TW201116928A - Photocurable resin composition - Google Patents

Photocurable resin composition Download PDF

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Publication number
TW201116928A
TW201116928A TW099123966A TW99123966A TW201116928A TW 201116928 A TW201116928 A TW 201116928A TW 099123966 A TW099123966 A TW 099123966A TW 99123966 A TW99123966 A TW 99123966A TW 201116928 A TW201116928 A TW 201116928A
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TW
Taiwan
Prior art keywords
group
compound
resin composition
manufactured
photocurable resin
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Application number
TW099123966A
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Chinese (zh)
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TWI489201B (en
Inventor
Shoji Minegishi
Masao Arima
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Taiyo Ink Mfg Co Ltd
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Publication of TW201116928A publication Critical patent/TW201116928A/en
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Publication of TWI489201B publication Critical patent/TWI489201B/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising 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
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • 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)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a photocurable resin composition which enables the prevention of absorption of moisture, and can be cured into a product that has improved thermal cycle resistance without deteriorating anti-migration properties when the product is used in a printed wiring board or the like. The photocurable resin composition comprises a resin containing a carboxyl group, a photopolymerization initiator, a compound containing a styryl group, and a maleimide compound.

Description

201116928 六、發明說明： 【發明所屬之技術領域】 本發明爲有關一種作爲印刷電路基板之焊料阻劑等使 用之硬化性樹脂組成物。 【先前技術】 光硬化性樹脂組成物，於應用照相法（光微影蝕刻） 之原理時，可進行微細加工。此外，因可得到具有優良物 性之硬化物，故被應用於電子機器或印刷版等。 該光硬化性樹脂組成物中具有溶劑顯影型與鹼顯影型 ，近年來，就環境對策之觀點，以使用可經由稀薄之弱鹼 水溶液顯影之鹼顯影型爲主流。例如，於印刷電路基板之 製造、液晶顯示板之製造，或印刷製版等之中，爲使用鹼 顯影型之光硬化性樹脂組成物。例如，印刷電路板製造中 ，作爲焊料阻劑使用之際，其硬化物中，多尋求一種於進 行焊接等，有關耐高溫條件下之處理的耐熱性或，耐水性 、耐濕性等之長期信賴性的特性。 近年來，伴隨電子機器之小型輕量化、多機能化、環 境對應性等，對於印刷電路板等則逐漸進入高密度實裝化 、薄層化等。特別是例如，爲進行高密度實裝而使用於具 有良好間距的圖型之高密度實裝基板之焊料阻劑，於硬化 物中則要求具有高耐移動（migration)性與耐冷熱循環性 。隨後，伴隨於此，也要求作爲焊料阻劑使用之光硬化性 樹脂組成物的低吸濕化、高純度化，即，降低吸水率及減 -5- 201116928 低樹脂組成物中之離子性雜質等。 可某種程度滿足作爲硬化物之耐移動性、耐冷熱循環 性之光硬化性樹脂組成物，也多使用一種於含羧基之環氧 基（甲基）丙烯酸酯之中，使用多官能之環氧樹脂或（甲 基）丙烯酸酯將多數雙鍵導入樹脂骨架所得之光硬化性樹 脂組成物。經由該些構成，可提高交聯密度、提升耐熱性 或提高尺寸安定性。 但是，交聯密度過高時，將會造成硬化塗膜脆化，而 會形成無法取得降低耐熱性與脆化之平衡等問題。降低脆 化之問題，已知揭示有使用由雙酚型之含羧基之環氧基（ 甲基）丙烯酸酯與酚醛清漆型之含羧基之環氧基（甲基） 丙烯酸酯所得混合物之方法（例如，專利文獻1等）。但 是，該些手法中，爲以改善柔軟性爲重點，而仍存在對於 溫度變化而無法充分得到尺寸安定性或耐水性等問題。 又，光硬化性樹脂組成物中，使用多官能硬化性樹脂 以提高交聯密度，多可尋求吸水率之降低。但是，另一方 面，則會造成其硬化物硬化·脆化，耐冷熱循環性降低等 問題。 [先行技術文獻] [專利文獻] [專利文獻1]日本國特許公開2000- 1 0954 1號公報 【發明內容】 -6- 201116928 本發明爲以提供一種可抑制吸濕性，其硬化物，於使 用於印刷電路板等之際，可無損耐移動特性下，可提升耐 冷熱循環性之光硬化性樹脂組成物爲目的。 爲達成該些目的，本發明之一實施態樣爲，提供一種 含有含羧基之樹脂、光聚合起始劑、含苯乙烯基之化合物 ，及馬來醯亞胺化合物之光硬化性樹脂組成物。 經具有該些構成內容時，可抑制吸濕性，其硬化物， 於使用於印刷電路板等之際，可無損耐移動特性下，可提 高耐冷熱循環性。 又，本發明之一實施態樣之光硬化性樹脂組成物中， 以再含有氫硫基化合物爲佳。經具有該些構成內容，可使 密著性向上提升。 又，本發明之一實施態樣之光硬化性樹脂組成物中， 含羧基之樹脂以具有感光性基爲佳。具有感光性基時，可 增大光硬化性樹脂組成物之光硬化性’而使感度提升。 又，本發明之一實施態樣之光硬化性樹脂組成物中， 光聚合起始劑以含有由下述通式（1)所表示之肟酯系光 聚合起始劑、下述通式（11)所表示之胺基苯乙酮系光聚 合起始劑，與下述通式（111)所表示之氧化酸膦系光聚 合起始劑所形成之群所選出之至少一種爲佳。 (I)201116928 【化1】 一C=N_0—C_R2[Technical Field] The present invention relates to a curable resin composition used as a solder resist or the like for a printed circuit board. [Prior Art] The photocurable resin composition can be microfabricated when the principle of photolithography (photolithography) is applied. Further, since a cured product having excellent physical properties can be obtained, it is applied to an electronic device or a printing plate. The photocurable resin composition has a solvent developing type and an alkali developing type. In recent years, from the viewpoint of environmental measures, an alkali developing type which can be developed through a thin weak alkali aqueous solution is mainly used. For example, in the production of a printed circuit board, the production of a liquid crystal display panel, or a printing plate, etc., an alkali-developable photocurable resin composition is used. For example, in the manufacture of printed circuit boards, when used as a solder resist, in the cured product, a long-term search for heat resistance, heat resistance, moisture resistance, and the like under high temperature conditions is often sought. The nature of trust. In recent years, with the miniaturization, weight reduction, multi-functionality, and environmental compatibility of electronic devices, printed circuit boards and the like have gradually entered high-density mounting and thinning. In particular, for example, a solder resist for a high-density mounting substrate having a pattern having a good pitch for high-density mounting is required to have high migration resistance and cold/heat cycle resistance in a cured product. Then, along with this, the photocurable resin composition used as the solder resist is required to have low moisture absorption and high purity, that is, to reduce the water absorption rate and reduce the ionic impurities in the low resin composition. Wait. A photocurable resin composition which is resistant to mobility and cold/heat cycle resistance of a cured product to some extent, and a polyfunctional ring is also used among a carboxyl group-containing epoxy group (meth)acrylate. Oxygen resin or (meth) acrylate A photocurable resin composition obtained by introducing a plurality of double bonds into a resin skeleton. With such a configuration, the crosslinking density can be improved, the heat resistance can be improved, or the dimensional stability can be improved. However, when the crosslink density is too high, the cured coating film becomes brittle, and the problem of lowering the balance between heat resistance and embrittlement cannot be achieved. In order to reduce the problem of embrittlement, it is known to disclose a method of using a mixture of a carboxyl group-containing epoxy group (meth) acrylate of a bisphenol type and a carboxyl group-containing epoxy group (meth) acrylate of a novolac type ( For example, Patent Document 1, etc.). However, in these methods, in order to improve the softness, there is still a problem that dimensional stability or water resistance cannot be sufficiently obtained with respect to temperature changes. Further, in the photocurable resin composition, a polyfunctional curable resin is used to increase the crosslinking density, and a decrease in water absorption can be sought. On the other hand, there is a problem that the hardened material is hardened and embrittled, and the cold and heat cycle resistance is lowered. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-100954 No. PCT Publication No. JP-A No. 2000-2011-08928 The present invention provides a cured product capable of suppressing hygroscopicity. When it is used for a printed circuit board or the like, it is possible to improve the composition of the photocurable resin which is resistant to cold and heat cycles without impairing the resistance to movement. In order to achieve the above object, an aspect of the present invention provides a photocurable resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, a styrene group-containing compound, and a maleic imine compound. . When the composition is contained, the hygroscopic property can be suppressed, and when it is used in a printed circuit board or the like, the cured product can be improved in cold cycle resistance without impairing the resistance to movement. Further, in the photocurable resin composition of one embodiment of the present invention, it is preferred to further contain a hydrogenthio group compound. With such a constituent content, the adhesion can be improved upward. Further, in the photocurable resin composition of one embodiment of the present invention, the carboxyl group-containing resin preferably has a photosensitive group. When the photosensitive group is provided, the photocurability of the photocurable resin composition can be increased to improve the sensitivity. In the photocurable resin composition of the embodiment of the present invention, the photopolymerization initiator contains an oxime ester photopolymerization initiator represented by the following formula (1), and has the following formula ( 11) The at least one selected from the group consisting of the amino acetophenone-based photopolymerization initiator and the phosphine oxide-based photopolymerization initiator represented by the following formula (111) is preferred. (I)201116928 【化1】一C=N_0—C_R2

—c—P (II) (III) (式中，R1表示，氫原子、苯基（可被碳數1〜6之院基 、苯基、或鹵素原子所取代）、碳數1~20之烷基（可被 1個以上之羥基所取代、烷鏈中可具有1個以上之氧原子 )、碳數5~8之環烷基、碳數2〜2 0之烷醯基或苯甲醯基 (可被碳數1〜6之烷基或苯基所取代）；R2表示’苯基 (可被碳數1〜6之烷基、苯基或鹵素原子所取代）、碳數 1〜20之烷基（可被1個以上之羥基所取代、烷鏈中可具 有1個以上之氧原子）、碳數5〜8之環烷基、碳數2〇 之烷醯基或苯甲醯基（可被碳數1〜6之烷基或苯基所取代 ):R3及R4表示分別獨立之碳數1〜12之烷基或芳基烷 基；R5及R6表示分別獨立之氫原子、碳數之烷基， 或2個鍵結所形成之環狀烷基醚基；R7及R8表示分別獨 立之碳數1~1〇之直鏈狀或支鏈狀之烷基、環己基、環戊 基、芳基，或鹵素原子、烷基或烷氧基所取代之芳基；但 ’ R7及R8之一者可表示R-C( = 0)-基（其中，R爲碳數 1〜20之烴基）） 201116928 使用該些光聚合起始劑時，於具有高濃度之顏料的阻 劑中，可得到高解析性。 又，本發明之一實施態樣之光硬化性樹脂組成物中， 以再含有熱硬化成份爲佳。含有熱硬化成份時，除賦予耐 熱性的同時，亦可增大硬化被膜之拉伸延伸率，耐龜裂性 、耐衝擊性等。 又，本發明之一實施態樣之光硬化性樹脂組成物中， 可再含有著色劑。含有著色劑時，極適合作爲焊料阻劑使 用。 又，本發明之一實施態樣，爲提供一種將上述光硬化 性樹脂組成物塗佈於載體薄膜上，並經由乾燥而得之乾薄 膜。使用該些乾薄膜時，於無須於基材上塗佈光硬化性樹 脂組成物，而可容易形成阻劑層。 又，本發明之一實施態樣中，爲可使用將上述光硬化 性樹脂組成物或乾薄膜，經由活性能量線照射進行光硬化 、而得之硬化物。 該些硬化物，於使用於印刷電路板等之際，可於無損 耐移動特性下，提高耐冷熱循環性等機能。 此外，本發明之一實施態樣中，爲可使用具有將上述 光硬化性樹脂組成物或其乾薄膜，經由活性能量線照射進 行光硬化而得之硬化物的圖型作爲印刷電路板使用。 該些印刷電路板，可於無損耐移動特性下，提高耐冷 熱循環性等機能。 本發明之一實施態樣之光硬化性樹脂組成物，可抑制 -9- 201116928 吸濕性，其硬化物，可於無損耐移動特性下，得到良好之 耐冷熱循環性。 本發明者們，發現於光硬化性樹脂組成物中，併用含 苯乙烯基之化合物與馬來醯亞胺化合物時，其硬化物，可 達成優良之電氣特性與耐移動性，因而完成本發明。經由 倂用含苯乙烯基之化合物與馬來醯亞胺化合物，進行交聯 反應時，可抑制本實施形態之光硬化性樹脂組成物所得之 硬化物的吸水性。 以下，將對本實施形態之光硬化性樹脂組成物進行詳 細之說明。 首先，構成本實施形態之光硬化性樹脂組成物的含羧 基之樹脂，於賦予鹼顯影性之目的上，可使用分子中具有 羧基之公知的各種含羧基之樹脂。特別是，分子中具有乙 烯性不飽和雙鍵之含羧基之感光性樹脂，就光硬化性或耐 顯影性之觀點而言爲較佳。又，該不飽和雙鍵，以由丙烯 酸或甲基丙烯酸或其衍生物所產生者爲佳。 該些含羧基之樹脂，以以下所列舉之化合物（寡聚物 及聚合物之任一者皆可）爲佳。 (1) (甲基）丙烯酸等之不飽和羧酸與，含有苯乙 烯、〇：-甲基苯乙烯、低級烷基（甲基）丙烯酸酯、異丁 烯等不飽和基之化合物經共聚所得之含羧基之樹脂。 (2) 脂肪族二異氰酸酯、支鏈脂肪族二異氰酸酯、 脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯與 ，二羥甲基丙酸、二羥甲基丁烷酸等之含羧基之二醇化合 -10- 201116928 物及聚碳酸酯系聚醇、聚醚系聚醇、聚酯系聚醇、聚烯烴 系聚醇、丙稀酸系聚醇、雙酚A系環氧烷加成物二醇、 具有酣性經基及醇性羥基之化合物等之二醇化合物聚加成 反應所得之含羧基之胺基甲酸酯樹脂。 (3) 二異氰酸酯與，雙酚a型環氧樹脂、氫化雙酚 A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂' 雙二甲酚型環氧樹脂、聯苯酚型環氧樹脂等之2官能環氧 樹脂之（甲基）丙烯酸酯或其部份酸酐改質物、含羧基之 二醇化合物及二醇化合物之聚加成反應所得之感光性含羧 基之胺基甲酸酯樹脂。 (4) 上述（2)或（3)之樹脂之合成中，羥烷基（ 甲基）丙烯酸酯等之分子內具有1個羥基與1個以上之（ 甲基）丙烯基之化合物以外，其末端（甲基）丙烯化之感 光性含羧基之胺基甲酸酯樹脂。 (5) 上述之（2)或（3)之樹脂之合成中，異佛爾 酮二異氰酸酯與季戊四醇三丙烯酸酯等莫耳反應物等，分 子內具有1個之異氰酸酯基與1個以上之（甲基）丙烯基 之化合物以外，其末端（甲基）丙烯基化之感光性含羧基 之胺基甲酸酯樹脂。 (6 )後述之2官能或其以上之多官能（固形）環氧 樹脂與（甲基）丙烯酸反應，於側鏈之存在之羥基上，附 加二元酸酐之感光性含羧基之樹脂。 (7 )後述2官能（固形）環氧樹脂之羥基再以表氯 醇環氧化所得之多官能環氧樹脂與（甲基）丙烯酸反應， -11 - 201116928 所生成之羥基附加二元酸酐所得之感光性含羧基之樹脂。 (8) 後述2官能環氧丙烷樹脂與二羧酸反應，所生 成之1級之羥基附加二元酸酐所得之含羧基之聚酯樹脂。 (9) 1分子中具有複數之酚性羥基的化合物與環氧 乙烷、環氧丙烷等之環氧烷反應所得之反應產物再與含不 飽和基之單羧酸反應，所得之反應產物再與多元酸酐反應 所得之含羧基之感光性樹脂。 (10) 1分子中具有複數之酚性羥基的化合物與乙烯 碳酸酯、丙烯碳酸酯等之環狀碳酸酯化合物反應所得之反 應產物再與含不飽和基之單羧酸反應，所得之反應產物與 多元酸酐反應所得之含羧基之感光性樹脂。 (11) 上述（1)〜（10)之樹脂再附加1分子內具有 1個之環氧基與1個以上之（甲基）丙烯基之化合物所得 之感光性含羧基之樹脂。 又，此處所稱之（甲基）丙烯酸酯，爲統稱丙烯酸酯 、甲基丙烯酸酯及該些混合物之用語，以下其他之類似表 現方式亦爲相同之內容。 該些含羧基之樹脂，因主鏈·聚合物之側鏈具有多數 個遊離之羧基，故可於稀鹼水溶液中進行顯影。 上述之含羧基之樹脂的酸價，以40〜200mgKOH/g爲 佳。含羧基之樹脂之酸價未達40mgKOH/g時，則不容易 進行鹼顯影，另外，超過200mgKOH/g時，因顯影液造成 曝光部持續進行溶解，故會使線路超過必要以上之狹窄， 某些情形中，會使曝光部與未曝光部無法區別，而受到顯 -12- 201116928 影液所溶解剝離，而不容易進行正常阻劑圖型之描繪。更 佳爲 45~120mgKOH/g。 又，含羧基之樹脂之重量平均分子量’依樹脂骨架而 有所不同，一般而言爲2,000〜1 50,000爲佳。重量平均分 子量未達2,000時，會降低硬化性能等，造成曝光後之塗 膜耐濕性惡化、顯影時產生膜消減，使解析度大幅劣化。 另外，重量平均分子量超過150,000時，顯影性會有顯著 惡化之情形，造成儲存安定性劣化。更佳爲 5,000~ 100,000° 該些含羧基之樹脂的添加量，於全組成物中，以 20~60質量％爲佳。添加量少於20質量％之情形，會造成 被膜強度降低。另外，多餘60質量％之情形，因組成物 之黏性過高，故會造成塗佈性等降低。更佳爲30〜50質量 %。 該些含羧基之樹脂，並不限定僅使用列舉之樹脂，其 可使用1種類或多數種混合所得者。 光聚合起始劑，以使用由具有下述通式（I)所表示 之基的肟酯系光聚合起始劑、具有下述通式（II )所表示 之基的α-胺基苯乙酮系光聚合起始劑，或/及具有下述通 式（III )所表示之基的氧化醯膦系光聚合起始劑所成群 所選出之1種以上之光聚合起始劑爲佳。 -13- 201116928 【化2】 —C=N-0-C-R2 (1) R1 0 —^C-έ-Ν, (ID if / —C一P (III) (式中’R1表示氫原子、苯基（可被碳數1~6之烷基、 苯基、或鹵素原子所取代）、碳數1〜20之烷基（可被1 個以上之羥基所取代、烷鏈中可具有1個以上之氧原子） 、碳數5〜8之環烷基、碳數2〜2 0之烷醯基或苯甲醯基（ 可被碳數1〜6之烷基或苯基所取代）；R2表示苯基（可 被碳數1〜6之烷基、苯基或鹵素原子所取代）、碳數 1~20之烷基（可被1個以上之羥基所取代、烷鏈中可具 有1個以上之氧原子）、碳數5〜8之環烷基、碳數2〜20 之烷醯基或苯甲醯基（可被碳數1〜6之烷基或苯基所取代 );R3及R4表示分別獨立之碳數1~12之烷基或芳基燒 基：R5及R6表示分別獨立之氫原子、碳數1〜6之烷基， 或2個鍵結所形成之環狀烷基醚基；R7及R8表示分別獨 立之碳數1〜10之直鏈狀或支鏈狀之烷基、環己基、環戊 基、芳基，或鹵素原子、烷基或烷氧基所取代之芳基；但 ，R7及R8之一者，可表示R-C( = 0)-基（其中，R爲碳數 1〜20之烴基）） 具有通式（I)所表示之基的肟酯系光聚合起始劑， -14- 201116928 較佳爲下述式（IV)所表示之2-(乙醯基氧代亞胺基甲 基）二苯并噻嘁喃（Thioxanthene) -9 -酮、通式（V)所 表示之化合物，及通式（VI )所表示之化合物等。