, etc. Among these (C1) alkylaminobenzene derivatives, N-phenylglycine, 2-methylaminobenzoic acid, and ethyl N,N-diethylaminobenzoate are preferred.

此等(C1)烷基胺基苯衍生物，可單獨使用一種，或將二種以上組合使用。又，使用上述烷基胺基苯衍生物時，亦可同時使用脂肪族胺化合物。作為具體例，可較佳地列舉例如：三乙醇胺、三乙胺等。These (C1) alkylaminobenzene derivatives may be used alone or in combination of two or more. Moreover, when using the said alkylamino benzene derivative, an aliphatic amine compound can also be used simultaneously. As a specific example, triethanolamine, triethylamine, etc. can be preferably mentioned.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(C1)烷基胺基苯衍生物的含量較佳是0.01～5質量份，更佳是0.1～3質量份、進而更佳是0.2～1.5質量份，特佳是0.2～1.0質量份。此含量為0.1質量份以上時，感光性樹脂組成物的溶液較不易凝膠化，為5質量份以下時，感光性不易下降，因此較佳。When the total solid content in the photosensitive resin composition is 100 parts by mass, the content of the (C1) alkylaminobenzene derivative is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and further More preferably, it is 0.2 to 1.5 parts by mass, and particularly preferably 0.2 to 1.0 part by mass. When this content is 0.1 part by mass or more, the solution of the photosensitive resin composition is less likely to gel, and when it is 5 parts by mass or less, the sensitivity is not likely to decrease, which is preferable.

〔(C2)吡唑啉系敏化劑或蒽系敏化劑〕 (C2)成分是吡唑啉系敏化劑或蒽系敏化劑。藉由添加(C2)吡唑啉系敏化劑，可獲得一種感光性樹脂組成物，即便是數位曝光(digital exposure)，也不會發生底部被挖空而成之底切、及阻劑層上部之缺損，能形成圖案輪廓直線性良好、阻劑層形狀優異、解析度優異的圖案。[(C2) Pyrazoline sensitizer or anthracene sensitizer] (C2) The component is a pyrazoline-based sensitizer or an anthracene-based sensitizer. By adding (C2) pyrazoline-based sensitizer, a photosensitive resin composition can be obtained, even under digital exposure, undercuts made by hollowing out the bottom and resist layer will not occur The defect in the upper part can form a pattern with good linearity of the pattern outline, excellent shape of the resist layer, and excellent resolution.

作為(C2)吡唑啉系敏化劑，只要是具有吡唑環的敏化劑即可，並無特別限制，較佳是下述通式(VI)所示的吡唑啉系敏化劑。The (C2) pyrazoline-based sensitizer is not particularly limited as long as it has a pyrazole ring, and preferably is a pyrazoline-based sensitizer represented by the following general formula (VI) .

Figure 02_image015
Figure 02_image015

通式(VI)中，R表示碳數4～12之烷基，a、b及c分別表示0～2之整數，a、b及c的總和為1～6。當a、b及c的總和為2～6時，同一分子中的複數的R可以相同亦可以不同。R的烷基可為直鏈，亦可為支鏈，且亦可為經鹵素原子、烷基、芳基、芳烷基、胺基、醯胺基、烷氧基等所置換之烷基。作為R，可較佳地列舉碳數4、8及12之烷基，更具體而言，較佳是正丁基、三級丁基、三級辛基、及正十二烷基，較佳是選自此等烷基之中的相同或不同的烷基。In the general formula (VI), R represents an alkyl group having 4 to 12 carbon atoms, a, b, and c represent integers of 0 to 2, respectively, and the total of a, b, and c is 1 to 6. When the sum of a, b, and c is 2 to 6, the plural R in the same molecule may be the same or different. The alkyl group of R may be linear or branched, and may also be an alkyl group substituted with a halogen atom, alkyl group, aryl group, aralkyl group, amine group, amide group, alkoxy group, or the like. R is preferably an alkyl group having 4, 8, and 12 carbon atoms, more specifically, preferably n-butyl, tertiary butyl, tertiary octyl, and n-dodecyl, preferably The same or different alkyl group selected from these alkyl groups.

作為此種吡唑啉系敏化劑，可較佳地列舉：1-(4-三級丁基-苯基)-3-苯乙烯基-5-苯基-吡唑啉、1-苯基-3-(4-三級丁基-苯乙烯基)-5-(4-三級丁基-苯基)-吡唑啉、1,5-雙-(4-三級丁基-苯基)-3-(4-三級丁基-苯乙烯基)-吡唑啉、1-(4-三級辛基-苯基)-3-苯乙烯基-5-苯基-吡唑啉、1-苯基-3-(4-三級辛基-苯乙烯基)-5-(4-三級辛基-苯基)-吡唑啉、1,5-雙-(4-三級辛基-苯基)-3-(4-三級辛基-苯乙烯基)-吡唑啉、1-(4-十二烷基-苯基)-3-苯乙烯基-5-苯基-吡唑啉、1-苯基-3-(4-十二烷基-苯乙烯基)-5-(4-十二烷基-苯基)-吡唑啉、1-(4-十二烷基-苯基)-3-(4-十二烷基-苯乙烯基)-5-(4-十二烷基-苯基)-吡唑啉、1-(4-三級辛基-苯基)-3-(4-三級丁基-苯乙烯基)-5-(4-三級丁基-苯基)-吡唑啉、1-(4-三級丁基-苯基)-3-(4-三級辛基-苯乙烯基)-5-(4-三級辛基-苯基)-吡唑啉、1-(4-十二烷基-苯基)-3-(4-三級丁基-苯乙烯基)-5-(4-三級丁基-苯基)-吡唑啉、1-(4-三級丁基-苯基)-3-(4-十二烷基-苯乙烯基)-5-(4-十二烷基-苯基)-吡唑啉、1-(4-十二烷基-苯基)-3-(4-三級辛基-苯乙烯基)-5-(4-三級辛基-苯基)-吡唑啉、1-(4-三級辛基-苯基)-3-(4-十二烷基-苯乙烯基)-5-(4-十二烷基-苯基)-吡唑啉、1-(2,4-二-正丁基-苯基)-3-(4-十二烷基-苯乙烯基)-5-(4-十二烷基-苯基)-吡唑啉、1-苯基-3-(3,5-二-三級丁基-苯乙烯基)-5-(3,5-二-三級丁基-苯基)-吡唑啉、1-苯基-3-(2,6-二-三級丁基-苯乙烯基)-5-(2,6-二-三級丁基-苯基)-吡唑啉、1-苯基-3-(2,5-二-三級丁基-苯乙烯基)-5-(2,5-二-三級丁基-苯基)-吡唑啉、1-苯基-3-(2,6-二-正丁基-苯乙烯基)-5-(2,6-二-正丁基-苯基)-吡唑啉、1-(3,4-二-三級丁基-苯基)-3-苯乙烯基-5-苯基-吡唑啉、1-(3,5-二-三級丁基-苯基)-3-苯乙烯基-5-苯基-吡唑啉、1-(4-三級丁基-苯基)-3-(3,5-二-三級丁基-苯乙烯基)-5-(3,5-二-三級丁基-苯基)-吡唑啉、及1-(3,5-二-三級丁基-苯基)-3-(3,5-二-三級丁基-苯乙烯基)-5-(3,5-二-三級丁基-苯基)-吡唑啉等。As such a pyrazoline sensitizer, preferably, 1-(4-tertiary butyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl -3-(4-tertiary butyl-styryl)-5-(4-tertiary butyl-phenyl)-pyrazoline, 1,5-bis-(4-tertiary butyl-phenyl )-3-(4-tertiary butyl-styryl)-pyrazoline, 1-(4-tertiary octyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-tertiary octyl-styryl)-5-(4-tertiary octyl-phenyl)-pyrazoline, 1,5-bis-(4-tertiary octyl -Phenyl)-3-(4-tertiary octyl-styryl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-styryl-5-phenyl- Pyrazoline, 1-phenyl-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecane -Phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-tertiary octyl-benzene Group)-3-(4-tertiary butyl-styryl)-5-(4-tertiary butyl-phenyl)-pyrazoline, 1-(4-tertiary butyl-phenyl)- 3-(4-tertiary octyl-styryl)-5-(4-tertiary octyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-( 4-tertiary butyl-styryl)-5-(4-tertiary butyl-phenyl)-pyrazoline, 1-(4-tertiary butyl-phenyl)-3-(4-dec Dialkyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(4-tertiary octyl -Styryl)-5-(4-tertiary octyl-phenyl)-pyrazoline, 1-(4-tertiary octyl-phenyl)-3-(4-dodecyl-styrene Yl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(2,4-di-n-butyl-phenyl)-3-(4-dodecyl-styrene Group)-5-(4-dodecyl-phenyl)-pyrazoline, 1-phenyl-3-(3,5-di-tertiary-butyl-styryl)-5-(3, 5-di-tertiary butyl-phenyl)-pyrazoline, 1-phenyl-3-(2,6-di-tertiary butyl-styryl)-5-(2,6-di- Tertiary butyl-phenyl)-pyrazoline, 1-phenyl-3-(2,5-di-tertiary butyl-styryl)-5-(2,5-di-tertiary butyl -Phenyl)-pyrazoline, 1-phenyl-3-(2,6-di-n-butyl-styryl)-5-(2,6-di-n-butyl-phenyl)-pyridine Oxazoline, 1-(3,4-di-tertiary butyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(3,5-di-tertiary butyl- Phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(4-tertiary butyl-phenyl)-3-(3,5-di-tertiary butyl-styryl )-5-(3,5-di-tertiary butyl-phenyl)-pyrazoline, and 1-(3,5-di-tertiary butyl-phenyl)-3-(3,5-di-tertiary butyl-styryl)-5-(3,5-di-tertiary butyl) -Phenyl)-pyrazoline and so on.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(C2)吡唑啉系敏化劑的含量較佳是0.01～10.0質量份，更佳是0.01～5質量份，進而更佳是0.02～1質量份，特佳是0.03～0.5質量份，極佳是0.03～0.2質量份。(C2)吡唑啉系敏化劑的含量為0.01質量份以上時，曝光部較不易在顯影中溶出，10質量份以下時，耐熱性則較不易下降。When the total solid content in the photosensitive resin composition is 100 parts by mass, the content of the (C2) pyrazoline-based sensitizer is preferably 0.01 to 10.0 parts by mass, more preferably 0.01 to 5 parts by mass, and More preferably, it is 0.02 to 1 part by mass, particularly preferably 0.03 to 0.5 part by mass, and very preferably 0.03 to 0.2 part by mass. (C2) When the content of the pyrazoline-based sensitizer is 0.01 parts by mass or more, the exposed portion is less likely to elute during development, and when it is 10 parts by mass or less, the heat resistance is less likely to decrease.

本實施形態的感光性樹脂組成物，較佳是添加(C2)蒽系敏化劑。 本實施形態的感光性樹脂組成物所使用的(C2)蒽系敏化劑，藉由使光硬化性提升，而能形成阻劑層形狀優異、解析度優異的圖案。 作為(C2)蒽系敏化劑，可較佳地列舉例如下述通式(XI)所示的化合物。In the photosensitive resin composition of this embodiment, it is preferable to add (C2) an anthracene sensitizer. The (C2) anthracene-based sensitizer used in the photosensitive resin composition of the present embodiment can form a pattern with excellent shape of the resist layer and excellent resolution by improving photocurability. Examples of the (C2) anthracene-based sensitizer include compounds represented by the following general formula (XI).

Figure 02_image017
Figure 02_image017

通式(XI)中，I11 為1～10之整數，R3 表示氫原子、碳數1～8之烷基、碳數3～20之脂環族基、碳數2～8之烯基、芳基、雜芳基、或-N(R4 )2 基，2個以上的R3 可互相結合形成環狀結構，該環狀結構可含有雜原子，又，烷基、烯基可為直鏈，亦可為支鏈，且亦可為經鹵素原子、烷基、芳基、芳烷基、胺基、醯胺基、烷氧基等所置換之烷基、烯基。又，複數的R3 、R4 可為相同亦可為不同。 X表示單鍵、氧原子、硫原子、羰基、磺醯基、-N(R’)-基、-C(=O)-O-基、-C(=O)-S-基、-SO2 -O-基、-SO2 -S-基、-SO2 -N(R’)-基、-O-CO-基、-S-C(=O)-基、-O-SO2 -基、或-S-SO2 -基。但是，排除X為單鍵且R3 為氫原子之組合(亦即無置換之蒽)。又，複數的X可為相同亦可為不同。 此處，R4 表示氫原子、碳數1～8之烷基、碳數3～20之脂環族基、碳數2～8之烯基、芳基、或雜芳基，R4 彼此可互相結合形成環狀結構，該環狀結構可含有雜原子，烷基、烯基可為直鏈，亦可為支鏈，且亦可為經鹵素原子、烷基、芳基、芳烷基、胺基、醯胺基、烷氧基等所置換之烷基、烯基。In the general formula (XI), I 11 is an integer of 1 to 10, R 3 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms. , Aryl, heteroaryl, or -N(R 4 ) 2 groups, two or more R 3 may be combined with each other to form a cyclic structure, the cyclic structure may contain hetero atoms, and alkyl, alkenyl may be The straight chain may also be a branched chain, and may also be an alkyl group or an alkenyl group substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amine group, an amide group, an alkoxy group, or the like. In addition, plural R 3 and R 4 may be the same or different. X represents a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, -N(R')- group, -C(=O)-O- group, -C(=O)-S- group, -SO 2 -O- group, -SO 2 -S- group, -SO 2 -N(R')- group, -O-CO- group, -SC(=O)- group, -O-SO 2 -group, Or -S-SO 2 -group. However, it is excluded that X is a single bond and R 3 is a combination of hydrogen atoms (that is, anthracene without substitution). Moreover, the plural X may be the same or different. Here, R 4 represents a hydrogen atom, a C 1-8 alkyl group, a C 3-20 cycloaliphatic group, a C 2-8 alkenyl group, an aryl group, or a heteroaryl group, and R 4 may be Combining with each other to form a cyclic structure, the cyclic structure may contain heteroatoms, alkyl, alkenyl groups may be linear or branched, and may also be halogen atoms, alkyl, aryl, aralkyl, Alkyl and alkenyl substituted by amine, amide, alkoxy, etc.

作為上述R3 及R4 中的碳數3～20之脂環族基，可較佳地列舉：環丙基、環丁基、環戊基、環己基，此外還有例如降莰基、三環癸醯基、四環十二烷基、金剛烷基、甲基金剛烷基、乙基金剛烷基、及丁基金剛烷基等碳數6～20之橋環烴基等。 作為芳基，可較佳地列舉如R13 之芳基所例示者，作為雜芳基，可較佳地列舉將構成此等芳基之任意的環原子的一個以上置換為硫原子、氧原子、氮原子等雜原子而獲得的芳基。Examples of the alicyclic groups having 3 to 20 carbon atoms in R 3 and R 4 include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and for example, norbornyl, tris Bridged cyclic hydrocarbon groups with 6 to 20 carbon atoms, such as cyclodecanoyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, and butyladamantyl. As the aryl group, preferably exemplified as the aryl group of R 13 , and as the heteroaryl group, preferably, one or more ring atoms constituting any of these aryl groups are replaced with a sulfur atom or an oxygen atom. Aryl groups derived from heteroatoms such as nitrogen atoms and nitrogen atoms.

作為上述的R3 及R4 ，可較佳地列舉例如：氫原子、甲基、乙基、正丙基、異丙基、正丁基、三級丁基、正戊基、正己基、正庚基、正辛基、環戊基、環己基、樟腦醯基、降莰基、對甲苯甲醯基、苯甲基、苯基、及1-萘基等。Examples of the above R 3 and R 4 include hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, n-pentyl, n-hexyl, and n Heptyl, n-octyl, cyclopentyl, cyclohexyl, camphor acetyl, norbornyl, p-toluoyl, benzyl, phenyl, and 1-naphthyl.

又，作為上述通式(XI)所示的(C2)蒽系敏化劑，可較佳地列舉例如：1-甲蒽、2-甲蒽、2-乙蒽、2-三級丁基蒽、9-甲基蒽等烷基蒽；9,10-二甲蒽、9,10-二丙蒽、9,10-二丁蒽等二烷基蒽；9-(羥甲基)蒽、9-(2-羥乙基)蒽等羥烷基蒽；9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二丁氧基蒽、9,10-二(2-乙基己基氧基)蒽等二烷氧基蒽；9-乙烯基蒽、9-烯丙基蒽等烯基蒽；1-胺基蒽、2-胺基蒽、9-(甲基胺基甲基)蒽等胺基蒽；9-蒽甲醛、10-甲基-9-蒽甲醛等蒽甲醛；其他如9-苯基蒽、9-乙醯基蒽、9,10-二苯基蒽、1,2-苯并蒽、1,8,9-三乙醯氧基蒽(1,8,9-triacetoxyanthracene)、1,4,9,10-四羥基蒽等，此等蒽系敏化劑，可單獨使用一種，或將二種以上組合使用。Moreover, as the (C2) anthracene sensitizer represented by the general formula (XI), preferably, for example, 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-tertiary butylanthracene , 9-methylanthracene and other alkylanthracenes; 9,10-dimethylanthracene, 9,10-dipropylanthracene, 9,10-dibutylanthracene and other dialkylanthracenes; 9-(hydroxymethyl)anthracene, 9 -Hydroxyalkylanthracene such as (2-hydroxyethyl)anthracene; 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di (2-ethylhexyloxy) anthracene and other dialkoxy anthracene; 9-vinyl anthracene, 9-allyl anthracene and other alkenyl anthracene; 1-aminoanthracene, 2-aminoanthracene, 9-(methyl Amino anthracene) anthracene such as anthracene; 9-anthracene formaldehyde, 10-methyl-9-anthracene formaldehyde and other anthracene formaldehyde; others such as 9-phenylanthracene, 9-acetoanthracene, 9,10-di Phenylanthracene, 1,2-benzoanthracene, 1,8,9-triacetoxyanthracene (1,8,9-triacetoxyanthracene), 1,4,9,10-tetrahydroxyanthracene, etc. The sensitizer can be used alone or in combination of two or more.

此等之中，較佳是：二苯基蒽、二烷基蒽、及二烷氧基蒽，更佳是：9,10-二甲蒽、9,10-二苯基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二丁氧基蒽、及9,10-二(2-乙基己基氧基)蒽，進而更佳：是9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二丁氧基蒽、及9,10-二(2-乙基己基氧基)蒽等9,10-二烷氧基蒽。本實施形態中，若使用此等蒽系敏化劑，則可獲得一種特別對於波長300～450nm的放射線具有感光性的感光性樹脂組成物，能提升光硬化性，因此能形成阻劑層形狀優異、解析度優異的圖案。Among these, preferred are: diphenylanthracene, dialkylanthracene, and dialkoxyanthracene, more preferably: 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10 -Diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene, which is even better: is 9 ,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene, etc. Dialkoxyanthracene. In this embodiment, if such an anthracene-based sensitizer is used, a photosensitive resin composition that is particularly sensitive to radiation having a wavelength of 300 to 450 nm can be obtained, and the photocurability can be improved, so that the shape of the resist layer can be formed Excellent pattern with excellent resolution.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(C2)蒽系敏化劑的含量較佳是0.001～10質量份。(C2)蒽系敏化劑的含量在上述範圍內時，能提升光硬化性，因此能形成阻劑層形狀優異、解析度優異的圖案。根據同樣的理由，(C2)蒽系敏化劑的含量更佳是0.01～5質量份，進而更佳是0.03～3質量份，特佳是0.1～1.5質量份。 又，相對於(A)含有酸改質乙烯基之環氧樹脂100質量份，(C2)蒽系敏化劑的含量較佳是0.001～10質量份，更佳是0.01～5質量份，進而更佳是0.03～3質量份。When the total solid content in the photosensitive resin composition is 100 parts by mass, the content of (C2) anthracene-based sensitizer is preferably 0.001 to 10 parts by mass. (C2) When the content of the anthracene-based sensitizer is within the above range, the photocurability can be improved, so that a pattern with an excellent shape of the resist layer and excellent resolution can be formed. For the same reason, the content of the (C2) anthracene sensitizer is more preferably 0.01 to 5 parts by mass, still more preferably 0.03 to 3 parts by mass, and particularly preferably 0.1 to 1.5 parts by mass. Moreover, the content of (C2) anthracene-based sensitizer is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass relative to (A) 100 parts by mass of the epoxy resin containing acid-modified vinyl. More preferably, it is 0.03 to 3 parts by mass.

〔(C3)選自咪唑系光聚合起始劑、吖啶系光聚合起始劑及二茂鈦系光聚合起始劑中的至少一種光聚合起始劑〕 (C3)成分，是選自咪唑系光聚合起始劑、吖啶系光聚合起始劑及二茂鈦系光聚合起始劑中的至少一種光聚合起始劑。 本實施形態中，從形成圖案輪廓直線性良好、阻劑層形狀優異、解析度優異的圖案的觀點而言，上述(B)醯基氧化膦系光聚合起始劑與(C3)成分的組合特別有效。[(C3) At least one photopolymerization initiator selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators and titanocene-based photopolymerization initiators] The component (C3) is at least one photopolymerization initiator selected from imidazole-based photopolymerization initiators, acridine-based photopolymerization initiators, and titanocene-based photopolymerization initiators. In this embodiment, from the viewpoint of forming a pattern with good linearity of the pattern outline, excellent shape of the resist layer, and excellent resolution, the combination of the (B) phosphinyl oxide-based photopolymerization initiator and the (C3) component Especially effective.

作為咪唑系光聚合起始劑，只要是分子中具有咪唑環的光聚合起始劑即可，並無特別限制，可較佳地列舉：2,2’-雙(o-氯苯基)-4,5,4’,5’-四苯基-1,2’-聯咪唑；並且還有2-(o-氯苯基)-4,5-二苯基咪唑二聚物、2-(o-氯苯基)-4,5-二(m-甲氧基苯基)咪唑二聚物、2-(o-氟苯基)-4,5-二苯基咪唑二聚物、2-(o-甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(p-甲氧基苯基)-4,5-二苯基咪唑二聚物、2,4-二(p-甲氧基苯基)-5-苯基咪唑二聚物、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚物；及，2-(p-甲基巰基苯基)-4,5-二苯基咪唑二聚物等2,4,5-三芳基咪唑二聚物等。The imidazole-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an imidazole ring in the molecule, and preferably 2,2'-bis(o-chlorophenyl)- 4,5,4',5'-tetraphenyl-1,2'-biimidazole; and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-( o-chlorophenyl)-4,5-bis(m-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- Bis(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; and, 2 -(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer etc. 2,4,5-triarylimidazole dimer etc.

