TW200827402A - Photo-setting and thermosetting resin composition and its cured product, printed circuit board - Google Patents

Photo-setting and thermosetting resin composition and its cured product, printed circuit board Download PDF

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TW200827402A
TW200827402A TW096125321A TW96125321A TW200827402A TW 200827402 A TW200827402 A TW 200827402A TW 096125321 A TW096125321 A TW 096125321A TW 96125321 A TW96125321 A TW 96125321A TW 200827402 A TW200827402 A TW 200827402A
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compound
group
carboxyl group
acid
epoxy
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TW096125321A
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TWI351421B (en
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Shouji Minegishi
Takahiro Yoshida
Takeshi Yoda
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Taiyo Ink Mfg Co Ltd
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Priority claimed from JP2007020884A external-priority patent/JP5183073B2/en
Priority claimed from JP2007020873A external-priority patent/JP5164386B2/en
Priority claimed from JP2007025467A external-priority patent/JP2008189803A/en
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of TW200827402A publication Critical patent/TW200827402A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)

Abstract

To provide a photo-setting and thermosetting resin composition and its cured product having excellent soldering heat-resistance necessary as a solder resist or a resist for package substrates, adhesiveness, electrical insulation and HAST resistance and giving a substrate having low curing shrinkage and free from warpage. The resin composition includes (A) a carboxyl-containing photosensitive resin produced by reacting (a) an epoxy compound having two or more epoxy groups in one molecule with (b) a compound having one or more hydroxyl groups and one reactive group except for hydroxyl group and reactive with epoxy group and (c) a monocarboxylic acid having an unsaturated group, and reacting the obtained reaction product with (d) a polybasic acid anhydride, (B) a urethane (meth)acrylate compound having carboxyl group, c a photopolymerization initiator, (D) a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups in one molecule, and (E) a diluent.

Description

200827402 九、發明說明 【發明所屬之技術領域】. 本發明係有關，適合於製造經小型輕量化之電子機器 中所使用的半導體封裝基板之光硬化性•熱硬化性樹脂組 " 成物，其硬化物及印刷電路板者。[Technical Field] The present invention relates to a photocurable/thermosetting resin group which is suitable for manufacturing a semiconductor package substrate used in an electronic device that is small and lightweight, Its hardened and printed circuit board.