—c—P (II) (III) (wherein R1 represents a hydrogen atom, a phenyl group (which may be substituted by a substituent having a carbon number of 1 to 6, a phenyl group, or a halogen atom), and a carbon number of 1 to 20 An alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkylene group having 2 to 20 carbon atoms or benzamidine a group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R2 represents a 'phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and a carbon number of 1 to 20 An alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the alkyl chain), a cycloalkyl group having a carbon number of 5 to 8, an alkylene group having a carbon number of 2 or a benzhydryl group. (Can be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group): R3 and R4 each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms; and R5 and R6 represent independently hydrogen atoms and carbon; a number of alkyl groups, or a cyclic alkyl ether group formed by two bonds; R7 and R8 represent a linear or branched alkyl group having a carbon number of 1 to 1 Å, a cyclohexyl group, and a cyclopentyl group. a aryl group substituted with a aryl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group; However, 'one of R7 and R8 can represent RC(=0)-group (wherein R is a hydrocarbon group having a carbon number of 1 to 20)) 201116928 When using these photopolymerization initiators, the resistance of the pigment having a high concentration In the agent, high resolution can be obtained. Further, in the photocurable resin composition of one embodiment of the present invention, it is preferred to further contain a thermosetting component. When the thermosetting component is contained, in addition to imparting heat resistance, the tensile elongation of the cured film, crack resistance, impact resistance, and the like can be increased. Further, in the photocurable resin composition of one embodiment of the present invention, a coloring agent may be further contained. When it contains a coloring agent, it is very suitable as a solder resist. Further, in one embodiment of the present invention, there is provided a dry film obtained by applying the photocurable resin composition onto a carrier film and drying it. When these dry films are used, the resist layer can be easily formed without applying a photocurable resin composition to the substrate. Further, in an embodiment of the present invention, a cured product obtained by photocuring the photocurable resin composition or the dry film by irradiation with an active energy ray can be used. When used on a printed circuit board or the like, the cured product can improve the resistance to cold and heat cycle characteristics without impairing the movement resistance. Furthermore, in one embodiment of the present invention, a pattern having a cured product obtained by photocuring the photocurable resin composition or a dry film thereof by active energy ray irradiation can be used as a printed circuit board. These printed circuit boards can improve the thermal cycle resistance and the like under the characteristics of non-destructive movement resistance. The photocurable resin composition of one embodiment of the present invention can suppress the hygroscopicity of -9-201116928, and the cured product can obtain good cold and heat cycle resistance under the non-destructive resistance characteristics. The present inventors have found that when a styrene group-containing compound and a maleic imide compound are used in combination in a photocurable resin composition, the cured product can achieve excellent electrical properties and mobility resistance, thereby completing the present invention. . When the crosslinking reaction is carried out by using a styrene group-containing compound and a maleic imine compound, the water absorbing property of the cured product obtained by the photocurable resin composition of the present embodiment can be suppressed. Hereinafter, the photocurable resin composition of the present embodiment will be described in detail. First, the carboxyl group-containing resin constituting the photocurable resin composition of the present embodiment can be used for the purpose of imparting alkali developability, and various known carboxyl group-containing resins having a carboxyl group in the molecule can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferred from the viewpoint of photocurability and development resistance. Further, the unsaturated double bond is preferably produced from acrylic acid or methacrylic acid or a derivative thereof. The carboxyl group-containing resin is preferably a compound (any of an oligomer and a polymer) listed below. (1) an unsaturated carboxylic acid such as (meth)acrylic acid and a compound containing an unsaturated group such as styrene, fluorene-methyl styrene, lower alkyl (meth) acrylate or isobutylene Carboxyl resin. (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; and carboxyl groups of dimethylolpropionic acid, dimethylolbutanoic acid, etc. Glycol compound-10-201116928 and polycarbonate-based polyalcohol, polyether-based polyalcohol, polyester-based polyalcohol, polyolefin-based polyalcohol, acrylic acid-based polyalcohol, bisphenol A-based alkylene oxide addition A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as a diol having a hydrazine group and an alcoholic hydroxy group. (3) Diisocyanate and bisphenol a type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin 'bisxylenol type epoxy resin, joint Photosensitive carboxyl group-containing amine obtained by polyaddition reaction of a (meth) acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound of a bifunctional epoxy resin such as a phenol type epoxy resin Carbamate resin. (4) In the synthesis of the resin of the above (2) or (3), the hydroxyalkyl (meth) acrylate or the like has a hydroxyl group and one or more (meth) propylene groups in the molecule. A terminal (meth) propylene-based photosensitive carboxyl group-containing urethane resin. (5) In the synthesis of the resin of the above (2) or (3), a molar reactant such as isophorone diisocyanate or pentaerythritol triacrylate has one or more isocyanate groups in the molecule (one or more) ( A terminally (meth)acrylylated photosensitive carboxyl group-containing urethane resin other than a methyl)propenyl compound. (6) A polyfunctional (solid) epoxy resin having a bifunctional or higher functional group described later is reacted with (meth)acrylic acid, and a photosensitive carboxyl group-containing resin of a dibasic acid anhydride is added to the hydroxyl group present in the side chain. (7) The hydroxyl group of the bifunctional (solid) epoxy resin described later is further reacted with (meth)acrylic acid obtained by epoxidizing epichlorohydrin, and the hydroxyl group formed by -11 - 201116928 is added with a dibasic acid anhydride. Photosensitive carboxyl group-containing resin. (8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional propylene oxide resin with a dicarboxylic acid to form a hydroxyl group of a first stage to which a dibasic acid anhydride is added. (9) a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and then reacting with a monocarboxylic acid containing an unsaturated group, and the obtained reaction product is further A carboxyl group-containing photosensitive resin obtained by reacting with a polybasic acid anhydride. (10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and then reacting with a monocarboxylic acid containing an unsaturated group, and the obtained reaction product A carboxyl group-containing photosensitive resin obtained by reacting with a polybasic acid anhydride. (11) A photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) propylene groups in one molecule to the resin of the above (1) to (10). Further, the term "(meth)acrylate" as used herein is collectively referred to as acrylate, methacrylate, and the like, and the following other similar expressions are also the same. These carboxyl group-containing resins can be developed in a dilute aqueous alkali solution because the side chain of the main chain/polymer has a plurality of free carboxyl groups. The acid value of the above carboxyl group-containing resin is preferably from 40 to 200 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkali development is not easy, and when it exceeds 200 mgKOH/g, the exposed portion is continuously dissolved by the developer, so that the line is more than necessary and narrow. In some cases, the exposed portion and the unexposed portion are indistinguishable from each other, and are dissolved and peeled off by the visible liquid of the -12-201116928, and the normal resist pattern is not easily drawn. More preferably, it is 45 to 120 mgKOH/g. Further, the weight average molecular weight ' of the carboxyl group-containing resin' varies depending on the resin skeleton, and is generally preferably 2,000 to 150,000. When the weight average molecular weight is less than 2,000, the curing property and the like are lowered, and the moisture resistance of the coating film after exposure is deteriorated, and film reduction occurs during development, and the resolution is largely deteriorated. Further, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, resulting in deterioration of storage stability. More preferably, it is 5,000 to 100,000°. The amount of the carboxyl group-containing resin to be added is preferably from 20 to 60% by mass based on the total composition. When the amount added is less than 20% by mass, the strength of the film is lowered. Further, in the case of 60% by mass or more, since the viscosity of the composition is too high, the coating property and the like are lowered. More preferably 30 to 50% by mass. The carboxyl group-containing resin is not limited to use only the listed resins, and it can be used in a mixture of one type or a plurality of types. The photopolymerization initiator is an α-aminophenylbenzene having an oxime ester photopolymerization initiator having a group represented by the following formula (I) and having a group represented by the following formula (II) One or more photopolymerization initiators selected from the group consisting of a ketone photopolymerization initiator or a phosphine oxide-based photopolymerization initiator having a group represented by the following formula (III) . -13- 201116928 [Chemical 2] - C = N-0 - C - R2 (1) R1 0 - ^ C - έ - Ν, (ID if / - C - P (III) (wherein R1 represents a hydrogen atom a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) or an alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups and may have 1 in the alkyl chain) More than one oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R2 represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, and may have 1 in the alkyl chain) More than one oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R3 And R4 represents an independently substituted alkyl group having 1 to 12 carbon atoms or an aryl group: R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkane formed by bonding two bonds. Alkyl groups; R7 and R8 each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, An aryl group substituted with a pentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group; however, one of R7 and R8 may represent an RC(=0)- group (wherein R is a carbon number of 1 to 20) The hydrocarbyl group)) an oxime ester photopolymerization initiator having a group represented by the formula (I), -14-201116928 is preferably 2-(ethenyloxyimide) represented by the following formula (IV) Thiomethylanthene -9-ketone, a compound represented by the formula (V), a compound represented by the formula (VI), and the like.

(IV)(IV)

(式中，R9表示氫原子、鹵素原子、碳數1〜12之院基、 環戊基、環己基、苯基、苄基、苯甲醯基、碳數2~12之 院酿基、碳數2〜12之院氧基幾基（構成院氧基之院基之 碳數爲2以上之情形’烷基可被丨個以上之羥基所取代 院鏈中可具有1個以上之氧原子）’或苯氧基擬基· | 、R12表示分別獨立之苯基（可被碳數丨〜6之院基、％ 或鹵素原子所取代）、碳數丨〜冗之烷基（可被丨個以 之羥基所取代、烷鏈中可具有1個以上之氧原 、上 5~8之環烷基、碳數2〜20之烷醯基或苯甲醯基（ 數1〜6之烷基或苯基所取代）；Rll表示氫原子、苯基咴 可被碳數1〜6之烷基、苯基或鹵素原子所 （ 、碳數 -15- 201116928 1〜20之烷基（可被1個以上之羥基所取代、烷鏈中可具 有1個以上之氧原子）、碳數5-8之環烷基、碳數2〜20 之烷醯基或苯甲醯基（可被碳數1〜6之烷基或苯基所取代 【化5】 R16 R15(wherein R9 represents a hydrogen atom, a halogen atom, a group having a carbon number of 1 to 12, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamidine group, a carbon number of 2 to 12, and a carbon The number of the oxy group of 2 to 12 (the number of carbon atoms forming the courtyard of the oxy group is 2 or more) The alkyl group may have more than one oxygen atom in the chain substituted by more than one hydroxy group. 'or phenoxy-based group ·, R12 represents a separate phenyl group (which can be substituted by a carbon number 丨~6, a base or a halogen atom), a carbon number 冗~ a redundant alkyl group (can be 丨Substituted by a hydroxyl group, the alkyl chain may have one or more oxygen atoms, a cycloalkyl group of 5 to 8 carbon atoms, an alkanoyl group having a carbon number of 2 to 20 or an alkylidene group (alkyl group of 1 to 6 or Phenyl substituted); Rll represents a hydrogen atom, phenyl fluorene can be alkyl having 1 to 6 carbon atoms, phenyl or halogen atom (C, -15-201116928 1~20 alkyl group (can be 1 The above hydroxyl group may be substituted, the alkyl chain may have one or more oxygen atoms), the carbon number is 5-8, the alkyl group having 2 to 20 carbon atoms or the benzamidine group (the number of carbon atoms may be 1). 6 alkyl or phenyl substituted 5] R16 R15

(式中’ R13、R14及R19表示分別獨立之碳數U2之烷 基；R15、R16、R17及Ris表示分別獨立之氫原子或碳數 1〜6之烷基；Μ表示0、S或NH; X及y表示分別獨立之 〇〜5之整數）。 肟酯系光聚合起始劑中，又以上述通式（IV )所表示 之2_(乙釀基氧代亞|女基甲基）一苯并唾峨喃（ Thioxanthene ) -9-酮’及式（V)所表示之化合物爲更佳 。市售品例如CGI-3 2 5、IRGACURE (登記商標）OXEO 1 、IRGACURE OXE02 (皆爲汽巴-日本公司製）、Ν·1919 (ADEKA公司製）等。該些肟酯系光聚合起始劑，可單 獨使用或將2種以上組合使用。 具有通式（II)所表示之基的胺基苯乙酮系光聚 合起始劑，例如2-甲基-1-〔 4-(甲基硫基）苯基〕_2_嗎 啉基丙酮-1、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基）· -16- 201116928 丁烷-1-酮、2-(二甲基胺基）-2-〔 （4-甲基苯基）甲基 〕-l-〔 4-(4-嗎啉基）苯基〕-1-丁酮、Ν,Ν-二甲基胺基 苯乙酮等。市售品例如 IRGACURE 907 ' IRGACURE 369 、11^八(：01^ 379 (皆爲汽巴-日本公司製）等。 具有通式（III )所表示之基的氧化醯膦系光聚合起始 劑，例如 2,4,6 -三甲基苯甲醯基二苯基膦氧化物、雙 (2,4,6-三甲基苯甲醯基）_苯基膦氧化物、雙（2,6-二甲氧基 苯甲醯基）-2,4,4-三甲基-戊基膦氧化物等。市售品例如 LUCIRIN TPO ( BASF 公司製）、IRGACURE 819 (汽巴-曰本公司製）等。 該些光聚合起始劑之添加量，相對於含羧基之樹脂 100質量份，以0.01〜30質量份爲佳。添加量未達0_01質 量份時，會造成銅上之光硬化性不足，塗膜產生剝離、耐 藥性等塗膜特性降低。另外，超過3 0質量份時，因光聚 合起始劑於焊料阻劑塗膜表面會產生劇烈光吸收，而會有 深部硬化性降低之傾向。更佳爲〇·5〜15質量份。 又，具有通式（I)所表示之基的肟酯系光聚合起始 劑之情形，其添加量相對於含羧基之樹脂1 〇〇質量份，以 0 · 0 1〜2 0質量份爲佳。少於〇 · 〇 1質量份之情形，於銅上之 光硬化性會不足，除塗膜會產生剝離的同時，也會降低耐 藥性等之塗膜特性。又’多於2〇質量份之情形，因光聚 合起始劑於焊料阻劑塗膜表面會產生劇烈光吸收，而會有 深部硬化性降低之傾向。更佳爲〇.〇1〜5質量份。 本實施形態之光硬化性樹脂組成物中，較適合使用之 -17- 201116928 光聚合起始劑、光起始助劑及增感劑，其他例如苯偶姻化 合物、苯乙酮化合物、蒽醌化合物、噻頓酮化合物、縮酮 化合物、二苯甲酮化合物、氧葱酮化合物，及三級胺化合 物等。 苯偶姻化合物，例如，苯偶姻、苯偶姻甲基醚、苯偶 姻乙基醚、苯偶姻異丙基醚。 苯乙酮化合物，例如，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、1，1-二氯苯乙酮。 蒽醌化合物，例如，2-甲基蒽醌、2-乙基蒽醌、2-t-丁基蒽醌、1-氯蒽醌。 噻頓酮化合物，例如，2,4 -二甲基噻頓酮、2,4 -二乙 基噻頓酮、2-氯噻頓酮、2，4-二異丙基噻頓酮。 縮酮化合物，例如，苯乙酮二甲基縮酮、苄基二甲基 縮酮。 二苯甲酮化合物，例如，二苯甲酮、4 -苯甲醯基二苯 基硫化物、4-苯甲醯基-4’-甲基二苯基硫化物、4-苯甲醯 基-4’-乙基二苯基硫化物、4-苯甲醯基-4’-丙基二苯基硫 化物。 三級胺化合物，例如乙醇胺化合物、具有二烷基胺基 苯構造之化合物，例如，4,4’-二甲基胺基二苯甲酮（日本 曹達公司製NISSOCURE MABP) 、4,4’-二乙基胺基二苯 甲酮（保土之谷化學公司製EAB )等之二烷基胺基二苯甲 酮；7-(二乙基胺基）-4-甲基-2H-1·苯倂吡喃-2-酮（7-(二乙基胺基）-4-甲基香豆素）等之含二烷基胺基之香 -18- 201116928 豆素化合物；4·二甲基胺基苯甲酸乙酯（日本化藥公司製 KAYACURE (登記商標）ΕΡΑ ) 、2-二甲基胺基苯甲酸乙 酯（國際微生物-科技公司製Quantacure DMB ) ' 4-二甲 基胺基苯甲酸（η-丁氧基）乙基（國際微生物-科技公司 製Quantacure ΒΕΑ) 、ρ-二甲基胺基苯甲酸異戊基乙基酯 (日本化藥公司製 KAYACURE DMBI ) 、4-二甲基胺基 苯甲酸2-乙基己基（Van Dyk公司製Esolol 5 07 )等二院 基胺基苯甲酸酯等。 特別是以具有二烷基胺基苯構造之化合物爲佳，其中 又以二烷基胺基二苯甲酮化合物、最大吸收波長爲 3 5 0〜4 10 nm之含有二烷基胺基之香豆素化合物爲特佳。二 烷基胺基二苯甲酮化合物，以4,4’-二乙基胺基二苯甲酮 具有較低毒性而爲較佳。最大吸收波長爲3 50~410nm之 含有二烷基胺基之香豆素化合物，因最大吸收波長位於紫 外線區域，故可作爲著色較少、無色透明之感光性組成物 ，於使用著色顏料時，可反應著色顏料本身之顏色而可提 供作爲著色焊料阻劑膜。