在2,4,5-三芳基咪唑二聚物中，構成該二聚物的兩個2,4,5-三芳基咪唑，分別可具有相同的結構，亦可具有不同的結構。亦即，2,4,5-三芳基咪唑二聚物中的三芳基的種類可相同亦可不同。In the 2,4,5-triarylimidazole dimer, the two 2,4,5-triarylimidazoles constituting the dimer may have the same structure or different structures, respectively. That is, the types of triaryl groups in the 2,4,5-triarylimidazole dimer may be the same or different.

作為此種2,4,5-三芳基咪唑二聚物，可較佳地列舉例如：2,2’-雙(o-氯苯基)-4,5,4’,5’-四苯基-1,2’-聯咪唑、2-(o-氯苯基)-4,5-二苯基咪唑二聚物、2,2’-雙(o-氯苯基)-4,4’,5,5’-四(p-氯苯基)咪唑二聚物、2-(o-氯苯基)-4,5-二(m-甲氧基苯基)咪唑二聚物、2,2’-雙(o-氯苯基)-4,4’,5,5’-四(p-氟苯基)咪唑二聚物、2,2’-雙(o-溴苯基)-4,4’,5,5’-四(p-氯p-甲氧基苯基)咪唑二聚物、2,2’-雙(o-氯苯基)-4,4’,5,5’-四(o,p-二氯苯基)咪唑二聚物、2,2’-雙(o-氯苯基)-4,4’,5,5’-四(o,p-二溴苯基)咪唑二聚物、2,2’-雙(o-氯苯基)-4,4’,5,5’-四(p-氯萘基)咪唑二聚物、2,2’-雙(m,p-二氯苯基)-4,4’,5,5’-四苯基咪唑二聚物、2,2’-雙(o,pー二氯苯基)-4,4’,5,5’-四苯基咪唑二聚物、2,2’-雙(o,p-二氯苯基)-4,4’,5,5’-四(o,p-二氯苯基)咪唑二聚物、2-(o-氟苯基)-4,5-二苯基咪唑二聚物、2-(o-甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(p-甲氧基苯基)-4,5-二苯基咪唑二聚物、2,4-二(p-甲氧基苯基)-5-苯基咪唑二聚物、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(p-甲基巰基苯基)-4,5-二苯基咪唑二聚物、2,2’-雙(p-溴苯基)-4,4’,5,5’-四苯基咪唑二聚物、2,2’-雙(o-溴苯基)-4,4’,5,5’-四(o,p-二氯苯基)咪唑二聚物、2,2’-雙(o-溴苯基)-4,4’,5,5’-四(p-碘苯基)咪唑二聚物、2,2’-雙(m-溴苯基)-4,4’,5,5’-四苯基咪唑二聚物、2,2’-雙(m,p-二溴苯基)-4,4’,5,5’-四苯基咪唑二聚物等。Examples of such 2,4,5-triarylimidazole dimers include, for example, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl -1,2'-biimidazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2,2'-bis(o-chlorophenyl)-4,4', 5,5'-Tetra(p-chlorophenyl)imidazole dimer, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer, 2,2 '-Bis(o-chlorophenyl)-4,4',5,5'-tetra(p-fluorophenyl)imidazole dimer, 2,2'-bis(o-bromophenyl)-4, 4',5,5'-tetrakis(p-chlorop-methoxyphenyl)imidazole dimer, 2,2'-bis(o-chlorophenyl)-4,4',5,5'- Tetra(o,p-dichlorophenyl)imidazole dimer, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(o,p-dibromophenyl )Imidazole dimer, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(p-chloronaphthyl)imidazole dimer, 2,2'-bis( m,p-dichlorophenyl)-4,4',5,5'-tetraphenylimidazole dimer, 2,2'-bis(o,pーdichlorophenyl)-4,4', 5,5'-tetraphenylimidazole dimer, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetra(o,p-dichlorophenyl )Imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer Substance, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-bis(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer , 2,2'-bis(p-bromophenyl)-4,4',5,5'-tetraphenylimidazole dimer, 2,2'-bis(o-bromophenyl)-4,4 ',5,5'-tetra(o,p-dichlorophenyl)imidazole dimer, 2,2'-bis(o-bromophenyl)-4,4',5,5'-tetra(p -Iodophenyl)imidazole dimer, 2,2'-bis(m-bromophenyl)-4,4',5,5'-tetraphenylimidazole dimer, 2,2'-bis(m ,p-dibromophenyl)-4,4',5,5'-tetraphenylimidazole dimer, etc.

此等2,4,5-三芳基咪唑二聚物，其芳基可進而以下述來置換：鹵素原子、碳數1～20之烷基、碳數3～10之環烷基、碳數6～14之芳基、胺基、碳數1～10之烷胺基、硝基、氰基、巰基、碳數1～10之烷基巰基、碳數2～20之二烷胺基、烯丙基、碳數1～20之羥烷基、烷基碳數為1～10之羧烷基、烷基碳數為1～10之醯基、碳數1～20之烷氧基或包含雜環之基等。For these 2,4,5-triarylimidazole dimers, the aryl group can be further replaced by the following: halogen atom, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, and 6 carbon atoms ～14 aryl group, amine group, C 1-10 alkyl amine group, nitro group, cyano group, mercapto group, C 1-10 alkyl mercapto group, C 2-20 dialkyl amine group, allyl group Group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyalkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or containing a heterocyclic ring The basis and so on.

作為吖啶系光聚合起始劑，只要是分子中具有吖啶環的光聚合起始劑即可，並無特別限制，可較佳地列舉：1,4-伸丁基雙-β-(吖啶-9-基)丙烯酸酯、p-伸苯二甲基雙[β-(吖啶-9-基)丙烯酸酯]、三伸乙二醇雙[β-(吖啶-9-基)丙烯酸酯]、9-苯基吖啶、1,7-雙(9,9’-吖啶基)庚烷等。The acridine-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an acridine ring in the molecule, and preferably includes 1,4-butylene-β-( Acridine-9-yl)acrylate, p-xylylene bis[β-(acridin-9-yl)acrylate], triethylene glycol bis[β-(acridin-9-yl) Acrylate], 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, etc.

作為二茂鈦系光聚合起始劑，只要是含有鈦作為金屬之茂金屬(metallocene)化合物的光聚合起始劑即可，並無特別限制，可較佳地列舉：雙(η5 -環戊二烯基)-雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦、雙(2,4-環戊二烯基)-雙(2,6-二氟-3-(1-吡咯基)苯基)鈦等。此等光聚合起始劑，可單獨使用一種，或將二種以上組合使用。The titanocene-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator containing a metallocene compound of titanium as a metal, and preferably includes bis(η 5 -ring Pentadienyl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, bis(2,4-cyclopentadienyl)-bis(2,6- Difluoro-3-(1-pyrrolyl)phenyl) titanium, etc. These photopolymerization initiators may be used alone or in combination of two or more.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(C3)光聚合起始劑的含量較佳是0.01～15質量份，更佳是0.01～5質量份，進而更佳是0.01～3.5質量份，特佳是0.02～1.0質量份。此含量在0.01質量份以上時，感光性樹脂組成物的溶液較不易凝膠化，為15質量份以下時，感光性不易下降，因此較佳。 將感光性樹脂組成物中的固形成分總量設為100質量份時，(B)醯基氧化膦系光聚合起始劑和(C3)光聚合起始劑的合計含量，較佳是0.2～15質量份。兩者的合計含量為0.2質量份以上時，曝光部較不易在顯影中溶出，15質量份以下時，耐熱性則較不易下降。又，根據同樣的理由，(B)光聚合起始劑和(C3)光聚合起始劑的合計含量，更佳是0.2～10質量份，進而更佳是0.2～5質量份，特佳是0.5～5質量份，極佳是0.5～3質量份。 上述(B)醯基氧化膦系光聚合起始劑與(C3)光聚合起始劑的質量比，較佳是100：0.5～100：8，更佳是100：1～100：6，進而更佳是100：1～100：5。質量比在上述範圍內時，會有阻劑層形狀優異且底部硬化性、導通孔徑(via diameter)精度提升的傾向，因此較佳。When the total solid content in the photosensitive resin composition is 100 parts by mass, the content of the (C3) photopolymerization initiator is preferably 0.01 to 15 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably It is 0.01 to 3.5 parts by mass, particularly preferably 0.02 to 1.0 part by mass. When the content is 0.01 parts by mass or more, the solution of the photosensitive resin composition is less likely to gel, and when it is 15 parts by mass or less, the sensitivity is not likely to decrease, which is preferable. When the total solid content in the photosensitive resin composition is set to 100 parts by mass, the total content of (B) amide phosphine oxide photopolymerization initiator and (C3) photopolymerization initiator is preferably 0.2 to 15 parts by mass. When the total content of the two is 0.2 parts by mass or more, the exposed portion is less likely to be eluted during development, and when it is 15 parts by mass or less, the heat resistance is less likely to decrease. Also, for the same reason, the total content of (B) photopolymerization initiator and (C3) photopolymerization initiator is more preferably 0.2 to 10 parts by mass, still more preferably 0.2 to 5 parts by mass, particularly preferably 0.5 to 5 parts by mass, preferably 0.5 to 3 parts by mass. The mass ratio of the (B) acetylphosphine oxide-based photopolymerization initiator to the (C3) photopolymerization initiator is preferably 100: 0.5 to 100: 8, more preferably 100: 1 to 100: 6, and More preferably, it is 100:1 to 100:5. When the mass ratio is within the above range, the shape of the resist layer is excellent, and the bottom hardenability and the accuracy of the via diameter tend to improve, which is preferable.

〔(C4)選自受阻酚系抗氧化劑、醌系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑及磷系抗氧化劑中的至少一種抗氧化劑〕 (C4)成分是選自受阻酚系抗氧化劑、醌系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑及磷系抗氧化劑中的至少一種抗氧化劑。 藉由採用(C4)成分，可獲得一種感光性樹脂組成物，該感光性樹脂組成物能形成阻劑層形狀優異、解析度優異的圖案，且能形成具有優異的焊料耐熱性與耐助焊劑(flux)腐蝕性之圖案。[(C4) At least one antioxidant selected from hindered phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants] (C4) The component is at least one antioxidant selected from hindered phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants. By using the (C4) component, a photosensitive resin composition can be obtained which can form a pattern with excellent shape and resolution of the resist layer, and can form an excellent solder heat resistance and flux resistance (flux) Corrosive patterns.

作為受阻酚系抗氧化劑，可較佳地列舉：季戊四醇四[3-(3,5-二-三級丁基-4-羥苯基)丙酸酯](BASF Japan Ltd.製造，IRGANOX 1010(商品名))、雙[3-(3,5-二叔丁基-4-羥苯基)丙酸]硫代二伸乙酯(BASF Japan Ltd.製造，IRGANOX 1035(商品名))、[3-(3,5-二-三級丁基-4-羥苯基)丙酸]十八烷酯(BASF Japan Ltd.製造，IRGANOX 1076(商品名))、1-3,5-二-三級丁基-4-羥基-氫化肉桂酸辛酯(BASF Japan Ltd.製造，IRGANOX 1135(商品名))，及4,6-雙(辛硫甲基)鄰甲酚(BASF Japan Ltd.製造，IRGANOX 1520L)等市售品，並且還有3-(3’5’-二-三級丁基-4’-羥苯基)-丙酸正十八烷酯、3-(3’-甲基-5’-三級丁基-4’-羥苯基)-丙酸正十八烷酯、3-(3’,5’-二-三級丁基-4’-羥苯基)-丙酸正十四烷酯、1,6-己二醇-雙-(3-(3,5-二-三級丁基-4-羥苯基)-丙酸酯)、1,4-丁二醇-雙-(3-(3,5-二-三級丁基-4-羥苯基)-丙酸酯)、三乙二醇-雙-(3-(3-三級丁基-5-甲基-4-羥苯基)-丙酸酯)、四-(亞甲基-3-(3’,5’-二-三級丁基-4’-羥苯基)丙酸酯)甲烷、3,9-雙(2-(3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基)-1,1-二甲基乙基)2,4,8,10-四氧雜螺(5,5)十一烷、N,N’-雙-3-(3’5’-二-三級丁基-4-羥基苯)丙醯基六亞甲二胺、N,N’-四亞甲基雙-3-(3’-甲基-5’-三級丁基-4-羥基苯)丙醯基二胺、N,N’-雙-(3-(3,5-二-三級丁基-4-羥基苯)丙烯基)肼、N-柳醯基-N’-亞柳基肼、3-(N-柳醯基)胺基-1,2,4-***，及N,N’-雙(2-(3-(3,5-二-丁基-4-羥苯基)丙醯氧基)乙基)氧基醯胺等，此等抗氧化劑可單獨使用一種，或將二種以上組合使用。又，作為醌系抗氧化劑，可較佳地列舉：氫醌、2-三級丁基氫醌、氫醌單甲醚、甲萘醌(metaquinone)、苯醌等醌系抗氧化劑，此等抗氧化劑可單獨使用一種，或將二種以上組合使用。此等具有酚式羥基的抗氧化劑，可期待其對於過氧化自由基(ROO‧)、烷基自由基(R‧)等的捕捉效果。As the hindered phenol-based antioxidant, preferably, pentaerythritol tetra[3-(3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd., IRGANOX 1010( Trade name)), bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] thiodiethylidene (made by BASF Japan Ltd., IRGANOX 1035 (trade name)), [ 3-(3,5-di-tertiarybutyl-4-hydroxyphenyl)propionic acid]octadecyl ester (manufactured by BASF Japan Ltd., IRGANOX 1076 (trade name)), 1-3,5-di- Tertiary butyl-4-hydroxy-hydrocinnamic acid octyl ester (manufactured by BASF Japan Ltd., IRGANOX 1135 (trade name)), and 4,6-bis(octylthiomethyl) o-cresol (manufactured by BASF Japan Ltd., IRGANOX 1520L) and other commercial products, and also 3-(3'5'-di-tertiary butyl-4'-hydroxyphenyl)-n-octadecyl propionate, 3-(3'-methyl -5'-tertiary butyl-4'-hydroxyphenyl)-n-octadecyl propionate, 3-(3',5'-di-tertiary butyl-4'-hydroxyphenyl)-propane N-tetradecyl acid, 1,6-hexanediol-bis-(3-(3,5-di-tertiarybutyl-4-hydroxyphenyl)-propionate), 1,4-butanedi Alcohol-bis-(3-(3,5-di-tertiarybutyl-4-hydroxyphenyl)-propionate), triethylene glycol-bis-(3-(3-tertiarybutyl-5 -Methyl-4-hydroxyphenyl)-propionate), tetra-(methylene-3-(3',5'-di-tertiarybutyl-4'-hydroxyphenyl)propionate) Methane, 3,9-bis(2-(3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl) 2, 4,8,10-tetraoxaspiro(5,5)undecane, N,N'-bis-3-(3'5'-di-tertiary butyl-4-hydroxybenzene)propionyl hexa Methylenediamine, N,N'-tetramethylenebis-3-(3'-methyl-5'-tert-butyl-4-hydroxybenzene)propanediamine, N,N'-bis -(3-(3,5-di-tertiarybutyl-4-hydroxybenzene)propenyl)hydrazine, N-salyl-N'-salicylidene hydrazide, 3-(N-salicylidene)amino-1, 2,4-triazole, and N,N'-bis(2-(3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxy)ethyl)oxyamide, etc., These antioxidants can be used alone or in combination of two or more. Further, as the quinone-based antioxidant, preferably, quinone-based antioxidants such as hydroquinone, 2-tertiary butyl hydroquinone, hydroquinone monomethyl ether, metaquinone, benzoquinone, etc. The oxidant may be used alone or in combination of two or more. Antioxidants with phenolic hydroxyl groups are expected to capture peroxide radicals (ROO‧), alkyl radicals (R‧), etc.

作為胺系抗氧化劑，可較佳地列舉：苯基萘胺、4,4’-二甲氧基二苯胺、4,4’-雙(α,α-二甲基苯甲基)二苯胺、二-三級丁基-二苯胺、N,N’-二(辛苯基)胺、4-異丙氧基二苯胺、N,N’-二(2-萘基)-p-伸苯二胺、雙(2,2,6,6-四甲基-4-哌啶基)-癸二酸酯、啡噻口井等，此等抗氧化劑可單獨使用一種，或將二種以上組合使用。胺系抗氧化劑，可期待其對於過氧化自由基(ROO‧)的捕捉效果。Examples of the amine-based antioxidants include phenylnaphthylamine, 4,4′-dimethoxydiphenylamine, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, Di-tertiary butyl-diphenylamine, N,N'-bis(octylphenyl)amine, 4-isopropoxydiphenylamine, N,N'-bis(2-naphthyl)-p-phenylenediphenyl Amine, bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate, phenothiazine, etc. These antioxidants can be used alone or in combination of two or more . Amine-based antioxidants can be expected to capture peroxide radicals (ROO‧).

作為硫系抗氧化劑，可較佳地列舉：3,3’-硫代二丙酸二-十二烷酯、3,3’-硫代二丙酸二-十四烷酯、3,3’-硫代二丙酸二-十八烷酯、3,3’-硫代二丙酸二-十三烷酯、季戊四醇四(3-十二烷基硫代丙酸酯)、季戊四醇四(3-十四烷基硫代丙酸酯)、季戊四醇四(3-十三烷基硫代丙酸酯)、3,3-硫代二丙酸二月桂酯、3,3-硫代二丙酸二肉豆蔻酯、3,3-硫代二丙酸二硬脂酯、季戊四醇四(3-月桂基硫代二丙酸酯)、2-巰基苯并咪唑、硫代二丙酸月桂基硬脂基酯、2-巰基甲基苯并咪唑之鋅鹽、2-巰基苯并咪唑之鋅鹽、2-巰基甲基苯并咪唑、二丁基硫代胺基甲酸鋅等，此等抗氧化劑可單獨使用一種，或將二種以上組合使用。As the sulfur-based antioxidant, preferably, there are: 3,3′-di-dodecyl thiodipropionate, 3,3′-di-tetradecane thiodipropionate, 3,3′ -Di-octadecyl thiodipropionate, di-tridecyl 3,3'-thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate), pentaerythritol tetrakis (3 -Tetradecyl thiopropionate), pentaerythritol tetrakis (3-tridecyl thiopropionate), dilauryl 3,3-thiodipropionate, 3,3-thiodipropionic acid Dimyristyl ester, distearyl 3,3-thiodipropionate, pentaerythritol tetrakis(3-laurylthiodipropionate), 2-mercaptobenzimidazole, lauryl thiodipropionate Ester, zinc salt of 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc dibutylthiocarbamate, etc. These antioxidants may One kind is used alone, or two or more kinds are used in combination.

作為磷系抗氧化劑，可較佳地列舉：亞磷酸三苯基酯、亞磷酸三(甲基苯基)酯、亞磷酸三異辛基酯、亞磷酸三癸基酯、亞磷酸三(2-乙基己基)酯、亞磷酸三(壬基苯基)酯、亞磷酸三(辛基苯基)酯、亞磷酸三[癸基聚(氧伸乙基)]酯、亞磷酸三(環己基苯基)酯、亞磷酸三環己基酯、硫代亞磷酸三(癸基)酯、硫代亞磷酸三異癸基酯、苯基-雙(2-乙基己基)亞磷酸酯、亞磷酸苯基-二異癸基酯、四癸基聚(氧伸乙基)-雙(乙基苯基)亞磷酸酯、苯基-二環己基亞磷酸酯、苯基-二異辛基亞磷酸酯、苯基-二(十三烷基)亞磷酸酯、二苯基-環己基亞磷酸酯、二苯基-異辛基亞磷酸酯、二苯基-2-乙基己基亞磷酸酯、二苯基-異癸基亞磷酸酯、二苯基-環己基苯基亞磷酸酯、二苯基-(十三烷基)硫代亞磷酸酯等，此等抗氧化劑可單獨使用一種，或將二種以上組合使用。Examples of the phosphorus-based antioxidant include triphenyl phosphite, tri(methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, and tri(2 -Ethylhexyl) ester, tris(nonylphenyl) phosphite, tris(octylphenyl) phosphite, tris[decyl poly(oxyethyl)] phosphite, tris(cyclophosphite) Hexylphenyl) ester, tricyclohexyl phosphite, tri(decyl) thiophosphite, triisodecyl thiophosphite, phenyl-bis(2-ethylhexyl) phosphite, Phenyl-diisodecyl phosphate, tetradecyl poly(oxyethyl)-bis(ethylphenyl) phosphite, phenyl-dicyclohexyl phosphite, phenyl-diisooctyl phosphite Phosphate, phenyl-di(tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite , Diphenyl-isodecyl phosphite, diphenyl-cyclohexylphenyl phosphite, diphenyl-(tridecyl) thiophosphite, etc., these antioxidants can be used alone, Or a combination of two or more.

硫系抗氧化劑和磷系抗氧化劑，可期待其分解過氧化物的效果。作為硫系抗氧化劑和磷系抗氧化劑的市售品，例如可以列舉：ADK STAB TPP (ADEKA CORPORATION製造，商品名)、MARK AO 412S (ADEKA CORPORATION製造，商品名)、Sumilizer TPS (Sumitomo Chemical Co., Ltd.製造，商品名)等市售品。Sulfur-based antioxidants and phosphorus-based antioxidants can be expected to decompose peroxide. Examples of commercially available products of sulfur-based antioxidants and phosphorus-based antioxidants include ADK STAB TPP (manufactured by ADEKA CORPORATION, trade name), MARK AO 412S (manufactured by ADEKA CORPORATION, trade name), Sumilizer TPS (Sumitomo Chemical Co. , Ltd., trade name) and other commercially available products.

又，本實施形態中，從使阻劑層形狀良好、獲得優良的焊料耐熱性和耐助焊劑腐蝕性的觀點而言，特佳是將受阻酚系抗氧化劑與硫系抗氧化劑、磷系抗氧化劑等合併使用。In addition, in the present embodiment, from the viewpoint of making the shape of the resist layer good and obtaining excellent solder heat resistance and flux corrosion resistance, it is particularly preferable to combine the hindered phenol-based antioxidant with the sulfur-based antioxidant and the phosphorus-based antioxidant Combined use of oxidants.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(C4)抗氧化劑的含量較佳是0.2～15質量份。(C4)抗氧化劑的含量為0.2質量份以上時，曝光部較不易在顯影中溶出，15質量份以下時，耐熱性則較不易下降。又，根據同樣的理由，(C4)抗氧化劑的含量更佳是0.2～10質量份，進而更佳是0.5～5質量份，特佳是0.5～3質量份。When the total solid content in the photosensitive resin composition is 100 parts by mass, the content of the (C4) antioxidant is preferably 0.2 to 15 parts by mass. (C4) When the content of the antioxidant is 0.2 parts by mass or more, the exposed part is less likely to be eluted during development, and when it is 15 parts by mass or less, the heat resistance is less likely to decrease. In addition, for the same reason, the content of (C4) antioxidant is more preferably 0.2 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass.