V 【先前技術】 • 最近之電子機器，如行動電話所代表的，有小型輕量 化、高性能化、多功能化之傾向；對應於此，此等電子機 器中所使用之半導體積體電路（以下稱爲1C)，亦要求進一 步的高積體化、小型化、薄型化。爲對應於如此之要求， 收容半導體1C之封裝，以使用簧片結橫與封閉樹脂之 QFP(四方偏平封裝）、稱呼爲SOP(小外型封裝）等的1C封 裝替代；使用以焊劑光阻塗佈之絕緣基板與封閉樹脂，稱 爲BGA(球閘陣列封裝）或CSP(晶片尺寸封裝）之1C封裝 # 亦登場。如此之封裝中，在塗佈焊劑光阻之絕緣印刷基板 ^ 的單面，全面排列球珠狀的焊劑，在另外的單面將1C晶 片熔黏，藉由與金屬連接或凸塊，進行印刷基板上之接頭 或電路的電連接，將1C晶片以樹脂封閉。 如此構造之I c封裝中，如上所述，要求小型化，薄 型化的結果，要求形成搭載1C晶片之印刷基板的核心材 料亦薄型化。例如在稱呼爲UT-CSP之封裝中，使用厚度 爲3 0〜6 0 μπι之玻璃環氧基板作爲核心材料。如此之IC封 裝的製造步驟，在構成基板之核心材料的雙面；即焊劑球 -6- 200827402 固黏之面、及形成與IC晶片之輸出入接頭的連接用配線 之其他面，如將此等焊劑球及配線圖型之去除部份被覆似 的’塗佈光阻油墨後，使此等硬化形成絕緣保護皮膜。但 是，如此之基板極薄時，塗佈於核心材料表面之光阻，由 • 於燒成之際的硬化而收縮，在基板上造成翹曲或起伏，於 v 晶片實裝時產生問題。進而，在1C封裝之製造步驟的例 如塑模步驟或附置焊劑步驟等，包含將印刷基板曝露於 φ 170〜27 0 °C之高溫的步驟。因此，在光阻材料中，要求焊 劑耐熱等高耐熱性、同時要求電特性、HAST(Highly Accelerated Temperature and Humidity Stress Test)特性等 之高信賴性。 進而，藉由核心材料之薄化，由於光阻之硬化收縮造 成翹曲的問題。使用如此之核心材料時，採用滾筒對滾筒 (roll-to-roll)的方法’從操作性、信賴性、膜厚精確度、 平滑性的觀點而言，謀求乾燥薄膜型之焊劑光阻。又，如 • 此之乾燥薄膜型的焊劑光阻，係以薄片或滾筒狀供給，其 ^ 形態中之特性，以樹脂組成物中含有柔軟性，造膜性優越 之樹脂成份爲必要性。 以往，爲防止印刷基板之翹曲或起伏，使用含有可動 性優越之胺基甲酸酯（甲基）丙烯酸酯化合物的感光性樹脂 作爲燒結時之硬化收縮低的焊劑光阻油墨（參照專利文獻 1)。但是，使用此感光性樹脂之焊劑光阻，雖可防止印刷 基板之翹曲或起伏，在如此所述之1C封裝的製造步驟中 不耐高溫之熱處理；又，有不能獲得必要的電特性之缺點 -7- 200827402 又有，以往在1分子中具有至少1個羧基及2個羥基 之化合物、與二醇化合物、及聚異氰酸酯化合物之反應物 的末端異氰酸酯化合物中，使1分子中具有聚合性不飽和 基、羧基及至少1個羥基之化合物反應所得的含感光性樹 脂之焊劑光阻的提案（參照專利文獻2)。不過，如此之感 光性樹脂亦同樣的，相對於如上所述之高溫的熱處理，有 必要的耐熱性不充分之問題。 另一方面，以往亦有耐熱性、密著性、電絕緣性優越 之焊劑光阻用的感光性樹脂組成物（參照專利文獻3)。此 樹脂係耐熱性、密著性、電絕緣性優越；適合使用於某程 度厚之核心材料的以往之封裝基板，相對於如上所述之極 薄的核心材料，難以滿足所要求之防止翹曲或起伏。 專利文獻1 :特開2002-2292 01號公報（專利申請範圍） 專利文獻2 :特開2003-1 92760號公報（專利申請範圍） 專利文獻3 :特開2001-27 8 947號公報（專利申請範圍） 【發明內容】 [發明所欲解決之課題] 本發明鑑於上述以往技術之各項問題，其目的爲提供 焊劑光阻，尤其半導體封裝基板用光阻所必要之焊劑耐熱 性、密著性、電絕緣性、HAST耐性優越，且相對於硬化 收縮甚少之極薄的核心材料亦不翹曲之基板的光硬化性· 熱硬化性樹脂組成物；提供其硬化物及印刷電路板。 -8- 200827402 [課題之解決手段] 爲達成該目的，本發明之基本形態爲提一種光硬化性 •熱硬化性樹脂組成物，其特徵爲含有： 、 （A-1)在1分子中具有2個以上環氧基之環氧化合物 v (a)、與1分子中具有1個以上之醇性羥基，和與此醇性 羥基以外的環氧基反應之1個反應基的化合物（b)、及含 φ 有不飽和基之單羧酸（Ο的反應生成物中，使多元酸酐（d) 反應而得之含羧基的感光性樹脂； (A-2)使1分子中含有2個以上酚性羥基之化合物（e) 與環氧烷（f)或環碳酯酯化合物（g)反應而得的反應生成物 ，與含不飽和基之單羧酸（Ο的反應生成物中，使多元酸 酐（d)反應而得含羧基之感光性樹脂；及 (A-3)使二官能環氧化合物與環氧基反應之具有2個 反應基的化合物進行交互聚合，在生成之羥基與環氧氯丙 • 烷反應而得的線狀多官能環氧化合物（h)、與含不飽和基 ' 之單羧酸（c)的反應生成物中，使多元酸酐（d)反應所得的 含羧基的感光性樹脂； 之任一種或二種以上、與 (B) 含羧基之胺基甲酸酯（甲基）丙烯酸酯化合物、 (C) 光聚合引發劑、 (D) l分子中具有2個以上環狀醚基及/或環狀硫醚基 之熱硬化性成份、及 (E) 稀釋劑。 -9- 200827402 又，提供一種光硬化性•熱硬化性樹脂組成物，其特 徵爲在上述組成物中含有： (F)硬化觸媒。 其他之形態，提供在載體上將該光硬化性•熱硬化性 樹脂組成物以有機溶劑（E-1 )稀釋後，塗佈於載體上，使有 機溶劑（E-1)揮發，進行乾燥所得之乾燥薄膜。 進而，將該光硬化性•熱硬化性樹脂組成物，藉由活 性能量線照射及/或加熱硬化而得爲特徵之硬化物，及在電 路基板上形成具有導體層之作爲永久保護膜的焊劑光阻皮 膜；提供在印刷電路板中，該焊劑光阻皮膜爲由該光硬化 性•熱硬化性樹脂組成物之硬化塗膜所成的印刷電路板。 [發明之功效] 本發明之光硬化性·熱硬化性樹脂組成物，係倂用耐 熱性、耐藥品性優越之含羧基感光性樹脂，與柔軟性、造 • 膜性優異之含羧基胺基甲酸酯（甲基）丙烯酸酯化合物之故 ^ ，光硬化性、鹼顯像性或相對於基材之密著性優越，同時 耐熱性、耐水性、耐無電解電鍍性、耐藥品性、電絕緣性 、可撓性、PCT耐性等優異，能使用於要求高絕緣信賴性 之QFP、BGA、CSP等的封裝基板。 又，本發明之光硬化性•熱硬化性樹脂組成物，可提 供硬化收縮極少且無翹曲的基板之故，能對應於TAB、T_. BGA、T-CSP、UT-CSP。 • 10 - 200827402 [發明之實施形態] 本發明的工作同仁，爲解決上述課題，經深入探討不 斷硏究之結果發現，——種光硬化性·熱硬化性樹脂組成物 能提供焊劑耐熱性、密著性、電絕緣性、hast耐性優越 ' ，且硬化收縮極少之無翹曲基板，完成本發明。其特徵爲 、 含有： (A-1)在1分子中具有2個以上環氧基之環氧化合物 φ (a)、與1分子中具有1個以上之醇性羥基，和與此醇性 羥基以外的環氧基反應之1個反應基的化合物（b)、及含 有不飽和基之單羧酸（c)的反應生成物中，使多元酸酐（d) 反應而得之含羧基的感光性樹脂； (A-2)使1分子中含有2個以上酚性羥基之化合物（e) 與環氧烷（f)或環碳酯酯化合物（g)反應而得的反應生成物 ，在與含不飽和基之單羧酸（c)的反應生成物中，使多元 酸酐（d)反應而得含羧基之感光性樹脂；及 # (A-3)使二官能環氧化合物與環氧基反應之具有2個 ~ 反應基的化合物進行交互聚合，在生成之羥基與環氧氯丙 烷反應而得的線狀多官能環氧化合物（h)、與含不飽和基 之單羧酸（c)的反應生成物中，使多元酸酐（d)反應所得的 含羧基的感光性樹脂； 之任一種或二種以上、與 (B) 含羧基之胺基甲酸酯（甲基）丙烯酸酯化合物、 (C) 光聚合引發劑、 (D) l分子中具有2個以上環狀醚基及/或環狀硫醚基 -11 - 200827402 之熱硬化性成份、及 (E)稀釋劑。 即，發現藉由倂用焊劑耐熱性、密著性、電絕緣性、 HAST耐性優越之含羧基感光性樹脂（A-l、A-2、A-3之任 、 一種或二種以上），與硬化收縮極少能提供無翹曲基板之 - 該含羧基的胺基甲酸酯（甲基）丙烯酸酯化合物（B)，全不 降低相互間之特性，可達成本發明之目的。 φ 爲達成上述目的，該含羧基之感光性樹脂（A-l、A-2 、A-3之任一種或二種以上）、與該含羧基之胺基甲酸酯（ 甲基）丙烯酸酯化合物（B)的配合比率，以85: 15〜15: 8 5, 之比例予以配合爲佳。 重視焊劑耐熱性、密著性、電絕緣性、HAST耐性時 ，該含羧基之感光性樹脂（A-l、A-2、A-3之任一種或二 種以上）的比率，以在該範圍內之較高者進行；重視硬化 收縮少而無翹曲之特性時，該含羧基的胺基甲酸酯（甲基） # 丙烯酸酯化合物（B)之比率，以在該範圍內之較高者爲佳 〇 該含羧基之感光性樹脂（A-l、A-2、A-3之任一種或 二種以上）之比率比85質量％高時，翹曲惡化；相反的比 1 5質量％低時，耐熱硬化之故，甚不適合。 還有，本說明中所謂含羧基之胺基甲酸酯（甲基）丙烯 酸酯化合物，係指含羧基之胺基甲酸酯丙烯酸酯化合物、 含羧基之胺基甲酸酯甲基丙烯酸酯化合物、及此等之混合 物的總稱，其他以此類推。 -12- 200827402 就本發明之光硬化性•熱硬化性樹脂組成物的構成成 份，詳細說明如下。首先’就本發明之含羧基的感光性樹 脂組成物（A-l)、(A-2)、及（A_3)予以說明。 含羧基之感光性樹脂（A-1)，係在1分子中具有2個 以上環氧基之環氧化合物U)(以下稱爲多官能環氧樹脂）、 與1分子中具有1個以上之醇性羥基，和與此醇性羥基以 外的環氧基反應之1個反應基的化合物（b)、及含有不飽 和基之單羧酸（Ο的反應生成物中，使多元酸酐（d)反應而 得之含羧酸的感光性樹脂。 此含羧基之感光性樹脂（A- 1 )，係在多官能環氧樹脂 (a)中，與僅使含不飽和基之單羧酸（〇反應後，使多元酸 酐（d)反應之樹脂比較，具有感光基密度低、硬化物之應 變較少的特徵。 又，在多官能環氧化合物（a)中，藉由使1分子中具 有1個以上之羥基和與此羥基以外羥基的環氧基反應之1 個反應基的化合物（b)、及含有不飽和基之單羧酸（c)的反 應，在環氧樹脂骨架中導入感光性之不飽和基與一級羥基 ，其後藉由將多元酸酐之酸酐加成於一級羥基，成爲 HAST耐性優越之樹脂。 其次，含羧基之感光性樹脂（A-2)，係使1分子中含 有2個以上酚性羥基之化合物（e)與環氧烷（f)或環碳酸酯 化合物（g)反應而得的反應生成物，在與含不飽和基之單 羧酸（〇的反應生成物中，使多元酸酐（d)反應而得的含羧 基之感光性樹脂。 -13- 200827402 此含羧基之感光性樹脂（A · 2)，係藉由1分子中具有2 個以上之酚性羥基的化合物（e)與環氧烷（f)或環碳酸酯化 合物（g)之加成反應，而得在離開主鏈之位置具有酚性羥 基的樹脂，藉由此酚性羥基之一部份與含不飽和基之單羧 ' 酸（c)的酯化反應’賦予感光性後，在剩餘的酚性羥基之 ^ 一部份或全部中，使多元酸酐（句加成之樹脂，如此在離 開主鏈之位置，具有感光性的不飽和基之故，光反應性優 φ 越；又，在離開主鏈之位置，具有游離的羧基之故，交聯 後之切斷極少，能賦予電特性、HAST耐性優異之硬化物 〇 進而，含羧基之感光性樹脂（A-3)，係使二官能環氧 化合物與環氧基反應之具有2個反應基的化合物進行交互 聚合，在生成之羥基中使環氧氯丙烷反應而得的線狀多官 能環氧化合物（h)、與含不飽和基之單羧酸（c)的反應生成 中，使多元酸酐（d)反應所得之含線狀的羧基感光性樹脂 •。 ^ 此含羧基之感光性樹脂（A-3)，係以線狀之多官能環 氧化合物爲基質之故、富有柔軟性；進而，藉由使用二官 能芳香族環氧化合物與二官能苯酚化合物及/或芳香族二 羧酸作爲較佳之原材料，能賦予耐水性優越，電特性、 HAST耐性優異之硬化物。 該含羧基之感光性樹脂（A-1)的合成中所使用之1分 子中具有2個以上環氧基的環氧化合物（a)，有眾所周知 的慣用之多官能環氧化合物，例如雙酚A型環氧樹脂、 •14- 200827402 雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙苯基型環氧樹 脂、雙二甲酚型環氧樹脂、三羥基苯基甲烷型環氧樹脂、 四苯基乙烷型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛 型環氧樹脂、雙酚A之酚醛型環氧樹脂、（甲基）丙烯酸環 氧丙基酯之共聚樹脂等。此等之中，從所得樹脂之耐熱性 、感光性之面而言，以使用苯酚酚醛型環氧樹脂、或甲酚 酚醛型環氧樹脂爲佳，尤其以軟化點爲50 °C以上之甲酚 酚醛型環氧樹更佳。 又，該含羧基之感光性樹脂（A-1)的合成中所使用之1 分子中具有1個以上之羥基和與此羥基以外的環氧基反應 之1個反應基的化合物（b)有，例如乙醇酸、二羥甲基乙 酸、二羥甲基丙酸、二羥甲基丁酸、二羥甲基戊酸、二羥 甲基己酸等含羥基之單羧酸類；二乙醇胺、二異丙醇胺等 二烷醇胺類等；羥基甲基二叔丁基酚、對-羥基苯乙基醇 、對-羥基苯基-3-丙醇、對-羥基苯基-4-丙醇、羥基乙基 甲酚、2,6-二甲基-4-羥基甲基酹、2,4-二羥基甲基-2-環己 基酚、三羥甲基酚、3,5_二甲基-2,4,6-三羥基甲基酚、雙（ 羥基甲基）酚、雙（羥基甲基）甲酚等雙（羥基烷基）酚類等。 更佳者爲二羥甲基丙酸、二羥甲基丁酸、及對-羥基苯乙 基醇。 如此之化合物，具有一級的羥基之故，在和環氧基與 含不飽和基之單羧酸的反應而得之二級羥基比較，其後， 加成的多元酸酐（d)，即使在高溫高濕下亦難以脫離。 該含羧基之感光性樹脂（A-l)、（A-2)、及（A-3)的合成 -15- 200827402 中所使用之含不飽和基的單羧酸（c)，有丙烯酸、甲基丙 烯酸、巴豆酸、乙烯基乙酸、肉桂酸、α -氰基肉桂酸、 冷·苯乙烯基丙烯酸、糠基丙烯酸、或在（甲基）丙烯酸 2-羥基乙基酯、（甲基）丙烯酸2-羥基丙基酯、（甲基）丙烯 、 酸4-羥基丁基酯、三羥甲基丙烷二（甲基）丙烯酸、季戊四 - 醇三（甲基）丙烯酸酯等含羥基之（甲基）丙烯酸酯化合物中 ，加成二元酸酐之化合物等。此等之中，從反應性等之面 φ 而言，以丙烯酸、或甲基丙烯酸爲佳。此等含不飽和基之 單羧酸，可單獨或2種以上組合使用。 該含竣基之感光性樹脂（A-l)、（Α-2)、及（Α-3)之合成 中所使用之多元酸酐（d)，有苯二甲酸酐、四氫苯二甲酸 酐、甲基四氫苯二甲酸酐、六氫苯二甲酸酐、甲基六氫苯 二甲酸酐、琥珀酸酐、馬來酸酐、衣康酸酐、納去庫酸酐 、八烯琥珀酸酐、五（十二烯琥珀酸酐）、3,6-內（部）亞甲 基四氫苯二甲酸酐、甲基（內）亞甲基四氫苯二甲酸酐、四 馨 溴苯二甲酸酐、偏苯三酸酐等二元酸或三元酸之酸酐、或 ' 聯苯基四羧酸二酐、二苯基醚四羧酸二酐、丁烷四羧酸二 酐、環戊烷四羧酸二酐、均苯四甲酸酐、二苯甲酮四羧酸 酐等脂肪族或芳香族四元酸二酐等。此等之中可使用1種 或2種以上。此等之中從顯像性、硬化物之塗膜特性而言 ，以四氫苯二甲酸酐、甲基四氫苯二甲酸酐、六氫苯二甲 酸酐、四基六氫苯二甲酸酐、琥珀酸酐爲佳。 此等多元酸酐（d)之加成量，係本發明所使用之含羧 基感光性樹脂（A-l、A-2、A-3)的酸價爲30〜100 mgKOH/g -16 - 200827402 之範圍、更佳爲40〜80 mgKOH/g的範圍。酸價比上述範 圍少，而加成多元酸酐（d)時’以稀鹼水溶液之顯像性降 低、耐熱性下降之故’甚不適合。另一方面，比上述範圍 高，而加成多元酸酐（d)時，耐顯像性降低，電絕緣性、 ' 無電解電鍍耐性等下降之故’甚不適合。 • 其次，該含羧基之感光性樹脂（A-2)的合成中所使用 之1分子中具有2個以上酚性羥基的化合物（e)有，鄰苯 φ 二酚、間苯二酚、對苯二酚、二羥基甲苯、萘二醇叔丁基 鄰苯二酚、叔丁基對苯二酚、苯三酚、間苯三酚、雙酚A 、雙酚F、雙酚S、聯酚、雙二甲酚、酚醛型苯酚樹脂、 酚醛型烷基苯酚樹脂、雙酚A之酚醛樹脂、二環戊二烯 型酚樹脂、Xyl〇k型酚樹脂、萜烯改性酚樹脂、聚乙烯基 酚類、酚類與具有酚性羥基之芳香族醛等的縮合物、1 -萘 酚或2-苯酚與芳香族醛類之縮合物等。並非限定於此等 。此等含有酚性羥基之化合物，可單獨或2種以上混合使 • 用。 ~ 該含羧基之感光性樹脂（A-2)的合成中所使用之環氧 烷（f)，有環氧乙烷、環氧丙烷、氧雜環丁烷、四氫呋喃 、四氫吡喃等。 又，環碳酸酯化合物（g)，可使用眾所周知的慣用之 碳酸酯化合物’例如碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯 酯、2,3-碳酸酯丙基甲基丙烯酸酯等。較佳之5員環的碳 酸乙烯酯、碳酸丙烯酯，從反應性、供給體制之面而言， 甚爲適合。 -17- 200827402 此等環氧烷（f)或環碳酸酯化合物（g)，可單獨或2種 以上混合使用。 該環氧烷（f)或環碳酸酯化合物（g) ’係在該含有酚性 羥基之化合物的酚性羥基中，使用鹼性觸媒，藉由加成反 應，可由酚性羥基改性爲具有醇性羥基之樹脂。此時之加 成量，相當於酚性羥基每1當量爲0·3〜10莫耳之範圍、 較佳爲0.8〜5莫耳之範圍、更佳爲1·〇〜3莫耳之範圍。 加成量比上述範圍少時，難以引起與該含不飽和基之 單羧量（c)惑多元酸酐（d)之反應，相對於感光性及稀鹼水 溶液的溶解性降低之故，極不適合。另一方面，加成量超 過上述範圍時，由於生成之醚鍵結，耐水性降低，電絕緣 性、HAST耐性等下降之故，甚不適合。 該反應中所使用之鹼性觸媒，適合使用碳酸鉀、碳酸 鈉、碳酸鈣、氫氧化鈉、氫氧化鉀、氫氧化鋇等.金屬化 合物；三乙胺等三級胺；2-乙基-4-甲基咪唑等咪唑化合 物；三苯基膦等磷化合物；氯化四甲基銨、溴化四丁基銨 、鹵化三甲基苄基銨、四甲基銨苯甲酸酯、氫氧化四甲基 銨、氫氧化四乙基銨、氫氧化四甲基銹等第4級鹼性鹼化 合物；環烷酸、月桂酸、硬脂酸、油酸或辛酸之鋰、鉻、 鉻、鉀、鈉等有機酸之金屬鹽等。此等觸媒，可單獨或2 種以上混合使用。 使用如此之鹼性觸媒，該反應以在常溫〜250 °C進行爲 佳。反應溶劑可使用苯、甲苯、二甲苯、四甲基苯、正己 烷、環己烷、甲基環己烷、乙基環己烷、辛烷、甲異丁酮 -18- 200827402 、二異丙醚等。此等有機溶劑，可單獨或2種以上混合使 用。 該含羧基之感光性樹脂（A- 3 )的合成中所使用之二官 能環氧化合物有，1，6-己烷二醇二環氧丙基醚、季戊二醇 二環氧丙基醚、聯酚型二環氧丙基醚、聯甲酚型二環氧丙 基醚、雙酚型二環氧丙基醚、萘型二環氧丙基醚等。藉由 與具有下述式（1)〜（4)所示之芳香環的聯酚型二環氧丙基醚 、聯甲酚型二環氧丙基醚、雙酚型二環氧丙基醚、萘型二 環氧丙基醚等之至少一種二官能芳香族醇的交互共聚體之 一方，作爲單體成份，可獲得硬化物之強度、耐熱性、電 絕緣性等優越之環氧化合物。V [Prior Art] • Recently, electronic devices, such as mobile phones, have a tendency to be small, lightweight, high-performance, and multi-functional; accordingly, semiconductor integrated circuits used in such electronic devices ( Hereinafter, it is called 1C), and further high integration, miniaturization, and thinning are required. In order to meet such requirements, the package for housing the semiconductor 1C is replaced with a 1C package using a reed-like junction and a QFP (quadruple flat package) for sealing resin, and a SOP (small outline package); a solder resist is used. The coated insulating substrate and the sealing resin, also known as BGA (Ball Gate Array Package) or CSP (Chip Size Package) 1C package # are also on the scene. In such a package, a ball-shaped flux is integrally arranged on one side of an insulating printed circuit board coated with a solder resist, and a 1C wafer is melted on another single side, and printed by being connected to a metal or a bump. The electrical connection of the connector or circuit on the substrate encloses the 1C wafer with resin. In the Ic package having such a configuration, as described above, it is required to be smaller and thinner, and it is required that the core material for forming the printed circuit board on which the 1C wafer is mounted is also thinned. For example, in a package called UT-CSP, a glass epoxy substrate having a thickness of 30 to 60 μm is used as a core material. The manufacturing process of such an IC package is performed on both sides of the core material constituting the substrate, that is, the surface of the solder ball-6-200827402, and the other surface of the wiring for forming the connection to the IC chip. After the solder ball and the wiring pattern are partially removed, the photoresist is coated and then hardened to form an insulating protective film. However, when such a substrate is extremely thin, the photoresist applied to the surface of the core material shrinks due to hardening at the time of firing, causing warpage or undulation on the substrate, which causes problems when the wafer is mounted. Further, in the manufacturing step of the 1C package, for example, a molding step or a soldering step, the step of exposing the printed substrate to a high temperature of φ 170 to 27 ° C is included. Therefore, in the photoresist material, high heat resistance such as heat resistance of the solder is required, and high reliability such as electrical characteristics and HAST (Highly Accelerated Temperature and Humidity Stress Test) characteristics are required. Further, by the thinning of the core material, the hardening shrinkage of the photoresist causes a problem of warpage. When such a core material is used, the roll-to-roll method is used to achieve a dry film type solder resist from the viewpoints of workability, reliability, film thickness precision, and smoothness. Further, the dry film type solder resist is supplied in the form of a sheet or a roll, and it is necessary to have a resin composition having flexibility and a film-forming property in the resin composition. Conventionally, in order to prevent warpage or undulation of a printed substrate, a photosensitive resin containing a highly operable urethane (meth) acrylate compound is used as a solder resist ink having low curing shrinkage during sintering (refer to the patent literature). 1). However, the use of the solder resist of the photosensitive resin prevents warpage or undulation of the printed substrate, and is not resistant to high temperature heat treatment in the manufacturing steps of the 1C package as described above; and, the necessary electrical characteristics are not obtained. Disadvantages -7- 200827402 In the case of a terminal isocyanate compound having a compound having at least one carboxyl group and two hydroxyl groups in one molecule and a reaction product with a diol compound and a polyisocyanate compound, polymerizability is obtained in one molecule. A proposal of a solder resist containing a photosensitive resin obtained by reacting an unsaturated group, a carboxyl group, and a compound having at least one hydroxyl group (see Patent Document 2). However, similarly to such a photosensitive resin, there is a problem that heat resistance is insufficient for the heat treatment at a high temperature as described above. On the other hand, there is a photosensitive resin composition for solder resist which is excellent in heat resistance, adhesion, and electrical insulation (see Patent Document 3). This resin is excellent in heat resistance, adhesion, and electrical insulation. It is suitable for a conventional package substrate which is suitable for a core material having a certain thickness, and it is difficult to satisfy the required warpage prevention with respect to the extremely thin core material as described above. Or ups and downs. Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-2292 No. (Patent Application No.) Patent Document 2: JP-A-2003-1 92760 (Patent Application Scope) Patent Document 3: JP-A-2001-27 8 947 (Patent Application) Scope of the Invention [Problems to be Solved by the Invention] The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide solder resist, particularly solder heat resistance and adhesion necessary for photoresist for a semiconductor package substrate. A photocurable/thermally curable resin composition of a substrate which is excellent in electrical insulating properties and HAST resistance and which is not warped with respect to an extremely thin core material having little hardening shrinkage; and a cured product and a printed circuit board are provided. -8- 200827402 [Means for Solving the Problem] In order to achieve the object, a basic form of the present invention is to provide a photocurable thermosetting resin composition comprising: (A-1) having one molecule An epoxy compound v (a) having two or more epoxy groups, and a compound (b) having one or more alcoholic hydroxyl groups in one molecule and one reactive group reactive with an epoxy group other than the alcoholic hydroxyl group And a monocarboxylic acid containing φ having an unsaturated group (a photosensitive resin containing a carboxyl group obtained by reacting a polybasic acid anhydride (d) in a reaction product of ruthenium; (A-2) containing two or more molecules per molecule a reaction product obtained by reacting a compound having a phenolic hydroxyl group (e) with an alkylene oxide (f) or a cyclic carbon ester ester compound (g), and a reaction product of a monocarboxylic acid (anthracene containing an unsaturated group) The polybasic acid anhydride (d) is reacted to obtain a carboxyl group-containing photosensitive resin; and (A-3) a compound having two reactive groups in which a difunctional epoxy compound and an epoxy group are reacted, and a hydroxyl group and a ring are formed. a linear polyfunctional epoxy compound (h) obtained by reacting oxychloropropane with an alkane In the reaction product of the acid (c), a carboxyl group-containing photosensitive resin obtained by reacting the polybasic acid anhydride (d); or two or more kinds thereof, and (B) a carboxyl group-containing urethane (methyl) An acrylate compound, (C) a photopolymerization initiator, (D) a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group in the molecule, and (E) a diluent. Further, a photocurable thermosetting resin composition is characterized in that: (F) a curing catalyst is contained in the above composition. In other embodiments, the photocuring property and thermosetting property are provided on a carrier. After the resin composition is diluted with an organic solvent (E-1), it is applied onto a carrier, and the organic solvent (E-1) is volatilized to dry the obtained dried film. Further, the photocurable thermosetting resin is composed of the resin composition. a cured film characterized by active energy ray irradiation and/or heat hardening, and a solder resist film having a conductor layer as a permanent protective film on a circuit substrate; the solder is provided in a printed circuit board The photoresist film is made of the light hardening and hot hard The printed circuit board formed by the hardened coating film of the resin composition. [Effect of the invention] The photocurable and thermosetting resin composition of the present invention is a carboxyl group-containing photosensitive resin excellent in heat resistance and chemical resistance. And a carboxyl group-containing urethane (meth) acrylate compound excellent in flexibility and film properties, photocurability, alkali developability or adhesion to a substrate, and heat resistance It is excellent in properties such as properties, water resistance, electroless plating resistance, chemical resistance, electrical insulation properties, flexibility, and PCT resistance, and can be used for package substrates such as QFP, BGA, and CSP which require high insulation reliability. The photocurable/thermosetting resin composition of the present invention can provide a substrate having little curing shrinkage and