特別是7-(二乙基胺基）-4-甲 基-2H-1-苯倂吡喃-2-酮對於波長400〜410nm之雷射光可 顯示出優良之增感效果，而爲較佳。 其中又以噻頓酮化合物及三級胺化合物爲佳。特別是 ，含有噻頓酮化合物之部分，就深部硬化性之觀點爲較佳 ，其中又以2,4-二甲基噻頓酮、2,4-二乙基噻頓酮、2-氯 噻頓酮、2,4-二異丙基噻頓酮等之噻頓酮化合物爲佳。 該些噻頓酮化合物之添加量，相對於含羧基之樹脂 -19- 201116928 1 〇〇質量份，以20質量份以下之比例爲佳。添加量超過 20質量份時，會造成厚膜硬化性降低，而與製品之費用 提升有所關連。更佳爲1 〇質量份以下。 又，三級胺化合物之添加量，相對於含羧基之樹脂 100質量份，以0.1〜20質量份之比例爲佳。添加量未達 0.1質量份時，會有不能得到充分增感效果之傾向。另外 ，超過20質量份時，因三級胺化合物所造成之乾燥焊料 阻劑塗膜的表面具有劇烈之光吸收，而會有深部硬化性降 低之傾向。更佳爲0.1〜1 0質量份。該些光聚合起始劑、 光起始助劑及增感劑，可單獨或以2種類以上之混合物方 式使用。 該些光聚合起始劑、光起始助劑，及增感劑之總量， 相對於含羧基之樹脂100質量份，以0.01〜35質量份爲佳 。超過35質量份時，會因該些光吸收而造成深部硬化性 降低之傾向。另外，未達0 · 0 1時，於銅上之光硬化性不 足，除造成塗膜剝離的同時，也會降低耐藥性等塗膜特性 。更佳爲0.0 1〜20質量份。特別是本實施形態中，較適合 使用之起始劑，於使用芳香族馬來醯亞胺之情形中，因芳 香族馬來醯亞胺本身具有較大之紫外線吸收，故以肟酯爲 特佳。 本實施形態之光硬化性樹脂組成物中，爲提高感度所 使用之鏈移轉劑，可使用公知之N苯基甘胺酸類、苯氧 基乙酸類、硫代苯氧基乙酸類、氫硫基噻唑等。 鏈移轉劑’例如，氫硫基琥珀酸、氫硫基乙酸、氫硫 -20- 201116928 基丙酸、蛋胺酸、半胱胺酸、硫代水楊酸及其衍生物等。 該些鏈移轉劑，可單獨或倂用2種以上之成份。 本實施形態所使用之含苯乙烯基之化合物，爲賦予與 馬來醯亞胺化合物進行硬化反應的而得之硬化物的耐熱性 所使用者。該些含苯乙烯基之化合物，可依一般方法合成 者亦可，其可使用市售者。含苯乙烯基之化合物之合成方 法之例如單•多官能酚類與鹵化甲基苯乙烯之反應、具有 可與環氧基反應而得之官能基（例如，胺基、羥基、羧基 等）的單•多官能化合物與乙烯基苄基縮水甘油基醚之反 應等。 列舉含苯乙烯基之化合物之具體例如，乙烯基萘、二 乙烯基萘、二乙烯基聯苯、聚酚與乙烯基苄基鹵化物反應 所得之聚乙烯基苄基醚化合物、末端苯乙烯之寡伸苯基醚 化合物（三菱氣體化學公司製 〇PE-2St )、雙酚A與鹵 化甲基苯乙烯之縮合反應所得之化合物（昭和高分子公司 製 RIPOKIN (登記商標）BPV-1X)等。該些含苯乙烯 基之化合物可單獨使用1種或將2種以上組合使用。 該些含苯乙烯基之化合物的添加量，相對於含羧基之 樹脂100質量份，以1〜50質量份爲佳。添加量未達1質 量份時，將無法得到充分之耐熱性。另外，超過5 0質量 份時，因組成物之顯影性降低而會產生顯影殘渣。更佳爲 1〜25質量份。 本實施形態所使用之馬來醯亞胺化合物，例如爲促進 與苯乙烯基化合物之硬化反應及/或光硬化以提高耐熱性 -21 - 201116928 等目的使用。該些馬來醯亞胺化合物，例如多官能脂肪族 /脂環族馬來醯亞胺、多官能芳香族馬來醯亞胺等。 多官能脂肪族/脂環族馬來醯亞胺，例如，Ν,Ν’ ·伸 甲基雙馬來醯亞胺、Ν，Ν’ -乙烯雙馬來醯亞胺、三（羥基 乙基）異氰脲酸酯與脂肪族/脂環族馬來醯亞胺羧酸經脫水 酯化所得之具有異氰脲酸酯骨架的馬來醯亞胺酯化合物； 三（胺基甲酸酯己基）異氛脲酸酯與脂肪族/脂環族馬來醯亞 胺醇經胺基甲酸酯化所得之具有異氰脲酸酯骨架的馬來醯 亞胺胺基甲酸酯化合物等具有異三聚氰胺骨架之聚馬來醯 亞胺類；異佛爾酮雙胺基甲酸酯雙（Ν-乙基馬來醯亞胺） 、三乙二醇雙（馬來醯亞胺乙基碳酸酯）、脂肪族/脂環族馬 來醯亞胺羧酸與各種脂肪族/脂環族聚醇經脫水酯化，或 脂肪族/脂環族馬來醯亞胺羧酸酯與各種脂肪族/脂環族聚 醇經酯交換反應所得之脂肪族/脂環族聚馬來醯亞胺酯化 合物類；脂肪族/脂環族馬來醯亞胺羧酸與各種脂肪族/脂 環族聚環氧烷經醚開環反應所得之脂肪族/脂環族聚馬來 醯亞胺酯化合物類；脂肪族/脂環族馬來醯亞胺醇與各種 脂肪族/脂環族聚異氰酸酯經胺基甲酸酯化反應所得之脂 肪族/脂環族聚馬來醯亞胺胺基甲酸酯化合物類等。 多官能芳香族馬來醯亞胺，例如馬來醯亞胺羧酸與各 種芳香族聚醇經脫水酯化，或馬來醯亞胺羧酸酯與各種芳 香族聚醇經酯交換反應所得之芳香族聚馬來醯亞胺酯化合 物類；馬來醯亞胺羧酸與各種芳香族聚環氧烷經醚開環反 應所得之芳香族聚馬來醯亞胺酯化合物類；馬來醯亞胺醇 -22- 201116928 與各種芳香族聚異氰酸酯經胺基甲酸酯化反應所得之芳香 族聚馬來醯亞胺胺基甲酸酯化合物類等芳香族多官能馬來 醯亞胺類等。 該些多官能芳香族馬來醯亞胺，例如，N，N’- ( 4,4’-二苯基甲烷）雙馬來醯亞胺、Ν,Ν’-2,4-甲伸苯基雙馬來醯 亞胺、>^川’-2,6-甲伸苯基雙馬來醯亞胺、1-甲基-2,4-雙馬 來醯亞胺苯、伸苯基雙馬來醯亞胺、Ν，Ν’-ρ-伸苯 基雙馬來醯亞胺、N，N’-m-甲伸苯基雙馬來醯亞胺、Ν,Ν’-4,4’-聯苯基雙馬來醯亞胺、Ν，Ν’-4,4’-〔 3,3’-二甲基-聯苯 基〕雙馬來醯亞胺、1>^’-4,4’-〔3,3’-二甲基二苯基甲烷 〕雙馬來醯亞胺、1：^-4,4’-〔3,3’-二乙基二苯基甲烷〕 雙馬來醯亞胺、Ν,Ν’-4,4’-二苯基甲烷雙馬來醯亞胺、 氺『-4,4’-二苯基丙烷雙馬來醯亞胺、：^，；^-4,4’-二苯基醚 雙馬來醯亞胺、Ν,Ν’-3,3’-二苯基颯雙馬來醯亞胺、Ν,Ν’-4,4’-二苯基颯雙馬來醯亞胺、2,2-雙〔4- (4-馬來醯亞胺 苯氧基）苯基〕丙烷、2,2-雙〔3-t-丁基-4·(4-馬來醯亞 胺苯氧基）苯基〕丙烷、2,2-雙〔3-s-丁基-4-(4-馬來醯 亞胺苯氧基）苯基〕丙烷、1，1-雙〔4-(4-馬來醯亞胺苯 氧基）苯基〕癸烷、1，1-雙〔2-甲基-4- (4 -馬來醯亞胺苯 氧基）-5-t-丁基苯基〕-2 -甲基丙烷、4,4’-環亞己基-雙〔 1-(4-馬來醯亞胺苯氧基）-2-(1,1-二甲基乙基）苯〕、 4,4’ -伸甲基-雙〔1- ( 4-馬來醯亞胺苯氧基）-2,6_雙（ 1,1-二甲基乙基）苯〕、4,4’-伸甲基-雙〔1- ( 4-馬來醯亞 胺苯氧基）-2,6 -二-s-丁基苯〕、4,4’-環亞己基-雙〔丨_( -23- 201116928 4·馬來醯亞胺苯氧基）-2-環己基苯、4,4’-伸甲基雙〔1-(馬來醯亞胺苯氧基）-2-壬基苯〕、4,4’-(1-甲基亞乙 基）-雙〔1-(馬來醯亞胺苯氧基）-2,6-雙（1，1-二甲基乙 基）苯〕、4,4’-(2-乙基亞己基）-雙〔1-(馬來醢亞胺 苯氧基）·苯〕、4,4’-(1-甲基庚烯（heptylidene ))-雙 〔1-(馬來醯亞胺苯氧基）-苯〕、4,4’·環亞己基-雙〔1-(馬來醯亞胺苯氧基）-3-甲基苯〕、2,2-雙〔4-(4-馬來 醯亞胺苯氧基）苯基〕六氟丙烷、2,2-雙〔3-甲基-4-(4-馬來醯亞胺苯氧基）苯基〕丙烷、2，2-雙〔3-甲基-4-( 4-馬來醯亞胺苯氧基）苯基〕六氟丙烷、2,2-雙〔3,5-二甲 基-4-(4-馬來醯亞胺苯氧基）苯基〕丙.院、2,2-雙〔3,5-二甲基_4-(4-馬來醯亞胺苯氧基）苯基〕六氟丙烷、2,2-雙〔3-乙基-4-(4-馬來醯亞胺苯氧基）苯基〕丙烷、2,2-雙〔3-乙基-4-(4-馬來醯亞胺苯氧基）苯基〕六氟丙烷、 雙〔3-甲基- (4-馬來醯亞胺苯氧基）苯基〕甲烷、雙〔 3,5-二甲基- (4-馬來醯亞胺苯氧基）苯基〕甲烷、雙〔3-乙基_(4_馬來醯亞胺苯氧基）苯基〕甲烷、3,8-雙〔4-( 4-馬來醯亞胺苯氧基）苯基〕-三環〔5.2.1 ·02’6〕癸烷、 4,8-雙〔4- ( 4-馬來醯亞胺苯氧基）苯基〕-三環〔 5.2.1.02,6〕癸烷、3,9 -雙〔4- (4 -馬來醯亞胺苯氧基）苯 基〕-三環〔5.2.1 ·〇2’6〕癸烷、4,9-雙〔4- ( 4-馬來醯亞胺 苯氧基）苯基〕-三環〔5.2.1.02’6〕癸烷、1，8-雙〔4-(4-馬來醯亞胺苯氧基）苯基〕薄荷院、雙〔3 -甲基- 4-( 4-馬來醯亞胺苯氧基）苯基〕薄荷烷' 1,8-雙〔3，5-二甲 -24- 201116928 基-4- ( 4-馬來醯亞胺苯氧基）苯基〕薄荷烷等。 該些雙馬來醯亞胺衍生物可依一般方法予以合成，或 使用市售品亦可。特別是雙馬來醯亞胺衍生物之中，就不 致對環境造成負擔之觀點，以使用分子內不含鹵素原子者 爲佳。該些可單獨使用1種或將2種以上組合使用。 該些馬來醯亞胺化合物之添加量，相對於含羧基之樹 脂1〇〇質量份，以1〜50質量份爲佳。添加量未達1質量 份時，將無法得到充分之耐熱性。另外，超過5 0質量份 時，組成物之顯影性降低而生成顯影殘渣。更佳爲1〜2 5 質量份。 本實施形態之光硬化性樹脂組成物中，就與乙烯基、 馬來醯亞胺基之加成反應與交聯爲目的時，可添加氫硫基 化合物。添加氫硫基化合物時，可防止乙烯基之氧化所造 成之塗膜特性降低等。又，多官能氫硫基化合物之情形， 因可得到交聯，故可提高PCT耐性、HAST耐性等特性。 此外，該些氫硫基化合物因具有作爲鏈移轉劑，及/或密 著提供劑之作用，故可同時得到提高感度、提高密著性等 效果。 該些氫硫基化合物，例如，氫硫基乙醇、氫硫基丙醇 、氫硫基丁醇、氫硫基丙烷二醇、氫硫基丁烷二醇、羥基 苯硫醇及其衍生物；1-丁烷硫醇、丁基-3-氫硫基丙酸酯 、甲基-3-氫硫基丙酸酯、2,2-(乙烯二氧代）二乙烷硫醇 、乙垸硫醇、4 -甲基苯硫醇、十一院基硫醇、丙院硫醇、 丁烷硫醇、戊烷硫醇、1 -辛烷硫醇、環戊烷硫醇、環己烷 -25- 201116928 硫醇、硫代甘油、4,4-硫代雙苯硫醇等。 該些之市售品，例如，BMPA、MPM、EHMP、NOMP 、MBMP、STMP、TMMP、PEMP、DPMP ·與 TEMPIC ( 皆爲堺化學工業公司製）、CURRANTS MT (登記商標）-PEI、CURRANTS MT-BD1，與 CURRANTS (登記商標 )-NR1 (皆爲昭和電工公司製）等。 具有雜環之氫硫基化合物，例如，氫硫基-4-丁內酯 (別名：2 -氫硫基-4 -丁內醋（butanolide) ) 、2 -氫硫基- 4-甲基-4-丁內酯、2-氫硫基-4-乙基-4-丁內酯、2-氫硫基-4-丁基硫內酯、2-氫硫基-4·丁內醯胺、N-甲氧基-2-氫硫 基-4-丁內醯胺、N-乙氧基-2-氫硫基-4-丁內醯胺、N-甲 基-2-氫硫基-4_丁內醯胺、N-乙基-2-氫硫基-4-丁內醯胺 、N-(2-甲氧基）乙基-2-氫硫基-4-丁內醯胺、N-(2-乙 氧基）乙基-2 -氫硫基-4 -丁內酿胺、2 -氣硫基-5-戊內醋、 2-氫硫基-5·戊內醯胺、N-甲基-2-氫硫基-5-戊內醯胺、N-乙基-2-氫硫基-5-戊內醯胺、N- ( 2-甲氧基）乙基-2-氫硫 基-5-戊內醯胺、N-( 2-乙氧基）乙基-2-氫硫基-5-戊內醯 胺、2-氫硫基苯倂咪唑、2-氫硫基苯倂鸣唑、2-氫硫基苯 倂噻唑（川口化學工業公司製 AKUSERU Μ ) 、2-氫硫 基-5-甲基硫基-硫雜二唑、3-氫硫基-4-甲基-4Η-1，2,4-三 唑、5-甲基·1，3,4-硫雜二唑-2-硫醇、1-苯基-5-氫硫基-1Η-四哩、2-氫硫基-6·己內醯胺、2,4,6-三氫硫基-s-三哄（ 三協化成公司製ZISNETF)、2-二丁基胺基-4,6-二氫硫 基-s-三哄（三協化成公司製 ZISNET (登記商標）DB、 -26- 201116928 ZISNET AF)等。該些之氫硫基化合物可單獨或將2種以 上合倂使用。 該些氫硫基化合物之添加量，相對於含羧基之樹脂 1〇〇質量份，以〇.〇1〜2 0質量份爲佳。添加量未達〇.〇1質 量份時，因氫硫基化合物未能發發揮硬化效果，故未能觀 察到耐熱性之提高。另外，超過2 0質量份時，因產生顯 影殘渣，故爲不佳。更佳爲〇 . 1〜5質量份。 本實施形態之光硬化性樹脂組成物中，爲賦予耐熱性 等目的，可加入熱硬化成份。該些熱硬化成份例如可使用 三聚氰胺樹脂、苯倂胍樹脂、三聚氰胺衍生物、苯倂胍衍 生物等之胺基樹脂、環碳酸酯化合物等之公知熱硬化性樹 脂。特佳者爲分子中具有2個以上之環狀醚基及/或環狀 硫醚基（以下，簡稱爲環狀（硫）醚基）之熱硬化成份。 該些分子中具有複數之環狀（硫）醚基之熱硬化成份 爲，分子中具有2個以上含有3、4或5員環之環狀（硫 )醚基之任一者或2種類之基的化合物，例如，分子內具 有複數環氧基之化合物，即多官能環氧化合物、分子內具 有複數之環氧丙烷基之化合物，即多官能環氧丙烷化合物 、分子內具有複數之硫醚基之化合物、即環硫化物樹脂等 〇 胺基樹脂，例如，羥甲基三聚氰胺化合物、羥甲基苯 倂胍化合物、羥甲基乙炔脲化合物與羥甲基尿素化合物等 。此外，烷氧基甲基化三聚氰胺化合物、烷氧基甲基化苯 併胍化合物、烷氧基甲基化乙炔脲化合物與烷氧基甲基化 -27- 201116928 尿素化合物，可經由各個羥甲基三聚氰胺化合物、羥甲基 苯倂胍化合物、羥甲基乙炔脲化合物與羥甲基尿素化合物 之羥甲基基變換爲烷氧基甲基之方式而得。該些烷氧基甲 基之種類並未有特別限定，例如可爲，甲氧基甲基、乙氧 基甲基、丙氧基甲基、丁氧基甲基等。特別是對人體或環 境爲和善之甲醛水濃度爲0.2%以下之三聚氰胺衍生物爲 佳。 該些之市售品，例如，SAIMEL (登記商標）3 00、 同 301 、同 303 ' 同 370 、同 325 、同 327 、同 701 、同 266、问 267、同 238、同 1141、同 272、同 202、同 1156 、同 1158、同 1123、同 1170、同 1 174、同 UFR65、同 3 00 (皆爲三井氰酸酯公司製）、NIKARAKU (登記商標 )Mx-7 5 0、同 Mx-03 2、同 Mx-270、同 Mx-2 80、同 Mx-290、同 Mx-706、同 Mx-7 08、同 Mx-40、同 Mx-31、同 Ms-11、同 Mw-30、同 Mw-30HM、同 Mw-3 90、同 Mw-100LM、同 Mw-750LM、（皆爲三和化學公司製）等。該 些熱硬化成份可單獨或將2種以上合倂使用。 環碳酸酯化合物，只要環狀化合物且具有碳酸酯鍵結 者，並未有特別限定。例如，具有多官能構造之伸烷基碳 酸酯化合物等。 多官能環氧化合物，例如，jER (登記商標）82 8 ' jER834、jERlOOl、jER1 004 (皆爲三菱化學公司製）、 EPICLON.(登記商標）840、EPICLON. 8 5 0、EPICLON. 1050、EPICLON. 2055 (皆爲 DIC 公司製）、EPOTOT ( -28- 201116928 登記商標）YD-011、YD-013、YD-127、YD-128(皆爲新 日鐵化學公司製）、D.E.R.317、D.E.R.331、D.E.R.661、 D.E.R.664 (皆爲陶氏學公司製）、ARALDITE 607 1、 ARALDITE 6084 ' ARALDITE GY250 ' ARALDITE GY260 (皆爲汽巴-日本公司）、SUMI環氧基£8八-011、丑3八· 014、ELA-115、ELA-128 (皆爲住友化學工業公司製）、 A.E.R.330 、 A.E.R.331 、 A.E.R.661 、 A.E.R.664 等（皆爲 旭化成工業公司製）之雙酚A型環氧樹脂；jERYL903 ( 三菱化學公司製）、EPICLON. 152、EPICLON. 165(皆 爲 DIC 公司製）、EPOTOT YDB-400、YDB-500 (皆爲新 日鐵化學公司製）、D.E.R.542 (陶氏學公司製）、 ARALDITE 8011(汽巴-日本公司製）、SUMI 環氧基 ESB-400、ESB-700 (皆爲住友化學工業公司製）、 A_E.R.711、A.E.R.714(皆爲旭化成工業公司製）等之溴 化環氧樹脂；jER152、jER154 (皆爲三菱化學公司製）、 D.E.N.431、D.E.N.438 (皆爲陶氏學公司製）、EPICLON. N- 73 0、EPICLON. N-770、E PI C L Ο N · N - 8 6 5 (皆爲 DIC 公 司製）、EPOTOT YDCN-701、YDCN-704 (皆爲新日鐵化 學公司製）、ARALDITE ECN 1 23 5、ARALDITE ECN1273 、ARALDITE ECN1299、 ARALDITE XPY307(皆爲汽巴-日本公司製）、ΕΡΡΝ-201、EOCN (登記商標）- 1 025、 EOCN-1020、EOCN-104S、RE-306 (皆爲日本化藥公司製 )、SUMI 環氧基 ESCN-195X、E S CN - 2 2 0 (皆爲住友化 學工業公司製）、A.E.R.ECN-235、ECN-299 (皆爲旭化 -29- 201116928 成工業公司製）等之酚醛清漆型環氧樹脂；EPICLON. 83 0 ( DIC公司製）、jER807 (三菱化學公司製）、 EPOTOT YDF-170、YDF-175、YDF-2004、（皆爲新日鐵 化學公司製）YSLV-80XY (新日鐵化學公司製）、 ARALDITE XPY306 (汽巴-日本公司製）等之雙酚F型環 氧樹月旨；EPOTOT ST-2004、ST-2007、ST-3 000 (皆爲新 日鐵化學公司製）等之氫化雙酚A型環氧樹脂；jER6 04 (三菱化學公司製）、EPOTOT YH-434(新日鐵化學公司 製）、ARALDITE MY720 (汽巴-日本公司製）、SUMI 環氧基ELM· 120 (住友化學工業公司製）等之縮水甘油基 胺型環氧樹脂；ARALDITE CY-350 (汽巴-日本公司製） 等之乙內醯脲型環氧樹脂；SEROKISAIDO (登記商標） 202 1 ( DAISEL 化學工業公司製）、ARALDITE CY175、 CY1 79 (皆爲汽巴-日本公司製）等之脂環式環氧樹脂； YL-93 3 (三菱化學公司製）、T.E.N.、EPPN (登記商標 )-501、EPPN-502 (皆爲日本化藥公司製）等之三羥苯基 甲烷型環氧樹脂；YL-6056、YX-4000、YL-6121 (皆爲三 菱化學公司製）等之雙二甲酚型或聯苯酚型環氧樹脂或該 些之混合物；EBPS-200(日本化藥公司製）、EPX-30 ( ADEKA公司製）、EXA-1514(DIC公司製）等之雙酚 S 型環氧樹脂；jER157S (三菱化學公司製）等之雙酚A酚 醛清漆型環氧樹脂；jERYL-931 (三菱化學公司製）、 ARALDITE 163(汽巴-日本公司製）等之四苯基酚醇（ PHENYLOL )型環氧樹脂；ARALDITE PT810 (汽巴-日本 -30- 201116928 公司製）、TEPIC (日產化學工業公司製）等之雜環式環 氧樹脂；BLEMMER (登記商標）D GT (曰油公司製）等 之二縮水甘油基苯甲酸酯樹脂；Ζχ-] 063 (新日鐵化學公 司製）等之四縮水甘油基二甲酚基乙烷樹脂；ESN-190、 ESN-360 (皆爲新日鐵化學公司製）、；^-4032、£\八-4750、EXA-4700 (DIC公司製）等之含萘基之環氧樹脂 ;HP-7200、HP-7200H(DIC公司製）等之具有二環戊二 烯骨架之環氧樹脂；CP-50S、CP-50M (日油公司製）等 之縮水甘油基甲基丙烯酸酯共聚系環氧樹脂；此外，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；環氧基改質之聚丁二烯橡膠衍生物（例如，DAISEL 化學工業公司製PB-3600等）、CTBN改質環氧樹脂（例 如，新日鐵化學公司製之YR-102、YR-450等）等，但並 不僅限定於此。該些環氧樹脂，可單獨或將2種以上組合 使用。其中，特別是以酚醛清漆型環氧樹脂、雜環式環氧 樹脂、雙酚A型環氧樹脂或該些之混合物爲佳。 多官能環氧丙烷化合物，例如，雙〔（3-甲基-3-環 氧丙烷基甲氧基）甲基〕醚、雙〔（3-乙基-3-環氧丙烷 基甲氧基）甲基〕醚、1,4-雙〔（3-甲基-3-環氧丙烷基甲 氧基）甲基〕苯、1,4-雙〔（3-乙基-3-環氧丙烷基甲氧基 )甲基〕苯、（3 -甲基-3 -環氧丙院基）甲基丙稀酸醋、 (3 -乙基-3-環氧丙烷基）甲基丙烯酸酯、（3 -甲基-3-環 氧丙烷基）甲基甲基丙烯酸酯、（3 -乙基-3 -環氧丙烷基 )甲基甲基丙烯酸酯或該些之寡聚物或共聚物等之多官能 -31 - 201116928 環氧丙院類’其他例如’環氧丙烷醇與酚醛清漆樹脂、聚 (P-羥基苯乙烯）、CARDO型雙酚類、籠狀芳烴類、籠 狀間苯二酣芳烴類’或倍半矽氧烷等之具有羥基之樹脂等 醚化物等。其他’例如具有環氧丙烷環之不飽和單體與烷 基（甲基）丙烯酸酯之共聚物等。 分子中具有複數之環狀硫醚基之化合物，例如，三菱 化學公司製之雙酚A型環硫化物樹脂 YL7000等。又， 亦可使用以同樣之合成方法，將酚醛清漆型環氧樹脂之環 氧基的氧原子取代爲硫原子所得之環硫化物樹脂等。 又’分子中具有複數之環狀（硫）醚基的熱硬化成份 之情形’相對於含羧基之樹脂的羧基1當量，以0.6〜2.5 當量爲佳。添加量未達0 · 6之情形，焊料阻劑膜中將殘留 羧基，而會造成耐熱性、耐鹼性、電氣絕緣性等降低。另 外，超過2.5當量之情形，因低分子量之環狀（硫）醚基 殘留於乾燥塗膜中，故會造成塗膜之強度等降低。更佳爲 0.8〜2.0當量。 又，本實施形態之光硬化性樹脂組成物中，可提升感 光性樹脂組成物之硬化性及所得硬化膜之強韌性等所使用 之熱硬化成份，可於1分子內加入複數之具有異氰酸酯基 ，或嵌段化異氰酸酯基之化合物。該些1分子內具有複數 之異氰酸酯基，或嵌段化異氰酸酯基之化合物，例如1分 子內具有複數之異氰酸酯基之化合物，即聚異氰酸酯化合 物，或1分子內具有複數之嵌段化異氰酸酯基之化合物， 即嵌段異氰酸酯化合物等。 -32- 201116928 聚異氰酸酯化合物’例如，可使用芳香族聚異氰酸酯 、脂肪族聚異氰酸酯或脂環式聚異氰酸酯。 芳香族聚異氰酸酯’例如，4,4’-二苯基甲烷二異氰酸 酯、2,4 -甲伸苯基二異氰酸酯、2,6 -甲伸苯基二異氰酸酯 、萘-1，5-二異氰酸酯、〇-苯二甲基二異氰酸酯、m-苯二甲 基二異氰酸酯及2,4 -甲伸苯基二聚物等。 脂肪族聚異氰酸酯’例如’四伸甲基二異氰酸酯、六 伸甲基二異氰酸酯、伸甲基二異氰酸酯、三甲基六伸甲基 二異氰酸酯、4,4 -伸甲基雙（環己基異氰酸酯）及異佛爾 酮二異氰酸酯等。 脂環式聚異氰酸酯之具體例如’二環庚烷三異氰酸酯 等。又，及先前所列舉之異氰酸酯化合物之加成物、二縮 脲體及異三聚氰酸體等。 嵌段異氰酸酯化合物所含之嵌段化異氰酸酯基，經由 異氰酸酯基與嵌段劑反應而形成被保護之暫時性鈍化之基 。經加熱至一定溫度時，其加熱時該嵌段劑會產生解離而 生成異氰酸酯基。 嵌段異氰酸酯化合物可使用異氰酸酯化合物與異氰酸 酯嵌段劑所得加成反應產物。與嵌段劑反應所得之異氰酸 酯化合物，例如上述聚異氰酸酯化合物等。 異氰酸酯嵌段劑，例如，酚、甲酚、二甲酚、氯酚及 乙基酚等之酚系嵌段劑；ε-己內醯胺、戊內醯胺' Τ - 丁內醯胺及/3 -丙內醯胺等之內醯胺系嵌段劑；乙醯乙 酸乙酯及乙醯基丙酮等之活性伸甲基系嵌段劑；甲醇 '乙 -33- 201116928 醇、丙醇、丁醇、戊基醇、乙二醇單甲基醚、乙二醇單乙 基醚、乙二醇單丁基醚、二乙二醇單甲基醚、丙二醇單甲 基醚、苄基醚、二醇酸甲酯、二醇酸丁酯、二丙酮醇、乳 酸甲酯及乳酸乙酯等之醇系嵌段劑；甲醛肟、乙醛肟、丙 酮肟、甲基乙基酮肟、二乙醯單肟、環己烷肟等之肟系嵌 段劑；丁基硫醇、己基硫醇、t-丁基硫醇、噻酚、甲基噻 酚、乙基噻酚等硫醇系嵌段劑；乙酸醯胺、苯倂醯胺等酸 醯胺系嵌段劑；琥珀酸醯亞胺及馬來酸醯亞胺等之醯亞胺 系嵌段劑；二甲苯胺、苯胺、丁基胺、二丁基胺等胺系嵌 段劑；咪唑、2 -乙基咪唑等之咪唑系嵌段劑；伸甲基亞胺 及伸丙基亞胺等之亞胺系嵌段劑等。 嵌段異氰酸酯化合物可使用市售之化合物’例如， SUMIDUR (登記商標）BL-3175、BL-4165、BL-1 100、 BL- 1 265 、DESMODUR (登記商標）TPLS-2957 、 TPLS-2062、TPLS-2078、TPLS-2117、DESMOSAM 2 170 、DESMOSAM 2265 (皆爲住友拜耳胺基甲酸酯公司製） 、KORONEDO (登記商標）2512、KORONEDO 2513、 KORONEDO 2520 (皆爲日本聚胺基甲酸酯工業公司製） 、B-830 ' B-815、 B-846、 B-870、 B-874、 B-882 (皆爲三 井武田化學公司製）、TPA-B80E、17B-60PX、E402-B8 0T (皆爲旭化成化學公司製）等。又，SUMIDUR BL-3 175、BL-4265爲可作爲嵌段劑之使用甲基乙基肟所得者 〇 該些1分子內具有複數之異氰酸酯基，或嵌段化異氰 -34- 201116928 酸酯基之化合物，可單獨使用1種或將2種以上組合使用 〇 1分子內具有複數之異氰酸酯基，或嵌段化異氰酸酯 基之化合物的添加量，相對於含羧基之樹脂1 00質量份爲 1〜1 00質量份，添加量未達1質量份之情形，將未能得到 充分之塗膜強韌性。另外，超過1 00質量份之情形，其保 存安定性會降低。更佳爲2〜70質量份。 使用分子中具有複數之環狀（硫）醚基的熱硬化知成 份之情形，以含有熱硬化觸媒者爲佳。 該些熱硬化觸媒，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）-2 -乙基-4-甲基 咪唑等之咪唑衍生物；二氰二醯胺、苄基二甲基胺、4_ ( 二甲基胺基）-N，N-二甲基苄基胺、4-甲氧基-Ν,Ν-二甲基 苄基胺、4-甲基-Ν，Ν-二甲基苄基胺等之胺化合物、己二 酸二醯肼、癸二酸二醯肼等之肼化合物；三苯基膦等之磷 化合物等。 又’市售物品中，咪唑系化合物，例如，2ΜΖ-Α、 2ΜΖ-ΟΚ、2ΡΗΖ ' 2Ρ4ΒΗΖ、2Ρ4ΜΗΖ (皆爲四國化成工業 公司製）’二甲基胺之嵌段異氰酸酯化合物例如，^ CAT3 5 0 3 N、U-CAT (登記商標）3 5 02 Τ (皆爲 San-Apro 公司製）’二環式脒化合物及其鹽例如，DBU、DBN、U-CATSA (登記商標）1〇2、U-CAT5 002 (皆爲 San-Apro 公 司製）等。特別是並不限定於此’只要爲環氧樹脂或環氧 -35- 201116928 丙烷化合物之熱硬化觸媒，或可促進環氧基及/或環氧丙 烷基與羧基反應之化合物即可，其可單獨或將2種以上混 合使用。 又，亦可使用胍、乙醯胍、苯倂胍、三聚氰胺、2,4-二胺基·6-甲基丙烯醯氧代乙基-S-三哄、2-乙烯基-2,4-二 胺基-S-三哄、2·乙烯基-4,6-二胺基-S-三哄.異三聚氰酸 加成物、2,4-二胺基-6-甲基丙烯醯氧代乙基-S-三哄.異 三聚氰酸加成物等之S-三哄衍生物。該些具有密著性提 供劑之機能的化合物以與熱硬化觸媒合倂使用爲佳。 該些熱硬化觸媒之添加量，只要爲通常量的比例即屬 充分，例如，相對於含羧基之樹脂或分子中具有2個以上 之環狀（硫）醚基之熱硬化成份100質量份，較佳爲 0.1〜20質量份，更佳爲〇_5~15質量份。 本實施形態之光硬化性樹脂組成物，可添加著色劑。 著色劑，例如’可使用紅、藍、綠、黃等之公知著色劑、 顏料、染料、色素等任一者皆可。但，就降低環境負荷與 對人體之影響等觀點，以不含鹵素者爲佳。 紅色著色劑，例如，單偶氮系、二偶氮系、單偶氮螯 合物系、苯倂咪唑啉酮系、茈系、二酮吡咯吡咯烷系、縮 合偶氮系、蒽醌系、喹吖酮系等，例如，可使用附有以下 色彩指數（C.I· ; The Society of Dyers and Colourists 發 行）號碼之色劑。 單偶氮系：Pigment Red 1, 2，3, 4，5，6，8，9，12，14, 15，16，17，21，22, 2 3，31，32，112, 114，146，147，151， -36- 201116928 170，184，187，188，193，210，245，25 3，2 5 8，266, 267, 268, 269 » 二偶氮系：Pigment Red 37，38, 41。 單偶氮螯合物系：Pigment Red 48:1，48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1,63:2,64:1,68。 苯倂咪哩_ 酮系：Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208 〇 花系：Solvent Red 135、Solvent Red 179、Pigment Red 123、Pigment Red 149、Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、P i g m e n t R e d 2 2 4。 一嗣 D比略啦咯院系：pigment Red 254、Pigment Red 25 5、Pigment Red 264、Pigment Red 270、Pigment Red 272 〇 縮合偶氮系：Pigment Red 220、Pigment Red 144、 Pigment Red 166、Pigment Red 214、Pigment Red 220、 Pigment Red 221 ' Pigment Red 242 〇 葱醌系：Pigment Red 168、Pigment Red 177、 Pigment Red 216、Solvent Red 149、Solvent Red 150、 Solvent Red 52、Solvent Red 207 o 喹 D丫酮系：Pigment Red 122、Pigment Red 202、 Pigment Red 206 ' Pigment Red 207 ' P i g m e n t R e d 2 0 9。 -37- 201116928 藍色著色劑，例如，酞藍素系、蒽醌系等，顔料系， 例如可使用 Pigment Blue 15、Pigment Blue 15:1、 Pigment Blue 15:2、Pigment Blue 15:3、Pigment Blue 15:4、Pigment Blue 15:6、Pigment Blue 16、Pigment Blue 60，染料系例如，Solvent Blue 35、Solvent Blue 63 、Solvent Blue 68 、 Solvent Blue 70 、 Solvent Blue 83 、 Solvent Blue 87 、 Solvent Blue 94 、 Solvent Blue 97 、 Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、 Solvent Blue 70等。上述以外，亦可使用金屬取代或無取 代之酞藍素化合物。 綠色著色劑’例如，同樣地例如酞藍素系、蒽醌系、 菲系等’具體而言，例如可使用Pigment Green 7、 Pigment Green 36、Solvent Green 3、Solvent Green 5、 Solvent Green 20、Solvent Green 28 等。上述以外，亦可 使用金屬取代或無取代之酞藍素化合物。 黃色著色劑，例如，單偶氮系、二偶氮系、縮合偶氮 系、苯倂咪唑啉酮系、異吲哚啉酮系、蒽醌系等，具體而 言例如以下之內容等。 恵醒系.Solvent Yellow 163、Pigment Yellow 24、 Pigment Yellow 108 ' Pigment Yellow 193 ' Pigment Y e Π o w 1 4 7、P i g m e n t Y e 11 o w 1 9 9、P i g m e n t Y e 11 o w 2 0 2。 