TW201106096A - Photosensitive resin composition, and dry film and printed circuit board using the same - Google Patents

Photosensitive resin composition, and dry film and printed circuit board using the same Download PDF

Info

Publication number
TW201106096A
TW201106096A TW099109420A TW99109420A TW201106096A TW 201106096 A TW201106096 A TW 201106096A TW 099109420 A TW099109420 A TW 099109420A TW 99109420 A TW99109420 A TW 99109420A TW 201106096 A TW201106096 A TW 201106096A
Authority
TW
Taiwan
Prior art keywords
resin composition
photosensitive resin
compound
group
film
Prior art date
Application number
TW099109420A
Other languages
Chinese (zh)
Other versions
TWI498673B (en
Inventor
Daichi Okamoto
Masao Arima
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of TW201106096A publication Critical patent/TW201106096A/en
Application granted granted Critical
Publication of TWI498673B publication Critical patent/TWI498673B/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The present invention provides a cured material capable of manufacturing the dry film having excellent finger-touch, tack free property, soldering-flux heat resistance, electroless gold-plating resistance, and electrical isolation, and particularly is capable of forming the photosensitive resin composition of the hard coat of the solder resist preventing from the ion migration in the fine pitch circuit, and its dry film and the printed circuit board containing hard coat formed by adopting the same. In more detail, the photosensitive resin composition of the present invention contains the lamellar double hydroxide (A), and even better the hydrotalcite, in addition to the alkaline image-development photosensitive resin composition containing the resin (B) containing the carboxylic group and photo-polymerization initiator (D), while even more better containing the vinyl unsaturated-group compound (C). The best is to contain the thermo-curable ingredient (E) to prepare the photo-curable and thermo-curable resin composition.

Description

201106096 六、發明說明： 【發明所屬之技術領域】 本發明有關一種能製得乾燥塗膜的指觸乾燥性（tack free )優異、銲劑耐熱性、無電解鍍金耐性、電氣絕緣性 等優異的硬化物，特別是能形成防止於精細節距電路（ fine pitch circuit)中之離子遷移（i〇n migration)之阻焊 劑（solder resist)等的硬質塗膜（hard coat)之感光性 樹脂組成物。本發明，又有關採用此種感光性樹脂組成物 之乾式薄膜（dry film )及硬化物、以及採用此等所形成 之具有硬質塗膜之印刷電路板》 【先前技術】 再來，鹼化合物顯像（alkaline image development) 式的感光性樹脂組成物，係作爲印刷電路板用的阻焊劑而 大量在使用。阻焊劑，係以保護印刷電路板的表層電路爲 目的所使用者，故需要具備高的銲劑耐熱性（soft solder resistance)及電氣絕緣性。特別是，最近印刷電路板的高 密度化頗有進展，其電路係以最小計，成爲線（line ) ΙΟμιη、間隙（space) ΙΟμπι，較在來者需要具備離子遷移 耐性（ion migration resistance)。然而，由於用爲阻焊 劑之感光性樹脂係光反應性快速的丙烯酸酯系化合物之故 ，疏水性、耐鹼性劣差，容易引起在高溫加濕條件下的離 子遷移，以致有引起電路間的短.路之問題。 另一方面，熱硬化式的阻焊劑而言，曾提案有一種分 -5- 201106096 子中作爲必須成分而含有具有2個以上的環氧基之環氧樹 脂、聚合酸酐（polyacid anhydride)、以及偶合劑（ coupling agent)，再含有無機離子交換劑或阻燃劑，再含 有水合金屬化合物之組成物（參考專利文獻1)。然而， 如將無機離子交換劑作爲鹼顯像性阻焊劑使用時，則將碳 酸鈉等的鹼化合物顯像液的無機成分大量吸收於光阻劑（ resist )內部，其結果有使離子遷移耐性更爲惡化之問題 〇 又，爲鹼化合物顯像式的感光性樹脂組成物而使用無 機層狀化合物之例而言，曾提案有一種感光性樹脂組成物 ，其特徵爲：含有；含有具有羧基之環氧（甲基）丙烯酸 酯化合物（B1)或具有羧基之聚胺基甲酸酯（甲基）丙烯 酸酯化合物（B2 )中之至少1種之具有乙烯性不飽和基之 化合物（B)、及環氧樹脂（E)、及光聚合引發劑（D) 、以及對無機層狀化合物（inorganic lamellar compound )中***有選自胺、四級銨鹽、酸酐、聚醯胺、含氮雜環 化合物、有機金屬化合物所成群之至少1種熱聚合觸媒（ thermal polymerization catalyst )之夾雜化合物（ intercalation compound)者（參考專利文獻 2)。此種感 光性樹脂組成物，係使熱聚合觸媒***於無機層狀化合物 中，以提升阻焊劑的儲存穩定性作爲目的者，惟電氣絕緣 性的效果並不明確。如使聚合觸媒***於無機層狀化合物 中時’一般認爲阻焊劑的熱硬化反應變成極低而對儲存穩 定性爲有效者，惟相反地，由於反應難於完結（ -6- 201106096 complation)之故，所得硬化塗膜的絕緣電阻變低，以致 可能有容易發生離子遷移之問題。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本專利特開2006-229127號公報（ 申請專利範圍） 〔專利文獻2〕日本專利特開2003-195486號公報（ 申請專利範圍） 【發明內容】 〔發明所欲解決之課題〕 本發明，係鑑於如前述之在來技術所開發者，其主要 目的在於提供一種乾燥塗膜的指觸乾燥性優異、銲劑耐熱 性、無電解鍍金耐性、電氣絕緣性等優異，特別是能形成 防止於精細節距電路中之離子遷移之阻焊劑等的硬質塗膜 之感光性樹脂組成物。 再者，本發明之目的在於提供一種由於採用此種感光 性樹脂組成物之結果所得之如上述般的各種特性優異的乾 式薄膜及硬化物，以及使用該乾式薄膜或硬化物而形成有 阻焊劑等的硬質塗膜之印刷電路板。 〔用於解決課題之手段〕 如爲達成前述目的而採用本發明，則可提供一種感光 性樹脂組成物，係含有：含羧基之樹脂（B )及光聚合引 201106096 發劑（D )之鹼顯像性的感光性樹脂組成物，其特徵爲： 再含有層狀雙氫氧化合物（lamellar double hydroxide)( A)。較佳爲再含有具有乙烯性不飽和基之化合物（C)。 於合適的狀態下，如再含有熱硬化性成分（E )，則可作 成光硬化性熱硬化性樹脂組成物。於其他合適的狀態中， 再含有著色劑。 於合適的狀態下，前述層狀雙氫氧化合物（A)，係 可以下述一般構造式（I)表示之化合物。 【化1】 [M2+ M3+(OH) ][An_ *mH2〇] (I) l-X X 2 X/n 、” 式中，M2 +表示 Mg2+、Fe2+、Zn2+、Ca2+、Li2+、Ni2 + 、（：o2+、Cu2 +等2價的金屬陽離子，M3 +表示Al3+、Fe3+、 Mn3 +等3價的金屬陽離子，An_表示ri價的陰離子，各元 素及原子團的下腳註字表示各元素及原子團的比例，X爲 〇<XS〇.33，m2〇。m 雖爲 2 0，惟因脫水（dehydration) 而會變大。 特別是，於上述一般構造式（I)中，2價的金屬陽離 子M2 +爲以Mg2+、3價的金屬陽離子M3 +爲以Al3+、陰離 子An_爲以C〇32·所構成之水滑石（hydrotalcite)型化合物 〇 含有此種感光性樹脂組成物，特別是含有熱硬化性成 分（E )之光硬化性·熱硬化性樹脂組成物，係很適合採 旨 月 樹 性 光 感 述 前 將 tlrnl- 種 1 。 供-成提-ft 形可 之則 劑’ 焊明 阻發 的本 板用 路採 電如 刷， 印又 於 用 201106096 組成物塗佈於薄膜並乾燥所成之乾式薄膜、或再將前述感 光性樹脂組成物或將使該感光性樹脂組成物塗佈於載體薄 膜（carrier film)並乾燥所得乾式薄膜進行光硬化或再加 以熱硬化所得之硬化物、特別是在銅上進行光硬化所得之 硬化物、或使其光硬化爲圖型狀或再加以熱硬化所得之硬 化物，再者，如採用本發明，則亦可提供具有上述硬化物 之印刷電路板。 〔發明之效果〕 本發明之感光性樹脂組成物，係含有含羧基之樹脂（ B )及光聚合引發劑（D )之鹼顯像性之感光性樹脂組成物 ，由於再含有層狀雙氫氧化合物（A)、特別是含有具有 可以前述一般式（1)表示之構造式之水滑石及水滑石型 化合物之故，可形成乾燥塗膜的指觸乾燥性優異、銲劑耐 熱性、無電解鍍金耐性、電氣絕緣性，特別是高溫加濕時 的離子遷移耐性高的硬質塗膜。又，由於與上述層狀雙氫 氧化合物（A) —起含有羧基之樹脂（B)之故，所得感光 性樹脂組成物，係能實施使用鹼化合物水溶液之顯像。 因而，本發明之感光性樹脂組成物，可有利適用於印 刷電路板或軟性印刷電路板的阻焊劑等硬質塗膜之形成。 〔發明之最佳實施形態〕 如前述，本發明之感光性樹脂組成物的特徵在於’含 有含羧基之樹脂（B)(含羧基之感光性樹脂（B-1)、或 -9 - 201106096 經與具有乙烯性不飽和基之化合物（c )組合之非感光性 的羧基之樹脂（B-2 ))及光聚合引發劑（D )之鹼性顯像 性的感光性樹脂組成物中，再採用有層狀雙氫氧化合物（ A)，特別是採用有可以前述一般式（Π表示之化合物之 處。 經本發明人等的硏究之結果發現，如含有層狀雙氫氧 化合物（Α)，特別是含有可以前述一般式（1)表示之化 合物時，則所得感光性樹脂組成物的乾燥塗膜會在指觸乾 燥性方面優異，且硬化被膜在高溫加濕條件下較不含有前 述層狀雙氫氧化合物（A )之情形爲能長時間抑制離子遷 移的發生之事實。此乃可設想爲源自前述層狀雙氫氧化合 物（A )在酸性條件下能作.爲陰離子交換劑發揮作用之性 質。亦即，一般周知，在高溫加濕條件下的銅電路，會因 電壓的施加而陽極成爲酸性、陰極成爲鹼性之事實。並且 ’可設想爲氯化物離子等陰離子會被陽極所拉攏之故，在 酸性條件下具有陰離子交換作用之層狀雙氫氧化合物（A )則極有效率地成爲離子遷移的原因物質之鹵素離子、特 別是成爲經將氯離子取進構造內者，並因此而能長時間抑 制離子遷移的發生。此種現象，係其他離子交換劑所不能 具有之有效率的效果，再者，可設想爲前述層狀雙氫氧化 合物（A) ’特別是如作爲陰離子而具有c〇32-者，即使在 採用碳酸鈉等鹼化合物顯像液之顯像過程中，仍然不致於 進行鹼化合物顯像液的陰離子（例如，C〇32·)之離子交換 之下獲得穩定的效果者。此種現象，係其他離子交換劑所 -10- 201106096 不能具有之特別優異的效果。 又’ 一般’當將感光性樹脂組成物塗佈於基板等時， 有時以抑制塌邊（Shear drop )之發生爲目的而使用有機 膨土（organic bentonite)或微晶高嶺石（montmorillonite )等層狀無機化合物之情形。然而一般周知，此種化合物 會對電氣特性有不良影響的事實。相對於此，經調配如本 發明之水滑石化合物等的層狀雙氫氧化合物（Α)之組成 物，則除能顯著提升電氣特性之外，尙獲得能改善搖變性 (thixotropy)，以控制當對基板等塗佈感光性樹脂組成 物時之塌邊之發生等相乘的效果。 水滑石及水滑石型化合物，係天然產出之黏土礦物中 的一種，例如，係由帶電爲正之基本層〔Mgl-XA1X(0H)2 〕X +與帶電爲負之中間層〔（C03 ) x/2 · mH20〕χ·所成層 狀的無機化合物。多數的2價、3價的金屬採取與此者同 樣的層狀構造，而一般構造式爲可以前述式（〇表示者 〇 於此等水滑石及水滑石型化合物中，雖具有如陰離子 交換能力（anion exchanging capacity)或熱分解·再水化 (thermal d e co m p o s i t i ο η - r eh y d r a t i ο η )等般，微晶高嶺石 等其他無機層狀化合物所不能具有之幾種特性，惟對聚合 物的適合例卻並不多見》 前述層狀雙氫氧化合物（Α)的具體例而言，可舉： Indigirite Mg2Al2 ( ( C03 ) 4 ( 〇H ) 2〕 · 15H20、201106096 VI. Description of the Invention: [Technical Field] The present invention relates to an excellent hardening of a dry coating film which is excellent in tack dryness, solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. In particular, it is a photosensitive resin composition which can form a hard coat such as a solder resist which prevents ion migration in a fine pitch circuit. The present invention relates to a dry film and a cured product using such a photosensitive resin composition, and a printed circuit board having a hard coating film formed by using the same. [Prior Art] A photosensitive resin composition of the type "alkaline image development" is used in a large amount as a solder resist for a printed circuit board. Since the solder resist is intended to protect the surface circuit of the printed circuit board, it is required to have high solder resistance and electrical insulation. In particular, recently, the density of printed circuit boards has been progressing, and the number of circuits has become a line ΙΟμιη, a space ΙΟμπι, and it is necessary to have ion migration resistance. However, since the photosensitive resin which is a solder resist is a photoreactive acrylate-based compound, the hydrophobicity and the alkali resistance are inferior, and ion migration under high-temperature humidification conditions is liable to occur, so that an inter-circuit is caused. The short road problem. On the other hand, in the case of a thermosetting solder resist, an epoxy resin, a polyacid anhydride having two or more epoxy groups, and an essential component in the sub-5-201106096 have been proposed. A coupling agent further contains an inorganic ion exchanger or a flame retardant, and further contains a composition of a hydrated metal compound (refer to Patent Document 1). However, when an inorganic ion exchanger is used as the alkali-developing solder resist, the inorganic component of the alkali compound developing solution such as sodium carbonate is absorbed in a large amount in the resist, and as a result, ion mobility resistance is obtained. Further, in the case of using an inorganic layered compound as an alkali compound developing type photosensitive resin composition, a photosensitive resin composition characterized by containing and having a carboxyl group has been proposed. a compound having an ethylenically unsaturated group (B) of at least one of an epoxy (meth) acrylate compound (B1) or a carboxyl group-containing (meth) acrylate compound (B2) And an epoxy resin (E), and a photopolymerization initiator (D), and an inorganic layered compound (inorganic lamellar compound) are selected from the group consisting of an amine, a quaternary ammonium salt, an acid anhydride, a polyamine, and a nitrogen-containing compound. An intercalation compound of at least one thermal polymerization catalyst in which a ring compound or an organometallic compound is grouped (refer to Patent Document 2). Such a photosensitive resin composition is intended to cause a thermal polymerization catalyst to be inserted into the inorganic layered compound to improve the storage stability of the solder resist, but the effect of electrical insulation is not clear. When the polymerization catalyst is inserted into the inorganic layered compound, it is generally considered that the heat hardening reaction of the solder resist becomes extremely low and is effective for storage stability, but conversely, since the reaction is difficult to complete (-6-201106096 complation) Therefore, the insulation resistance of the obtained hardened coating film becomes low, so that there is a possibility that ion migration easily occurs. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. 2006-229127 (Patent Application) [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-195486 (Application No.) [Problems to be Solved by the Invention] The present invention has been made in view of the above-described prior art, and its main object is to provide a dry coating film which is excellent in finger-drying property, solder heat resistance, electroless gold plating resistance, and electrical It is excellent in insulating properties, and the like, and is particularly a photosensitive resin composition capable of forming a hard coating film such as a solder resist which prevents ion migration in a fine pitch circuit. Further, an object of the present invention is to provide a dry film and a cured product which are excellent in various properties as described above as a result of using such a photosensitive resin composition, and a solder resist formed by using the dry film or cured product. A hard coated film printed circuit board. [Means for Solving the Problem] If the present invention is used to achieve the above object, a photosensitive resin composition containing a carboxyl group-containing resin (B) and a photopolymerization primer 201106096 hair agent (D) base can be provided. A photosensitive photosensitive resin composition characterized by further comprising a lamellar double hydroxide (A). It is preferred to further contain the compound (C) having an ethylenically unsaturated group. When a thermosetting component (E) is further contained in a suitable state, it can be used as a photocurable thermosetting resin composition. In other suitable states, a colorant is further included. In the appropriate state, the layered double hydroxide (A) may be a compound represented by the following general structural formula (I). [M1+M3+(OH)][An_*mH2〇] (I) lX X 2 X/n , where M2 + represents Mg2+, Fe2+, Zn2+, Ca2+, Li2+, Ni2 + , (:o2+ a divalent metal cation such as Cu2+, M3+ represents a trivalent metal cation such as Al3+, Fe3+, or Mn3+, An_ represents an anion of ri, and a lower leg of each element and atomic group indicates a ratio of each element and atomic group. X is 〇<XS〇.33, m2〇.m although it is 20, it becomes large due to dehydration. In particular, in the above general structural formula (I), the divalent metal cation M2 + The hydrotalcite type compound which is composed of Mg2+ and a trivalent metal cation M3 + as Al3+ and an anion An_ as C〇32· contains such a photosensitive resin composition, particularly containing thermosetting property. The photocurable and thermosetting resin composition of the component (E) is suitable for the tlrnl-species 1 before the end of the tree-like light perception. The supply-forming-ft-shaped agent can be soldered. The board is made of a road, such as a brush, and the composition is coated with a composition of 201106096 and dried to form a dry film, or The photosensitive resin composition or a cured product obtained by applying the photosensitive resin composition to a carrier film and drying the obtained dry film to be photocured or thermally cured, in particular, photohardening on copper The obtained cured product or a cured product obtained by photohardening the image into a pattern or thermally hardened, and according to the present invention, a printed circuit board having the cured product described above can also be provided. The photosensitive resin composition of the present invention is a photosensitive resin composition containing a carboxyl group-containing resin (B) and a photopolymerization initiator (D), and further contains a layered double hydroxide (A). In particular, it contains a hydrotalcite and hydrotalcite-type compound having a structural formula represented by the above general formula (1), and can form a dry coating film with excellent dryness to the touch, solder heat resistance, electroless gold plating resistance, electrical insulation. a hard coating film having high ion mobility resistance at the time of high temperature humidification, and further, a resin containing a carboxyl group (B) together with the above layered double hydroxide (A) The obtained photosensitive resin composition can be developed by using an aqueous solution of an alkali compound. Therefore, the photosensitive resin composition of the present invention can be suitably applied to a hard coating film such as a solder resist of a printed circuit board or a flexible printed circuit board. [Preferred Embodiment of the Invention] As described above, the photosensitive resin composition of the present invention is characterized by 'containing a carboxyl group-containing resin (B) (a carboxyl group-containing photosensitive resin (B-1), or -9 - 201106096 In a photosensitive resin composition of a non-photosensitive carboxyl group (B-2) combined with a compound (c) having an ethylenically unsaturated group, and a photopolymerization initiator (D) Further, a layered double hydroxide (A) is used, and in particular, a compound which can be represented by the above general formula (Π) is used. As a result of investigation by the inventors of the present invention, it has been found that when a layered double hydroxide (Α) is contained, particularly a compound represented by the above formula (1), the dried coating film of the obtained photosensitive resin composition is obtained. It is excellent in the dryness of the touch, and the case where the hardened film is less contained in the above-mentioned layered double hydroxide (A) under high-temperature humidification conditions is a fact that the occurrence of ion migration can be suppressed for a long period of time. This is conceivable to be derived from the fact that the layered double hydroxide (A) described above can function as an anion exchanger under acidic conditions. That is, it is generally known that in a copper circuit under high temperature humidification conditions, the anode becomes acidic and the cathode becomes alkaline due to application of a voltage. And 'it is conceivable that an anion such as a chloride ion is attracted by the anode, and the layered double hydroxide (A) having anion exchange under acidic conditions is a halogen ion which is a cause of ion migration very efficiently. In particular, it is a phenomenon in which chlorine ions are taken into the structure, and thus ion migration can be suppressed for a long period of time. Such a phenomenon is an inefficient effect that other ion exchangers cannot have. Further, it is conceivable that the layered double hydroxide (A) 'in particular, as an anion having c〇32-, even in In the development process using an alkali compound imaging solution such as sodium carbonate, it is still not possible to obtain a stable effect under ion exchange of an anion (for example, C〇32·) of an alkali compound developing solution. This phenomenon is a particularly excellent effect of other ion exchangers -10- 201106096. In the case of applying a photosensitive resin composition to a substrate or the like, organic bentonite or montmorillonite may be used for the purpose of suppressing the occurrence of a shear drop. The case of a layered inorganic compound. However, it is generally known that such compounds have an adverse effect on electrical characteristics. On the other hand, in the composition of the layered double hydroxide (Α) such as the hydrotalcite compound of the present invention, in addition to the remarkable improvement in electrical characteristics, the enthalpy can improve the thixotropy to control The effect of multiplication of the occurrence of sag when the photosensitive resin composition is applied to a substrate or the like. Hydrotalcite and hydrotalcite-type compounds, one of the naturally occurring clay minerals, for example, a base layer that is positively charged (Mgl-XA1X(0H)2)X + and a negative intermediate layer (C03) x/2 · mH20] χ · The layered inorganic compound. Most of the divalent and trivalent metals have the same layered structure as the above, and the general structural formula is the above formula (〇 indicates that the hydrotalcite and the hydrotalcite-type compound are present in such a compound, and have an anion exchange ability. (anion exchanging capacity) or thermal decomposition / rehydration (thermal de co mpositi ο η - r eh ydrati ο η ), other inorganic layered compounds such as microcrystalline kaolinite can not have several characteristics, but the polymerization Suitable examples of the material are not common. For the specific example of the layered double hydroxide (Α), Indigirite Mg2Al2 ((C03) 4 ( 〇H ) 2] · 15H20,

Fe2 + 4A12〔 （ OH ) 12C03〕 · 3 Η 2 〇、Qu i n t i ni t e M g4 A12 ( -11 - 201106096 OH) 12C03 · H20、Mariasseite (水鎂銘石）Mg6Al2〔（ OH ) 16C03〕. 4H20、SjOegrenite (水鎂鐵石）Mg6Fe3 + 2 〔（OH) 16〇〇3 ] · 4H2〇、Zaccagnaite Zn4 Al2 ( CO3 )( OH) 12 · 3H2〇、Desautelsite Mg6Mn3 + 2〔 （ OH) 16CO3〕 • 4H2〇、Hydrotalcite (水滑石）Mg6Al2〔 （ OH) i6C03〕 • 4H20 ' Pyroaurite (鱗鎂鐵礦）Mg6Fe3 + 2〔 （ OH) i6C03 〕· 4H20、Reevesite Ni6Fe3 + 2〔 ( OH ) 16C03 ) · 4H20、Fe2 + 4A12[ ( OH ) 12C03 ] · 3 Η 2 〇, Qu inti ni te M g4 A12 ( -11 - 201106096 OH) 12C03 · H20, Mariasseite (Mgite Mingshi) Mg6Al2[( OH ) 16C03]. 4H20, SjOegrenite (Mgite) Mg6Fe3 + 2 [(OH) 16〇〇3 ] · 4H2〇, Zaccagnaite Zn4 Al2 (CO3 )( OH) 12 · 3H2〇, Desautelsite Mg6Mn3 + 2[ ( OH) 16CO3] • 4H2〇, Hydrotalcite (Water talc) Mg6Al2[ ( OH) i6C03] • 4H20 ' Pyroaurite (Grainite) Mg6Fe3 + 2[ ( OH) i6C03 〕 · 4H20, Reevesite Ni6Fe3 + 2[ ( OH ) 16C03 ) · 4H20,

Stichtite (鉻鱗鎂礦）Mg6Cr2〔 （ OH ) 16C03〕· 4H20、Stichtite (chromium porphyrite) Mg6Cr2[ ( OH ) 16C03] · 4H20,