no warpage, and can correspond to TAB, T_. BGA, T-CSP, and UT-CSP. 10 - 200827402 [Embodiment of the Invention] In order to solve the above problems, the inventors of the present invention have found that the photocurable and thermosetting resin composition can provide solder heat resistance. The present invention is completed by a non-warping substrate having excellent adhesion, electrical insulation, and hast resistance, and having few hardening shrinkage. And (A-1) an epoxy compound φ (a) having two or more epoxy groups in one molecule, and one or more alcoholic hydroxyl groups in one molecule, and an alcoholic hydroxyl group Photosensitive property of a carboxyl group obtained by reacting a polybasic acid anhydride (d) with a reaction product of one reactive group (b) in which an epoxy group is reacted and a monocarboxylic acid (c) containing an unsaturated group (A-2) a reaction product obtained by reacting a compound (e) containing two or more phenolic hydroxyl groups in one molecule with an alkylene oxide (f) or a cyclic ester ester compound (g), a reaction product of an unsaturated group of a monocarboxylic acid (c), which is obtained by reacting a polybasic acid anhydride (d) to obtain a carboxyl group-containing photosensitive resin; and #(A-3) reacting a difunctional epoxy compound with an epoxy group a linear polyfunctional epoxy compound (h) obtained by reacting a compound having two reactive groups with a reactive hydroxyl group and epichlorohydrin, and a monocarboxylic acid (c) containing an unsaturated group Any one or two or more kinds of carboxyl group-containing photosensitive resins obtained by reacting the polybasic acid anhydride (d) in the reaction product, and (B) a urethane (meth) acrylate compound, (C) a photopolymerization initiator, (D) a molecule having two or more cyclic ether groups and/or a cyclic thioether group - 11 to 27,027,402 a thermosetting component, and (E) a diluent. In other words, it has been found that a carboxyl group-containing photosensitive resin (any one or two or more of Al, A-2, and A-3) having excellent heat resistance, adhesion, electrical insulating properties, and HAST resistance is used, and hardening is observed. The shrinkage rarely provides a warp-free substrate - the carboxyl group-containing urethane (meth) acrylate compound (B), which does not degrade the mutual properties, can achieve the object of the invention. φ is a carboxyl group-containing photosensitive resin (either one or two or more of Al, A-2, and A-3) and the carboxyl group-containing urethane (meth) acrylate compound (for the above purpose) The blending ratio of B) is preferably in the ratio of 85: 15 to 15: 8 5 . When the heat resistance, the adhesion, the electrical insulating property, and the HAST resistance of the solder are important, the ratio of the carboxyl group-containing photosensitive resin (either one or two or more of Al, A-2, and A-3) is within this range. The higher one is carried out; the ratio of the carboxyl group-containing urethane (meth) # acrylate compound (B) is considered to be higher in the range when the hardening shrinkage is less and the warpage is not observed. When the ratio of the carboxyl group-containing photosensitive resin (either one or two or more of Al, A-2, and A-3) is higher than 85% by mass, warpage is deteriorated; when the ratio is lower than 15% by mass It is not suitable for heat hardening. In addition, the carboxyl group-containing urethane (meth) acrylate compound in the present specification means a carboxyl group-containing urethane acrylate compound, a carboxyl group-containing urethane methacrylate compound. And the general name of the mixture of these, and so on. -12- 200827402 The constituent components of the photocurable thermosetting resin composition of the present invention are described in detail below. First, the carboxyl group-containing photosensitive resin compositions (A-1), (A-2), and (A_3) of the present invention will be described. The carboxyl group-containing photosensitive resin (A-1) is an epoxy compound U) having two or more epoxy groups in one molecule (hereinafter referred to as a polyfunctional epoxy resin), and has one or more molecules in one molecule. An alcoholic hydroxyl group, a compound (b) having one reactive group reactive with an epoxy group other than the alcoholic hydroxyl group, and a monocarboxylic acid containing an unsaturated group (a reaction product of hydrazine, a polybasic acid anhydride (d) A carboxylic acid-containing photosensitive resin obtained by the reaction. The carboxyl group-containing photosensitive resin (A-1) is used in the polyfunctional epoxy resin (a), and only the unsaturated group-containing monocarboxylic acid (〇) After the reaction, the resin which reacts the polybasic acid anhydride (d) has a characteristic that the photosensitive base density is low and the strain of the cured product is small. Further, in the polyfunctional epoxy compound (a), one molecule has 1 Reaction of one or more hydroxyl groups and one reactive group (b) which reacts with an epoxy group of a hydroxyl group other than the hydroxyl group, and a monocarboxylic acid (c) containing an unsaturated group, and introduces photosensitivity into the epoxy resin skeleton An unsaturated group and a primary hydroxyl group, which are then formed by adding an acid anhydride of a polybasic acid anhydride to the primary hydroxyl group. The resin having excellent HAST resistance. Next, the carboxyl group-containing photosensitive resin (A-2) is a compound (e) containing two or more phenolic hydroxyl groups in one molecule, and an alkylene oxide (f) or a cyclic carbonate compound. (g) a reaction product obtained by the reaction, a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride (d) with a monocarboxylic acid containing an unsaturated group (reaction product of hydrazine). -13 - 200827402 The carboxyl group-containing photosensitive resin (A · 2) is an addition of the compound (e) having two or more phenolic hydroxyl groups in one molecule to the alkylene oxide (f) or the cyclic carbonate compound (g). The reaction is carried out to obtain a resin having a phenolic hydroxyl group at a position away from the main chain, whereby the esterification reaction of a part of the phenolic hydroxyl group with the unsaturated group-containing monocarboxylic acid (c) imparts photosensitivity. In a part or all of the remaining phenolic hydroxyl group, a polybasic acid anhydride (sentence-added resin, such that it has a photosensitive unsaturated group at a position away from the main chain, the photoreactivity is superior to φ; Moreover, since it has a free carboxyl group at a position away from the main chain, there is little cutting after cross-linking, and A cured product having excellent electrical properties and HAST resistance, and a carboxyl group-containing photosensitive resin (A-3) is a cross-polymerization of a compound having two reactive groups in which a difunctional epoxy compound and an epoxy group are reacted. In the reaction between the linear polyfunctional epoxy compound (h) obtained by reacting epichlorohydrin in the generated hydroxyl group and the monocarboxylic acid (c) containing an unsaturated group, the polybasic acid anhydride (d) is reacted. A linear carboxyl group-containing photosensitive resin•. ^ This carboxyl group-containing photosensitive resin (A-3) is based on a linear polyfunctional epoxy compound and is flexible; further, by using a difunctional The aromatic epoxy compound, the difunctional phenol compound, and/or the aromatic dicarboxylic acid are preferred materials, and can provide a cured product excellent in water resistance and excellent in electrical properties and HAST resistance. The epoxy compound (a) having two or more epoxy groups in one molecule used for the synthesis of the carboxyl group-containing photosensitive resin (A-1) is a well-known conventional polyfunctional epoxy compound such as bisphenol. A type epoxy resin, • 14- 200827402 Bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenyl type epoxy resin, bisxylenol type epoxy resin, trihydroxyphenylmethane type ring Oxygen resin, tetraphenylethane type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, phenolic epoxy resin of bisphenol A, copolymerization of (meth)acrylic acid epoxypropyl ester Resin, etc. Among these, from the viewpoint of heat resistance and photosensitivity of the obtained resin, it is preferred to use a phenol novolak type epoxy resin or a cresol novolac type epoxy resin, especially a softening point of 50 ° C or higher. A phenol novolac type epoxy tree is preferred. Further, the compound (b) having one or more hydroxyl groups in one molecule used for the synthesis of the carboxyl group-containing photosensitive resin (A-1) and one reactive group reactive with an epoxy group other than the hydroxyl group is , for example, glycolic acid, dimethylol acetic acid, dimethylolpropionic acid, dimethylol butyric acid, dimethylol valeric acid, dihydroxymethylhexanoic acid and other hydroxyl-containing monocarboxylic acids; diethanolamine, two a dialkanolamine such as isopropanolamine; hydroxymethyldi-tert-butylphenol, p-hydroxyphenylethyl alcohol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-propanol , hydroxyethyl cresol, 2,6-dimethyl-4-hydroxymethyl hydrazine, 2,4-dihydroxymethyl-2-cyclohexyl phenol, trimethylol phenol, 3,5-dimethyl - Bis(hydroxyalkyl)phenols such as 2,4,6-trihydroxymethylphenol, bis(hydroxymethyl)phenol, and bis(hydroxymethyl)cresol. More preferred are dimethylolpropionic acid, dimethylolbutanoic acid, and p-hydroxyphenylethyl alcohol. Such a compound having a first-order hydroxyl group is compared with a secondary hydroxyl group obtained by reacting an epoxy group with a monocarboxylic acid containing an unsaturated group, and thereafter, the addition of the polybasic acid anhydride (d) even at a high temperature It is also difficult to break off under high humidity. The unsaturated group-containing monocarboxylic acid (c) used in the carboxyl group-containing photosensitive resin (Al), (A-2), and (A-3), -15-200827402, having acrylic acid or methyl group Acrylic acid, crotonic acid, vinyl acetic acid, cinnamic acid, α-cyanocinnamic acid, cold styryl acrylic acid, mercaptoacrylic acid, or 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2 Hydroxypropyl ester, (meth) propylene, 4-hydroxybutyl acrylate, trimethylolpropane di(meth) acrylate, pentaerythritol tris (meth) acrylate, etc. Among the acrylate compounds, a compound of a dibasic acid anhydride or the like is added. Among these, acrylic acid or methacrylic acid is preferred from the viewpoint of reactivity φ or the like. These unsaturated groups-containing monocarboxylic acids may be used singly or in combination of two or more kinds. The polybasic acid anhydride (d) used in the synthesis of the mercapto group-containing photosensitive resin (Al), (Α-2), and (Α-3), phthalic anhydride, tetrahydrophthalic anhydride, and A Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, sodium de-storage anhydride, octaolefin succinic anhydride, penta (dodecene) Succinic anhydride), 3,6-endo (m)methylenetetrahydrophthalic anhydride, methyl (internal) methylenetetrahydrophthalic anhydride, tetrahedral bromophthalic anhydride, trimellitic anhydride, etc. Or a tribasic acid anhydride, or 'biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride An aliphatic or aromatic tetrabasic dianhydride such as benzophenonetetracarboxylic anhydride. One or two or more of these may be used. Among these, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrakis hexahydrophthalic anhydride are used in terms of film properties of the developing property and the cured product. Succinic anhydride is preferred. The addition amount of the polybasic acid anhydride (d) is such that the acid value of the carboxyl group-containing photosensitive resin (Al, A-2, A-3) used in the present invention is in the range of 30 to 100 mgKOH/g -16 - 200827402. More preferably, it is in the range of 40 to 80 mgKOH/g. The acid value is less than the above range, and when the polybasic acid anhydride (d) is added, the decrease in the developability of the aqueous dilute alkali solution and the decrease in heat resistance are not suitable. On the other hand, it is higher than the above range, and when the polybasic acid anhydride (d) is added, the development resistance is lowered, and the electrical insulating properties and the "electroless plating resistance are lowered" are not suitable. • The compound (e) having two or more phenolic hydroxyl groups in one molecule used in the synthesis of the carboxyl group-containing photosensitive resin (A-2) includes ortho-benzene φ diol, resorcin, and Hydroquinone, dihydroxytoluene, naphthalenediol tert-butyl catechol, tert-butyl hydroquinone, benzenetriol, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, bisphenol , bisxylenol, novolac type phenol resin, phenolic type alkyl phenol resin, phenolic resin of bisphenol A, dicyclopentadiene type phenol resin, Xyl〇k type phenol resin, terpene modified phenol resin, polyethylene a condensate of a phenol or a phenol and an aromatic aldehyde having a phenolic hydroxyl group, a 1-naphthol or a condensate of a 2-phenol and an aromatic aldehyde. Not limited to this. These phenolic hydroxyl group-containing compounds may be used alone or in combination of two or more. The alkylene oxide (f) used in the synthesis of the carboxyl group-containing photosensitive resin (A-2) may, for example, be ethylene oxide, propylene oxide, oxetane, tetrahydrofuran or tetrahydropyran. Further, as the cyclic carbonate compound (g), a well-known conventional carbonate compound such as ethylene carbonate, propylene carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate or the like can be used. A preferred 5-membered ring of vinyl carbonate or propylene carbonate is suitable from the viewpoint of reactivity and supply system. -17- 200827402 These alkylene oxide (f) or cyclic carbonate compound (g) may be used alone or in combination of two or more. The alkylene oxide (f) or the cyclic carbonate compound (g)' is modified from a phenolic hydroxyl group to a phenolic hydroxyl group of the phenolic hydroxyl group-containing compound by an addition reaction using a basic catalyst. A resin having an alcoholic hydroxyl group. The amount of addition at this time corresponds to a range of from 0. 3 to 10 moles per 1 equivalent of the phenolic hydroxyl group, preferably from 0.8 to 5 moles, more preferably from 1 to 3 moles. When the amount of addition is less than the above range, it is difficult to cause a reaction with the monocarboxylic acid group (c) of the unsaturated group-containing polybasic acid anhydride (d), and the solubility in the photosensitive and dilute aqueous alkali solution is lowered, which is extremely unsuitable. . On the other hand, when the amount of addition exceeds the above range, water resistance is lowered due to the ether bond formed, and electrical insulation properties, HAST resistance, and the like are lowered, which is not preferable. The basic catalyst used in the reaction is preferably potassium carbonate, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide or the like. a metal compound; a tertiary amine such as triethylamine; 2-ethyl Imidazole compound such as 4-methylimidazole; phosphorus compound such as triphenylphosphine; tetramethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium halide, tetramethylammonium benzoate, hydrogen a fourth-grade basic base compound such as tetramethylammonium oxide, tetraethylammonium hydroxide or tetramethyl rust; lithium, chromium, chromium, naphthenic acid, lauric acid, stearic acid, oleic acid or octanoic acid; a metal salt of an organic acid such as potassium or sodium. These catalysts may be used alone or in combination of two or more. With such an alkaline catalyst, the reaction is preferably carried out at a normal temperature of from -250 °C. The reaction solvent may be benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone-18-200827402, diisopropyl Ether, etc. These organic solvents may be used singly or in combination of two or more kinds. The difunctional epoxy compound used in the synthesis of the carboxyl group-containing photosensitive resin (A-3) is 1,6-hexanediol diepoxypropyl ether or pentaerythritol diepoxypropyl ether. , bisphenol type diepoxypropyl ether, cresol type diepoxypropyl ether, bisphenol type diepoxypropyl ether, naphthalene type diepoxypropyl ether and the like. By a phenol type diepoxypropyl ether having an aromatic ring represented by the following formulas (1) to (4), a cresol type diepoxypropyl ether, a bisphenol type diglycidyl ether One of the interpolymers of at least one difunctional aromatic alcohol such as naphthalene type di-glycidyl ether can be used as a monomer component to obtain an epoxy compound excellent in strength, heat resistance and electrical insulating properties of a cured product.