異卩引噪琳酮I 系：Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、(wherein R13, R14 and R19 represent alkyl groups independently of carbon number U2; R15, R16, R17 and Ris represent independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms; Μ represents 0, S or NH ; X and y represent independent integers of 55. In the oxime ester photopolymerization initiator, 2_(ethyl oxo oxo-female methyl)-benzoxanthene-9-one represented by the above formula (IV) and The compound represented by the formula (V) is more preferably. Commercially available products are, for example, CGI-3 2 5, IRGACURE (registered trademark) OXEO 1 , IRGACURE OXE02 (all manufactured by Ciba-Japan), Ν·1919 (made by ADEKA). These oxime ester-based photopolymerization initiators may be used singly or in combination of two or more kinds. An aminoacetophenone photopolymerization initiator having a group represented by the formula (II), for example, 2-methyl-1-[4-(methylthio)phenyl]_2-morpholinylacetone- 1, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)·-16-201116928 butan-1-one, 2-(dimethylamino)-2- [(4-Methylphenyl)methyl]-l-[4-(4-morpholinyl)phenyl]-1-butanone, anthracene, fluorenyl-dimethylaminoacetophenone and the like. Commercially available products such as IRGACURE 907 'IRGACURE 369, 11^8 (: 01^ 379 (all manufactured by Ciba-Japan), etc. Phosphonium oxide-based photopolymerization initiator having a group represented by the formula (III) , for example, 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, double (2,6 -Dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, etc. Commercially available products such as LUCIRIN TPO (manufactured by BASF Corporation) and IRGACURE 819 (Ciba-曰本公司The amount of the photopolymerization initiator to be added is 0.1% by mass based on 100 parts by mass of the carboxyl group-containing resin. 01 to 30 parts by mass is preferred. When the amount of addition is less than 0_01 by mass, the photocurability on the copper is insufficient, and the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when it exceeds 30 parts by mass, the light polymerization initiator will cause intense light absorption on the surface of the solder resist coating film, and the deep curing property tends to decrease. More preferably, it is 5 to 15 parts by mass. Further, in the case of the oxime ester-based photopolymerization initiator having a group represented by the formula (I), the amount thereof is from 0. 0 1 to 20 parts by mass based on 1 part by mass of the carboxyl group-containing resin. good. When the amount is less than 〇 · 〇 1 part by mass, the photohardenability on copper may be insufficient, and the coating film may be peeled off, and the film properties such as the chemical resistance may be lowered. Further, in the case of more than 2 parts by mass, the light-polymerizing initiator has a strong light absorption on the surface of the solder resist coating film, and tends to lower the deep hardenability. Better for you. 〇 1 to 5 parts by mass. In the photocurable resin composition of the present embodiment, a photopolymerization initiator, a photoinitiator, and a sensitizer, which are preferably used, for example, a benzoin compound, an acetophenone compound, or an anthracene are preferably used. A compound, a thiotonone compound, a ketal compound, a benzophenone compound, an oxonone compound, a tertiary amine compound, and the like. A benzoin compound, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. Acetophenone compounds, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-di Chloroacetophenone. Anthraquinone compounds, for example, 2-methylindole, 2-ethylindole, 2-t-butylindole, 1-chloroindole. A thiotonone compound, for example, 2,4-dimethylthiophenone, 2,4-diethyl thiodone, 2-chlorothione, 2,4-diisopropyl thiodone. A ketal compound, for example, acetophenone dimethyl ketal, benzyl dimethyl ketal. Benzophenone compound, for example, benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene group- 4'-Ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide. A tertiary amine compound such as an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (NISSOCURE MABP, manufactured by Nippon Soda Co., Ltd.), 4, 4'- Dialkylaminobenzophenone, etc.; 2-(diethylamino)-4-methyl-2H-1, etc., such as diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.) Dialkylamino group-containing fragrance of benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), etc.-18- 201116928 Soybean compound; 4·dimethyl Ethyl benzoate (KAYACURE (registered trademark) 日本 manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Microbiology-Technology Co., Ltd.) 4-Dimethylaminobenzene Formic acid (η-butoxy)ethyl (Quantacure®, manufactured by International Microorganisms, Inc.), isoamylethyl p-dimethylaminobenzoate (KAYACURE DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethyl A 2-aminohexyl benzoate such as 2-ethylhexyl benzoate (Esolol 5 07 manufactured by Van Dyk Co., Ltd.). In particular, it is preferably a compound having a dialkylaminobenzene structure, wherein a dialkylaminobenzophenone compound and a dialkylamine group-containing fragrance having a maximum absorption wavelength of 305 to 4 10 nm are used. The soy compound is particularly good. The dialkylaminobenzophenone compound is preferred because it has a lower toxicity with 4,4'-diethylaminobenzophenone. The coumarin compound having a dialkylamine group having a maximum absorption wavelength of 3 to 50 nm is used as a photosensitive composition having less coloration and colorless transparency because the maximum absorption wavelength is in the ultraviolet region. When a coloring pigment is used, It can be provided as a colored solder resist film by reacting the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one exhibits excellent sensitizing effect for laser light having a wavelength of 400 to 410 nm, and is preferred. . Among them, a thiotonone compound and a tertiary amine compound are preferred. In particular, the portion containing the thiotonone compound is preferred from the viewpoint of deep hardenability, wherein 2,4-dimethylthione, 2,4-diethylthione, 2-chlorothiazide A thiotonone compound such as a ketone or a 2,4-diisopropyl thiodone is preferred. The amount of the thiotonone compound to be added is preferably 20 parts by mass or less based on the carboxyl group-containing resin -19-201116928 1 part by mass. When the amount is more than 20 parts by mass, the thick film hardenability is lowered, which is related to the increase in the cost of the product. More preferably, it is 1 part by mass or less. Further, the amount of the tertiary amine compound added is 0.1% by mass based on 100 parts by mass of the carboxyl group-containing resin. A ratio of 1 to 20 parts by mass is preferred. The amount added is less than 0. When it is 1 part by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. On the other hand, when it exceeds 20 parts by mass, the surface of the dried solder resist coating film due to the tertiary amine compound has a strong light absorption, and tends to have a deep hardenability. More preferably 0. 1 to 10 parts by mass. These photopolymerization initiators, photoinitiating aids, and sensitizers can be used singly or in combination of two or more types. The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is 0.1% by mass based on 100 parts by mass of the carboxyl group-containing resin. 01 to 35 parts by mass is preferred. When it exceeds 35 parts by mass, the deep curing property tends to decrease due to the absorption of the light. Further, when it is less than 0 · 0 1 , the photocurability on copper is insufficient, and in addition to peeling off of the coating film, coating properties such as chemical resistance are also lowered. More preferably 0. 0 1 to 20 parts by mass. In particular, in the present embodiment, in the case where an aromatic maleimide is used, in the case of using an aromatic maleimide, since the aromatic maleimide itself has a large ultraviolet absorption, it is characterized by an oxime ester. good. In the photocurable resin composition of the present embodiment, a known N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid or hydrogen sulfide can be used for the chain transfer agent used for improving the sensitivity. Thiazole and the like. The chain transfer agent' is, for example, thiosulfosuccinic acid, thioacetic acid, hydrogen sulfoxide-20-201116928 propylpropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof. These chain transfer agents may be used alone or in combination of two or more. The styrene group-containing compound used in the present embodiment is a heat-resistant user of a cured product obtained by imparting a curing reaction with a maleimide compound. The styrene group-containing compound may be synthesized by a usual method, and it may be used commercially. A method for synthesizing a styry group-containing compound, for example, a reaction of a mono-polyfunctional phenol with a halogenated methylstyrene, and a functional group (for example, an amine group, a hydroxyl group, a carboxyl group, etc.) which is reactive with an epoxy group. Reaction of a mono-polyfunctional compound with vinylbenzyl glycidyl ether and the like. Specific examples of the styryl group-containing compound include vinyl naphthalene, divinyl naphthalene, divinyl biphenyl, polyvinyl benzyl ether compound obtained by reacting a polyphenol with a vinyl benzyl halide, and terminal styrene. An oligophenylene ether compound (PE-2St manufactured by Mitsubishi Gas Chemical Co., Ltd.), a compound obtained by a condensation reaction of bisphenol A and a halogenated methylstyrene (RIPOKIN (registered trademark) BPV-1X, manufactured by Showa Polymer Co., Ltd.), and the like. These styrene group-containing compounds may be used alone or in combination of two or more. The amount of the styrene group-containing compound to be added is preferably 1 to 50 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount added is less than 1 part by mass, sufficient heat resistance cannot be obtained. On the other hand, when it exceeds 50 parts by mass, development residue may be generated due to a decrease in developability of the composition. More preferably, it is 1 to 25 parts by mass. The maleated imine compound used in the present embodiment is used for the purpose of promoting curing reaction with a styryl compound and/or photohardening to improve heat resistance, for example, from 21 to 201116928. These maleimide compounds, for example, polyfunctional aliphatic/alicyclic maleimide, polyfunctional aromatic maleimide, and the like. Polyfunctional aliphatic/alicyclic maleimide, for example, Ν, Ν' · methyl bis-maleimide, hydrazine, Ν'-ethylene bismaleimide, tris(hydroxyethyl) A maleic imidate compound having an isocyanurate skeleton obtained by dehydration esterification of an isocyanurate with an aliphatic/alicyclic maleimine carboxylic acid; tris(urethane hexyl) An isomeric urethane and an aliphatic/alicyclic maleimide alcohol obtained by the ureidotylation of a maleic imide urethane compound having an isocyanurate skeleton, etc., having isomeric melamine Poly-maleimide of the skeleton; isophorone bis-carbamate bis(indole-ethylmaleimide), triethylene glycol bis(maleimide ethyl carbonate), Aliphatic/alicyclic maleic imine carboxylic acid and various aliphatic/alicyclic polyalcohols are dehydrated and esterified, or aliphatic/alicyclic maleic imide carboxylic acid esters and various aliphatic/alicyclic rings Aliphatic/alicyclic polymaleimide ester compounds obtained by transesterification of aliphatic alcohols; aliphatic/alicyclic maleimide carboxylic acids and various aliphatic/alicyclic polycyclic rings Aliphatic/alicyclic polymaleimide ester compounds obtained by ether ring opening reaction; aliphatic/alicyclic maleimide alcohols and various aliphatic/alicyclic polyisocyanates via amine groups An aliphatic/alicyclic polymaleimide urethane compound obtained by a formic acidification reaction or the like. A polyfunctional aromatic maleimide, such as a maleidino carboxylic acid, is dehydrated and esterified with various aromatic polyalcohols, or a maleimide carboxylic acid ester is transesterified with various aromatic polyalcohols. Aromatic polymaleimide compound; aromatic polymaleimide compound obtained by ring-opening reaction of maleic imine carboxylic acid with various aromatic polyalkylene oxides; Malayan Amino alcohol-22-201116928 An aromatic polyfunctional maleimide such as an aromatic polymaleimide urethane compound obtained by a urethanization reaction of various aromatic polyisocyanates. The polyfunctional aromatic maleimine, for example, N,N'-(4,4'-diphenylmethane) bismaleimide, anthracene, Ν'-2,4-methylphenylene Bismaleimide, >^chuan '-2,6-methylphenylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, phenyl biphenyl醯iimine, anthracene, Ν'-ρ-phenylene bismaleimide, N,N'-m-methylphenylene bismaleimide, anthracene, Ν'-4,4'- Biphenyl dimaleimide, anthracene, Ν'-4,4'-[3,3'-dimethyl-biphenyl] bismaleimide, 1>^'-4,4' -[3,3'-dimethyldiphenylmethane] bismaleimide, 1:^-4,4'-[3,3'-diethyldiphenylmethane] Amine, hydrazine, Ν'-4,4'-diphenylmethane bismaleimide, 氺"-4,4'-diphenylpropane bismaleimide, :^,;^-4, 4'-diphenyl ether bismaleimide, anthracene, Ν'-3,3'-diphenylfluorene bismaleimide, anthracene, Ν'-4,4'-diphenylfluorene double Maleate, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-t-butyl-4·(4-horse醯iminophenoxy) Phenyl]propane, 2,2-bis[3-s-butyl-4-(4-maleimidophenoxy)phenyl]propane, 1,1-bis[4-(4-malay)醯iminophenoxy)phenyl]decane, 1,1-bis[2-methyl-4-(4-maleimidophenoxy)-5-t-butylphenyl]-2 -methylpropane, 4,4'-cyclohexylene-bis[1-(4-maleimidophenoxy)-2-(1,1-dimethylethyl)benzene], 4,4 '-Methyl-bis[1-(4-maleimidophenoxy)-2,6-bis(1,1-dimethylethyl)benzene], 4,4'-methyl - bis [1-(4-maleimidophenoxy)-2,6-di-s-butylbenzene], 4,4'-cyclohexylene-double [丨_( -23- 201116928 4 ·Maleimine phenoxy)-2-cyclohexylbenzene, 4,4'-extended methyl bis[1-(maleimide phenoxy)-2-mercaptobenzene], 4,4 '-(1-Methylethylidene)-bis[1-(maleimide phenoxy)-2,6-bis(1,1-dimethylethyl)benzene], 4,4' -(2-ethylhexylene)-bis[1-(maleimide phenoxy)·benzene], 4,4′-(1-methylheptene)-bis[1-( Maleimide phenoxy)-benzene], 4,4'-cyclohexylene-bis[1-(醯iminophenoxy)-3-methylbenzene], 2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3] -Methyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-maleimidophenoxy)phenyl Hexafluoropropane, 2,2-bis[3,5-dimethyl-4-(4-maleimidophenoxy)phenyl]propene. , 2,2-bis[3,5-dimethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-ethyl-4- (4-maleimide phenoxy)phenyl]propane, 2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane, double [3-Methyl-(4-maleimidophenoxy)phenyl]methane, bis[3,5-dimethyl-(4-maleimidophenoxy)phenyl]methane, Bis[3-ethyl-(4-maleimide phenoxy)phenyl]methane, 3,8-bis[4-(4-maleimidophenoxy)phenyl]-tricyclic [5. 