Takovite Ni6Al2〔 （ OH) 16C03〕· 4H20 等，而可以單獨 或組合2種以上之方式使用。 又，合成水滑石類的市售品而言，可舉：協和化學工 業（股）製；阿爾卡麥撒、DHT-4A、協和特500、協和特 1000、堺化學（股）STABIACE 系歹ϋ 的 ΗΤ-1、ΗΤ-7、ΗΤ-Ρ等。 特佳者爲合成水滑石類，而平均粒徑較佳爲2μπι以下 ，更佳爲1 μπι以下者。又，此等水滑石類，可直接以水合 物的狀態使用，或燒成後亦可以無水物的狀態使用。 前述層狀雙氫氧化合物（Α)之適當的調配量，係對 後述之含羧基之樹脂（Β ) 1 00質量份，爲1至50重量份 ，較佳爲2至50質量份，更佳爲5至40質量份，如前述 層狀雙氫氧化合物（A )的調配量較上述範圍爲多時，則 組成物的黏度及搖變性會過高，而有印刷性降低，硬化物 變脆之情形之故不宜。另一方面，如在1質量份以下時， 則會損及耐離子遷移效果之故不宜。 -12- 201106096 依照本發明而將調配前述層狀雙氫氧化合物（A)之 組成物，係含有鹼顯像性的感光性樹脂組成物，亦即含羧 基之感光性樹脂（B-1 )、或經與具有乙烯性不飽和基之 化合物（C )組合之非感光性的含羧基之樹脂（B-2 )之同 時，含有光聚合引發劑（D)之組成物，或再含有熱硬化 成分（E)、例如於後述般之分子中具有2個以上的環狀 酸基及/或環狀硫醚基之熱硬化性成分（E)之光硬化性熱 硬化性樹脂組成物。 前述含羧基之樹脂（B)而言，可使用以賦與鹼顯像 性爲目的而分子中具有羧基之在來周知的各種含羧基之樹 月旨。從光硬化性或耐顯像性之方面來看，特佳爲分子中具 有乙烯性不飽和雙鍵之含羧基之感光性樹脂（B-1)。並 且’該不飽和雙鍵較佳爲丙烯酸或者甲基丙烯酸或源自其 等衍生物者。再者，在僅使用不具有乙烯性不飽和雙鍵之 含羧基之樹脂（B-2 )之情形，如欲使作成光硬化性時， 則需要倂用於後述之分子中具有2個以上的乙烯性不飽和 基之化合物（C )，亦即光聚合性單體。 含羧基之樹脂（B)的具體例而言，很適用使用如下 述所列舉之化合物（低聚物及聚合物均可）。 - (1)由（甲基）丙烯酸等不飽和羧酸、與苯乙烯、 α -甲基苯乙烯、低級烷基（甲基）丙烯酸酯、異丁烯等的 酯酯 酸酸 〇m氰 旨異異 樹二二 之族的 基肪等 羧脂醋 含枝酸 之分氰 得、異 所酯二 合酸族 聚氰香 共異芳 的二、 物族醋 合力酸 化Z氰 之SS異 基}二 和2 式 飽 C 環 不脂 含、 -13- 201106096Takovite Ni6Al2[(OH)16C03]·4H20, etc., may be used singly or in combination of two or more. In addition, commercially available products of synthetic hydrotalcites include: Concord Chemical Industry Co., Ltd.; Alkamasa, DHT-4A, Concord 500, Concord 1000, and Chemicals (STA) STABIACE system ΗΤ-1, ΗΤ-7, ΗΤ-Ρ, etc. Particularly preferred are synthetic hydrotalcites, and the average particle diameter is preferably 2 μm or less, more preferably 1 μπι or less. Further, these hydrotalcites may be used as they are in the form of a hydrate or may be used in the form of an anhydrate after firing. The amount of the above-mentioned layered double hydroxide (Α) is preferably from 1 to 50 parts by weight, preferably from 2 to 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (Β) described later. When the amount of the layered double hydroxide (A) is more than the above range, the viscosity and the shake of the composition are too high, and the printability is lowered, and the hardened material becomes brittle. The situation is not appropriate. On the other hand, when it is 1 part by mass or less, the ion migration resistance is impaired. -12-201106096 The composition of the layered double hydroxide (A) is formulated according to the present invention, and is a photosensitive resin composition containing an alkali-developing property, that is, a carboxyl group-containing photosensitive resin (B-1) Or a non-photosensitive carboxyl group-containing resin (B-2) in combination with the compound (C) having an ethylenically unsaturated group, and a composition containing the photopolymerization initiator (D), or further containing thermosetting The component (E), for example, a photocurable thermosetting resin composition having a thermosetting component (E) having two or more cyclic acid groups and/or a cyclic thioether group in a molecule as described below. In the carboxyl group-containing resin (B), various carboxyl group-containing trees known to have a carboxyl group in the molecule for the purpose of imparting alkali developability can be used. From the viewpoint of photocurability or development resistance, a carboxyl group-containing photosensitive resin (B-1) having an ethylenically unsaturated double bond in the molecule is particularly preferred. And the unsaturated double bond is preferably acrylic acid or methacrylic acid or a derivative derived therefrom. In the case where only the carboxyl group-containing resin (B-2) having no ethylenic unsaturated double bond is used, if it is intended to be photocurable, it is necessary to use it in two or more molecules to be described later. The ethylenically unsaturated group compound (C), that is, a photopolymerizable monomer. As a specific example of the carboxyl group-containing resin (B), the compounds (both oligomers and polymers) exemplified below can be suitably used. - (1) an unsaturated carboxylic acid such as (meth)acrylic acid, or an ester ester of styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene The carboxy fat vinegar of the genus of the tree and the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus of the genus 2 type full C ring non-fat, -13- 201106096

元醇化合物及聚碳酸酯系多元醇、聚醚系多元醇、聚 多元醇、聚烯烴系多元醇、丙烯基系多元醇、雙酚A 化烷烯加成物二元醇，具有酚性羥基及醇性羥基之化 等的二元醇化合物的附加成反應（polyaddition reacti 所得之含羧基之聚胺基甲酸酯。 (3)對因脂肪族二異氰酸酯、分枝脂肪族二異 酯、脂環式二異氛酸酯、芳香族二異氰酸酯等的二異 酯化合物、與聚碳酸酯系多元醇、聚醚系多元醇、聚 多元醇、聚烯烴系多元醇、丙烯基系多元醇、雙酚A 化烷烯加成物二元醇、具有酚性羥基及醇性羥基之化 等的二元醇化合物的附加成反應所得之聚胺基甲酸酯 的末端使酸酐進行反應所成之末端含羧基之聚胺基甲 樹脂。 (4) 因二異氰酸酯、與雙酚A型環氧樹脂、.加 酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧 '雙二甲苯酚型環氧樹脂、雙酚型環氧樹脂等的2官 氧樹脂的（甲基）丙烯酸酯或者其部分酸酐改性物、 基之二元醇化合物及二元醇化合物的附加成反應所得 羧基之感光性聚胺基甲酸酯樹脂。 (5) 於上述（2)或（4)的樹脂的合成中，於 烷基（甲基）丙烯酸酯等的分子中添加具有1個羥基 個以上的（甲基）丙烯醯基之化合並經末端（甲基） 基化之含羧基之聚胺基甲酸酯樹脂。 之二 酯系 系氧 合物 on ) 氰酸 氰酸 酯系 系氧 合物 樹脂 酸酯 氫雙 樹脂 能環 含羧 之含 羥基 及1 丙烯 -14- 201106096 (6)於上述（2)或（4)的樹脂之合成中，添加異 佛爾酮二異氰酸酯與季戊四醇三丙烯酸酯的等莫耳反應物 (equimolar reactant)等，於分子中具有1個異氰酸酯基 及1個以上的（甲基）丙烯醯基之化合物，經末端（甲基 )丙烯基化之含羧基之聚胺基甲酸酯樹脂。 (7 )於如後述之2官能或以上之多官能（固態）環 氧樹脂中，使（甲基）丙烯酸進行反應而經對存在於支鏈 上之羥基加成鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰 苯二甲酸酐等的2元酸酐之含羧基之感光性樹脂。 (8 )於經使如後述.之2官能（固態）環氧樹脂的羥 基，再使用表氯醇（epichlorohydrin)加以環氧化之多官 能環氧樹脂中使（甲基）丙烯酸進行反應，並經對所生成 之羥基加成2元酸酐之含羧基之感光性樹脂。 (9)於如酚醛清漆環氧樹脂（novolack )般之多官能 苯酚化合物上加成如氧化乙烯般的環狀醚，如丙烯碳酸酯 般的環狀碳酸酯，並將所得羥基，使用（甲基）丙烯酸加 以部分酯化，而經對餘部的羥基進行多元酸酐反應之含羥 基之感光性樹脂。 (1 〇 )對上述（1 )至（9 )的樹脂中再加成如縮水甘 油基（甲基）丙烯酸酯、α-甲基縮水甘油基（甲基）丙烯 酸酯等在分子中具有1個環氧基及1個以上的（甲基）丙 烯醯基之化合物所成之含羧基之感光性樹脂》 此等含羧基之樹脂（Β )，並不限定於前述所列舉者 而均可使用，可以單獨1種或混合複數種之方式使用。 -15- 201106096 再者，本說明書中，（甲基）丙烯酸酯，係總稱丙烯 酸酯、甲基丙烯酸酯以及此等的混合物之用語，就其他類 似的表現亦爲同樣。 前述含羧基之樹脂（B)之中，不以環氧樹脂作爲起 始原料（starting materials)之前述（1) 、（2) 、（3) 、（5 )以及（9 )的含羧基之樹脂係氯離子不純物極少者 ，惟發現如依照本發明而添加層狀雙氫氧化合物（A )， 則電氣特性會更加改善之事實。此乃可設想爲層狀雙氫氧 化合物不僅作爲陰離子交換劑，尙有能使酸成分穩定化之 效果所致。又，以環氧樹脂作爲起始原料之含羧基之樹脂 ，例如於前述（7 )的含羧基之感光性樹脂中加成縮水甘 油基（甲基）丙烯酸酯所成含羧基之感光性樹脂（相當於 前述（7) + (10))，係較作爲其起始原料之含羧基之感 光性樹脂（7 )爲氯離子不純物多，惟如依照本發明而倂 用層狀雙氫氧化合物（A )時，則能確認較作爲起始原料 之含有含羧基之感光性樹脂（7)及層狀雙氫氧化合物（A )之組成物爲能飛躍性的電氣特性之改善之事實。此種事 實與爲未能預測之效果。因而，更有效果的含羧基之樹脂 (B )，係前述含羧基之樹脂之中不以（1) 、（2) 、（3 )以及（9 )中記載的環氧樹脂作爲起始原料之含羧基之 樹脂及使用（5 ) 、（ 6 )所得之改性物、以及對從前述（ 1)至（9)爲止的含羧基之樹脂實施如（10)般的改性之 化合物。 由於如上述之含羧基之樹脂（B)，係於架構聚合物 -16- 201106096 (back bone polymer)的支鏈上具有多數的游離之駿基之 故，能實施使用稀鹼化合物水溶液之顯像。 又，前述含羧基之樹脂（B)的酸値，爲在40至 200mgKOH/g的範圍，更佳爲在45至120mgKOH/g的範圍 。如含羧基之樹脂的酸値在40mgKOH/g以下時，則鹼化 合物顯像將成困難，另一方面，如在200mgKOH/g以上時 ，則會進展因顯像液所引起之曝光部的溶解之故，線會過 度消瘦，有時曝光部與未曝光部的分別之下被顯像液所溶 解剝離，結果正常的光阻圖型（resit pattern)的描畫（ writing)將成爲困難之故不宜。 又，上述含羧基之樹脂（B)的重量平均分子量，雖 因樹脂骨架而有所不同，一般較佳爲在2,000至150,000 、更佳爲在5,000至1 00,000的範圍者。如重量平均分子 量在2,0 00以下時，則可能tack free (指觸乾燥）性能會 劣差，曝光後之塗膜之耐濕性差，可能在顯像時發生膜減 極（membrane diminution)，以致解相度（resolutino) 大爲劣差。另一方面，如重量平均分子量在150,000以上 時，則可能顯像性顯著惡化，而儲存穩定性劣差。 此種含羧基之樹脂（B )的適當的調配量，在全組成 物中爲在20至80質量％、較佳爲在30至60質量％的範 圍。如含羧基之樹脂（B)的調配量較上述範圍爲少時， 則由於被膜強度會降低之故不宜。另一方面，如較上述範 圍爲多時，則由於組成物的黏度增高、或塗佈性等降低之 故不宜。 -17- 201106096 用於本發明之感光性樹脂組成物中之分子中具有2個 以上之乙烯性不飽和基之化合物（C )，係利用活性能量 射線照射（active energy ray irradiation)而使其光硬化 (photohardening)，以使前述含羧基之樹脂（B )在鹼化 合物水溶液中成爲不溶化或對不溶化有助益者。此種化合 物而言，可例舉：乙二醇、甲氧四乙二醇、聚乙二醇、丙 二醇等甘醇的二丙烯酸酯類；己二醇、三羥甲基丙烷、季 戊四醇、二季戊四醇、參羥基乙基異三聚氰酸酯等多元醇 或此等氧化烯加成物或者氧化丙烯加成物等多元丙烯酸酯 類；苯氧丙烯酸酯、雙酚A二丙烯酸酯、以及此等的酚類 的氧化乙烯加成物或者氧化丙烯等多元丙烯酸酯類；甘油 二縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水 甘油醚、三縮水甘油基異三聚氰酸酯等縮水甘油醚的多元 丙烯酸酯類；以及三聚氰胺丙烯酸酯、及/或對應於上述 丙烯酸酯之各甲基丙烯酸酯類等，而可以單獨1種或組合 2種以上之方式使用。 再者’可例舉：對甲酚清漆型環氧樹脂等多官能環氧 樹脂’使丙烯酸反應所得環氧基丙烯酸酯、或再對其環氧 基丙烯酸酯的羥基，使季戊四醇三丙烯酸酯等的羥基丙烯 酸酯與異佛爾酮二異氰酸酯等的二異氰酸酯的半胺基甲酸 酯（half urethane )化合物反應所得環氧基胺基甲酸酯丙 烯酸酯化合物等。此等環氧基丙烯酸酯系樹脂，可在不致 於降低指觸乾燥性之下，提升光硬化性。 此等於分子中具有乙燃性不飽和基2個以上之化合物 -18- 201106096 (C)的適當的調配量，係對前述含羧基之樹脂（B) 100 質量份，爲100質量份以下，更佳爲5至70重量份。如 前述調配量爲5質量份以下，則光硬化性會降低，並因活 化能量射線照射後的鹼化合物顯像而致使圖型構成（ patterning )成爲困難之故不宜。另一方面，如爲1〇〇質 量份以上時，則對鹼化合物水溶液之溶解性會降低而致使 塗膜變脆之故不宜。 光聚合引發劑（D)而言，較佳爲使用選自具有可以 下述一般式（Π)表示之聘酯（oxime ester)系光聚合引 發劑（D1) ’具有可以下述一般式（III )表示之基之α- 胺基乙醯苯系光聚合引發劑（D2)、及/或具有可以下述 式（IV)表不之基之醯基氧化滕系光聚合引發劑（〇3)所 成群之1種以上的光聚合引發劑。 【化2】 ——C=N-〇—C—R2a phenolic hydroxyl group, a polycarbonate polyol, a polyether polyol, a polyhydric alcohol, a polyolefin polyol, a propylene polyol, a bisphenol A alkene adduct diol, and a phenolic hydroxyl group And an additional reaction of a diol compound such as an alcoholic hydroxyl group (a carboxyl group-containing polyurethane obtained by polyaddition reacti. (3) A pair of aliphatic diisocyanate, branched aliphatic diisoester, fat a diisoester compound such as a cyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, a polypolyol, a polyolefin polyol, a propylene polyol, and a double An end of a polyphenolic ester obtained by an additional reaction of a phenol A-alkylene adduct diol, a phenolic hydroxyl group, and an alcoholic hydroxyl group, and an acid anhydride is reacted at the end Carboxyl group-containing polyamine-based resin (4) Diisocyanate, bisphenol A type epoxy resin, phenolic A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy 'double Dioxin type epoxy resin, bisphenol type epoxy resin, etc. (meth) acrylate or a partial acid anhydride modified product thereof, a diol compound of a base, and a photosensitive polyurethane resin obtained by addition of a carboxyl group obtained by a reaction of the diol compound. (5) In the above (2) In the synthesis of the resin of (4), a (meth)acryloyl group having one or more hydroxyl groups is added to a molecule such as an alkyl (meth) acrylate, and a terminal (methyl) group is added thereto. a carboxyl group-containing polyurethane resin. The diester system oxygenate on) Cyanate cyanate ester oxygenate resin ester hydrogen double resin can contain a carboxyl group containing a hydroxyl group and 1 propylene-14- 201106096 (6) In the synthesis of the resin of the above (2) or (4), an equimolar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added, and one isocyanate is contained in the molecule. A carboxyl group-containing polyurethane resin having a terminal (meth) acrylylated terminal compound and one or more (meth) acrylonitrile groups. (7) In a polyfunctional (solid) epoxy resin having a bifunctional or higher functionality as described later, (meth)acrylic acid is reacted to form phthalic anhydride, tetrahydrogen by addition of a hydroxyl group present on the branch. A carboxyl group-containing photosensitive resin of a dibasic acid anhydride such as phthalic anhydride or hexahydrophthalic anhydride. (8) reacting (meth)acrylic acid with a hydroxyl group of a bifunctional (solid) epoxy resin as described later, and then using an epichlorohydrin epoxidized polyfunctional epoxy resin, and A carboxyl group-containing photosensitive resin is added to the produced hydroxyl group to form a dibasic acid anhydride. (9) adding a cyclic ether such as ethylene oxide to a polyfunctional phenol compound such as a novolack epoxy resin, such as a propylene carbonate-like cyclic carbonate, and using the obtained hydroxyl group (A) A hydroxyl group-containing photosensitive resin which is partially esterified with acrylic acid and subjected to a polybasic acid anhydride reaction to a hydroxyl group of the remainder. (1 〇) Further addition of the resin of the above (1) to (9) such as glycidyl (meth) acrylate or α-methyl glycidyl (meth) acrylate has one in the molecule. The carboxyl group-containing photosensitive resin formed by the epoxy group and the compound of one or more (meth)acryl fluorenyl groups. The carboxyl group-containing resin (Β) is not limited to the above-mentioned ones and can be used. It can be used alone or in combination of plural kinds. -15- 201106096 In addition, in the present specification, the term "(meth)acrylate", collectively referred to as acrylate, methacrylate, and the like, is similar to other similar expressions. Among the above carboxyl group-containing resins (B), the carboxyl group-containing resins of the above (1), (2), (3), (5) and (9) which do not use an epoxy resin as starting materials (starting materials) There are few chloride ion impurities, but it has been found that the addition of the layered double hydroxide (A) according to the present invention improves the electrical characteristics. It is conceivable that the layered dihydrogen oxide is not only used as an anion exchanger but also has an effect of stabilizing the acid component. Further, a carboxyl group-containing resin using an epoxy resin as a starting material, for example, a carboxyl group-containing photosensitive resin obtained by adding a glycidyl group (meth) acrylate to the carboxyl group-containing photosensitive resin of the above (7) Corresponding to the above (7) + (10)), the carboxyl group-containing photosensitive resin (7) as a starting material thereof is more than a chloride ion impurity, but a layered double hydroxide (such as a layered double hydroxide is used according to the present invention) In the case of A), it can be confirmed that the composition containing the carboxyl group-containing photosensitive resin (7) and the layered double hydroxide (A) as a starting material is an improvement in the electrical characteristics which are capable of flying. Such facts are unpredictable effects. Therefore, the more effective carboxyl group-containing resin (B) is one in which the epoxy resin described in (1), (2), (3), and (9) is not used as a starting material among the carboxyl group-containing resins. The carboxyl group-containing resin and the modified product obtained by using the above (5) and (6), and the compound modified as described in (10) on the carboxyl group-containing resin from the above (1) to (9). Since the carboxyl group-containing resin (B) as described above has a large number of free radicals on the branch of the framework polymer-16-201106096 (back bone polymer), development using an aqueous solution of a dilute alkali compound can be carried out. . Further, the acid group of the carboxyl group-containing resin (B) is in the range of 40 to 200 mgKOH/g, more preferably 45 to 120 mgKOH/g. When the acid hydrazine of the carboxyl group-containing resin is 40 mgKOH/g or less, the alkali compound development becomes difficult. On the other hand, if it is 200 mgKOH/g or more, the dissolution of the exposed portion due to the developing solution progresses. Therefore, the line will be excessively thin, and sometimes the exposed portion and the unexposed portion are dissolved and peeled off by the developing liquid, and as a result, the writing of the normal resist pattern will become difficult. . Further, the weight average molecular weight of the carboxyl group-containing resin (B) varies depending on the resin skeleton, and is usually preferably from 2,000 to 150,000, more preferably from 5,000 to 1,000,000. If the weight average molecular weight is less than 2,00, the tack free performance may be inferior, and the moisture resistance of the coating film after exposure may be poor, and a membrane diminution may occur during development. So that the degree of dissolving (resolutino) is greatly worse. On the other hand, when the weight average molecular weight is 150,000 or more, the developability is remarkably deteriorated, and the storage stability is inferior. The appropriate amount of such a carboxyl group-containing resin (B) is in the range of 20 to 80% by mass, preferably 30 to 60% by mass in the total composition. When the amount of the carboxyl group-containing resin (B) is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when the amount is more than the above range, the viscosity of the composition is increased, or the coatability or the like is lowered. -17-201106096 The compound (C) having two or more ethylenically unsaturated groups in the molecule in the photosensitive resin composition of the present invention is made light by active energy ray irradiation. It is photohardening to make the carboxyl group-containing resin (B) insoluble or insoluble in an aqueous alkali compound solution. Such a compound may, for example, be a diacrylate of glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol; hexanediol, trimethylolpropane, pentaerythritol or dipentaerythritol; a polyhydric alcohol such as hydroxyethyl isomeric cyanurate or a polyacrylate such as an alkylene oxide adduct or a propylene oxide adduct; phenoxy acrylate, bisphenol A diacrylate, and the like a phenolic ethylene oxide adduct or a polybasic acrylate such as propylene oxide; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. The polyacrylates of the glycidyl ethers, the melamine acrylates, and/or the methacrylates corresponding to the acrylates, and the like may be used alone or in combination of two or more. Further, 'exemplified by a polyfunctional epoxy resin such as a p-cresol varnish-type epoxy resin, an epoxy acrylate obtained by reacting acrylic acid, or a hydroxyl group of the epoxy acrylate thereof, such as pentaerythritol triacrylate, etc. An epoxy group urethane acrylate compound obtained by reacting a hydroxy acrylate with a half urethane compound of a diisocyanate such as isophorone diisocyanate. These epoxy acrylate-based resins can improve photocurability without impairing finger-drying properties. This is equivalent to an appropriate amount of the compound -18-201106096 (C) having two or more flammable unsaturated groups in the molecule, and is 100 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (B). It is preferably 5 to 70 parts by weight. When the amount of the compound is 5 parts by mass or less, the photocurability is lowered, and the patterning of the alkali compound after the activation of the energy ray is difficult, which makes the patterning difficult. On the other hand, when the amount is more than 1 part by mass, the solubility in the aqueous solution of the alkali compound is lowered to cause the coating film to become brittle, which is not preferable. In the case of the photopolymerization initiator (D), it is preferred to use an oxime ester-based photopolymerization initiator (D1) which has the following general formula (Π) and has the following general formula (III) The α-aminoethylbenzene-based photopolymerization initiator (D2) represented by the formula, and/or the fluorenyl-based photopolymerization initiator having a base represented by the following formula (IV) (〇3) One or more kinds of photopolymerization initiators in a group. [Chemical 2] ——C=N-〇—C—R2

(m)(m)

R RR R

8 / p—c—II o (17) 式中’ R1表示氫原子、苯基（可被碳數！至$的烷基 、苯基、或者鹵素原子所取代）、碳數1至20的院基（ -19 - 201106096 可被1個以上之羥基所取代，亦可於烷基鏈中間具有1個 以上的氧原子）、碳數5至8的環烷基、碳數2至20的 鏈院醯基或苄醯基（可被碳數1至6的烷基或者苯基所取 代）， R2表示苯基（可被碳數1至6的烷基，苯基或者鹵素 原子所取代）、碳數1至20的烷基（可被1個以上的羥 基所取代，亦可於烷基鏈中間具有1個以上的氧原子）、 碳數5至8的環院基、碳數2至20的鏈垸醯基或节醯基 (可被碳數1至6的烷基或者苯基所取代）， R3及R4分別獨立表示碳數1至12的烷基或芳基烷基 R5及R6係分別獨立表示氣原子，碳數1至6之院基 或2結合之環狀烷醚基， R7及R8分別獨立表示碳數1至ίο的直鏈狀或分枝狀 的烷基、環己基、環戊基、芳基、或鹵素原子、烷基或者 被烷氧基所取代之芳基，但，R7及R8的一方，可表示R_ C(=0)-基（在此，R爲碳數1至20的烴基）。 具有可以前述一般式（II)表示之照醋系光聚合引發 劑而言，較佳爲可舉：可以下述式（V)表示之2-(乙醯 氧亞胺基甲基）噻曜（thioxanthene) -9 -酮，可以下述― 般式（VI )表示之化合物，以及可以下述一般式（VI〇 表示之化合物。 -20- 201106096 化8 / p-c-II o (17) where R1 represents a hydrogen atom, a phenyl group (which can be substituted by a carbon number! to an alkyl group, a phenyl group, or a halogen atom), and a carbon number of 1 to 20 Base ( -19 - 201106096 can be substituted by more than one hydroxyl group, and can have more than one oxygen atom in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, and a chain having 2 to 20 carbon atoms Mercapto or benzhydryl (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R2 represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), carbon a number of 1 to 20 alkyl groups (which may be substituted by one or more hydroxyl groups, or may have one or more oxygen atoms in the middle of the alkyl chain), a ring number of 5 to 8 carbon atoms, and a carbon number of 2 to 20 a sulfhydryl group or a fluorenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group R5 and R6, respectively. Independently represents a gas atom, a carbon number of 1 to 6 or a 2 bonded cyclic alkyl ether group, and R7 and R8 each independently represent a linear or branched alkyl group having a carbon number of 1 to ίο, a cyclohexyl group, and a ring. Pentyl, aryl, or halogen An alkyl group or an aryl group substituted by an alkoxy group, but one of R7 and R8 may represent an R_C(=0)- group (wherein R is a hydrocarbon group having 1 to 20 carbon atoms). The vinegar-based photopolymerization initiator which can be represented by the above formula (II) is preferably 2-(ethoximinoiminomethyl)thiazide which can be represented by the following formula (V). Thioxanthene) -9-ketone, which can be represented by the following formula (VI), and a compound represented by the following general formula (VI〇) -20- 201106096