R5 P9 R7R5 P9 R7

⑴ ⑵(1) (2)

如之聯酚型、聯甲酚型、雙酚型或萘型之二環氧丙基 -19- 200827402 醚，可使用由例如聯酚化合物、聯甲酚化合物、雙酚化合 物或二羥基萘與環氧氯丙烷之反應所製造者。又，亦可手 市售之環氧化合物；例如聯酚型二環氧丙基醚有，油化榭 魯環氧股份有限公司製之商品名「耶皮口得YL-6056」等 - ;聯甲酚型二環氧丙基醚有，油化榭魯環氧股份有限公司 * 製之商品名「耶皮口得YX-4000」等；雙酚型二環氧丙基 醚有，旭吉巴股份有限公司製之商品名「阿拉魯萊得#260 φ 」、「阿拉魯萊得#607 1」等之雙酚A型環氧化合物、或 大曰本油墨化學工業股份有限公司製之商品名「耶皮庫龍 83 0S」等雙酚F型環氧化合物、或大日本油墨化學工業股 份有限公司製之商品名「耶皮庫龍EXA1 514」等雙酚S 型環氧化合物；萘型二環氧丙基醚有，大日本油墨化學工 業股份有限公司製之商品名「耶皮庫龍HP-4032(D)」等 。此等可單獨或2種以上組合使用。以具有芳香環之聯酚 型二環氧丙基醚、聯甲酚型二環氧丙基醚、雙酚型二環氧 • 丙基醚、萘型二環氧丙基醚等爲佳。此等二官能環氧化合 物，可單獨或2種以上混合使用。 該含羧基之感光性樹脂（A-3)的合成中所使用之具有2 個可與環氧基反應的反應基之化合物，有二官能酚化合物 、二羧酸、具有2個活性氫之胺化合物、二硫醇化合物等 ;從樹脂之穩定性或反應的容易性而言，以二官能酚化合 物、二羧酸爲佳。 二官能酚化合物，其構造中具有特徵、使耐熱性增高 之故具有芳香環，可使用具有對稱構造或剛直構造者。如 -20- 200827402 此之化合物有’例如1，4 -二羥基萘、1，5 -二羥基萘、1，6 -二經基萘、2,6-二羥基萘、2,7_二羥基萘、2,8_二羥基萘 等二經基萘衍生物；聯甲酚、聯酚等聯酚衍生物；雙酚A 、雙酚F、雙酚S、烷基取代雙酚等雙酚衍生物；對苯二 酚、甲基對苯二酚、三甲基對苯二酚等對苯二酚衍生物等 。此等可單獨或2種以上組合使用。 又’二羧酸有，琥珀酸、反丁烯二酸、苯二甲酸、衣 康酸、己二酸、壬二酸、癸二酸、苯二甲酸、異苯二甲酸 、對苯二甲酸、四氫苯二甲酸、六氫苯二甲酸，進而均苯 四甲酸二酐或二苯甲酮四羧酸二酐等四元酸二酐，與2-羥基甲基（甲基）丙烯酸酯等之半酯等。 二官能環氧化合物、與二官能酚化合物或二羧酸之反 應中所使用的觸媒，以環氧丙基與酚性羥基或羧基在定量 上反應之膦類、鹼金屬化合物、單獨或倂用胺類爲佳。此; 以外之觸媒，和環氧丙基與酚性羥基之反應生成的醇性羥 基反應，予以膠化飲故，甚不適合。 膦類有，三丁基膦、三苯基膦等三烷基或三芳基膦或 此等之氧化物的鹽類等。鹼金屬化合物有，鈉、鋰、鉀等 鹼金屬之氫氧化物、鹵化物、烷氧基金屬、醯胺等，此等 可單獨或2種以上組合使用。 胺類有，脂肪族或芳香族之第一級、第二級、第三級 、第四級胺類等，此等可單獨或2種以上組合使用。胺類 之具體例有，三乙醇類、N，N-二甲基哌嗪、三乙胺、三正 丙胺、六亞甲基四胺、吡啶、四甲基銨溴化物等。 -21 - 200827402 此等之觸媒，相對於二官能環氧化合物及二官能酚化 合物或二羧酸之加料量100質量份爲0.001〜1質量份、較 佳爲0 · 0 1〜1質量份之範圍。此理由係，觸媒之使用量未 達0 · 0 0 1質量份時，需要很長之反應時間很不經濟；另一 ' 方面，超過1質量份時’相反的反應過快難以控制之故， 、 甚不適合。 二官能芳香族感光性樹脂化合物與二官能酚化合物或 Φ 二羧酸，在惰性氣體氣流中或空氣中，於該觸媒下，以在 13 0〜18 0°c之溫度範圍反應爲佳。 該線狀之多官能環氧化合物（h)，可藉由在二甲基亞 颯、N，N-二甲基甲醯胺、N，N-二甲基乙醯胺等非質子性極 性溶劑；甲苯、二甲苯等芳香族烴類等眾所周知的溶劑中 ，與鹼金屬氫氧化之存在下，於上述二官能環氧化合物及 二官能酚化合物或二羧酸之反應生成物中，使醇性羥基與 環氧氯丙烷反應予以製作。 • 該環氧鹵丙烷，可使用例如環氧鹵丙烷、環氧溴丙烷 ^ 、環氧碘丙烷、）甲基環氧氯丙烷、-甲基環氧溴丙烷 、泠·甲基環氧碘丙烷等。 該線狀之多官能環氧化合物（h)中，該環氧氯丙烷之 使用量，相對於上述二官能環氧化合物與二官能酚化合物 或二羧酸之反應生成物中的醇性羥基1當量，約使用0 .1 倍當量以上爲佳。但，使用相對於羥基1當量，超過1 5 倍當量之量時，容積效率惡化，甚不適合。 又，鹼金屬氫氧化物，可使用苛性鈉、苛性鉀、氫氧 -22- 200827402 化鋰、氫氧化鈣；以苛性鈉爲佳。此鹼金屬氫氧化物之使 用量，以使用相對於該二官能芳香族環氧化合物與該二官 能芳香族醇之反應生成物中的環氧化醇性羥基1當量之 0.5〜2倍當量爲佳。 二官能芳香族環氧化合物與二官能酚化合物或二羧酸 之反應生成物中，醇性羥基與環氧氯丙烷的反應溫度，以 20〜100 °C爲佳。此理由係，反應溫度未達20 °C時，反應 緩慢、必要長時間之反應。另一方面，反應溫度超過1 00 °C時，引起多數之副反應，極不適合。 又，二官能芳香族環氧化合物與二官能酚化合物或二 羧酸之反應生成物中，該醇性羥基與該環氧鹵丙烷之反應 ，在二甲基亞礪或四級銨鹽或1,3-二甲基-2-咪唑啉與鹼 金屬氫氧化物之共存下，可藉由調整該鹼金屬氫氧化物之 量進行。此時，溶劑可倂用甲醇或乙醇等醇類；甲苯、二 甲苯等芳香族烴類；甲異丁酮、甲乙酮等酮類；四氫呋喃 等環狀醚化合物等。 四級銨鹽之具體例，可使用氯化四甲基銨、溴化四甲 基銨、氯化三甲基銨等；其使用量，相對於作爲原料使用 之環氧樹脂的環氧化的羥基1當量，以〇·3〜5 0g爲佳。相 對於環氧化之羥基1當量，未達〇.3g時，作爲原料使用 之環氧樹脂的醇性羥基與環氧鹵丙烷之反應緩慢，必要長 時間的反應’甚不適合。另一方面，相對於環氧化之羥基 1當量，超過5 0g時，幾乎全無增量之硬化、同時成本增 加，極不適合。 -23- 200827402 該線狀之多官能環氧化合物（h)中，使含不飽和單羧 酸（c)反應，可獲得不飽和環氧丙烯酸酯化合物；於該線 狀之多官能環氧化合物（h)中，以相對於該化合物中所含 環氧基1莫耳之含不飽和基的單羧酸0.8〜1.3莫耳之比例 - 配合，在惰性溶劑中或無溶劑下，於60〜150乞、較佳爲 一 70〜130°C加熱，較佳爲在空氣之存在下進行反應，藉由反 •應中之聚合可防止膠化之故，以使用甲基對苯二酚、對苯 φ 二酚等對苯二酚類；對-苯醌、對-甲苯醌等苯醌類等眾所 周知的聚合抑制劑爲佳。又，爲縮短反應時間，以使用酯 化觸媒爲佳；酯化觸媒可使用，例如N，N -二甲基苯胺、 吡啶、三乙胺等三級胺及其鹽酸鹽或溴酸鹽；氯化四甲基 銨、氯化三乙基苄基銨等四級銨鹽；對-甲苯磺酸等磺酸 •，二甲基亞颯、甲基亞楓等鎏鹽；三苯基膦、三正丁基膦 等膦類；氯化鋰、溴仡鋰、氯化亞錫、氯化鋅等金屬鹵化 物等眾所周知的慣用者。 φ 該含羧基之感光性樹脂（A-3)的數平均分子量爲 ' 400〜1 0,000、較佳爲500〜7,000、更佳爲500〜3,000。活性 能量線硬化性樹脂之數平均分子量未達4 0 0時，所得硬化 物之強靭性不充分；另一方面，超過1 0，0 0 0時，相對於 溶劑之溶解性降低，甚不適合。 其次，具有本發明之第二特徵的含羧基之胺基甲酸酯 (甲基）丙烯酸酯化合物（B)，係使含羥基（甲基）丙烯酸酯化 合物（i)、二羥甲基烷酸（j)、及二異氰酸酯化合物（k)反應 所得之化合物，及/或含羥基之（甲基）丙烯酸酯化合物（i) -24- 200827402 、二羥基烷酸（j)、二異氰酸酯化合物（k)、及聚合物聚醇 (m)反應所得之化合物；其係酸價爲30〜100 mgK〇H/g的 化合物。 該含羧基之胺基甲酸酯（甲基）丙烯酸酯化合物（B)， 係基本上含有具線狀之胺基甲酸酯鍵結之含羧基的感光性 樹脂之故，具有柔軟性，具減低由於硬化收縮之翹曲的效 果。 該含羧基胺基甲酸酯（甲基）丙烯酸酯化合物（B)之合 成中所使用的含羥基（甲基）丙烯酸酯化合物（i)，係基本上 含有1個羥基之（甲基）丙烯酸酯化合物（i-Ι)、或含有2個 羥基之（甲基）丙烯酸酯化合物（i-2)。 該具有1個羥基之（甲基）丙烯酸酯化合物（i-Ι)有，例 如2-羥基乙基（甲基）丙烯酸酯、2-羥基丙基（甲基）丙烯酸 酯、4-羥基丁基（甲基）丙烯酸酯、三羥甲基丙烷二（甲基）·. 丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、或環氧丙基（甲 基）丙烯酸酯與（甲基）丙烯酸酯之反應物等。如此之具有1 個羥基之（甲基）丙烯酸酯化合物，係加成於本發明之含羧 基胺基甲酸酯（甲基）丙烯酸酯化合物的末端，作用爲停止 分子成長之抑制劑。 另一方面，具有2個羥基之（甲基）丙烯酸酯（i-2)，有 在二官能環氧化合物中，加成（甲基）丙烯酸之二官能環氧 (甲基）丙烯酸酯化合物，或在二官能氧雜環丁烷化合物中 ，加成（甲基）丙烯酸之二官能氧雜環丁烷（甲基）丙烯酸酯 化合物等。 -25- 200827402 具體而言，以雙酚A型環氧樹脂、雙酚F型環氧樹 脂、雙酚S型環氧樹脂、聯酚型環氧樹脂、聯甲酚型環氧 樹脂等具有芳香環之二官能環氧樹脂的（甲基）丙烯酸酯化 合物爲佳。此等二官能環氧（甲基）丙烯酸酯化合物之分子 • 量，以在450〜2,000之範圍者，從硬化塗膜特性之面而言 » ，極爲適合。 該二羥甲基烷酸（j)，爲具有2個三級之羧基與一級之 φ 羥基的化合物；具體而言有，二羥甲基丙酸、二羥甲基丁 酸、二羥甲基戊酸、二羥甲基己酸等。此等之中，從硬化 塗膜的特性等之面而言，以二羥甲基丙酸、二羥甲基丁酸 爲佳。 該二異氰酸酯化合物（k)，有苯基二異氰酸酯、甲苯 基二異氰酸酯、二甲苯基二異氰酸酯、六亞甲基二異氰酸 酯、異佛爾酮二異氰酸酯、環己烷二異氰酸酯、三甲基苯 基二異氰酸酯、二苯基甲烷二異氰酸酯、二環己基甲烷二 # 異氰酸酯、四甲基二甲苯基二異氰酸酯等。此等之中，尤 ' 其以異佛爾酮二異氰酸酯，反應的控制容易之故，甚爲適 合。 本發明之光硬化性•熱硬化性樹脂組成物中所使用的 含羧基之胺基甲酸酯（甲基）丙烯酸酯化合物（B)的合成時 ，進而爲減低硬化收縮，可使用聚合物聚醇（m )。 該聚合物聚醇（m)，基本上以難三維化之二醇化合物 爲佳，具有支化構造之故，亦可添加三醇類。 具體而言，有聚醚聚醇類、聚酯聚醇類、聚碳酸酯聚 -26- 200827402 醇類、聚丁二烯二醇類等。 尤其’二醇或雙酚類時，由二甲基碳酸酯等碳酸酯類 所衍生之聚碳酸酯聚醇，從耐藥品性等之面而言，甚爲適 合。 ‘ 此等含羥基之（甲基）丙烯酸化合物（〇，藉由該二羥甲 • 基院酸（j)、該二異氰酸酯化合物（k)、或進而該聚合物聚 醇（m)，以眾所周知的慣用之方法胺基甲酸酯化，可合成 # 本發明所使用之含羧基胺基甲酸酯（甲基）丙烯酸酯化合物 (B)。 具體而言，以異氰酸酯基與羥基，當量比爲 ’且所得含羧基胺基甲酸酯（甲基）丙烯酸酯化合物（B)之 酸價爲30〜100 mgKOH/g加料，進行反應。反應條件使用 難以三維化之金屬觸媒，在無溶劑或非質子性溶劑中，藉 由常溫〜150°C、較佳爲60〜120。(：反應可予以合成。 _ 該含羧基胺基甲酸酯（甲基）丙烯酸酯化合物（B)之酸 ® 價’未達30 mgKOH/g時，藉稀鹼水溶液不能獲得顯像性 之故’極不適合。另一方面，酸價超過1〇〇 mgK〇H/g時 ’不能獲得耐顯像性、無電解電鍍耐性等降低之故，甚不 適合。 本發明之光硬化性·熱硬化性樹脂組成物，爲使該含 竣基之感光性樹脂（A)、及該含羧基之胺基甲酸酯（甲基） 丙燒酸酯化合物（B)的效率良好、進行光硬化之故，而使 用（C)光聚合引發劑。 該光聚合引發劑（C)有，例如苯偶姻、苯偶姻甲基醚 •27- 200827402 、苯偶姻乙基醚、苯偶姻異丙基醚等苯偶姻與苯偶姻院基 醚類；苯乙酮、2，2·二甲氧基-2·苯基苯乙酮、2,2_二乙氧 基-2 -苯基苯乙酮、1，卜二氯苯乙酮等苯乙酮類；2•甲基_ 1-[4-(甲硫基）苯基]-2·嗎啉代丙院·1·酮、2·节基-2-二甲基 胺基-1-(4-嗎啉代苯基）丁酮-1、2-(二甲基胺基）_2-[(心甲 基本基）甲基]-嗎啉基）苯基]-1-丁酿等胺基苯乙酮 類；2_甲基蒽醌、2 -乙基蒽醌、2 -叔丁基蒽醌、氯蒽醌 等蒽醌類；2,4-二甲基噻噸酮、2,4·二乙基噻噸酮、2,4_氯 噻噸酮、2,4-二異丙基噻噸酮等噻噸酮類；苯乙酮二甲基 縮酮、苄基二甲基縮酮等縮酮類；苯偶醯、二苯甲酮等二 苯甲酮類；或咕噸酮類；（2,6-二甲氧基苯甲醯基）_2,4,4一 戊基膦氧化物、雙（2,4,6-三甲基苯甲醯基）苯基膦氧化物 、：2，4,6 -三甲基苯甲醯基二苯基膦氧化物、乙基- 2,4,6 -三 甲基苯甲醯基苯基次膦酸酯之膦氧化物類；進而（2-(乙醯 基氧亞胺基甲基）噻噸-9-酮）、（1，2-辛烷二酮，；u[4-(苯硫 基）·，2-(0 -苯甲醯基肟）]、乙酮，1-[9 -乙基-6-(2 -甲基苯 甲醯基）·9Η-昨唑·3·基]…1-(0-乙醯基肟）)等肟酯類等。 此等眾所周知的慣用之光聚合引發劑，可單獨或2種 以上組合使用。該光聚合引發劑（C)之配合比例，相對於 該含羧基感光性樹脂（A)、及該含羧基胺基甲酸酯（甲基） 丙烯酸酯化合物（B)之合計量100質量份，以〇.〇1〜30質 量份較適當；爲上述之肟系光聚合引發劑時爲0.01〜20質 量份、較佳爲0.01〜5質量份。光聚合引發劑之使用量比 上述範圍少時，光硬化性惡化；另一方面，多時，硬化塗 -28 - 200827402 膜特性降低之故，甚不適合。 本發明之光硬化性·熱硬化性樹脂組成物，可含有作 爲引發助劑之3級胺化合物、或二苯甲酮化合物如此之3 級胺類有，乙醇胺類、4,4’ -二甲基胺基二苯甲酮（日本曹 — 達公司製，日曹丘爾MABP)、4_二甲基胺基苯甲酸乙酯（ 、 日本化藥公司製卡牙丘爾EPA)、2-二甲基胺基苯甲酸乙 酯（國際拜歐新榭技術公司製昆達丘爾DMB)、4-二甲基胺 • 基苯甲酸（正丁氧基）乙酯（昆達丘爾BEA)、對-二甲基胺基 苯甲酸異戊基乙基酯（日本化藥公司製卡牙丘爾DMBI)、 4-二甲基胺基苯甲酸2-乙基己基酯（Van Dyk公司製1 solol 5 0 7)、4，4’-二乙基胺基二苯甲酮（保土谷化學公司製 EAB)等。此等眾所周知慣用之3級胺化合物，可單獨或2 種以上混合使用。較佳之3級胺化合物爲4,4’·二乙基胺 基二苯甲酮；並非限定於此等者，藉由倂用在波長 300〜420nm之區域吸收光的脫氫型光聚合引發劑，能發揮 # 增感效果時，不限於光聚合引發劑、光引發助劑，可單獨 或複數倂用。 本發明之光硬化性·熱硬化性樹脂組成物，爲提升硬 化物之耐熱性，配合在1分子中具有2個以上之環狀醚基 及/或環狀硫醚基的該熱硬化性成份（D)[以下簡稱爲環狀（ 硫）醚化合物]。 如此之1分子中具有2個以上的環狀醚基及/或環狀 硫醚基之熱硬化性成份（D)，有1分子中具有2個以上之 3、4或5員環的環狀醚基，或環狀硫醚基的任一方或2 -29- 200827402 種之基的化合物。例如1分子中具有至少2個以上之環氧 基的化合物，即多官能環氧化合物（D-1 ); 1分子中具有至 少2個以上之氧雜環丁烷基的化合物，即多官能氧雜環丁 烷化合物（D-2) 分子中具有2個以上之硫醚基的化合物 ;即表位硫化物樹脂等。For example, a diphenolic propyl-19-200827402 ether of a biphenol type, a cresol type, a bisphenol type or a naphthalene type may be used, for example, from a bisphenol compound, a cresol compound, a bisphenol compound or dihydroxynaphthalene. Manufacturer of the reaction of epichlorohydrin. Further, an epoxy compound which is commercially available; for example, a biphenol-type diglycidyl ether, a product name of "Jeppei YL-6056" manufactured by the Oil-based Lulu Epoxy Co., Ltd., etc. The cresol type diepoxypropyl ether is available under the trade name "Yipidou YX-4000" manufactured by Oil Chemical Lulu Epoxy Co., Ltd.; bisphenol type diepoxypropyl ether, Xujiba A bisphenol A type epoxy compound such as "Alaruide #260 φ" and "Alaruide #607 1", or a product name of Otsuka Ink Chemical Industry Co., Ltd. Bisphenol F-type epoxy compound such as "Yepikron 83 0S" or bisphenol S-type epoxy compound such as "Yippikron EXA1 514" manufactured by Dainippon Ink and Chemicals Co., Ltd.; naphthalene type II The epoxy propyl ether is available under the trade name "Yepikulon HP-4032 (D)" manufactured by Dainippon Ink Chemical Industry Co., Ltd. These may be used alone or in combination of two or more. It is preferably a phenol type diepoxypropyl ether having an aromatic ring, a cresol type diepoxypropyl ether, a bisphenol type diepoxy group propyl ether, or a naphthalene type diepoxypropyl ether. These difunctional epoxides may be used singly or in combination of two or more kinds. A compound having two reactive groups reactive with an epoxy group used in the synthesis of the carboxyl group-containing photosensitive resin (A-3), having a difunctional phenol compound, a dicarboxylic acid, an amine having two active hydrogens A compound, a dithiol compound, or the like; a difunctional phenol compound or a dicarboxylic acid is preferred from the viewpoint of stability of the resin or ease of reaction. The difunctional phenol compound has a characteristic in structure and has an aromatic ring because of its high heat resistance, and a structure having a symmetrical structure or a rigid structure can be used. For example, -20- 200827402 compounds such as 1,4 -dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-di-perylene, 2,6-dihydroxynaphthalene, 2,7-dihydroxy Bis-naphthalene derivatives such as naphthalene and 2,8-dihydroxynaphthalene; biphenol derivatives such as cresol and biphenol; bisphenol derivatives such as bisphenol A, bisphenol F, bisphenol S and alkyl substituted bisphenol Hydroquinone derivatives such as hydroquinone, methyl hydroquinone, trimethyl hydroquinone, and the like. These may be used alone or in combination of two or more. Also, 'dicarboxylic acids are, succinic acid, fumaric acid, phthalic acid, itaconic acid, adipic acid, sebacic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, Tetrahydrophthalic acid, hexahydrophthalic acid, tetracarboxylic acid dianhydride such as pyromellitic dianhydride or benzophenone tetracarboxylic dianhydride, and 2-hydroxymethyl (meth) acrylate Half esters, etc. a difunctional epoxy compound, a catalyst used in the reaction with a difunctional phenol compound or a dicarboxylic acid, a phosphine, an alkali metal compound, or a ruthenium which is quantitatively reacted with a propylene group and a phenolic hydroxyl group or a carboxyl group. It is preferred to use an amine. This is a catalyst other than the reaction, and reacts with an alcoholic hydroxyl group formed by the reaction of a glycidyl group with a phenolic hydroxyl group, which is not suitable for gelatinization. Examples of the phosphine include a trialkyl or triarylphosphine such as tributylphosphine or triphenylphosphine or a salt of such an oxide. The alkali metal compound may be a hydroxide, a halide, an alkoxide metal or a guanamine of an alkali metal such as sodium, lithium or potassium, and these may be used singly or in combination of two or more kinds. The amines may be aliphatic, aromatic or the first, second, third, and fourth amines, and these may be used alone or in combination of two or more. Specific examples of the amines include triethanols, N,N-dimethylpiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide and the like. -21 - 200827402 These catalysts are 0.001 to 1 part by mass, preferably 0 · 0 1 to 1 part by mass, based on 100 parts by mass of the difunctional epoxy compound and the difunctional phenol compound or dicarboxylic acid. The scope. For this reason, when the amount of catalyst used is less than 0. 01 parts by mass, it takes a very long reaction time to be uneconomical; on the other side, when it exceeds 1 part by mass, the opposite reaction is too fast to control. , , is not suitable. The difunctional aromatic photosensitive resin compound and the difunctional phenol compound or Φ dicarboxylic acid are preferably reacted in the inert gas stream or in the air at a temperature ranging from 130 to 180 ° C under the catalyst. The linear polyfunctional epoxy compound (h) can be obtained by an aprotic polar solvent such as dimethyl hydrazine, N,N-dimethylformamide or N,N-dimethylacetamide. In a well-known solvent such as an aromatic hydrocarbon such as toluene or xylene, in the presence of an alkali metal hydroxide, the alcohol is formed in the reaction product of the difunctional epoxy compound and the difunctional phenol compound or the dicarboxylic acid. The hydroxyl group is reacted with epichlorohydrin to produce. • For the epihalohydrin, for example, an epihalohydrin, an epoxy bromide, an epoxidized iodine, a methyl epichlorohydrin, a methylepoxybromopropane, a hydrazine methyl epoxide propane Wait. In the linear polyfunctional epoxy compound (h), the amount of the epichlorohydrin used is relative to the alcoholic hydroxyl group in the reaction product of the difunctional epoxy compound and the difunctional phenol compound or the dicarboxylic acid. The equivalent weight is preferably about 0.1 times or more. However, when the amount is more than 15 equivalents per equivalent of the hydroxyl group, the volumetric efficiency is deteriorated, which is not suitable. Further, as the alkali metal hydroxide, caustic soda, caustic potash, oxyhydrogen -22-200827402, and calcium hydroxide can be used; and caustic soda is preferred. The alkali metal hydroxide is preferably used in an amount of from 0.5 to 2 equivalents per equivalent of the epoxidized alcoholic hydroxyl group in the reaction product of the difunctional aromatic epoxy compound and the difunctional aromatic alcohol. . In the reaction product of a difunctional aromatic epoxy compound and a difunctional phenol compound or a dicarboxylic acid, the reaction temperature of the alcoholic hydroxyl group and epichlorohydrin is preferably 20 to 100 °C. For this reason, when the reaction temperature is less than 20 °C, the reaction is slow and it takes a long time to react. On the other hand, when the reaction temperature exceeds 100 ° C, most of the side reactions are caused, which is extremely unsuitable. Further, in the reaction product of a difunctional aromatic epoxy compound and a difunctional phenol compound or a dicarboxylic acid, the alcoholic hydroxyl group is reacted with the epihalohydrin, in the dimethyl hydrazine or quaternary ammonium salt or The coexistence of 3-dimethyl-2-imidazoline and an alkali metal hydroxide can be carried out by adjusting the amount of the alkali metal hydroxide. In this case, the solvent may be an alcohol such as methanol or ethanol; an aromatic hydrocarbon such as toluene or xylene; a ketone such as methyl isobutyl ketone or methyl ethyl ketone; or a cyclic ether compound such as tetrahydrofuran. As a specific example of the quaternary ammonium salt, tetramethylammonium chloride, tetramethylammonium bromide, trimethylammonium chloride or the like can be used; the amount used is an epoxidized hydroxyl group relative to the epoxy resin used as a raw material. 1 equivalent, preferably 〇·3~5 0g. When the amount of the epoxidized hydroxyl group is 1 equivalent, the reaction between the alcoholic hydroxyl group of the epoxy resin used as a raw material and the epihalohydrin is slow, and the reaction for a long period of time is not suitable. On the other hand, when it exceeds 50 g with respect to the hydroxyl group of the epoxidation, almost no increase in the number of hardenings and an increase in cost is extremely unsuitable. -23- 200827402 In the linear polyfunctional epoxy compound (h), an unsaturated epoxy acrylate compound is obtained by reacting an unsaturated monocarboxylic acid (c); and the linear polyfunctional epoxy compound is obtained. In (h), in a ratio of 0.8 to 1.3 mol per mol of the monocarboxylic acid containing 1 mol of the epoxy group contained in the compound, in an inert solvent or without a solvent, in 60~ 150 乞, preferably a temperature of 70 to 130 ° C, preferably in the presence of air, the reaction can be prevented by the polymerization in the reverse, to use methyl hydroquinone, A well-known polymerization inhibitor such as hydroquinone or a benzoquinone such as p-benzoquinone or p-toluene is preferable. Further, in order to shorten the reaction time, it is preferred to use an esterification catalyst; an esterification catalyst can be used, for example, a tertiary amine such as N,N-dimethylaniline, pyridine or triethylamine, or a hydrochloride or bromic acid thereof. a salt; a tetra-ammonium salt such as tetramethylammonium chloride or triethylbenzylammonium chloride; a sulfonic acid such as p-toluenesulfonic acid; a sulfonium salt such as dimethyl sulfoxide or methyl sulfoxide; Phosphines such as phosphine and tri-n-butylphosphine; and well-known conventional compounds such as lithium chloride, lithium bromo lithium, stannous chloride, and zinc chloride. φ The number average molecular weight of the carboxyl group-containing photosensitive resin (A-3) is '400 to 1,000,000, preferably 500 to 7,000, more preferably 500 to 3,000. When the number average molecular weight of the active energy ray-curable resin is less than 4,000, the toughness of the obtained cured product is insufficient. On the other hand, when it exceeds 10,000, the solubility with respect to a solvent is lowered, which is not preferable. Next, the carboxyl group-containing urethane (meth) acrylate compound (B) having the second feature of the present invention is a hydroxyl group-containing (meth) acrylate compound (i), dimethylol alkanoic acid. (j), and a compound obtained by reacting a diisocyanate compound (k), and/or a hydroxyl group-containing (meth) acrylate compound (i) -24-200827402, a dihydroxyalkanoic acid (j), a diisocyanate compound (k) And a compound obtained by reacting a polymer polyol (m); which is a compound having an acid value of 30 to 100 mgK〇H/g. The carboxyl group-containing urethane (meth) acrylate compound (B) basically contains a linear urethane-bonded carboxyl group-containing photosensitive resin, and has flexibility. Reduce the effect of warpage due to hardening shrinkage. The hydroxyl group-containing (meth) acrylate compound (i) used in the synthesis of the carboxyl group-containing urethane (meth) acrylate compound (B) is a (meth) acrylate having substantially one hydroxyl group. An ester compound (i-oxime) or a (meth) acrylate compound (i-2) containing two hydroxyl groups. The (meth) acrylate compound (i-oxime) having one hydroxyl group is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl group. (Meth) acrylate, trimethylolpropane di(methyl) acrylate, pentaerythritol tri(meth) acrylate, or epoxy propyl (meth) acrylate and (meth) acrylate Reactant, etc. Such a (meth) acrylate compound having one hydroxy group is added to the terminal of the carboxy group-containing urethane (meth) acrylate compound of the present invention to act as an inhibitor for stopping molecular growth. On the other hand, a (meth) acrylate (i-2) having two hydroxyl groups is a difunctional epoxy (meth) acrylate compound obtained by adding (meth)acrylic acid to a difunctional epoxy compound. Alternatively, a difunctional oxetane (meth) acrylate compound of (meth)acrylic acid may be added to the difunctional oxetane compound. -25- 200827402 Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, and cresol type epoxy resin have aroma A (meth) acrylate compound of a bifunctional epoxy resin is preferred. The molecular weight of these difunctional epoxy (meth) acrylate compounds, in the range of 450 to 2,000, is extremely suitable from the viewpoint of the characteristics of the cured coating film. The dimethylol alkanoic acid (j) is a compound having two tertiary carboxyl groups and a primary φ hydroxy group; specifically, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylol Valeric acid, dimethylolhexanoic acid, and the like. Among these, dimethylolpropionic acid and dimethylolbutanoic acid are preferred from the viewpoint of the properties of the cured coating film and the like. The diisocyanate compound (k) is phenyl diisocyanate, tolyl diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, trimethylphenyl group. Diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane bis # isocyanate, tetramethyl xylylene diisocyanate, and the like. Among them, it is particularly suitable for the control of the reaction of isophorone diisocyanate. In the synthesis of the carboxyl group-containing urethane (meth) acrylate compound (B) used in the photocurable thermosetting resin composition of the present invention, further, the curing shrinkage can be reduced, and polymer aggregation can be used. Alcohol (m). The polymer polyol (m) is preferably a diol compound which is difficult to be three-dimensionally formed, has a branched structure, and may be added with a triol. Specifically, there are polyether polyols, polyester polyols, polycarbonates -26-200827402 alcohols, polybutadiene diols, and the like. In particular, in the case of a diol or a bisphenol, a polycarbonate polyol derived from a carbonate such as dimethyl carbonate is suitable from the viewpoint of chemical resistance and the like. 'The hydroxyl group-containing (meth)acrylic compound (〇, by the dihydroxymethyl ketone acid (j), the diisocyanate compound (k), or further the polymer polyol (m), is well known The conventional method of urethanation can synthesize the carboxyl group-containing urethane (meth) acrylate compound (B) used in the present invention. Specifically, the isocyanate group and the hydroxyl group have an equivalent ratio of And the obtained carboxyl group-containing urethane (meth) acrylate compound (B) has an acid value of 30 to 100 mg KOH / g of a feed, and the reaction is carried out using a metal catalyst which is difficult to be three-dimensional, in the absence of a solvent or In the aprotic solvent, it is at a temperature of from -150 ° C, preferably from 60 to 120. (: The reaction can be synthesized. _ The acid of the carboxyl group-containing urethane (meth) acrylate compound (B) When the price is less than 30 mgKOH/g, it cannot be obtained by using a dilute aqueous solution. It is extremely unsuitable. On the other hand, when the acid value exceeds 1〇〇mgK〇H/g, it is not able to obtain image resistance. It is not suitable for the reduction of electrolytic plating resistance, etc. The photohardening of the present invention The thermosetting resin composition is excellent in light efficiency of the sulfhydryl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth)propionate compound (B). For curing, (C) a photopolymerization initiator is used. The photopolymerization initiator (C) is, for example, benzoin, benzoin methyl ether, 27-200827402, benzoin ethyl ether, benzoin Benzoin and benzoin-based ethers such as isopropyl ether; acetophenone, 2,2. dimethoxy-2-phenylphenone, 2,2-diethoxy-2-benzene Acetophenones such as acetophenone, 1, dichloroacetophenone, etc.; 2•methyl_1-[4-(methylthio)phenyl]-2·morpholinopropan-1-ketone, 2. benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-(dimethylamino)_2-[(heart methyl) methyl] -morpholinyl)phenyl]-1-butylene and other aminoacetophenones; 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, chloranil and the like ; 2,4-dimethylthioxanthone, 2,4·diethylthioxanthone, 2,4-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; benzene Ethyl ketone dimethyl ketal, benzyl di a ketal such as methyl ketal; a benzophenone such as benzophenone or benzophenone; or a xanthone; (2,6-dimethoxybenzhydryl)_2,4,4 Amylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, B a phosphine oxide of 2,4,6-trimethylbenzimidylphenylphosphinate; further (2-(ethylideneoxyiminomethyl)thioxan-9-one), (1,2-octanedione, u[4-(phenylthio)·, 2-(0-benzylhydrazinyl)], ethyl ketone, 1-[9-ethyl-6-(2 -Methylbenzhydryl)·9Η-Monthazole·3·yl]...1-(0-ethenylhydrazine)) and the like. These well-known conventional photopolymerization initiators may be used singly or in combination of two or more kinds. The blending ratio of the photopolymerization initiator (C) is 100 parts by mass based on the total amount of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B). It is preferably 1 to 30 parts by mass, and is 0.01 to 20 parts by mass, preferably 0.01 to 5 parts by mass, in the case of the above-mentioned fluorene photopolymerization initiator. When the amount of the photopolymerization initiator used is less than the above range, the photocurability is deteriorated. On the other hand, when the film properties of the cured coating -28 - 200827402 are lowered, it is not suitable. The photocurable and thermosetting resin composition of the present invention may contain a tertiary amine compound or a benzophenone compound as an initiator, such a tertiary amine, ethanolamine, 4,4'-dimethyl Amino benzophenone (manufactured by Japan Cao-Da Co., Ltd., Nicholas Chur MABP), 4-dimethylaminobenzoic acid ethyl ester (, Kasuga EPA manufactured by Nippon Kayaku Co., Ltd.), 2-two Ethyl methylaminobenzoate (Kundachuer DMB, manufactured by International Biotech Co., Ltd.), 4-dimethylammonium benzoic acid (n-butoxy)ethyl ester (Kundachuer BEA), p-Dimethylaminobenzoic acid isoamylethyl ester (Kapori DMBI manufactured by Nippon Kayaku Co., Ltd.), 4-ethylaminobenzoic acid 2-ethylhexyl ester (1 solol manufactured by Van Dyk Co., Ltd.) 5 0 7), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like. These well-known conventional tertiary amine compounds may be used alone or in combination of two or more. A preferred tertiary amine compound is 4,4'-diethylaminobenzophenone; and is not limited thereto, and is a dehydrogenation type photopolymerization initiator which absorbs light at a wavelength of 300 to 420 nm. When the sensitizing effect can be exerted, it is not limited to a photopolymerization initiator or a photoinitiator, and may be used singly or in plural. The photocurable and thermosetting resin composition of the present invention contains the thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups in one molecule in order to improve the heat resistance of the cured product. (D) [hereinafter referred to as a cyclic (thio)ether compound]. The thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in one molecule has a ring shape of two or more three, four or five member rings in one molecule. Any of an ether group, or a cyclic thioether group or a compound of the group 2-29-200827402. For example, a compound having at least two or more epoxy groups in one molecule, that is, a polyfunctional epoxy compound (D-1); a compound having at least two or more oxetanyl groups in one molecule, that is, a polyfunctional oxygen Heterocyclic butane compound (D-2) A compound having two or more thioether groups in a molecule; that is, an epitope sulfide resin or the like.