2. 1 · 02' 6 ] decane, 4,8-bis[4-(4-maleimidophenoxy)phenyl]-tricyclo[5. 2. 1. 02,6] decane, 3,9-bis[4-(4-maleimidophenoxy)phenyl]-tricyclo[5. 2. 1 · 〇 2'6] decane, 4,9-bis[4-(4-maleimide phenoxy)phenyl]-tricyclo[5. 2. 1. 02'6] decane, 1,8-bis[4-(4-maleimide phenoxy)phenyl] mint, bis[3-methyl-4-(4-maleimide) Phenoxy)phenyl]menthane ' 1,8-bis[3,5-dimethyl-24- 201116928 -4-(4-maleimidophenoxy)phenyl]mentane and the like. These bismaleimide derivatives can be synthesized by a usual method, or a commercially available product can be used. In particular, among the derivatives of the bismaleimide, it is not necessary to impose a burden on the environment, and it is preferred to use a halogen atom in the molecule. These may be used alone or in combination of two or more. The amount of the maleimide compound to be added is preferably 1 to 50 parts by mass based on 1 part by mass of the carboxyl group-containing resin. When the amount is less than 1 part by mass, sufficient heat resistance cannot be obtained. On the other hand, when it exceeds 50 parts by mass, the developability of the composition is lowered to form a development residue. More preferably 1 to 2 parts by mass. In the photocurable resin composition of the present embodiment, a hydrogenthio group compound may be added for the purpose of addition reaction and crosslinking with a vinyl group or a maleimide group. When a thiol compound is added, it is possible to prevent deterioration of coating properties due to oxidation of a vinyl group. Further, in the case of a polyfunctional thiol compound, since crosslinking can be obtained, characteristics such as PCT resistance and HAST resistance can be improved. Further, since these hydrogenthio-based compounds have a function as a chain transfer agent and/or a close-providing agent, the effects of improving sensitivity and adhesion can be simultaneously obtained. The mercaptan compounds, for example, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butane thiol, butyl-3-hydrothiopropionate, methyl-3-hydrothiopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanesulfonate Alcohol, 4-methylbenzenethiol, eleven-yard mercaptan, propyl thiol, butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane-25 - 201116928 Mercaptan, thioglycerol, 4,4-thiobisbenzenethiol, etc. Commercial products such as BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (all manufactured by Sigma Chemical Industry Co., Ltd.), CURRANTS MT (registered trademark)-PEI, CURRANTS MT - BD1, and CURRANTS (registered trademark) - NR1 (all manufactured by Showa Denko). A thiol compound having a heterocyclic ring, for example, thiothio-4-butyrolactone (alias: 2-hydrothio-4-butanolide), 2-hydrothio- 4-methyl- 4-butyrolactone, 2-hydrothio-4-ethyl-4-butyrolactone, 2-hydrothio-4-butylthiolactone, 2-hydrothio-4-buteneamine, N-methoxy-2-hydrothio-4-butylidene, N-ethoxy-2-hydrothio-4-butylidene, N-methyl-2-hydrothio-4 _butyrolactam, N-ethyl-2-hydrothio-4-butylidene, N-(2-methoxy)ethyl-2-hydrothio-4-butylidene, N -(2-ethoxy)ethyl-2-hydrothio-4-butane-lactamine, 2-sulfo-5-valerate, 2-hydrothio-5-pentalamine, N -methyl-2-hydrothio-5-pentalamine, N-ethyl-2-hydrothio-5-pentalamine, N-(2-methoxy)ethyl-2-hydrogen Thio-5-pentalinamide, N-(2-ethoxy)ethyl-2-hydrothio-5-pentalinamide, 2-hydrothiobenzimidazole, 2-hydrothiobenzene Oxime, 2-hydrothiobenzophenazole (AKUSERU® manufactured by Kawaguchi Chemical Industry Co., Ltd.), 2-hydrothio-5-methylthio-thiadiazole, 3-hydrothio-4-methyl -4Η-1,2,4-triazole, 5-methyl·1,3,4- Heterodiazole-2-thiol, 1-phenyl-5-hydroxythio-1Η-tetrazole, 2-hydrothio-6-caprolactam, 2,4,6-trihydrothio-s -Sanken (ZISNETF, manufactured by Sankyo Chemical Co., Ltd.), 2-dibutylamino-4,6-dihydrothio-s-tritium (ZISNET (registered trademark) DB, manufactured by Sankyo Chemical Co., Ltd., -26- 201116928 ZISNET AF) and so on. These thiol-based compounds may be used singly or in combination of two or more kinds. The amount of the hydrogen sulfide-based compound added is 1 part by mass relative to the carboxyl group-containing resin. 〇 1 to 2 0 parts by mass is preferred. The amount added is not up to 〇. In the case of 〇1 mass fraction, since the hydrogenthio group compound failed to exert a hardening effect, the improvement in heat resistance was not observed. On the other hand, when it exceeds 20 parts by mass, development residue is caused, which is not preferable. Better for you.  1 to 5 parts by mass. In the photocurable resin composition of the present embodiment, a thermosetting component can be added for the purpose of imparting heat resistance and the like. As the thermosetting component, for example, a known thermosetting resin such as a melamine resin, a benzoquinone resin, a melamine derivative, an amine-based resin such as a benzoquinone derivative, or a cyclic carbonate compound can be used. Particularly preferred is a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter, simply referred to as a cyclic (thio)ether group) in the molecule. The thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is one or two of two or more cyclic (thio)ether groups having a ring of 3, 4 or 5 members in the molecule. a compound having, for example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a complex propylene oxide group in the molecule, that is, a polyfunctional propylene oxide compound having a plurality of thioethers in the molecule; The base compound, that is, a guanamine-based resin such as an episulfide resin, for example, a methylol melamine compound, a hydroxymethyl benzoquinone compound, a methylol acetylene urea compound, a methylol urea compound, or the like. In addition, alkoxymethylated melamine compounds, alkoxymethylated benzofluorene compounds, alkoxymethylated acetylene urea compounds and alkoxymethylated -27- 201116928 urea compounds, via each hydroxyl group The melamine compound, the hydroxymethyl benzoquinone compound, the methylol acetylene urea compound and the methylol group of the methylol urea compound are converted into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Especially for the human body or the environment, the concentration of formaldehyde water is 0. More than 2% of the melamine derivative is preferred. Such commercial products, for example, SAIMEL (registered trademark) 3 00, same as 301, the same 303 'same as 370, the same 325, the same 327, the same 701, the same 266, the question 267, the same 238, the same 1141, the same 272, Same as 202, same as 1156, same as 1158, same as 1123, same as 1170, same as 1 174, same as UFR65, same as 00 (all manufactured by Mitsuijing Co., Ltd.), NIKARAKU (registered trademark) Mx-7 50, same as Mx- 03 2. Same as Mx-270, the same Mx-2 80, the same Mx-290, the same Mx-706, the same Mx-7 08, the same Mx-40, the same Mx-31, the same Ms-11, the same Mw-30, Same as Mw-30HM, Mw-3 90, Mw-100LM, Mw-750LM, (all manufactured by Sanwa Chemical Co., Ltd.). These thermosetting components may be used singly or in combination of two or more kinds. The cyclic carbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond. For example, an alkylene carbonate compound or the like having a polyfunctional structure. Polyfunctional epoxy compounds, for example, jER (registered trademark) 82 8 ' jER834, jERlOOl, jER1 004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON. (registered trademark) 840, EPICLON.  8 5 0, EPICLON.  1050, EPICLON.  2055 (all manufactured by DIC Corporation), EPOTOT (-28-201116928 registered trademark) YD-011, YD-013, YD-127, YD-128 (all manufactured by Nippon Steel Chemical Co., Ltd.), D. E. R. 317, D. E. R. 331, D. E. R. 661, D. E. R. 664 (all manufactured by Dow Scientific), ARALDITE 607 1, ARALDITE 6084 'ARALDITE GY250 'ARALDITE GY260 (all are Ciba-Japan), SUMI epoxide £8-8-01, ugly 3 VIII, 014, ELA -115, ELA-128 (all manufactured by Sumitomo Chemical Industries, Ltd.), A. E. R. 330, A. E. R. 331, A. E. R. 661, A. E. R. 664 (all are manufactured by Asahi Kasei Industrial Co., Ltd.) bisphenol A type epoxy resin; jERYL903 (made by Mitsubishi Chemical Corporation), EPICLON.  152, EPICLON.  165 (all manufactured by DIC Corporation), EPETOT YDB-400, YDB-500 (all manufactured by Nippon Steel Chemical Co., Ltd.), D. E. R. 542 (made by Dow Scientific), ARALDITE 8011 (made by Ciba-Japan), SUMI epoxy ESB-400, ESB-700 (all manufactured by Sumitomo Chemical Industries, Ltd.), A_E. R. 711, A. E. R. 724 (both manufactured by Asahi Kasei Industrial Co., Ltd.) and other brominated epoxy resins; jER152 and jER154 (all manufactured by Mitsubishi Chemical Corporation), D. E. N. 431, D. E. N. 438 (all manufactured by Dow Scientific), EPICLON.  N- 73 0, EPICLON.  N-770, E PI CL Ο N · N - 8 6 5 (all manufactured by DIC Corporation), EPOTOT YDCN-701, YDCN-704 (all manufactured by Nippon Steel Chemical Co., Ltd.), ARALDITE ECN 1 23 5, ARALDITE ECN1273 , ARALDITE ECN1299, ARALDITE XPY307 (all manufactured by Ciba-Japan), ΕΡΡΝ-201, EOCN (registered trademark) - 1 025, EOCN-1020, EOCN-104S, RE-306 (all manufactured by Nippon Kayaku Co., Ltd.) , SUMI epoxy ESCN-195X, ES CN - 2 2 0 (all manufactured by Sumitomo Chemical Industries, Ltd.), A. E. R. ECN-235, ECN-299 (all are manufactured by Asahi Kasei -29-201116928, manufactured by Seiko Industrial Co., Ltd.) and other novolac type epoxy resins; EPICLON.  83 0 (made by DIC Corporation), jER807 (made by Mitsubishi Chemical Corporation), EPOTOT YDF-170, YDF-175, YDF-2004, (all manufactured by Nippon Steel Chemical Co., Ltd.) YSLV-80XY (manufactured by Nippon Steel Chemical Co., Ltd.) And styrene F-type epoxy resin such as ARALDITE XPY306 (made by Ciba-Japan); hydrogenation doubles such as EPOTOT ST-2004, ST-2007, and ST-3 000 (all manufactured by Nippon Steel Chemical Co., Ltd.) Phenol A type epoxy resin; jER6 04 (manufactured by Mitsubishi Chemical Corporation), EPOTOT YH-434 (manufactured by Nippon Steel Chemical Co., Ltd.), ARALDITE MY720 (made by Ciba-Japan), SUMI epoxy ELM·120 (Sumitomo Chemical Co., Ltd.) Glycolylamine type epoxy resin, etc., manufactured by Industrial Co., Ltd.; Erythroyl type epoxy resin such as ARALDITE CY-350 (Ciba-Japan); SEROKISAIDO (registered trademark) 202 1 (DAISEL Chemical Industry Co., Ltd. )), ARALDITE CY175, CY1 79 (all are Ciba-Japan company) alicyclic epoxy resin; YL-93 3 (Mitsubishi Chemical Corporation), T. E. N. , EPPN (registered trademark)-501, EPPN-502 (all manufactured by Nippon Kayaku Co., Ltd.), etc., hydroxy-6 methane type epoxy resin; YL-6056, YX-4000, YL-6121 (all are Mitsubishi Chemical Corporation) Bis-bisphenol type or biphenol type epoxy resin or a mixture thereof; EBPS-200 (manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (made by ADEKA), EXA-1514 (manufactured by DIC Corporation) Bisphenol S type epoxy resin such as bisphenol A; jER157S (manufactured by Mitsubishi Chemical Corporation); bisphenol A novolac type epoxy resin; jERYL-931 (manufactured by Mitsubishi Chemical Corporation), ARALDITE 163 (made by Ciba-Japan) Phenylphenol (PHENYLOL) type epoxy resin; ARALDITE PT810 (Ciba-Japan-30-201116928 company), TEPIC (Nissan Chemical Industry Co., Ltd.) and other heterocyclic epoxy resin; BLEMMER (registered trademark) ) diglycidyl benzoate resin such as D GT (manufactured by Oyster Co., Ltd.); tetraglycidyl xylenyl ethane resin such as Ζχ-] 063 (manufactured by Nippon Steel Chemical Co., Ltd.); ESN-190 , ESN-360 (all manufactured by Nippon Steel Chemical Co., Ltd.); ^-4032, £\8-4750, EXA-4700 (made by DIC), etc. An epoxy resin containing a naphthyl group; an epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H (manufactured by DIC Corporation); and a shrinkage of CP-50S and CP-50M (manufactured by Nippon Oil Co., Ltd.) a glyceryl methacrylate copolymerized epoxy resin; in addition, a copolymerized epoxy resin such as cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative ( For example, PB-3600 (manufactured by DAISEL Chemical Co., Ltd.), CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Nippon Steel Chemical Co., Ltd.), etc., are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among them, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is preferable. A polyfunctional propylene oxide compound, for example, bis[(3-methyl-3-epoxypropenylmethoxy)methyl]ether, bis[(3-ethyl-3-epoxypropenylmethoxy) Methyl]ether, 1,4-bis[(3-methyl-3-epoxypropenylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-epoxypropanyl) Methoxy)methyl]benzene, (3-methyl-3-epoxypropyl)methacrylic acid vinegar, (3-ethyl-3-epoxypropane)methacrylate, (3 -Methyl-3-epoxypropenyl)methyl methacrylate, (3-ethyl-3-ethoxypropenyl) methyl methacrylate or many of these oligomers or copolymers Functional-31 - 201116928 Ethylene propylene compound 'others such as 'epoxypropanol and novolac resin, poly(P-hydroxystyrene), CARDO type bisphenols, caged aromatic hydrocarbons, caged benzodiazepines An etherified product such as a resin having a hydroxyl group such as a sesquioxane or the like. Other 'for example, a copolymer of an unsaturated monomer having a propylene oxide ring and an alkyl (meth) acrylate, or the like. A compound having a plurality of cyclic thioether groups in the molecule, for example, bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. 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. Further, the case of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is -1 equivalent to the carboxyl group of the carboxyl group-containing resin. 6~2. 