【化4】 π3c Ic=o - ο H\ / nmmmc \J/[Chemical 4] π3c Ic=o - ο H\ / nmmmc \J/

R9 式中，R9表示氫原子、鹵素原子、碳數1至12的烷 基、環戊基、環己基、苯基、苄基、苄醯基、碳數2至12 的鏈烷醯基、碳數2至12的烷氧羰基（如構成烷氧基之 院基的碳數爲2以上時，則烷基可被1個以上的羥基所取 代，亦可於烷基鏈的中間具有1個以上的氧原子）、或苯 氧羰基， R1<J、R12分別獨立表示苯基（可被碳數1至6的烷基 、苯基或者鹵素原子所取代）'碳數1至20的烷基（可 被1個以上的羥基所取代 '亦可於烷基鏈的中間具有1個 以上的氧原子）、碳數5至8的環院基、碳數2至20的 鍵院醯基或苄醯基（可被碳數1至6的烷基或者苯基所取 代）， -21 - 201106096 R11表示氫原子、苯基（可被碳數]至6的烷基、苯 基或者鹵素原子所取代）、碳數1至20的烷基（可被1 個以上的羥基所取代、亦可於烷基鏈的中間具有1個以上 的氧原子）、碳數5至8的環烷基、碳數2至20的鏈烷 醯基或节酿基（可被碳數〗至6的烷基或者苯基所取代） 〇 【化5】In the formula, R9 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzinyl group, an alkane group having 2 to 12 carbon atoms, and carbon. When the number of carbon atoms of the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, or may be one or more in the middle of the alkyl chain. Oxygen atom), or phenoxycarbonyl, R1 <J, R12 each independently represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) 'alkyl group having 1 to 20 carbon atoms ( It may be substituted by one or more hydroxyl groups 'may have one or more oxygen atoms in the middle of the alkyl chain), a ring-membered group having 5 to 8 carbon atoms, a bond group having 2 to 20 carbon atoms, or benzamidine a group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), -21 - 201106096 R11 represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 6 to 6 carbon atoms, a phenyl group or a halogen atom) An alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups or one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 2 To 20 Alkanoyl or acyl group brewing section (which may be substituted with an alkyl carbon atoms or phenyl〗 to 6) of square [5]