〔(C5)含有氫硫基之化合物〕 (C5)成分是含有氫硫基之化合物，該含有氫硫基之化合物被認為具有下述功效：作為氫供應體而有效地發揮功能，更加提升感光性樹脂組成物的感光性及經時穩定性。[(C5) Hydrogen-sulfur group-containing compound] (C5) The component is a compound containing a hydrogen sulfide group, and the compound containing a hydrogen sulfide group is considered to have the following functions: function effectively as a hydrogen supplier, and further improve the sensitivity and stability of the photosensitive resin composition over time Sex.

作為(C5)含有氫硫基之化合物，例如可列舉：巰基苯并口咢唑、巰基苯并噻唑、巰基苯并咪唑、乙硫醇、苯硫酚(benzenethiol)、巰基苯酚(mercaptophenol)、巰基甲苯、2-巰基乙胺、巰基乙醇、二甲基苯硫酚(mercaptoxylene)、硫代二甲苯酚、2-巰基喹啉、巰基乙酸、α-巰基丙酸、3-巰基丙酸、巰基琥珀酸、硫代水楊酸、環己硫醇(mercaptocyclohexane)、α-巰基二苯甲烷、C-巰基四唑、巰基萘、巰基萘酚、4-巰基聯苯、硫代黃嘌呤(mercaptohypoxanthine)、巰基吡啶、2-巰基嘧啶、巰嘌呤、硫代苯并口咢口井酮(thiocoumazone)、硫代苯并噻口井酮(thiocoumothiazone)、2,3-丁二硫醇、三聚硫氰酸、2,4,6-三巰基-均三口井、2-二丁胺基-4,6-二巰基-均三口井、2-苯胺基-4,6-二巰基-均三口井等。 此等(C5)含有氫硫基之化合物，可單獨使用一種，或將二種以上組合使用。其中，從可作為氫供應體而有效地發揮功能、更加提升感光性樹脂組成物的靈敏度及經時穩定性的觀點而言，較佳是巰基苯并口咢唑、巰基苯并噻唑、巰基苯并咪唑，更佳是巰基苯并咪唑。Examples of (C5) compounds containing a hydrogenthio group include mercaptobenzoxazole, mercaptobenzothiazole, mercaptobenzimidazole, ethanethiol, benzenethiol, mercaptophenol, and mercaptotoluene. , 2-mercaptoethylamine, mercaptoethanol, mercaptoxylene, thioxyllenol, 2-mercaptoquinoline, thioglycolic acid, α-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid , Thiosalicylic acid, mercaptocyclohexane, alpha-mercaptodiphenylmethane, C-mercaptotetrazole, mercaptonaphthalene, mercaptonaphthol, 4-mercaptobiphenyl, thioxanthine (mercaptohypoxanthine), mercapto Pyridine, 2-mercaptopyrimidine, mercaptopurine, thiocoumazone, thiocoumothiazone, 2,3-butanedithiol, thiocyanuric acid, 2 ,4,6-Trimercapto-Munisan wells, 2-Dibutylamino-4,6-dimercapto-Munisan wells, 2-Anilino-4,6-dimercapto-Munisan wells, etc. These (C5) compounds containing a hydrogen sulfide group may be used alone or in combination of two or more. Among them, mercaptobenzotriazole, mercaptobenzothiazole, and mercaptobenzo are preferred from the viewpoint of effectively functioning as a hydrogen supplier, and further improving the sensitivity and stability of the photosensitive resin composition over time. Imidazole, more preferably mercaptobenzimidazole.

從獲得能形成解析度優異之圖案的感光性樹脂組成物的觀點而言，感光性樹脂組成物中的(C5)含有氫硫基之化合物的含量，以感光性樹脂組成物的固形成分總量為基準時，較佳是0.01～5質量份，更佳是0.1～3質量份，進而更佳是0.2～1.5質量份。(C5)含有氫硫基之化合物的含量為0.01質量份以上時，感光性樹脂組成物的溶液有不易凝膠化的傾向，為5質量份以下時，可抑制靈敏度降低。From the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern with excellent resolution, the content of the (C5) hydrogen sulfide group-containing compound in the photosensitive resin composition is the total solid content of the photosensitive resin composition When it is a reference, it is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and still more preferably 0.2 to 1.5 parts by mass. (C5) When the content of the hydrogen-sulfur group-containing compound is 0.01 parts by mass or more, the solution of the photosensitive resin composition tends not to gel easily, and when it is 5 parts by mass or less, the decrease in sensitivity can be suppressed.

＜(D)光聚合性化合物＞ 本實施形態的感光性樹脂組成物，含有光聚合性化合物作為(D)成分。 (D)光聚合性化合物，只要是具有顯示光聚合性之官能基的化合物即可，並無特別限制，例如可較佳地列舉具有：乙烯基、烯丙基、炔丙基、丁烯基、乙炔基、苯乙炔基、馬來醯亞胺基、納迪克醯亞胺基(nadiimide)、(甲基)丙烯醯基等環氧乙烷性不飽和基之化合物；從反應性的觀點而言，較佳是具有(甲基)丙烯醯基之化合物。<(D) Photopolymerizable compound> The photosensitive resin composition of this embodiment contains a photopolymerizable compound as (D) component. (D) The photopolymerizable compound is not particularly limited as long as it has a functional group showing photopolymerization, and for example, preferably includes vinyl, allyl, propargyl, butenyl , Ethynyl, phenylethynyl, maleimide, nadiimide, (meth)acryloyl and other ethylene oxide unsaturated groups; from the point of view of reactivity In other words, a compound having a (meth)acryloyl group is preferred.

作為(D)光聚合性化合物，可較佳地列舉例如：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯等(甲基)丙烯酸羥烷基酯類；乙二醇、甲氧基四乙二醇、聚乙二醇等二醇的(甲基)丙烯酸單酯或二酯類；N,N-二甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺等(甲基)丙烯醯胺類；(甲基)丙烯酸N,N-二甲胺基乙酯等(甲基)丙烯酸胺烷基酯類；己二醇、三羥甲基丙烷、季戊四醇、雙(三羥甲基)丙烷、二季戊四醇、參(羥乙基)異三聚氰酸酯等多元醇，或此等的環氧乙烷或環氧丙烷加成物的多元(甲基)丙烯酸酯類；(甲基)丙烯酸苯氧基乙酯、雙酚A的聚乙氧基二(甲基)丙烯酸酯等酚類的環氧乙烷或環氧丙烷加成物的(甲基)丙烯酸酯類；甘油二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、異三聚氰酸三縮水甘油酯等縮水甘油醚的(甲基)丙烯酸酯類；三聚氰胺(甲基)丙烯酸酯等。此等(D)光聚合性化合物可單獨使用一種，或將二種以上組合使用。Examples of the (D) photopolymerizable compound include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; B (Meth)acrylic acid monoesters or diesters of diols such as diols, methoxytetraethylene glycol, and polyethylene glycol; N,N-dimethyl(meth)acrylamide, N-hydroxymethyl (Meth)acrylamide and other (meth)acrylamides; (meth)acrylic acid N,N-dimethylaminoethyl and other (meth)acrylic acid amine alkyl esters; hexanediol, tris Polyols such as methylolpropane, pentaerythritol, bis (trimethylol) propane, dipentaerythritol, ginseng (hydroxyethyl) isocyanurate, or these ethylene oxide or propylene oxide adducts Poly(meth)acrylates; phenoxyethyl (meth)acrylate, polyethoxydi(meth)acrylates of bisphenol A, phenols, ethylene oxide or propylene oxide addition (Meth)acrylates of the substance; (meth)acrylates of glycidyl ethers such as glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, isocyanuric acid triglycidyl ester; melamine ( Meth)acrylate etc. These (D) photopolymerizable compounds may be used alone or in combination of two or more.

將感光性樹脂組成物中的固形成分總量設為100質量份時，(D)光聚合性化合物的含量較佳是0.1～30質量份，更佳是1～20質量份，進而更佳是1～15質量份，特佳是1.5～10質量份。(D)成分的含量為0.1質量份以上時，曝光部較不易在顯影中溶出，且有提升感光性樹脂組成物的靈敏度及解析度的傾向，30質量份以下時，則有提升耐熱性的傾向。When the total solid content in the photosensitive resin composition is 100 parts by mass, the content of the (D) photopolymerizable compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 15 parts by mass, particularly preferably 1.5 to 10 parts by mass. (D) When the content of the component is 0.1 parts by mass or more, the exposed portion is less likely to be eluted during development, and there is a tendency to improve the sensitivity and resolution of the photosensitive resin composition, and when it is 30 parts by mass or less, heat resistance is improved tendency.

＜(E)無機填料＞ 本實施形態的感光性樹脂組成物，較佳是含有無機填料作為(E)成分。 (E)無機填料，是基於使感光性樹脂組成物的密著性、耐熱性、塗膜強度等各特性提升之目的，而較佳地使用。作為(E)無機填料，可較佳地列舉例如：二氧化矽(SiO2 )、氧化鋁(Al2 O3 )、二氧化鈦(TiO2 )、五氧化二鉭(Ta2 O5 )、二氧化鋯(ZrO2 )、氮化矽(Si3 N4 )、鈦酸鋇(BaO･TiO2 )、碳酸鋇(BaCO3 )、碳酸鎂、氫氧化鋁、氫氧化鎂、鈦酸鉛(PbO･TiO2 )、鋯鈦酸鉛(PZT)、鋯鈦酸鉛鑭(PLZT)、氧化鎵(Ga2 O3 )、尖晶石(MgO･Al2 O3 )、富鋁紅柱石(3Al2 O3 ･2SiO2 )、堇青石(2MgO･2Al2 O3 ･5SiO2 )、滑石(3MgO･4SiO2 ･H2 O)、鈦酸鋁(TiO2 ･Al2 O3 )、含有三氧化二釔之二氧化鋯(Y2 O3 ･ZrO2 )、矽酸鋇(BaO･8SiO2 )、氮化硼(BN)、碳酸鈣(CaCO3 )、硫酸鋇(BaSO4 )、硫酸鈣(CaSO4 )、氧化鋅(ZnO)、鈦酸鎂(MgO･TiO2 )、水滑石(hydrotalcite)、雲母、鍛燒高嶺土、碳等。此等(E)無機填料可單獨使用一種，或將二種以上組合使用。<(E) Inorganic filler> The photosensitive resin composition of this embodiment preferably contains an inorganic filler as the (E) component. (E) The inorganic filler is preferably used for the purpose of improving various characteristics such as adhesion, heat resistance, and coating film strength of the photosensitive resin composition. Examples of the (E) inorganic filler include silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), titanium dioxide (TiO 2 ), tantalum pentoxide (Ta 2 O 5 ), and dioxide. Zirconium (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO･TiO 2 ), barium carbonate (BaCO 3 ), magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate (PbO･ TiO 2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3 ), spinel (MgO･Al 2 O 3 ), mullite (3Al 2 O 3 ･2SiO 2 ), cordierite (2MgO･2Al 2 O 3 ･5SiO 2 ), talc (3MgO･4SiO 2 ･H 2 O), aluminum titanate (TiO 2 ･Al 2 O 3 ), containing yttrium trioxide Zirconium dioxide (Y 2 O 3 ･ZrO 2 ), barium silicate (BaO･8SiO 2 ), boron nitride (BN), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), calcium sulfate (CaSO 4 ), zinc oxide (ZnO), magnesium titanate (MgO･TiO 2 ), hydrotalcite, mica, calcined kaolin, carbon, etc. These (E) inorganic fillers may be used alone or in combination of two or more.

(E)無機填料，其最大粒徑為0.1～20μm時較佳，為0.1～10μm時更佳，為0.1～5μm時進而更佳，為0.1～1μm時特佳。最大粒徑為20μm以下時，可抑制電絕緣性降低。此處，(E)無機填料的最大粒徑，是藉由雷射繞射法(依據JIS Z8825-1(2001年))所測定。(E) An inorganic filler, the maximum particle size of which is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.1 to 5 μm, and particularly preferably 0.1 to 1 μm. When the maximum particle size is 20 μm or less, the reduction in electrical insulation can be suppressed. Here, (E) the maximum particle diameter of the inorganic filler is measured by the laser diffraction method (according to JIS Z8825-1 (2001)).

(E)無機填料之中，從使耐熱性提升的觀點而言，較佳是使用二氧化矽；從使焊料耐熱性、耐破裂性(耐熱衝擊性)提升及使耐PCT試驗(Pressure Cooker Test，壓力鍋試驗)後的底部填充(underfill)材料與硬化膜之間的黏接強度提升的觀點而言，較佳是硫酸鋇。又，上述硫酸鋇，從提升防止凝聚的效果的觀點而言，較佳是：經以選自氧化鋁及有機矽烷化合物中的一種以上進行表面處理之硫酸鋇。(E) Among the inorganic fillers, from the viewpoint of improving heat resistance, it is preferable to use silicon dioxide; from the viewpoint of improving solder heat resistance and crack resistance (heat shock resistance) and PCT resistance (Pressure Cooker Test) In view of the improvement of the adhesion strength between the underfill material and the hardened film after the pressure cooker test, barium sulfate is preferred. In addition, the barium sulfate is preferably barium sulfate surface-treated with one or more kinds selected from alumina and organosilane compounds from the viewpoint of enhancing the effect of preventing aggregation.

經以選自氧化鋁及有機矽烷化合物中的一種以上進行表面處理之硫酸鋇，其表面之鋁的元素組成，較佳是0.5～10原子%，更佳是1～5原子%，進而更佳是1.5～3.5原子%。硫酸鋇的表面之矽的元素組成，較佳是0.5～10原子%，更佳是1～5原子%，進而更佳是1.5～3.5原子%。又，硫酸鋇的表面之碳的元素組成，較佳是10～30原子%，更佳是15～25原子%，進而更佳是18～23原子%。此等元素組成，可使用XPS(X-ray photoelectron spectrometer，X射線光電子能譜儀)進行測定。The elemental composition of aluminum on the surface of barium sulfate surface-treated with one or more kinds selected from alumina and organosilane compounds is preferably 0.5 to 10 atomic %, more preferably 1 to 5 atomic %, and still more preferably It is 1.5 to 3.5 atomic %. The elemental composition of silicon on the surface of barium sulfate is preferably 0.5 to 10 atom%, more preferably 1 to 5 atom%, and still more preferably 1.5 to 3.5 atom%. In addition, the elemental composition of carbon on the surface of barium sulfate is preferably 10 to 30 atomic %, more preferably 15 to 25 atomic %, and still more preferably 18 to 23 atomic %. These elemental compositions can be measured using XPS (X-ray photoelectron spectrometer, X-ray photoelectron spectrometer).

作為經以選自氧化鋁及有機矽烷化合物中的一種以上進行表面處理之硫酸鋇，可在商業上取得的有例如：NanoFine BFN40DC(NIPPON SOLVAY K.K.製造，商品名)。As barium sulfate surface-treated with one or more kinds selected from alumina and organosilane compounds, commercially available are, for example, NanoFine BFN40DC (manufactured by NIPPON SOLVAY K.K., trade name).

在含有(E)無機填料的情形中，將感光性樹脂組成物中的固形成分總量設為100質量份時，(E)無機填料的含量較佳是15～80質量份，更佳是15～70質量份，進而更佳是20～70質量份，特佳是20～50質量份，極佳是20～45質量份。(E)無機填料的含量在上述範圍內時，可使感光性樹脂組成物的塗膜強度、耐熱性、絕緣可靠性、耐熱衝擊性、解析度等更加提升。In the case of containing (E) inorganic filler, when the total solid content in the photosensitive resin composition is set to 100 parts by mass, the content of (E) inorganic filler is preferably 15 to 80 parts by mass, more preferably 15 ∼70 parts by mass, more preferably 20-70 parts by mass, particularly preferably 20-50 parts by mass, and most preferably 20-45 parts by mass. (E) When the content of the inorganic filler is within the above range, the coating film strength, heat resistance, insulation reliability, thermal shock resistance, resolution, etc. of the photosensitive resin composition can be further improved.

又，在使用硫酸鋇作為(E)無機填料的情形中，將感光性樹脂組成物中的固形成分總量設為100質量份時，硫酸鋇的含量較佳是5～60質量份，更佳是10～50質量份，進而更佳是10～40質量份，特佳是10～35質量份。硫酸鋇的含量在上述範圍內時，可使耐熱性及耐PCT性試驗後的底部填充材料與硬化膜之間的黏接強度更加提升。In addition, in the case of using barium sulfate as the (E) inorganic filler, when the total solid content in the photosensitive resin composition is 100 parts by mass, the content of barium sulfate is preferably 5 to 60 parts by mass, more preferably It is 10 to 50 parts by mass, more preferably 10 to 40 parts by mass, and particularly preferably 10 to 35 parts by mass. When the content of barium sulfate is within the above range, the adhesion strength between the underfill material and the cured film after the heat resistance and PCT resistance tests can be further improved.

＜(F)顏料＞ 本實施形態的感光性樹脂組成物，較佳是含有顏料作為(F)成分。 (F)顏料，是在隱蔽配線圖案時，視所希望的顏色而較佳地使用。作為(F)顏料，只要適當選擇可使所希望的顏色顯色之著色劑而使用即可，作為著色劑，可較佳地列舉例如：酞花青藍(phthalocyanine blue)、酞花青綠(phthalocyanine green)、碘綠(iodine green)、重氮黃(diazo yellow)、結晶紫等公知的著色劑。＜(F) Pigment＞ The photosensitive resin composition of this embodiment preferably contains a pigment as the (F) component. (F) The pigment is preferably used depending on the desired color when concealing the wiring pattern. As the (F) pigment, it is only necessary to appropriately select and use a coloring agent that can develop a desired color, and examples of the coloring agent include phthalocyanine blue and phthalocyanine. green), iodine green, diazo yellow, crystal violet and other known coloring agents.

在含有(F)顏料的情形中，將感光性樹脂組成物中的固形成分總量設為100質量份時，(F)顏料的含量較佳是0.1～5質量份，更佳是0.1～3質量份。(F)顏料的含量在上述範圍內時，從隱蔽配線圖案的觀點而言較佳。When (F) pigment is contained, when the total amount of solid content in the photosensitive resin composition is 100 parts by mass, the content of (F) pigment is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 Quality parts. (F) When the content of the pigment is within the above range, it is preferable from the viewpoint of concealing the wiring pattern.

＜其他成分＞ 本實施形態的感光性樹脂組成物，可視需要而使用稀釋劑以調整黏度。作為稀釋劑，可較佳地列舉例如：有機溶劑、光聚合性單體等。有機溶劑，例如，可從下述溶劑中適當地選擇使用：作為上述環氧樹脂(a)與含有乙烯基之單羧酸(b)之反應中可使用之有機溶劑，而例示之溶劑。又，作為光聚合性單體，可較佳地列舉上述(D)光聚合性化合物所例示者。<Other ingredients> The photosensitive resin composition of this embodiment may use a diluent to adjust the viscosity as necessary. Examples of the diluent include organic solvents and photopolymerizable monomers. The organic solvent can be appropriately selected and used from the following solvents, for example, as the organic solvents that can be used in the reaction between the epoxy resin (a) and the vinyl-containing monocarboxylic acid (b). In addition, as the photopolymerizable monomer, those exemplified in the above (D) photopolymerizable compound can be preferably exemplified.

稀釋劑的使用量，較佳是設為使感光性樹脂組成物中的固形成分總量為50～90質量%之量，更佳是60～80質量%之量，進而更佳是65～75質量%之量。亦即，使用稀釋劑時的感光性樹脂組成物中的稀釋劑含量，較佳是10～50質量%，更佳是20～40質量%，進而更佳是25～35質量%。藉由將稀釋劑使用量設在上述範圍，會提升感光性樹脂組成物的塗佈性，而可形成更高精細度的圖案。The amount of the diluent used is preferably such that the total solid content in the photosensitive resin composition is 50 to 90% by mass, more preferably 60 to 80% by mass, and still more preferably 65 to 75 The amount of mass%. That is, the content of the diluent in the photosensitive resin composition when the diluent is used is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and still more preferably 25 to 35% by mass. By setting the amount of diluent used in the above range, the coatability of the photosensitive resin composition is improved, and a higher-definition pattern can be formed.

本實施形態的感光性樹脂組成物，可包含硬化劑。作為硬化劑，可較佳地列舉：其本身藉由熱、紫外線等進行硬化之化合物；或，藉由熱、紫外線等，與本實施形態的組成物中的光硬化性樹脂成分亦即(A)含有酸改質乙烯基之環氧樹脂的羧基、羥基，進行硬化之化合物。可藉由使用硬化劑，使最後硬化膜的耐熱性、密著性、耐化學性等提升。The photosensitive resin composition of this embodiment may contain a curing agent. As the curing agent, preferably, a compound that itself is cured by heat, ultraviolet rays, or the like; or, by heat, ultraviolet rays, or the like, the photo-curable resin component in the composition of this embodiment, that is, (A ) A compound that hardens the carboxyl and hydroxyl groups of an epoxy resin containing acid-modified vinyl. By using a curing agent, the heat resistance, adhesion, and chemical resistance of the final cured film can be improved.

作為硬化劑，可較佳地列舉例如下述化合物作為熱化性硬化劑：環氧化合物、三聚氰胺化合物、尿素化合物、口咢唑啉(oxazoline)化合物等。作為環氧化合物，可較佳地列舉例如：雙酚A型環氧樹脂、雙酚F型環氧樹脂、氫化雙酚A型環氧樹脂、溴化雙酚A型環氧樹脂、雙酚S型環氧樹脂等雙酚型環氧樹脂；酚醛清漆型環氧樹脂；聯苯型環氧樹脂；三聚異氰酸三縮水甘油酯等雜環環氧樹脂；聯二甲酚(bixylenol)型環氧樹脂等。作為三聚氰胺化合物，可較佳地列舉例如：三胺基三口井、六甲氧基三聚氰胺、六丁氧基化三聚氰胺等。作為尿素化合物，可較佳地列舉：二羥甲基尿素等。As the hardening agent, for example, the following compounds are preferably mentioned as the thermal curing agent: epoxy compound, melamine compound, urea compound, oxazoline compound and the like. Examples of the epoxy compound include bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, and bisphenol S. Bisphenol-type epoxy resins such as epoxy resins; novolac-type epoxy resins; biphenyl-type epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanate; bixylenol type Epoxy resin, etc. Examples of the melamine compound include triamine-based three wells, hexamethoxy melamine, and hexabutoxylated melamine. Examples of the urea compound include dimethylolurea and the like.