該多官能環氧化合物（D-1)有，例如日本環氧樹脂公 司製之耶皮口得828、耶皮口得834、耶皮口得1001、耶 皮口得1 004 ;大日本油墨化學工業公司製之耶皮庫龍840 、耶皮庫龍850、耶皮庫龍1050、耶皮庫龍2055;東都 化成公司製之耶波多多 YD-Oll'YD-OU'YD-UT'YD-US; 陶 化學公 司製之 D.E.R.317、 D.E.R.331、 D.E.R.661 'D.E.R.664;吉巴特殊化學品公司之阿拉魯萊多6071、 阿拉魯萊多 6084、阿拉魯萊多 GY250、阿拉魯萊多 GY260;住友化學工業公司製之斯密環氧£8八-11、£8入-014、ELA-115、ELA-128 ;旭化成工業公司製之 A.E.R.3 30、A.E.R.331、A.E.R.661、A.E.R.664 等（均爲商 品名）之雙酚A型環氧樹脂。日本環氧樹脂公司製之耶皮 口得YL-903 ;大日本油墨化學工業公司製之耶皮庫龍152 、耶皮庫龍165 ;東都化成公司製之耶波多 YDB-400、 YDB-5 00 ;陶氏化學公司製之D.E.R.542、汽巴特用化學 品公司製之阿拉魯萊多8 0 1 1、住友化學工業公司製之斯 密環氧 ESB-400、ESB-700、旭化成工業公司製之 A.E.R.711、A.E.R.714等（皆爲商品名）之溴化環氧樹脂； 日本環氧樹脂公司製之耶皮口得152、耶皮口得154、陶 * 30 - 200827402 氏化學公司製之D.E.N.431、D.E.N.438、大日本油墨化學 工業公司製之耶皮庫龍N-730、耶皮庫龍N-770、耶皮庫 龍 N_8 65、東都化成公司製之耶波多多 YDCN-701、 YDCN-704、汽巴特用化學品公司製之阿拉魯萊多 ECN1 23 5、阿拉魯萊多ECN 1 273、阿拉魯萊多ECN1 299、 阿拉魯萊多X PY3 07、日本化藥公司製之 EPPN-201、 EOCN-1025、EOCN-1020、EOCN-104S、RE-306、住友化The polyfunctional epoxy compound (D-1) is, for example, Yappoukou 828 manufactured by Japan Epoxy Resin Co., Ltd., 834, Yappoukou 834, Yappoukou 1001, and Yapikou 1 004; Yeppokulong 840, Yeppikuron 850, Yeppikuron 1050, Yeppikuron 2055 made by the industrial company; Yeboduo YD-Oll'YD-OU'YD-UT'YD- made by Dongdu Chemical Co., Ltd. US; DER317, DER331, DER661 'DER664 manufactured by Tao Chemical Co., Ltd.; Albaredo 6071 of Giba Specialty Chemicals Co., Araluledo 6084, Ala Luledo GY250, Ala Luledo GY260; Sumitomo Chemical Industries Co., Ltd. made Smith Epoxy 8 8 -11, £8 into -014, ELA-115, ELA-128; AER3 30, AER331, AER661, AER664, etc. by Asahi Kasei Industrial Co., Ltd. It is a bisphenol A type epoxy resin of the trade name). YE-903, Yeppei, made by Japan Epoxy Resin Co., Ltd.; Yapikulong 152, Yippikon 165, manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Yebodo YDB-400, YDB-5 00, manufactured by Dongdu Chemical Co., Ltd. DER542 manufactured by Dow Chemical Co., Ltd., Ala Luledo 801, manufactured by Suobat Chemical Co., Ltd., SEG ESP-400, ESB-700, manufactured by Sumitomo Chemical Industries Co., Ltd., manufactured by Asahi Kasei Industrial Co., Ltd. AER711, AER714, etc. (both trade names) of brominated epoxy resin; Japan Epoxy Resin Co., Ltd., Yepikoude 152, Yepikoude 154, Tao* 30 - 200827402 Chemical Company DEN431 , DEN438, Yapikulong N-730, Yapikulong N-770, Yippikron N_8 65, Yee Duoduo YDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd. , Albaredo ECN1 23 5, Albaredo ECN 1 273, Alaru Lado ECN1 299, Ala Luledo X PY3 07, EPPN-201, manufactured by Nippon Kayaku Co., Ltd. EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo

學工業公司製之斯密環氧ESCN-195X、ESCN-220、旭化 成工業公司製之 A.E.R.ECN-23 5、ECN-299等（皆爲商品 名）之酚醛氫漆型環氧樹脂；大日本油墨化學工業公司製 之耶皮庫龍83 0、日本環氧樹脂公司製耶皮口得807、東 都化成公司製之耶波多多YDF-170、YDF-175、YDF-2004 、汽巴特用化學品公司製之阿拉魯萊多XPY3 0 6等（皆爲 商品名）之雙酚F型環氧樹脂；東都化成公司製之耶波多 多ST-2004、ST-2007、ST-3 000(商品名）等之氫化雙酚A 型環氧樹脂；日本環氧樹脂公司製之耶皮口得604、東都 化成公司製之耶波多多YH-434、汽巴特用化學品公司製 之阿拉魯萊多MY720、住友化學工業公司製之斯密環氧 ELM-120等（皆爲商品名）之縮水甘油胺型環氧樹脂；汽巴 特用化學品公司製之阿拉魯萊多CY-3 50(商品名）等之乙 內醯（Hydantoin)型環氧樹脂；DA1CEL化學工業公司製之 仙羅賽2021、汽巴特用化學品公司製之阿拉魯萊多 CY175、CY179等（皆爲商品名）之脂環式環氧樹脂；日本 環氧樹脂公司製之YL-93 3、陶氏化學公司製之T.E.N.、 -31 · 200827402Benzene Epoxy ESCN-195X, ESCN-220, AERECN-23 5 from Asahi Kasei Industrial Co., Ltd., ECN-299, etc. (all are trade names), phenolic hydrogen lacquer type epoxy resin; Yeppikuron 83, manufactured by Chemical Industry Co., Ltd., 807, Yeppikou, made by Japan Epoxy Co., Ltd., Ypreto YDF-170, YDF-175, YDF-2004, manufactured by Dongdu Chemical Co., Ltd. Aleluledo XPY3 0 6 (all are trade names) of bisphenol F-type epoxy resin; Dongdu Chemical Co., Ltd. Yerbodot ST-2004, ST-2007, ST-3 000 (trade name), etc. Hydrogenated bisphenol A type epoxy resin; Yapikou 604 made by Japan Epoxy Resin Co., Ltd., Yeptodo YH-434 made by Dongdu Chemical Co., Ltd., Ala Luledo MY720 made by Steam Batt Chemical Company, Sumitomo Glycidylamine type epoxy resin of Smith's Epoxy ELM-120 (all trade name) manufactured by Chemical Industry Co., Ltd.; Alalu Lado CY-3 50 (trade name) manufactured by Kabat Chemical Co., Ltd. Hydantoin type epoxy resin; Xianluo 2021 manufactured by DA1CEL Chemical Industry Co., Ltd. Alicyclic CY175, CY179, etc. (all trade name) alicyclic epoxy resin manufactured by Chemicals Co., Ltd.; YL-93 manufactured by Japan Epoxy Resin Co., Ltd., TEN, -31 manufactured by Dow Chemical Co., Ltd. 200827402

EPPN-501、EPPN-502等（皆爲商品名）之三羥苯基甲烷型 環氧樹脂；日本環氧樹脂公司製之YL-6056、YX-4000、 YL-6121(皆爲商品名）等之雙二甲苯酚型型或雙酚型環氧 樹脂或其混合物·，日本化藥公司製EBP S-200、旭電化工 業公司製EPX-30、大日本油墨化學工業公司製之EXA-15 14(商品名）等之雙酚S型環氧樹脂；日本環氧樹脂公司 製之耶皮口得157S(商品名）等之雙酚A酚醛氫漆型環氧 樹脂；日本環氧樹脂公司製之耶皮口得YL-931、汽巴特 用化學品公司製之阿拉魯萊多163等（皆爲商品名）之四酚 乙烷型環氧樹脂；汽巴特用化學品公司製之阿拉魯萊多 PT810、日産化學工業公司製之TEPIC等（皆爲商品名）雜 環式環氧樹脂；日本油脂公司製之普萊瑪DGT等之二縮 水甘油苯甲酸酯樹脂；東都化成公司製ZX- 1063等之四縮 水甘油二甲苯乙烷樹脂；新日鐵化學公司製ESN-190、 ESN-3 60、大日本油墨化學工業公司製1^-4032、£又八-4750、EXA-4 700等之含萘基環氧樹脂；大日本油墨化學 工業公司製HP-7200、HP-7200H等之具有二環戊二烯骨 架之環氧樹脂；日本油脂公司製CP-5 0S、CP-5 0M等之縮 水甘油基甲基丙烯酸酯共聚系環氧樹脂；此外，例如環己 基馬來醯亞胺與縮水甘油基甲基丙烯酸酯之共聚環氧樹脂 :環氧變性之聚丁二烯橡膠衍生物（例如DAICEL化學工 業製PB-3600等）、CTBN改質環氧樹脂（例如東都化成公 司製之 YR-102 ' YR-450等）等，但並不僅限定於此。前 述環氧樹脂可單獨或將2種以上組合使用。其中特別是以 -32- 200827402 酚醛氫漆型環氧樹脂、雜環式環氧樹脂、雙酚A型環氧 樹脂或其混合物爲佳。EPPN-501, EPPN-502, etc. (all are trade names) of trishydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 (all are trade names) manufactured by Nippon Epoxy Co., Ltd. Bis-dimethylphenol type or bisphenol type epoxy resin or a mixture thereof, EBP S-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-15 14 manufactured by Dainippon Ink Chemical Industry Co., Ltd. Bisphenol S type epoxy resin (product name); bisphenol A phenolic hydrogen lacquer type epoxy resin such as 157S (trade name) manufactured by Nippon Epoxy Co., Ltd.; Yelpus YL-931, Alatole 163, etc. (all trade names) made by the company of Chemical Industry Co., Ltd. (all are trade names), tetraphenol ethane type epoxy resin; Alabuldo, manufactured by Kabat Chemicals Co., Ltd. PT810, TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all are trade names), heterocyclic epoxy resin; diglycidyl benzoate resin such as Prima DGT manufactured by Nippon Oil & Fats Co., Ltd.; ZX-1063 manufactured by Dongdu Chemical Co., Ltd. Wait for the fourth glycidyl xylene ethane resin; Nippon Steel Chemical Co., Ltd. ESN-190, ESN-3 60, large Naphthalene-based epoxy resin manufactured by Nippon Ink Chemical Industry Co., Ltd., 1^-4032, £8-4750, EXA-4700, etc.; HP-7200, HP-7200H, etc. manufactured by Dainippon Ink Chemical Industry Co., Ltd. An epoxy resin of a diene skeleton; a glycidyl methacrylate copolymer epoxy resin of CP-5 0S, CP-5 0M, etc. manufactured by Nippon Oil & Fats Co., Ltd.; and, for example, a cyclohexylmaleimide and a glycidyl group Epoxy resin of methacrylate: epoxy-denatured polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, YR-102 manufactured by Dongdu Chemical Co., Ltd.) YR-450, etc.), etc., but are not limited thereto. The above epoxy resins may be used singly or in combination of two or more kinds. Among them, a -32-200827402 phenolic hydrogen lacquer type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

前述多官能氧環丁烷（oxetane)化合物（D-2)例如雙[(3-甲基-3-氧環丁烷基甲氧基）甲基]醚、雙[(3-乙基-3-氧環丁 烷基甲氧基）甲基]醚、1，4-雙[(3-甲基-3-氧環丁烷基甲氧 基）甲基]苯、1，4-雙[(3-乙基-3-氧環丁烷基甲氧基）甲基] 苯、（3-甲基-3-氧環丁烷基）甲基丙烯酸酯、（3-乙基-3-氧 環丁烷基）甲基丙烯酸酯、（3-甲基-3-氧環丁烷基）甲基丙 烯酸甲酯、(3_乙基-3-氧環丁烷基）甲基丙烯酸甲酯或其低 聚物或共聚物等多官能氧環丁烷類以外，例如氧環丁烷與 酚醛氫漆樹脂、聚（P-羥基苯乙烯）、Cardo型雙酚類、 calixarene類、calixresorcinarene類、或倍半砂氧院等具 有羥基之樹脂所得之醚化物等。其他，例如具有氧環丁烷 環與不飽和單體與（甲基）丙烯酸烷酯之共聚物等。 一分子中具有2個以上環狀硫代醚基之化合物，例如 ，日本環氧樹脂公司製之雙酚A型環硫（Episulfide)樹脂 YL7 000等。又，亦可使用以相同之合成方法，將酚醛氫 漆型環氧樹脂之環氧基的氧原子以硫原子取代所得之環硫 (Episulfide)樹脂。 該些環狀（硫）醚化合物（D)之添加量，相對於前述含 羧基的感光性樹脂（A)，及前述含羧基的（甲基）丙烯酸胺 基甲酸酯化合物（B)之羧基的合計量1當量，以使用0.5〜 2·〇當量，較佳爲〇·8〜1.5當量之範圍。前述環狀（硫）醚 化合物（D)之添加量，較上述範圍爲少時，會殘留羧基， -33- 200827402 且會降低耐熱性、耐鹼性、電絶緣性等，而爲不佳。又， 超過上述範圍時，將會殘留低分子量之環狀（硫）醚化合物 (〇)’而會降低塗膜之強度等，亦爲不佳。The aforementioned polyfunctional oxetane compound (D-2) such as bis[(3-methyl-3-oxocyclobutanemethoxy)methyl]ether, bis[(3-ethyl-3) -oxycyclobutane methoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxocyclobutanemethoxy)methyl]benzene, 1,4-bis[( 3-ethyl-3-oxocyclobutanylmethoxy)methyl]benzene, (3-methyl-3-oxocyclobutane)methacrylate, (3-ethyl-3-oxo ring) Butyryl)methacrylate, (3-methyl-3-oxocyclobutane)methyl methacrylate, (3-ethyl-3-oxocyclobutane)methyl methacrylate or Other than polyfunctional oxycyclobutanes such as oligomers or copolymers, such as oxycyclobutane and novolac hydrogen lacquer resins, poly(P-hydroxystyrene), Cardo bisphenols, calixarenes, calixresorcinarenes, or An etherified product obtained from a resin having a hydroxyl group such as a semi-aerobic chamber. Other examples include a copolymer of an oxycyclobutane ring and an unsaturated monomer with an alkyl (meth)acrylate. A compound having two or more cyclic thioether groups in one molecule, for example, bisphenol A-type episulfide resin YL7 000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, an episulfide 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 cyclic (thio)ether compound (D) to be added to the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing (meth)acrylic acid urethane compound (B) The total amount is 1 equivalent, and is used in the range of 0.5 to 2 〇 equivalent, preferably 〇 8 to 1.5 equivalent. When the amount of the cyclic (thio)ether compound (D) added is less than the above range, the carboxyl group remains, -33-200827402, and heat resistance, alkali resistance, electrical insulation, and the like are lowered, which is not preferable. When the amount is more than the above range, a low molecular weight cyclic (thio)ether compound (〇) will remain, which will lower the strength of the coating film and the like, which is also undesirable.

此外’本發明之光硬化性·熱硬化性樹脂組成物，爲 合成前述含羧基的感光性樹脂（A)，及前述含羧基的（甲基 )丙烯酸胺基甲酸酯化合物（B)，或製作組成物等目的上， 或提高光硬化性等之際，可使用（E)稀釋劑。前述稀釋劑 (E)中，可使用非反應性之稀釋劑例如有機溶劑（E_ 1}，或 反應性之稀釋劑例如聚合性單體（E-2)。 前述有機溶劑（E-1 )，例如酮類、芳香族烴類、二醇 醚類、二醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系 溶劑等。更具體而言，例如甲基乙基酮、環己酮等之酮類 ;甲苯、二甲苯、四甲基苯等芳香族烴類；溶纖素、甲基 溶纖素、丁基溶纖素、卡必醇、甲基卡必醇、丁基卡必醇 、丙二醇單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基 醚、三乙二醇單乙基醚等二醇醚類；二丙二醇甲基醚乙酸 酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇 丁基醚乙酸酯等二醇醚乙酸酯類；乙酸乙酯、乙酸丁酯及 上述二醇醚類之乙酸酯化物等酯類；乙醇、丙醇、乙二醇 、丙二醇等醇類；辛烷、癸烷等之脂肪族烴；石油醚、石 油腦、氫化石油腦、溶劑石油腦等石油系溶劑等。前述有 機溶劑（E-1 )，可單獨或以2種以上之混合物形式使用。 前述有機溶劑（E-1)之添加量，並未有特別限定，其 可於考慮塗覆性或確保乾燥塗膜之膜厚度等觀點進行決定 -34- 200827402 ，一般以相對於於前述含羧基的感光性樹脂（A)，及前述 含羧基的（甲基）丙烯酸胺基甲酸酯化合物（B)之合計量100 . 質量份爲300質量份以下爲佳。Further, the photocurable thermosetting resin composition of the present invention is a synthetic carboxyl group-containing photosensitive resin (A) and a carboxyl group-containing (meth)acrylic acid urethane compound (B), or (E) A diluent can be used for the purpose of producing a composition or the like, or to improve photocurability and the like. In the above diluent (E), a non-reactive diluent such as an organic solvent (E_1), or a reactive diluent such as a polymerizable monomer (E-2) may be used. The aforementioned organic solvent (E-1), For example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, etc. More specifically, for example, methyl ethyl ketone, cyclohexyl Ketones such as ketones; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol , glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetic acid Glycol ether acetates such as ester, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; esters such as ethyl acetate, butyl acetate and acetate esters of the above glycol ethers; ethanol, C Alcohols such as alcohol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum brain, hydrogenated petroleum brain, A petroleum solvent such as a petroleum brain, etc. The organic solvent (E-1) may be used singly or in the form of a mixture of two or more kinds thereof. The amount of the organic solvent (E-1) to be added is not particularly limited, and The viewpoint of the coating property or the film thickness of the dried coating film is considered to be -34-200827402, generally based on the above-mentioned carboxyl group-containing photosensitive resin (A), and the above-mentioned carboxyl group-containing (meth)acrylic acid amine group. The total amount of the formic acid ester compound (B) is 100. The mass part is preferably 300 parts by mass or less.

又，作爲反應性之稀釋劑的前述聚合性單體（E-2)， 例如2-羥乙基丙烯酸酯、2-羥丙基丙烯酸酯等之羥烷基丙 烯酸酯類；乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇 等之二醇的單或二丙烯酸酯類；N，N-二甲基丙烯酸醯胺、 N-羥甲基丙烯酸醯胺、N，N-二甲基胺基丙基丙烯酸醯胺等 之丙烯酸醯胺類；N，N-二甲基胺基乙基丙烯酸酯、N，N-二 甲基胺基丙基丙烯酸酯等胺基烷基丙烯酸酯類：己烷二醇 、三羥甲基丙烷、季戊四醇、二季戊四醇、三-羥乙基三 聚異氰酸酯等多價醇或其環氧乙烷加成物或環氧丙烷加成 物等多價丙烯酸酯類；苯氧基丙烯酸酯、雙酚A二丙烯 酸酯，及其酚類之環氧乙烷加成物或環氧丙烷加成物等之 丙烯酸酯類；丙三醇二縮水甘油醚、丙三醇三縮水甘油醚 、三羥甲基丙烷三縮水甘油醚、三縮水甘油三聚異氰酸酯 等縮水甘油醚之丙烯酸酯類；及三聚氰胺丙烯酸酯、及/ 或對應上述丙烯酸酯之各甲基丙烯酸酯類等。其中，特別 是分子中具有2個以上之乙烯性不飽和基之化合物的多官 能（甲基）丙烯酸酯化合物，以其具有優良光硬化性而爲較 佳0 又，例如雙酚A、雙酚F型環氧樹脂、酚與甲酚酚醛 氫漆型環氧樹脂等多官能環氧樹脂與丙烯酸反應所得之環 氧丙烯酸酯樹脂，或該環氧丙烯酸酯樹脂之羥基與，季戊 -35- 200827402 四醇三丙烯酸酯等羥丙烯酸酯與異佛爾酮二異氰酸酯等二 異氰酸酯之半胺基甲酸酯化合物反應所得之丙烯酸環氧胺 基甲酸酯化合物等。前述環氧丙烯酸酯系樹脂，除不會降 低手指接觸乾燥性以外，亦可提高光硬化性。 前述聚合性單體（E-2)之添加量，相對於前述含羧基 的感光性樹脂（A)，及前述含羧基的（甲基）丙烯酸胺基甲 酸酯化合物（B)之合計量100質量份而言，爲5〜120質量 份，更佳爲10〜70質量份之比例。前述添加量超過120 質量份時，以其會降低電絕緣性等，而使塗膜脆化等而爲 不佳。 因此，全稀釋劑（E)之添加量，相對於前述含羧基的 感光性樹脂（A)及前述含羧基的（甲基）丙烯酸胺基甲酸酯 化合物（B)之合計量100質量份而言爲，前述有機溶劑（E-1)爲300質量份以下，與上述聚合性單體（E-2)5〜120質 量份之合計爲5〜420質量份。 本發明之光硬化性·熱硬化性樹脂組成物爲促進前述 含羧基的感光性樹脂（A-l，A-2，A-3)及前述含羧基的（甲 基）丙烯酸胺基甲酸酯化合物（B)之羧基，與分子中具有2 個以上之環狀醚基及/或環狀硫醚基之前述熱硬化性成分 (D)之硬化反應時，以添加（F)硬化觸媒爲佳。 前述硬化觸媒（F)，例如，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-氰基乙基-2-苯基咪唑、1-(2-氰基乙基乙基-4-甲基咪 唑等咪唑衍生物；二氰二醯胺、苄基二甲基胺、4-(二甲 -36- 200827402Further, the polymerizable monomer (E-2) which is a reactive diluent, for example, a hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate; ethylene glycol; Mono or diacrylates of diols such as oxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; N,N-dimethyl methacrylate, N-hydroxymethyl decylamine, N, N-di Ammonium acrylate such as methylaminopropyl decyl acrylate; aminoalkyl acrylate such as N,N-dimethylaminoethyl acrylate or N,N-dimethylaminopropyl acrylate Classes: polyvalent acrylics such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyltrimeric isocyanate, or the like thereof, or an ethylene oxide adduct or a propylene oxide adduct Esters; phenoxy acrylates, bisphenol A diacrylates, phenolic ethylene oxide adducts or propylene oxide adducts; glycerol diglycidyl ether, C Acrylic acid of glycidyl ether such as triol triglycidyl ether, trimethylolpropane triglycidyl ether or triglycidyl trimer isocyanate An ester; and a melamine acrylate, and/or a methacrylate corresponding to the above acrylate. Among them, a polyfunctional (meth) acrylate compound having a compound having two or more ethylenically unsaturated groups in a molecule is preferably one having excellent photocurability, for example, bisphenol A or bisphenol. Epoxy acrylate resin obtained by reacting polyfunctional epoxy resin such as F-type epoxy resin, phenol and cresol novolac hydrogenated epoxy resin with acrylic acid, or hydroxyl group of the epoxy acrylate resin, penta-35- 200827402 Acrylic epoxy urethane compound obtained by reacting a hydroxy acrylate such as a tetraol triacrylate with a semicarbamate compound of a diisocyanate such as isophorone diisocyanate. The epoxy acrylate-based resin can also improve photocurability in addition to not lowering finger contact drying property. The total amount of the polymerizable monomer (E-2) added to the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing (meth)acrylic acid urethane compound (B) is 100. The mass fraction is from 5 to 120 parts by mass, more preferably from 10 to 70 parts by mass. When the amount of the coating is more than 120 parts by mass, the coating film is embrittled or the like because of the decrease in electrical insulating properties and the like. Therefore, the amount of the total diluent (E) is 100 parts by mass based on the total amount of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing (meth)acrylic acid urethane compound (B). In the meantime, the organic solvent (E-1) is 300 parts by mass or less, and the total amount of the polymerizable monomer (E-2) is from 5 to 420 parts by mass in terms of 5 to 420 parts by mass. The photocurable thermosetting resin composition of the present invention is a carboxyl group-containing photosensitive resin (Al, A-2, A-3) and a carboxyl group-containing (meth)acrylic acid urethane compound ( When the carboxyl group of B) is hardened by the thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in the molecule, it is preferred to add (F) a curing catalyst. The aforementioned hardening catalyst (F), for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Imidazole derivatives such as 1-ethyl 2-phenylimidazole and 1-(2-cyanoethylethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4-(dimethyl -36- 200827402