(R14)m (R19)p (VII) 式中，R13、R14以及R19分別獨立表示碳數1至12 的烷基， R15、R16、R17以及r18分別獨立表示氫原子或碳數1 至6的烷基， Μ表示〇、s或NH， m及ρ分別獨立表示〇至5的整數。 前述肟酯系光聚合引發劑之中，更佳爲可以前述—般 式（V)表示之2-(乙醯氧亞胺基甲基）噻噸_9_酮、及可 以式（VI )表示之化合物。市售品而言，可例舉：千葉· 特殊化學品社製的CGI-3 25、伊爾加裘亞〇χΕ01、伊爾加 裘亞ΟΧΕ02、ADEKA社製的Ν-1919等。此等肟酯系光聚 -22- 201106096 合引發劑，可以單獨1種或組合2種以上之方式使用。 具有可以前述一般式（III )表示之基之α-胺基乙醯 苯系光聚合引發劑而言，可例舉：2-甲基-1 -〔 4-(甲基硫 )苯基〕-2-嗎啉代（morpholino)丙_-1，2 -节基-2-二甲 基胺基-1-(4-嗎啉代苯基）-丁烷-1-酮、2-(二甲基胺基 )-2-〔 （ 4-甲基苯基）甲基〕-1-〔 4- ( 4-嗎啉基（ morpholinyl ))苯基〕-1 -丁酮、n，N-二甲基胺基乙醯苯 等。市售品而言，可例舉：千葉•特殊化學品社製的伊爾 加裘亞-907、伊爾加裘亞-369、伊爾加裘亞-3 7 9等。 具有可以前述一般式（IV)表示之基之醯基氧化膦系 光聚合引發劑而言，可例舉：2,4,6-三甲基苄醯基二苯基 氧化膦、雙（2,4,6-三甲基苄醯基）-苯基氧化膦、雙（ 2,6-二甲氧苄醯基）-2,4,4-三甲基-戊基氧化膦等。市售品 而言，可例舉：BASF社製的盧西林TPO、千葉特殊化學 品社製的伊爾加裘亞8 1 9等。 此種光聚合引發劑（D)的適當的調配量，係對前述 含羧基之樹脂（B) 100質量份，爲0.01至30質量份，較 佳爲在0.5至1 5質量份的範圍。如光聚合引發劑（D )在 0.01質量份以下時，則於銅上的光硬化性不足以致塗膜會 剝離，結果耐藥品性等塗膜特性會降低之故不宜。另一方 面’如在3 0質量份以上時，則光聚合引發劑（D )於阻焊 劑塗膜表面的光吸收成爲激烈，以致有深部硬化性降低的 傾向之故不宜。 再者’在具有可以前述式（II)表示之基之肟酯系光 -23- 201106096 聚合引發劑的情形，其調配量，係對前述含羧基之樹脂（ B ) 100質量份，較佳爲在0.01至20質量份，更佳爲在 0.01至5質量份的範圍爲宜。 其他很適合採用於本發明之感光性樹脂組成物之光聚 合引發劑、光引發促進劑（photoinitiation promoter)以 及敏化劑而言，可例舉：苯偶姻（benzoin)化合物、乙醯 苯化合物、蒽醌化合物、噻噸酮（thioxanthone)化合物 、縮酮（ketal)化合物、二苯基酮（benzophenone)化合 物、Pdi酮（xanthone )化合物、以及三級胺化合物等。 如舉示苯偶姻化合物的具體例時，例如，爲苯偶姻、 苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚。 如舉示乙醯苯化合物的具體例時，例如，爲乙醯苯、 2,2-二甲氧-2-苯基乙醯苯、2,2-二乙氧-2-苯基乙醯苯、 1,1-二氯乙醯苯。 如舉示蒽醌化合物的具體例時，例如，爲2-甲基蒽醌 、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌。 如舉示噻噸酮化合物的具體例時，例如，爲2,4-二甲 基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙 基唾囉酮。 如舉示縮酮化合物的具體例時，例如，爲乙醯苯二甲 基縮酮、苄基二甲基縮酮。 如舉示二苯基酮化合物的具體例時，例如，爲二苯基 酮、4-苄醯基苯基硫化物、4-苄醯基-4’-甲基二苯基硫化 物、4-苄醯基-4’-乙基二苯基硫化物、4-苄醯基-4’-丙基二 -24 - 201106096 苯基硫化物。 如舉示三級胺化合物的具體例時，例如，爲乙醇胺化 合物、具有二烷基胺苯構造之化合物，例如，4,4’-二甲基 胺基二苯基酮（日本曹達社製尼素裘亞MABP) 、4,4’-二 乙基胺基二苯基酮（保土谷化學社製EAB)等二烷基胺基 二苯基酮、7-(二乙基胺基）-4-甲基-2H-1-苯并哌喃（ benzopyran) -2 -酮（7-(二乙基胺基）-4 -甲基董草素（ cumarin))等含二烷基胺基之董草素化合物、4-二甲基胺 基安息香酸乙酯（日本化藥社製咖雜裘亞EPA )、2-二甲 基胺基安息香酸乙酯（國際生物合成社製Quantacure (廣 達裘亞）DMB) 、4_二甲基胺基安息香酸（正丁氧）乙基 (國際生物合成社製Quantacure BEA)、對二甲基胺基安 息香酸異胺基乙酯（日本化藥社製咖雅裘亞DMBI )、4-二甲基胺基安息香酸2-乙基己酯（Van Dyk (九達克）社 製EsololC伊索羅）507) 、4,4’-二乙基胺基二苯基酮（ 保土谷化學社製EAB)。 於前述之化合物之中，較佳爲噻噸酮化合物及三級胺 化合物。於本發明之組成物中，從深部硬化性（depth hardening)的方面來看，較佳爲含有噻噸酮化合物，其中 ，較佳爲2,4 -二甲基噻噸酮、2,4 -二乙基噻噸酮、2-氯噻 噸酮、2,4-二異丙基噻噸酮等噻噸酮化合物。 此種噻噸酮化合物的適當的調配量而言，對前述含羧 基之樹脂（B) 100質量份，較佳爲20質量份以下，更佳 爲1 〇質量份以下的比例。如噻噸酮化合物的調配量過多 -25- 201106096 時，則厚膜硬化性（thick film hardening)會降低而導致 製品的成本上升之故不宜。 三級胺化合物而言，較佳爲具有二烷基胺基苯構造之 化合物，其中特佳爲二烷基胺基二苯基酮化合物、最大吸 收波長在350至41 Onm之含烷基胺基之董草素化合物。二 烷基胺基二苯基酮化合物而言，4,4’-乙基胺塞二苯基酮之 毒性低而較佳。最大吸收波長（maximum absorption wavelength)在350至410nm之含二烷基胺基之董草素化 合物，係由於最大吸收波長在紫外線區域之故，除能提供 著色小、且無色透明的感光性組成物之外，尙能提供經採 用著色顏料以反映著色顏料本身的顏色之著色阻焊劑膜。 特別是7-(二乙基胺基）-4-甲基-2H-1-苯并哌喃·2-酮係 能對波長400至41 Onm的雷射光顯示優異的敏化效果之故 爲宜。 此種三級胺化合物的適當的調配量而言，對含前述羧 基之樹脂（B) 100質量份，較佳爲0.1至20質量份，更 佳爲〇 . 1至1 0質量份的比例。如三級胺化合物的調配量 在〇. 1質量份以下時，則可能不能獲得充分的敏化效果。 另一方面，如在20質量份以上時，則於使用三級胺化合 物所得乾燥阻焊劑塗膜表面的光吸收（Photo absorption ) 成爲激烈，而有深部硬化性降低之傾向。 本發明之感光性樹脂組成物中，爲提升敏化度起見’ 可調配作爲鏈轉移劑所周知慣用之N-苯基甘胺酸（phenyl glycine)類、苯氧基乙酸類、硫苯氧基乙酸類、锍基噻唑 •26- 201106096 (mercapto thiazol)等。如舉示鏈轉移劑的具體例時，例 如，爲锍基琥珀酸、毓基乙酸、毓基丙酸、甲硫胺酸（ methionin )、半脫胺酸（crystenine)、鄰疏基苯甲酸（ thiosalicylic acid)以及其衍生物等具有翔基之鏈轉移劑 ;锍基乙醇、巯基丙醇、巯基丁醇、锍基丙二醇、锍基丁 二醇、羥基苯硫醇以及其衍生物等具有羥基之鏈轉移劑； 1-丁烷硫醇'丁基-3-锍基丙酸酯、甲基-3-锍基丙烯酸酯 、2，2-(乙烯二氧）二乙烷硫醇、乙烷硫醇、4-甲基苯硫 醇、十二烷基硫醇（mercaptan )、丙烷硫醇、丁烷硫醇、 戊烷硫醇、1-辛烷硫醇、環戊烷硫醇、環己烷硫醇、硫甘 油、4,4-硫基雙苯硫醇等。 又，多官能性硫醇系化合物而言，雖並不特別加以限 定，惟可例舉：己烷-1,6-二硫醇、癸烷-1,10-二硫醇、二 锍基二乙基醚、二锍基二乙基硫化物等脂肪族硫醇類；伸 茬基二硫醇、4,4’_二毓基二苯基硫化物、1，4-苯二硫醇等 芳香族硫醇類；乙二醇雙（锍基乙酸酯）、聚乙二醇雙（ 毓基乙酸酯）、丙二醇雙（锍基乙酸酯）、甘油參（毓基 乙酸酯）、三羥甲基乙烷參（毓基乙酸酯）、三羥甲基丙 烷參（巯基乙酸酯）、季戊四醇肆（锍基乙酸酯）、二季 戊四醇陸（巯基乙酸酯）等多元醇的聚（毓基乙酸酯）類 :乙二醇雙（3_锍基丙酸酯）、聚乙二醇雙（3 -锍基丙酸 酯）、丙二醇雙（3 -锍基丙酸酯）、甘油參（3 -锍基丙酸 酯）、三羥甲基乙烷參（巯基丙酸酯）、三羥甲基丙烷參 (3-毓基丙酸酯）、季戊四醇肆（3-锍基丙酸酯）、二季 -27- 201106096 戊四醇陸（3 -锍基丙酸酯）等多元醇的聚（3 -锍基丙酸酯 )類；I-4-雙（3-锍基丁氧）丁烷、1，3,5-參（3-锍基丁氧 乙基）-1，3,5-三哄（triazine) -2,4,6(1H，3H，5H)-三酮 、季戊四醇肆（3 -毓基丁酸酯）等聚（锍基丁酸酯）類等 〇 再者，作爲鏈轉移劑發揮作用之具有毓基之雜環化合 物而言，可例舉：1¾基-4-丁內醋（butyrolactone)(別名 :2-疏基-4-丁內醋（butanolide) ) 、2·疏基-4-甲基-4-丁 內酯、2-锍基-4-乙基-4-丁內酯、2-锍基-4-丁硫內酯（ butyrothio lactone) 、2-疏基-4-丁 內醯胺（butyro lactum )、N-甲氧-2-锍基-4-丁內醯胺、N-乙基-2-锍基-4-丁內醯 胺、N-甲基-2-锍基-4-丁內醯胺、N-乙基-2-毓基-4-丁內醯 胺、N- (2-甲氧）乙基-2-锍基-4-丁內醯胺、N- (2-甲氧 )乙基-2-毓基-4-丁內醯胺、2-锍基-5-戊內酯' 2_锍基-5-戊內酿胺、N -甲基-2-疏基-5-戊內醯胺、N -乙基-2 -疏基-5-戊內醯胺、N-(2-甲氧）乙基-2-锍基-5-戊內醯胺、N-( 2-乙氧）乙基-2-毓基-5-戊內醯胺以及2-锍基-6-己內醯胺 等。 作爲不影響感光性樹脂組成物之顯像性而本身爲鏈轉 移劑之具有巯基之雜環化合物，特佳爲毓基苯并噻唑、3 -锍基-4-甲基-4H-1，2,4-***、5-甲基-1，3,4-噻二唑（ thiadiazol) -2-硫醇、1-苯基-5-巯基-1H-四唑。此等鏈轉 移劑，可以單獨1種或倂用2種以上之方式使用。 此等光聚合引發劑、光引發促進劑、敏化劑以及鏈轉 -28- 201106096 移劑’可以單獨1種或作成2種以上的混合物使用。 此種光聚合引發劑、光引發促進劑、敏化劑以及鏈轉 移劑的總量，係對前述含羧基之樹脂（B ) 1 00質量份， 較佳爲成爲3 5質量份以下之範圍。如在3 5質量份以上時 ，則有因光吸收而深部硬化性會降低之傾向。 於本發明之感光性樹脂組成物中，爲賦與耐熱性起見 ’可採用熱硬化性成分（E)。可用於本發明之熱硬化成 分而言’可使用：三聚氰胺樹脂、苯并胍胺樹脂等胺樹脂 、嵌段異氰酸酯化合物、環碳酸酯化合物、多官能環氧化 合物、多官能雜環丁烷（oxetane )化合物、表硫化物（ api sulfide)樹脂、三聚氰胺衍生物、雙馬來醯亞胺、噚 哄（oxazine)化合物、啤Π坐啉（oxazoline)化合物、碳 化二亞胺（carbodiimide )樹脂等周知慣用的熱硬化性樹 脂。特佳爲於分子中具有2個以上的環狀醚基及/或環狀 硫醚基（以下簡稱爲環狀（硫）醚基）之熱硬化性成分（ E ) 〇 此等於分子中具有2個以上的環狀（硫）醚基之熱硬 化性成分（E)，係於分子中具有3、4或5員環的環狀醚 基、或環狀硫醚基的任一方或2種基2個以上之化合物， 可例舉：於分子中至少具有2個以上的環氧基之化合物， 亦即多官能環氧化合物（E-1)，於分子中具有至少2個 以上的氧雜環丁烷基之化合物、亦即多官能氧雜環丁烷化 合物（E-2)，於分子中具有2個以上的硫醚基之化合物 、亦即表硫化物樹脂（E-3)等。 -29- 201106096 前述多官能環氧化合物（E-I)而言，可例舉：曰本 環氧樹脂社製的 jER828、jER834、jERlOOl、jER1004， DIC社製的表克隆840、表克隆850、表克隆1050、表克 隆2055，東都化成社製的伊博東都 yd-011、YD-013、 YD-127 、 YD-128 ，陶氏化學社製的 D.E.R.317 、 D.E.R.331、 D.E.R.661、 D.E.R664，千葉特殊化學品社製 的阿拉爾泰斗 607 1、阿拉爾泰斗 6084、阿拉爾泰斗 GY250、阿拉爾泰斗GY260，住友化學工業社製的須美環 氧 ESA-011、ESA-014、ELA-115、ELA-128，旭化成工業 社製的 A.E.R.330、 A.E.R.331、 A.E.R.661、 A.E.R.664 等 (均爲商品名）的雙酚A型環氧樹脂；日本環氧樹脂社製 的jERYL903，DIC社製的表克隆152、表克隆165，東都 化成社製的伊博東都YDB-400、YDB-500，陶氏化學社製 的D.E.R.542，千葉特殊化學品社製的阿拉爾泰斗8011， 住友化學工業社製的須美環氧ESB-400、ESB-700,旭化 成工業社製的A.E.R.711、A.E.R.714等（均爲商品名）的 溴化環氧樹脂；日本環氧樹脂社製的jER152、jER154, 陶氏化學社製的D.E.N.431、D.E.N.438，大日本油墨化學 工業社製的表克隆N-730、表克隆N-770、表克隆N_865 ，東都化成社製的伊博東都YDCN-701、YDCN-704，千葉 特殊化學品社製的阿拉爾泰斗ECN1235、阿拉爾泰斗 ECN1273、阿拉爾泰斗ECN1299、阿拉爾泰斗XPY307， 日本化學社製的 EPPN-201 ' EOCN-1025、EOCN-1020 ' EOCN-104S、RE-3 06，住友化學工業社製的須美環氧 -30- 201106096 ESCN-195X、ESCN-220，旭化成工業社製的人^上匸!^-2 3 5、ECN-299等（均爲商品名）的酚醛清漆型環氧樹脂 ;DIC社製的表克隆8 3 0，日本環氧樹脂社製jER8 07，東 都化成社製的伊博東都 YDF-170、YDF-175、YDF-2004， 千葉特殊化學品社製的阿拉爾泰斗XPY3 06等（均爲商品 名）的雙酚F型環氧樹脂；東都化成社製的伊博東都ST-2004、 ST-2007、ST-3000 (商品名）等的加氫雙酚A型環 氧樹脂；日本環氧樹脂社製的jER6 04，東都化成社製的 伊博東都 YH-434，千葉特殊化學品社製的阿拉爾泰斗 ΜY720，住友化學工業社製的須美環氧ELM-120等（均爲 商品名）的縮水甘油基胺型環氧樹脂；千葉特殊化學品社 製的阿拉爾泰斗 CY-350 (商品名）等的尿囊素（ hydantoin)型環氧樹脂；黛色爾化學工業社製的色洛其塞 特202 1，千葉特殊化學品社製的阿拉爾泰斗 CY 175、 CY179等（均爲商品名）的脂環式環氧樹脂；日本環氧樹 脂社製的 YL- 9 3 3，陶氏化學社製的T.E.N.、EPPN-501、 EPPN-5 02等（均爲商品名）的三羥基苯基甲烷型環氧樹 脂；日本環氧樹脂社製的YL-6056、YX-4000、YL-6121 ( 均爲商品名）等的聯茬酚（bixyleno.l )型或聯苯酚（ biphenol )型環氧樹脂或其等的混合物；日本化藥社製 EBPS-200，旭電化工業社製 EPX-30，DIC社製的 EXA-1514(商品名）等的雙酚S型環氧樹脂；日本環氧樹脂社 製的jER157S (商品名）等的雙酚A酚醛型環氧樹脂；日 本環氧樹脂社製的jER YL-93 1，千葉特別化學品社製的阿 -31 - 201106096 拉爾泰斗163等（均爲商品名）的四苯酚基乙烷（tetra phenylol ethane)型環氧樹脂；千葉特別化學品社製的阿 拉爾泰斗PT810，日產化學工業社製的TEPIC等（均爲商 品名）的雜環式環氧樹脂；日本油脂社製布鏈瑪D G T等 的二縮水甘油基酞酸樹脂；東都化成社製ZX-1063等的四 縮水甘油基茬酚基乙烷樹脂；新日鐵化學社製ESN-190、 ESN-360，DIC 社製 HP-4032、EXA-4750、EXA-4700 等的 含萘基環氧樹脂；DIC社製HP-7200、HP-7200H等的具有 二環戊二烯骨架之環氧樹脂；日本油脂社製CP-50S ' CP-50M等的縮水甘油基甲基丙烯酸酯共聚物系環氧樹脂；以 及環己基馬來醯亞胺與縮水甘油基甲基丙烯酸酯的共聚合 環氧樹脂；環氧改性的聚丁二烯橡膠衍生物（例如黛色爾 化學工業製PB-3600等）、CTBN改性環氧樹脂（例如東 都化成社製的YR-102、YR-450等）等，惟並限定於此等 。此等環氧樹脂，可以單獨1種或組合2種以上之方式使 用。此等之中，特佳爲酚醛清漆型環氧樹脂、雜環式環氧 樹脂、雙酚A型環氧樹脂或此等的混合物。 前述多官能氧雜環丁烷化合物（E-2)而言，除可例 舉：雙〔（3-甲基-3-氧雜環丁烷基甲基）甲基〕醚、雙〔 3-乙基-3-氧雜環丁烷基甲氧）甲基〕醚、1，4-雙〔（3-甲 基-3-氧雜環丁烷基甲氧）甲基〕苯、I，4-雙〔（3-乙基-3-氧雜環丁烷基甲氧）甲基〕苯、（3-甲基-3-氧雜環丁烷基 )甲基丙烯酸酯、（3-乙基-3-氧雜環丁烷基）甲基丙烯酸 酯、（3-甲基-3-氧雜環丁烷基）甲基甲基丙烯酸酯、（3- •32- 201106096 乙基-3-氧雜環丁烷基）甲基甲基丙烯酸酯或此等的低聚物 或共聚物等的多官能氧雜環丁烷類之外，尙可例舉：與氧 雜環丁烷醇所成之酚醛清漆樹脂、與聚（對羥基苯乙烯） 、蒈基（cardo radical)型雙酣類、杯芳烴（calixarene) 類、杯雷瑣辛芳烴（calix resorcin arene)類、或倍半砂 氧烷（silsesqui oxane)等具有羥基之樹脂所成之醚化物 等。其他，亦可舉：具有氧雜環丁烷環之不飽和單體與烷 基（甲基）丙烯酸酯所成之共聚物等。 前述於分子中具有2個以上的環狀硫醚基之化合物（ E-3 )而言，可例舉：日本環氧樹脂社製的雙酚A型表硫 化物樹脂YL7 000等。又，亦可使用經採用同樣的合成方 法，而將酚醛清漆型環氧樹脂的環氧基的氧原子取代爲硫 原子之表硫化物樹脂等。 前述於分子中具有2個以上的環狀（硫）醚基之熱硬 化性成分（E )的適當的調配量，係對前述含羧基之樹脂 (B )的羧基1當量，能成爲較佳爲0.6至2.5當量、更佳 爲0.8至2.0當量之範圍。如於分子中具有2個以上的環 狀（硫）醚基之熱硬化性成分（E )的調配量爲0.6以下 時，則羧基將殘留於阻焊劑膜上，以致耐熱性、耐鹼性、 電氣絕緣性等會降低之故不宜。另一方面，如爲2.5當量 以上時，則低分子量的環狀（硫）醚基將殘留於乾燥塗膜 上，以致塗膜的強度等會降低之故不宜。 又，作爲熱硬化成分，可添加於1分子中具有2個以 上的異氰酸酯基或嵌段化異氰酸酯基之化合物。此種於】 -33- 201106096 分子中具有2個以上的異氰酸酯基或嵌段化異氰酸酯之化 合物，可例舉：於1分子中具有2個以上的異氰酸酯基之 化合物，亦即聚異氰酸酯化合物，或於1分子中具有2個 以上的嵌段化異氰酸酯基之化合物，亦即嵌段異氰酸酯化 合物等。 前述聚異氰酸酯化合物而言，例如，可採用芳香族聚 異氰酸酯、脂肪族聚異氰酸酯、或脂環式聚異氰酸酯。芳 香族聚異氰酸酯的具體例而言，可例舉：4,4’-二苯基甲烷 二異氰酸酯、2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二 異氰酸酯、萘-1，5-二異氰酸酯、鄰伸茬基二異氰酸酯、間 伸茬基二異氰酸酯以及2,4-甲伸苯基二聚物（dimer)。 脂肪族聚異氰酸酯的具體例而言，可舉：四伸甲基二異氰 酸酯、六伸甲基二異氰酸酯、伸甲基二異氰酸酯、三甲基 六伸甲基二異氰酸酯、4,4-伸甲基雙（環己基異氰酸酯） 以及異佛爾酮二異氰酸酯。脂環式聚異氰酸酯的具體例而 言，可例舉··聯環庚烷三異氰酸酯。以及先前所舉之異氛 酸酯化合物的加成物（adduct )體、縮二脲（biuret )體 以及異三聚氰酸酯（isocyanurate)體。 嵌段異氛酸酯化合物中所含之嵌段化異氰酸酯基，係 異氰酸酯基因與堵劑（blocking agent)之間的反應所保護 而暫時性被惰性化之基。當被加熱爲既定溫度時，其堵劑 將解離（dissociation)而生成異氰酸酯基。 嵌段異氛酸酯化合物而言，可採用異氰酸酯化合物與 異氛酸酯堵劑所成之加成反應生成物。能與堵劑反應之異 -34- 201106096 氰酸酯化合物而言，可舉：異三聚氰酸酯型（ isocyanurate type)、縮二脲型（biuret type)、加成物型 (adduct type)等。此種異氰酸酯化合物而言，例如可採 用：芳香族聚異氰酸酯 '脂肪族聚異氰酸酯或脂環式聚異 氰酸酯。芳香族聚異氰酸酯、脂肪族聚異氰酸酯、以及脂 環式聚異氰酸酯的具體例而言，可舉：如先前所例示之化 合物。 異氰酸酯堵劑而言，可例舉：苯酚、甲苯酚、二甲苯 酚、氯苯酚以及乙基苯酚等酚系堵劑；ε-己內醯胺、5-戊內醯胺、V-丁內醯胺以及Ρ-丙內醯胺等的內醯胺系堵 劑；乙醯乙酸乙酯及乙醯丙酮等的活性伸甲基系堵劑：甲 醇、乙醇、丙醇、丁醇、戊醇、乙二醇-甲基醚、乙二醇-乙基醚、乙二醇-丁基醚、二乙二醇-甲基醚、丙二醇·甲基 醚、苄基醚、乙醇酸甲酯、乙醇酸丁酯、雙丙酮醇、乳酸 甲酯以及乳酸乙酯等的醇系堵劑；甲醛肟、乙醛肟、丙醛 肟' 甲基乙基酮肟、二乙醯一肟、環己烷肟等的肟系堵劑 ;丁硫醇、己硫醇、第三丁硫醇、苯硫酚（thiophenol ) 、甲基苯硫酚、乙基苯硫酚等的硫醇系堵劑；乙醢胺、苯 甲醯胺等的醯胺系堵劑；琥珀醯亞胺及馬來醯亞胺等的醯 亞胺系堵劑；二甲代苯胺（X y 1 i d i n e )、苯胺、丁基胺、 二丁基胺等的胺系堵劑；咪唑、2 -乙基咪唑等的咪唑系堵 劑；伸甲基亞胺及伸丙基亞胺等的亞胺系堵劑等。 嵌段異氰酸酯化合物，可爲市售品，可例舉：須美裘 爾 BL-3175、BL-4165、BL-ll〇〇、BL-1265，第斯莫裘爾 -35- 201106096 TPLS-2957、TPLS-2062、TPLS-2078、TPLS-21 17，第斯 莫沙姆2170、第斯莫沙姆2265 (以上，住友拜爾聚胺酯 社製、商品名）、可樂耐特2512、可樂耐特2513、可樂 耐特2 520 (以上，日本聚胺酯工業社製，商品名）、B-830、 B-815、 B-846 ' B-870、 B-874 > Β·882(三井武田化 學社製，商品名）、ΤΡΑ-Β80Ε、17Β-60ΡΧ、Ε402-Β80Τ( 旭化成化學品社製，商品名）等。在此，須美裘爾81^-3 175、BL-4265係作爲堵劑而採用甲基乙基肟所製得者。 於上述的1分子中具有2個以上的異氰酸酯基或嵌段 化異氰酸酯基之化合物，可以單獨1種或組合2種以上之 方式使用。 此種於1分子中具有2個以上的異氰酸酯基或嵌段化 異氰酸酯基之化合物的適當的調配量，係對前述含羧基之 樹脂（Β ) 1 00質量份，較佳爲1至1 〇〇重量份，更佳爲2 至7 0重量份的比例。如前述調配量爲1質量份以下時， 則不能獲得充分的塗膜的強韌性之故不宜。另一方面，如 爲1 〇〇質量份以上時，則儲存穩定性會降低之故不宜。 再者，其他的熱硬化成分而言，可例舉：三聚氛胺衍 生物、苯并胍胺衍生物等。例如有：羥甲基三聚氰胺化合 物、羥甲基苯并胍胺化合物、羥甲基甘脲（methylol glycol uril )化合物以及羥甲基尿素化合物等。再者，烷 氧甲基化三聚氰胺化合物、烷氧甲基化苯并胍胺化合物、 烷氧甲基化甘脲化合物以及烷氧甲基化尿素化合物，如將 各羥甲基三聚氰胺化合物、羥甲基苯并胍胺化合物、羥甲 -36- 201106096 基甘脲化合物以及羥甲基尿素化合物的羥甲基變換爲烷氧 甲基，即可製得。對此種烷氧甲基的種類而言’並不特別 加以限定，而可作成甲氧甲基、乙氧甲基、丙氧甲基、丁 氧甲基等。特佳爲能保護人體或環境之福爾馬林（ formalin)濃度爲0.2%以下的三聚氰胺衍生物。 此等的市售品而言，可例舉：塞梅爾3 00、該301、 該 3 03、該 3 7 0、該 3 2 5、該 3 27、該 701、該 266 ' 該 267 、該 238、該 1141、該 272、該 202、該 1156、該 1158、 該 1123、該 1170、該 1174、該 UFR65、該 300(以上， 三井塞阿那米特（股）製），尼加拉克Mx-75〇、該Mx-0 3 2、該 Mx-270、該 Mx-280、該 Mx-290、該 Μχ·706、該 Μχ-708、該 Μχ-40、該 Mx-31、該 Ms-11、該 Mw-30、該 Mw-30HM、該 Mw-390、該 Mx-100LM、該 Mw-750LM ( 以上，三和化學（股）製）等。上述熱硬化成分，可以單 獨1種或倂用2種以上之方式使用。 如使用於上述分子中具有2個以上的環狀（硫）醚基 之熱硬化性成分（E )時，則含有熱硬化觸媒爲宜。此種 熱硬化觸媒而言，可例舉：咪唑、2 -甲基咪唑、2 -乙基咪 唑、2 -乙基-4-甲基咪唑、2_苯基咪唑、4 -苯基咪唑、1-氰 乙基-2-苯基咪唑、1-(2-氰乙基）-2-乙基-4-甲基咪唑等 的咪唑衍生物；雙氰胺、苄基二甲基胺、4-(二甲基胺基 )-N，N-二甲基苄基胺、4-甲氧-Ν,Ν-二甲基苄基胺、4·甲 基-Ν，Ν-二甲基苄基胺等的胺化合物，己二酸二醯肼、癸 二酸二醯肼等的肼（hydrazine)化合物；三苯基膦等的磷 -37- 201106096 化合物等。又，在市售者而言，可例舉：四國化成工業社 製的 2MZ-A、2MZ-OK、2PHZ ' 2P4BHZ、2P4MHZ (均爲 咪唑系化合物的商品名）、燦阿甫洛社製的U-CAT (註冊 商標）3503N、U-CAT3502T(均爲二甲基胺的嵌段異氰酸 酯化合物的商品名），DBU、DBN、U-CATSA102、U-CAT5002 (均爲雙環脒（bicyclic amidine)化合物及其鹽 )等。並不因此等而有所限制，只要是能促進環氧樹脂或 氧雜環丁烷化合物的熱硬化觸媒，或者環氧基及/或氧雜 環丁烷基與羧基之間的反應者即可，可以單獨1種或混合 2種以上之方式使用。又，亦可採用：胍胺（guanamine ) 、乙醯胍胺、苯并胍胺、三聚氰胺、2,4-二胺基-6-甲丙烯 醯氧乙基第二三哄、2-乙烯基-2,4-二胺基第二三畊、2-乙 烯基-4,6 -二胺基第二三哄·異三聚氰酸加成物、2,4 -二胺 基-6-甲基丙烯醯氧乙基第二三畊•異三聚氰酸加成物等的 第二三哄衍生物，較佳爲將此等亦能作爲密接性賦與劑發 揮作用之化合物與前述熱硬化觸媒倂用。 此等熱硬化觸媒的調配量，係按通常的量式比例即足 夠，例如，對含羧基之樹脂（B )或於分子中具有2個以 上的環狀（硫）醚基之熱硬化性成分（E) 100質量份， 較佳爲〇·1至20質量份’更佳爲0.5至15.0質量份。 於本發明之感光性樹脂組成物中，爲提升層間的密接 性，或感光性樹脂層與基材之間的密接性起見，亦可調配 密接賦與劑。可具體例舉：苯并咪唑、苯并噚唑、苯并噻 唑、2-毓基苯并咪唑、2-锍基苯并噚唑、2-锍基苯并噻唑 -38- 201106096 (商品名：川口化學工業（股）製，阿克色爾Μ ) 、3 -嗎 啉代甲基-1-苯基-***-2-硫羰（thion ) 、5-胺基-3-嗎啉 代甲基-噻唑-2-硫羰' 2-毓基-5-甲基硫-噻二唑、***、四 唑、苯并***、羧基苯并***、含胺基之苯并***、有機 砍院偶合劑（silane coupling agent)等。 於本發明之感光性樹脂組成物中，可調配著色劑（F )。著色劑而言，可使用：紅（F-1 )、藍（F-1 )、綠（ F-3 )、黃（F-4 )等的慣用周知的著色劑，而可爲顏料、 染料、色素之任一種。但，從降低環境負荷及對人體的影 響的觀點來看，較佳爲不含有鹵素。 紅色著色劑（F-1 ): 紅色著色劑而言，有：單偶氮（mono azo)系、雙偶 氮（dis azo)系、單偶氮色殿（mono azo lake)系、苯并 咪哩酮（benz imidazolone)系、莊（perylene)系、二氧 化吡略并卩比略（diketo pyrrolo pyrrole )系、縮合偶氣（ condeused azo)系、恵酿系、喹 Π丫 D定酮（quinacridone) 系等，具體上可舉下述者。 單偶氮系：Pigment Red (顏料紅）1，2, 3, 4, 5, 6，8, 9，12，14，15，16, 17, 21，22，23，3 1, 32, 1 1 2, 1 1 4, 1 46, 1 47, 1 5 1, 1 70, 1 84, 1 87, 1 8 8, 1 93, 2 1 0, 245，253, 25 8, 266, 267, 268, 269 〇 雙偶氮系：Pigment Red 3 7, 3 8, 4 1。 單偶氮色澱系：Pigment Red 48 : 1, 48 : 2，48 : 3，48 ：4，49: 1,49·· 2,50: 1, 52 ： 1,52: 2，53: 1, 5 3 ： 2, 57 -39 - 201106096 ：1,58: 4, 63 ： 1, 63 : 2， 64 :1, 68 ° 苯并 咪挫 酮系 :Pigment Red 171， Pigment Red 175, Pigment Red 176，Pigment Re d 1 85 ，P i gm ent Red 208 ° 茈系 ·_ Solvent Red (溶劑紅） 135, Solvent Red 179, Pigment Red 1 23 , Pigment Red 149， Pigment Red 166, Pigment Red 178, Pigment Red 179， Pigment Red 190,(R14)m (R19)p (VII) wherein R13, R14 and R19 each independently represent an alkyl group having 1 to 12 carbon atoms, and R15, R16, R17 and r18 each independently represent a hydrogen atom or a carbon number of 1 to 6 Alkyl, Μ represents 〇, s or NH, and m and ρ each independently represent an integer of 〇5. Among the above-mentioned oxime ester-based photopolymerization initiators, 2-(ethyloxyiminomethyl)thioxanthene-9-one represented by the above formula (V) is more preferable, and the formula (VI) can be represented. Compound. Commercially available products include CGI-3 25 manufactured by Chiba Special Chemicals Co., Ltd., Ilga Aachen 01, Ilga Aachen 02, and Ν-1919 manufactured by ADEKA. These oxime ester photopolymerization -22-201106096 initiators can be used singly or in combination of two or more. The α-aminoethyl benzene-based photopolymerization initiator having the group represented by the above general formula (III) may, for example, be 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholino propyl-1,2-hydroxy-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethyl Amino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, n,N-dimethyl Aminoaminobenzene and the like. As a commercial item, Ilgaia-907, Ilgaia-369, Ilgaia-37, and the like, which are manufactured by Chiba Special Chemicals Co., Ltd., may be mentioned. The fluorenylphosphine oxide-based photopolymerization initiator having a group represented by the above general formula (IV) may, for example, be 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide or bis(2, 4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lu Xilin TPO manufactured by BASF Corporation and Ilgayya 8 1 9 manufactured by Chiba Special Chemicals Co., Ltd., and the like. The amount of the photopolymerization initiator (D) to be added is preferably from 0.01 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (B). When the photopolymerization initiator (D) is at most 0.01 parts by mass, the photocurability on copper is insufficient to cause the coating film to peel off, and as a result, coating properties such as chemical resistance are lowered, which is not preferable. When the other side is at least 30 parts by mass, the photopolymerization initiator (D) is strongly absorbed by the light absorption on the surface of the solder resist coating film, so that the deep curing property tends to be lowered. In the case of the phthalocyanine-based photo-23-201106096 polymerization initiator having the group represented by the above formula (II), the compounding amount is preferably 100 parts by mass based on the carboxyl group-containing resin (B). It is preferably in the range of 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass. Other photoinitiators, photoinitiation promoters, and sensitizers which are suitably used in the photosensitive resin composition of the present invention may, for example, be a benzoin compound or an acetophenone compound. An anthracene compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a Panone (xanthone) compound, a tertiary amine compound, and the like. Specific examples of the benzoin compound are, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of the acetophenone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, and 2,2-diethoxy-2-phenyl acetophenone. 1,1-dichloroacetamidine. Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, and 1-chloroindole. Specific examples of the thioxanthone compound are, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diiso Propyl sulphonone. When a specific example of the ketal compound is exemplified, it is, for example, an acetophenone ketal or a benzyldimethylketal. Specific examples of the diphenyl ketone compound include, for example, diphenyl ketone, 4-benzyl phenyl sulfide, 4-benzyl fluorenyl 4'-methyl diphenyl sulfide, and 4- Benzylidene-4'-ethyldiphenyl sulfide, 4-benzylindolyl-4'-propyldi-24 - 201106096 Phenyl sulfide. Specific examples of the tertiary amine compound are, for example, an ethanolamine compound or a compound having a dialkylamine benzene structure, for example, 4,4'-dimethylaminodiphenyl ketone (Nippon Soda Co., Ltd.) Dialkylaminodiphenyl ketone, 7-(diethylamino)-4, such as sulphate MABP), 4,4'-diethylaminodiphenyl ketone (EAB manufactured by Hodogaya Chemical Co., Ltd.) a dialkylamino group-containing oxalyzin compound such as methyl-2H-1-benzopyran-2-(one)one (7-(diethylamino)-4-methyldonyl (cumarin)), 4-Dimethylamino benzoic acid ethyl ester (Kifu EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure, manufactured by International Biosynthesis Co., Ltd.) , 4-dimethylamino benzoic acid (n-butoxy) ethyl (Quantacure BEA, manufactured by International Biosynthesis Co., Ltd.), p-dimethylamino benzoic acid, isoamyl ethyl ester (Kanaiya, manufactured by Nippon Kayakusho Co., Ltd.) DMBI), 2-ethylhexyl benzoic acid 2-ethylhexyl ester (EsololC Isolo manufactured by Van Dyk) 507), 4,4'-diethylaminodiphenyl ketone (EAB of Chemical Industry Co., Ltd.)Among the above compounds, a thioxanthone compound and a tertiary amine compound are preferred. In the composition of the present invention, from the viewpoint of depth hardening, it is preferred to contain a thioxanthone compound, of which 2,4-dimethylthioxanthone, 2,4- A thioxanthone compound such as diethylthioxanthone, 2-chlorothioxanthone or 2,4-diisopropylthioxanthone. The amount of the thioxanthone compound to be added is preferably 20 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (B). If the blending amount of the thioxanthone compound is too large -25-201106096, the thick film hardening will be lowered and the cost of the product will rise. The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, particularly preferably a dialkylaminodiphenyl ketone compound, and an alkylamine group having a maximum absorption wavelength of 350 to 41 nm. Dongchong compound. In the case of a dialkylaminodiphenyl ketone compound, 4,4'-ethylamine-diphenyl ketone is less toxic and preferable. A dialkylamine-containing toxin compound having a maximum absorption wavelength of 350 to 410 nm is a photosensitive composition having a small color absorption and a colorless transparency because the maximum absorption wavelength is in the ultraviolet region. , 尙 can provide a color solder resist film that uses a coloring pigment to reflect the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopipene-2-one can exhibit excellent sensitizing effect on laser light having a wavelength of 400 to 41 Onm. . The appropriate amount of such a tertiary amine compound is preferably from 0.1 to 20 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the resin (B) containing the above carboxyl group. When the amount of the tertiary amine compound is less than 1 part by mass, sufficient sensitization may not be obtained. On the other hand, when it is 20 parts by mass or more, the light absorption on the surface of the dried solder resist coating film obtained by using the tertiary amine compound becomes intense, and the deep hardenability tends to be lowered. In the photosensitive resin composition of the present invention, in order to enhance the sensitization degree, N-phenylglycine, phenoxyacetic acid, thiophene oxide, which are conventionally used as a chain transfer agent, can be used. Acetic acid, mercaptothiazole • 26- 201106096 (mercapto thiazol), etc. Specific examples of the chain transfer agent are, for example, mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionin, crystenine, ortho-benzoic acid ( Thiosalicylic acid) and its derivatives have a chain transfer agent; mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof have hydroxyl groups Chain transfer agent; 1-butane thiol 'butyl-3-mercaptopropionate, methyl-3-mercapto acrylate, 2,2-(ethylenedioxy)diethane thiol, ethane sulphur Alcohol, 4-methylbenzenethiol, mercaptan, propane thiol, butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane Mercaptan, thioglycerol, 4,4-thiobisbenzenethiol, and the like. Further, the polyfunctional thiol compound is not particularly limited, and may, for example, be hexane-1,6-dithiol, decane-1,10-dithiol or dimercapto Aliphatic thiols such as ethyl ether and dimercapto diethyl sulfide; aromatics such as thiol dithiol, 4,4'-didecyl diphenyl sulfide, and 1,4-benzene dithiol Group thiols; ethylene glycol bis(mercaptoacetate), polyethylene glycol bis(mercaptoacetate), propylene glycol bis(mercaptoacetate), glycerol ginseng (mercaptoacetate), Polyols such as trimethylolethane thiol (mercaptoacetate), trimethylolpropane ginseng (mercaptoacetate), pentaerythritol bismuth (mercaptoacetate), dipentaerythritol tertyl (mercaptoacetate) Poly(mercaptoacetate) class: ethylene glycol bis(3- mercaptopropionate), polyethylene glycol bis(3-mercaptopropionate), propylene glycol bis(3-mercaptopropionate) ), glycerol ginseng (3-mercaptopropionate), trimethylolethane sulphate (mercaptopropionate), trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol bismuth (3-锍) Propionate), second season -27- 201106096 pentaerythritol Poly(3-mercaptopropionate) of polyhydric alcohols such as 3-mercaptopropionate; I-4-bis(3-mercaptobutoxy)butane, 1,3,5-para (3- Mercapto-oxyethyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione, pentaerythritol bismuth (3-mercaptobutyrate), etc. Further, a mercapto group-containing heterocyclic compound which functions as a chain transfer agent may, for example, be a 1⁄4 base-4-butyrolactone (alias: 2-spar Butanide vinegar (butanolide), 2, thiol-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4 - butyrothio lactone, 2-carbyl-4-butyrolactam, butyro lactum, N-methoxy-2-indolyl-4-butyrolactam, N-ethyl-2- Mercapto-4-butylide, N-methyl-2-mercapto-4-butylidene, N-ethyl-2-mercapto-4-butylidene, N-(2-A Oxy)ethyl-2-mercapto-4-butylidene, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, 2-mercapto-5-valerolactone ' 2_Mercapto-5-pentane, N-methyl-2-sulfo-5-pentalinamine, N-ethyl-2-disyl-5-pentalamine, N-( 2-methoxy)ethyl-2- Mercapto-5-valeroinamide, N-(2-ethoxy)ethyl-2-mercapto-5-pentalinamide, 2-mercapto-6-caprolactam and the like. As a heterocyclic compound having a mercapto group which is a chain transfer agent itself, which does not affect the development of the photosensitive resin composition, particularly preferably mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, 2 , 4-triazole, 5-methyl-1,3,4-thiadiazole (thiadiazol)-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents may be used singly or in combination of two or more. These photopolymerization initiators, photoinitiators, sensitizers, and chain-transfers -28-201106096 can be used singly or in combination of two or more. The total amount of the photopolymerization initiator, the photoinitiator, the sensitizer, and the chain transfer agent is preferably 100 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (B). When it is 35 parts by mass or more, there is a tendency that the deep hardenability is lowered by light absorption. In the photosensitive resin composition of the present invention, a thermosetting component (E) can be used for the purpose of imparting heat resistance. It can be used for the thermosetting component of the present invention. It can be used: an amine resin such as a melamine resin or a benzoguanamine resin, a blocked isocyanate compound, a cyclic carbonate compound, a polyfunctional epoxy compound, or a polyfunctional heterocyclobutane (oxetane). Compounds, api sulfide resins, melamine derivatives, bismaleimide, oxazine compounds, oxazoline compounds, carbodiimide resins, etc. Thermosetting resin. Particularly preferred is a thermosetting component (E) having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in the molecule, which is equivalent to 2 in the molecule. The thermosetting component (E) having one or more cyclic (thio)ether groups is one or two groups of a cyclic ether group having a 3, 4 or 5 membered ring or a cyclic thioether group in the molecule. The compound having at least two or more epoxy groups in the molecule, that is, the polyfunctional epoxy compound (E-1), having at least two or more oxygen heterocycles in the molecule, may be mentioned. A compound of a butane group, that is, a polyfunctional oxetane compound (E-2), a compound having two or more thioether groups in a molecule, that is, a surface sulfide resin (E-3). -29-201106096 The polyfunctional epoxy compound (EI) may, for example, be jER828, jER834, jER1001, jER1004 manufactured by Epoxy Epoxy Resin Co., Ltd., and the cloning 840, table clone 850, and table clone manufactured by DIC Corporation. 1050, Table clone 2055, Ibdong yd-011, YD-013, YD-127, YD-128, manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd., Chiba Special Alartai 607 of Chemical Industry Co., Ltd. 1, Alar Taidou 6084, Alartai GY250, Alartai GY260, Sumitomo Chemical Co., Ltd., Sumiy Epoxy ESA-011, ESA-014, ELA-115, ELA-128 , bisphenol A type epoxy resin of AER330, AER331, AER661, AER664, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd.; jERYL903 manufactured by Japan Epoxy Resin Co., Ltd. Table 165, IBO Dongdu YDB-400, YDB-500, manufactured by Toho Chemical Co., Ltd., DER542 manufactured by Dow Chemical Co., Ltd., Alar Taidou 8011 manufactured by Chiba Specialty Chemicals Co., Ltd., Sumitomo Epoxy Co., Ltd. ESB-400, ESB-700, A from Asahi Kasei Industrial Co., Ltd. ER711, AER714, etc. (both trade names), brominated epoxy resin; jER152 and jER154, manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438, manufactured by Dow Chemical Co., Ltd., manufactured by Dainippon Ink Chemical Industry Co., Ltd. Table clone N-730, table clone N-770, table clone N_865, IBO Dongdu YDCN-701, YDCN-704 manufactured by Dongdu Chemical Industry Co., Ltd., Alar Taidou ECN1235, Alar Taidou ECN1273, manufactured by Chiba Special Chemicals Co., Ltd. Alar Taidou ECN1299, Alar Taidou XPY307, EPPN-201 manufactured by Nippon Chemical Co., Ltd. 'EOCN-1025, EOCN-1020' EOCN-104S, RE-3 06, Sumitomo Chemical Co., Ltd., Sumi-Epoxy-30- 201106096 ESCN -195X, ESCN-220, a person made by Asahi Kasei Industrial Co., Ltd. ^2 3 5, ECN-299 (all are brand names), novolac type epoxy resin; DIC company's table clone 8 3 0 , JER8 07 made by Japan Epoxy Resin Co., Ltd., YB Dong-dong YDF-170, YDF-175, YDF-2004, manufactured by Dongdu Chemical Co., Ltd., Alar Teto XPY3 06 manufactured by Chiba Special Chemicals Co., Ltd. (all are trade names) Bisphenol F-type epoxy resin; Yibo Dongdu ST-2004, ST-2007, ST-3000 (made by Dongdu Chemical Industry Co., Ltd.) Hydrogenated bisphenol A type epoxy resin such as product name; jER6 04 manufactured by Japan Epoxy Resin Co., Ltd., IBO Dongdu YH-434 manufactured by Dongdu Chemical Co., Ltd., Alartai Dou Y720 manufactured by Chiba Special Chemicals Co., Ltd., Sumitomo Chemical Co., Ltd. An allergic acid such as a glycidylamine-based epoxy resin such as AK-350 (trade name) manufactured by Chiba Special Chemicals Co., Ltd. Hydantoin type epoxy resin; chromochelene made by 黛色尔化学工业有限公司 202 1, alicyclic CY 175, CY179, etc. (all trade names) alicyclic epoxy manufactured by Chiba Specialty Chemicals Co., Ltd. Resin; YL- 9 3 3 manufactured by Nippon Epoxy Co., Ltd., trihydroxyphenylmethane epoxy resin of TEN, EPPN-501, EPPN-5 02 (all trade names) manufactured by The Dow Chemical Co., Ltd.; Japan a mixture of bis-6056, YX-4000, YL-6121 (all trade name), such as bisphenol (bixyleno.l) type or biphenol type epoxy resin, or the like; EBPS-200 manufactured by Nippon Kasei Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Corporation Bisphenol S-type epoxy resin; bisphenol A phenolic epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; jER YL-93 manufactured by Japan Epoxy Resin Co., Ltd. A-31 - 201106096, a tetraphenyl ethane-type epoxy resin, which is a trade name, and an Alaer PT810, manufactured by Chiba Special Chemicals Co., Ltd., Nissan Chemical Industry Co., Ltd. Heterocyclic epoxy resin such as TEPIC (trade name) manufactured by the company, diglycidyl phthalic acid resin such as DGT, etc. manufactured by Nippon Oil & Fats Co., Ltd.; tetraglycidyl group such as ZX-1063 manufactured by Toshiro Kasei Co., Ltd. Anthraquinone ethane resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., naphthalene-based epoxy resin such as HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation; HP-7200 manufactured by DIC Corporation , epoxy resin having a dicyclopentadiene skeleton such as HP-7200H; glycidyl methacrylate copolymer epoxy resin such as CP-50S 'CP-50M manufactured by Nippon Oil & Fats Co., Ltd.; and cyclohexylmaline Copolymerized epoxy resin of quinone and glycidyl methacrylate; epoxy modified A butadiene rubber derivative (for example, PB-3600 manufactured by Seika Chemical Industry Co., Ltd.), a CTBN modified epoxy resin (for example, YR-102 manufactured by Tosho Kasei Co., Ltd., YR-450, etc.), etc., but are limited thereto. . These epoxy resins may be used singly or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferred. The above polyfunctional oxetane compound (E-2) may, for example, be bis[(3-methyl-3-oxetanylmethyl)methyl]ether, bis[3- Ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, I,4 - bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl 3-oxetanyl)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3- •32- 201106096 ethyl-3-oxo In addition to the polyfunctional oxetanes such as the heterocyclobutane)methyl methacrylate or such oligomers or copolymers, hydrazine may be exemplified by oxetane Novolac resin, with poly(p-hydroxystyrene), cardo radical biguanide, calixarene, calix resorcin arene, or sesquioxanes ( An etherified product such as a resin having a hydroxyl group such as silsesqui oxane). Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned. The compound (E-3) having two or more cyclic thioether groups in the molecule may, for example, be a bisphenol A-type sulfonate resin YL7 000 manufactured by Nippon Epoxy Resin Co., Ltd., or the like. Further, a surface sulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by the same synthesis method may be used. The amount of the thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is preferably 1 equivalent to the carboxyl group of the carboxyl group-containing resin (B). It is in the range of 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents. When the amount of the thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is 0.6 or less, the carboxyl group remains on the solder resist film, so that heat resistance and alkali resistance are caused. Electrical insulation and the like may be reduced, which is not appropriate. On the other hand, when the amount is 2.5 equivalent or more, the low molecular weight cyclic (thio)ether group remains on the dried coating film, so that the strength of the coating film or the like is lowered, which is not preferable. Further, as the thermosetting component, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule can be added. The compound having two or more isocyanate groups or blocked isocyanates in the molecule may, for example, be a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or A compound having two or more blocked isocyanate groups in one molecule, that is, a blocked isocyanate compound. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, and naphthalene- 1,5-Diisocyanate, o-decyl diisocyanate, m-decyl diisocyanate, and 2,4-methylphenyl dimer. Specific examples of the aliphatic polyisocyanate include tetramethylammonium diisocyanate, hexamethylene diisocyanate, methyl diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methyl group. Bis(cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. And an adduct body, a biuret body, and an isocyanurate body of the previously mentioned isophthalate compound. The blocked isocyanate group contained in the blocked isocyanate compound is a group which is temporarily inertized by a reaction between the isocyanate gene and a blocking agent. When heated to a predetermined temperature, the blocking agent will dissociate to form an isocyanate group. In the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. It can react with blocking agent-34-201106096 Cyanate ester compound: isocyanurate type, biuret type, adduct type Wait. As such an isocyanate compound, for example, an aromatic polyisocyanate 'aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include the compounds exemplified above. The isocyanate blocking agent may, for example, be a phenol blocking agent such as phenol, cresol, xylenol, chlorophenol or ethylphenol; ε-caprolactam, 5-valeroinamide, V-butene oxime Amine-blocking agent such as amine and guanidine-propionamide; active methyl blocking agent such as ethyl acetate and acetamidine acetone: methanol, ethanol, propanol, butanol, pentanol, and B Glycol-methyl ether, ethylene glycol-ethyl ether, ethylene glycol-butyl ether, diethylene glycol-methyl ether, propylene glycol methyl ether, benzyl ether, methyl glycolate, glycolic acid An alcohol-based blocking agent such as ester, diacetone alcohol, methyl lactate or ethyl lactate; formaldehyde oxime, acetaldehyde oxime, propionaldehyde oxime methyl ethyl ketone oxime, diethyl hydrazine, cyclohexane hydrazine, etc. Hydrazine blocking agent; thiol blocking agent such as butyl mercaptan, hexyl mercaptan, third butyl thiol, thiophenol, methyl thiophenol, ethyl thiophenol; acetamide, benzene a guanamine blocking agent such as formamide; a quinone imine blocking agent such as amber quinone and maleimine; X y 1 idine , aniline, butylamine, dibutyl An amine blocking agent such as an amine; Oxazole, 2 - ethylimidazole blocking agent such as imidazole; methylimine stretch and stretch propylene imine-based blocking agents such as imine. The block isocyanate compound may be a commercially available product, and may be exemplified by: Rembrandt BL-3175, BL-4165, BL-ll, BL-1265, Smolol-35-201106096 TPLS-2957, TPLS -2062, TPLS-2078, TPLS-21 17, Dis Mosham 2170, Smosam 2265 (above, Sumitomo Bayer Polyurethane Co., Ltd., trade name), Cole Knight 2512, Coke Knight 2513, Cola Nite 2 520 (above, manufactured by Japan Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B-846 'B-870, B-874 > Β·882 (Mitsui Takeda Chemical Co., Ltd., trade name ), ΤΡΑ-Β80Ε, 17Β-60ΡΧ, Ε402-Β80Τ (made by Asahi Kasei Chemicals Co., Ltd., trade name). Here, Summel 81^-3 175 and BL-4265 are used as blocking agents and are prepared by using methyl ethyl hydrazine. The compound having two or more isocyanate groups or blocked isocyanate groups in the above-mentioned one molecule may be used alone or in combination of two or more. A suitable compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is 100 parts by mass, preferably 1 to 1 part, to the above carboxyl group-containing resin (Β). The parts by weight are more preferably from 2 to 70 parts by weight. When the amount of the above formulation is 1 part by mass or less, it is not preferable to obtain sufficient toughness of the coating film. On the other hand, if it is 1 part by mass or more, the storage stability may be lowered, which is not preferable. Further, the other thermosetting component may, for example, be a trimeric amine derivative or a benzoguanamine derivative. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol uril compound, a methylol urea compound, and the like. Further, an alkoxymethylated melamine compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated glycoluril compound, and an alkoxymethylated urea compound, such as each methylol melamine compound, hydroxyl group The benzomethylamine compound, the methylol-36-201106096-based glycoluril compound, and the methylol group of the methylol urea compound can be obtained by converting the methylol group into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and may be used as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group or a butoxymethyl group. Particularly preferred is a melamine derivative having a formalin concentration of 0.2% or less which can protect the human body or the environment. Such commercially available products may, for example, be Semel 00, 301, 303, 307, 325, 327, 701, 266' 267, 238, the 1141, the 272, the 202, the 1156, the 1158, the 1123, the 1170, the 1174, the UFR65, the 300 (above, Mitsuisanamite (share) system), Niagara Mx -75〇, the Mx-0 3 2, the Mx-270, the Mx-280, the Mx-290, the Μχ706, the Μχ-708, the Μχ-40, the Mx-31, the Ms-11 The Mw-30, the Mw-30HM, the Mw-390, the Mx-100LM, the Mw-750LM (above, Sanwa Chemical Co., Ltd.), and the like. The above-mentioned thermosetting component can be used singly or in combination of two or more. When the thermosetting component (E) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst. The thermosetting catalyst may, for example, be imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 4-phenylimidazole. Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4 -(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-oxime, Ν-dimethylbenzylamine, 4·methyl-oxime, Ν-dimethylbenzyl An amine compound such as an amine, a hydrazine compound such as diammonium adipate or bismuth sebacate; a phosphorus-37-201106096 compound such as triphenylphosphine. In addition, as a commercially available product, 2MZ-A, 2MZ-OK, 2PHZ ' 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd. U-CAT (registered trademark) 3503N, U-CAT3502T (trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine) Compounds and their salts) and the like. It is not limited thereto, as long as it is a thermosetting catalyst capable of promoting an epoxy resin or an oxetane compound, or a reaction between an epoxy group and/or an oxetane group and a carboxyl group. These may be used alone or in combination of two or more. Also, it can be used: guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl second triterpene, 2-vinyl- 2,4-diamino second trimer, 2-vinyl-4,6-diamino second triterpene isomeric cyanide adduct, 2,4-diamino-6-methyl a second triterpene derivative such as a propylene oxyethylate second third ploughing or an isomeric cyanuric acid adduct, preferably a compound which functions as an adhesion imparting agent and the aforementioned thermosetting contact Media use. The amount of the thermosetting catalyst is sufficient in the usual amount ratio, for example, thermosetting property of the carboxyl group-containing resin (B) or having two or more cyclic (thio)ether groups in the molecule. The component (E) is 100 parts by mass, preferably from 1 to 20 parts by mass, more preferably from 0.5 to 15.0 parts by mass. In the photosensitive resin composition of the present invention, in order to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate, a close adhesion agent may be blended. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole-38-201106096 (trade name: Kawaguchi Chemical Industry Co., Ltd., Axel Μ), 3-morpholinomethyl-1-phenyl-triazole-2-thiocarbonyl (thion), 5-amino-3-morpholino Base-thiazole-2-thiocarbonyl '2-mercapto-5-methylsulfanyl-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, An organic silane coupling agent or the like. In the photosensitive resin composition of the present invention, a coloring agent (F) can be formulated. As the coloring agent, a conventionally known coloring agent such as red (F-1), blue (F-1), green (F-3), or yellow (F-4) may be used, and may be a pigment, a dye, or the like. Any of the pigments. However, from the viewpoint of reducing environmental load and affecting the human body, it is preferred that halogen is not contained. Red colorant (F-1): For red colorants, there are: mono azo, dis azo, mono azo lake, benzopyrim Benz imidazolone, perylene, diketo pyrrolo pyrrole, condeused azo, brewing, quinacridone ), etc., specifically, the following may be mentioned. Monoazo system: Pigment Red 1,2, 3, 4, 5, 6,8, 9,12,14,15,16, 17, 21,22,23,3 1, 32, 1 1 2, 1 1 4, 1 46, 1 47, 1 5 1, 1 70, 1 84, 1 87, 1 8 8, 1 93, 2 1 0, 245,253, 25 8, 266, 267, 268, 269 Bismuth azo system: Pigment Red 3 7, 3 8, 4 1. Monoazo lake system: Pigment Red 48 : 1, 48 : 2,48 : 3,48 :4,49: 1,49·· 2,50: 1, 52 : 1,52: 2,53: 1, 5 3 : 2, 57 -39 - 201106096 :1,58: 4, 63 : 1, 63 : 2, 64 :1, 68 ° Benzymidone: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Re d 1 85 , P i gm ent Red 208 ° · System·_ Solvent Red (Solvent Red) 135, Solvent Red 179, Pigment Red 1 23 , Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190,