作為硬化劑，從使硬化膜之耐熱性更加提升的觀點而言，較佳是包含選自環氧化合物(環氧樹脂)及封閉型異氰酸酯的一種以上，更佳是將環氧化合物及封閉型異氰酸酯合併使用。 作為封閉型異氰酸酯，是使用聚異氰酸酯化合物與異氰酸酯封閉劑之加成反應生成物。作為該聚異氰酸酯化合物，可較佳地列舉例如：甲苯二異氰酸酯、苯二甲基二異氰酸酯、苯基二異氰酸酯、萘基二異氰酸酯、雙(異氰酸甲基)環己烷、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯等聚異氰酸酯化合物，以及此等之加成物、縮二脲物、三聚異氰酸酯物等。As the curing agent, from the viewpoint of further improving the heat resistance of the cured film, it is preferable to contain one or more kinds selected from epoxy compounds (epoxy resins) and blocked isocyanates, and it is more preferable to use epoxy compounds and blocked types. Isocyanates are used in combination. As the blocked isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include toluene diisocyanate, xylylene diisocyanate, phenyl diisocyanate, naphthyl diisocyanate, bis(isocyanatomethyl)cyclohexane, and tetramethylene Polyisocyanate compounds such as diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and their adducts, biuret, Isocyanate compounds, etc.

作為異氰酸酯封閉劑，可較佳地列舉例如：酚、甲酚、二甲酚、氯酚、及乙酚等酚系封閉劑；ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺、及β-丙內醯胺等內醯胺系封閉劑；乙醯乙酸乙酯及乙醯丙酮等活性亞甲基系封閉劑；甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、丙二醇單甲基醚、苄醚、羥乙酸甲酯、羥乙酸丁酯、二丙酮醇、乳酸甲酯、及乳酸乙酯等醇系封閉劑；甲醛肟、乙醛肟、丙酮肟、甲乙酮肟、二乙醯單肟、環己酮肟等肟系封閉劑；丁硫醇、己硫醇、叔丁硫醇、硫酚、甲基硫酚、乙基硫酚等硫醇系封閉劑；乙醯胺、苄醯胺等酸醯胺系封閉劑；琥珀醯亞胺及馬來醯亞胺等醯亞胺系封閉劑；二甲苯胺、苯胺、丁胺、二丁胺等胺系封閉劑；咪唑、2-乙基咪唑等咪唑系封閉劑；亞甲基亞胺及丙烯基亞胺等亞胺系封閉劑等。Examples of the isocyanate blocking agent include phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol, and phenol; ε-caprolactam, δ-valerolactam, and γ-butane Internal amides and β-propionylamides and other internal amide-based sealants; ethyl acetate and ethyl acetone and other active methylene-based sealants; methanol, ethanol, propanol, butanol, pentanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate Alcohol-based sealants such as esters, diacetone alcohol, methyl lactate, and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, diethyl acetone oxime, cyclohexanone oxime and other oxime sealants; butyl Thiol, thiol, tert-butyl mercaptan, thiophenol, methylthiophenol, ethylthiophenol and other mercaptan-based blocking agents; acetamide, benzylamide and other acid-based amide blocking agents; succinimide And maleimide and other imide-based blocking agents; xylidine, aniline, butylamine, dibutylamine and other amine-based blocking agents; imidazole, 2-ethylimidazole and other imidazole-based blocking agents; methyleneimine And propylene imine and other imine sealants.

硬化劑可單獨使用一種，或將二種以上組合使用。使用硬化劑時，其含量相對於感光性樹脂組成物中的固形成分總量100質量份，較佳是2～50質量份，更佳是2～40質量份，進而更佳是3～30質量份，特佳是5～20質量份。藉由使硬化劑的含量為在上述範圍內，可一面維持良好之顯影性，一面更加提升所形成之硬化膜的耐熱性。One kind of hardener may be used alone, or two or more kinds may be used in combination. When the hardener is used, its content is preferably 2 to 50 parts by mass, more preferably 2 to 40 parts by mass, and still more preferably 3 to 30 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition. Parts, particularly preferably 5 to 20 parts by mass. By setting the content of the curing agent within the above range, while maintaining good developability, the heat resistance of the formed cured film is further improved.

可基於使最後硬化膜的耐熱性、密著性、耐化學性等各特性更進一步提升之目的，將環氧樹脂硬化劑合併使用於本實施形態的感光性樹脂組成物。For the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the final cured film, an epoxy resin hardener may be used in combination in the photosensitive resin composition of this embodiment.

作為此種環氧樹脂硬化劑的具體例，可較佳地列舉例如：2-甲基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基-5-羥甲基咪唑等咪唑類；乙胍口井、苯胍口井等胍口井(guanamine)類；二胺基二苯甲烷、間苯二胺、間苯二甲胺、二胺基二苯碸、二氰二胺(dicyandiamide)、尿素、尿素衍生物、三聚氰胺、多元醯肼等多胺類(polyamine)；選自此等的有機酸鹽及環氧加成物的一種以上；三氟化硼的胺錯合物；乙二胺基-均三口井、2,4-二胺基-均三口井、2,4-二胺基-6-二甲苯基-均三口井等三口井衍生物類；三甲胺、N,N-二甲辛基胺、N-苯甲基二甲胺、吡啶、N-甲基嗎啉、六(N-甲基)三聚氰胺、2,4,6-參(二甲胺基酚)、四甲胍、間胺基酚等三級胺類；聚乙烯酚、聚乙烯酚溴化物、苯酚酚醛清漆、烷基酚酚醛清漆等多酚類；三丁基膦、三苯膦、參(2-氰乙基)膦等有機膦類；三正丁基(2,5-二羥苯基)溴化鏻、六癸基三丁基氯化鏻等鏻鹽類；苄基三甲基氯化銨、苯基三丁基氯化銨等四級銨鹽類；前述多元酸酐；四氟硼酸二苯基錪、六氟銻酸三苯基鋶、六氟磷酸2,4,6-三苯基硫代哌喃(2,4,6-triphenylthiopyrylium hexafluoro phosphorate)等。Specific examples of such an epoxy resin hardener include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 2-benzene Imidazoles such as imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as etidine and guanidine; diamine diphenylmethane, m-benzene Polyamines such as diamine, m-xylylenediamine, diaminodiphenylbenzene, dicyandiamide, urea, urea derivatives, melamine, polyhydrazide; organic acids selected from these One or more salts and epoxy adducts; Amine complex of boron trifluoride; Ethylenediamine-all three wells, 2,4-diamine-all three wells, 2,4-diamine- Derivatives of three wells such as 6-xylyl-mesan wells; trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N -Methyl) melamine, 2,4,6-ginseng (dimethylaminophenol), tetramethylguanidine, m-aminophenol and other tertiary amines; polyvinyl phenol, polyvinyl phenol bromide, phenol novolak, alkane Polyphenols such as phenol novolak; organic phosphines such as tributylphosphine, triphenylphosphine, ginseng (2-cyanoethyl)phosphine; tri-n-butylphosphonium bromide (2,5-dihydroxyphenyl), Phosphonium salts such as hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyltributylammonium chloride; the aforementioned polyanhydrides; diphenylphosphonium tetrafluoroborate, Hexafluoroantimonate triphenyl alkane, hexafluoro phosphoric acid 2,4,6-triphenylthiopyran (2,4,6-triphenylthiopyrylium hexafluoro phosphorate), etc.

環氧樹脂硬化劑可單獨使用一種，或將二種以上組合使用，且在感光性樹脂組成物中，較佳是0.01～20質量%，更佳是0.1～10質量%。The epoxy resin hardener may be used alone or in combination of two or more, and in the photosensitive resin composition, it is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.

本實施形態的感光性樹脂組成物，可視需要而使用下述公知慣用之各種添加劑：氫醌、甲基氫醌、氫醌單甲基醚、兒茶酚、五倍子酚等聚合抑制劑；膨潤土(bentonite)、蒙脫土(montmorillonite)等增稠劑；聚矽氧系、氟系、乙烯樹脂等消泡劑；矽烷耦合劑等。 進而，可使用溴化環氧化合物、酸改質溴化環氧化合物、銻化合物、及磷系化合物之磷酸鹽化合物、芳香族縮合磷酸酯、含鹵素縮合磷酸酯等阻燃劑。The photosensitive resin composition of this embodiment may use the following well-known and commonly used additives as needed: polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, gallnut, etc.; bentonite ( (Bentonite), montmorillonite (montmorillonite) and other thickeners; polysiloxane-based, fluorine-based, vinyl resin and other defoamers; silane coupling agent. Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can be used.

(彈性體) 本實施形態的感光性樹脂組成物，可含有彈性體。尤其，將本實施形態的感光性樹脂組成物使用於製造半導體封裝基板時，可較佳地使用彈性體。藉由將彈性體添加至本實施形態的感光性樹脂組成物中，可抑制可撓性及黏著性下降情形，該可撓性及黏著性下降情形是由下述原因所引起：由於以紫外線或熱等進行硬化反應，使(A)含有酸改質乙烯基之環氧樹脂硬化收縮，而導致樹脂內部變形(內部應力)。(Elastomer) The photosensitive resin composition of this embodiment may contain an elastomer. In particular, when the photosensitive resin composition of this embodiment is used for manufacturing a semiconductor package substrate, an elastomer can be preferably used. By adding an elastomer to the photosensitive resin composition of the present embodiment, the decrease in flexibility and adhesiveness can be suppressed. The decrease in flexibility and adhesiveness is caused by the following reasons: Heat or the like undergoes a hardening reaction to harden and shrink (A) the epoxy resin containing acid-modified vinyl, which causes internal deformation of the resin (internal stress).

作為彈性體，可較佳地列舉：苯乙烯系彈性體、烯烴系彈性體、胺甲酸乙酯系彈性體、聚酯系彈性體、聚醯胺系彈性體、丙烯酸系彈性體、及聚矽氧系彈性體等。此等彈性體是由硬質段成分和軟質段成分所構成，通常前者有助於耐熱性及強度，而後者則有助於柔軟性及強韌性。Examples of the elastomer include preferably styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and polysilicon Oxygen elastomers, etc. These elastomers are composed of hard segment components and soft segment components. Generally, the former contributes to heat resistance and strength, while the latter contributes to flexibility and toughness.

又，除了上述彈性體以外，可使用經橡膠改質之環氧樹脂。經橡膠改質之環氧樹脂，例如，是以雙末端羧酸改質型丁二烯-丙烯腈橡膠、末端胺改質聚矽氧橡膠等，將上述雙酚F型環氧樹脂、雙酚A型環氧樹脂、三酚甲烷型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂的一部分或全部的環氧基進行改質而獲得。此等彈性體之中，從剪切黏著性的觀點而言，可較佳地列舉：雙末端羧基改質丁二烯-丙烯腈共聚物；ESPEL(Hitachi Chemical Co., Ltd.製造，ESPEL 1612、1620(商品名))，其為具有羥基之聚酯系彈性體。In addition to the above-mentioned elastomers, rubber-modified epoxy resins can be used. Rubber-modified epoxy resin, for example, butadiene-acrylonitrile rubber modified with double-terminal carboxylic acid, modified polysiloxane rubber with terminal amine, etc., the above-mentioned bisphenol F-type epoxy resin, bisphenol Part A or all of the epoxy groups of the A-type epoxy resin, triphenol methane-type epoxy resin, phenol novolak-type epoxy resin, and cresol novolak-type epoxy resin are obtained by modifying. Among these elastomers, from the viewpoint of shear adhesiveness, preferably include: double-terminal carboxyl modified butadiene-acrylonitrile copolymer; ESPEL (manufactured by Hitachi Chemical Co., Ltd., ESPEL 1612) , 1620 (trade name)), which is a polyester-based elastomer having a hydroxyl group.

彈性體的調配量，相對於(A)含有酸改質乙烯基之環氧樹脂100質量份，較佳是2～30質量份，更佳是4～20質量份，進而更佳是10～20質量份。彈性體的調配量為2質量份以上時，會有硬化膜在高溫區域的彈性模數變低之傾向，且30質量份以下時，會有未曝光部分溶於顯影液之傾向。The blending amount of the elastomer is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass, and still more preferably 10 to 20 parts by mass relative to (A) 100 parts by mass of the epoxy resin containing acid-modified vinyl groups. Quality parts. When the blending amount of the elastomer is 2 parts by mass or more, the elastic modulus of the cured film in the high-temperature region tends to be low, and when it is 30 parts by mass or less, the unexposed portion tends to dissolve in the developer.

可藉由以輥磨機(roll mill)、珠磨機(beads mill)等，將主要的上述(A)～(D)成分，以及視希望而使用之各種成分，均勻揉合、混合而獲得本實施形態的感光性樹脂組成物。 又，本發明的感光性樹脂組成物較佳是液體狀。可藉由使該感光性樹脂組成物為液體狀，並用後述各種塗佈方法，而輕易形成永久遮罩阻劑層。It can be obtained by uniformly kneading and mixing the main components (A) to (D) and various components used as desired with a roll mill, beads mill, etc. The photosensitive resin composition of this embodiment. In addition, the photosensitive resin composition of the present invention is preferably liquid. It is possible to easily form a permanent mask resist layer by making the photosensitive resin composition liquid and using various coating methods described later.

[感光性元件、永久遮罩阻劑層及印刷電路板] 本實施形態的感光性樹脂組成物，適合使用於形成感光性元件及永久遮罩阻劑層，且本實施形態的感光性元件及永久遮罩阻劑層，是使用本實施形態的感光性樹脂組成物所形成而成。 本實施形態的感光性元件，其具備：支撐體；感光層，其為將本實施形態的感光性樹脂組成物使用於該支撐體上而成。作為支撐體，可較佳地列舉例如下述具有耐熱性及耐溶劑性之樹脂薄膜：聚對酞酸乙二酯等之聚酯樹脂薄膜；聚乙烯、聚丙烯等聚烯烴樹脂薄膜等；從透明性的觀點而言，較佳是使用聚對酞酸乙二酯薄膜。又，支撐體的厚度，若考量到獲得機械性強度、良好之解析度等，較佳是1～100μm，更佳是1～50μm，進而更佳是1～30μm。[Photosensitive element, permanent mask resist layer and printed circuit board] The photosensitive resin composition of this embodiment is suitable for forming a photosensitive element and a permanent mask resist layer, and the photosensitive element and permanent mask resist layer of this embodiment use the photosensitive resin of this embodiment Formed by the composition. The photosensitive element of this embodiment includes: a support; and a photosensitive layer obtained by using the photosensitive resin composition of this embodiment on the support. As the support, for example, the following resin films having heat resistance and solvent resistance are preferably mentioned: polyester resin films such as polyethylene terephthalate; polyolefin resin films such as polyethylene and polypropylene; From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film. In addition, the thickness of the support is preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 1 to 30 μm in consideration of obtaining mechanical strength, good resolution, and the like.

可用例如浸漬法、噴霧塗佈法、刮條塗佈法、輥塗法、旋轉塗佈法等方法，將本實施形態的感光性樹脂組成物，依對應於用途之膜厚(乾燥後：10～200μm)，塗佈於上述支撐體上，而形成塗膜，並以70～150℃，5～30分鐘左右的條件乾燥形成感光層，而獲得本實施形態的感光性元件。The photosensitive resin composition of this embodiment can be prepared according to the film thickness corresponding to the application by methods such as dipping method, spray coating method, blade coating method, roll coating method, spin coating method (after drying: 10 ~200 μm), coated on the above support to form a coating film, and dried at 70 to 150° C. for about 5 to 30 minutes to form a photosensitive layer to obtain a photosensitive element of this embodiment.

本實施形態的永久遮罩阻劑層及具備該永久遮罩阻劑層之印刷電路板，例如，是如下進行而形成圖像。首先，以網版印刷法、噴霧塗佈法、輥塗法、簾塗佈法、靜電塗裝法等方法，將本實施形態的感光性樹脂組成物，依對應於用途之膜厚(乾燥後：10～200μm)，塗佈於欲形成阻劑層之基材(例如，印刷電路板用之覆銅積層板等)上，而形成塗膜，並以60～110℃使該塗膜乾燥。又，亦可將感光性元件的感光層轉印(貼合，laminate)至該欲形成阻劑層之基材上，而代替該塗膜。此時，視需要而使用常壓貼合機或真空貼合機，將支撐體上之經乾燥而成之塗膜，貼至基材上。 在基材上形成感光層(塗膜)後，使負片直接接觸，或透過透明薄膜，照射紫外線等活性光線(較佳是以10～1000mJ/cm2 之能量)，已貼附樹脂薄膜時，將該薄膜剝離，並以稀鹼水溶液，將未曝光部分溶解去除(顯影)。 繼而，藉由後曝光(紫外線曝光)、後加熱、或後曝光及後加熱，使曝光部分充分硬化而獲得硬化膜。後曝光，例如，較佳是1～5 J/cm2 ，後加熱較佳是以100～200℃進行30分鐘～12小時。The permanent mask resist layer of this embodiment and the printed circuit board provided with the permanent mask resist layer are formed as follows, for example, to form an image. First, the photosensitive resin composition of this embodiment is prepared according to the film thickness (after drying) of the photosensitive resin composition of this embodiment by screen printing method, spray coating method, roll coating method, curtain coating method, electrostatic coating method, etc. : 10 to 200 μm), coated on a substrate to be formed with a resist layer (for example, a copper-clad laminate for printed circuit boards, etc.) to form a coating film, and drying the coating film at 60 to 110°C. Alternatively, the photosensitive layer of the photosensitive element may be transferred (laminated) to the substrate to be formed with the resist layer instead of the coating film. At this time, if necessary, use an atmospheric pressure laminator or a vacuum laminator to apply the dried coating film on the support to the substrate. After the photosensitive layer (coating film) is formed on the substrate, the negative film is directly contacted, or the transparent film is irradiated with active light such as ultraviolet rays (preferably with an energy of 10 to 1000 mJ/cm 2 ), and the resin film is attached, The film was peeled off, and the unexposed portion was dissolved and removed with a dilute alkaline aqueous solution (development). Subsequently, the exposed portion is sufficiently cured by post exposure (ultraviolet exposure), post heating, or post exposure and post heating to obtain a cured film. The post-exposure is, for example, preferably 1 to 5 J/cm 2 , and the post-heating is preferably performed at 100 to 200° C. for 30 minutes to 12 hours.

如此進行而獲得之永久遮罩阻劑層，較不易產生底部被挖空而成之底切，且較不易產生阻劑層上部之缺損，故相對於表面部分的線寬而言，圖案剖面的中間部分(中心部)及最深部分(底部)的線寬較不易變大，因此，此永久遮罩阻劑層具有圖案輪廓的直線性佳、阻劑層形狀優異、且解析度優異之圖案。又，此永久遮罩阻劑層具有一種圖案，該圖案的孔徑大小和孔間的間隔間距伴隨近年來的電子機器小型化及高性能化而微細化，且形成穩定性優異。 [實施例]The permanent mask resist layer obtained in this way is less likely to produce an undercut made by hollowing out the bottom, and is less likely to cause defects in the upper part of the resist layer. Therefore, relative to the line width of the surface portion, the pattern cross section The line width of the middle part (center part) and the deepest part (bottom part) is less likely to become larger. Therefore, this permanent mask resist layer has a pattern with good linearity of the pattern outline, excellent resist layer shape, and excellent resolution. In addition, the permanent mask resist layer has a pattern in which the size of the hole diameter and the pitch between the holes have become finer as the electronic devices have been miniaturized and improved in recent years, and the formation stability is excellent. [Example]

以下藉由實施例，進而具體地說明本實施形態，但是本實施形態並未限定於此等實施例。Hereinafter, the present embodiment will be described more specifically by way of examples, but the present embodiment is not limited to these examples.

(評估方法) (1)表面硬化性評估 以塗抹器(applicator)將各實施例及比較例的感光性樹脂組成物，以乾燥後的膜厚為35μm的方式，塗佈於厚度35μm之PET薄膜上，而形成塗膜。繼而，使用熱風循環式乾燥機，以80℃乾燥20分鐘。所得之塗膜表面的紅外線吸收光譜(ATR(Attenuated total reflection，衰減全反射)法) 是依下述條件來測定。 ‧測定裝置：Thermo Fisher Scientific K.K.製造，商品名：Nicolet iS50R ‧累加次數：128次 繼而，使用紫外線曝光裝置(HI-TECH CO.,LTD製造，商品名：HTE-5102S)，以600mJ/cm2 的曝光量進行曝光。依與前述相同條件，測定曝光後的塗膜表面的紅外線吸收光譜(ATR法)，由下述算式求得曝光前後之碳-碳雙鍵(出現於1470cm-1 )的變化率，以累加次數3次的平均值作為表面硬化性(%)。 雙鍵的變化率(%)＝100－(曝光後的碳-碳雙鍵量/曝光前的碳-碳雙鍵量×100)(Evaluation method) (1) Evaluation of surface hardening property The photosensitive resin composition of each example and comparative example was applied to a PET film with a thickness of 35 μm so that the film thickness after drying was 35 μm by an applicator (applicator) To form a coating film. Then, a hot air circulation dryer was used and dried at 80°C for 20 minutes. The infrared absorption spectrum (ATR (Attenuated total reflection) method) of the surface of the obtained coating film was measured under the following conditions. ‧Measurement device: manufactured by Thermo Fisher Scientific KK, trade name: Nicolet iS50R ‧Number of accumulations: 128 times, using an ultraviolet exposure device (manufactured by HI-TECH CO., LTD, trade name: HTE-5102S) at 600mJ/cm 2 Exposure. Under the same conditions as above, the infrared absorption spectrum (ATR method) of the coating film surface after exposure was measured, and the rate of change of the carbon-carbon double bond (appearing at 1470 cm -1 ) before and after exposure was determined by the following formula, and the cumulative number of times The average value of three times is regarded as the surface hardenability (%). Double bond change rate (%) = 100-(carbon-carbon double bond amount after exposure/carbon-carbon double bond amount before exposure × 100)

(2)感光性評估 以塗抹器將各實施例及比較例的感光性樹脂組成物，以乾燥後的膜厚為35μm的方式，塗佈於厚度35μm之PET薄膜上，而形成塗膜。繼而，使用熱風循環式乾燥機，以80℃乾燥20分鐘。然後，使Step Tablet 41段(格數片，Hitachi Chemical Co., Ltd.製造)密著於塗膜，並以規定的累積曝光量之紫外線(Dainippon Screen Mfg. Co., Ltd.製造之直接成像曝光機，「LI9200 (型號)」)50 mJ/cm2 照射其全面。繼而，以1質量%之碳酸鈉水溶液顯影60秒後，確認未顯影而殘留的塗膜的段數。根據段數，依以下基準來評估。 A (優良)：10段以上 B (良)：6～9段 C (不良)：5段以下(2) Sensitivity evaluation The photosensitive resin composition of each Example and the comparative example was apply|coated to the PET film of 35 micrometers in thickness so that the film thickness after drying might be 35 micrometers, and the coating film was formed. Then, a hot air circulation dryer was used and dried at 80°C for 20 minutes. Then, the Step Tablet 41 segment (number of cells, manufactured by Hitachi Chemical Co., Ltd.) was adhered to the coating film, and directly imaged with ultraviolet rays (Dainippon Screen Mfg. Co., Ltd. manufactured by a specified cumulative exposure amount) Exposure machine, "LI9200 (model)") 50 mJ/cm 2 to illuminate its full range. Then, after developing with a 1% by mass sodium carbonate aqueous solution for 60 seconds, the number of stages of the coating film remaining without development was confirmed. According to the number of segments, the evaluation is based on the following criteria. A (Excellent): 10 steps or more B (Good): 6 to 9 steps C (Poor): 5 steps or less