基胺基）-N，N-二甲基苄基胺、4-甲氧基-N，N-二甲基苄基胺 、4-甲基-N，N-二甲基苄基胺等之胺化合物、己二酸醯肼 、癸二酸醯肼等醯肼化合物；三苯基膦等磷化合物等，或 市售之產品，例如四國化成工業公司製之2]^2-八、2^42-OK、2PHZ、2P4BHZ、2P4MHZ(皆爲咪唑系化合物之商品 名），聖保羅公司製之U-CAT350 3N、U-CAT35 0 2T(皆爲二 甲基胺之嵌段異氰酸酯化合物之商品名）、DBU、DBN、 U-CATSA102、U-CAT5 002(皆爲二環式脒化合物及其鹽） 等。但並不僅限定於此，只要爲環氧樹脂或氧環丁烷化合 物之熱硬化觸媒，或可促進環氧基及/或氧環丁烷基與羧 基之反應之物質皆可使用，其可單獨或將2種以上混合使 用。又，亦可使用具有密著性賦予劑之機能的胍胺、乙醯 胍胺、苯倂胍胺、三聚氰胺、2,4·二胺基-6-甲基丙烯醯氧 乙基-S-三嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪·三聚異氰酸加成物、2,4-二胺基-6·甲 基丙烯醯氧乙基-S-三嗪•三聚異氰酸酸加成物等之S-三 嗪衍生物，較佳爲將前述具有密著性賦予劑機能之化合物 與上述熱硬化觸媒合倂使用。 前述硬化觸媒（F)之添加量只要通常之量的比例即爲 充分，例如相對於全樹脂組成物100質量份，爲0.1〜20 質量份，較佳爲0.5〜15.0質量份之比例。前述硬化觸媒 (F)之添加量，低於上述範圍時，因硬化時間增長，作業 性降低以外，亦會造成銅箔等之劇烈氧化而爲不佳。又， 前述硬化觸媒（F)之添加量，超過上述範圍時，因電氣特 -37- 200827402 性降低，或預乾燥後之放置壽命減短等而爲不佳。 又’本發明之光硬化性·熱硬化性樹脂組成物，就提 高硬化物之密著性、機械性強度、線膨脹係數等特性之目 的上，可添加無機充塡材料。例如，硫酸鋇、鈦酸鋇、氧 化矽粉、微粉狀氧化矽、無定形二氧化矽、滑石、黏土、 碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母粉等公知慣用 之無機充塡劑等。其添加比率爲樹脂組成物之〇〜80質量 % 〇 本發明之光硬化性·熱硬化性樹脂組成物，更必要時 可再添加酞菁•藍、酞菁·綠、碘·綠、二重氮黃、結晶 紫、氧化鈦、碳黑、萘黑等公知慣用之著色劑，氫醌、氫 醌單甲基醚' t- 丁機兒茶酚、焦培酚、吩噻嗪等公知慣用 之熱聚合阻礙劑、微粉二氧化矽、有機鎳黃鐵、蒙脫石等 公知慣用之增黏劑，聚矽氧系、氟系、高分子系等消泡劑 及/或塗平劑，咪唑系、噻唑系、三唑系等矽烷偶合劑等 公知慣用之添加劑類等。 本發明之光硬化性·熱硬化性樹脂組成物，例如可將 前述稀釋劑（E)配合塗佈方法調整其黏度，於形成電路之 基板上，使用浸漬塗佈法、流動塗佈法、滾筒塗佈法、條 狀塗佈法、網板印刷法、簾狀塗佈法等方法全面塗布於其 上，再於6 0〜100 °C之溫度下，將組成物中所含之有機溶 劑揮發乾燥（預乾燥）後，形成不含溶劑之塗膜。其後，經 由接觸式（或非接觸方式），通過形成有圖案之光罩以活性 能量線進行選擇性曝光，未曝光部經由稀鹼水溶液（例如 -38- 200827402 0.3〜3%碳酸鈉水溶液）顯影而形成光阻圖案。 被利用作爲上述形成電路之基板所使用之基材，例如 使用紙酚樹脂、紙環氧樹脂、玻璃布環氧樹脂、玻璃聚醯 亞胺樹脂、玻璃布/不織布環氧樹脂、玻璃布/紙環氧樹脂 " 、合成纖維環氧樹脂、氟·聚乙烯· ΡΡΌ ·氰酸酯樹脂等 - 等之高周波電路用鋪銅層合板等之材質所得之全部等級 (FR-4等）的鋪銅層合板，其他聚醯亞胺薄膜、PET薄膜、 # 玻璃基板、陶瓷基板、晶圓板等。 鹼水溶液，例如可使用氫氧化鉀、氫氧化鈉、碳酸鈉 、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等鹼水溶液。 又，照射活性能量線所使用之照射光源，例如低壓水 銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈 或金屬鹵化物燈等。其他，亦可利用雷射光線等活性能量 線。 前述顯影方法例如可使用浸漬法、淋灑法、噴霧法、 # 刷塗法等方式進行，顯影液例如可使用氫氧化鉀、氫氧化 鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等鹼水 溶液。 此外，例如加熱至140〜180 °C之溫度使其熱硬化結 果，可使前述含羧基的感光性樹脂（A)，及前述含羧基的（ 甲基）丙烯酸胺基甲酸酯化合物（B)之羧基，與一分子中具 有2個以上之環狀醚基及/或環狀硫代醚基之前述熱硬化 性成分（D)反應，而形成具有優良之耐熱性、耐藥品性、 耐吸濕性、密著性、電氣特性等各種特性之硬化塗膜。 -39- 200827402 本發明之光硬化性•熱硬化性組成物作爲乾薄膜使用 之情形，例如以下所示者。 光硬化性·熱硬化性乾薄膜爲具有載體薄膜與將前述 光硬化性•熱硬化性樹脂組成物塗佈•乾燥於於載體薄膜 β 或包覆薄膜所得之光硬化性•熱硬化性樹脂層，與樹脂層 - 上可剝離之包覆薄膜之物。 載體薄膜例如可使用10〜150μηι厚度之PET等聚酯 • 薄膜、聚醯亞胺薄膜等。 光硬化性·熱硬化性樹脂層，例如將光硬化性·熱硬 化性組成物平板塗佈、條狀塗佈、點狀塗佈、薄膜塗佈等 於載體薄膜或包覆薄膜上均勻塗佈 10〜150μιη厚度，並 經乾燥而形成。 包覆薄膜例如可使用聚乙烯薄膜、聚丙烯薄膜等，其 與光硬化性·熱硬化性樹脂層之黏著力而言，以較支持薄 ^ 膜更小者爲佳。 ® 將包覆薄膜剝離，使光硬化性·熱硬化性樹脂層與形 成電路之基材重疊，使用貼合器等使其層合，而於形成電 路之基材上形成光硬化性·熱硬化性樹脂層。所形成之光 硬化性•熱硬化性樹脂層，與前述方法相同般經曝光、顯 影、加熱硬化後，即可形成硬化塗膜。載體薄膜，可於曝 光前或曝光後中任一時點予以剝離即可。 【實施方式】 實施例 -40- 200827402 以下將以實施例與比較例對本發明作具體之説明，但 本發明並不受下述實施例所限定。 合成例1 :含羧基的感光性樹脂（A-1)之合成1 將甲酚酚醛氫漆型環氧樹脂（日本化藥（股）製，EOCN-104S，軟化點92°C，環氧當量220)22 0 0g、二羥甲基丙酸 13 4g、丙烯酸 648.5g、甲基氫醌4.6g、卡必醇乙酸酯 113 1g及溶劑石油腦484.9g混合，於90°C下加熱、攪拌 ，使反應混合物溶解。其次，將反應液冷卻至60 °C，加 入三苯基膦13.8g，加熱至100 °C，再反應約32小時，得 酸價爲〇.5mgKOH/g之反應物。其次，於其中加入四氫苯 甲酸酐364.7g、卡必醇乙酸酯137.5g及溶劑石油腦58.8g ，加熱至95 °C，使其反應約6小時後，冷卻，得固體成 份之酸價40mgKOH/g、不揮發成份65%之含羧基的感光 性樹脂。以下，將此反應溶液稱爲清漆（varnish)(A-卜1)。Amino group)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. An anthracene compound, an antimony compound such as bismuth adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine, or a commercially available product, for example, manufactured by Shikoku Chemical Industry Co., Ltd. 2]^2-eight, 2 ^42-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are the trade names of imidazole compounds), U-CAT350 3N, U-CAT35 0 2T (all are the trade names of the blocked isocyanate compounds of dimethylamine) ), DBU, DBN, U-CATSA102, U-CAT5 002 (all are bicyclic guanidine compounds and their salts). However, it is not limited thereto, and any material which is an epoxy resin or an oxycyclobutane compound, or a substance which can promote the reaction of an epoxy group and/or an oxocyclobutane group with a carboxyl group can be used. These may be used alone or in combination of two or more. Further, it is also possible to use a guanamine, acetamide, benzoguanamine, melamine, 2,4. diamino-6-methylpropenyloxyethyl-S-three having the function of an adhesion imparting agent. Pyrazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·trimeric isocyanate adduct, 2,4 An S-triazine derivative such as a diamino-6-methacryloyloxyethyl-S-triazine/trimeric isocyanate addition product, preferably having the above-mentioned adhesion imparting agent function The compound is used in combination with the above-mentioned thermosetting catalyst. The amount of the hardening catalyst (F) to be added is sufficient as long as it is a normal amount, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass, based on 100 parts by mass of the total resin composition. When the amount of the hardening catalyst (F) added is less than the above range, the hardening time is increased, and the workability is lowered, which also causes severe oxidation of the copper foil or the like, which is not preferable. In addition, when the amount of the hardening catalyst (F) added exceeds the above range, the electrical properties are lowered, or the shelf life after pre-drying is shortened, which is not preferable. Further, the photocurable thermosetting resin composition of the present invention can be added with an inorganic filling material for the purpose of improving properties such as adhesion of the cured product, mechanical strength, and coefficient of linear expansion. For example, barium sulfate, barium titanate, cerium oxide powder, finely powdered cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc. Tincture, etc. The addition ratio is 〇 to 80% by mass of the resin composition. The photocurable and thermosetting resin composition of the present invention may be further added with phthalocyanine blue, phthalocyanine, green, iodine, green, and double Known conventional coloring agents such as nitrogen yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc., hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrophenol, phenothiazine, etc. Known conventional tackifiers such as thermal polymerization inhibitors, fine powder of cerium oxide, organic nickel yellow iron, montmorillonite, antifoaming agents such as polyfluorene, fluorine, and polymer, and/or coating agents, imidazole A well-known conventional additive such as a thiazole coupling agent such as a thiazole system or a triazole system. In the photocurable thermosetting resin composition of the present invention, for example, the diluent (E) can be adjusted to have a viscosity by a coating method, and a dip coating method, a flow coating method, and a roller can be used on a substrate on which a circuit is formed. A coating method, a strip coating method, a screen printing method, a curtain coating method, and the like are uniformly applied thereto, and the organic solvent contained in the composition is volatilized at a temperature of 60 to 100 ° C. After drying (pre-drying), a coating film containing no solvent is formed. Thereafter, the contact lens (or non-contact method) is selectively exposed by the active energy ray through the patterned photomask, and the unexposed portion is passed through a dilute aqueous alkali solution (for example, -38-200827402 0.3 to 3% sodium carbonate aqueous solution). Developed to form a photoresist pattern. It is used as a substrate used for the substrate for forming the above-mentioned circuit, for example, paper phenol resin, paper epoxy resin, glass cloth epoxy resin, glass polyimide resin, glass cloth/non-woven epoxy resin, glass cloth/paper Bronze of all grades (FR-4, etc.) obtained from materials such as epoxy resin, synthetic fiber epoxy resin, fluorine/polyethylene, bismuth, cyanate resin, etc. for high-frequency circuits such as copper-clad laminates Laminates, other polyimide films, PET films, #玻璃 substrates, ceramic substrates, wafer boards, etc. As the aqueous alkali solution, for example, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine can be used. Further, an irradiation light source used for irradiating the active energy ray is, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp. Others can also use active energy lines such as laser light. The developing method can be carried out, for example, by a dipping method, a shower method, a spray method, a #brush coating method, or the like. For the developer, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, or the like can be used. An aqueous alkali solution such as ammonia or an amine. Further, for example, by heating to a temperature of 140 to 180 ° C to thermally harden, the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing (meth)acrylic acid urethane compound (B) may be used. The carboxyl group is reacted with the thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in one molecule to form excellent heat resistance, chemical resistance, and moisture absorption resistance. A hardened coating film of various properties such as properties, adhesion, and electrical properties. -39- 200827402 In the case where the photocurable/thermosetting composition of the present invention is used as a dry film, for example, it is as follows. The photocurable/thermosetting dry film is a photocurable/thermosetting resin layer obtained by coating and drying the photocurable thermosetting resin composition on a carrier film β or a film. And the resin layer - the peelable coated film. As the carrier film, for example, a polyester such as PET having a thickness of 10 to 150 μm, a film, a polyimide film, or the like can be used. For the photocurable and thermosetting resin layer, for example, a photocurable/thermosetting composition is plate-coated, strip-coated, dot-coated, and film-coated is uniformly coated on a carrier film or a coated film. ~150μιη thickness and formed by drying. For the coating film, for example, a polyethylene film, a polypropylene film or the like can be used, and the adhesion to the photocurable thermosetting resin layer is preferably smaller than that of the supporting film. ® The film is peeled off, and the photocurable/thermosetting resin layer is superposed on the substrate on which the circuit is formed, and laminated by a bonding machine or the like to form photocuring and thermosetting on the substrate on which the circuit is formed. Resin layer. The formed photohardenable/thermosetting resin layer is formed into a cured coating film by exposure, development, and heat curing as in the above-described method. The carrier film can be peeled off before or at any time after exposure. [Embodiment] Embodiments - 40 - 200827402 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples. Synthesis Example 1 Synthesis of a carboxyl group-containing photosensitive resin (A-1) 1 A cresol novolac hydrogenated epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent) 220) 22 0 0g, 13 4g of dimethylolpropionic acid, 648.5g of acrylic acid, 4.6g of methylhydroquinone, 113g of carbitol acetate and 484.9g of solvent petroleum brain, heated and stirred at 90 °C The reaction mixture was dissolved. Next, the reaction liquid was cooled to 60 ° C, 13.8 g of triphenylphosphine was added, and the mixture was heated to 100 ° C for further about 32 hours to obtain a reactant having an acid value of 0.5 mg KOH / g. Next, 364.7 g of tetrahydrobenzoic anhydride, 137.5 g of carbitol acetate and 58.8 g of solvent petroleum brain were added thereto, and the mixture was heated to 95 ° C to be reacted for about 6 hours, and then cooled to obtain an acid value of a solid component. 40 mg KOH/g, a carboxyl group-containing photosensitive resin having 65% nonvolatile content. Hereinafter, this reaction solution is referred to as varnish (A-Bu 1).