Pigment Red 1 94，Pigment Red 224 o 二氧代吡咯并吡咯系：Pigment Red 2 54，Pigment Red 2 5 5，Pigment Red 264，Pigment Red 270，Pigment Red 272Pigment Red 1 94, Pigment Red 224 o Dioxopyrrolopyrrole: Pigment Red 2 54, Pigment Red 2 5 5, Pigment Red 264, Pigment Red 270, Pigment Red 272

O 縮合偶氮系：Pigment Red 220，Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, P i gm e n t R e d 2 4 2。 恵醌系：Pigment Red 16 8, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent R ed 1 5 0, Solvent Red 52, Solvent Red 207° 喹吖啶酮系：Pigment Red 122，Pigment Red 202, Pigment Red 206，Pigment Red 20 7，Pigment Red 209 o 藍色著色劑（F - 2 ): 藍色著色劑而言，有：酞菁（phthalocyanine)系、 蒽醌系，而顏料系係被分類爲Pigment (顏料）之化合物 ，具體上可舉：附有如下述之色指數（color index )( C.I_;染工及色彩設計家學會（The Society of Dyers and Colourists)發行）.號碼者；Pigment Blue (顏料藍）15, -40- 201106096O condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, P i gm e n t R e d 2 4 2 .恵醌: Pigment Red 16 8, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent R ed 1 5 0, Solvent Red 52, Solvent Red 207° quinacridone: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 20 7, Pigment Red 209 o Blue colorant (F - 2 ): For blue colorants, there are: phthalocyanine, lanthanide, and pigment systems are classified as Pigment (pigment) compound, specifically: color index (C.I_; issued by The Society of Dyers and Colourists). Numbers; Pigment Blue (pigment blue) 15, -40- 201106096

Pigment Blue 15 : 1, Pigment Blue 15 : 2, Pigment Blue 15 :3，Pigment Blue 15 : 4，Pigment Blue 15 : 6，PigmentPigment Blue 15 : 1, Pigment Blue 15 : 2, Pigment Blue 15 : 3, Pigment Blue 15 : 4, Pigment Blue 15 : 6, Pigment

Blue 1 6 , P i gm en t B1 ue 6 0 o 染 料系而言， 可使用 :S 〇 1 v 1 snt B lue (溶劑藍） 35, S o 1 v ent Blue 63, Solvent Blue 68, Solvent Blue 70, S ο 1 v ent Blue 8 3, Solvent Blue 87, Solvent Blue 97, S ο 1 v ent Blue 122: (Solvent Blue 136, Solvent Blue 67, S ol v ent Blue 70 等 ο 除上述者以上 ，亦可使 用金屬 取代 或無取代 的酞菁 化 合物 ο 綠色著色劑（ F-3 )： 綠色著色劑而 言，同樣 有：酞 菁系 、蒽醌系 、茈系 > 具體 上 可使用： Pigment Green (顏； 料綠）7, P i gm ent G r e e η 36， Solvent Green ( 溶劑綠 :)3, Solvent Green 5, S ο 1 v ent Green 2 0, Solvent Green 28等 ^除上述 者以外， 亦可 使f s金屬取代 或無取代 的酞菁 化合i 物。 黃色著色劑（ F-4 )： 黃色著色劑而 言，有單 偶氮系 、雙 偶氮系、 縮合偶 氮 系、 苯并咪唑酮系 、異吲哚 啉酮（ iso i n d ο 1 i η ο n e )系、 蒽 驅系 等 ，具體上可 舉如下述 者。 蒽 醒系.S 〇 ] [vent Yellow ( 溶劑 黃）163, P i gm entBlue 1 6 , P i gm en t B1 ue 6 0 o For dye systems, use: S 〇1 v 1 snt B lue (solvent blue) 35, S o 1 v ent Blue 63, Solvent Blue 68, Solvent Blue 70, S ο 1 v ent Blue 8 3, Solvent Blue 87, Solvent Blue 97, S ο 1 v ent Blue 122: (Solvent Blue 136, Solvent Blue 67, S ol v ent Blue 70, etc. ο A metal-substituted or unsubstituted phthalocyanine compound can be used. 绿 Green colorant (F-3): For green colorants, there are also: phthalocyanine, lanthanide, lanthanide > Specifically: Pigment Green ( Yan; Green) 7, P i gm ent G ree η 36, Solvent Green (Solvent Green:) 3, Solvent Green 5, S ο 1 v ent Green 2 0, Solvent Green 28, etc. a f-metal substituted or unsubstituted phthalocyanine compound. Yellow colorant (F-4): For yellow colorants, there are monoazo, bisazo, condensed azo, benzimidazolone Isoindolinone (iso ind ο 1 i η ο ne ) The system can be exemplified by the following: 蒽 醒系.S 〇 ] [vent Yellow (solvent yellow) 163, P i gm ent

Yellow (顏料黃）24, Pigment Yellow 108，PigmentYellow (Pigment Yellow) 24, Pigment Yellow 108, Pigment

Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202 o -41 - 201106096 異 D引哄啉酮系：Pigment Yellow 110，Pigment Yellow 109，Pigment Yellow 139，Pigment Yellow 179，Pigment Yellow 1 8 5 o 縮合偶氮系：Pigment Yellow 93，Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 15 5, Pigment Yellow 166, Pigment Yellow 180 o 苯并味嗤嗣系：p i g m e n t Y e 11 o w 1 2 0，P i g m e n t Y e 11 o w 151， Pigment Y ellow 154, Pigment Yellow 156， Pigment Yellow 175，Pigment Yellowl81 o 單偶 氮系： Pigm ent Yellow 1 ，2, 3, 4, 5, 6, 9, 10, 12, 61, 62:1, 65, 73 ,74, 75, 97, 1 00, 1 04, 105, 111， 116, 167, 168, 169, 182, 1 83 ° 雙偶 氮系： Pigm lent Yellow 12, 13, 1 4， 16， 17, 55, 63 , 8 1 , 8 3, 8 7, 126, 127， 152, 1 70, 172, 174, 176, 188, 198 ° 其他，亦可爲調整色調（tone)之目的，而添加紫色 、橙色、棕色、黑色等的著色劑。 具體性例示時，則有：Pigment Violet (顏料紫）19, 23，29, 3 2, 3 6, 3 8, 42，Solvent Violet (溶齊ij 紫）13，36, C.I.Pigment Orange (色指數顏料橙）1，C.I.Pigment Orange 5， C.I.Pigment Orange 13， C. I.Pigment Orange 14， C.I.Pigment Orange 16， C.I.Pigment Orange 17, C.I.Pigment Orange 24, C.I.Pigment Orange 34, C.I.Pigment Orange 36, C.I.Pigment Orange 38, -42- 201106096 C . I. Pigment Orange 40, C . I. P i gm ent Orange 43, C.I.Pigment Orange 46, C . I. P i gm en t Orange 49, C.I.Pigment Orange 51, C . I. P i gm ent Orange 61, C . I. P i gm en t Orange 63, C . I. P i gment Orange 64, C.I.Pigment Orange 71, C.I.Pigment Orange 73, C.I.Pigment Brown (色指數顏料棕）23， C.I.Pigment Brown 25， C.I.Pigment Black (色指數顏料黑）1， C.I.Pigment Black 7 等。 如前述之著色劑（F )的調配比例，並不特別加以限 制，惟對前述含羧基之樹脂（B ) 100質量份，較佳爲0 至1 〇質量份，特佳爲〇. 1至5質量份的比例即足夠。 本發明之感光性樹脂組成物中，爲提升其塗膜的物理 性強度等，需要時，亦可調合塡料（filler ) ( G )。此種 塡料（G)而言，可使用周知慣用的無機或有機塡料，惟 等別是硫酸鋇、球狀二氧化矽以及滑石很好用。再者，爲 獲得白色的外觀或阻燃性起見，亦可將氧化鈦或金屬氧化 物、氫氧化鋁等的金屬氫氧化物作爲底質顏料塡料（body pigment filler )。塡料（G)的調配量，在於較佳爲組成 物全體量的7 5質量％以下，更佳爲〇 · 1至6 0質量％的比例 。如塡料的調配量爲組成物全體量的7 5質量％以上時，由 於絕緣組成物的黏度增高、塗佈、成型性降低、或硬化物 變脆弱之故不宜。 再者，本發明之感光性樹脂組成物中，爲前述含有羧 基之樹脂（B)的合成或組成物的調製、或者爲塗佈於基 -43- 201106096 板或載體薄膜之用的黏度調整起見’可使用有機溶劑 此種有機溶劑而言，可例舉：酮類、芳香族烴類 二醇醚類、乙二醇醚乙酸酯類、酯類、醇類'脂肪族 石油系溶劑等。更具體而言，爲：甲基乙基甲酮、環 等的酮類；甲苯、二甲苯、四甲基苯等的芳香族烴類 纖素（cellosolve)、甲基溶纖素、丁基溶纖素、卡 (carbitol)、甲基卡必醇、丁基卡必醇、丙二醇一 醚、二丙二醇一甲基醚、二丙二醇二乙基醚、三乙二 乙基醚等的二乙醇醚類；乙酸乙酯、乙酸丁酯、二丙 甲基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚 酯、丙二醇丁基醚乙酸酯等的酯類；乙醇、丙醇、乙 、丙二醇等的醇類；辛烷、癸烷等的脂肪族烴；石油 石油腦（petroleum naphtha)、氫化石油腦、溶劑石 等的石油系溶劑等。此種有機溶劑，可以單獨1種或 2種以上的混合物使用。 一般，多數的高分子材料，由於如一旦開始氧化 則連續不斷地發生連鎖性氧化劣化，而引起高分子素 功能低落之故，對本發明的感光性樹脂組成物中，爲 氧化起見，可添加（1 )使所發生之自由基無效化之 基捕獲劑（radical scavenger) (H-1)及 / 或（2)使 生之過氧化物分解爲無害物質，並作成不致於發生新 基之方式之過氧化物分解劑（peroxide docomposer) 2)等的抗氧化劑（antioxidant) (Η)。 作爲自由基捕獲劑發生作用之抗氧化劑（Η-1) 、乙 烴、 己酮 :溶 必醇 甲基 醇一 二醇 乙酸 二醇 醚、 油腦 作成 時， 材的 防止 自由 所發 自由 (Η- 而言 -44- 201106096 ，具體性化合物而言，可例舉：氫醌、4 -第三丁基兒茶酚 (catechol) 、2-第三丁基氫醌、氫醌一甲基醚、2,6-二第 三丁基對甲酚、2,2-伸甲基雙（4-甲基-6-第三丁基苯酚） 、1，1，3-參（2 -甲基-4-羥基-5-第三丁基苯基）丁烷、 1，3,5-三甲基-2,4,6-參（3,5-二第三丁基-4-羥基苄基）苯 、1，3,5-參（3’，5’_二第三丁基-4-羥苄基）-第二三哄· 2,4,6- ( 1H，3H,5H)三酮等的酚系化合物，間醌、苯醌等 的醌系化合物，雙（2,2,6,6-四甲基-4-哌啶基）-癸二酸酯 (sebacate)、啡唾哄（phenothiazine)等的胺系化合物 〇 自由基捕獲劑，可爲市售者，可例舉：阿提卡斯塔布 AO-30、阿提卡斯塔布AO-330、阿提卡斯塔布AO-20、阿 提卡斯塔布AL-77、阿提卡斯塔布LA-57、阿提卡斯塔布 LA-67、阿提卡斯塔布LA-68、阿提卡斯塔布LA-87(以 上’均爲旭電化社製，商品名），IRGANOX (伊爾加諾克 斯) 1010 、 IRG AN 0X1035 、 IRGAN0X1076 、 IRGANOX1135、TINUVIN (提奴評）111FDL、TINUVIN 123、TINUVIN 144、TINUVIN 152、TINUVIN 292、 TINUVIN 5 100 (以上，均爲千葉特殊化學品社製，商品名 )等。 作爲過氧化物分解劑發生作用之抗氧化劑（H-2 )而 言，具體性化合物而言，可例舉：三苯基亞磷酸酯等的磷 系化合物，季戊四醇四月桂基硫丙酸酯、二月桂基硫二丙 酸酯、二硬脂基3,3’-硫二丙酸酯等的硫系化合物等。 -45- 201106096 過氧化物分解劑’可爲市售者’可例舉：阿提卡斯塔 布TPP (旭電化社製，商品名）、馬克AO-412SC阿提卡 •阿卡斯化學社製，商品名）、須美賴莎TP S (住友化學 社製，商品名）等。 上述的抗氧化劑（Η ) ’可以單獨1種或組合2種以 上之方式使用。 又，一般，高分子材料吸收光線後會因而發生分解· 劣化之故，本發明之感光性樹脂組成物中，爲實施對紫外 線之穩定化對策起見，除上述抗氧化劑之外，尙可使用紫 外線吸收劑（I )。 紫外線吸收劑（I)而言，可例舉：二苯基酮衍生物 、苯甲酸酯衍生物、苯并***衍生物、三畊衍生物、苯并 噻唑衍生物、肉桂酸酯衍生物、胺基苯甲酸酯（ anthranilate)衍生物、二苯甲醯甲烷衍生物等。二苯基酮 衍生物的具體性例而言，可舉：2-羥基-4-甲氧二苯基酮、 2-羥基-4-正辛氧二苯基酮' 2,2’-二羥基-4-甲氧二苯基酮 以及2,4-二羥基二苯基酮等。苯甲酸酯衍生物的具體性例 而言，可舉：2-乙基己基水楊酸酯、苯基水楊酸酯、對第 三丁基苯基水楊酸酯、2，4-二第三丁基苯基-3,5-二第三丁 基-4-羥基苯甲酸酯以及十六烷基-3, 5-二第三丁基-4-羥基 苯甲酸酯等。苯并***衍生物的具體性例而言，可舉：2-(2’-羥基-5’-第三丁基苯基）苯并***、2- (2，-羥基- 5’-甲基苯基）苯并***、2- (2’-羥基- 3’-第三丁基_5’_甲基 苯基）-5-氯苯并***、2- (2，·羥基- 3’，5’-二第三丁基苯 -46- 201106096 基）-5-氯苯并***、2- (2’-羥基- 5’-甲基苯基）苯并*** 以及2- (2，-羥基- 3’，5’-二第三戊基苯基）苯并***等。三 哄衍生物的具體性例而言，可舉：羥基苯基三哄、雙乙基 己氧苯酚甲氧苯基三哄等。 紫外線吸收劑（I )而言，可爲市售者，可例舉： TINUVIN PS ' TINUVIN 99-2、TINUVIN 109、TINUVIN 3 84-2、TINUVIN 900、TINUVIN 928、TINUVIN 1130、 TINUVIN 400、TINUVIN 405、TINUVIN 460、TINUVIN 479 (以上，均爲千葉特殊化學品社製，商品名）等。 上述的紫外線吸收劑（I )，可以單獨1種或組合2 種以上之方式使用，如與前述抗氧化劑（Η )併用，則可 達成由本發明之感光性樹脂組成物所得之成型物的穩定化 〇 本發明之感光性樹脂組成物中，再依照需要，可調配 周知慣用的熱聚合抑制劑（thermo polymerization inhibitor)、微粉二氧化矽、有機膨潤土、微晶高嶺石等 的周知慣用的搖變性賦與劑（thixotropy endower)、聚矽 氧系、氟系、高分子素等的消泡劑（defoaming agent)及 /或調平劑（leveling agent)、咪哩系、噻哩系、三哩.系 等的砂院偶合劑、抗氧化劑、防銹劑等的周知慣用的添加 劑等。 前述熱聚合抑制劑，可用於防止前述聚合性化合物的 熱性聚合或經時性聚合。熱聚合抑制劑而言，可例舉：4 -甲氧苯酹、氫醌、烷基或芳基取代氫醌、第三丁基兒茶酚 -47- 201106096 、五倍子酚（pyrogallol) 、2-羥基二苯基酮、4-甲氧-2-羥基二苯基酮、氯化亞酮、啡噻哄、氯醌（chloranil )、 萘胺、P-萘酮、2,6-二第三丁基-4-甲苯酚、2,2’-亞甲雙（ I甲基-6-第三丁基苯酚）、吡啶、硝基苯、二硝基苯、苦 味酸（picric acid) 、4 -甲苯胺（tolaidine)、亞甲藍（ Methylene Blue)、與銅之有機鉗合劑（organic chelating compound )之反應物、水楊酸甲酯、以及啡噻哄、亞硝基 化合物與A1 (鋁）所成之鉗合物（chelate)等。 本發明之感光性樹脂組成物，例如使用前述有機溶劑 以調整爲適合於塗佈方法之黏度後，於基材上按照浸漬塗 佈法（dip coating)、流挺塗佈法（flow coating)、輕式 塗佈法（roll coating)、鑲條塗佈法（bar coating)、絲 網印刷法（screen printing)、簾流塗佈法（curtain coating)等方法加以塗佈，約以60~ 10(TC的溫度使組成 物中所含之有機溶劑揮發乾燥（預乾燥）即可形成指觸乾 燥性（tack free )的塗膜。又，如將上述組成物塗佈於載 體薄膜上，並將經使其乾燥後作爲薄膜捲取後者貼合於基 材上，即可形成樹脂絕緣層。然後，利用接觸式（或非接 觸式），透過形成有圖型之光罩（photo mask )而選擇性 利用活性能量射線（a c t i v e e n e r g y r a y )加以曝光或者利 用雷射直接曝光機（laser direct exposing machine)加以 直接圖型曝光（direct pattern exposure)，並將未曝光部 使用稀鹼化合物水溶液（例如，0.3至3 wt (重量）％碳酸 鈉水溶液）加以顯像即可形成光阻劑圖型（resist pattern -48- 201106096 )。再者，在含有熱硬化性成分（E )之組成物的情 則例如，加熱爲約140至180°C的溫度以使其熱硬化 前述含羧基之樹脂（B)的羧基、與分子中具有2個 的環狀醚基及/或環狀硫醚基之熱硬化性成分（E)進 應，結果可形成耐熱性、耐藥品性、耐吸濕性、密接 電氣特性等各特性方面優異的優異的硬化塗膜。再者 使在不含有熱硬化性成分（E )的情形，如施加熱處 則由於在曝光時以未反應的狀態所殘留之乙烯性不飽 即進行熱自由基聚合，並塗膜特性將獲改善之故，可 目的•用途，而加以熱處理（熱硬化）。 上述基材而言，除可採用預先形成有電路之印刷 板或軟性印刷電路板（flexible print circuit board) ’尙可採用：紙-苯酣樹脂、紙-環氧樹脂、玻璃布-環 脂、玻璃-聚醯亞胺、玻璃布/不織布-環氧樹脂、玻: 紙-環氧樹脂，經採用合成纖維-環氧樹脂、含氟樹脂 乙烯· PP0 (聚苯醚）•氰酸酯等的複合材料之所有 (FR-4等）的覆銅范層合板、聚醯亞胺薄膜、pet ( )薄膜、玻璃基板、陶瓷基板、晶圓（wafer )板等。 經塗佈本發明之感光性樹脂組成物後所實施之揮 燥’可採用：熱風循環式乾燥爐、IR爐、熱板（hot )、對流烘箱（convection oven)等（採用具備有使 氣之空氣加熱方式的熱源者以使乾燥機內的熱風進行 接觸（counter-current contact)之方法及從噴嘴噴向 體之方式）以實施。 形， ，即 以上 行反 性、 ，即 理， 和鍵 視其 電路 之外 氧樹 离布/ .聚 等級 聚酯 發乾 plate 用蒸 逆流 支撐 -49- 201106096 經下述方式塗佈本發明之感光性樹脂組成物並揮發乾 燥後，對所得之塗膜實施曝光（活性能量射線的照射）。 塗膜，係曝光部份（被活性能量射線所照射之部分）所硬 化者。 可採用於上述活性能量射線照射之曝光機而言，可採 用：直接描畫裝置（direct writing apparatus)(例如， 利用來自電腦的CAD (電腦輔助設計）而直接利用雷射以 描畫影像之雷射直接影像裝置（laser direct imaging apparatus))、裝載有金屬鹵化物燈（metal halide lamp )之曝光機、裝載有（超）高壓水銀燈之曝光機、水銀短 路弧燈（mercury short arc lamp )之曝光機、或者經使用 (超）高壓水銀燈等的紫外線燈之直接描畫裝置。活性能 量射線而言，只要是採用最大波長在350至410nm的範圍 之雷射光則可爲氣體雷射（gas laser)或固體雷射（solid state laser)中之任一種。又，其曝光量雖因膜厚等而有 所異，惟一般可作成5至200mJ (兆焦耳）/cm2、較佳爲 5至100mJ/cm2、更佳爲5至50mJ/cm2的範圍內。上述直 接描畫裝置而言，例如，可使用日本歐爾波科技社製、遍 達克斯社製等者，只要是能振盪（oscillation )最大波長 爲350至410nm的雷射光之裝置則可採用任一種裝置。 前述顯像（developing)方法而言，可利用：浸漬法 (dipping)、簇射法（shower)、噴霧法（spray)、電 刷法（brush)等，顯像液而言，可使用：氫氧化鉀、氫 氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨氣、胺類 -50- 201106096 等的鹼化合物溶液。 本發明之感光性樹脂組成物，除以液狀直接塗佈於基 材上之方法以外，尙可以具有經預先對聚對苯二甲酸乙二 醇酯等的薄膜上塗佈，乾燥而形成有阻焊劑之阻焊劑層之 乾式薄膜（dry film )之形態使用。將本發明之感光性樹 脂組成物作爲乾式薄膜使用之情形，表示如下述。 乾式軟片，係具有依序層合有載體薄膜、及阻焊劑層 、以及需要時所用之能剝離的舖罩薄膜（cover film )之 構造者。阻焊劑層，係將鹼顯像性的感光性樹脂組成物塗 佈，乾燥於載體薄膜或舖罩薄膜上所得之層。經於載體薄 膜上形成阻焊劑層後，於其上層合舖罩薄膜，或經於舖罩 薄膜上形成阻焊劑層，並如將此層合物層合於載體薄膜上 則可製得乾式薄膜。 載體薄膜而言，可採用2至150 μιη的厚度的聚酯薄膜 等的熱塑性薄膜。 阻焊劑層，係將鹼顯像性的感光性樹脂組成物使用： 刮板塗佈器（blade coater )、模唇塗佈器（lip coater ) 、逗號塗佈器（comma coater)、薄膜塗佈器（film coater)等，按10至150μιη的厚度均勻塗佈於載體薄膜 或舖罩薄膜上並乾燥以形成者。 舖罩薄膜而言，可使用聚乙烯薄膜、聚丙烯薄膜等， 惟較佳爲採用與阻焊劑層之間的膠黏力（bonding strength )較載體薄膜者爲小者。 如欲採用乾式薄膜而於印刷電路板上製作保護膜（永 -51 - 201106096 久保護膜）時，則剝離舖罩薄膜後，重疊阻焊劑 有電路之基材，採用層壓機（laminator )以使其 於形成有電路之基材上形成阻焊劑層。如對所形 劑層，與前述同樣方式進行曝光、顯像、加熱硬 形成硬化塗膜。載體薄膜，可於曝光前或曝光後 期剝離。 【實施方式】 〔實施例〕 以下，將舉示實施例及比較例以具體性說明 容，惟當然，本發明並不因下述實施例而有所限 ，下述中之「份」及「％」，除非有備註，均爲 者。 合成例1(含羧基之樹脂（B)之合成） 於具備有攪拌裝置、溫度計、電容器之反應 作爲具有2個以上的醇性羥基之化合物而飼給： 二醇與1,6-己二醇所衍生之聚碳酸酯二醇（旭化 (股）製，TJ5650J、數平均分子量800) 360g( )、二羥甲基丁酸81.4g(0.55莫耳），及作爲 整劑（反應停止劑（reacti on termination agent 給正丁醇11.8g ( 0.16莫耳）。接著，作爲不具 之異氰酸酯化合物而飼給三甲基六亞甲基二 200.9g ( 1.08莫耳）·，在攪拌之下加熱爲60°C後 層及形成 貼合’而 成之阻焊 化，則可 之任一時 本發明內 定。再者 質量基準 容器中， 由1,5-戊 成化學品 0.45莫耳 分子量調 ))而飼 有芳香環 異氰酸酯 停止，當 -52- 201106096 反應容器內溫度開始降低時再度加熱並在80°C時繼續攪拌 ，當使用紅外線吸收光譜而確認異氰酸酯基的吸收光譜（ absorption spectrum) ( 2280CTTT1)已消失之事實後即終 止反應。接著，按固態分能成爲60 wt%之方式添加卡必醇 乙酸酯後，製得含有稀釋劑之黏稠液體的含羧基之聚胺基 甲酸酯。將此簡稱B-1漆（varnish)。此乃相當於先前就 含羧基之樹脂（B)所說明之（2)的含羧基之聚胺基甲酸 酯樹脂。 合成例2(含羧基之樹脂（B)之合成） 於具備有攪拌裝置、溫度計、電容器之反應容器中， 飼給由1，5-戊二醇與1，6-己二醇所衍生之聚碳酸酯二醇（ 旭化成化學品（股）製，TJ565〇J、數平均分子量800) 2400g(3莫耳）、二羥甲基丙酸603g(4.5莫耳），以及 作爲一羥基化合物之2-羥基乙基丙烯酸酯238g(2.6莫耳 )。接著，作爲聚異氰酸酯而飼給異佛爾酮二異氰酸酯 1 8 8 7g ( 8.5莫耳），在攪拌下加熱爲6〇t後停止，當反 應容器的內溫度開始降低時再度加熱並在8 0 °C時繼續攪拌 ，當使用紅外線吸收光譜而確認異氰酸酯的吸收光譜（ 22 8 0(^1^1 )已消失之事實後即終止反應。按固體成分能成 爲50質量％之方式添加卡必醇乙酸酯。將此簡稱爲b_2漆 。此乃相當於先前就含羧基之樹脂（B )所說明之（5 )的 經末端（甲基）丙烯基化之含羧基之聚胺基甲酸酯樹脂。 -53- 201106096 合成例3(含羧基之樹脂（B)之合成） 於具備有溫度計、氮氣導入裝置兼氧化烷烯導入裝置 以及攪拌裝置之高壓釜（autoclave)中，飼給酚醛清漆型 甲酚樹脂（昭和高分子（股）製，商品名「蕭諾爾 CRG951」，OH 當量：119.4) 119.4g，氫氧化鉀 l.l9g 以 及甲苯119.4g，在攪拌之下進行系內之氮氣取代，並加熱 升溫。接著，徐徐滴下氧化丙烯63.8g，在125至132 °C ，0至4.8 kg/cm2下反應16小時。然後，冷卻爲室溫後， 對此反應溶液中添加混合89%磷酸1.56g以中和氫氧化鉀 ，製得不揮發分62.1%、羥値爲182.2g/eq.(當量）之酚 醛清漆型甲酚樹脂的氧化丙烯反應溶液。此乃對每酚性羥 基1當量，加成有平均1.08莫耳之氧化丙烯者。將所得 酚醛清漆型甲酚樹脂的氧化烷烯反應溶液293.0g、丙烯酸 4 3.2 g ' 甲擴酸（methane sulfonic acid) 11.53g、甲基氫 醌0.18g以及甲苯252.9g飼給於具備有攪拌機、溫度計以 及空氣噴入管之反應器中，按l〇ml/分鐘的速度噴入空氣 ，在攪拌之下，於1 1 〇°C進行反應1 2小時。因反應所生成 之水，則作爲與甲苯的共沸混合物（aze〇tr〇Pic mixture) ，餾出有12.6g的水。然後，冷卻爲室溫，並將所得反應 溶液，使用15%氫氧化鈉水溶液3 5.3 5g加以中和’接著 加以水洗。然後使用蒸發器（evaporator )在將甲苯以乙 二醇一乙基醚乙酸酯118.lg進行取代之下餾除，製得酚 醛清漆型丙烯酸酯樹脂溶液。接著，將所得酚醛清漆型丙 烯酸酯樹脂溶液332.5g及三苯基膦1.22g’飼給於具備有 -54- 201106096 攪拌器、溫度計以及空氣噴入管之反應器中，將空氣以 10ml/分鐘的速度噴入，在攪拌之下徐徐添加四氫酞酸酐 60.8g，於95至101 °C反應6小時。製得固態物的酸値 88mgKOH/g，不揮發物71%的含羧基之感光性樹脂。將此 簡稱爲樹脂溶液B-3漆。此乃相當於先前就含羧基之樹脂 (B )所說明之（9 )的含羧基之感光性樹脂。 將表1中所示各種成分按表1所示比例（質量份）加 以調配，並經於攪拌機預備混合後，使用3只輥磨（roll mill )進行混練，以調製阻焊劑用感光性樹脂組成物。將 在此所得之感光性樹脂組成物的分散度（degree of dispersion )，按使用伊利克仙社製硏磨計（grind meter )之粒度測定（particle size measurement)加以評價之結 果，爲15μηι以下者^ -55- 201106096 〔表1〕 組成 (質量份） 實想 酬 比較例 1 2 3 4 1 2 3 4 5 6 層狀雙氫氧化合物(αΓ 1 5 10 20 無機離子交換劑= 5 10 20 層狀無機化合物_3 5 10 含羧基之感光性樹脂Μ 150 150 150 150 150 150 150 150 150 150 光硬化性化合物(c) •5 20 20 20 20 20 20 20 20 20 20 光聚合引發劑 D-Γ6 5 5 5 5 5 5 5 5 5 5 D-2·7 1 1 1 1 1 1 1 1 1 1 熱硬化性成分 Ε-Γ8 15 15 15 15 15 15 15 15 15 15 Ε-2*9 25 25 25 25 25 25 25 25 25 25 硬化觸媒三聚氰胺 5 5 5 5 5 5 5 5 5 5 著色劑％ 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 著色劑+11 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 硫酸鋇”2 100 100 100 100 100 100 100 100 100 100 聚矽氧系消泡劑 3 3 3 3 3 3 3 3 3 3 有機溶劑DPM”3 3 3 3 3 3 3 3 3 3 3 * 1水滑石化合物：阿爾加邁莎 *2陽離子交換劑:1XE-100東亞合成(股)製 *3膨潤土 :〇rbenM白石工業(股)製 *4 DIC社製R-2000 (固態物65%)相當於前述含羧基之樹脂的說明(7) *5二季戊四醇己基丙烯酸酯：日本化藥(股)製 備 * ό伊爾加製亞907.千葉特殊化學品社製 註 * 7伊爾加裘亞ΟΧΕ02.千葉特殊化學品社製 *8酚醛清漆型環氧樹脂:DEN438陶氏化學社製 *9雙二甲苯酚型環氧樹脂:YX-4000日本環氧樹脂(股)製 氺 10 C.I.Pigment Blue 15:3 氺 11 C.I.Pigment Yellow 147 *12硫酸鋇:B-30堺化學(股)製 *13二丙二醇一甲基醚 -56- 201106096 性能評價： &lt; 塌邊性（Shear drop) &gt; 將銅厚35 μιη的電路圖型基板施加皮革磨光輥之拋光 (buff-roll grinding )後水洗、並乾燥後，採用簾流印刷 法而將前述實施例及比較例的光硬化性.熱硬化樹脂組成 物加以全面塗佈，並評價經將此基板垂直豎立60分鐘後 之塌邊程度。 〇：未能確認塌邊之發生 △:稍能確認塌邊之發生 X:確認有塌邊之存在 &lt;最適曝光量&gt; 將銅厚35 μιη的電路圖型基板施加皮革磨光輥之拋光 後水洗並乾燥後，採用簾流印刷法而將前述實施例及比較 例的光硬化性•熱硬化性樹脂組成物加以全面塗佈，並於 8 〇°C的熱風循環式乾燥爐中乾燥60分鐘。乾燥後，採用 裝載有高壓水銀燈（短路弧燈）之曝光裝置並藉由步進小 平板（step-tablet) (kodak (柯達）No.2)而曝光，並以 顯像（30°C、〇.2MPa (兆帕）、1 w t % N a2 C Ο 3 (碳酸鈉） 水溶液）60秒鐘時所殘留之步進小平板的圖型在7段時作 爲最適曝光量。 &lt;指觸乾燥性&gt; 於分別形成有圖型之銅箔基板上，採用簾流印刷法而 -57- 201106096 將表1記載之光硬化性樹脂組成物加以全面塗佈，並於80 °C的熱風循環式乾燥爐乾燥3 0分鐘後放冷至室溫。對此 基板上按壓PET薄膜，然後當剝離負底片（nega film )時 的薄膜的貼附狀態加以評價。 ◎:當剝離薄膜時，完全無阻力，且塗膜上無痕跡。 〇：當剝離薄膜時，完全無阻力，惟塗膜上稍有痕跡 〇 △:當剝離薄膜時，稍有阻力，而塗膜上有痕跡。 X:當剝離薄膜時，有阻力，而塗膜上明顯有痕跡。 &lt;解像性（resolation) &gt; 將線（line) /間隙（space)爲 300/300μηι、銅厚 35μπι的電路圖型基板施加皮革磨光輥之拋光後水洗、並 乾燥後，採用簾流印刷法而將實施例及比較例的光硬化性 •熱硬化性樹脂組成物加以塗佈，並於80°C的熱風循環式 乾燥爐中乾燥30分鐘。乾燥後，採用裝載有高壓水銀燈 (短路弧燈）之曝光裝置加以曝光。曝光圖型係使用於間 隙部描畫20/30/40/50/60/70/80/90/1 00μιη的線之玻璃乾片 (glass dry plate )。曝光量則按能成爲感光性樹脂組成 物的最適曝光量之方式照射活性能量射線。曝光後，利用 30°C的lwt%Na2C03水溶液而進行顯像以描畫圖型，並於 1 5 〇°C實施熱硬化60分鐘之結果，製得硬化塗膜。 使用經調整爲200倍之光學顯微鏡求出所得阻焊劑用 感光性樹脂組成物的硬化塗膜的最小殘留線（解像性）。 -58- 201106096 〈最大顯像壽命（maximum developing life) &gt; 於形成有圖型之銅箔基板上，採用簾流印刷法而將實 施例及比較例的光硬化性樹脂組成物按乾燥塗膜能成爲 2〇μηι之方式加以全面塗佈，並於8(TC之下進行乾燥。然 後，從20分鐘至80分鐘按每隔10分鐘取出基板，並分 別放冷至室溫。 將乾燥時間不相同的基板分別採用 3 0 °C的 1 wt% Na2C03水溶液，依噴霧壓〇.2MPa的條件進行顯像60秒 鐘，並以不殘留殘渣之最大容許乾燥時間作爲最大顯像壽 命。 &lt;色調（color tone) &gt; 依目視判斷阻焊劑用感光性樹脂組成物的硬化物的顏 色。 特性試驗： 於形成有圖型之銅箔基板上’採用簾流印刷法而將上 述各實施例及比較例的組成物按乾燥後的膜厚能成爲 20μιη之方式加以全面塗佈’並於8〇°C2下乾燥3〇分鐘後 ’放冷至室溫。對此基板，採用裝載有高壓水銀燈（短路 弧燈）之曝光裝置以最適曝光量進行阻焊劑圖型之曝光， 將3 0°C的1 wt%Na2C〇3水溶液依噴霧壓〇2MPa的條件實 施顯像60秒鐘後’製得光阻劑圖型（resist pattern)。將 此基板’利用uv (紫外線）輸送帶爐依累積曝光量 -59- 201106096 1 0 0 0 m J / c m2的條件進行紫外線照射後，於1 5 0 °C加熱6 0 分鐘使其硬化。對所得印刷基板（評價基板）按照下述方 式評價特性。 &lt;靜料耐熱性（solder heat resistance) &gt; 將塗佈有松香系助熔劑（rosin type flux)之評價基 板，浸漬於經預先設定爲2 6 0 °C之銲料槽（ solder tank ) 內，並使用變性酒精（denatured alcohol)洗滌助熔劑後 ，依目視之就光阻劑層的膨脹（bulging ) •剝落（ peeling )加以評價。判定基準爲如下所述。 ◎:即使重複1 〇秒鐘浸漬6次以上，仍不能認出剝 落。 〇：即使重複1 〇秒鐘浸漬3次以上，仍不能認出剝 落。 △:如重複1 〇秒鐘浸漬3次以上時，則會少量剝離 〇 X :如重複1 〇秒鐘浸漬3次以下時，則光阻劑層有膨 脹、剝落。 〈無電解鍍金耐性（nonelectrolytic gold plating resistance ) &gt; 採用市售品的無電解鑛錬浴（nonelectrolytic nickel plating bath)及無電解鍍金浴，依鎳〇·5μιη、金 0·03μηι 的條件進行電鍍，依膠黏帶剝離（tape peeling)後的目視 -60- 201106096 ，以評價有無光阻劑層的剝離或有無電鍍的滲 osmosis)的發生。判定基準爲如下所示。 ◎:未能確認滲透、或剝離之發生。 〇：電鍍後可確認少量滲透，惟膠黏帶剝離後則 離。 △:電鍍後可確認僅少量滲透，膠黏帶剝離後亦 離。 X :電鍍後有剝離之發生。 &lt;電氣特性1 (絕緣可靠性、電極腐蝕性）&gt; 採用線/間隙=50/5 0μπι的梳形電極圖型（comb electrode pattern)，依上述條件製作評價基板，以進 氣特性（絕緣可靠性、電極腐蝕性）的評價。 評價方法，係將此梳形電極在1 2 1 °C、97%R.H. 對濕度）的加溫加濕條件下施加DC (直流）30V (伏 的偏電壓（bias voltage)，以測定至絕緣開始劣化爲 時間。在此，當電阻値下降至1 X 1 〇·6 Ω (歐姆）時， 爲絕緣開始劣化。 又’將於上述條件下之100小時後的電極的腐蝕 (樹枝狀晶體（dendrite)的產生程度），依下述判 準加以評價。 ◎:並無樹枝狀晶體的產生，且變色亦輕微。 〇：雖無樹枝狀晶體的產生，惟可確認變色。 △:可確認輕微之樹枝狀晶體的產生。 透（ 無剝 有剝 type 行電 (相 特） 止的 判定 程度 定基 201106096 X :涵蓋陽極-陰極間大大成長有樹枝狀 &lt;耐鹼性&gt; 將評價基板在50°c之下浸漬30分鐘於 (氫氧化鈉）水溶液中，以確認有無滲透， 及因膠黏帶剝離之發生。判定基準爲如下所5 〇：無滲透、溶化、剝離之發生。Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202 o -41 - 201106096 Iso-P-pyrrolidone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 1 8 5 o Condensation Azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 15 5, Pigment Yellow 166, Pigment Yellow 180 o Benzoflavonoid: pigment Y Y 11 ow 1 2 0,P Igment Y e 11 ow 151, Pigment Y ellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellowl81 o Monoazo system: Pigm ent Yellow 1 ,2, 3, 4, 5, 6, 9, 10, 12, 61 , 62:1, 65, 73,74, 75, 97, 1 00, 1 04, 105, 111, 116, 167, 168, 169, 182, 1 83 ° Diazo: Pigm lent Yellow 12, 13, 1 4, 16, 17, 55, 63 , 8 1 , 8 3, 8 7, 126, 127, 152, 1 70, 172, 174, 176, 188, 198 ° Others, can also adjust the tone (tone) For the purpose, a coloring agent such as purple, orange, brown, or black is added. For specific examples, there are: Pigment Violet 19, 23, 29, 3 2, 3 6, 3 8, 42, Solvent Violet 13, 36, CIPigment Orange Orange) 1, CIPigment Orange 5, CIPigment Orange 13, CIPigment Orange 14, CIPigment Orange 16, CIPigment Orange 17, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 38, - 42- 201106096 C. I. Pigment Orange 40, C. I. P i gm ent Orange 43, CIPigment Orange 46, C. I. P i gm en t Orange 49, CIPigment Orange 51, C . I. P i Gm ent Orange 61, C . I. P i gm en t Orange 63, C . I. P i gment Orange 64, CIPigment Orange 71, CIPigment Orange 73, CIPigment Brown 23, CIPigment Brown 25, CIPigment Black 1, CIPigment Black 7, etc. The proportion of the above-mentioned coloring agent (F) is not particularly limited, but it is preferably 0 to 1 part by mass, more preferably 0 to 1 part by mass, based on 100 parts by mass of the above-mentioned carboxyl group-containing resin (B). The ratio of parts by mass is sufficient. In the photosensitive resin composition of the present invention, in order to improve the physical strength of the coating film and the like, a filler (G) may be blended as needed. For the purpose of such a raw material (G), a well-known inorganic or organic tantalum can be used, but it is preferably used as barium sulfate, spherical cerium oxide and talc. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, metal oxide or aluminum hydroxide may be used as a base pigment filler. The blending amount of the raw material (G) is preferably 75 mass% or less, more preferably 〇1 to 60 mass%, based on the total amount of the composition. When the blending amount is more than 75 mass% of the total amount of the composition, the viscosity of the insulating composition is increased, coating, moldability is lowered, or the cured product is weak. Further, in the photosensitive resin composition of the present invention, the synthesis or composition of the carboxyl group-containing resin (B) is adjusted, or the viscosity is applied to the base-43-201106096 plate or carrier film. The organic solvent which can be used as an organic solvent may, for example, be a ketone, an aromatic hydrocarbon glycol ether, a glycol ether acetate, an ester or an alcohol, or an aliphatic petroleum solvent. More specifically, it is a ketone of methyl ethyl ketone or a ring; an aromatic hydrocarbon fibrin (toluene, xylene, tetramethylbenzene, etc.), methyl cellosolve, butyl cellosolve , carbitol, methyl carbitol, butyl carbitol, propylene glycol monoether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol ether and other diethanol ethers; acetic acid Esters of ethyl ester, butyl acetate, dipropyl methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether ester, propylene glycol butyl ether acetate, etc.; ethanol, propanol, ethylene glycol, propylene glycol Alcohols such as alcohols; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum naphtha, hydrogenated petroleum brain, and solvent stone. Such an organic solvent may be used singly or in combination of two or more kinds. In general, many polymer materials are continuously oxidatively degraded as soon as they start to oxidize, which causes a decrease in the function of the polymer. Therefore, the photosensitive resin composition of the present invention can be added for oxidation. (1) A radical scavenger (H-1) and/or (2) that deactivates the generated radicals to decompose the raw peroxide into a harmless substance and to form a new base. Antioxidant (Η) such as peroxide docomposer 2). Antioxidant (Η-1), ethylene glycol, ketone: bisphenol alcohol methyl alcohol monoglycol acetate glycol ether, which acts as a radical scavenger, prevents freedom from being produced when the oil brain is produced (Η - In terms of -44-201106096, specific compounds may, for example, be hydroquinone, 4-tert-butylcatechol (catechol), 2-tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-extended methyl bis(4-methyl-6-tert-butylphenol), 1,1,3-parade (2-methyl-4) -hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-glucosin (3,5-di-t-butyl-4-hydroxybenzyl)benzene 1,3,5-paran (3',5'-di-t-butyl-4-hydroxybenzyl)-second triterpene, 2,4,6-(1H,3H,5H)trione, etc. a phenolic compound, an anthraquinone compound such as hydrazine or benzoquinone, bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, phenothiazine The amine-based compound 〇 radical scavenger may be a commercially available one, and may be exemplified by: Atticasta AO-30, Atticasta AO-330, Atticasta AO-20 Ati Stubbs AL-77, Atticasta LA-57, Atticasta LA-67, Atticasta LA-68, Atticasta LA-87 (above 'both For Asahi Denki Co., Ltd., trade name), IRGANOX 1010, IRG AN 0X1035, IRGAN0X1076, IRGANOX1135, TINUVIN 111NDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5 100 (all of them are manufactured by Chiba Special Chemicals Co., Ltd., trade name), etc. As the antioxidant (H-2) which acts as a peroxide decomposing agent, specific compounds may, for example, be triphenyl A phosphorus-based compound such as a phosphite, a thiol compound such as pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate or distearyl 3,3'-thiodipropionate. 45- 201106096 The peroxide decomposing agent 'can be a commercial one' can be exemplified: Atticasta TPP (made by Asahi Denki Co., Ltd., trade name), Mark AO-412SC Attica Akas Chemical Co., Ltd. , the product name), Sumi Risa TP S (manufactured by Sumitomo Chemical Co., Ltd., trade name). The above-mentioned antioxidants (Η)' may be used singly or in combination of two or more. In addition, in the photosensitive resin composition of the present invention, in order to prevent the stabilization of ultraviolet rays, in addition to the above-mentioned antioxidant, 尙 can be used. UV absorber (I). The ultraviolet absorber (I) may, for example, be a diphenyl ketone derivative, a benzoate derivative, a benzotriazole derivative, a tri-negative derivative, a benzothiazole derivative or a cinnamate derivative. An anthranilate derivative, a benzamidine methane derivative or the like. Specific examples of the diphenyl ketone derivative include 2-hydroxy-4-methoxydiphenyl ketone and 2-hydroxy-4-n-octyloxydiphenyl ketone '2,2'-dihydroxyl 4-methoxydiphenyl ketone and 2,4-dihydroxydiphenyl ketone and the like. Specific examples of the benzoate derivative include 2-ethylhexylsalicylate, phenylsalicylate, p-tert-butylphenylsalicylate, and 2,4-di Tert-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate and the like. Specific examples of the benzotriazole derivative include 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole and 2-(2,-hydroxy-5'- Methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2,·hydroxyl - 3',5'-di-t-butylbenzene-46- 201106096 base)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2 - (2,-Hydroxy-3',5'-di-p-pentylphenyl)benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine and bisethylhexyloxyphenol methoxyphenyl triazine. The ultraviolet absorber (I) may be a commercially available one, and may be exemplified by TINUVIN PS ' TINUVIN 99-2, TINUVIN 109, TINUVIN 3 84-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405 , TINUVIN 460, TINUVIN 479 (above, all are manufactured by Chiba Specialty Chemicals Co., Ltd., trade name). The above-mentioned ultraviolet absorbers (I) may be used singly or in combination of two or more kinds, and when used in combination with the above-mentioned antioxidant (Η), stabilization of a molded product obtained from the photosensitive resin composition of the present invention can be achieved. In the photosensitive resin composition of the present invention, a conventionally known thermal polymerization inhibitor, a fine powder of cerium oxide, an organic bentonite, a microcrystalline kaolinite, etc., may be blended as needed. Defoaming agent and/or leveling agent, imipenem, thiazide, triterpene, etc. of thixotropy endower, polyoxane, fluorine, and polymer Well-known additives such as sand yard coupling agents, antioxidants, and rust inhibitors. The aforementioned thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the above polymerizable compound. The thermal polymerization inhibitor may, for example, be 4-methoxybenzoquinone, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butylcatechol-47-201106096, pyrophenol (pyrogallol), 2- Hydroxydiphenyl ketone, 4-methoxy-2-hydroxydiphenyl ketone, chlorinated ketone, morphine, chloranil, naphthylamine, P-naphthone, 2,6-di 3rd 4-methylphenol, 2,2'-methylenebis(Imethyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-A Tolaidine, Methylene Blue, a reaction with copper organic chelating compound, methyl salicylate, and morphine, nitroso compound and A1 (aluminum) Chelate and the like. The photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method by using the organic solvent, for example, and then applied to a substrate by dip coating, flow coating, or flow coating. Coating by a light coating method, a bar coating method, a screen printing method, a curtain coating method, or the like, about 60 to 10 ( The temperature of the TC is such that the organic solvent contained in the composition is volatilized and dried (pre-dried) to form a coating film which is tack free. Further, if the above composition is coated on a carrier film, After drying, the film is wound as a film, and the latter is bonded to the substrate to form a resin insulating layer. Then, by contact (or non-contact), it is selectively transmitted through a photo mask formed with a pattern. Exposing with active energy rays (activeenergyray) or direct pattern exposure using a laser direct exposing machine, and using an alkalized unexposed portion An aqueous solution (for example, 0.3 to 3 wt% of sodium carbonate aqueous solution) is developed to form a photoresist pattern (resist pattern -48-201106096). Further, it contains a thermosetting component (E). The composition is heated, for example, to a temperature of about 140 to 180 ° C to thermally harden the carboxyl group of the carboxyl group-containing resin (B), and has two cyclic ether groups and/or cyclic sulfur in the molecule. When the thermosetting component (E) of the ether group is applied, it is possible to form an excellent cured coating film which is excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, and electrical properties of adhesion. Further, it does not contain heat curing. In the case of the component (E), if the heat is applied, the thermal radical polymerization is carried out due to the ethylenic unsaturation remaining in the unreacted state at the time of exposure, and the film properties are improved. And heat treatment (thermosetting). In addition to the above-mentioned substrate, a printed board or a flexible print circuit board in which a circuit is formed in advance can be used: paper-benzoquinone resin, paper-ring Oxygen resin, glass cloth - ring , glass-polyimine, glass cloth/non-woven fabric-epoxy resin, glass: paper-epoxy resin, synthetic fiber-epoxy resin, fluorine resin, vinyl, PP0 (polyphenylene ether), cyanate, etc. All of the composite materials (FR-4, etc.) are copper-clad laminates, polyimide films, pet films, glass substrates, ceramic substrates, wafer plates, and the like. The slewing method after the application of the photosensitive resin composition of the present invention can be: a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. The heat source of the air heating method is implemented by a method of counter-current contact in the dryer and a method of spraying from the nozzle to the body. Shape, that is, the above-mentioned inverse, that is, the rational, and the key depends on the circuit outside the oxygen tree off the cloth /. Poly grade polyester hair dry plate with steam countercurrent support -49- 201106096 The invention is coated in the following manner After the photosensitive resin composition is evaporated and dried, the obtained coating film is exposed (irradiation of active energy rays). The coating film is hardened by the exposed portion (the portion irradiated with the active energy ray). For the exposure machine of the above active energy ray irradiation, a direct writing apparatus (for example, using a CAD (Computer Aided Design) from a computer and directly using a laser to draw an image directly can be used. a laser direct imaging apparatus, an exposure machine loaded with a metal halide lamp, an exposure machine loaded with a (super) high pressure mercury lamp, and an exposure machine of a mercury short arc lamp. Or a direct drawing device using an ultraviolet lamp such as a (super) high pressure mercury lamp. For the active energy ray, any one of a gas laser or a solid state laser may be used as long as the laser light having a maximum wavelength in the range of 350 to 410 nm is used. Further, although the exposure amount varies depending on the film thickness or the like, it is generally in the range of 5 to 200 mJ (megajoules)/cm 2 , preferably 5 to 100 mJ/cm 2 , more preferably 5 to 50 mJ/cm 2 . For the above-mentioned direct drawing device, for example, it can be manufactured by Nippon Technology Co., Ltd., manufactured by Nendase Co., Ltd., etc., and any device capable of oscillating laser light having a maximum wavelength of 350 to 410 nm can be used. A device. In the above development method, a dipping method, a shower method, a spray method, a brush method, or the like can be used, and in the case of a developing liquid, hydrogen can be used. A solution of an alkali compound such as potassium oxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, or amines-50-201106096. In addition to the method of directly applying a photosensitive resin composition of the present invention to a substrate, the ruthenium may be formed by coating a film of polyethylene terephthalate or the like in advance and drying it. The form of a dry film of the solder resist layer of the solder resist is used. The case where the photosensitive resin composition of the present invention is used as a dry film is as follows. The dry film is a structure having a carrier film, a solder resist layer, and a cover film which can be peeled off as needed. The solder resist layer is a layer obtained by coating a base photosensitive photosensitive resin composition and drying it on a carrier film or a cover film. After the solder resist layer is formed on the carrier film, the mask film is laminated thereon, or a solder resist layer is formed on the mask film, and a dry film can be obtained by laminating the laminate on the carrier film. . For the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used. The solder resist layer is used as a photosensitive resin composition for alkali development: a blade coater, a lip coater, a comma coater, and a film coating. A film coater or the like is uniformly coated on a carrier film or a cover film at a thickness of 10 to 150 μm and dried to form a film. For the cover film, a polyethylene film, a polypropylene film, or the like can be used, but it is preferable to use a bonding strength with the solder resist layer which is smaller than that of the carrier film. If a protective film (Yong-51 - 201106096 long-lasting protective film) is to be formed on a printed circuit board by using a dry film, after peeling off the mask film, the solder resist has a circuit substrate, and a laminator is used. A solder resist layer is formed on the substrate on which the circuit is formed. For the coating layer, exposure, development, and heating are carried out in the same manner as described above to form a hardened coating film. The carrier film can be peeled off before or after exposure. [Embodiment] The following is a description of the embodiments and comparative examples, but the present invention is not limited by the following examples, the following "parts" and " %", unless there is a note, it is all. Synthesis Example 1 (Synthesis of a carboxyl group-containing resin (B)) A reaction having a stirring device, a thermometer, and a capacitor is fed as a compound having two or more alcoholic hydroxyl groups: a diol and 1,6-hexanediol Derived polycarbonate diol (manufactured by Asahi Kasei Co., Ltd., TJ5650J, number average molecular weight 800) 360 g ( ), dimethylol butyric acid 81.4 g (0.55 mol), and as a complete agent (reaction stop agent ( Reacti on termination agent 11.8 g (0.16 mol) of n-butanol. Then, as a non-isocyanate compound, it was fed to trimethylhexamethylene 200.9g (1.08 mol)·, and heated to 60 with stirring. In the case of the rear layer of °C and the formation of the soldering of the bonding, the invention may be determined at any time. In addition, the mass-based container is fed by a 1,5-pentane chemical 0.45 molar molecular weight adjustment) The aromatic cyclic isocyanate was stopped. When the temperature in the -52-201106096 reaction vessel began to decrease, it was heated again and stirring was continued at 80 ° C. When the infrared absorption spectrum was used, it was confirmed that the absorption spectrum ( 2280CTTT1) of the isocyanate group disappeared. After the facts The reaction was stopped. Next, carbitol acetate was added in such a manner that the solid fraction was 60 wt%, and a carboxyl group-containing polyurethane having a viscous liquid of a diluent was obtained. This is referred to as B-1 varnish. This is equivalent to the carboxyl group-containing polyurethane resin (2) previously described for the carboxyl group-containing resin (B). Synthesis Example 2 (Synthesis of a carboxyl group-containing resin (B)) In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, a polycondensation derived from 1,5-pentanediol and 1,6-hexanediol was fed. Carbonate diol (manufactured by Asahi Kasei Chemicals Co., Ltd., TJ565〇J, number average molecular weight 800) 2400g (3 moles), dimethylglycolic acid 603g (4.5 moles), and 2-hydroxyl compounds Hydroxyethyl acrylate 238 g (2.6 mol). Next, as a polyisocyanate, 1 8 8 7 g (8.5 mol) of isophorone diisocyanate was fed, and the mixture was heated to 6 〇t with stirring, and then stopped. When the internal temperature of the reaction vessel began to decrease, it was heated again at 80. Stirring was continued at ° C. When the absorption spectrum of the isocyanate was confirmed by the infrared absorption spectrum (22 8 0 (^1^1) disappeared, the reaction was terminated. The carbitol was added in such a manner that the solid content was 50% by mass. Acetate. This is abbreviated as b_2 lacquer. This is equivalent to the terminal (meth) acrylated carboxyl group-containing polyurethane of (5) previously described for the carboxyl group-containing resin (B). -53-201106096 Synthesis Example 3 (Synthesis of carboxyl group-containing resin (B)) It is fed to a novolac type in an autoclave equipped with a thermometer, a nitrogen gas introduction device, an oxidizing alkene introduction device, and a stirring device. Cresol resin (produced by Showa Polymer Co., Ltd., trade name "Xeonor CRG951", OH equivalent: 119.4) 119.4 g, potassium hydroxide 1.19 g and toluene 119.4 g, and nitrogen substitution in the system under stirring And heating up. 63.8 g of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C, 0 to 4.8 kg/cm 2 for 16 hours. Then, after cooling to room temperature, 1.56 g of 89% phosphoric acid was added to the reaction solution for neutralization. Potassium hydroxide, a propylene oxide reaction solution of a novolac type cresol resin having a nonvolatile content of 62.1% and a oxindole of 182.2 g/eq. (equivalent), which is an average of 1 equivalent per phenolic hydroxyl group. 1.08 mole of propylene oxide. The obtained oxyalkylene reaction solution of the novolac type cresol resin was 293.0 g, acrylic acid 4 3.2 g 'methane sulfonic acid 11.53 g, methylhydroquinone 0.18 g, and toluene 252.9. g is fed to a reactor equipped with a stirrer, a thermometer and an air injection tube, and air is sprayed at a rate of l〇ml/min, and the reaction is carried out at 1 1 ° C for 12 hours while stirring. The resulting water was distilled as azeotrope with toluene (aze〇tr〇Pic mixture), and 12.6 g of water was distilled off. Then, it was cooled to room temperature, and the resulting reaction solution was treated with a 15% aqueous sodium hydroxide solution. 5.3 5g for neutralization' followed by water washing. Then use An evaporator was distilled off by substituting toluene with ethylene glycol monoethyl ether acetate 118.lg to prepare a novolac type acrylate resin solution. Next, the obtained novolac type acrylate resin solution was obtained. 332.5 g and triphenylphosphine 1.22 g' were fed to a reactor equipped with a -54-201106096 stirrer, a thermometer and an air injection tube, and air was sprayed at a rate of 10 ml/min, and four were added under stirring. 60.8 g of hydroquinone anhydride was reacted at 95 to 101 ° C for 6 hours. A carboxyl group-containing photosensitive resin having a solid content of 88 mg KOH/g and a nonvolatile content of 71% was obtained. This is simply referred to as resin solution B-3 paint. This is equivalent to the carboxyl group-containing photosensitive resin of (9) previously described for the carboxyl group-containing resin (B). The various components shown in Table 1 were blended in the proportions shown in Table 1 (parts by mass), and after mixing in a mixer, three rolls were used for kneading to prepare a solder resist for the solder resist. Things. The degree of dispersion of the photosensitive resin composition obtained here was evaluated by particle size measurement using a grind meter manufactured by Ilyssen Co., Ltd., and the result was 15 μηι or less. ^ -55- 201106096 [Table 1] Composition (parts by mass) Really compare Comparative Example 1 2 3 4 1 2 3 4 5 6 Layered double hydroxide (αΓ 1 5 10 20 inorganic ion exchanger = 5 10 20 layers Inorganic compound_3 5 10 Photosensitive resin containing carboxyl group 150 150 150 150 150 150 150 150 150 150 150 Photocurable compound (c) • 5 20 20 20 20 20 20 20 20 20 20 Photopolymerization initiator D-Γ6 5 5 5 5 5 5 5 5 5 5 D-2·7 1 1 1 1 1 1 1 1 1 1 Thermosetting component Ε-Γ8 15 15 15 15 15 15 15 15 15 15 Ε-2*9 25 25 25 25 25 25 25 25 25 25 Hardening catalyst melamine 5 5 5 5 5 5 5 5 5 5 Colorant % 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Colorant +11 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Barium sulfate 2 100 100 100 100 100 100 100 100 100 100 Polyoxygen defoamer 3 3 3 3 3 3 3 3 3 3 Organic Agent DPM"3 3 3 3 3 3 3 3 3 3 3 * 1 Hydrotalcite compound: Alga Mesa * 2 cation exchanger: 1XE-100 East Asia synthesis (stock) system * 3 bentonite: 〇rbenM white stone industry (shares) *4 DIC company R-2000 (solid matter 65%) is equivalent to the description of the above carboxyl group-containing resin (7) *5 dipentaerythritol hexyl acrylate: Nippon Chemical Co., Ltd. preparation * όIrga ya 907 .Notes by Chiba Specialty Chemicals Co., Ltd. * 7 Ilga 裘 ΟΧΕ 02. Chiba Special Chemicals Co., Ltd. *8 Novolak type epoxy resin: DEN438 by Dow Chemical Co., Ltd. *9 bis xylenol type epoxy resin: YX -4000 Japan Epoxy Resin Co., Ltd. C10 CIPigment Blue 15:3 氺11 CIPigment Yellow 147 *12 Barium Sulfate: B-30 堺Chemical (Unit)*13 Dipropylene Glycol Monomethyl Ether-56- 201106096 Performance evaluation: &lt;Shear drop &gt; A circuit pattern substrate having a copper thickness of 35 μm was subjected to buff-roll grinding, washed with water, and dried, and then subjected to curtain flow printing. The photocurable and thermosetting resin compositions of the foregoing examples and comparative examples were fully coated, and evaluated by vertically erecting the substrate 60. The degree of sagging after the bell. 〇: Failure to confirm the occurrence of sag △: Slightly confirm the occurrence of sag X: Confirm the presence of sag &lt; Optimum exposure> Apply a circuit pattern substrate with a copper thickness of 35 μm to the polishing surface of the leather polishing roller After washing with water and drying, the photocurable thermosetting resin composition of the above examples and comparative examples was completely coated by a curtain flow printing method, and dried in a hot air circulating drying oven at 8 ° C for 60 minutes. . After drying, exposure was carried out using a high-pressure mercury lamp (short-circuit arc lamp) and exposed by a step-tablet (kodak No. 2), and the image was developed (30 ° C, 〇 .2 MPa (MPa), 1 wt % N a2 C Ο 3 (sodium carbonate) aqueous solution) The pattern of the stepped small plate remaining at 60 seconds is used as the optimum exposure amount in the 7th step. &lt;Touch-drying property&gt; The photocurable resin composition described in Table 1 was applied to the copper foil substrate on which the pattern was formed, respectively, by a curtain flow printing method, -57-201106096, at 80 ° The hot air circulating drying oven of C was dried for 30 minutes and then allowed to cool to room temperature. The PET film was pressed against the substrate, and then the attached state of the film when the negative film (nega film) was peeled off was evaluated. ◎: When the film was peeled off, there was no resistance at all, and there was no trace on the coating film. 〇: When the film is peeled off, there is no resistance at all, but there is a slight trace on the film 〇 △: When the film is peeled off, there is a slight resistance, and there is a trace on the film. X: When the film was peeled off, there was resistance, and there was a marked trace on the film. &lt;Resolation &gt; A circuit pattern substrate having a line/space of 300/300 μm and a copper thickness of 35 μm is applied to a polishing pad of a leather polishing roll, washed, dried, and then subjected to curtain flow printing. The photocurable thermosetting resin compositions of the examples and the comparative examples were applied and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, it was exposed using an exposure apparatus equipped with a high pressure mercury lamp (short-circuit arc lamp). The exposure pattern is used to draw a glass dry plate of 20/30/40/50/60/70/80/90/1 00 μιη in the gap. The exposure amount is irradiated to the active energy ray in such a manner as to be an optimum exposure amount of the photosensitive resin composition. After the exposure, development was carried out by using an aqueous solution of 1 wt% Na2C03 at 30 ° C to draw a pattern, and heat hardening was carried out at 150 ° C for 60 minutes to obtain a cured coating film. The minimum residual line (resolution) of the cured coating film of the obtained photosensitive resin composition for a solder resist was determined using an optical microscope adjusted to 200 times. -58-201106096 <maximum developing life> &gt; Drying coating of the photocurable resin composition of the examples and the comparative examples on the copper foil substrate on which the pattern was formed by the curtain flow printing method It can be fully coated in a manner of 2〇μηι, and dried under 8 (TC). Then, the substrate is taken out every 10 minutes from 20 minutes to 80 minutes, and then allowed to cool to room temperature. The same substrate was respectively subjected to a 1 wt% Na2CO3 aqueous solution at 30 ° C, and developed under the conditions of a spray pressure of 2 MPa for 60 seconds, and the maximum allowable drying time without residual residue was taken as the maximum development life. (color tone) &gt; The color of the cured product of the photosensitive resin composition for the solder resist was visually judged. Characteristic test: On the copper foil substrate on which the pattern was formed, the above embodiments and comparisons were carried out by the curtain flow printing method. The composition of the example was fully coated in a manner that the film thickness after drying was 20 μm, and dried at 8 ° C for 3 minutes, and then allowed to cool to room temperature. The substrate was loaded with a high pressure mercury lamp (short circuit). The exposure device of the arc lamp is exposed to the solder resist pattern at an optimum exposure amount, and a 1 wt% Na2C〇3 aqueous solution at 30 ° C is subjected to development under the conditions of a spray pressure of 2 MPa for 60 seconds to prepare a photoresist. Resist pattern. The substrate was irradiated with ultraviolet light under the conditions of cumulative exposure -59-201106096 1 0 0 m J / c m2 using a uv (ultraviolet) conveyor belt furnace at 150 °C. The obtained printed circuit board (evaluation substrate) was evaluated for the following manner by heating for 60 minutes. &lt;Solder heat resistance &gt; Coating with rosin type flux The substrate was evaluated, immersed in a solder tank set to 260 ° C in advance, and after using a denatured alcohol to wash the flux, the bulging of the photoresist layer was visually observed. Peeling was evaluated and the evaluation criteria were as follows: ◎: Peeling was not recognized even after immersion for 6 times or more in 1 sec. 〇: Even if it was immersed 3 times or more after repeating 1 〇 second, it was not recognized. Peeling off △: If repeating 1 〇 When the bell is immersed three times or more, the 〇X is peeled off in a small amount: if the immersion is performed three times or less after repeating for one 〇 second, the photoresist layer is swollen and peeled off. <nonelectrolytic gold plating resistance> Commercially available nonelectrolytic nickel plating bath and electroless gold plating bath, electroplated according to conditions of nickel 〇·5μιη, gold 0·03μηι, visual peeling after tape peeling-60 - 201106096, to evaluate the occurrence of peeling of the photoresist layer or the presence or absence of electroplating osmosis. The judgment criteria are as follows. ◎: Failure to confirm the occurrence of penetration or peeling. 〇: A small amount of penetration can be confirmed after plating, but the adhesive tape is peeled off. △: After plating, it was confirmed that only a small amount of penetration was observed, and the adhesive tape was peeled off after peeling off. X: Peeling occurred after plating. &lt;Electrical Characteristics 1 (Insulation Reliability, Electrode Corrosion)&gt; Using a comb electrode pattern of line/gap = 50/5 0 μm, an evaluation substrate was fabricated under the above conditions to have an air intake characteristic (insulation) Evaluation of reliability, electrode corrosion). The evaluation method is to apply DC (DC) 30V (volts bias voltage) under the heating and humidification condition of the comb electrode at 1 2 1 ° C, 97% RH to humidity) to determine the insulation start. Deterioration is time. Here, when the resistance 値 drops to 1 X 1 〇·6 Ω (ohm), the insulation starts to deteriorate. Also, the corrosion of the electrode after 100 hours under the above conditions (dendrites (dendrite) The degree of production was evaluated according to the following criteria: ◎: There was no occurrence of dendrites, and the discoloration was slight. 〇: Although no dendrites were produced, discoloration was confirmed. △: Minor was confirmed. The production of dendrites. Permeation (no peeling and stripping type). The degree of determination is fixed. 201106096 X: Covers the anode-cathode greatly grows with dendritic &lt;alkaline resistance&gt; The substrate is evaluated at 50 ° C The mixture was immersed for 30 minutes in an aqueous solution of (sodium hydroxide) to confirm the presence or absence of penetration and the occurrence of peeling of the adhesive tape. The criterion was as follows: No osmosis, dissolution, or peeling occurred.