(3)底部硬化性評估 以塗抹器將各實施例及比較例的感光性樹脂組成物，以乾燥後的膜厚為35μm的方式，塗佈於厚度35μm之PET薄膜上，而形成塗膜。繼而，使用熱風循環式乾燥機，以80℃乾燥20分鐘。依下述條件測定所得之塗膜底面的紅外線吸收光譜(ATR法)。 ‧測定裝置：Thermo Fisher Scientific K.K.製造，商品名：Nicolet iS50R ‧累加次數：128次 繼而，使用紫外線曝光裝置(HI-TECH CO.,LTD製造，商品名：HTE-5102S)，以600mJ/cm2 的曝光量進行曝光。之後，從PET薄膜上剝除已曝光之塗膜，依與前述相同條件，測定曝光後的PET薄膜面側之塗膜的紅外線吸收光譜(ATR法)。由下述算式求得曝光前後之碳-碳雙鍵(出現於1470cm-1 )的變化率，以累加次數3次的平均值作為塗膜底部硬化性(%)。 雙鍵的變化率(%)＝100－(曝光後的碳-碳雙鍵量/曝光前的碳-碳雙鍵量×100)(3) Bottom hardening evaluation The photosensitive resin composition of each Example and the comparative example was apply|coated to the PET film of 35 micrometers in thickness so that the film thickness after drying might be 35 micrometers, and the coating film was formed. Then, a hot air circulation dryer was used and dried at 80°C for 20 minutes. The infrared absorption spectrum (ATR method) of the bottom surface of the obtained coating film was measured under the following conditions. ‧Measurement device: manufactured by Thermo Fisher Scientific KK, trade name: Nicolet iS50R ‧Number of accumulations: 128 times, using an ultraviolet exposure device (manufactured by HI-TECH CO., LTD, trade name: HTE-5102S) at 600mJ/cm 2 Exposure. After that, the exposed coating film was peeled from the PET film, and the infrared absorption spectrum (ATR method) of the coating film on the side of the exposed PET film surface was measured under the same conditions as described above. The rate of change of the carbon-carbon double bond (appearing at 1470 cm -1 ) before and after exposure was determined from the following formula, and the average value of the cumulative number of times of three times was taken as the bottom film curability (%). Double bond change rate (%) = 100-(carbon-carbon double bond amount after exposure/carbon-carbon double bond amount before exposure × 100)

(4)阻劑層形狀評估 以網版印刷法，將各實施例及比較例的感光性樹脂組成物，以乾燥後的膜厚為35μm的方式，塗佈於大小為50cm×50cm且厚度為0.6mm之覆銅積層基板(Hitachi Chemical Co., Ltd.製造，商品名：MCL-E-67)，而形成塗膜後，使用熱風循環式乾燥機，以80℃乾燥20分鐘。 繼而，使具有如第2圖所示之圖案(孔徑大小為100μm且孔間的間隔間距為100μm的圖案、及孔徑大小為80μm且孔間的間隔間距為80μm的圖案)的負光罩，各自密著於塗膜，並使用紫外線曝光裝置(HI-TECH CO.,LTD製造，商品名：HTE-5102S)，以表1～6所示之規定的曝光量進行曝光。 之後，用1質量%之碳酸鈉水溶液，以0.18MPa(1.8kgf/cm2 )的壓力進行噴霧顯影60秒，將未曝光部分溶解顯影。繼而，使用紫外線曝光裝置(GS Yuasa International Ltd.製造，商品名：輸送帶型UV照射裝置)，以1000mJ/cm2 的曝光量進行曝光後，以150℃加熱1小時，而製作成試片。 以環氧樹脂(Mitsubishi Chemical Corporation製造，商品名：Epikote 828)、和使用三伸乙四胺作為硬化劑之熱硬化性樹脂，將經形成圖案之試片進行澆注成型，並充分硬化後，以研磨機(Refine Tec Ltd.製造，商品名：Refine Polisher)進行研磨，削出圖案剖面，以金相顯微鏡觀察阻劑層形狀，並依以下基準進行評估。阻劑層剖面形狀概略地表示於第1圖。 A (優良)：阻劑層形狀呈現矩形或梯形，並且圖案輪廓的直線性佳。 B (不良)：阻劑層形狀經確認有底切、拖尾或增厚，或圖案輪廓的直線性差。(4) Evaluation of the shape of the resist layer Using the screen printing method, the photosensitive resin composition of each example and comparative example was applied to a size of 50 cm×50 cm and a thickness of 50 cm×50 cm so that the film thickness after drying was 35 μm. A 0.6-mm copper-clad laminate substrate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67) was used to form a coating film, followed by drying at 80°C for 20 minutes using a hot air circulation dryer. Then, a negative mask having a pattern as shown in FIG. 2 (a pattern with an aperture size of 100 μm and an interval between holes of 100 μm, and a pattern with an aperture size of 80 μm and an interval between holes of 80 μm), each Adhering to the coating film, and using an ultraviolet exposure device (manufactured by HI-TECH CO., LTD, trade name: HTE-5102S), exposure was performed with the prescribed exposure amounts shown in Tables 1 to 6. After that, spray development was carried out using a 1% by mass sodium carbonate aqueous solution at a pressure of 0.18 MPa (1.8 kgf/cm 2 ) for 60 seconds, and the unexposed portion was dissolved and developed. Then, using an ultraviolet exposure device (manufactured by GS Yuasa International Ltd., trade name: conveyor belt type UV irradiation device), after exposure at an exposure amount of 1000 mJ/cm 2 , it was heated at 150° C. for 1 hour to prepare a test piece. Using epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: Epikote 828), and thermosetting resin using triethylenetetramine as a hardener, the patterned test piece is cast and fully cured, after A grinder (manufactured by Refine Tec Ltd., trade name: Refine Polisher) grinds, cuts a pattern cross section, observes the shape of the resist layer with a metallurgical microscope, and evaluates according to the following criteria. The cross-sectional shape of the resist layer is schematically shown in Fig. 1. A (Excellent): The shape of the resist layer is rectangular or trapezoidal, and the linearity of the pattern outline is good. B (Bad): The shape of the resist layer is confirmed to have undercut, trailing or thickening, or the linearity of the pattern outline is poor.

(5)導通孔徑(via diameter)精度評估 以網版印刷法，將各實施例及比較例的感光性樹脂組成物，以乾燥後的膜厚為35μm的方式，塗佈於大小為50cm×50cm且厚度為0.6mm之覆銅積層基板(Hitachi Chemical Co., Ltd.製造，MCL-E-67)，而形成塗膜後，使用熱風循環式乾燥機，以80℃乾燥20分鐘。 繼而，使具有如第2圖所示之圖案的負光罩，各自密著於塗膜上，使用紫外線曝光裝置(HI-TECH CO.,LTD製造，商品名：HTE-5102S)，以600mJ/cm2 的曝光量進行曝光。之後，用1質量%碳酸鈉水溶液，以0.18MPa(1.8kgf/cm2 )的壓力進行噴霧顯影60秒，將未曝光部分溶解顯影，而製作成試片。針對所得之試片的圖案，依以下基準進行評估。 A (優良)：100μm及80μm的圖案重現80%以上。 B (不良)：100μm及80μm的圖案僅重現小於80%。 此處，是使用顯微鏡放大至700倍，觀察100μm及80μm的圖案，若為100μm的圖案，其圖案底部能形成80μm以上(相對於圖案直徑為80%以上)的大小時，視為已能重現該圖案。若為80μm的圖案，其圖案底部能形成64μm以上的大小時，則視為已能重現該圖案。再者，判斷「A」、「B」時，相對於100μm及80μm的圖案的總數，能形成之圖案的總數為80%以上時，則評估為「A」。(5) Evaluation of accuracy of via diameter (via diameter) The photosensitive resin composition of each example and comparative example was applied to a size of 50 cm × 50 cm so that the film thickness after drying was 35 μm by screen printing. A copper-clad laminate substrate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-67) with a thickness of 0.6 mm was used to form a coating film, followed by drying at 80° C. for 20 minutes using a hot air circulation dryer. Then, each of the negative masks having the pattern shown in FIG. 2 was adhered to the coating film, using an ultraviolet exposure device (manufactured by HI-TECH CO., LTD, trade name: HTE-5102S) at 600 mJ/ The exposure amount of cm 2 is exposed. After that, spray development was carried out with a 1% by mass sodium carbonate aqueous solution at a pressure of 0.18 MPa (1.8 kgf/cm 2 ) for 60 seconds, and the unexposed portion was dissolved and developed to prepare a test piece. The pattern of the obtained test piece was evaluated according to the following criteria. A (Excellent): Patterns of 100 μm and 80 μm are reproduced by more than 80%. B (bad): The patterns of 100 μm and 80 μm only reproduce less than 80%. Here, it is magnified to 700 times using a microscope to observe the patterns of 100 μm and 80 μm. If the pattern is 100 μm, the size of the bottom of the pattern can be more than 80 μm (80% or more relative to the diameter of the pattern), it is considered to be heavy. Now the pattern. If the pattern is 80 μm, and the bottom of the pattern can form a size of 64 μm or more, it is considered that the pattern can be reproduced. Furthermore, when judging "A" and "B", when the total number of patterns that can be formed is 80% or more of the total number of patterns of 100 μm and 80 μm, it is evaluated as “A”.

(6)焊料耐熱性評估(i) 依與上述(4)阻劑層形狀的評估所用之試片相同的條件，製作試片，將水溶性助焊劑(Alpha Metals Co., Ltd.製造，商品名：K-183)塗佈於該試片上，並浸漬於設定為265℃之焊料槽10秒鐘後，從焊料槽取出。將浸漬和取出設為1循環，重複6循環之後，目視觀察塗膜外觀，依下述基準進行評估。 A (優良)：在塗膜30cm×30cm之範圍內，未確認到外觀變化。 B (良)：在塗膜30cm×30cm之範圍內，確認到1個～5個塗膜之浮起或膨脹處。 C (不良)：在塗膜30cm×30cm之範圍內，確認到6個以上的塗膜之浮起或膨脹處。(6) Solder heat resistance evaluation (i) A test piece was prepared under the same conditions as the test piece used for the evaluation of the shape of the resist layer (4) above, and a water-soluble flux (manufactured by Alpha Metals Co., Ltd., trade name: K-183) was applied to this After being immersed in the solder bath set at 265°C for 10 seconds on the test piece, it was taken out from the solder bath. The immersion and removal were set to 1 cycle, and after 6 cycles were repeated, the appearance of the coating film was visually observed and evaluated according to the following criteria. A (Excellent): In the range of 30 cm × 30 cm of the coating film, no change in appearance was confirmed. B (good): Within the range of 30 cm × 30 cm of the coating film, the floating or swelling of 1 to 5 coating films was confirmed. C (Poor): Within the range of 30 cm × 30 cm of the coating film, the floating or swelling of more than 6 coating films was confirmed.

(7)焊料耐熱性評估(ii) 依與上述(4)阻劑層形狀的評估所用之試片相同的條件，製作試片，將免清洗型助焊劑(SENJU METAL INDUSTRY CO., LTD.製造，商品名：RMA SR-209)塗佈於該試片上，並浸漬於設定為280℃之焊料槽10秒鐘後，從焊料槽取出。將浸漬和取出設為1循環，重複10循環後，目視觀察該取出之試片的塗膜外觀，依下述基準進行評估。 A：確認阻劑塗膜沒有外觀變化。 B：確認阻劑塗膜有略微剝落，但該剝落是實用上並無問題的程度。 C：確認有阻劑塗膜起泡及剝落。(7) Solder heat resistance evaluation (ii) Prepare the test piece under the same conditions as the test piece used in the evaluation of the shape of the resist layer (4) above, and apply no-clean flux (manufactured by SENJU METAL INDUSTRY CO., LTD., trade name: RMA SR-209) It was placed on the test piece, immersed in a solder bath set at 280°C for 10 seconds, and then taken out from the solder bath. The immersion and removal were set to 1 cycle, and after 10 cycles were repeated, the appearance of the coating film of the removed test piece was visually observed and evaluated according to the following criteria. A: It was confirmed that there was no change in appearance of the resist coating film. B: It was confirmed that the resist coating film was slightly peeled off, but the peeling off was to a degree that was practically no problem. C: Blistering and peeling of the resist coating film are confirmed.

(8)耐破裂性評估 依與上述(4)阻劑層形狀的評估所用之試片相同的條件，製作試片，將該試片以-65℃保持30分鐘後再以150℃保持30分鐘，將此步驟設為1循環，重複1000循環之後，目視觀察試片之塗膜外觀，依下述基準進行評估。 A (優良)：在塗膜30cm×30cm之範圍內，未確認到外觀變化。 B (良)：在塗膜30cm×30cm之範圍內，確認到1個～5個塗膜之浮起或膨脹。 C (不良)：在塗膜30cm×30cm之範圍內，確認到6個以上的塗膜之浮起或膨脹。(8) Crack resistance evaluation A test piece was prepared under the same conditions as the test piece used for the evaluation of the shape of the resist layer (4) above, and the test piece was kept at -65°C for 30 minutes, then held at 150°C for 30 minutes, and this step was set to 1 After repeating 1000 cycles, the appearance of the coating film of the test piece was visually observed and evaluated according to the following criteria. A (Excellent): In the range of 30 cm × 30 cm of the coating film, no change in appearance was confirmed. B (Good): Within the range of 30 cm × 30 cm of the coating film, the floating or swelling of 1 to 5 coating films was confirmed. C (Poor): Within the range of 30 cm × 30 cm of the coating film, floating or swelling of more than 6 coating films was confirmed.

(9)密著性評估 以網版印刷法，將各實施例及比較例的感光性樹脂組成物，以乾燥後的膜厚為35μm的方式，塗佈於銅表面經拋光輪研磨(於深度方向粗糙化5μm)之厚度為0.6mm之覆銅積層基板(Hitachi Chemical Co., Ltd.製造，商品名：MCL-E-67)，和經化學研磨(使用MEC COMPANY LTD.製造之研磨劑CZ8101，於深度方向粗糙化0.5μm)之厚度為0.6mm之覆銅積層基板(Hitachi Chemical Co., Ltd.製造，商品名：MCL-E-67)，而形成塗膜後，使用熱風循環式乾燥機，以80℃乾燥20分鐘。 繼而，使具有如第2圖所示之圖案的負光罩，各自密著於塗膜上，使用紫外線曝光裝置(HI-TECH CO.,LTD製造，商品名：HTE-5102S)，以600mJ/cm2 的曝光量進行曝光。之後，用1質量%碳酸鈉水溶液，以0.18MPa(1.8kgf/cm2 )的壓力進行噴霧顯影60秒，將未曝光部分溶解顯影。繼而，使用紫外線曝光裝置(GS Yuasa International Ltd.製造，商品名：輸送帶型UV照射裝置)，以1000mJ/cm2 的曝光量進行曝光後，以150℃加熱1小時，而製作成試片。 針對所得之試片，依照JIS K5600，製作100個邊長1mm的棋盤方格，並貼上透明膠帶(Nichiban Co., Ltd.製造，商品名：Cellotape (註冊商標))後，進行下述剝離試驗：將透明膠帶朝90°方向強制性剝離。觀察棋盤方格的剝離狀態，並依以下基準進行評估。 A (優良)：90/100以上未剝離。 B (良)：50/100以上且小於90/100未剝離。 C (不良)：0/100以上且小於50/100未剝離。(9) Adhesion evaluation Using the screen printing method, the photosensitive resin compositions of the examples and comparative examples were applied to the copper surface so that the film thickness after drying was 35 μm, and then polished by a polishing wheel (at depth Directional roughening 5 μm) 0.6 mm thick copper-clad laminate substrate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67), and chemically polished (using abrasive CZ8101 manufactured by MEC COMPANY LTD. , Roughened in the depth direction by 0.5 μm) a copper-clad laminate substrate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67) with a thickness of 0.6 mm, and after forming the coating film, it was dried using hot air circulation Machine to dry at 80°C for 20 minutes. Then, each of the negative masks having the pattern shown in FIG. 2 was adhered to the coating film, using an ultraviolet exposure device (manufactured by HI-TECH CO., LTD, trade name: HTE-5102S) at 600 mJ/ The exposure amount of cm 2 is exposed. Thereafter, spray development was carried out using a 1% by mass sodium carbonate aqueous solution at a pressure of 0.18 MPa (1.8 kgf/cm 2 ) for 60 seconds, and the unexposed portion was dissolved and developed. Then, using an ultraviolet exposure device (manufactured by GS Yuasa International Ltd., trade name: conveyor belt type UV irradiation device), after exposure at an exposure amount of 1000 mJ/cm 2 , it was heated at 150° C. for 1 hour to prepare a test piece. For the obtained test piece, 100 checkerboard squares with a length of 1 mm were produced in accordance with JIS K5600, and after applying transparent tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)), the following peeling was performed Test: Forcibly peel the transparent tape towards 90°. Observe the peeling status of the checkerboard grid and evaluate according to the following criteria. A (Excellent): 90/100 or more without peeling. B (good): 50/100 or more and less than 90/100 without peeling. C (defective): 0/100 or more and less than 50/100 without peeling.

(10)耐溶劑性評估 依與上述(4)阻劑層形狀的評估所用之試片相同條件，製作試片，將該試片在室溫浸漬於異丙醇中30分鐘，並目視確認外觀有無異常。繼而，在浸漬後之試片的塗膜上貼上透明膠帶(Nichiban Co., Ltd.製造，商品名：Cellotape (註冊商標))後，進行下述剝離試驗：將透明膠帶朝90°方向強制性剝離，並目視確認塗膜有無剝離，依以下基準進行評估。 A (優良)：塗膜外觀確認沒有異常，並且無剝離。 B (不良)：塗膜外觀確認有異常，或已剝離。(10) Evaluation of solvent resistance A test piece was prepared under the same conditions as the test piece used in the evaluation of the shape of the resist layer (4) above, and the test piece was immersed in isopropyl alcohol at room temperature for 30 minutes, and visually confirmed whether the appearance was abnormal. Then, after applying a transparent tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) to the coating film of the test piece after immersion, the following peeling test was performed: the transparent tape was forced toward 90° Sexual peeling, and visually confirm whether there is peeling of the coating film, and evaluate according to the following criteria. A (Excellent): There was no abnormality in the appearance of the coating film, and no peeling. B (Bad): The appearance of the coating film was confirmed to be abnormal or peeled.

(11)耐酸性 依與上述(4)阻劑層形狀的評估所用之試片相同條件，製作試片，將該試片在室溫浸漬於10質量%鹽酸水溶液中30分鐘，並目視確認外觀有無異常。繼而，在浸漬後之試片的塗膜上貼上透明膠帶(Nichiban Co., Ltd.製造，商品名：Cellotape (註冊商標))後，進行下述剝離試驗：將透明膠帶朝90°方向強制性剝離，並目視確認塗膜有無剝離，依以下基準進行評估。 A (優良)：塗膜外觀確認沒有異常，並且無剝離。 B (不良)：塗膜外觀確認有異常，或已剝離。(11) Acid resistance A test piece was prepared under the same conditions as the test piece used for the evaluation of the shape of the resist layer (4) above, and the test piece was immersed in a 10% by mass hydrochloric acid aqueous solution at room temperature for 30 minutes, and visually confirmed whether the appearance was abnormal. Then, after applying a transparent tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) to the coating film of the test piece after immersion, the following peeling test was performed: the transparent tape was forced toward 90° Sexual peeling, and visually confirm whether there is peeling of the coating film, and evaluate according to the following criteria. A (Excellent): There was no abnormality in the appearance of the coating film, and no peeling. B (Bad): The appearance of the coating film was confirmed to be abnormal or peeled.

(12)耐鹼性 依與上述(4)阻劑層形狀的評估所用之試片相同條件，製作試片，將該試片在室溫浸漬於5質量%氫氧化鈉水溶液中30分鐘，並目視確認外觀有無異常。繼而，在浸漬後之試片的塗膜上貼上透明膠帶(Nichiban Co., Ltd.製造，商品名：Cellotape (註冊商標))後，進行下述剝離試驗：將透明膠帶朝90°方向強制性剝離，並目視確認塗膜有無剝離，依以下基準進行評估。 A (優良)：塗膜外觀確認沒有異常，並且無剝離。 B (不良)：塗膜外觀確認有異常，或已剝離。(12) Alkali resistance A test piece was prepared under the same conditions as the test piece used in the evaluation of the shape of the resist layer (4) above, and the test piece was immersed in a 5 mass% sodium hydroxide aqueous solution at room temperature for 30 minutes, and visually confirmed whether the appearance was abnormal. Then, after applying a transparent tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) to the coating film of the test piece after immersion, the following peeling test was performed: the transparent tape was forced toward 90° Sexual peeling, and visually confirm whether there is peeling of the coating film, and evaluate according to the following criteria. A (Excellent): There was no abnormality in the appearance of the coating film, and no peeling. B (Bad): The appearance of the coating film was confirmed to be abnormal or peeled.