5 equivalents are preferred. When the amount of addition is less than 0.6, the carboxyl group remains in the solder resist film, which may cause deterioration in heat resistance, alkali resistance, electrical insulation, and the like. In addition, more than 2. In the case of 5 equivalents, since the low molecular weight cyclic (thio)ether group remains in the dried coating film, the strength of the coating film and the like are lowered. More preferably 0. 8~2. 0 equivalents. Further, in the photocurable resin composition of the present embodiment, the thermosetting component used for the curability of the photosensitive resin composition and the toughness of the obtained cured film can be increased, and a plurality of isocyanate groups can be added in one molecule. Or a compound that blocks an isocyanate group. a compound having a plurality of isocyanate groups or a blocked isocyanate group in one molecule, for example, a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. A compound, that is, a blocked isocyanate compound or the like. -32- 201116928 Polyisocyanate compound ' For example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Aromatic polyisocyanate', for example, 4,4'-diphenylmethane diisocyanate, 2,4-methylphenyl diisocyanate, 2,6-methylphenylene diisocyanate, naphthalene-1,5-diisocyanate, 〇-Benzyl diisocyanate, m-benzenedimethyl diisocyanate, and 2,4-methylphenyl dimer. Aliphatic polyisocyanates such as 'tetramethyl diisocyanate, hexamethylene diisocyanate, methyl diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methyl bis(cyclohexyl isocyanate) And isophorone diisocyanate and the like. Specific examples of the alicyclic polyisocyanate include 'bicycloheptane triisocyanate and the like. Further, an adduct of an isocyanate compound, a diuret or an isomeric cyanide or the like which has been enumerated above. The blocked isocyanate group contained in the blocked isocyanate compound reacts with the block agent via an isocyanate group to form a protected temporary passivation group. Upon heating to a certain temperature, the blocker will dissociate upon heating to form an isocyanate group. As the blocked isocyanate compound, an addition reaction product obtained by using an isocyanate compound and an isocyanate block agent can be used. The isocyanate compound obtained by the reaction with a block agent, for example, the above polyisocyanate compound or the like. Isocyanate block agents, for example, phenolic blockers such as phenol, cresol, xylenol, chlorophenol and ethyl phenol; ε-caprolactam, valeroin' Τ-butylide and/ 3 -Protonamine blocker such as propaneamine; active methyl group blocker such as ethyl acetate and ethyl acetonate; methanol 'B-33- 201116928 alcohol, propanol, butyl Alcohol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, two Alcohol blocker such as methyl alkoxide, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazine a thiol blocker such as monoterpene or cyclohexane hydrazine; a thiol blocker such as butyl thiol, hexyl thiol, t-butyl thiol, thiophene, methyl thiophene or ethyl thiophene An amide-based blocker such as decylamine or benzoguanamine; a quinone imide blocker such as succinimide succinate or succinimide; xylidine, aniline, butylamine, Amine blocker such as dibutylamine; imidazole 2 - ethylimidazole, etc. imidazole-based blocking agent; methylimine stretch and stretch propylene imine imine block, etc., and the like. As the blocked isocyanate compound, a commercially available compound can be used, for example, SUMIDUR (registered trademark) BL-3175, BL-4165, BL-1 100, BL-1 265, DESMODUR (registered trademark) TPLS-2957, TPLS-2062, TPLS. -2078, TPLS-2117, DESMOSAM 2 170, DESMOSAM 2265 (both manufactured by Sumitomo Bayeramide), KORONEDO (registered trademark) 2512, KORONEDO 2513, KORONEDO 2520 (all are Japanese polyurethane products) Company system), B-830 'B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B8 0T ( All are made by Asahi Kasei Chemical Co., Ltd.). Further, SUMIDUR BL-3 175 and BL-4265 are those obtained by using methyl ethyl hydrazine as a blocker, and having a plurality of isocyanate groups in one molecule or blocking isocyanide-34-201116928 acid ester The compound may be used singly or in combination of two or more kinds thereof. The compound having a plurality of isocyanate groups in one molecule or a compound having a blocked isocyanate group is added in an amount of 1 part by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is not more than 1 part by mass, the coating film strength and toughness are not obtained. In addition, in the case of more than 100 parts by mass, the stability of storage will be lowered. More preferably 2 to 70 parts by mass. In the case of using a thermosetting compound having a plurality of cyclic (thio)ether groups in the molecule, it is preferred to contain a thermosetting catalyst. The thermosetting catalysts, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Imidazole derivatives such as ethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-imidazole; dicyanodiamide, benzyldimethylamine, 4_ (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-indole, fluorene-dimethylbenzylamine, 4-methyl-indole, fluorene-dimethylbenzyl An amine compound such as an amine, a ruthenium compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine or the like. Further, in the commercially available article, an imidazole-based compound, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ ' 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (all manufactured by Shikoku Chemicals Co., Ltd.) 'blocked isocyanate compound of dimethylamine, for example, ^CAT3 5 0 3 N, U-CAT (registered trademark) 3 5 02 Τ (all manufactured by San-Apro Co., Ltd.) 'Bicyclic oxime compound and its salt, for example, DBU, DBN, U-CATSA (registered trademark) 1〇2 , U-CAT5 002 (all manufactured by San-Apro), etc. In particular, it is not limited to this, as long as it is a thermosetting catalyst of an epoxy resin or epoxy-35-201116928 propane compound, or a compound which can promote the reaction of an epoxy group and/or an oxypropylene group with a carboxyl group, These may be used alone or in combination of two or more. Further, ruthenium, acetamidine, benzoquinone, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2,4- can also be used. Diamino-S-triterpene, 2·vinyl-4,6-diamino-S-triterpene. Iso-cyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-triterpene. An S-triterpene derivative such as an isomeric cyanuric acid addition product. The compounds having the function of the adhesion promoter are preferably used in combination with a thermosetting catalyst. The amount of the thermosetting catalyst to be added is sufficient as long as it is a normal amount. For example, 100 parts by mass of the thermosetting component having two or more cyclic (thio)ether groups in the carboxyl group-containing resin or molecule. , preferably 0. 1 to 20 parts by mass, more preferably 〇5 to 15 parts by mass. A coloring agent can be added to the photocurable resin composition of the present embodiment. For the coloring agent, for example, any of known coloring agents such as red, blue, green, and yellow, pigments, dyes, and dyes may be used. However, it is preferable to reduce the environmental load and the influence on the human body. a red coloring agent, for example, a monoazo type, a diazo type, a monoazo chelate type, a benzoimidazolidinone type, an anthraquinone type, a diketopyrolrolidine type, a condensed azo type, a lanthanide type, Quinophthalones, etc., for example, can be used with the following color index (C. I· ; The Society of Dyers and Colourists issued a number of toners. Single azo system: Pigment Red 1, 2,3, 4,5,6,8,9,12,14, 15,16,17,21,22, 2 3,31,32,112, 114,146, 147,151, -36- 201116928 170,184,187,188,193,210,245,25 3,2 5 8,266, 267, 268, 269 » Diazo system: Pigment Red 37, 38, 41. Monoazo chelate system: Pigment Red 48:1,48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68. Benzene oxime ketone system: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208 〇 系: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166 , Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment R ed 2 2 4. A 嗣 D slightly slightly faculty: pigment Red 254, Pigment Red 25 5, Pigment Red 264, Pigment Red 270, Pigment Red 272 〇 condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 ' Pigment Red 242 Leek 醌: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207 o quinoxaline Line: Pigment Red 122, Pigment Red 202, Pigment Red 206 ' Pigment Red 207 'P igment R ed 2 0 9. -37- 201116928 Blue colorants, for example, indigo, lanthanide, etc., pigments, for example, Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60, dyes such as Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94 , Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. In addition to the above, a metal substituted or unsubstituted indigo compound may also be used. The green colorant 'for example, for example, indigo, lanthanide, phenanthrene, etc., specifically, for example, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent can be used. Green 28 and so on. In addition to the above, a metal-substituted or unsubstituted indigo compound may also be used. The yellow coloring agent is, for example, a monoazo type, a diazo type, a condensed azo type, a benzoxazolidinone type, an isoindolinone type, an anthraquinone type, etc., and specifically, the following, etc. are mentioned. Wake up. Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108 ' Pigment Yellow 193 ' Pigment Y e Π o w 1 4 7 , P i g m e n t Y e 11 o w 1 9 9 , P i g m e n t Y e 11 o w 2 0 2 . Isoindole-inducing linketone I series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179,

Pigment Yellow 185 〇 -38- 201116928 縮合偶氮系：Pigment Yellow 93、Pigment Yellow 94 、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180。 苯倂咏哩_ 酮系：Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、 Pigment Yellow 175、Pigment Yellow 181 o 單偶氮系：Pigment Yellow 1，2，3，4，5，6，9，10，12, 61，62，62:1, 65，73，74，75，97，100，104，105，111, 116, 167， 168， 169， 182， 183 。 二偶氮系：Pigment Yellow 12，13，14，16，17，55, 63, 81，83，87，1 2 6, 1 27，152，170，172，174，176，188, 198 ° 其他，就調整色調等目的上，亦可添加紫、橙、茶色 、黑等之著色劑。具體而言，例如Pigment Violet 19、23 、2 9、3 2、3 6、3 8、4 2、Solvent Violet 1 3、3 6、Pigment Orange 1 、 Pigment Orange 5 、 Pigment Orange 13 、 Pigment Orange 14、Pigment Orange 16、Pigment Orange 17、Pigment Orange 24、Pigment Orange 3 4、Pigment Orange 3 6、Pigment Orange 38、Pigment Orange 40、 Pigment Orange 43、Pigment Orange 46、Pigment Orange 49、Pigment Orange 51、Pigment Orange 61、Pigment Orange 63、Pigment Orange 64、Pigment Orange 71、 Pigment O range 73、Pigment Brown 2 3、Pigment Brown 25、Pigment Black 1、Pigment Black 7 ^。 39- 201116928 該些著色劑之添加比例，並未有特別限制，相對於含 羧基之樹脂1〇〇質量份，較佳爲10質量份以下，特佳者 爲0」〜5質量份之比例即屬充分。 又，本實施形態之光硬化性樹脂組成物中，爲使含有 乙烯性不飽和基之含羧基之樹脂於鹼水溶液中之不溶化， 或輔助其不溶化等目的，分子中可添加具有複數之乙烯性 不飽和基的化合物。該些化合物，例如乙二醇、甲氧基四 乙二醇、聚乙二醇、丙二醇等之二醇之二丙烯酸酯類；己 烷二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、三-羥 基乙基異氰脲酸酯等之多元醇或該些之環氧乙烷加成物或 環氧丙烷加成物等之多價丙烯酸酯類；苯氧基丙烯酸酯、 雙酚A二丙烯酸酯，及該些之酚類的環氧乙烷加成物或 環氧丙烷加成物等之多價丙烯酸酯類；甘油二縮水甘油醚 、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、三縮 水甘油基異氰脲酸酯等之縮水甘油基醚的多價丙烯酸酯類 :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。 此外，例如甲酚-酚醛清漆型環氧樹脂等之多官能環 氧樹脂與丙烯酸反應之環氧基丙烯酸酯樹脂或，該些之環 氧基丙烯酸酯樹脂的羥基再與，季戊四醇三丙烯酸酯等之 羥基丙烯酸酯與異佛爾酮二異氰酸酯等之二異氰酸酯之半 胺基甲酸酯化合物反應所得之環氧基胺基甲酸酯丙烯酸酯 化合物等。該些環氧基丙烯酸酯系樹脂，於不會降低指觸 乾燥性的同時，可提高光硬化性》 -40- 201116928 該些分子中具有複數之乙烯性不飽和基的化合物之添 加量，相對於含羧基之樹脂100質量份，以5〜100質量份 之比例爲佳。添加量未達5質量份之情形，會造成光硬化 性降低，且於活性能量線照射後之鹼顯影，也不容易進行 圖型形成。另外，超過1 〇〇質量份之情形，對於鹼水溶液 之溶解性會降低，造成塗膜脆化。更佳爲1 0〜7 0質量份。 本實施形態之光硬化性樹脂組成物，爲提高其塗膜之 物理性強度等，必要時可添加塡料。該些塡料，可使用公 知之無機或有機塡料，特別是硫酸鋇、球狀氧化矽、水滑 石及滑石等爲佳。此外，爲得白色之外觀或難燃性等，可 添加氧化鈦或金屬氧化物、氫氧化鋁等之金屬氫氧化物作 爲體質顏料塡料使用。 該些塡料之添加量，以組成物全體量之75質量％以 下爲佳。塡料之添加量，超過組成物全體量之75質量％ 之情形，會造成絕緣組成物之黏度增加，降低塗佈、成形 性的同時，使硬化物脆化。更佳爲〇. 1〜60質量％。 此外，本實施形態之光硬化性樹脂組成物，就含羧基 之樹脂之合成或組成物之製作等目的，或調整塗佈於基板 或載體薄膜的黏度等目的，可使用有機溶劑。 該些有機溶劑，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、四甲基苯等之芳香族烴類；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 -41 - 201116928 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之二醇醚類；乙酸乙酯、乙酸丁酯、 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之酯類；乙醇、丙醇 、乙二醇、丙二醇等之醇類；辛烷、癸烷等之脂肪族烴： 石油醚、石油腦、氫化石油腦、溶劑腦等之石油系溶劑等 。該些有機溶劑，可單獨或以2種以上之混合物方式使用 〇 高分子材料中大部分爲一開始氧化時，將引起連續之 氧化劣化反應，而會造成高分子原料之機能降低，本實施 形態之光硬化性樹脂組成物中，爲防止氧化產生，可添加 使發生之自由基無效化之自由基捕捉劑及/或使發生之過 氧化物分解爲無害物質，而不會發生新的自由基之過氧化 物分解劑等之抗氧化劑。 具有作爲自由基捕捉劑機能之抗氧化劑，例如，對苯 二酚、4-t-丁基鄰苯二酚、2-t-丁基對苯二酚、對苯二酚 單甲基醚、2,6-二-t-丁基-P-甲酚、2,2-伸甲基-雙（4-甲 基-6-t-丁基酚）、1,1，3-三（2-甲基-4-羥基-5-卜丁基苯基 )丁烷、1，3,5-三甲基-2,4,6-三（3,5-二-卜丁基-4-羥基苄 基）苯、1,3,5-三（3’，5’-二-1-丁基-4-羥基苄基）-3-三哄-2,4,6-(lH，3H，5H)三酮等之酚系、甲醌、苯併醌等之 醌系化合物、雙（2,2,6,6-四甲基-4-哌啶基）-癸二酸酯、 苯噻畊等之胺系化合物等。 自由基捕捉劑可使用市售之物品，例如，ADEK ( -42- 201116928 登記商標）AO-30、ADEK AO-330、ADEK AO-20、ADEK LA-77、ADEK LA-57、ADEK LA-67、ADEK LA-68、 ADEK LA-87 (皆爲 ADEKA 公司製）、IRGANOX1010、 IRGANOX (登記商標）1035 、 IRGANOX 1 076 、 IRGANOX1 1 3 5 、 TINUVIN (登記商標）111FDL 、 TINUVIN 123' TINUVIN 144、TINUVIN 152、TINUVIN 292、TINUVIN 5100(皆爲汽巴-日本公司製）等。 具有過氧化物分解劑作用之抗氧化劑之具體化合物， 例如三苯基亞磷酸酯等之磷系化合物、季戊四醇四月桂基 硫代丙酸酯、二月桂基硫代二丙酸酯、二硬脂基3,3’-硫 代二丙酸酯等之硫系化合物等。 過氧化物分解劑可使用市售之物品，例如，ADEK TPP ( ADEKA 公司製）、MARK AO-412S ( ADEK · AKS 化學公司製）、SUMIRAIZA (登記商標）TPS (住友化學 公司製）等。該些抗氧化劑可單獨使用1種或將2種以上 組合使用。 又，高分子材料可吸收光，並經由吸光引起分解•劣 化，爲使本實施形態之光硬化性樹脂組成物對紫外線爲安 定化之對策，除上述抗氧化劑以外，亦可使用紫外線吸收 劑。 該些紫外線吸收劑，例如，2 -羥基-4 -甲氧基-二苯甲 酮、2 -羥基-4-甲氧基二苯甲酮、2 -羥基-4-n -辛氧基二苯 甲酮、2,2’-二羥基-4-甲氧基二苯甲酮及2,4-二羥基二苯 甲酮等之二苯甲酮衍生物；2-乙基己基水楊酸酯、苯基水 -43- 201116928 楊酸酯、p-t-丁基苯基水楊酸酯、2,4-二-t-丁基苯基-3,5-二-t-丁基-4-羥基苯甲酸酯及六癸基-3,5-二-t-丁基-4-羥基 苯甲酸酯等之苯甲酸酯衍生物；2- (2’-羥基-5’-t-丁基苯 基）苯倂***、2-(2’-羥基-5’-甲基苯基）苯倂***、ΙΟ’-羥基 -3’-t-丁基-5’-甲 基苯基 ）-5-氯苯倂 ***、 2-(2’-羥 基·3’，5’-二-t-丁基苯基）-5-氯苯倂***、2-(2’-羥基-5’-甲 基苯基）苯倂***及2-(2’-羥基-3’，5’-二-t-戊基苯基）苯倂 ***等之苯倂***衍生物；羥苯基三哄、雙（乙基己基氧 代酚）甲氧基苯基三哄等之三哄衍生物；甲基2,4-二異丙 基桂皮醯胺、2乙基己基-P-甲氧基桂皮醯胺等之桂皮醯胺 衍生物；甲基銻酸酯、苯基銻酸酯、苄基銻酸酯等之銻酸 酯衍生物；t-丁基甲氧基二苯甲醯基甲烷等之二苯甲醯基 甲烷衍生物等。