△:稍可確認滲透、溶化、或者剝離之I X :可大大確認滲透、溶化、或者剝離之 &lt;乾式薄膜製作&gt; 經分別以甲基乙基甲酮適當稀釋實施例 的阻焊劑用感光性樹脂組成物後，採 applicator)，按乾燥後的膜厚能成爲20μιη PET 薄膜（東麗（股）製，FB-50:l6pm). 燥3 0分鐘後，製得乾式薄膜。 &lt;基板製作&gt; 經將形成有電路之基板加以皮革磨光輥 真空層壓機（vacuum laminator)(名機製‘ ，MVLP-500 )依加壓度：0.8MPa ' 70°C、1 :133.3Pa的條件進行由上述方法所製作之 熱層壓後，製得具有未曝光之阻焊劑層之基 基板）。 體。 1 0 w t % NaOH 塗膜的溶化以 费生。 發生。 1及比較例1 用塗佈器（ 之方式塗佈於 在80°C下乾 拋光後，採用 作所（股）製 分鐘、真空度 乾式薄膜之加 板（未曝光之 -62- 201106096 將其評價結果表示於表2。 〔表2〕 特性 實施例 比較例 1 2 3 L 1 2 3 1 5 6 阻焊劑形態 (D:乾式薄膜,L:液狀） L L L L D L L L L D L L 塌邊性 Δ 〇 〇 〇 / X △ Δ Δ / 〇 〇 最適曝光量(mJ/cm2) 110 110 110 110 90 100 110 110 110 90 110 110 指觸乾燥性 X Δ 〇 〇 / X Δ Δ 〇 / 〇 〇 解像性 (最小殘留線寬幅:μη) 50 50 50 50 50 50 50 50 50 50 50 50 最大顯像壽命(分鐘） 60 60 60 60 / 60 60 60 60 / 60 60 色調 綠 綠 綠 綠 綠 綠 綠 綠 綠 綠 綠 綠 銲料耐熱性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 無電解 球度金耐性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 電氣 特性1 絕緣可靠性(hr) 150 190 250 260 255 95 70 75 75 80 65 55 電極腐蝕性 Δ 〇 ◎ ◎ ◎ X X X X X X X 耐鹼性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 實施例5至1 3及比較例7至1 5 將表3中所示各成分按表3所示比例（質量份）加以 調配，並經於攪拌機預備混合後，使用3只輥磨進行混練 ，以調製阻焊劑用感光性樹脂組成物。將在此所得之感光 性樹脂組成物的分散度，按使用伊利克仙社製硏磨計之粒 度測定加以評價之結果，爲1 5 μηι以下者。 -63- 201106096 〔表3〕 組成 (質量份） 細例 比較例 5 6 7 8 9 10 11 12 13 7 8 9 10 11 12 13 14 15 層狀雙氫氧化合物 (A)*M 10 10 10 10 10 10 10 10 10 含 羥 基 之 樹 脂 Β.15 150 150 Β·16 220 220 Β*17 150 150 Β-1漆 170 170 Β*18 150 150 Β-2漆 200 200 Β.19 150 150 Β-3漆 140 140 140 140 光硬化性化合物(C).20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 光聚合 引發劑 D-Γ2' 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 D-2·22 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 熱硬化 性成分 E-1·23 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 E-2·24 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 Ε-3·ί5 15 15 硬化觸媒三聚氰胺 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 著色劑·26 0.3 0.3 0.3 0,3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 著色劑π 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 硫酸鋇·28 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 聚矽氧系消泡劑 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 有榜 隨劑DPM·29 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 * 14水滑石化合物：阿爾加邁莎，協和化學工業(股)製 *15日本化藥(股)製，ZFR-1401H(固態分65%)，相當於前述含羧基之樹脂的說明(8) * 16黛色爾化學工業社製，塞克羅瑪P(ACA)Z250(固態分45%)，相當於前述含羧基之樹脂的說明 (1+10) * 17 DIC社製，R-2000(固態分65%)，相當於前述含羧基之樹脂的說明⑺ *18昭和高分子(股)製SPV-1000L-4個態分65%)，相當於前述含羧基之樹脂的說明(4) * 19 DIC(股)製，UE-9210(固態分65%),相當於前述含羧基之樹脂的說明(7)以及使縮水甘油基甲基 備 丙烯酸酯與竣基進行反應，以增加光反應性基之酸改性環氧丙烯酸酯 註*20二季戊四醇六丙烯酸酯，日本化藥(股)製 *21伊爾加裘亞907千葉特殊化學品社製 *22伊爾加裘亞OXE02千葉特殊化學品社製 *23苯酚酚醛清漆型環氧樹脂:DEN438陶氏化學社製 *24雙二甲苯酚型環氧樹脂:YX-4000日本環氧樹脂(股)製 *25尼加拉克MW-100LM(三和化學社製） * 26 C.I.Pigment Blue 15:3 *27 C.I.Pigment Yellow 147 *28硫酸鋇:B-3Q堺化學(股)製 |*29二丙二醇一甲基醚 -64 - 201106096 &lt;電氣特性2 (絕緣可靠性、電極腐蝕性）&gt; 於線/間隙=3 0/ 3 0 μπι的梳形電極圖型基板上’ 流印刷法而將上述實施例5至1 3及比較例7至1 5 成物按乾燥後的膜厚能成爲20μηι之方式加以全面 並於80 °C之下進行30分鐘乾燥後’放冷至室溫。 板，採用裝載有高壓水銀燈（短路弧燈）之曝光裝 適曝光量進行阻焊劑圖型之曝光，將30°C的lwt% 水溶液依噴霧壓〇.2MPa的條件顯像60秒鐘後，製 劑圖型。將此基板，利用 UV輸送帶爐依累積 lOOOmJ/cm2的條件進行紫外線照射後，於1 5 0 °C 1 分鐘使其硬化。對所得梳狀電極圖型基板進行電氣 絕緣可靠性、電極腐蝕性）的評價。 評價方法，係將此梳形電極在1 2 1 °C、97%R 溫加濕條件下施加DC30V的偏電壓，以測定絕緣 化爲止的時間。在此，當電阻値下降至1 X 1 Ο·6 Ω時 爲絕緣開始劣化。 又，將於上述條件下之1 0 0小時後的電極的腐 (樹枝狀晶體的產生程度），依下述判定基準加以 〇：並無樹枝狀晶體的產生 △:稍可確認樹枝狀晶體的產生 X:涵蓋陽極-陰極間大大成長有樹枝狀晶體 將評價結果，表示於表4。 採用簾 的各組 塗佈， 對此基 置以最 Na2C03 得光阻 曝光量 ]口 熱 6 0 特性（ .H.的加 開始劣 ，判定 :蝕程度 評價。 -65 - 201106096 〔表4〕 電氣特性2 實施例 匕較例 5 6 7 8 9 10 11 12 13 7 8 9 10 11 12 13 14 15 絕緣可靠性(hr) 100 150 100 250 200 250 300 360 300 50 50 70 70 70 70 100 120 120 電極腐蝕性 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X X X X X Δ Δ Δ 如上述表2及表4所示，在本發明之實施例1至13 的情形，當與比較例1至1 5相比較時，可確認其係在維 持各物性之下，不致於發生離子遷移，而在電氣特性，特 別是在電極腐蝕性上極爲優異，作爲鹼顯像性的感光性樹 脂組成物非常有用者之事實。 -66-△: IX which can be confirmed to be infiltrated, melted, or peeled off: "Immediate film formation" which can be confirmed to be infiltrated, melted, or peeled off. The photosensitivity of the solder resist of the example was appropriately diluted with methyl ethyl ketone, respectively. After the resin composition, the applicator was used, and the film thickness after drying was 20 μm PET film (manufactured by Toray Industries, Inc., FB-50: l6 pm). After drying for 30 minutes, a dry film was obtained. &lt;Substrate preparation&gt; The substrate on which the circuit was formed was subjected to a leather laminator vacuum laminator (name mechanism ', MVLP-500) according to the degree of pressurization: 0.8 MPa '70 ° C, 1:133.3 The conditions of Pa were subjected to thermal lamination by the above method to prepare a base substrate having an unexposed solder resist layer. body. 1 0 w t % NaOH The dissolution of the coating film is laborious. occur. 1 and Comparative Example 1 Using an applicator (applied to dry-washing at 80 ° C, using a dry film of a minute, vacuum dry film made by the manufacturer (unexposed -62-201106096 The evaluation results are shown in Table 2. [Table 2] Characteristic Example Comparative Example 1 2 3 L 1 2 3 1 5 6 Solder resist form (D: dry film, L: liquid) LLLLDLLLLDLL Collapse Δ 〇〇〇 / X Δ Δ Δ / 〇〇 optimum exposure amount (mJ/cm2) 110 110 110 110 90 100 110 110 110 90 110 110 Finger touch drying X Δ 〇〇 / X Δ Δ 〇 / 〇〇 resolution (minimum residual line width) Amplitude: μη) 50 50 50 50 50 50 50 50 50 50 50 50 Maximum development life (minutes) 60 60 60 60 / 60 60 60 60 / 60 60 Tone green green green green green green green green green green solder heat resistance 〇〇〇〇〇 〇〇〇〇〇〇〇 Electroless sphericity Gold resistance 〇〇〇〇〇〇〇〇〇〇〇〇 Electrical characteristics 1 Insulation reliability (hr) 150 190 250 260 255 95 70 75 75 80 65 55 Electrode corrosivity Δ 〇◎ ◎ ◎ XXXXXXX alkali resistance〇〇〇 〇〇〇〇〇〇〇〇〇Examples 5 to 13 and Comparative Examples 7 to 1 5 The components shown in Table 3 were blended in the proportions shown in Table 3 (parts by mass), and after mixing in a mixer The mixture was kneaded by three roll mills to prepare a photosensitive resin composition for a solder resist. The degree of dispersion of the photosensitive resin composition obtained herein was evaluated by particle size measurement using a honing meter manufactured by Illik As a result, it is 1 5 μηι or less. -63- 201106096 [Table 3] Composition (parts by mass) Example Comparative Example 5 6 7 8 9 10 11 12 13 7 8 9 10 11 12 13 14 15 Layered double hydroxide (A)*M 10 10 10 10 10 10 10 10 10 Hydroxyl-containing resin 15.15 150 150 Β·16 220 220 Β*17 150 150 Β-1 lacquer 170 170 Β*18 150 150 Β-2 lacquer 200 200 Β.19 150 150 Β-3 lacquer 140 140 140 140 Photocurable compound (C).20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Photopolymerization initiator D-Γ2' 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 D-2·22 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Thermosetting component E-1·23 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 E-2·24 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 Ε-3·ί5 15 15 Hardening catalyst melamine 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Colorant·26 0.3 0.3 0.3 0,3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Colorant π 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Barium sulfate · 28 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Polyoxynoxy defoamer 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Listed with DPM·29 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 * 14 Hydrotalcite compound: Alga Mesa, Concord Chemical Industry Co., Ltd. *15 Nippon Chemical Co., Ltd., ZFR-1401H (solid state: 65%), equivalent to the description of the above-mentioned carboxyl group-containing resin (8) * 16 Seychelles Chemical Industry Co., Ltd., Sekroma P (ACA) Z250 (solid state: 45%), equivalent to the description of the above-mentioned carboxyl group-containing resin (1+10) * 17 DIC, R- 2000 (solid content: 65%), equivalent to the description of the above-mentioned carboxyl group-containing resin (7) *18: SPV-1000L-4 of the Showa Polymer Co., Ltd. (65%), which corresponds to the description of the carboxyl group-containing resin (4) * 19 DIC (share) system, UE-9210 (solid state 65%), corresponding to the description of the above carboxyl group-containing resin (7) and reacting glycidyl methyl acrylate with sulfhydryl groups to increase light Reactive group acid-modified epoxy acrylate injection *20 dipentaerythritol hexaacrylate, Nippon Chemical Co., Ltd. *21 Ilga 裘 907 Chiba Special Chemicals Co., Ltd. *22 Ilga 裘 OXE02 Chiba Special Chemicals Co., Ltd. *23 Phenolic novolak type epoxy resin: DEN438* Doubly phenol type epoxy resin manufactured by The Dow Chemical Co., Ltd.: YX-4000 Japanese epoxy resin (share) *25 Nigarak MW- 100LM (manufactured by Sanwa Chemical Co., Ltd.) * 26 CIPigment Blue 15:3 *27 CIPigment Yellow 147 *28 Barium sulfate: B-3Q 堺Chemical (stock) system|*29 dipropylene glycol monomethyl ether-64 - 201106096 &lt; Electrical characteristics 2 (insulation reliability, electrode corrosion)&gt; After 5-1 Example 3 and Comparative Examples 7 to 15 to a film thickness after drying was to become the embodiment 20μηι be fully and below the 80 ° C for 30 minutes and dried 'allowed to cool to room temperature. The plate is exposed to a solder resist pattern by exposure exposure with a high-pressure mercury lamp (short-circuit arc lamp), and the lwt% aqueous solution at 30 ° C is imaged by a spray pressure of 2 MPa for 60 seconds. Graphic type. The substrate was subjected to ultraviolet irradiation under the conditions of a cumulative lOOOmJ/cm2 in a UV conveyor belt furnace, and then cured at 150 ° C for 1 minute. The obtained comb-shaped electrode pattern substrate was evaluated for electrical insulation reliability and electrode corrosion resistance. In the evaluation method, a bias voltage of DC 30 V was applied to the comb-shaped electrode under a humidification condition of 1 21 ° C and 97% R to measure the time until the insulation. Here, when the resistance 値 drops to 1 X 1 Ο·6 Ω, the insulation starts to deteriorate. Further, the rot of the electrode (the degree of occurrence of dendrites) after 100 hours under the above conditions was entangled according to the following criteria: no occurrence of dendrites Δ: slight confirmation of dendrites Generation X: Covering the anode-cathode greatly grown with dendrites will be evaluated as shown in Table 4. The coating of each group of the curtain is used, and the exposure amount of the most Na2C03 is set to the base. The characteristics of the mouth heat 60 (the beginning and the end of the .H. are judged: the degree of corrosion is evaluated. -65 - 201106096 [Table 4] Electrical Characteristic 2 Example 匕 Comparative Example 5 6 7 8 9 10 11 12 13 7 8 9 10 11 12 13 14 15 Insulation reliability (hr) 100 150 100 250 200 250 300 360 300 50 50 70 70 70 70 100 120 120 Electrode Corrosive 〇〇〇〇〇〇〇〇〇XXXXXX Δ Δ Δ As shown in Tables 2 and 4 above, in the case of Examples 1 to 13 of the present invention, when compared with Comparative Examples 1 to 5, It is confirmed that it is excellent in electrical properties, particularly in electrode corrosion, while maintaining various physical properties, and is very useful as a photosensitive resin composition for alkali development. -