(13)耐助焊劑腐蝕性評估 除了將上述(4)阻劑層形狀的評估中的如第2圖所示之圖案，設為如第3圖所示之1mm見方的格子狀圖案以外，其餘與上述(4)阻劑層形狀的評估同樣地進行，而獲得試片。繼而，將高活性的水溶性助焊劑(Alpha Metals Co., Ltd.製造，商品名：K-183)塗佈於所獲得之試片之全面，直立放置3分鐘而去除多餘的助焊劑。然後，將試片以130℃預熱1分鐘，再浸漬於280℃之焊料槽20秒鐘後，從焊料槽取出。於室溫放置冷卻1分鐘之後進行水洗，拭去水滴之後，目視觀察外觀。又，在試片的最小電路寬的地方貼上24mm寬的透明膠帶(Nichiban Co., Ltd.製造，商品名：Cellotape (註冊商標))後，進行下述剝離試驗：將透明膠帶朝90°方向強制性剝離，目視觀察剝離後的試片外觀，並依以下基準進行評估。 5：剝離試驗後，完全沒有確認到存在有阻劑層的部分之剝離情形。 4：剝離試驗後，確認到存在有阻劑層的部分有20%以下的剝離情形。 3：剝離試驗前存在有阻劑層的部分確認到輕微的白化情形，剝離試驗後確認到存在有阻劑層的部分有20%以下的剝離情形，但實用上並無問題。 2：剝離試驗前存在有阻劑層的部分確認到白化情形，剝離試驗後確認到存在有阻劑層的部分有20%以上的剝離情形。 1：剝離試驗前存在有阻劑層的部分確認到顯著的白化情形，剝離試驗後確認到顯著的剝離情形。(13) Corrosion resistance evaluation of flux In addition to the pattern shown in Fig. 2 in the evaluation of the shape of the (4) resist layer described above, the grid pattern of 1 mm square shown in Fig. 3 is used, and the rest is the same as the shape of the resist layer (4) The evaluation is performed in the same way, and a test piece is obtained. Then, a highly active water-soluble flux (manufactured by Alpha Metals Co., Ltd., trade name: K-183) was coated on the entire surface of the obtained test piece, and stood upright for 3 minutes to remove excess flux. Then, the test piece was preheated at 130°C for 1 minute, and then immersed in a solder bath of 280°C for 20 seconds, and then taken out from the solder bath. After leaving to cool at room temperature for 1 minute, it was washed with water, and after removing water drops, the appearance was visually observed. In addition, after attaching a 24 mm wide transparent tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) to the minimum circuit width of the test piece, the following peel test was conducted: the transparent tape was oriented at 90° Forced peeling in the direction, visually observe the appearance of the test piece after peeling, and evaluate according to the following criteria. 5: After the peeling test, the peeling of the portion where the resist layer is present is not confirmed at all. 4: After the peeling test, it is confirmed that there is peeling of less than 20% in the portion where the resist layer is present. 3: The part where the resist layer was present before the peeling test was confirmed to be slightly whitened, and the part where the resist layer was present after the peeling test was found to have a peeling condition of 20% or less, but there was no problem in practical use. 2: The portion where the resist layer was present before the peeling test was confirmed to be whitened, and the portion where the resist layer was confirmed to be peeled off after the peeling test was more than 20% peeled. 1: Before the peeling test, there is a part of the resist layer where significant whitening is confirmed, and after the peeling test, a significant peeling is confirmed.

(14)無電鍍覆耐性 依與上述(4)阻劑層形狀的評估所用之試片相同條件，製作試片，對於該試片使用市售品之無電鍍覆鎳浴(electroless nickel plating bath)及無電鍍覆金浴，以鎳5μm、金0.05μm之厚度的條件進行鍍覆。鍍覆後，目視確認鍍覆液有無滲入。繼而，在浸漬後之試片的塗膜上貼上透明膠帶(Nichiban Co., Ltd.製造，商品名：Cellotape (註冊商標))後，進行下述剝離試驗：將透明膠帶朝90°方向強制性剝離，並目視確認塗膜有無剝離，依以下基準進行評估。 A：未見到滲入及剝落。 B：鍍覆後可見到滲入，但是未見到剝落。 C：鍍覆後可見到剝落。(14) Electroless plating resistance A test piece was prepared under the same conditions as the test piece used in the evaluation of the shape of the resist layer (4) above, and a commercially available electroless nickel plating bath and electroless gold plating bath were used for the test piece. The plating was performed under the conditions of nickel 5 μm and gold 0.05 μm. After plating, visually confirm whether the plating solution has penetrated. Then, after applying a transparent tape (manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark)) to the coating film of the test piece after immersion, the following peeling test was performed: the transparent tape was forced toward 90° Sexual peeling, and visually confirm whether there is peeling of the coating film, and evaluate according to the following criteria. A: No infiltration and peeling are seen. B: Penetration was seen after plating, but no flaking was seen. C: Peeling can be seen after plating.

(合成例1；含有酸改質乙烯基之環氧樹脂(I)之合成) 將甲酚酚醛清漆型環氧樹脂(NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.製造，商品名：YDCN704，通式(I)中，Y1 ＝縮水甘油基，R11 ＝甲基)220質量份、丙烯酸72質量份、氫醌1.0質量份、卡必醇乙酸酯180質量份混合，加熱至90℃，並攪拌而溶解反應混合物。繼而，冷卻至60℃後，添加苄基三甲基氯化銨1質量份，加熱至100℃，並使其反應至固形成分酸價為1mgKOH/g為止。繼而，添加四氫酞酸酐152質量份和卡必醇乙酸酯100質量份，並加熱至80℃，攪拌6小時。冷卻至室溫為止後，以卡必醇乙酸酯稀釋至固形成分濃度成為60質量%，而獲得包含了含有酸改質乙烯基之環氧樹脂(I)的溶液。 再者，實施例中的固形成分酸價，是藉由中和滴定法來測定。具體而言，添加丙酮30g至包含了含有酸改質乙烯基之環氧樹脂的溶液1g中，進而使其均勻溶解後，將指示劑之酚酞，適量添加至上述包含了含有酸改質乙烯基之環氧樹脂之溶液中，並使用0.1N氫氧化鉀水溶液進行滴定，藉此進行測定。(Synthesis Example 1: Synthesis of epoxy resin (I) containing acid-modified vinyl group) Cresol novolac epoxy resin (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD., trade name: YDCN704, general formula In (I), Y 1 = glycidyl, R 11 = methyl) 220 parts by mass, acrylic acid 72 parts by mass, hydroquinone 1.0 parts by mass, carbitol acetate 180 parts by mass, and heated to 90°C, and Stir to dissolve the reaction mixture. Then, after cooling to 60°C, 1 part by mass of benzyltrimethylammonium chloride was added, heated to 100°C, and allowed to react until the solid component acid value was 1 mgKOH/g. Then, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of carbitol acetate were added, heated to 80°C, and stirred for 6 hours. After cooling to room temperature, the solution was diluted with carbitol acetate to a solid content concentration of 60% by mass to obtain an epoxy resin (I) containing acid-modified vinyl. In addition, the acid value of the solid content in the examples was measured by a neutralization titration method. Specifically, after adding 30 g of acetone to 1 g of a solution containing an epoxy resin containing an acid-modified vinyl group and dissolving it uniformly, an appropriate amount of phenolphthalein as an indicator is added to the above-mentioned solution containing an acid-modified vinyl group. The solution of epoxy resin was titrated with a 0.1N potassium hydroxide aqueous solution to measure.

(合成例2；含有酸改質乙烯基之環氧樹脂(II)-a之合成) 將雙酚F型環氧樹脂(NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.製造，商品名：YDF2001，通式(II)中，Y2 ＝縮水甘油基，R12 ＝H)475質量份、丙烯酸72質量份、氫醌0.5質量份、卡必醇乙酸酯120質量份混合，加熱至90℃，並攪拌而溶解反應混合物。繼而，冷卻至60℃後，混合苄基三甲基氯化銨2質量份，加熱至100℃，並使其反應至固形成分酸價為1mgKOH/g為止。繼而，添加四氫酞酸酐230質量份和卡必醇乙酸酯85質量份，並加熱至80℃，攪拌6小時。冷卻至室溫為止後，以卡必醇乙酸酯稀釋至固形成分濃度成為60質量%，而獲得包含了含有酸改質乙烯基之環氧樹脂(II)-a的溶液。(Synthesis Example 2; synthesis of epoxy resin (II)-a containing acid-modified vinyl group) Bisphenol F type epoxy resin (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD., trade name: YDF2001, Tong In formula (II), Y 2 = glycidyl group, R 12 = H) 475 parts by mass, 72 parts by mass of acrylic acid, 0.5 parts by mass of hydroquinone, and 120 parts by mass of carbitol acetate are mixed, heated to 90°C, and Stir to dissolve the reaction mixture. Then, after cooling to 60°C, 2 parts by mass of benzyltrimethylammonium chloride was mixed, heated to 100°C, and allowed to react until the solid component acid value was 1 mgKOH/g. Then, 230 mass parts of tetrahydrophthalic anhydride and 85 mass parts of carbitol acetate were added, and it heated at 80 degreeC, and stirred for 6 hours. After cooling to room temperature, the solution was diluted with carbitol acetate to a solid content concentration of 60% by mass to obtain an epoxy resin (II)-a containing an acid-modified vinyl group.

(合成例3；含有酸改質乙烯基之環氧樹脂(IV)-a之合成) 將以80℃溶解之雙(4-羥苯基)甲烷272質量份，裝入設置有溫度計、滴液漏斗、冷卻管及攪拌機之燒瓶中，並在80℃時開始攪拌。添加甲磺酸3質量份，以維持液體溫度在80～90℃的範圍內的方式，歷時1小時滴加聚甲醛水溶液(濃度：92質量%)16.3質量份。結束滴加後，加熱至110℃為止，並攪拌2小時。繼而，進而添加甲基異丁酮1000質量份，並轉移至分液漏斗進行水洗。持續進行水洗至清洗水顯示中性為止後，在加熱減壓下(溫度：220℃，壓力：66.7Pa)，將溶媒及未反應之雙(4-羥苯基)甲烷從有機層中去除，而獲得褐色固體之雙酚系酚醛清漆樹脂164質量份。所得之雙酚系酚醛清漆樹脂的軟化點為74℃，羥基當量為154g/eq。(Synthesis Example 3; Synthesis of epoxy resin (IV)-a containing acid-modified vinyl group) 272 parts by mass of bis(4-hydroxyphenyl)methane dissolved at 80°C was placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, and stirring was started at 80°C. 3 parts by mass of methanesulfonic acid was added, and 16.3 parts by mass of a polyoxymethylene aqueous solution (concentration: 92% by mass) was added dropwise over 1 hour to maintain the liquid temperature in the range of 80 to 90°C. After the dropwise addition was completed, it was heated to 110°C and stirred for 2 hours. Then, 1000 parts by mass of methyl isobutyl ketone was added, and transferred to a separatory funnel and washed with water. After the water washing is continued until the washing water shows neutrality, the solvent and unreacted bis(4-hydroxyphenyl)methane are removed from the organic layer under heating and reduced pressure (temperature: 220°C, pressure: 66.7 Pa), As a result, 164 parts by mass of bisphenol novolak resin was obtained as a brown solid. The softening point of the obtained bisphenol novolak resin was 74°C, and the hydroxyl equivalent weight was 154 g/eq.

繼而，於設置有溫度計、滴液漏斗、冷卻管及攪拌機之燒瓶中，一面進行氮氣沖洗(nitrogen purge)，一面將上述所得之雙酚系酚醛清漆樹脂154質量份、環氧氯丙烷463質量份、正丁醇139質量份、及四乙苄基氯化銨2質量份混合並溶解。繼而，加熱至65℃為止，並減壓至共沸之壓力為止後，歷時5小時並固定滴入速度而滴加氫氧化鈉水溶液(濃度：49質量%)90質量份，攪拌30分鐘。在此期間，將藉由共沸所餾出之餾出成分，以迪安-斯塔克分離器(Dean-Stark trap)進行分離，去除水層，並一面使油層回到燒瓶(反應系)中，一面使其反應。之後，藉由減壓蒸餾(溫度：22℃，壓力：1.87kPa)將未反應之環氧氯丙烷餾除而獲得粗環氧樹脂，並添加甲基異丁酮590質量份、正丁醇177質量份至該粗環氧樹脂中，而使其溶解。繼而，於此溶液中添加氫氧化鈉水溶液(濃度：10質量%)10質量份，在80℃時使其反應2小時後，以水150質量份反覆進行水洗三次直到清洗液的pH為中性為止。確認第三次水洗所用之清洗液的pH為中性。繼而，藉由共沸將燒瓶內(反應系內)脫水，並進行微過濾(microfiltration)後，在減壓(壓力：1.87kPa)下餾除溶媒，而獲得褐色黏稠液體，亦即本發明所用之雙酚系酚醛清漆型環氧樹脂(環氧樹脂(a)，其具有通式(IV)中Y4 =縮水甘油基且R13 =H之結構單元)。此環氧樹脂的羥基當量為233g/eq。Then, in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, while performing nitrogen purge, 154 parts by mass of the bisphenol novolak resin obtained above and 463 parts by mass of epichlorohydrin , 139 parts by mass of n-butanol, and 2 parts by mass of tetraethylbenzyl ammonium chloride are mixed and dissolved. Then, after heating to 65°C and reducing the pressure to azeotropic pressure, 90 parts by mass of a sodium hydroxide aqueous solution (concentration: 49% by mass) was added dropwise over 5 hours at a fixed dropping rate, and stirred for 30 minutes. During this period, the distillate components distilled by azeotrope were separated by a Dean-Stark trap, the water layer was removed, and the oil layer was returned to the flask (reaction system) In the middle, make it react. After that, unreacted epichlorohydrin was distilled off by vacuum distillation (temperature: 22° C., pressure: 1.87 kPa) to obtain crude epoxy resin, and 590 parts by mass of methyl isobutyl ketone and n-butanol 177 were added Mass parts are added to the crude epoxy resin to dissolve it. Next, 10 parts by mass of an aqueous solution of sodium hydroxide (concentration: 10% by mass) was added to this solution, and after reacting at 80°C for 2 hours, water was repeatedly washed three times with 150 parts by mass of water until the pH of the cleaning solution was neutral until. Confirm that the pH of the cleaning solution used for the third water wash is neutral. Then, after dehydrating the flask (inside the reaction system) by azeotrope and performing microfiltration, the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a brown viscous liquid, which is used in the present invention The bisphenol novolac-type epoxy resin (epoxy resin (a), which has the structural unit of Y 4 = glycidyl group and R 13 = H in the general formula (IV)). The hydroxyl equivalent of this epoxy resin is 233g/eq.

於上述所得之環氧樹脂(a)450質量份中，混合丙烯酸124質量份、氫醌1.5質量份、卡必醇乙酸酯250質量份，並加熱至90℃，攪拌而溶解反應混合物。繼而，冷卻至60℃後，添加苄基三甲基氯化銨2質量份，並加熱至100℃，使其反應至酸價為1mgKOH/g為止。繼而，將四氫酞酸酐230質量份和卡必醇乙酸酯180質量份與上述反應物混合，並加熱至80℃，使其反應6小時。繼而，冷卻至室溫為止，以卡必醇乙酸酯稀釋至固形成分濃度成為60質量%，而獲得包含了含有酸改質乙烯基之環氧樹脂(IV)-a的溶液。 再者，樹脂的軟化點，是依據JIS-K7234:1986所制定之環球法(ring and ball method)進行測定(升溫速度：5℃/分鐘)。To 450 parts by mass of the epoxy resin (a) obtained above, 124 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone, and 250 parts by mass of carbitol acetate were mixed, heated to 90°C, and stirred to dissolve the reaction mixture. Then, after cooling to 60°C, 2 parts by mass of benzyltrimethylammonium chloride was added and heated to 100°C to react until the acid value was 1 mgKOH/g. Then, 230 parts by mass of tetrahydrophthalic anhydride and 180 parts by mass of carbitol acetate were mixed with the above reactant, and heated to 80° C. to react for 6 hours. Then, after cooling to room temperature, it was diluted with carbitol acetate to a solid content concentration of 60% by mass, and a solution containing an epoxy resin (IV)-a containing an acid-modified vinyl group was obtained. In addition, the softening point of the resin is measured in accordance with the ring and ball method established in JIS-K7234:1986 (heating rate: 5°C/min).

(合成例4；含有酸改質乙烯基之環氧樹脂(IV)-b之合成) 將以80℃溶解之2,2-雙(4-羥苯基)丙烷272質量份，裝入設置有溫度計、滴液漏斗、冷卻管及攪拌機之燒瓶中，並在80℃時開始攪拌。添加甲磺酸3質量份，以維持液體溫度在80～90℃的範圍內的方式，歷時1小時滴加聚甲醛水溶液(92質量%)16.3質量份。結束滴加後，加熱至110℃為止，並攪拌2小時。繼而，進而添加甲基異丁酮1000質量份，並轉移至分液漏斗進行水洗。持續進行水洗至清洗水顯示中性為止後，在加熱減壓下(溫度：240℃，壓力：26.7Pa)，將溶媒及未反應之2,2-(4-羥苯基)丙烷從有機層中去除，而獲得褐色固體之雙酚系酚醛清漆樹脂164質量份。所得之雙酚系酚醛清漆樹脂的軟化點為87℃，羥基當量為174g/eq。(Synthesis Example 4; synthesis of epoxy resin (IV)-b containing acid-modified vinyl group) 272 parts by mass of 2,2-bis(4-hydroxyphenyl)propane dissolved at 80°C was put into a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, and stirring was started at 80°C. 3 parts by mass of methanesulfonic acid was added, and 16.3 parts by mass of a polyoxymethylene aqueous solution (92% by mass) was added dropwise over 1 hour so as to maintain the liquid temperature in the range of 80 to 90°C. After the dropwise addition was completed, it was heated to 110°C and stirred for 2 hours. Then, 1000 parts by mass of methyl isobutyl ketone was added, and transferred to a separatory funnel and washed with water. After the water washing was continued until the washing water showed neutrality, under heating and reduced pressure (temperature: 240°C, pressure: 26.7 Pa), the solvent and unreacted 2,2-(4-hydroxyphenyl)propane were removed from the organic layer 164 parts by mass of bisphenol-based novolak resin as a brown solid was obtained. The softening point of the obtained bisphenol novolak resin was 87° C., and the hydroxyl equivalent was 174 g/eq.

繼而，於設置有溫度計、滴液漏斗、冷卻管及攪拌機之燒瓶中，一面進行氮氣沖洗，一面將上述所得之雙酚系酚醛清漆樹脂154質量份、環氧氯丙烷463質量份、正丁醇139質量份、及四乙苄基氯化銨2質量份混合並溶解。繼而，加熱至65℃為止，並減壓至共沸之壓力為止後，歷時5小時並固定滴入速度而滴加氫氧化鈉水溶液(濃度：49質量%)90質量份，攪拌30分鐘。在此期間，將藉由共沸所餾出之餾出成分，以迪安-斯塔克分離器(Dean-Stark trap)進行分離，去除水層，並一面使油層回到燒瓶(反應系)中，一面使其反應。之後，藉由減壓蒸餾(溫度：22℃，壓力：1.87kPa)將未反應之環氧氯丙烷餾除而獲得粗環氧樹脂，並添加甲基異丁酮590質量份、正丁醇177質量份至該粗環氧樹脂中，而使其溶解。繼而，於此溶液中添加氫氧化鈉水溶液(濃度：10質量%)10質量份，在80℃時使其反應2小時後，以水150質量份反覆進行水洗三次直到清洗液的pH為中性為止。確認第三次水洗所用之清洗液的pH為中性。繼而，藉由共沸將燒瓶內(反應系內)脫水，並進行微過濾後，在減壓(壓力：1.87kPa)下餾除溶媒，而獲得褐色黏稠液體，亦即本發明所用之雙酚系酚醛清漆型環氧樹脂(環氧樹脂(a)，其具有通式(IV)中Y4 =縮水甘油基且R13 =甲基之結構單元)。此環氧樹脂的羥基當量為233g/eq。Then, in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, while purging with nitrogen, 154 parts by mass of the bisphenol novolak resin obtained above, 463 parts by mass of epichlorohydrin, and n-butanol 139 parts by mass and 2 parts by mass of tetraethylbenzyl ammonium chloride were mixed and dissolved. Then, after heating to 65°C and reducing the pressure to azeotropic pressure, 90 parts by mass of a sodium hydroxide aqueous solution (concentration: 49% by mass) was added dropwise over 5 hours at a fixed dropping rate, and stirred for 30 minutes. During this period, the distillate components distilled by azeotrope were separated by a Dean-Stark trap, the water layer was removed, and the oil layer was returned to the flask (reaction system) In the middle, make it react. After that, unreacted epichlorohydrin was distilled off by vacuum distillation (temperature: 22° C., pressure: 1.87 kPa) to obtain crude epoxy resin, and 590 parts by mass of methyl isobutyl ketone and n-butanol 177 were added Mass parts are added to the crude epoxy resin to dissolve it. Next, 10 parts by mass of an aqueous solution of sodium hydroxide (concentration: 10% by mass) was added to this solution, and after reacting at 80°C for 2 hours, water was repeatedly washed three times with 150 parts by mass of water until the pH of the cleaning solution was neutral until. Confirm that the pH of the cleaning solution used for the third water wash is neutral. Then, after dehydrating the flask (inside the reaction system) by azeotrope and performing microfiltration, the solvent was distilled off under reduced pressure (pressure: 1.87 kPa) to obtain a brown viscous liquid, that is, bisphenol used in the present invention Novolac-type epoxy resin (epoxy resin (a), which has a structural unit of Y 4 = glycidyl group and R 13 = methyl group in general formula (IV)). The hydroxyl equivalent of this epoxy resin is 233g/eq.

於上述所得之環氧樹脂(a)450質量份中，混合丙烯酸124質量份、氫醌1.5質量份、卡必醇乙酸酯250質量份，並加熱至90℃，攪拌而溶解反應混合物。繼而，冷卻至60℃後，混合苄基三甲基氯化銨2質量份，並加熱至100℃，使其反應至酸價為1mgKOH/g為止。繼而，將四氫酞酸酐230質量份和卡必醇乙酸酯180質量份與上述反應物混合，並加熱至80℃，使其反應6小時。繼而，冷卻至室溫為止，以卡必醇乙酸酯稀釋至固形成分濃度成為60質量%，而獲得包含了含有酸改質乙烯基之環氧樹脂(IV)-b的溶液。To 450 parts by mass of the epoxy resin (a) obtained above, 124 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone, and 250 parts by mass of carbitol acetate were mixed, heated to 90°C, and stirred to dissolve the reaction mixture. Then, after cooling to 60°C, 2 parts by mass of benzyltrimethylammonium chloride was mixed and heated to 100°C to react until the acid value was 1 mgKOH/g. Then, 230 parts by mass of tetrahydrophthalic anhydride and 180 parts by mass of carbitol acetate were mixed with the above reactant, and heated to 80° C. to react for 6 hours. Then, after cooling to room temperature, it was diluted with carbitol acetate to a solid content concentration of 60% by mass, and a solution containing an epoxy resin (IV)-b containing an acid-modified vinyl group was obtained.