Pigment Yellow 185 〇 -38- 201116928 Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180. Benzoquinone ketone system: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 o Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6 , 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183. Diazo system: Pigment Yellow 12,13,14,16,17,55,63,81,83,87,1 2 6, 1 27,152,170,172,174,176,188, 198 ° Other, For the purpose of adjusting the color tone, a coloring agent such as purple, orange, brown or black may be added. Specifically, for example, Pigment Violet 19, 23, 2 9, 3 2, 3 6 , 3 8 , 4 2, Solvent Violet 1 3, 3 6 , Pigment Orange 1 , Pigment Orange 5 , Pigment Orange 13 , Pigment Orange 14, Pigment Orange 16, Pigment Orange 17, Pigment Orange 24, Pigment Orange 3 4, Pigment Orange 3 6, Pigment Orange 38, Pigment Orange 40, Pigment Orange 43, Pigment Orange 46, Pigment Orange 49, Pigment Orange 51, Pigment Orange 61, Pigment Orange 63, Pigment Orange 64, Pigment Orange 71, Pigment O range 73, Pigment Brown 2 3, Pigment Brown 25, Pigment Black 1, Pigment Black 7 ^. 39- 201116928 The addition ratio of the coloring agents is not particularly limited, and is preferably 10 parts by mass or less based on 1 part by mass of the carboxyl group-containing resin, and particularly preferably 0 to 5 parts by mass. It is full. Further, in the photocurable resin composition of the present embodiment, in order to insolubilize the carboxyl group-containing resin containing an ethylenically unsaturated group in an aqueous alkali solution, or to assist insolation thereof, a plurality of ethylene groups may be added to the molecule. An unsaturated group of compounds. Such compounds, for example, diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; hexane diol, trimethylolpropane, pentaerythritol, dipentaerythritol, three Polyols such as hydroxyethyl isocyanurate or polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylic acid a polyvalent acrylate such as an ester, or an oxirane ethylene oxide adduct or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane tricondensate A polyvalent acrylate of a glycidyl ether such as glyceryl ether or triglycidyl isocyanurate: and a melamine acrylate, and/or a methacrylate corresponding to the above acrylate. Further, an epoxy acrylate resin which reacts with a polyfunctional epoxy resin such as a cresol novolak type epoxy resin and acrylic acid, or a hydroxyl group of the epoxy acrylate resin, pentaerythritol triacrylate, etc. An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate with a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate. These epoxy acrylate-based resins can improve the photocuring property without lowering the dryness of the touch, and the addition amount of the compound having a plurality of ethylenically unsaturated groups in the molecules is relatively small. It is preferably a ratio of 5 to 100 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 5 parts by mass, the photocurability is lowered, and the alkali development after the irradiation of the active energy ray is not easy to form. Further, in the case of more than 1 part by mass, the solubility in the aqueous alkali solution is lowered to cause embrittlement of the coating film. More preferably, it is 1 0 to 7 0 parts by mass. In the photocurable resin composition of the present embodiment, the physical strength of the coating film or the like is increased, and if necessary, a dip material can be added. As the tanning materials, known inorganic or organic tanning materials, particularly barium sulfate, spherical cerium oxide, hydrotalcite and talc, may be preferably used. Further, in order to obtain a white appearance, flame retardancy or the like, a metal hydroxide such as titanium oxide, metal oxide or aluminum hydroxide may be added as a body pigment pigment. The amount of the tanning materials added is preferably 75% by mass or less based on the total amount of the composition. When the amount of the coating material is more than 75% by mass based on the total amount of the composition, the viscosity of the insulating composition is increased, and the coating and formability are lowered, and the cured product is embrittled. More preferably 〇. 1~60% by mass. In addition, the photocurable resin composition of the present embodiment may be an organic solvent for the purpose of synthesizing or synthesizing a resin containing a carboxyl group, or adjusting the viscosity applied to a substrate or a carrier film. These organic solvents are, for example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, Carbitol, methyl carbitol, butyl carbitol, propyl-41 - 201116928 diol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And other glycol ethers; esters of ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc. Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent brain, and the like. These organic solvents may be used singly or in combination of two or more kinds. When most of the polymer materials are initially oxidized, a continuous oxidative degradation reaction is caused, and the function of the polymer raw material is lowered. In the photocurable resin composition, in order to prevent oxidation, a radical scavenger which invalidates the generated radicals may be added and/or the generated peroxide may be decomposed into harmless substances without generating new radicals. An antioxidant such as a peroxide decomposing agent. An antioxidant having a function as a radical scavenger, for example, hydroquinone, 4-t-butyl catechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2 ,6-di-t-butyl-P-cresol, 2,2-extended methyl-bis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-A 4-hydroxy-5-bubutylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-butyl-4-hydroxybenzyl)benzene, 1 , 3,5-tris(3',5'-di-1-butyl-4-hydroxybenzyl)-3-tris-2,4,6-(lH,3H,5H)trione An anthraquinone compound such as guanidine, formazan or benzopyrene; an amine compound such as bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate or phenylthidium chloride. Commercially available articles can be used as the radical scavenger, for example, ADEK (-42-201116928 registered trademark) AO-30, ADEK AO-330, ADEK AO-20, ADEK LA-77, ADEK LA-57, ADEK LA-67 , ADEK LA-68, ADEK LA-87 (all manufactured by ADEKA), IRGANOX1010, IRGANOX (registered trademark) 1035, IRGANOX 1 076, IRGANOX1 1 3 5 , TINUVIN (registered trademark) 111FDL, TINUVIN 123' TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (all are Ciba-Japan company) and so on. Specific compounds of antioxidants having a peroxide decomposing agent, such as phosphorus compounds such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl A sulfur-based compound such as a 3,3'-thiodipropionate or the like. As the peroxide decomposing agent, commercially available articles such as ADEK TPP (made by ADEKA), MARK AO-412S (made by ADEK AKS Chemical Co., Ltd.), SUMIRAIZA (registered trademark) TPS (manufactured by Sumitomo Chemical Co., Ltd.), and the like can be used. These antioxidants may be used alone or in combination of two or more. In addition, the polymer material absorbs light and is decomposed and deteriorated by light absorption. In order to stabilize the ultraviolet curable resin composition of the present embodiment, an ultraviolet absorber may be used in addition to the above-mentioned antioxidant. The ultraviolet absorbers, for example, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxydiphenyl a benzophenone derivative such as ketone, 2,2'-dihydroxy-4-methoxybenzophenone or 2,4-dihydroxybenzophenone; 2-ethylhexylsalicylate; Phenyl water-43- 201116928 Salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzene Benzoate derivatives such as formate and hexamethylene-3,5-di-t-butyl-4-hydroxybenzoate; 2-(2'-hydroxy-5'-t-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ΙΟ'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5 '-Methylphenyl)benzoxazole and benzotriazole derivatives of 2-(2'-hydroxy-3',5'-di-t-pentylphenyl)benzotriazole; hydroxybenzene a triterpene derivative such as hydrazine, bis(ethylhexyl oxophenol) methoxyphenyl triterpene; methyl 2,4-diisopropyl laurate a cinnamylamine derivative such as picoguanamine or 2-ethylhexyl-P-methoxycinnamate; a phthalate derivative such as methyl phthalate, phenyl phthalate or benzyl phthalate; a benzoylmethane derivative such as t-butylmethoxybenzhydrylmethane or the like.

紫外線吸收劑，可使用市售物品亦可，例如， TINUVIN PS、TINUVIN 99-2、TINUVIN 109、TINUVIN 3 84-2 ' TINUVIN 900、TINUVIN 928、TINUVIN 1130、 TINUVIN 400、TINUVIN 405、TINUVIN 460 &gt; TINUVIN 479 (皆爲汽巴-日本公司製）等。 該些紫外線吸收劑，可單獨使用1種或將2種以上組 合使用亦可，與抗氧化劑合倂使用時，可使由本實施形態 之光硬化性樹脂組成物所得之成形物安定化。 本實施形態之光硬化性樹脂組成物，於必要時，可添 加微粉氧化矽、有機黏土、蒙脫土等之公知之增黏劑、聚 矽氧系、氟系、高分子系等之消泡劑及/或滑劑、咪唑系 -44- 201116928 、噻唑系、***系等之矽烷偶合劑、抗氧化劑、防錡劑等 公知之添加劑類。 又，本實施形態之光硬化性樹脂組成物所含之聚合性 化合物於防止熱聚合或存放時之聚合等目的，可使用抗聚 合劑。 該些抗熱聚合劑，例如，4 -甲氧基酚、氫醌、烷基或 芳基取代氫醌、t-丁基鄰苯二酚、五倍子酚、2-羥基二苯 甲酮、4 -甲氧基-2 -經基二苯甲酮、氯化第一銅、酣嚷哄 、氯醌、萘基胺、/3-萘酚、2,6-二-t-丁基-4-甲酚、2,2 ’-伸甲基雙（4-甲基-6-t-丁基酚）、吡啶、硝基苯、二 硝基苯、苦味酸、4 -甲苯胺、甲基藍、銅與有機螯合劑反 應物、水楊酸甲酯，及酚噻哄、亞硝基化合物、亞硝基化 合物與A1之螯合劑等。 本實施形態之光硬化性樹脂組成物中，爲促進層間之 密著性，或感光性樹脂層與基材之密著性等，可使用密著 促進劑。該些密著促進劑，例如，苯倂咪唑、苯倂噚唑、 苯倂噻唑、3-嗎啉基甲基-1-苯基-***-2·硫酮、5_胺基-3-嗎啉基甲基-噻唑-2 -硫酮、*** '四唑、苯倂***、羧基 苯倂***、胺基含有苯倂***、矽烷偶合劑等。 該些所構成之本實施形態之光硬化性樹脂組成物，於 依特定組成製作後，例如可使用有機溶劑調整爲適..合塗佈 方法之黏度，於基材上以浸潤塗佈法、流動塗佈法、滾筒 塗佈法、條狀塗佈法、網版印刷法、簾幕塗佈法等之方法 進行塗佈。 -45- 201116928 塗佈後之揮發乾燥，可使用熱風循環式乾燥爐、IR 爐、熱壓板、渦輪烤箱等（於使用具備有以蒸汽加熱空氣 方式之熱源的乾燥機內，以熱風向流動接觸之方法及以噴 嘴吹拂支撐體之方式）以約60〜100 °c之溫度下進行。 又，光硬化性樹脂組成物形成乾薄膜，將其貼合於基 材上時，可形成樹脂絕緣層。 乾薄膜，例如，具有依序將聚乙烯對苯甲酸酯等之載 體薄膜，與焊料阻劑層等之樹脂絕緣層，與必要時所使用 之可剝離之包覆薄膜層合所得之構造之物。 樹脂絕緣層爲，光硬化性樹脂組成物塗佈於載體薄膜 或包覆薄膜後，經乾燥所得之層。該些樹脂絕緣層，爲將 本實施形態之光硬化性樹脂組成物以片狀塗佈機、肋狀塗 佈機、點狀塗佈機、薄膜塗佈機等，於載體薄膜上均勻地 塗佈10〜150μηι之厚度，經乾燥所形成。隨後，再於必要 時，以層合包覆薄膜之方式形成乾薄膜。此時，可將光硬 化性樹脂組成物塗佈於包覆薄膜，經乾燥後，層合於載體 薄膜亦可。 載體薄膜，例如，可使用厚度2〜15 Ομηι之聚酯薄膜 等之熱可塑性薄膜。 包覆薄膜，可使用聚乙烯薄膜、聚丙烯薄膜等，其與 焊料阻劑層之黏著力，可小於載體薄膜。 使用該些乾薄膜時，於使用包覆薄膜之情形中，經由 將其剝離、使樹脂絕緣層與基材重疊，層合等方式貼合後 ，可於基材上形成樹脂絕緣層。又，載體薄膜可於後述曝 -46- 201116928 光前或後剝離即可。 此時’形成塗膜，或貼合乾薄膜之基材，例如可爲酚 紙、環氧紙、環氧玻璃布、聚醯亞胺玻璃、玻璃布/環氧 不織布、玻璃布/環氧紙、環氧合成纖維、氟.聚乙烯. PPO ·氰酸酯等所得之高周波電路用銅箔層合板等之材質 之全層級（FR- 4等）之銅箔層合板，其他聚醯亞胺薄膜 、PET薄膜、坡璃基板、陶瓷基板、晶圓板等。 此外’使用接觸式（或非接觸方式）之方式，以曝光 或雷射直接曝光機經由形成有圖型之光遮罩以選擇性活性 能量線進行直接圖型曝光（照射活性能量線）。 活性能量線照射所使用之曝光機，例如可使用直接描 繪裝置（例如由電腦將CAD數據以直接雷射描繪圖像之 雷射直接影像描繪裝置）、搭載金屬鹵素燈之曝光機、搭 載（超）高壓水銀燈之曝光機、搭載水銀短弧燈之曝光機 ，或（超）高壓水銀燈等之紫外線燈所進行之直接描繪裝 置。 活性能量線，以使用波長爲3 5 0〜4 1 0 n m之雷射光爲 佳。波長於此範圍時，可有效地由光起始劑生成自由基。 使用該範圍之雷射光時，以使用氣體雷射、固體雷射之任 一者皆可。又，該曝光量依膜厚等而有所相異，一般而言 爲 5〜200mJ/cm2 ’ 較佳爲 5〜l〇〇mj/cm2 ， 更佳爲 5~5 OmJ/cm2。 直接描繪裝置例如，可使用日本Orbotech公司製、 Pantax公司製等之裝置，只要可發出最大波長爲 -47- 201116928 3 5 0〜4 10nm之雷射光之裝置時，無論任何裝置皆可使用。 隨後，經由曝光後之結果，使曝光部（經活性能量線 照射之部份）硬化，使未曝光部於稀鹼水溶液（例如， 0.3~3wt%Na2CO3水溶液）中顯影，形成硬化物（圖型） 〇 此時’顯影方法可使用浸漬法、噴灑法、噴霧法、刷 動法等’顯影液可使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳 酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液。 此外，含熱硬化成份之情形，例如，經由加熱至約 1 4 0~1 80 °C之溫度進行熱硬化時，可使含羧基之樹脂之羧 基與’分子中具有複數之環狀（硫）醚基之熱硬化成份反 應，可形成具有優良耐熱性、耐藥性、耐吸濕性、密著性 、電氣特性等各種特性之硬化物。 【實施方式】 [實施例] 以下將以實施例及比較例作具體之說明，但本發明並 不受該些實施例所限定。又，以下中，稱爲「份」及「％ 」，於無特別限定下，係爲全質量基準。 〔含羧基之樹脂（A-1)之合成〕 於具備有溫度計、氮導入裝置兼環氧烷導入裝置及攬 拌裝置之高壓釜中，混合酚醛清漆型甲酚樹脂（昭和高分 子公司製，商品名「Shonol. CRG951」、OH當量：119.4 -48- 201116928 )119.4g、氫氧化鉀l.i9g及甲苯il9.4g，攪拌中，將反 應系內以氮取代，進行加熱昇溫。 其次’徐徐滴入環氧丙烷63.8g，於125〜132 t、 〇〜4.8kg/cm2下反應16小時。隨後，冷卻至室溫，該反應 溶液中’添加混合89%磷酸1.56g，以氫氧化鉀中和，得 不揮發分62.1%'羥基價爲丨82.2g/eq.之酚醛清漆型甲酚 樹脂的環氧丙烷反應溶液。其爲，酚性羥基1當量附加平 均1.08莫耳環氧院所得者。 所得之酚醛清漆型甲酚樹脂之環氧烷反應溶液293.0g 、丙烯酸43_2g、甲烷磺酸u.53g、甲基氫醌0.18g及甲 苯25 2.9g ’於具備有攪拌機、溫度計及空氣吹入管之反應 器中，將空氣以l〇ml /分之速度吹入，於攪拌中，11〇它 下反應1 2小時。反應所生成之水，以與甲苯作爲共沸混 合物之方式’餾出1 2 · 6 g之水。隨後，冷卻至室溫，所得 之反應溶液以1 5 %氫氧化鈉水溶液3 5.3 5 g中和，其次進 行水洗。 隨後，於蒸發器中，將甲苯以二乙二醇單乙基醚乙酸 酯118.lg取代後餾除’得酚醛清漆型丙烯酸酯樹脂溶液 。其次，將所得之酚醛清漆型丙烯酸酯樹脂溶液3 3 2 · 5 g 及三苯基膦l.22g於具備有攪拌器、溫度計及空氣吹入管 之反應器中混合，將空氣以10ml/分之速度吹入，攪拌中 ，緩緩加入四氫苯甲酸酐6 0.8 g，於9 5〜1 〇 1。(：下反應6小 時。得固形物之酸價爲8 8 m g Κ Ο H / g、不揮發分7 1 %之含 羧基之感光性樹脂。以下，該反應溶液稱爲樹脂溶液A- 1 -49 - 201116928 〔含羧基之樹脂（A-2 )之合成〕 於二乙二醇單乙基醚乙酸酯600g中，加入鄰甲酚-酚 醛清漆型環氧樹脂〔DIC公司製、EPICLON N-695、軟化 點95°C、環氧基當量214、平均官能基數7.6〕1070g (縮 水甘油基數（芳香環總數）：5.0莫耳）、丙烯酸360g( 5.0莫耳），及氫醌1.5g，加熱攪拌至100 °C，使其均勻 溶解。 其次，加入三苯基膦4.3g，加熱至110t後使其反應 2小時後，升溫至1 20t再進行1 2小時之反應。所得之反 應液中加入芳香族系烴（Solvesso 150) 415g、四氫苯甲 酸酐456.0g(3.0莫耳），於110°C下進行4小時之反應 ，冷卻後，得固體成份酸價89mgKOH/g、固體成份65% 之樹脂溶液。將其作爲樹脂溶液A-2。 使用該些樹脂溶液A-1、A-2及市售之樹脂溶液A-3 、A-4，將表1所示各種成份、比例（質量份）進行添加 ，於攪拌機中進行預混合後，以3輥硏磨機混練，以製作 焊料阻劑用光硬化性樹脂組成物。其中，所得之樹脂組成 物之分散度爲使用ERICHSEN公司製粒度測定劑進行粒 度測定並進行評估結果，得知爲1 5 μπι以下。 -50- 201116928 [表1] 組成 實施例 比較例 (質量' 份） 2 3 4 5 6 7 6 2 3 4 A-1 141 141 141 141 141 含羧基 A-2 154 154 154 154 154 之樹脂 A-3*1 154 A - 4*2 154 聚合起始劑 B-1*3 5 5 5 5 5 5 5 5 5 B-2*4 2 2 1 1 1 1 2 1 1 1 含苯乙烯基 C-1*5 20 5 5 5 5 5 5 5 5 5 之化合物 C-2*' 20 D-1*7 20 5 10 馬來醯亞胺 D-2*8 20 化合物 D-3*9 5 5 5 5 5 D-4*'0 5 氫硫基 化合物 Ε-Γ11 1 1 1 1 1 E-2·'2 0.5 E-3*13 0.2 0.2 F-Γ'4 5 5 5 35 30 15 熱硬化成分 F-2*15 35 35 35 10 40 40 40 40 F-3*,s 5 5 F-4*17 10 10 苯併胍 2 2 1 1 1 1 3 3 三聚氰胺 2 2 2 2 2 2 2 2 2 2 酚噻吩 0.2 0.2 0.2 0.2 1RGANOX1010*'9 1 1 1 2 2 水滑石 10 10 10 10 10 10 10 DPHA*'9 15 15 15 15 15 15 15 15 15 15 15 15 硫酸鋇&quot;° 100 100 100 100 100 100 100 100 100 100 100 100 G-1*2' 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 G-2*m 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 聚矽氧系消泡劑 3 3 3 3 3 3 3 3 3 3 3 3 DPM*’3 3 3 3 3 3 3 3 3 3 3 3 3 備考 * 1 : ZFR-1401H (固體成份：65.0%、固體成份酸價： 100日本化藥公司製） * 2 : ZCR_1601H (固體成份：65.0%、固體成份酸價： 100日本化藥公司製） -51 - 201116928 *3: 2 -甲基-1-( 4 -甲基硫代苯基）-2 -嗎啉基丙烷-1-酮（ 汽巴-日本公司製IRGACURE9 07 ) *4:乙酮’ 1·〔 9 -乙基-6- (2 -甲基苯甲醯基）-9H -卡必 醇-3-基〕1,1-(0-乙醯基肟）（汽巴·日本公司製 IRGACURE OXE02) *5:雙酚A與鹵化甲基苯乙烯縮合反應所得之化合物（ 昭和高分子公司製：RIPOKIN BPV-1X) *6:末端苯乙烯之寡伸苯基醚化合物（三菱氣體化學公 司製） * 7 :雙馬來醯亞胺化合物（DIC公司製 MIA-2〇〇 ) *8: 4，4’-二苯基甲烷雙馬來醯亞胺（大和化成工業公司 製 BMI- 1 000H) *9: 3,3’-二甲基-5，5’-二乙基-4,4’-二苯基甲烷雙馬來醯 亞胺（大和化成工業公司製 BMI-5100) *10: 1,6-雙馬來醯亞胺-(2，2,4-三甲基）己烷（大和化 成工業公司製 BMI-TMH) * 1 1 : 2,4,6_三氫硫基-S-三畊（三協化成公司製 ZISNET F) *12: 1,4-雙（3-氫硫基丁醯氧基）丁烷（昭和電工公司 製 CURRANTS MTBD1) * 13 : 2-氫硫基苯倂噻唑（川口化學工業公司製 AKUSERU Μ) *14:聚丁二烯骨架環氧樹脂（DAISEL化學公司製 ΡΒ3600) -52- 201116928 *15:雙酚型環氧樹脂（新日鐵化學公司製 YSLV-80XY) *16:嵌段異氰酸酯（旭化成化學公司製 TPA-B80E) * 17 :甲基化三聚氰胺樹脂（三和化學公司製 Mw-1 0 0 L Μ ) *18:抗氧化劑（汽巴-日本公司製） *19:二季戊四醇六丙烯酸酯（日本化藥公司製） * 20 : Β-30 (堺化學公司製） 氺 21 : C.I.Pigment Blue 15:3 * 22 ： C.I.Pigment Yellow 147 * 23 :二丙二醇單甲基醚 性能評估： &lt;最佳曝光量&gt; 於將表1所記載之各實施例及比較例之組成物，經拋 光滾筒硏磨後、水洗、乾燥所得之銅厚35μπι電路圖型基 板上’分別使用網版印刷法全面塗佈，以80 t之熱風循 環式乾燥爐乾燥60分鐘。 乾燥後，使用搭載有高壓水銀燈（短弧燈）之曝光裝 置’介由步進機（Kodak Νο·2)進行曝光、顯影（30。(：、 〇‘2MPa、丨wt%Na2C03水溶液）60秒之際，殘存之步進機 的圖型爲7段之時作爲最佳曝光量。 &lt;顯影性&gt; 將表1所記載之實施例及比較例之組成物，以乾燥後 -53- 201116928 形成約25μιη之方式以網版印刷法塗佈於鋪銅基板 8(TC之熱風循環式乾燥爐進行30分鐘之乾燥。乾 以1質量％碳酸鈉水溶液進行顯影，以碼表計算乾 被去除爲止所需要之時間。 特性試驗： 將表1所記載之各實施例及比較例之組成物， 後之膜厚形成約20μιη之方式，以網版印刷全面塗 成圖型之銅箔基板上，於80 °C下乾燥30分鐘，冷 溫。