Claims (1)

201106096 七、申請專利範園： !· 一種感光性樹脂組成物，其係含有：含羧基之樹 脂（B)及光聚合引發劑（D )之鹼顯像性的感光性樹脂組 成物’其特徵爲再含有層狀雙氫氧化合物（A)。 2.如申請專利範圍第1項之感光性樹脂組成物，其 中再含有具有乙烯性不飽和基之化合物（C)。 3 .如申請專利範圍第1項之感光性樹脂組成物，其 中再含有熱硬化性成分（E )。 4.如申請專利範圍第1項之感光性樹脂組成物，其 中該層狀雙氫氧化合物（A)係以下述一般構造式（I)表 示之化合物， 【化1】 [〇3:_9][八二.mH20] (I) 1 *~Λ X ‘ Χ/η (式中，Μ2 +表示2價的金屬陽離子，Μ3 +表示3價的 金屬陽離子，Αη_表示η價的陰離子，各元素及原子團的 下腳註字表示各元素及原子團的比例，X爲0&lt;Χ各0.33, m ^ 0 ) 〇 5 .如申請專利範圔第4項之感光性樹脂組成物，其 中於該一般構造式（I)中，2價的金屬陽離子M2 +爲Mg2 + 、3價的金屬陽離子M3 +爲Al3+、陰離子Αη·爲C〇32-。 6.如申請專利範圍第1項至第5項之任一項之感光 性樹脂組成物，其係阻焊劑形成用者。 7- —種乾式薄膜，其係將申請專利範圍第1項至第5 項之任一項之感光性樹脂組成物塗佈於薄膜並乾燥所成者 •67- 201106096 8. —種硬化物，其係將經將申請專利範圍第1項至 第5項之任一項之感光性樹脂組成物塗佈於基材上並乾燥 所得乾燥塗膜，或將前述感光性樹脂組成物塗佈於載體薄 膜並乾燥所成之乾式薄膜層壓於基材上所得之乾燥塗膜， 進行光硬化或再加以熱硬化所得者。 9· 一種印刷電路板，其係具有前述申請專利範圍第8 項之硬化物者。 -68 - 201106096 四 指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無 201106096 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201106096 VII. Application for Patent Park: !· A photosensitive resin composition containing a carboxyl group-containing resin (B) and a photopolymerization initiator (D) for alkali-developing photosensitive resin composition' It is further contained in the layered double hydroxide (A). 2. The photosensitive resin composition of claim 1, further comprising a compound (C) having an ethylenically unsaturated group. 3. The photosensitive resin composition of claim 1, wherein the thermosetting component (E) is further contained. 4. The photosensitive resin composition of claim 1, wherein the layered double hydroxide (A) is a compound represented by the following general structural formula (I), [Chemical Formula 1] [〇3:_9] [八二.mH20] (I) 1 *~Λ X ' Χ/η (wherein Μ2 + represents a divalent metal cation, Μ3 + represents a trivalent metal cation, Αη_ represents an η valent anion, each element And the lower footnote of the atomic group indicates the ratio of each element and the atomic group, X is 0 &lt; Χ each 0.33, m ^ 0 ) 〇5. The photosensitive resin composition of claim 4, wherein the general structural formula In (I), the divalent metal cation M2 + is Mg2+, the trivalent metal cation M3+ is Al3+, and the anion Αη is C〇32-. 6. The photosensitive resin composition according to any one of claims 1 to 5, which is used as a solder resist. 7- a dry film which is obtained by applying a photosensitive resin composition according to any one of the above claims 1 to 5 to a film and drying it. 67-201106096 8. The photosensitive resin composition according to any one of claims 1 to 5 is applied onto a substrate and dried to obtain a dried coating film, or the photosensitive resin composition is applied to a carrier. The dry film obtained by laminating the film and drying the dry film is subjected to photohardening or heat hardening. 9. A printed circuit board comprising the hardened material of item 8 of the aforementioned patent application. -68 - 201106096 Four designated representatives: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201106096 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no
TW099109420A 2009-03-30 2010-03-29 A photosensitive resin composition, a dry film and a printed circuit board using the same TWI498673B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009082407A JP5349113B2 (en) 2009-03-30 2009-03-30 Photosensitive resin composition, dry film and printed wiring board using the same

Publications (2)

Publication Number Publication Date
TW201106096A true TW201106096A (en) 2011-02-16
TWI498673B TWI498673B (en) 2015-09-01

Family

ID=42804524

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099109420A TWI498673B (en) 2009-03-30 2010-03-29 A photosensitive resin composition, a dry film and a printed circuit board using the same

Country Status (4)

Country Link
JP (1) JP5349113B2 (en)
KR (1) KR101201077B1 (en)
CN (2) CN105353588A (en)
TW (1) TWI498673B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI718164B (en) * 2015-07-14 2021-02-11 美商羅門哈斯電子材料有限公司 Light-sensitive resin composition

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5734604B2 (en) * 2010-08-30 2015-06-17 太陽ホールディングス株式会社 Curable resin composition, dry film and cured product thereof, and printed wiring board using them
JP6084353B2 (en) * 2010-12-28 2017-02-22 太陽インキ製造株式会社 Photocurable resin composition manufacturing method, dry film manufacturing method, cured product manufacturing method, and printed wiring board manufacturing method
JP5854600B2 (en) * 2010-12-28 2016-02-09 太陽インキ製造株式会社 Photocurable resin composition
JP6061449B2 (en) * 2011-03-31 2017-01-18 太陽インキ製造株式会社 Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them
JP6028360B2 (en) * 2011-06-29 2016-11-16 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and cured product thereof, and method for producing photosensitive resin
JP2013217954A (en) * 2012-04-04 2013-10-24 Hitachi Chemical Co Ltd Method for forming resist pattern, permanent mask resist and photosensitive resin composition
TWI485512B (en) * 2013-03-22 2015-05-21 Everlight Chem Ind Corp White photosensitive resin composition and use thereof
WO2016052653A1 (en) * 2014-09-30 2016-04-07 太陽インキ製造株式会社 Photosensitive resin composition, dry film of same, cured coating film of same, and printed wiring board using said cured coating film
WO2017057431A1 (en) 2015-09-30 2017-04-06 太陽インキ製造株式会社 Curable resin composition, dry film and printed wiring board using same
TWI630457B (en) 2016-02-05 2018-07-21 南韓商Ｌｇ化學股份有限公司 Photo-curable and heat-curable resin composition and dry film solder resist
US11609493B2 (en) 2017-02-07 2023-03-21 Arisawa Mfg. Co., Ltd. Photosensitive resin composition, solder resist film using said photosensitive resin composition, flexible printed circuit and image display device
JP2019183012A (en) * 2018-04-11 2019-10-24 Dic株式会社 Active energy ray-curable resin composition, active energy ray-curable printing ink and printed matter
KR102656174B1 (en) * 2019-03-15 2024-04-08 동우 화인켐 주식회사 Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11186718A (en) * 1997-12-18 1999-07-09 Hitachi Chem Co Ltd Buildup multilayered wiring board, manufacture thereof and photosensitive resin compsn.
US7195857B2 (en) * 2001-07-04 2007-03-27 Showa Denko K.K. Resist curable resin composition and cured article thereof
JP2003131362A (en) * 2001-10-25 2003-05-09 Showa Denko Kk Curable resin composition for resist and hardened material of the same
JP2003162055A (en) * 2001-11-26 2003-06-06 Ube Ind Ltd Photosensitive resin composition, photosensitive film, insulating film, and method for forming the same
JP4180844B2 (en) * 2002-06-06 2008-11-12 昭和電工株式会社 Curable flame retardant composition, cured product thereof and production method thereof
JP2006098658A (en) * 2004-09-29 2006-04-13 Fuji Photo Film Co Ltd Lithographic printing original plate
TWI318235B (en) * 2005-08-29 2009-12-11 Univ Chung Yuan Christian Liquid crystal composite material
JP5144323B2 (en) * 2007-04-27 2013-02-13 太陽ホールディングス株式会社 Method for manufacturing printed wiring board
JP4616863B2 (en) * 2007-06-04 2011-01-19 太陽ホールディングス株式会社 Photosensitive resin composition and flexible wiring board obtained using the same
JP5210657B2 (en) * 2007-07-18 2013-06-12 太陽ホールディングス株式会社 Pattern comprising photosensitive composition and fired product thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI718164B (en) * 2015-07-14 2021-02-11 美商羅門哈斯電子材料有限公司 Light-sensitive resin composition

Also Published As

Publication number Publication date
KR101201077B1 (en) 2012-11-14
TWI498673B (en) 2015-09-01
KR20100109442A (en) 2010-10-08
CN101852988A (en) 2010-10-06
CN105353588A (en) 2016-02-24
JP5349113B2 (en) 2013-11-20
JP2010237270A (en) 2010-10-21

Similar Documents

Publication Publication Date Title
TWI415896B (en) A hardened resin composition, a dry film and a printed circuit board using the same
JP5415923B2 (en) Photosensitive resin composition, dry film thereof, and printed wiring board using them
TWI498673B (en) A photosensitive resin composition, a dry film and a printed circuit board using the same
TWI420240B (en) Photosensitive resin composition
JP5537864B2 (en) Photocurable resin composition
KR101588159B1 (en) Photocurable resin composition, printed wiring board, and method for producing photocurable resin composition
TWI506088B (en) A photohardenable resin composition
TWI506356B (en) A photohardenable thermosetting resin composition, a dry film and a cured product thereof, and a printed wiring board
TW201128308A (en) Photocurable resin composition
JP6211780B2 (en) Flame-retardant curable resin composition, dry film, flame-retardant coating and printed wiring board
JP5559999B2 (en) Photocurable resin composition
TW201042387A (en) Photo-curable and heat-curable resin composition
KR101174983B1 (en) Curable resin composition
TW201430491A (en) Photocurable thermosetting resin composition
KR20130035952A (en) Photosensitive resin composition, cured film thereof and printed wiring board
JP2011043565A (en) Photosetting resin composition
JP5091353B2 (en) Photocurable resin composition
KR101473556B1 (en) Flame-retardant curable resin composition, dry film, flame-retardant coat and printed wiring board
TW201042386A (en) Photo-curable and heat-curable resin composition
JP5864524B2 (en) Photocurable resin composition
JP5506885B2 (en) Curable resin composition, dry film and printed wiring board using the same
JP5385680B2 (en) Curable resin composition
JP6211781B2 (en) Flame-retardant curable resin composition, dry film, flame-retardant coating and printed wiring board