(合成例5；含有酸改質乙烯基之環氧樹脂(IV)-c之合成) 於設置有溫度計、滴液漏斗、冷卻管及攪拌機之燒瓶中，將雙酚F酚醛清漆型環氧樹脂(DIC Corporation製造，商品名：EXA-7376，通式(IV)中，Y4 及Y5 ＝縮水甘油基、R13 ＝氫原子)350質量份、丙烯酸70質量份、甲基氫醌0.5質量份、卡必醇乙酸酯120質量份混合，加熱至90℃並攪拌以使其反應，將混合物完全溶解。繼而，將所獲得之溶液冷卻至60℃後，添加三苯基膦2質量份，加熱至100℃，並使其反應至溶液酸價為1mgKOH/g為止。於反應後之溶液中，添加四氫酞酸酐(THPAC)98質量份和卡必醇乙酸酯85質量份，並加熱至80℃，使其反應6小時。之後，冷卻至室溫，獲得固形成分濃度為73質量%的包含了含有酸改質乙烯基之環氧樹脂(IV)-c的溶液。(Synthesis Example 5; synthesis of epoxy resin (IV)-c containing acid-modified vinyl group) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, bisphenol F novolac-type epoxy resin (Manufactured by DIC Corporation, trade name: EXA-7376, in general formula (IV), Y 4 and Y 5 = glycidyl group, R 13 = hydrogen atom) 350 parts by mass, acrylic acid 70 parts by mass, methylhydroquinone 0.5 parts by mass Parts and 120 parts by mass of carbitol acetate are mixed, heated to 90°C and stirred to react, and the mixture is completely dissolved. Then, after cooling the obtained solution to 60°C, 2 parts by mass of triphenylphosphine was added, heated to 100°C, and allowed to react until the acid value of the solution was 1 mgKOH/g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate were added, heated to 80°C, and allowed to react for 6 hours. After that, it was cooled to room temperature to obtain a solution containing an epoxy resin (IV)-c containing an acid-modified vinyl group with a solid content concentration of 73% by mass.

(合成例6；含有酸改質乙烯基之環氧樹脂(II)-b之合成) 於設置有溫度計、滴液漏斗、冷卻管及攪拌機之燒瓶中，將雙酚F型環氧樹脂(Mitsubishi Chemical Corporation製造，商品名：Epikote 4004，環氧當量：526g/eq，通式(II)中，Y2 ＝氫原子、R12 ＝氫原子)1052質量份、丙烯酸(b)144質量份、甲基氫醌1質量份、卡必醇乙酸酯850質量份、及溶劑石腦油100質量份混合，於70℃加熱攪拌，使混合物溶解。繼而，將溶液冷卻至50℃後，與三苯基膦2質量份、溶劑石腦油75質量份混合，加熱至100℃，並使其反應至固形成分酸價為1mgKOH/g為止。繼而，將所得之溶液冷卻至50℃後，添加四氫酞酸酐(THPAC)745質量份、卡必醇乙酸酯75質量份、及溶劑石腦油75質量份，並加熱至80℃，使其反應6小時。之後，冷卻至室溫，獲得固形成分酸價為80mgKOH/g、固形成分為62質量%的包含了含有酸改質乙烯基之環氧樹脂(II)-b的溶液。(Synthesis Example 6; synthesis of epoxy resin (II)-b containing acid-modified vinyl group) In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, bisphenol F-type epoxy resin (Mitsubishi Chemical Corporation, trade name: Epikote 4004, epoxy equivalent: 526g/eq, in the general formula (II), Y 2 = hydrogen atom, R 12 = hydrogen atom) 1052 parts by mass, acrylic acid (b) 144 parts by mass, A 1 part by mass of hydroquinone, 850 parts by mass of carbitol acetate, and 100 parts by mass of solvent naphtha were mixed and heated and stirred at 70°C to dissolve the mixture. Then, after cooling the solution to 50°C, it was mixed with 2 parts by mass of triphenylphosphine and 75 parts by mass of solvent naphtha, heated to 100°C, and allowed to react until the solid component acid value was 1 mgKOH/g. Then, after cooling the resulting solution to 50°C, 745 parts by mass of tetrahydrophthalic anhydride (THPAC), 75 parts by mass of carbitol acetate, and 75 parts by mass of solvent naphtha were added, and heated to 80°C to make It reacted for 6 hours. Thereafter, it was cooled to room temperature to obtain a solution containing an acid-modified vinyl group-containing epoxy resin (II)-b having a solid content acid value of 80 mgKOH/g and a solid content of 62% by mass.

[實施例1～32及比較例1～32] 依表1～6所示之調配組成而調配組成物，以三輥磨機進行揉合，而調製感光性樹脂組成物。添加卡必醇乙酸酯，以使固形成分濃度為70質量%的方式，而獲得感光性樹脂組成物。使用所得之感光性樹脂組成物，依照上述評估方法進行評估。評估結果表示於表1～6。再者，表1中各成分的調配量的單位為質量份，表中(A)成分的調配量，是代表各合成例所得之包含了環氧樹脂的溶液的量。[Examples 1 to 32 and Comparative Examples 1 to 32] The composition was prepared according to the composition shown in Tables 1 to 6, and kneaded with a three-roll mill to prepare a photosensitive resin composition. The carbitol acetate was added so that the solid content concentration was 70% by mass to obtain a photosensitive resin composition. Using the obtained photosensitive resin composition, evaluation was performed according to the above evaluation method. The evaluation results are shown in Tables 1 to 6. In addition, the unit of the formulation amount of each component in Table 1 is a mass part, and the formulation amount of (A) component in the table represents the amount of the solution containing the epoxy resin obtained by each synthesis example.

[實施例33、34及比較例33、34] 依表6所示之調配組成而調配組成物，以與實施例1同樣的方法來調製感光性樹脂組成物。以甲基乙基酮將所得之各感光性樹脂組成物稀釋，塗佈於PET薄膜上，之後以90℃乾燥10分鐘，形成厚度為25μm之由感光性樹脂組成物所構成之感光層。進而在感光層上貼合聚乙烯薄膜(保護層)而製作成感光性元件。 從上述所得之感光性元件上剝除保護層，將該感光性元件熱壓合於覆銅的銅箔基板上。繼而，使具有如第2圖所示之圖案(孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或孔徑大小為80μm且孔間的間隔間距為80μm的圖案)的負光罩密著於塗膜，並使用紫外線曝光裝置(HI-TECH CO.,LTD製造，商品名：HTE-5102S)，以表6所示之規定的曝光量進行曝光。之後，用1質量%之碳酸鈉水溶液，以0.18MPa(1.8kgf/cm2 )的壓力進行噴霧顯影60秒，將未曝光部分溶解顯影。繼而，使用紫外線曝光裝置(GS Yuasa International Ltd.製造，商品名：輸送帶型UV照射裝置)，以1000mJ/cm2 的曝光量進行曝光後，以150℃加熱1小時，而製作成試片。使用所獲得之試片，進行與實施例31同樣的評估。評估結果顯示於表6。[Examples 33 and 34 and Comparative Examples 33 and 34] The composition was prepared according to the composition shown in Table 6, and the photosensitive resin composition was prepared in the same manner as in Example 1. Each of the obtained photosensitive resin compositions was diluted with methyl ethyl ketone, coated on a PET film, and then dried at 90°C for 10 minutes to form a photosensitive layer composed of the photosensitive resin composition with a thickness of 25 μm. Furthermore, a polyethylene film (protective layer) was laminated on the photosensitive layer to produce a photosensitive element. The protective layer was peeled off from the photosensitive element obtained above, and the photosensitive element was thermocompression-bonded on a copper-clad copper foil substrate. Then, a negative mask having a pattern as shown in FIG. 2 (a pattern with an aperture size of 100 μm and an interval between holes of 100 μm, or a pattern with an aperture size of 80 μm and an interval between holes of 80 μm) is adhered The coating film was exposed at a prescribed exposure amount shown in Table 6 using an ultraviolet exposure device (manufactured by HI-TECH CO., LTD, trade name: HTE-5102S). After that, spray development was carried out using a 1% by mass sodium carbonate aqueous solution at a pressure of 0.18 MPa (1.8 kgf/cm 2 ) for 60 seconds, and the unexposed portion was dissolved and developed. Then, using an ultraviolet exposure device (manufactured by GS Yuasa International Ltd., trade name: conveyor belt type UV irradiation device), after exposure at an exposure amount of 1000 mJ/cm 2 , it was heated at 150° C. for 1 hour to prepare a test piece. Using the obtained test piece, the same evaluation as in Example 31 was performed. The evaluation results are shown in Table 6.

[表1]

Figure 108117792-A0304-0001
＊1：代表含有環氧樹脂(I)之溶液 (固形成分濃度：60質量%)。 ＊2：代表含有環氧樹脂(II)-a之溶液 (固形成分濃度：60質量%)。 ＊3：根據顯影時曝光量600mJ/cm2 進行之評估。[Table 1]
Figure 108117792-A0304-0001
 *1: Represents a solution containing epoxy resin (I) (solid content concentration: 60% by mass). *2: Represents a solution containing epoxy resin (II)-a (solid content concentration: 60% by mass). *3: Evaluation based on an exposure of 600 mJ/cm 2 during development.

註)表1中各材料的詳細內容如下所述。 IRGACURE 819：雙(2,4,6-三甲基苄醯基)苯基氧化膦(BASF Japan Ltd.製造，商品名) DAROCUR TPO：2,4,6-三甲基苄醯基二苯基氧化膦(BASF Japan Ltd.製造，商品名) IRGACURE 907：2-甲基-[4-(甲硫基)苯基]嗎啉基-1-丙酮(BASF Japan Ltd.製造，商品名) IRGACURE OXE01：1,2-辛二酮,1-[4-(苯硫基)-,2-(o-苯甲醯肟)] (BASF Japan Ltd.製造，商品名) KAYARAD DPHA：二季戊四醇五丙烯酸酯(Nippon Kayaku Co.,Ltd.製造，商品名) BaSO4 ：SAKAI CHEMICAL INDUSTRY CO., LTD.製造 SiO2 ：TATSUMORI LTD.製造 Epikote 828：雙酚A型環氧樹脂(Mitsubishi Chemical Corporation製造，商品名)Note) The details of each material in Table 1 are as follows. IRGACURE 819: bis(2,4,6-trimethylbenzyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., trade name) DAROCUR TPO: 2,4,6-trimethylbenzyl diphenyl Phosphine oxide (manufactured by BASF Japan Ltd., trade name) IRGACURE 907: 2-methyl-[4-(methylthio)phenyl] morpholinyl-1-acetone (manufactured by BASF Japan Ltd., trade name) IRGACURE OXE01 : 1,2-octanedione, 1-[4-(phenylthio)-,2-(o-benzoyl oxime)] (manufactured by BASF Japan Ltd., trade name) KAYARAD DPHA: dipentaerythritol pentaacrylate (Manufactured by Nippon Kayaku Co., Ltd., trade name) BaSO 4 : manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD. SiO 2 : manufactured by TATSUMORI LTD. Epikote 828: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name) )

由表1所示之結果可確認到，實施例1～6的本發明之感光性樹脂組成物，即便永久遮罩阻劑層(焊料阻劑層)的圖案是孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或者孔徑大小為80μm且孔間的間隔間距為80μm之類的高精細度圖案，也能維持優異的表面硬化性和底部硬化性，獲得阻劑層形狀優異的導通孔形狀，圖案周圍增厚的情形亦能減低，導通孔徑精度優異。而且可確認到，不僅阻劑層形狀優異，焊料耐熱性等其他性狀亦很優異。此情形被認為是藉由本發明之感光性樹脂組成物，尤其是(B)醯基氧化膦系光聚合起始劑與作為氫供應體之(C1)烷基胺基苯衍生物的組合所獲得的效果。 相對於此，比較例1～4並未解決底部硬化性和阻劑層形狀的問題，而且也發生永久遮罩阻劑層(焊料阻劑層)的圖案周圍增厚的情形，是不充分的結果。From the results shown in Table 1, it can be confirmed that the photosensitive resin compositions of the present invention of Examples 1 to 6, even if the pattern of the permanent mask resist layer (solder resist layer) is 100 μm in pore size and between the pores Patterns with a spacing pitch of 100 μm, or high-definition patterns with a pore size of 80 μm and a pitch between holes of 80 μm, can also maintain excellent surface hardening and bottom hardening, and obtain via holes with excellent resist layer shapes The shape and thickening around the pattern can also be reduced, and the accuracy of the conduction aperture is excellent. Furthermore, it was confirmed that not only the shape of the resist layer is excellent, but also other properties such as solder heat resistance are also excellent. This case is considered to be obtained by the combination of the photosensitive resin composition of the present invention, especially (B) acetylphosphine oxide-based photopolymerization initiator and (C1) alkylaminobenzene derivative as a hydrogen donor Effect. On the other hand, Comparative Examples 1 to 4 did not solve the problems of the bottom hardenability and the shape of the resist layer, and the pattern surrounding the permanent mask resist layer (solder resist layer) thickened, which was insufficient. result.

[表2]

Figure 108117792-A0304-0002
＊1：代表含有環氧樹脂(I)之溶液 (固形成分濃度：60質量%)。 ＊2：代表含有環氧樹脂(II)-a之溶液 (固形成分濃度：60質量%)。 ＊3：根據顯影時曝光量600mJ/cm2 進行之評估。[Table 2]
Figure 108117792-A0304-0002
 *1: Represents a solution containing epoxy resin (I) (solid content concentration: 60% by mass). *2: Represents a solution containing epoxy resin (II)-a (solid content concentration: 60% by mass). *3: Evaluation based on an exposure of 600 mJ/cm 2 during development.

註)表2中各材料的詳細內容如下所述。 IRGACURE 819：雙(2,4,6-三甲基苄醯基)苯基氧化膦(BASF Japan Ltd.製造，商品名) DAROCUR TPO：2,4,6-三甲基苄醯基二苯基氧化膦(BASF Japan Ltd.製造，商品名) IRGACURE 907：2-甲基-[4-(甲硫基)苯基]嗎啉基-1-丙酮(BASF Japan Ltd.製造，商品名) IRGACURE 369：2-苄醯基-2-二甲胺基-1-(4-嗎啉基-苯基)丁-1-酮(BASF Japan Ltd.製造，商品名) 吡唑啉系敏化劑：1-苯基-3-(4-三級丁基-苯乙烯基)-5-(4-三級丁基-苯基)-吡唑啉 EAB：4,4’-二乙胺基二苯甲酮(Hodogaya Chemical Co.,Ltd.製造) DETX-S：2,4-二乙基噻噸酮(Nippon Kayaku Co.,Ltd.製造，商品名) KAYARAD DPHA：二季戊四醇五丙烯酸酯(Nippon Kayaku Co.,Ltd.製造，商品名) BaSO4 ：SAKAI CHEMICAL INDUSTRY CO., LTD.製造 SiO2 ：TATSUMORI LTD.製造 Epikote 828：雙酚A型環氧樹脂(Mitsubishi Chemical Corporation製造，商品名)Note) The details of each material in Table 2 are as follows. IRGACURE 819: bis(2,4,6-trimethylbenzyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., trade name) DAROCUR TPO: 2,4,6-trimethylbenzyl diphenyl Phosphine oxide (manufactured by BASF Japan Ltd., trade name) IRGACURE 907: 2-methyl-[4-(methylthio)phenyl]morpholinyl-1-acetone (manufactured by BASF Japan Ltd., trade name) IRGACURE 369 : 2-benzyl-2-methylamino-1-(4-morpholinyl-phenyl)butan-1-one (manufactured by BASF Japan Ltd., trade name) Pyrazoline-based sensitizer: 1 -Phenyl-3-(4-tertiary butyl-styryl)-5-(4-tertiary butyl-phenyl)-pyrazoline EAB: 4,4'-diethylaminodibenzoyl Ketone (manufactured by Hodogaya Chemical Co., Ltd.) DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name) KAYARAD DPHA: dipentaerythritol pentaacrylate (Nippon Kayaku Co ., Ltd., trade name) BaSO 4 : SAKAI CHEMICAL INDUSTRY CO., LTD., SiO 2 : TATSUMORI LTD., Epikote 828: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, trade name)

由表2所示之結果可知，實施例7～12的本發明之感光性樹脂組成物，即便是數位曝光(DIGITAL EXPOSURE)，其感光性仍優異，維持底部硬化性，而獲得阻劑層形狀優異的導通孔形狀。而且可確認到，即便永久遮罩阻劑層(焊料阻劑膜)的圖案是孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或者孔徑大小為80μm且孔間的間隔間距為80μm之類的高精細度圖案，圖案周圍增厚的情形亦能減低，導通孔徑精度優異。而且可確認到，不僅阻劑層形狀優異，焊料耐熱性等其他性狀亦很優異。此情形被認為是藉由本發明之感光性樹脂組成物，尤其是(B)醯基氧化膦系光聚合起始劑與(C2)吡唑啉系敏化劑之組合所獲得的效果。 相對於此，比較例5～12並未解決底部硬化性和阻劑層形狀的問題，而且也發生永久遮罩阻劑層(焊料阻劑層)的圖案(孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或者孔徑大小為80μm且孔間的間隔間距為80μm的圖案)周圍增厚的情形，是不充分的結果。From the results shown in Table 2, it can be seen that the photosensitive resin compositions of the present invention of Examples 7 to 12 have excellent photosensitivity even with digital exposure (DIGITAL EXPOSURE), maintain the bottom hardenability, and obtain the shape of the resist layer Excellent via hole shape. Furthermore, it can be confirmed that even if the pattern of the permanent mask resist layer (solder resist film) is a pattern with an aperture size of 100 μm and an interval between holes of 100 μm, or an aperture size of 80 μm and an interval between holes of 80 μm For high-definition patterns like this, the thickening around the pattern can also be reduced, and the accuracy of the conduction aperture is excellent. Furthermore, it was confirmed that not only the shape of the resist layer is excellent, but also other properties such as solder heat resistance are also excellent. This case is considered to be the effect obtained by the combination of the photosensitive resin composition of the present invention, especially (B) acetylphosphine oxide-based photopolymerization initiator and (C2) pyrazoline-based sensitizer. In contrast, Comparative Examples 5 to 12 did not solve the problems of bottom hardening and the shape of the resist layer, and the pattern of the permanent mask resist layer (solder resist layer) (aperture size of 100 μm and spacing between holes) also occurred A pattern with a pitch of 100 μm or a pattern with an aperture size of 80 μm and a pitch between holes of 80 μm) is thickened around the circumference, which is an insufficient result.

[表3]

Figure 108117792-A0304-0003
＊1：代表含有環氧樹脂(I)之溶液(固形成分濃度：60質量%)。 ＊2：代表含有環氧樹脂(II)-a之溶液(固形成分濃度：60質量%)。 ＊3：代表含有環氧樹脂(IV)-a之溶液(固形成分濃度：60質量%)。 ＊4：根據顯影時曝光量600mJ/cm2 進行之評估。[table 3]
Figure 108117792-A0304-0003
 *1: Represents a solution containing epoxy resin (I) (solid content concentration: 60% by mass). *2: Represents a solution containing epoxy resin (II)-a (solid content concentration: 60% by mass). *3: Represents a solution containing epoxy resin (IV)-a (solid content concentration: 60% by mass). *4: Evaluation based on an exposure of 600 mJ/cm 2 during development.

註)表3中各材料的詳細內容如下所述。 IRGACURE 819：雙(2,4,6-三甲基苄醯基)苯基氧化膦(BASF Japan Ltd.製造，商品名) DAROCUR TPO：2,4,6-三甲基苄醯基二苯基氧化膦(BASF Japan Ltd.製造，商品名) IRGACURE 907：2-甲基-[4-(甲硫基)苯基]嗎啉基-1-丙酮(BASF Japan Ltd.製造，商品名) 蒽系敏化劑1：9,10-二丁氧基蒽 蒽系敏化劑2：9,10-二乙氧基蒽 蒽系敏化劑3：9,10-二丙氧基蒽 EAB：4,4’-二乙胺基二苯甲酮(Hodogaya Chemical Co.,Ltd.製造) DETX-S：2,4-二乙基噻噸酮(Nippon Kayaku Co.,Ltd.製造，商品名) KAYARAD DPHA：二季戊四醇五丙烯酸酯(Nippon Kayaku Co.,Ltd.製造，商品名) BaSO4 ：SAKAI CHEMICAL INDUSTRY CO., LTD.製造 SiO2 ：TATSUMORI LTD.製造 Epikote 828：雙酚A型環氧樹脂(Mitsubishi Chemical Corporation製造，商品名)Note) The details of each material in Table 3 are as follows. IRGACURE 819: bis(2,4,6-trimethylbenzyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., trade name) DAROCUR TPO: 2,4,6-trimethylbenzyl diphenyl Phosphorus oxide (manufactured by BASF Japan Ltd., trade name) IRGACURE 907: 2-methyl-[4-(methylthio)phenyl]morpholinyl-1-acetone (manufactured by BASF Japan Ltd. trade name) Anthracene Sensitizer 1:9,10-dibutoxyanthracene sensitizer 2:9,10-diethoxyanthracene sensitizer 3:9,10-dipropoxyanthracene EAB: 4, 4'-Diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd.) DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name) KAYARAD DPHA : Dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name) BaSO 4 : SiO 2 manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.: Epikote 828 manufactured by TATSUMORI LTD.: bisphenol A type epoxy resin (Mitsubishi Manufactured by Chemical Corporation, trade name)

由表3所示之結果可確認到，實施例13～18的本發明之感光性樹脂組成物，具有優異的光硬化性，即便永久遮罩阻劑層(焊料阻劑層)的圖案是孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或者孔徑大小為80μm且孔間的間隔間距為80μm之類的高精細度圖案，也能具有優異的底部硬化性，不會有底切、拖尾、或增厚被確認的情形，或是圖案輪廓直線性不良的情形，而會獲得優異的阻劑層形狀、導通孔徑精度優異。而且可確認到，不僅具有優異的焊料耐熱性和耐助焊劑腐蝕性，密著性、耐溶劑性、耐藥品性(耐酸性、耐鹼性)等各種性能亦很優異。 相對於此，比較例13～20則是光硬化性及底部硬化性低下，阻劑層形狀呈現底切情形，阻劑層形狀不良。From the results shown in Table 3, it can be confirmed that the photosensitive resin compositions of the present invention of Examples 13 to 18 have excellent photocurability, even if the pattern of the permanent mask resist layer (solder resist layer) is an aperture A pattern with a size of 100 μm and a spacing between holes of 100 μm, or a high-definition pattern with a hole size of 80 μm and a spacing between holes of 80 μm, can also have excellent bottom hardening without undercuts, In cases where smearing, thickening is confirmed, or pattern outline linearity is poor, an excellent resist layer shape and excellent on-hole accuracy are obtained. Moreover, it is confirmed that not only excellent solder heat resistance and flux corrosion resistance, but also various properties such as adhesion, solvent resistance, chemical resistance (acid resistance and alkali resistance) are excellent. On the other hand, in Comparative Examples 13 to 20, the photocurability and the bottom curability were low, the shape of the resist layer was undercut, and the shape of the resist layer was poor.

[表4]

Figure 108117792-A0304-0004
＊1：代表含有環氧樹脂(I)之溶液 (固形成分濃度：60質量%)。 ＊2：代表含有環氧樹脂(II)-a之溶液 (固形成分濃度：60質量%)。 ＊3：根據顯影時曝光量600mJ/cm2 進行之評估。[Table 4]
Figure 108117792-A0304-0004
 *1: Represents a solution containing epoxy resin (I) (solid content concentration: 60% by mass). *2: Represents a solution containing epoxy resin (II)-a (solid content concentration: 60% by mass). *3: Evaluation based on an exposure of 600 mJ/cm 2 during development.