合成例2 :含羧基的感光性樹脂（A-1)之合成2 將甲酚酚醛氫漆型環氧樹脂（日本化藥（股）製，EOCN-104S，軟化點92°C，、環氧當量220)2200g放入附有攪拌 機及冷卻器之四口燒瓶中，加入丙二醇單甲基醚乙酸酯 2072g，加熱溶解後，加入甲基氫醌4.6g與三甲基膦 13.8g。將此混合物加熱至95〜105°C，將丙烯酸504§、 p-羥基苯乙基醇4〗5 g徐徐滴下，進行約1 6小時之反應。 將該反應物冷卻至80〜90 °C，並於其中加入四氫苯甲酸 -41 - 200827402 酐73 0g，使其反應約8小時後，冷卻，得固體成份之酸 價70mgKOH/g、不揮發成份65%之含羧基的感光性樹脂 。以下，將該反應溶液稱爲清漆（A-1-2)。 * 合成例3 :含羧基的感光性樹脂（A-2)之合成 • 於具備有溫度計、兼具氮氣導入裝置與環氧烷烴導入 裝置及攪拌裝置之高壓釜中，加入酚醛氫漆型甲酚樹脂（ ©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1.19g及甲苯 119.4g，於攪拌 中，使反應系内替換爲氮氣，並加熱昇溫。其次，將環氧 丙烷63.8g徐徐滴下，於125〜132°C、〇〜4.8kg/cm2下反 應1 6小時。其後，冷卻至室溫，於該反應溶液中添加 89%磷酸1.56g後，混合，並以氫氧化鉀中和，得不揮發 成份62」％、羥基價爲182.2g/eq.之酚醛氫漆型甲酚樹脂 . 之環氧丙烷反應溶液。其爲相當1當量酚性羥基平均附加 ^ 環氧烷烴1.08莫耳所得者。 所得之酚醛氫漆型甲酚樹脂的環氧烷烴反應溶液 293.0g、丙嫌酸43.2g、甲烷磺酸1 1 .53g、甲基氫醌0.1 8g 及甲苯252.9g加入具備有攪拌機、溫度計及空氣吹入管 之反應器內，並使空氣以l〇ml/分鐘速度吹入，於攪拌中 ，於U 〇 °C下反應1 2小時。將反應所生成之水，使其與 甲苯之共沸混合物方式，餾出12.6g之水。其後，冷卻至 室溫，將所得反應溶液以15%氫氧化鈉水溶液3 5.3 5 g中 和’其次進行水洗。其後，於蒸發器中，將甲苯以乙二醇 -42- 200827402 單乙基醚乙酸酯η 8 · 1 g取代予以餾除，得酚醛氫漆型丙 烯酸酯樹脂溶液。其次，將所得之酚醛氫漆型丙烯酸酯樹 脂溶液3 32.5g及三苯基膦1.22g加入具備有攪拌器、溫 度計及空氣吹入管之反應器中，將空氣以10ml/分鐘速度 吹入，於攪拌中，將四氫苯甲酸酐60.8g徐徐加入，於9 5 ’ 〜l〇l°C下反應6小時。得固體成份之酸價88mgKOH/g、 不揮發成份71%之含羧基的感光性樹脂。以下，將此反應 φ 溶液稱爲清漆（Α·2)。 合成例4 :含羧基的感光性樹脂（Α· 3)之合成 於具備有氣體導入管、攪拌裝置、冷卻管、溫度計、 及鹼金屬氫氧化物水溶液之連續滴下用之滴下漏斗的反應 容器中，加入羥基當量80g/當量之1，5_二羥基萘224份與 雙酚A型環氧樹脂之耶皮口得828(日本環氧樹脂公司製 、環氧當量189g/當量）1 075份，於氮氣環境、攪拌下、 Φ 於1 10°c使其溶解。其後，加入三苯基膦0.65份，使反應 容器内之溫度昇溫至15(TC，於將溫度保持於150°C中， 進行約9〇分鐘之反應，得環氧當量452g/當量之環氧化合 物（h-Ο)。其次，將燒瓶内之溫度冷卻至40°C，再加入環 氧氯丙烷1920份、甲苯1 690份、四甲基銨溴化物70份 ，於攪拌下昇溫至45 °C後保持。其後，將48%氫氧化鈉 水溶液364份以60分鐘時間連續滴下，其後，再使其反 應6小時。反應結束後，將過剩之環氧氯丙烷及大部份甲 苯以減壓蒸餾回收，將副產鹽與含有二甲基亞碾之反應產 -43- 200827402 物溶解於甲基異丁基酮後’水洗。使有機溶劑層與水層分 離後’有機溶劑層中將甲基異丁基酮以減壓蒸餾餾除，得 環氧虽重2 7 7 g /當量之線狀多官能環氧化合物（h)。所得線 狀之多官能環氧化合物（h)，以環氧當量計算時，得知環 氧化合物（h - 0 )中，醇性羥基1 · 9 8個之中，約1 · 5 9個爲環 - 氧化。因此，醇性羥基之環氧化率爲約80%。其次，將線 狀之多官能環氧化合物（h)2 77份加入具備有攪拌裝置、冷 # 卻管及溫度計之燒瓶中，加入卡必醇乙酸酯290份，加熱 溶解後，加入甲基氫醌0.46份，與三苯基膦1.38份，加 熱至95〜105 °C後，將丙烯酸72份徐徐滴下，進行16小 時之反應。將該反應產物冷卻至80〜90 °C，加入四氫苯 甲酸酐1 29份，進行8小時之反應。反應使用電位差測定 反應液之酸價、全氧化測定，並追蹤所得之加成率，以反 應率95%以上爲終點。依此方式所得之含羧基的感光性性 樹脂，其固體成份爲62%、酸價爲100mgKOH/g。以下， w • 將該反應溶液稱爲清漆（A-3)。 % 合成例5:含羧基的（甲基）丙烯酸胺基甲酸酯化合物之合成 於具備有溫度計、攪拌機及迴流冷卻器之5L分隔式 燒瓶中，分別加入聚合物多價醇之聚己內醯胺二醇 (DAICEL化學工業公司製PLACCEL208、分子量83 0)1， 245g、含羧基的二羥基化合物之二羥甲基丙酸201g、聚 異氰酸酯之異佛爾酮二異氰酸酯777g及含有羥基之（甲基 )丙烯酸酯之2-羥乙基丙烯酸酯119g’與p-甲氧基酚及 -44 - 200827402 二-t-丁基-羥基甲苯各〇.5g。於攪拌中，加熱至60°C後， 停止加熱，加入二丁基錫二月桂酸酯0.8g。反應容器内之 溫度開始降低時再度進行加熱，於8 0 °C下持續攪拌，確 認紅外線吸收光譜中異氰酸酯基之吸收光譜（2280CITT1)消 ^ 失時點爲反應結束，得黏稠液體之丙烯酸胺基甲酸酯化合 ， 物。使用PMA調整至不揮發成份二50質量％。製得固體 成份之酸價爲47mg KOH/g、不揮發成份爲50%之含羧基 • 的（甲基）丙烯酸胺基甲酸酯化合物。以下，將該反應溶液 稱爲清漆B。 合成例6 :與本發明相異之常用含羧基的感光性樹脂之合成 將甲酚酚醛氫漆型環氧樹脂（耶皮庫龍N-695，大曰 本油墨化學工業公司製，環氧當量220)33 0g加入具備有 氣體導入管、攪拌裝置、冷卻管及溫度計之燒瓶中，加入 PMA340g，使其力口熱溶解，再力口入氫醌0.46g，與三苯基 # 膦1.38g。將該混合物加熱至95〜105°C，將丙烯酸l〇8g ' 徐徐滴下，進行16小時之反應。將該反應生成物冷卻至 80〜90 °C，加入四氫苯甲酸酐68g，使其反應8小時後， 冷卻。得固體成份之酸價爲50mg KOH/g、不揮發成份 6 0%之含羧基的感光性樹脂。以下，將該反應溶液稱爲清 漆R。 實施例1〜1 2及比較例1〜1 〇 使用前述合成例1〜6所得之清漆（A-1-1)、（A-卜2)、 -45- 200827402 (A-2)、(A-3)、清漆B、及清漆R依表1〜3所示添加成分 ，以3桿滾筒硏磨器混練。得光硬化性·熱硬化性樹脂組 成物。 [表1]Synthesis Example 2: Synthesis of carboxyl group-containing photosensitive resin (A-1) 2 Cresol phenolic hydrogen lacquer type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy Equivalent 220) 2200 g was placed in a four-necked flask equipped with a stirrer and a cooler, and 2072 g of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated and dissolved, and then 4.6 g of methylhydroquinone and 13.8 g of trimethylphosphine were added. The mixture was heated to 95 to 105 ° C, and 504 § p, p-hydroxyphenethyl alcohol 4 5 g was slowly dropped, and the reaction was carried out for about 16 hours. The reaction mixture was cooled to 80 to 90 ° C, and 73 0 g of tetrahydrobenzoic acid-41 - 200827402 anhydride was added thereto, and the mixture was allowed to react for about 8 hours, and then cooled to obtain an acid value of 70 mg KOH/g of a solid component, which was not volatile. 65% of a carboxyl group-containing photosensitive resin. Hereinafter, the reaction solution is referred to as varnish (A-1-2). * Synthesis Example 3: Synthesis of a carboxyl group-containing photosensitive resin (A-2) • A phenolic hydrogen cresol type cresol was added to an autoclave equipped with a thermometer, a nitrogen gas introduction device, an alkylene oxide introduction device, and a stirring device. Resin (manufactured 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 the reaction system was replaced with nitrogen gas under stirring. Heat up. Next, 63.8 g of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C for 1 4.8 kg/cm 2 for 16 hours. Thereafter, the mixture was cooled to room temperature, and after adding 1.56 g of 89% phosphoric acid to the reaction solution, the mixture was mixed and neutralized with potassium hydroxide to obtain a phenolic hydrogen having a nonvolatile content of 62% by weight and a hydroxyl group of 182.2 g/eq. Paint cresol resin. The propylene oxide reaction solution. It is equivalent to an equivalent of 1 equivalent of phenolic hydroxyl groups plus 1.0 alkylene oxide of 1.08 moles. 293.0 g of an alkylene oxide reaction solution of the obtained phenolic hydrogen varnish type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were added with a stirrer, a thermometer and air. The tube was blown into the tube, and air was blown at a rate of 10 μm/min, and reacted at U 〇 ° C for 12 hours while stirring. The water formed by the reaction was subjected to an azeotropic mixture with toluene to distill off 12.6 g of water. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with a 15% aqueous sodium hydroxide solution of 3 5.3 5 g, followed by washing with water. Thereafter, toluene was distilled off in an evaporator with ethylene glycol-42-200827402 monoethyl ether acetate η 8 · 1 g to obtain a phenolic hydrogen lacquer type acrylate resin solution. Next, 3 32.5 g of the obtained phenolic hydrogen lacquer type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min. While stirring, 60.8 g of tetrahydrobenzoic anhydride was slowly added, and the mixture was reacted at 95 ° to 1 ° 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. Hereinafter, this reaction φ solution is referred to as varnish (Α·2). Synthesis Example 4: Synthesis of a carboxyl group-containing photosensitive resin (Α·3) in a reaction vessel equipped with a dropping funnel for continuous dropping of a gas introduction pipe, a stirring device, a cooling pipe, a thermometer, and an alkali metal hydroxide aqueous solution 226 parts of 1,5-dihydroxynaphthalene having a hydroxyl equivalent weight of 80 g/eq., and 1,075 parts of a bisphenol A type epoxy resin, which is 828 (manufactured by Nippon Epoxy Co., Ltd., epoxy equivalent: 189 g/eq), Dissolve in a nitrogen atmosphere with stirring at Φ 10 °c. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the reaction vessel was raised to 15 (TC, and the temperature was maintained at 150 ° C, and the reaction was carried out for about 9 minutes to obtain an epoxy equivalent of 452 g/eq. Oxygen compound (h-Ο). Next, the temperature in the flask was cooled to 40 ° C, and then 1920 parts of epichlorohydrin, 1 690 parts of toluene, and 70 parts of tetramethylammonium bromide were added, and the temperature was raised to 45 with stirring. After the temperature was maintained at ° C. Thereafter, 364 parts of a 48% aqueous sodium hydroxide solution was continuously dropped over a period of 60 minutes, and thereafter, the reaction was further carried out for 6 hours. After the completion of the reaction, excess epichlorohydrin and most of toluene were left. It is recovered by distillation under reduced pressure, and the by-produced salt and the reaction product containing dimethyl argon are dissolved in methyl isobutyl ketone, and then washed with water. After separating the organic solvent layer from the aqueous layer, the organic solvent layer is removed. Methyl isobutyl ketone is distilled off under reduced pressure to obtain a linear polyfunctional epoxy compound (h) having an epoxy weight of 27 g/e. The linear polyfunctional epoxy compound (h) is obtained. When calculated in terms of epoxy equivalent, it is found that among the epoxy compounds (h - 0 ), among the alcoholic hydroxyl groups 1 · 9 8 1 · 5 9 are ring-oxidized. Therefore, the epoxidation ratio of the alcoholic hydroxyl group is about 80%. Secondly, the linear polyfunctional epoxy compound (h) 2 77 parts is added with a stirring device, cold # 290 parts of carbitol acetate was added to the flask of the tube and the thermometer, and after heating and dissolving, 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added, and after heating to 95-105 ° C, 72 parts of acrylic acid was added. The reaction was carried out for 16 hours, and the reaction product was cooled to 80 to 90 ° C, and 12 parts of tetrahydrobenzoic anhydride was added thereto for 8 hours. The reaction was determined by using the potential difference to determine the acid value and total oxidation of the reaction solution. And tracking the obtained addition rate, and the reaction rate is 95% or more as the end point. The carboxyl group-containing photosensitive resin obtained in this manner has a solid content of 62% and an acid value of 100 mgKOH/g. This reaction solution is called varnish (A-3). % Synthesis Example 5: Synthesis of a carboxyl group-containing (meth)acrylic acid urethane compound in a 5 L separator flask equipped with a thermometer, a stirrer, and a reflux condenser. Polycaprolactamdiol with polymer polyvalent alcohol added separately (PLACCEL208 manufactured by DAICEL Chemical Industry Co., Ltd., molecular weight 83 0) 1, 245 g, 201 g of hydroxylpropionic acid containing a carboxyl group-containing dihydroxy compound, 777 g of isophorone diisocyanate of polyisocyanate, and (meth)acrylic acid containing a hydroxyl group Ester 2-hydroxyethyl acrylate 119g' with p-methoxyphenol and -44 - 200827402 di-t-butyl-hydroxytoluene each. 5g. After heating, heating to 60 ° C, stop heating And adding 0.8 g of dibutyltin dilaurate. When the temperature in the reaction vessel began to decrease, the temperature was again heated, and stirring was continued at 80 ° C to confirm that the absorption spectrum of the isocyanate group (2280 CITT1) in the infrared absorption spectrum was eliminated. At the end of the reaction, a urethane amide compound of a viscous liquid is obtained. The PMA was adjusted to 50% by mass of the nonvolatile component. A (meth)acrylic acid urethane compound having a solid content of 47 mg KOH/g and a nonvolatile content of 50% carboxyl group was obtained. Hereinafter, the reaction solution is referred to as varnish B. Synthesis Example 6: Synthesis of a common carboxyl group-containing photosensitive resin different from the present invention A cresol novolac hydrogenated epoxy resin (Yepikul N-695, manufactured by Otsuka Ink Chemical Industry Co., Ltd., epoxy equivalent) 220) 33 0g was placed in a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, and 340 g of PMA was added thereto to dissolve the solution, and then 0.45 g of hydroquinone was added thereto, and 1.38 g of triphenyl #phosphine was added. The mixture was heated to 95 to 105 ° C, and 8 g of acrylic acid was gradually dropped to carry out a reaction for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 68 g of tetrahydrobenzoic anhydride was added thereto, and the mixture was reacted for 8 hours, followed by cooling. A carboxyl group-containing photosensitive resin having a solid content of 50 mg KOH/g and a nonvolatile content of 60% was obtained. Hereinafter, the reaction solution is referred to as varnish R. Examples 1 to 2 and Comparative Examples 1 to 1 清 The varnishes (A-1-1), (A-Bu 2), -45-200827402 (A-2), (A) obtained in the above Synthesis Examples 1 to 6 were used. -3), varnish B, and varnish R were added as shown in Tables 1 to 3, and mixed with a three-bar drum honing machine. A photocurable thermosetting resin composition is obtained. [Table 1]

實» _ 比較例 1 2 3 4 5 6 I 2 3 4 清漆(A-1-1) 123 77 31 嫌 · 齡 154 • 丨 清漆(A-1-2) 123 77 33 • 154 清漆B 40 100 160 40 100 160 100 _ 200 清漆R _ • _ • 嫌 丨 84 丨 海 TPO*1 10 10 10 10 10 10 10 10 10 10 三聚氰胺 3 3 3 3 3 3 3 3 3 3 DPHA*2 20 20 20 20 20 20 20 20 20 20 RE306*3 25 25 25 25 25 25 25 25 25 25 酞菁•綠 2 2 2 2 2 2 2 2 2 2 備 考 *1 : 2,4,6-三甲基苯醯二苯基膦氧化物 *2 :二季戊四醇六丙烯酸酯 *3 :日本化藥公司製，酚酚醛清漆型環氧樹脂 -46- 200827402 [表2]实» _ Comparative Example 1 2 3 4 5 6 I 2 3 4 Clear lacquer (A-1-1) 123 77 31 Suspect age 154 • 丨 varnish (A-1-2) 123 77 33 • 154 Varnish B 40 100 160 40 100 160 100 _ 200 Varnish R _ • _ • Disgusting 84 Sea TPO*1 10 10 10 10 10 10 10 10 10 10 Melamine 3 3 3 3 3 3 3 3 3 3 DPHA*2 20 20 20 20 20 20 20 20 20 20 RE306*3 25 25 25 25 25 25 25 25 25 25 Phthalocyanine • Green 2 2 2 2 2 2 2 2 2 2 Remarks *1 : 2,4,6-trimethylphenylhydrazine diphenylphosphine Oxide*2: Dipentaerythritol hexaacrylate*3: Made by Nippon Kayaku Co., Ltd., phenol novolak type epoxy resin-46- 200827402 [Table 2]

實施例 比較例 7 8 9 5 6 7 清漆(A-2) 112 70 28 • 140 麵 清漆B 40 100 160 100 200 清漆R 編 一 84 • TPO*1 10 10 10 10 10 10 三聚氰胺 3 3 3 3 3 3 DPHA*2 20 20 20 20 20 20 RE306*3 25 25 25 25 25 25 酞菁•綠 2 2 2 2 2 2 備 考 *1 : 2,4,6-三甲基苯醯二苯基膦氧化物 *2 :二季戊四醇六丙烯酸酯 *3 :日本化藥公司製，酚酚醛清漆型環氧樹脂 [表3] 實施例 比較例 10 11 12 8 9 10 清漆(A-3) 133 83 33 峰 167 清漆B 40 100 160 100 • 200 清漆R 擊 • 義 84 擊 TPO*1 10 10 10 10 10 10 三聚氰胺 3 3 3 3 3 3 DPHA*2 20 20 20 20 20 20 RE306*3 25 25 25 25 25 25 酞菁•綠 2 2 2 2 2 2 備 考 *1 : 2,4,6-三甲基苯醯二苯基膦氧化物 *2 :二季戊四醇六丙烯酸酯 *3 :日本化藥公司製，酚酚醛清漆型環氧樹脂 -47- 200827402 性能評價： < 乾薄膜製作> 將上述實施例1〜1 2及比較例1〜1 0之鹼顯影型之具 有熱硬化性的光硬化性·熱硬化性樹脂組成物，分別使用 ^ 薄膜塗佈器塗佈乾燥後膜厚爲約30μιη之PET薄膜（三菱 • 聚酯公司製R310 : 16μχη)，於40〜100°C下乾燥後得乾薄 膜。 <基板製作> 將形成電路形成之FR-4基板使用拋光機硏磨後，依 上述方法將所製得之薄膜使用真空層合機（名機製作所製 MVLP-5 00)，於 0.8MPa、8 0 °C、1 分鐘、1 3 3 · 3 P a 之條件 下加熱層合製得評估用基板。 (1)焊劑耐熱性EXAMPLES Comparative Example 7 8 9 5 6 7 Varnish (A-2) 112 70 28 • 140 varnish B 40 100 160 100 200 Varnish R 编84 • TPO*1 10 10 10 10 10 10 Melamine 3 3 3 3 3 3 DPHA*2 20 20 20 20 20 20 RE306*3 25 25 25 25 25 25 Phthalocyanine • Green 2 2 2 2 2 2 Preparation *1 : 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide *2: Dipentaerythritol hexaacrylate *3: phenol novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd. [Table 3] Example Comparative Example 10 11 12 8 9 10 Varnish (A-3) 133 83 33 Peak 167 Varnish B 40 100 160 100 • 200 Varnish R Strike • Right 84 Strike TPO*1 10 10 10 10 10 10 Melamine 3 3 3 3 3 3 DPHA*2 20 20 20 20 20 20 RE306*3 25 25 25 25 25 25 Turnip • Green 2 2 2 2 2 2 Remarks *1 : 2,4,6-Trimethylphenylhydrazine diphenylphosphine oxide *2 : Dipentaerythritol hexaacrylate *3 : Made by Nippon Kayaku Co., Ltd., phenol novolak type Epoxy resin-47-200827402 Performance evaluation: < Dry film preparation> The photocurable and thermosetting resin having thermosetting properties of the alkali-developing type of the above-mentioned Examples 1 to 12 and Comparative Examples 1 to 10 group Were, respectively, using the film thickness after drying ^ coater film PET film of about 30μιη (manufactured by Mitsubishi Polyester Corporation • R310: 16μχη), after dried at 40~100 ° C to obtain a dry film. <Substrate preparation> After the FR-4 substrate formed by the circuit was honed by a polisher, the obtained film was subjected to a vacuum laminator (MVLP-5 00 manufactured by Nihon Seisakusho Co., Ltd.) at 0.8 MPa according to the above method. The substrate for evaluation was prepared by heating and laminating under conditions of 80 ° C, 1 minute, and 1 3 3 · 3 P a . (1) Solder heat resistance

分別使用上述之評估用基板，以柯達No.2之階段式 曝光表（step tablets)求取其6段之曝光量。對上述各評估 用基板使用描繪有焊劑光阻圖案之負型圖案，照射前述結 果之曝光量，使用30°C之1質量％碳酸鈉水溶液，以噴壓 〇.2MPa之顯影機進行顯影，以形成圖案。其後，於150°C 、60分鐘時間進行熱硬化，得硬化塗膜。 於此硬化塗膜上，塗佈松香系焊劑（flux)，於260 °C 之焊劑槽中浸瀆3 0秒間，該硬化塗膜之狀態依以下基準 進行評估。 -48- 200827402 〇：硬化塗膜未發生起泡、剝離、變色者 △:硬化塗膜發生少許起泡、剝離、變色者 X:硬化塗膜發生起泡、剝離、變色者 (2)無電解鍍金耐性Using the above-mentioned evaluation substrate, the exposure amount of the six stages was determined by a Kodak No. 2 stage sheet. A negative pattern in which a solder resist pattern was drawn was used for each of the evaluation substrates described above, and the exposure amount of the above result was irradiated, and development was carried out by using a 1% by mass aqueous sodium carbonate solution at 30° C. and a developing machine having a pressure of 2 2 MPa. Form a pattern. Thereafter, thermal curing was carried out at 150 ° C for 60 minutes to obtain a cured coating film. On the hardened coating film, a rosin-based flux was applied and immersed in a flux bath at 260 ° C for 30 seconds, and the state of the cured coating film was evaluated according to the following criteria. -48- 200827402 〇: The smear film does not blister, peel, or discolor. △: The foamed film is slightly foamed, peeled, and discolored. X: The cured film is foamed, peeled, or discolored. (2) Electroless Gold plating resistance

與上述方法相同般進行曝光、顯影後，經熱硬化以製 作評估用基板。將各評估用基板，浸漬於3 0 °C之酸性脫 脂液（日本麥克達公司製，Metex L-5B之20v〇l%水溶液）3 分鐘後脫脂，其次，於流水中浸漬3分鐘進行水洗。將此 評估用基板於室溫下浸漬於14.3 wt%過硫酸硝銨水溶液3 分鐘，進行軟式蝕刻，其次浸漬於流水中3分鐘進行水洗 。將試驗基板於室溫下浸漬於1 Ονο 1 %硫酸水溶液1分鐘 後，再於流水中浸漬3 0秒〜1分鐘進行水洗。將該評估 用基板浸漬於30°C之觸媒液（美克達公司製，美克達菲瑞 達3 5 0之lOvol%水溶液）中7分鐘，於進行賦予觸媒後， 於流水中浸漬3分鐘進行水洗。將進行賦予觸媒支評估用 基板’浸漬於85 °C之鑛錬液（美克達公司製，美菲達Ni-8 6 5 Μ之2 0 ν ο 1 %水溶液，ρ Η 4 · 6)中20分鐘，進行無電解 鍍鎳處理。於室溫下，將評估用基板浸漬於1 0 ν ο 1 %硫酸 水溶液1分鐘後，於流水中浸漬3 0秒〜1分鐘以進行水 洗。其次，將該試験基板浸漬於9 5 °C之鍍金液（美克達公 司製，歐屋羅克斯U Ρ 1 5 ν ο 1 %與氰化金鉀3 ν ο 1 %之水溶液 ，pH6)中1〇分鐘，進行無電解鍍金處理後，於流水中浸 漬3分鐘進行水洗，再於6 0 °C之溫水中浸漬3分鐘進行 -49· 200827402 熱水洗。於充分水洗後，將水充分去除、乾燥後，得無電 解鍍金之評估用基板。 使用該無電解金鍍金之基板，黏著膠布進行黏著強度 試驗，對於塗膜之剝離、變色等，依以下之基準進行評估 〇 - 〇：完全未發現出變化。 △:塗膜產生些許剝離，或發現變色情形。 • X:塗膜發現剝離現象。 (3)HAST 耐性 與上述相同般，進行曝光、顯影後，經熱硬化處理， 以製作評估用基板。將該評估用基板，放入1 2 1 °C、2氣 壓、濕度1〇〇°/。之高壓高溫高濕槽中168小時，評估其硬 化塗膜之變化狀態。並依以下之評估基準進行評估。 〇：未有剝離、變色及溶出。 • △:出現剝離、變色、溶出的任一現象。 X :出現許多剝離、變色、溶出。 (5)HAST試驗後之絶緣性After exposure and development as in the above method, it was thermally cured to prepare a substrate for evaluation. Each of the evaluation substrates was immersed in an acidic degreasing liquid (20 〇l% aqueous solution of Metex L-5B, manufactured by Japan's McDonnell Co., Ltd.) at 30 ° C for 3 minutes, and then degreased. Then, it was immersed in running water for 3 minutes to be washed with water. The evaluation substrate was immersed in a 14.3 wt% aqueous solution of ammonium persulfate for 3 minutes at room temperature, and subjected to soft etching, followed by immersion in running water for 3 minutes for water washing. The test substrate was immersed in a 1 Ονο 1 % sulfuric acid aqueous solution at room temperature for 1 minute, and then immersed in running water for 30 seconds to 1 minute for water washing. The substrate for evaluation was immersed in a catalyst liquid (manufactured by Meikeda Co., Ltd., a 10% by volume aqueous solution of Mecco Ferrida 305) at 30 ° C for 7 minutes, and then immersed in running water after the catalyst was supplied. Wash in 3 minutes. A mineral immersion liquid immersed in a catalyst support evaluation substrate at 85 ° C (manufactured by Meikeda, Mefida Ni-8 6 5 Μ 2 0 ν ο 1 % aqueous solution, ρ Η 4 · 6) In the middle of 20 minutes, electroless nickel plating was performed. The evaluation substrate was immersed in a 10 ν ο 1 % sulfuric acid aqueous solution for 1 minute at room temperature, and then immersed in running water for 30 seconds to 1 minute to be washed with water. Next, the test substrate was immersed in a gold plating solution at 95 ° C (manufactured by Meikeda Co., Ltd., Oufang Rox U Ρ 1 5 ν ο 1 % and an aqueous solution of potassium cyanide 3 ν ο 1 %, pH 6) After 1 minute, the electroless gold plating treatment was carried out, and the mixture was immersed in running water for 3 minutes, washed with water, and further immersed in warm water at 60 ° C for 3 minutes to carry out -49.200827402 hot water washing. After sufficiently washing with water, the water was sufficiently removed and dried to obtain a substrate for evaluation without electrolytic gold plating. The electroless gold-plated substrate and the adhesive tape were used for the adhesion strength test, and the peeling and discoloration of the coating film were evaluated according to the following criteria. 〇 - 〇: No change was observed at all. △: The coating film was slightly peeled off, or a discoloration was observed. • X: The film was peeled off. (3) HAST resistance In the same manner as described above, after exposure and development, it was subjected to heat curing treatment to prepare a substrate for evaluation. The evaluation substrate was placed at 1 2 1 ° C, 2 gas pressure, and humidity 1 〇〇 ° /. In the high-pressure high-temperature and high-humidity tank for 168 hours, the state of change of the hard coating film was evaluated. And evaluate according to the following evaluation criteria. 〇: No peeling, discoloration and dissolution. • △: Any phenomenon of peeling, discoloration, or dissolution. X: Many peeling, discoloration, and dissolution occurred. (5) Insulation after HAST test

與上述相同般，使用前述光硬化性·熱硬化性樹脂組 成物全面印刷於形成梳型電極（線路/空間=50μ/50μ)之 FR-4基板上，於曝光、顯影後，經熱硬化處理以製作評 估用基板。將該評估用基板放入130°C、濕度85 %環境下 之高溫高濕槽中，以電壓5V荷電，進行168小時、HAST -50 - 200827402 試驗。並對hast試驗後之電氣絶緣性進行測定。 〇：1 0 1 0 Ω以上 △ : 1 0 1 0 〜108 Ω X : 1 0 8 Ω以下 ' (6)翹曲評估 與上述相同方法，使用前述光硬化性•熱硬化性樹脂 • 組成物全面印刷於基材厚度60/X之FR-4基板上，於曝光 、顯影後，經熱硬化處理以製作評估用基板。將此評估用 基板（400mmx300mm)作爲試驗片，於平面上測定試驗片之 四角，將其測定値之合計作爲變形量。 〇：20mm以下 △ : 20mm 〜40mm ^ X : 40mm 以上 ^ / 如上所述般，對於實施例1〜1 2及比較例1〜1 0之光 ^ 硬化性•熱硬化性樹脂組成物之評估結果，係如以下之表 4〜6所示。 [表4]In the same manner as described above, the photocurable and thermosetting resin composition was printed on the FR-4 substrate on which a comb-shaped electrode (line/space = 50 μ/50 μ) was formed, and subjected to heat hardening after exposure and development. To produce a substrate for evaluation. The evaluation substrate was placed in a high-temperature and high-humidity bath at 130 ° C and a humidity of 85%, and charged at a voltage of 5 V for 168 hours and HAST -50 - 200827402 test. The electrical insulation after the hast test was measured. 〇: 1 0 1 0 Ω or more △ : 1 0 1 0 ～ 108 Ω X : 1 0 8 Ω or less ' (6) Warpage evaluation The same method as above, using the above-mentioned photocurability•thermosetting resin•Comprehensive composition It was printed on an FR-4 substrate having a substrate thickness of 60/X, and after exposure and development, it was subjected to a heat hardening treatment to prepare a substrate for evaluation. The evaluation substrate (400 mm x 300 mm) was used as a test piece, and the four corners of the test piece were measured on a flat surface, and the total amount of the test pieces was measured as the amount of deformation. 〇: 20 mm or less Δ: 20 mm to 40 mm ^ X : 40 mm or more ^ / Evaluation results of the light-curing and thermosetting resin compositions of Examples 1 to 12 and Comparative Examples 1 to 10 as described above , as shown in Tables 4 to 6 below. [Table 4]

實S _ 比較例 1 2 3 4 5 6 1 2 3 4 (1)焊劑耐熱性 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 (2)無電解鍍金耐性 〇 〇 〇 〇 〇 〇 〇 〇 Δ 〇 (3)HAST 耐性 〇 〇 〇 〇 〇 〇 Δ 〇 〇 〇 ⑷HAST試驗後之絕緣性 〇 〇 〇 〇 〇 〇 △ 〇 Δ 〇 (4)翹曲之評估 Δ 〇 〇 △ 〇 〇 X X 〇 X 200827402 [表5] 實施例 比較例 7 8 9 5 6 7 ⑴焊劑耐熱性 〇 〇 〇 〇 〇 X (2)無電解鍍金耐性 〇 〇 〇 〇 〇 〇 (3)HAST 耐性 〇 〇 〇 △ 〇 〇一 (4)HAST試驗後之絕緣性 〇 〇 〇 Δ 〇 Δ (4)翹曲之評估 〇 〇 〇 X Δ 〇—Real S _ Comparative Example 1 2 3 4 5 6 1 2 3 4 (1) Solder heat resistance 〇〇〇〇〇〇〇〇X 〇 (2) Electroless gold plating resistance 〇〇〇〇〇〇〇〇 Δ 〇 (3 ) HAST resistance 〇〇〇〇〇〇 Δ 〇〇〇 (4) Insulation 〇〇〇〇〇〇 Δ 〇 Δ 〇 4 4 〇 4 (4) Evaluation of warpage Δ 〇〇 △ 〇〇 XX 〇 X 200827402 [Table 5] EXAMPLES Comparative Example 7 8 9 5 6 7 (1) Solder heat resistance 〇〇〇〇〇X (2) Electroless gold plating resistance 〇〇〇〇〇〇 (3) HAST resistance 〇〇〇 △ 〇〇 (4) HAST test Insulation 〇〇〇Δ 〇Δ (4) Evaluation of warpage 〇〇〇X Δ 〇—

m 6] 實施例 比較例 10 11 12 8 9 10 ⑴焊劑耐熱性 〇 〇 〇 〇 〇 X (2)無電解鍍金耐性 〇 〇 〇 〇 〇 △_ (3)HAST 耐性 〇 〇 〇 △ 〇 〇 (4)HAST試驗後之絕緣性 〇 〇 〇 △ 〇 △__ (4)翹曲之評估 △ 〇 〇 X X 〇— 由表4〜6可明確得知，本發明之光硬化性•熱硬化 性樹脂組成物，具有焊劑光阻或裝置基板用光阻所尋求之 優良焊劑耐熱性、無電解鍍金耐性、PCT耐性、HAST試 驗後之絶緣性，此外，即使用於QFP、BGA、CSP等裝置 基板所使用之薄板時，亦僅顯示出極低之翹曲。 又，使用常用之含羧基的感光性樹脂與含羧基的（甲 基）丙烯酸胺基甲酸酯化合物（B)之比較例1、5及8 ’顯示 出其翹曲較大，且PCT耐性、HAST試驗後之絶緣性亦較 -52- 200827402 爲低劣。 又，僅使用本發明之前述含羧基的感光性樹脂（A-1、 A-2、A-3)之比較例2、4、6及9，顯示出較大之翹曲， 而無法使用於QFP、BGA、CSP等裝置基板所使用之薄板 基板。 此外，僅使用含羧基的（甲基）丙烯酸胺基甲酸酯化合 物（B)之比較例3、7及1 0，顯示出較低之焊劑耐熱性。m 6] Example Comparative Example 10 11 12 8 9 10 (1) Solder heat resistance 〇〇〇〇〇X (2) Electroless gold plating resistance 〇〇〇〇〇 _ (3) HAST resistance 〇〇〇 △ 〇〇 (4 )Insulation 〇〇〇△ 〇△__ after HAST test (4) Evaluation of warpage △ 〇〇 XX 〇 - It can be clearly seen from Tables 4 to 6 that the photocurable thermosetting resin composition of the present invention Excellent solder heat resistance, electroless gold plating resistance, PCT resistance, and insulation after HAST test, which are required for solder resist or device substrate photoresist, and are used even for device substrates such as QFP, BGA, and CSP. When the sheet is thin, it also shows only a very low warpage. Further, Comparative Examples 1, 5 and 8' using a conventional carboxyl group-containing photosensitive resin and a carboxyl group-containing (meth)acrylic acid urethane compound (B) showed large warpage and PCT resistance, The insulation after the HAST test is also inferior to that of -52-200827402. Further, Comparative Examples 2, 4, 6, and 9 using only the carboxyl group-containing photosensitive resin (A-1, A-2, and A-3) of the present invention showed large warpage and could not be used. A thin-plate substrate used for a device substrate such as QFP, BGA, or CSP. Further, Comparative Examples 3, 7 and 10 using only the carboxyl group-containing (meth)acrylic acid urethane compound (B) showed low solder heat resistance.

Claims (1)

200827402 十、申請專利範圍 1.一種光硬化性•熱硬化性樹脂組成物，其特徵爲含 有： (A-1)在1分子中具有2個以上環氧基之環氧化合物200827402 X. Patent application scope 1. A photocurable/thermosetting resin composition characterized by comprising: (A-1) an epoxy compound having two or more epoxy groups in one molecule (a)、與1分子中具有〗個以上之醇性羥基，和與此醇性 羥基以外的環氧基反應之1個反應基的化合物（b)、及含 有不飽和基之單羧酸（c)的反應生成物中，使多元酸酐（d) 反應而得之含羧基的感光性樹脂； (A-2)使1分子中含有2個以上酚性羥基之化合物（e) 與環氧烷（f)或環碳酯酯化合物（g)反應而得的反應生成物 ，在與含不飽和基之單羧酸（c)的反應生成物中，使多元 酸酐（d)反應而得含羧基之感光性樹脂；及 (A-3)使二官能環氧化合物與具有可與環氧基反應之2 個反應基的化合物進行交互.聚合，在生成之羥基與環氧氯 丙烷反應而得的線狀多官能環氧化合物（h)、與含不飽和 基之單羧酸（c)的反應生成物中，使多元酸酐（d)反應所得 的含羧基的感光性樹脂； 之任一種或二種以上、與 (B) 含羧基之胺基甲酸酯（甲基）丙烯酸酯化合物、 (C) 光聚合引發劑、 (D)l分子中具有2個以上環狀醚基及/或環狀硫醚基 之熱硬化性成份、及 (E)稀釋劑。 2 .如申請專利範圍第丨項之光硬化性•熱硬化性樹脂 •54- 200827402 組成物，其中該含羧基之感光性樹脂（A· 1 )中，1分子中具 有1個以上之醇性羥基和與此醇性羥基以外之環氧基反應 的1個反應基之化合物（b)，爲1分子中具有1個以上之 醇性羥基與1個羧基的化合物。 3 ·如申請專利範圍第1項之光硬化性•熱硬化性樹脂 * 組成物，其中該含羧基之感光性樹脂（A-1)中，1分子中具 有1個以上之醇性羥基，和與此醇性羥基以外之環氧基反 ® 應的1個反應基之化合物（b)，爲1分子中具有1個以上 之醇性羥基的苯酚化合物。 4.如申請專利範圍第1項之光硬化性•熱硬化性樹脂 組成物，其中該含羧基之感光性樹脂（A-3)中，線狀之多 官能環氧化合物（h)，爲二官能芳香族環氧化合物與二官 能苯酚化合物及/或芳香族二羧酸反應而得的多官能環氧 化合物。(a) a compound (b) having one or more alcoholic hydroxyl groups in one molecule and one reactive group reactive with an epoxy group other than the alcoholic hydroxyl group, and a monocarboxylic acid containing an unsaturated group ( (a-2) a compound containing a carboxyl group and having two or more phenolic hydroxyl groups in one molecule; (f) or a reaction product obtained by reacting a cyclic carbamate compound (g), reacting a polybasic acid anhydride (d) with a reaction product of a monocarboxylic acid (c) containing an unsaturated group to obtain a carboxyl group-containing compound a photosensitive resin; and (A-3) a difunctional epoxy compound which interacts with a compound having two reactive groups reactive with an epoxy group, and is obtained by reacting a generated hydroxyl group with epichlorohydrin. a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride (d) with a linear polyfunctional epoxy compound (h) and a reaction product of an unsaturated group-containing monocarboxylic acid (c); And above (B) carboxyl group-containing urethane (meth) acrylate compound, (C) photopolymerization initiator (D) l molecule having two or more cyclic ether groups and / or cyclic thioether groups of the heat curable composition, and (E) a diluent. 2. The composition of the photocurable/thermosetting resin of the Scope of the Patent Application No. 54-200827402, wherein the carboxyl group-containing photosensitive resin (A·1) has one or more alcoholicities in one molecule. The compound (b) having one hydroxyl group and one reactive group which reacts with an epoxy group other than the alcoholic hydroxyl group is a compound having one or more alcoholic hydroxyl groups and one carboxyl group in one molecule. 3. The photocurable thermosetting resin* composition according to the first aspect of the invention, wherein the carboxyl group-containing photosensitive resin (A-1) has one or more alcoholic hydroxyl groups in one molecule, and The compound (b) which is one reactive group of the epoxy group other than the alcoholic hydroxyl group is a phenol compound having one or more alcoholic hydroxyl groups in one molecule. 4. The photocurable thermosetting resin composition according to the first aspect of the invention, wherein the linear polyfunctional epoxy compound (h) is in the carboxyl group-containing photosensitive resin (A-3). A polyfunctional epoxy compound obtained by reacting a functional aromatic epoxy compound with a difunctional phenol compound and/or an aromatic dicarboxylic acid. 5.如申請專利範圍第！項之光硬化性•熱硬化性樹脂 組成物，其中該含羧基之胺基甲酸酯（甲基）丙烯酸酯化合 物（B)，爲使含有羥基之（甲基）丙烯酸酯化合物（i)、二羥 甲基烷酸（j)、及二異氰酸酯化合物（k)反應所得的化合物 ，其酸價爲30〜100 mgKOH/g。 6·如申請專利範圍第1或2項之光硬化性•熱硬化性 樹脂組成物，其中該含羧基之胺基甲酸酯（甲基）丙烯酸酯 化合物（B)，爲使含有羥基之（甲基）丙烯酸酯化合物（i)、 一經甲基院酸（j)、及二異氰酸酯化合物（k)、及聚合物聚 醇（B1)反應所得的化合物，其酸價爲30〜100 mgKC)]H/g。 -55- 200827402 7.如申請專利範圍第6項之光硬化性•熱硬化性樹脂 組成物，其中該二羥甲基烷酸（j )，爲二羥基甲基丙酸及二 羥甲基丁酸之任一的至少一種。 8·如申請專利範圍第7項之光硬化性•熱硬化性樹脂 組成物，其中該二羥甲基烷酸（j )，爲二羥基甲基丙酸及二 ~ 羥甲基丁酸之任一的至少一種。 9 ·如申請專利範圍第1項之光硬化性•熱硬化性樹脂 ^ 組成物，其中該含羧基之感光性樹脂（A-1、A-2、A-3之 任一種或二種以上）、與該含羧基之胺基甲酸酯（甲基）丙 烯酸酯化合物（B)的配合比率，爲85 : 15〜15 : 85之比例5. If you apply for a patent range! The photocurable thermosetting resin composition, wherein the carboxyl group-containing urethane (meth) acrylate compound (B) is a hydroxyl group-containing (meth) acrylate compound (i), The compound obtained by reacting dimethylol alkanoic acid (j) and a diisocyanate compound (k) has an acid value of 30 to 100 mgKOH/g. 6. The photocurable thermosetting resin composition according to claim 1 or 2, wherein the carboxyl group-containing urethane (meth) acrylate compound (B) is a hydroxyl group-containing compound (B) a methyl acrylate compound (i), a compound obtained by reacting a methyl acid (j), a diisocyanate compound (k), and a polymer polyol (B1), having an acid value of 30 to 100 mg KC)] H/g. -55- 200827402 7. The photocurable thermosetting resin composition of claim 6 wherein the dimethylol alkanoic acid (j) is dihydroxymethylpropionic acid and dimethylol At least one of any of the acids. 8. The photocurable thermosetting resin composition according to item 7 of the patent application, wherein the dimethylol alkanoic acid (j) is a dihydroxymethylpropionic acid and a bishydroxymethylbutyric acid At least one of one. (9) The photocurable/thermosetting resin according to the first aspect of the invention, wherein the carboxyl group-containing photosensitive resin (either one or more of A-1, A-2, and A-3) The compounding ratio of the carboxyl group-containing urethane (meth) acrylate compound (B) is 85:15 to 15:85. 10.—種光硬化性•熱硬化性樹脂組成物，其特徵爲 ，在該申請專利範圍第1項之光硬化性•熱硬化性樹脂組 成物中，該光聚合引發劑（C)之配合量，相對於該含羧基 之感光性樹脂（A)及該含羧基之胺基甲酸酯（甲基）丙烯酸 酯化合物（B)的合計量100質量份，爲0.01〜30質量份； 該熱硬化成份（D)之配合量，相對於該含羧基之感光性樹 脂（A)及該有羧基之胺基甲酸酯（甲基）丙烯酸酯化合物（B) 的羧基的合計量1當量，爲0.5〜2.0當量；且該稀釋劑（E) 之配合量，相對於該含羧基之感光性樹脂（A)、及該含羧 基之胺基甲酸酯（甲基）丙烯酸酯化合物（B)的合計量100 質量份，爲5〜420質量份。 11· 一種乾燥薄膜，其特徵爲申請專利範圍第1項之 光硬化性·熱硬化性樹脂組成物，塗佈於載體薄膜上、進 -56- 200827402 行乾燥而得。 12·如申請專利範圍第1項之光硬化性•熱硬化性樹 脂組成物，其中尙含有（F)硬化觸媒，其配合量相對於全 樹脂組成物100質量份爲0.1〜20質量份。 # 1 3 . —種硬化物，其特徵爲將該申請專利範圍第1項 " 之光硬化性·熱硬化性樹脂組成物、或申請專利範圍第 1 1項之乾燥薄膜，藉由以活性能量線照射及加熱予以硬 ® 化而得。 14.一種印刷電路板，其係在具有經形成圖型之導體 層的電路基板上，形成作爲永久保護膜之焊劑光阻皮膜的 印刷電路板；其特徵該焊劑光阻皮膜係由該申請專利範圍 第1項之光硬化性•熱硬化性樹脂組成物、或申請專利範 圍第11項之乾燥薄膜的硬化皮膜所成。 ♦ -57- 200827402 V 七 明 說 單 無簡 ••號 為符 圖件 表元 代之 定圖 ••指表 圖案代 表本本 代 定一二 指c C 無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無10. A photocurable/thermosetting resin composition characterized by the photopolymerization initiator (C) in the photocurable thermosetting resin composition of the first aspect of the patent application. The amount is 0.01 to 30 parts by mass based on 100 parts by mass of the total of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B); The amount of the hardening component (D) is 1 equivalent of the total amount of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B). 0.5 to 2.0 equivalents; and the amount of the diluent (E) is relative to the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B) The total amount is 100 parts by mass, and is 5 to 420 parts by mass. A dry film comprising the photocurable and thermosetting resin composition of the first application of the patent application, which is applied onto a carrier film and dried in -56-200827402. 12. The photocurable and thermosetting resin composition of the first aspect of the invention, wherein the cerium contains (F) a curing catalyst, and the amount thereof is 0.1 to 20 parts by mass based on 100 parts by mass of the total resin composition. #1 3 . A cured product characterized by the photocurable thermosetting resin composition of the first application " or the dried film of claim 1 of the patent application, by active Energy line irradiation and heating are obtained by hardening. A printed circuit board formed on a circuit substrate having a patterned conductor layer to form a solder resist film as a permanent protective film; characterized in that the solder photoresist film is patented by the patent application The photocurable/thermosetting resin composition of the first item or the hardened film of the dried film of claim 11 of the invention. ♦ -57- 200827402 V 七明说单无简••号 is the diagram of the map element on behalf of the map •• The table design represents the book one or two fingers c C No eight, if there is a chemical formula in this case, please reveal the most Chemical formula that can show the characteristics of the invention: none
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