註)表4中各材料的詳細內容如下所述。 IRGACURE 819：雙(2,4,6-三甲基苄醯基)苯基氧化膦(BASF Japan Ltd.製造，商品名) DAROCUR TPO：2,4,6-三甲基苄醯基二苯基氧化膦(BASF Japan Ltd.製造，商品名) IRGACURE 907：2-甲基-[4-(甲硫基)苯基]嗎啉基-1-丙酮(BASF Japan Ltd.製造，商品名) 咪唑：2-(o-氯苯基)-4,5-二苯基咪唑二聚物 吖啶：1,7-雙(9,9’-吖啶基)庚烷 二茂鈦：雙(η5 -環戊二烯基)-雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦 IRGACURE OXE01：1,2-辛二酮,1-[4-(苯硫基)-,2-(o-苯甲醯肟)] (BASF Japan Ltd.製造，商品名) KAYARAD DPHA：二季戊四醇五丙烯酸酯(Nippon Kayaku Co.,Ltd.製造，商品名) BaSO4 ：SAKAI CHEMICAL INDUSTRY CO., LTD.製造 SiO2 ：TATSUMORI LTD.製造 Epikote 828：雙酚A型環氧樹脂(Mitsubishi Chemical Corporation製造，商品名)Note) The details of each material in Table 4 are as follows. IRGACURE 819: bis(2,4,6-trimethylbenzyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., trade name) DAROCUR TPO: 2,4,6-trimethylbenzyl diphenyl Phosphine oxide (manufactured by BASF Japan Ltd., trade name) IRGACURE 907: 2-methyl-[4-(methylthio)phenyl]morpholinyl-1-acetone (manufactured by BASF Japan Ltd., trade name) Imidazole: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer acridine: 1,7-bis(9,9'-acridinyl)heptane titanocene: bis(η 5- Cyclopentadienyl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium IRGACURE OXE01: 1,2-octanedione, 1-[4-(phenylsulfide Base)-,2-(o-benzoyl oxime)] (manufactured by BASF Japan Ltd., trade name) KAYARAD DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name) BaSO 4 : SAKAI SiO 2 manufactured by CHEMICAL INDUSTRY CO., LTD.: Epikote 828 manufactured by TATSUMORI LTD.: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name)

由表4所示之結果可確認到，實施例19～24的本發明之感光性樹脂組成物，會維持底部硬化性，穩定地獲得阻劑層形狀優異的導通孔形狀，即便永久遮罩阻劑層(焊料阻劑層)的圖案是孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或者孔徑大小為80μm且孔間的間隔間距為80μm之類的高精細度圖案，也仍能減低周圍增厚的情形，且導通孔精度優異。而且可確認到，不僅阻劑層形狀優異，焊料耐熱性等其他性狀亦很優異。此情形被認為是藉由本發明之感光性樹脂組成物，尤其是(B)醯基氧化膦系光聚合起始劑與(C3)光聚合起始劑之組合所獲得的效果。 相對於此，比較例21～24並未解決底部硬化性和阻劑層形狀的問題，而且也發生永久遮罩阻劑層的圖案周圍增厚的情形，是不充分的結果。From the results shown in Table 4, it can be confirmed that the photosensitive resin compositions of the present invention of Examples 19 to 24 maintain the bottom hardenability and stably obtain the via hole shape excellent in the shape of the resist layer even if the permanent mask resists The pattern of the flux layer (solder resist layer) is a pattern with a pore size of 100 μm and a spacing between holes of 100 μm, or a high-definition pattern with a pore size of 80 μm and a spacing between holes of 80 μm, etc. The surrounding thickening is reduced, and the via hole accuracy is excellent. Furthermore, it was confirmed that not only the shape of the resist layer is excellent, but also other properties such as solder heat resistance are also excellent. This case is considered to be the effect obtained by the photosensitive resin composition of the present invention, especially the combination of (B) acetylphosphine oxide-based photopolymerization initiator and (C3) photopolymerization initiator. On the other hand, Comparative Examples 21 to 24 did not solve the problems of the bottom hardenability and the shape of the resist layer, and the surroundings of the pattern that permanently masked the resist layer thickened, which was an insufficient result.

[表5]

Figure 108117792-A0304-0005
＊1：代表含有環氧樹脂(I)之溶液(固形成分濃度：60質量%)。 ＊2：代表含有環氧樹脂(II)-a之溶液(固形成分濃度：60質量%)。 ＊3：代表含有環氧樹脂(IV)-a之溶液(固形成分濃度：60質量%)。 ＊4：代表含有環氧樹脂(IV)-b之溶液(固形成分濃度：60質量%)。[table 5]
Figure 108117792-A0304-0005
 *1: Represents a solution containing epoxy resin (I) (solid content concentration: 60% by mass). *2: Represents a solution containing epoxy resin (II)-a (solid content concentration: 60% by mass). *3: Represents a solution containing epoxy resin (IV)-a (solid content concentration: 60% by mass). *4: Representative solution containing epoxy resin (IV)-b (solid content concentration: 60% by mass).

註)表5中各材料的詳細內容如下所述。 IRGACURE 819：雙(2,4,6-三甲基苄醯基)苯基氧化膦(BASF Japan Ltd.製造，商品名) DAROCUR TPO：2,4,6-三甲基苄醯基二苯基氧化膦(BASF Japan Ltd.製造，商品名) IRGACURE 907：2-甲基-[4-(甲硫基)苯基]嗎啉基-1-丙酮(BASF Japan Ltd.製造，商品名) IRGANOX 1010：季戊四醇四[3-(3,5-二-三級丁基-4-羥苯基)丙酸酯] (BASF Japan Ltd.製造，商品名) IRGANOX 1035：雙[3-(3,5-二叔丁基-4-羥苯基)丙酸]硫代二伸乙酯(BASF Japan Ltd.製造，商品名) IRGANOX 1076：[3-(3,5-二-三級丁基-4-羥苯基)丙酸]十八烷酯(BASF Japan Ltd.製造，商品名) KAYARAD DPHA：二季戊四醇五丙烯酸酯(Nippon Kayaku Co.,Ltd.製造，商品名) BaSO4 ：SAKAI CHEMICAL INDUSTRY CO., LTD.製造 SiO2 ：TATSUMORI LTD.製造 Epikote 828：雙酚A型環氧樹脂(Mitsubishi Chemical Corporation製造，商品名)Note) The details of each material in Table 5 are as follows. IRGACURE 819: bis(2,4,6-trimethylbenzyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., trade name) DAROCUR TPO: 2,4,6-trimethylbenzyl diphenyl Phosphine oxide (manufactured by BASF Japan Ltd., trade name) IRGACURE 907: 2-methyl-[4-(methylthio)phenyl]morpholinyl-1-acetone (manufactured by BASF Japan Ltd. trade name) IRGANOX 1010 : Pentaerythritol tetrakis[3-(3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd., trade name) IRGANOX 1035: bis[3-(3,5- Di-tert-butyl-4-hydroxyphenyl) propionic acid] thiodiethylidene (manufactured by BASF Japan Ltd., trade name) IRGANOX 1076: [3-(3,5-di-tertiary butyl-4- Hydroxyphenyl) propionic acid] octadecyl ester (manufactured by BASF Japan Ltd., trade name) KAYARAD DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name) BaSO 4 : SAKAI CHEMICAL INDUSTRY CO. , LTD. Manufacturing SiO 2 : TATSUMORI LTD. Manufacturing Epikote 828: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, trade name)

由表5所示之結果可確認到，實施例25～30的本發明之感光性樹脂組成物，即便永久遮罩阻劑層(焊料阻劑層)的圖案是孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或者孔徑大小為80μm且孔間的間隔間距為80μm之類的高精細度圖案，也能維持優異的表面硬化性和底部硬化性，不會有底切、拖尾、或增厚被確認的情形，或是圖案輪廓直線性不良的情形，而會獲得優異的阻劑層形狀、導通孔徑精度優異。而且可確認到，不僅具有優異的焊料耐熱性和耐助焊劑腐蝕性，密著性、耐溶劑性、耐藥品性(耐酸性、耐鹼性)等各種性能亦很優異。 相對於此，比較例25～30則是表面硬化性及底部硬化性低下，阻劑層形狀呈現底切情形，比較例29及30則因為增大顯影時的照射線量，所以表面硬化性及底部硬化性良好，但光暈變大，圖案剖面的中間部(中心部)及最深部(底部)的線寬相對於表面部(上部)的線寬而言變大，以致阻劑層形狀惡化。From the results shown in Table 5, it can be confirmed that the photosensitive resin compositions of the present invention of Examples 25 to 30, even if the pattern of the permanent mask resist layer (solder resist layer) is 100 μm in pore size and between the pores Patterns with a spacing pitch of 100 μm, or high-definition patterns with a pore size of 80 μm and a pitch between holes of 80 μm, can also maintain excellent surface hardening and bottom hardening without undercutting, tailing, Either the thickening is confirmed, or the pattern outline is poorly linear, an excellent shape of the resist layer and an excellent accuracy of the via diameter are obtained. Moreover, it is confirmed that not only excellent solder heat resistance and flux corrosion resistance, but also various properties such as adhesion, solvent resistance, chemical resistance (acid resistance and alkali resistance) are excellent. In contrast, in Comparative Examples 25 to 30, the surface hardening and bottom hardening are low, and the shape of the resist layer is undercut. In Comparative Examples 29 and 30, the surface hardening and bottom are hardened because the amount of radiation during development is increased. The curability is good, but the halo becomes larger, and the line width of the middle part (center part) and the deepest part (bottom part) of the pattern cross section becomes larger than the line width of the surface part (upper part), so that the shape of the resist layer deteriorates.

[表6]

Figure 108117792-A0304-0006
＊1：代表含有環氧樹脂(IV)-c之溶液 (固形成分濃度：73質量%)。 ＊2：代表含有環氧樹脂(II)-b之溶液 (固形成分濃度：60質量%)。 ＊3：根據顯影時曝光量600mJ/cm2 進行之評估。[Table 6]
Figure 108117792-A0304-0006
 *1: Represents a solution containing epoxy resin (IV)-c (solid content concentration: 73% by mass). *2: Represents a solution containing epoxy resin (II)-b (solid content concentration: 60% by mass). *3: Evaluation based on an exposure of 600 mJ/cm 2 during development.

註)表6中各材料的詳細內容如下所述。 IRGACURE 819：雙(2,4,6-三甲基苄醯基)苯基氧化膦(BASF Japan Ltd.製造，商品名) IRGACURE 907：2-甲基-[4-(甲硫基)苯基]嗎啉基-1-丙酮(BASF Japan Ltd.製造，商品名) DETX-S：2,4-二乙基噻噸酮(Nippon Kayaku Co.,Ltd.製造，商品名) MBI：巰基苯并咪唑 酞青系顏料：Sanyo Color Works, LTD.製造 ARONIX M402：二季戊四醇六丙烯酸酯(TOAGOSEI CO., LTD.製造，商品名) BaSO4 ：SAKAI CHEMICAL INDUSTRY CO., LTD.製造 SiO2 ：TATSUMORI LTD.製造 YSLV-80XY：四甲基雙酚F型環氧樹脂(Nippon Steel Chemical Co., Ltd.製造，商品名) RE-306：酚醛清漆型多官能環氧樹脂(Nippon Kayaku Co.,Ltd.製造，商品名) PB-3600：環氧化聚丁二烯(Daicel Corporation製造，商品名) SP1108：聚酯樹脂(Hitachi Chemical Co., Ltd.製造，商品名) DICY 7：二氰二胺Note) The details of each material in Table 6 are as follows. IRGACURE 819: bis(2,4,6-trimethylbenzyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., trade name) IRGACURE 907: 2-methyl-[4-(methylthio)phenyl ] Morpholin-1-acetone (manufactured by BASF Japan Ltd., trade name) DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name) MBI: mercaptobenzo Imidazole phthalocyanine pigment: manufactured by Sanyo Color Works, LTD. ARONIX M402: dipentaerythritol hexaacrylate (manufactured by TOAGOSEI CO., LTD., trade name) BaSO 4 : manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD. SiO 2 : TATSUMORI LTD . Manufacturing YSLV-80XY: tetramethyl bisphenol F type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name) RE-306: novolac type multifunctional epoxy resin (Nippon Kayaku Co., Ltd. Manufacturing, trade name) PB-3600: Epoxidized polybutadiene (manufactured by Daicel Corporation, trade name) SP1108: Polyester resin (manufactured by Hitachi Chemical Co., Ltd., trade name) DICY 7: Dicyandiamide

由表6所示之結果可確認到，實施例31～34的本發明之感光性樹脂組成物，即便感光性元件及永久遮罩阻劑層(焊料阻劑層)的圖案是孔徑大小為100μm且孔間的間隔間距為100μm的圖案、或者孔徑大小為80μm且孔間的間隔間距為80μm之類的高精細度圖案，也不會有底切、拖尾、或增厚被確認的情形，或是圖案輪廓直線性不良的情形，而會獲得優異的阻劑層形狀。 而且可確認到，無電鍍覆耐性、焊料耐熱性、耐破裂性、密著性、耐溶劑性、耐藥品性(耐酸性、耐鹼性)等各種性能亦很優異。 相對於此，比較例31～34的感光性樹脂組成物，阻劑層形狀惡化，而且焊料耐熱性和耐破裂性亦差。 [產業上之可利用性]From the results shown in Table 6, it can be confirmed that the photosensitive resin composition of the present invention of Examples 31 to 34 has a pore size of 100 μm even if the pattern of the photosensitive element and the permanent mask resist layer (solder resist layer) is There is no possibility of undercutting, trailing, or thickening of patterns with a pitch of 100 μm between holes or high-definition patterns with a pore size of 80 μm and a pitch of 80 μm between holes. Or, if the linearity of the pattern outline is poor, an excellent resist layer shape will be obtained. Furthermore, it can be confirmed that various properties such as electroless plating resistance, solder heat resistance, crack resistance, adhesion, solvent resistance, chemical resistance (acid resistance, alkali resistance) and the like are also excellent. On the other hand, in the photosensitive resin compositions of Comparative Examples 31 to 34, the shape of the resist layer deteriorates, and the solder heat resistance and crack resistance are also poor. [Industry availability]

根據本發明，可獲得一種感光性樹脂組成物，其不會發生底部被挖空而成之底切、及阻劑層上部之缺損，能形成圖案輪廓直線性良好、阻劑層形狀優異、解析度優異的圖案，根據本發明亦可獲得一種永久遮罩阻劑層，其能形成一種圖案，該圖案的孔徑大小和孔間的間隔間距微細化且形成穩定性優異。永久遮罩阻劑層適合使用於印刷電路板。According to the present invention, a photosensitive resin composition can be obtained which does not cause undercuts made by hollowing out the bottom and defects on the upper part of the resist layer, can form a pattern with good linearity of outline, excellent shape of the resist layer, and analysis According to the present invention, a pattern having an excellent degree of degree can also be obtained as a permanent mask resist layer, which can form a pattern whose pore size and interval between pores are finer and have excellent formation stability. The permanent mask resist layer is suitable for printed circuit boards.

無no

第1圖是使用本發明之感光性樹脂組成物而形成的阻劑層的剖面概略圖。 第2圖是表示實施例中所使用之負型遮罩的圖案形狀的圖。 第3圖是表示實施例中所使用之負型遮罩的圖案形狀的圖。FIG. 1 is a schematic cross-sectional view of a resist layer formed using the photosensitive resin composition of the present invention. FIG. 2 is a diagram showing the pattern shape of the negative mask used in the examples. FIG. 3 is a diagram showing the pattern shape of the negative mask used in the examples.

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Claims (10)

一種感光性樹脂組成物，其含有：(A)含有酸改質乙烯基之環氧樹脂；(B)醯基氧化膦系光聚合起始劑；(C)添加劑，該(C)添加劑是選自(C2)吡唑啉系敏化劑或蒽系敏化劑、及(C5)含有氫硫基之化合物中的至少一種；及，(D)光聚合性化合物。 A photosensitive resin composition comprising: (A) an epoxy resin containing an acid-modified vinyl group; (B) a phosphine oxide photopolymerization initiator; (C) an additive, and the (C) additive is selected At least one of (C2) pyrazoline-based sensitizer or anthracene-based sensitizer, and (C5) a compound containing a hydrogen sulfide group; and (D) a photopolymerizable compound. 如請求項1所述之感光性樹脂組成物，其中，(A)含有酸改質乙烯基之環氧樹脂是使樹脂(a’)與含有飽和基或不飽和基之多元酸酐(c)反應而獲得之樹脂，該樹脂(a’)是使環氧樹脂(a)與含有乙烯基之單羧酸(b)反應而獲得，該環氧樹脂(a)是選自具有通式(I)所示的結構單元之環氧樹脂、具有通式(II)所示的結構單元之環氧樹脂、具有通式(III)所示的結構單元之環氧樹脂、具有通式(IV)所示的結構單元之雙酚酚醛清漆型環氧樹脂、及具有通式(V)所示的結構單元之雙酚酚醛清漆型環氧樹脂中的至少一種，
Figure 108117792-A0305-02-0097-1
 式(I)中，R11表示氫原子或甲基，Y1表示縮水甘油基；
Figure 108117792-A0305-02-0098-2
 式(II)中，R12表示氫原子或甲基，Y2表示縮水甘油基，複數的R12可為相同亦可為不同；
Figure 108117792-A0305-02-0098-3
 式(III)中，Y3表示氫原子或縮水甘油基，且至少一個Y3表示縮水甘油基，複數的Y3可為相同亦可為不同；
Figure 108117792-A0305-02-0099-4
 式(IV)中，R13表示氫原子、烷基、芳基、芳烷基、磺基或三鹵甲基，Y4表示氫原子或縮水甘油基，且至少一個Y4表示縮水甘油基，複數的R13可為相同亦可為不同；
Figure 108117792-A0305-02-0099-5
 式(V)中，R14表示氫原子、烷基、芳基、芳烷基、磺基或三鹵甲基，Y5表示氫原子或縮水甘油基，且至少一個Y5表示縮水甘油基，複數的R14可為相同亦可為不同。 The photosensitive resin composition according to claim 1, wherein (A) the epoxy resin containing an acid-modified vinyl group is to react the resin (a') with a polybasic acid anhydride (c) containing a saturated group or an unsaturated group The obtained resin, the resin (a') is obtained by reacting the epoxy resin (a) with a vinyl-containing monocarboxylic acid (b), the epoxy resin (a) is selected from the general formula (I) Epoxy resin with structural unit shown, epoxy resin with structural unit shown with general formula (II), epoxy resin with structural unit shown with general formula (III), with general formula (IV) At least one of a bisphenol novolak-type epoxy resin of the structural unit of, and a bisphenol novolak-type epoxy resin of the structural unit represented by the general formula (V),
Figure 108117792-A0305-02-0097-1
 In formula (I), R 11 represents a hydrogen atom or a methyl group, and Y 1 represents a glycidyl group;
Figure 108117792-A0305-02-0098-2
 In formula (II), R 12 represents a hydrogen atom or a methyl group, Y 2 represents a glycidyl group, and plural R 12 may be the same or different;
Figure 108117792-A0305-02-0098-3
 In formula (III), Y 3 represents a hydrogen atom or a glycidyl group, and at least one Y 3 represents a glycidyl group, and plural Y 3 may be the same or different;
Figure 108117792-A0305-02-0099-4
 In formula (IV), R 13 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfo group, or a trihalomethyl group, Y 4 represents a hydrogen atom or a glycidyl group, and at least one Y 4 represents a glycidyl group, The plural R 13 may be the same or different;
Figure 108117792-A0305-02-0099-5
 In formula (V), R 14 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfo group, or a trihalomethyl group, Y 5 represents a hydrogen atom or a glycidyl group, and at least one Y 5 represents a glycidyl group, The plural R 14 may be the same or different. 如請求項1或2所述之感光性樹脂組成物，其中，(B)醯基氧化膦系光聚合起始劑是選自(2,6-二甲氧基苄醯基)-2,4,6-三甲基苄醯基-戊基氧化膦、雙(2,4,6-三甲基苄醯基)-苯基氧化膦、2,4,6-三甲基苄醯基二苯基氧化膦、2,4,6-三甲基苄醯基苯基次膦酸乙酯、雙(2,4,6-三甲基苄醯基)-苯基氧化膦、(2,5-二羥基苯基)二苯基氧化膦、(對羥苯基)二苯基氧化膦、雙(對羥苯基)苯基氧化膦、及參(對羥苯基)氧化膦中的至少一種。 The photosensitive resin composition according to claim 1 or 2, wherein the (B) acetylphosphine oxide-based photopolymerization initiator is selected from (2,6-dimethoxybenzyl)-2,4 ,6-trimethylbenzyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyl diphenyl Phosphine oxide, ethyl 2,4,6-trimethylbenzyl phenylphosphinate, bis(2,4,6-trimethylbenzyl phenyl)-phenylphosphine oxide, (2,5- At least one of dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, and ginseng (p-hydroxyphenyl)phosphine oxide. 如請求項1或2所述之感光性樹脂組成物，其中，(C)添加劑是(C5)含有氫硫基之化合物，該(C5)含有氫硫基之化合物是選自巰基苯并
Figure 108117792-A0305-02-0100-6
唑、巰基苯并噻唑、及巰基苯并咪唑中的至少一種。 The photosensitive resin composition according to claim 1 or 2, wherein the (C) additive is (C5) a compound containing a hydrogen sulfide group, and the compound (C5) is selected from mercaptobenzo
Figure 108117792-A0305-02-0100-6
At least one of azole, mercaptobenzothiazole, and mercaptobenzimidazole. 如請求項1或2所述之感光性樹脂組成物，其中，該(D)光聚合性化合物是含有(甲基)丙烯醯基之化合物。 The photosensitive resin composition according to claim 1 or 2, wherein the (D) photopolymerizable compound is a compound containing a (meth)acryloyl group. 如請求項1或2所述之感光性樹脂組成物，其中，進而包含(E)無機填料。 The photosensitive resin composition as described in Claim 1 or 2 which further contains (E) an inorganic filler. 如請求項1或2所述之感光性樹脂組成物，其用於形成永久遮罩阻劑層。 The photosensitive resin composition according to claim 1 or 2, which is used to form a permanent mask resist layer. 一種感光性元件，其具備：支撐體；及，感光層，該感光層是將如請求項1~7中任一項所述之感光 性樹脂組成物使用於該支撐體上而成。 A photosensitive element comprising: a support; and, a photosensitive layer, which is a photosensitive member according to any one of claims 1 to 7 The resin composition is used for this support. 一種永久遮罩阻劑層，其由如請求項1~7中任一項所述之感光性樹脂組成物所形成。 A permanent mask resist layer formed of the photosensitive resin composition according to any one of claims 1 to 7. 一種印刷電路板，其具備如請求項9所述之永久遮罩阻劑層。 A printed circuit board provided with the permanent mask resist layer according to claim 9.
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