使用搭載有高壓水銀燈（短弧燈）搭載之曝光 以最佳曝光量對基板上之焊料阻劑圖型進行曝光， 3 0°C之1 wt%Na2C03水溶液以噴壓2kg/cm2之條件 6 〇秒鐘之顯影，得阻劑圖型。 將此基板於 UV旋風搬運爐中以積算| 1 000mJ/Cm2之條件下照射紫外線後，於i7(TC下力 分鐘使其硬化。對所得之印刷基板（評估基板）評 之特性。 &lt;耐無電解鍍金性&gt; 使用市售品之無電解鍍鎳浴及無電解鍍金浴 0.5μΐη、金0·03μιη之條件下進行鍍敷，經由膠布剝 ’於評估阻劑層是否產生剝離或鍍敷是否產生滲入 ’作爲是否可經由膠布剝離試驗剝離阻劑層之評估 基準係如以下所示內容。 上，以 燥後， 燥塗膜 以乾燥 佈於形 卻至室 裝置， 再使用 下進行 光量 熱60 t以下 ’於鎳 離試驗 之結果 。判定 -54- 201116928 ◎:滲入、未出現剝離。 〇：鍍敷後確認有少許之滲入，膠布剝離試驗後並未產生 剝離。 △:鍍敷後僅發生些許滲入，膠布剝離試驗後發現剝離現 象。 X :鍍敷後產生剝離。 &lt;加濕試驗（hast )後之絕緣性&gt; 將表1所記載之各實施例及比較例之組成物塗佈於形 成有柵型電極（線路/空間=50μπι/50μπι )之基板，經曝光 •顯影後，經熱硬化以製作評估基板。將該評估基板置入 1 3 0 °C、濕度8 5 %氛圍下之高溫高濕槽中，以電壓5 V荷 電，進行 192 小時、HAST(Highly Accelerated Stress Test)。測定HAST後之電氣絕緣性。 &lt; TCT耐性&gt; 將表1所記載之各實施例及比較例的組成物，塗佈於 形成有2mm之銅線圖型的基板上，經曝光.顯影後，再 經熱硬化，以製作於銅線上形成有3 mm四方的阻劑圖型 之評估基板。將該評估基板置入於-65 °C與1 50 °C之間進 行溫度循環之冷熱循環機中，進行T C T (Thermal Cycle Test)。隨後，觀察600循環時、800循環時與1000循環 時之外觀。 ◎ : 1000循環後也未產生異常。 -55- 201116928 〇：800循環未出現異常，於looo循環發生龜 △ : 600循環未出現異常，800循環發生龜裂。 X : 600循環發生龜裂。 &lt; PCT耐性&gt; 物形成有 ：(ESPEC ，於 1 2 1 192 小時 之塗膜狀 將依表1所記載之各實施例及比較例之組成 硬化物（硬化被膜）之評估基板，使用PCT裝置 股份有限公司製 HAST SYSTEM TPC-412MD) °C 、飽和、0.2MPa之條件下，進行 168、 PCT(Pressure Cooker Test)。隨後，評估處理後 態。判定基準係如以下所示。. ◎ : 1 92小時未出現膨漲、剝離、變色、溶出者 〇：1 68小時未出現膨漲、剝離、變色、溶出者 △:出現些許膨漲、剝離、變色、溶出者。 X:出現多處膨漲、剝離、變色、溶出者。 乾薄膜評估： ，依以下 將實施例1及比較例1之感光性樹脂組成物 所示方法製作評估基板，進行相同之評估。 &lt;乾薄膜製作&gt; 物分別使 之膜厚形 FB-50 ： 將實施例1及比較例1之光硬化性樹脂組成 用甲基乙基酮適當稀釋後，以塗佈機，以乾燥後 成20μηι之方式塗佈於PET薄膜（東麗公司製 -56- 201116928 1 6 μηι ) ’並於8 0 °C下進行3 0分鐘乾燥製得乾薄膜。 &lt;基板製作&gt; 將形成有電路之基板進行緩衝硏磨後，將依上述方法 所製作之乾薄膜使用真空層合機（名機製作所製 MVLP (登記商標）-500)，以加壓度：〇.8MPa、70°C、1分鐘 、真空度：133 .3Pa之條件下進行加熱層合，製得具有未 曝光之焊料阻劑層的基板（未曝光之基板）。 評估結果係如表2所示。 [表2] 特性 實施例 比較例 1 2 3 4 5 6 7 8 1 2 3 4 焊料阻劑 「D:乾薄膜1 L L:液狀」 L D L L L L L L L L D L L L 最佳曝光量 (mJ/cm2) 80 70 80 80 90 90 90 80 90 110 100 100 90 100 顯影性(秒） 20 20 20 25 25 25 30 30 25 20 20 20 25 20 耐無電解鍍金性 〇 0 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ HAST(X108Q) 1 2 2 0.3 0.2 O.t 5 2 6 0.08 0.1 0.01 0.1 0.3 TCT耐性 0 〇 Ο 〇 0 〇 ◎ ◎ ◎ X △ Δ △ Δ PCT耐性 〇 ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ X △ △ 〇 〇 如表2所示般，使用含苯乙烯基之化合物與馬來醯亞 胺化合物之實施例1 ~8的情形，與比較例i〜4比較時得知 ，不會降低其光硬化性’且可得到良好之H A S T、T C T耐 性及PCT耐性。特別是於含有含羧基之樹脂的a- 1之實 施例（實施例1、2、6~ 8 )’因具有優良之絕緣信賴性， 故適合作爲焊料阻劑。 -57- 201116928 另外，於無使用馬來醯亞胺化合物之比較例2〜4中， 其TCT耐性及PCT耐性低劣，所得之硬化塗膜亦爲脆化 之塗膜。此外，不使用含苯乙烯基之化合物與馬來醯亞胺 化合物的比較例1之情形’則形成除1'CT耐性及PCT耐 性更爲低劣以外’其感度也不佳且電氣特性降低之結果。 -58-For the ultraviolet absorber, commercially available articles may be used, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 3 84-2 'TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460 &gt; TINUVIN 479 (all are Ciba-Japan company) and so on. These ultraviolet absorbing agents may be used alone or in combination of two or more. When used in combination with an antioxidant, the molded article obtained from the photocurable resin composition of the present embodiment can be stabilized. In the photocurable resin composition of the present embodiment, if necessary, a known tackifier such as fine powder of cerium oxide, organic clay or montmorillonite, or a defoaming agent such as a polyfluorene, a fluorine or a polymer may be added. Agents and/or slip agents, known additives such as imidazole-44-201116928, thiazole coupling agents such as thiazoles and triazoles, antioxidants, and anti-caries agents. Further, the polymerizable compound contained in the photocurable resin composition of the present embodiment can be used for the purpose of preventing polymerization during thermal polymerization or storage, and an anti-polymerizing agent can be used. The heat-resistant polymerization agents, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butyl catechol, gallic phenol, 2-hydroxybenzophenone, 4- Methoxy-2-pyridylbenzophenone, chlorinated first copper, hydrazine, chloranil, naphthylamine, /3-naphthol, 2,6-di-t-butyl-4-methyl Phenol, 2,2 '-extended methyl bis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methyl blue, copper A reaction with an organic chelating agent, methyl salicylate, a phenol thiazide, a nitroso compound, a chelating agent of a nitroso compound and A1, and the like. In the photocurable resin composition of the present embodiment, an adhesion promoter can be used to promote adhesion between the layers, adhesion between the photosensitive resin layer and the substrate, and the like. Such adhesion promoters, for example, benzazole, benzoxazole, benzothiazole, 3-morpholinylmethyl-1-phenyl-triazole-2.thione, 5-amino-3- Morpholinylmethyl-thiazole-2-thione, triazole 'tetrazole, benzotriazole, carboxybenzotriazole, amine group containing benzotriazole, decane coupling agent and the like. After the photocurable resin composition of the present embodiment, which is formed according to the specific composition, for example, an organic solvent can be used to adjust the viscosity of the coating method, and the substrate can be immersed and coated. Coating is carried out by a method such as a flow coating method, a roll coating method, a strip coating method, a screen printing method, or a curtain coating method. -45- 201116928 Volatile and dry after coating, hot air circulating drying oven, IR furnace, hot platen, turbine oven, etc. (flowing in a hot air direction using a dryer equipped with a heat source that uses steam to heat the air) The method of contacting and the method of blowing the support by a nozzle are carried out at a temperature of about 60 to 100 ° C. Further, the photocurable resin composition forms a dry film, and when it is bonded to a substrate, a resin insulating layer can be formed. The dry film has, for example, a structure in which a carrier film such as polyethylene terephthalate or the like is laminated with a resin insulating layer such as a solder resist layer, and a peelable coating film used as necessary. Things. The resin insulating layer is a layer obtained by applying a photocurable resin composition to a carrier film or a coating film and then drying the film. In the resin insulating layer, the photocurable resin composition of the present embodiment is uniformly coated on a carrier film by a sheet coater, a rib coater, a dot coater, a film coater or the like. The thickness of the cloth 10~150μηι is formed by drying. Subsequently, a dry film is formed by laminating the film as necessary. In this case, the light-hardening resin composition may be applied to the coating film, and after drying, it may be laminated to the carrier film. As the carrier film, for example, a thermoplastic film such as a polyester film having a thickness of 2 to 15 Å μηι can be used. As the coating film, a polyethylene film, a polypropylene film or the like can be used, and the adhesion to the solder resist layer can be smaller than that of the carrier film. When these dry films are used, in the case of using a cover film, a resin insulating layer can be formed on the substrate by peeling off the resin insulating layer and laminating the substrate, laminating or the like. Further, the carrier film may be peeled off before or after exposure to -46-201116928 as described later. At this time, the substrate for forming a coating film or a dry film may be, for example, phenol paper, epoxy paper, epoxy glass cloth, polyimide glass, glass cloth/epoxy non-woven fabric, glass cloth/epoxy paper. , epoxy synthetic fiber, fluorine, polyethylene, PPO, cyanate ester, copper foil laminate for high-frequency circuit, etc., full-grade (FR-4, etc.) copper foil laminate, other polyimide film , PET film, glass substrate, ceramic substrate, wafer board, etc. In addition, direct pattern exposure (irradiation of active energy rays) is performed by selective exposure or laser direct exposure through a photomask having a pattern of selective active energy lines using a contact (or non-contact) method. For the exposure machine used for the active energy ray irradiation, for example, a direct drawing device (for example, a laser direct image drawing device that draws CAD data by a computer with a direct laser), an exposure machine equipped with a metal halide lamp, and the like can be used. A direct drawing device for an exposure machine for a high-pressure mercury lamp, an exposure machine equipped with a mercury short-arc lamp, or an ultraviolet lamp such as a (super) high-pressure mercury lamp. The active energy ray is preferably a laser light having a wavelength of 3 5 0 to 4 10 n m . When the wavelength is in this range, radicals can be efficiently generated from the photoinitiator. When using laser light in this range, either a gas laser or a solid laser can be used. Further, the exposure amount varies depending on the film thickness or the like, and is generally 5 to 200 mJ/cm 2 ', preferably 5 to 1 μm/cm 2 , more preferably 5 to 5 OmJ/cm 2 . For the direct drawing device, for example, a device manufactured by Orbotech Co., Ltd., Pantax, etc. can be used, and any device can be used as long as it can emit a laser having a maximum wavelength of -47 to 201116928 3 5 0 to 4 10 nm. Subsequently, the exposed portion (the portion irradiated with the active energy ray) is hardened by the result of the exposure, and the unexposed portion is developed in a dilute aqueous alkali solution (for example, 0.3 to 3 wt% of an aqueous solution of Na 2 CO 3 ) to form a cured product (pattern). 〇 At this time, the development method may use a dipping method, a spraying method, a spraying method, a brushing method, etc. 'developing solution may use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, An aqueous solution of an alkali such as an amine. Further, in the case of a thermosetting component, for example, when thermally hardened by heating to a temperature of about 140 to 180 ° C, the carboxyl group of the carboxyl group-containing resin may have a plurality of cyclic (sulfur) groups in the molecule. The thermosetting component of the ether group reacts to form a cured product having various properties such as excellent heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. [Embodiment] [Examples] Hereinafter, the examples and comparative examples will be specifically described, but the present invention is not limited by the examples. In addition, hereinafter, "parts" and "%" are referred to as full quality standards unless otherwise specified. [Synthesis of the carboxyl group-containing resin (A-1)] The phenol novolak type cresol resin (made by Showa Polymer Co., Ltd.) was mixed in an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a mixing device. The product name "Shonol. CRG951", OH equivalent: 119.4 - 48 - 201116928 ) 119.4 g, potassium hydroxide 1. i9 g and toluene il 9.4 g, and the inside of the reaction system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was slowly added dropwise, and the mixture was reacted at 125 to 132 t, 〇 to 4.8 kg/cm 2 for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added in the reaction solution, and neutralized with potassium hydroxide to obtain a novolac type cresol resin having a nonvolatile content of 62.1% 'hydroxyl group 丨82.2 g/eq. The propylene oxide reaction solution. It is obtained by adding 1 eq of a phenolic hydroxyl group to an average of 1.08 moles of epoxy. 293.0 g of an alkylene oxide reaction solution of the obtained novolac type cresol resin, 43_2 g of acrylic acid, u.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 2.9 g of toluene 25 were provided with a stirrer, a thermometer, and an air blowing tube. In the reactor, air was blown at a rate of 10 ml/min, and under stirring, it was reacted for 11 hours under 11 Torr. The water formed by the reaction was distilled in a manner of azeotropic mixture with toluene to distill 1 2 · 6 g of water. Subsequently, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 3 5.3 5 g of a 15 % aqueous sodium hydroxide solution, followed by water washing. Subsequently, toluene was replaced with diethylene glycol monoethyl ether acetate 118.lg in an evaporator, and then the novolac type acrylate resin solution was distilled off. Next, the obtained novolac type acrylate resin solution 3 3 2 · 5 g and triphenylphosphine 1.22 g were mixed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and the air was 10 ml/min. While blowing at a speed, while stirring, slowly add 6 0.8 g of tetrahydrobenzoic anhydride to 9 5 to 1 〇1. (: The reaction is carried out for 6 hours. The acid value of the solid matter is 8 8 mg Κ Ο H / g, and the nonvolatile matter is 7 1 % of the carboxyl group-containing photosensitive resin. Hereinafter, the reaction solution is referred to as a resin solution A-1 - 49 - 201116928 [Synthesis of carboxyl group-containing resin (A-2)] To 600 g of diethylene glycol monoethyl ether acetate, o-cresol-novolac type epoxy resin (made by DIC, EPICLON N-) was added. 695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6] 1070 g (glycidyl number (total aromatic ring): 5.0 mol), acrylic acid 360 g (5.0 mol), and hydroquinone 1.5 g, heating After stirring to 100 ° C, it was uniformly dissolved. Next, 4.3 g of triphenylphosphine was added, and after heating to 110 t, the reaction was carried out for 2 hours, and then the temperature was raised to 1200 m and further reacted for 12 hours. 415 g of aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydrobenzoic anhydride were reacted at 110 ° C for 4 hours. After cooling, the solid content acid value was 89 mg KOH / g, and the solid content was 65%. Resin solution, which is used as resin solution A-2. These resin solutions A-1, A-2 and commercially available resins are used. Liquids A-3 and A-4 were added to various components and ratios (mass parts) shown in Table 1, and premixed in a mixer, and then kneaded in a 3-roll honing machine to prepare photocuring properties for solder resists. In the resin composition, the dispersion degree of the obtained resin composition was measured by particle size measurement using a particle size measuring agent manufactured by ERICHSEN Co., Ltd., and it was found to be 15 μπι or less. -50- 201116928 [Table 1] Comparison of composition examples Example (mass 'parts) 2 3 4 5 6 7 6 2 3 4 A-1 141 141 141 141 141 Resin with carboxyl group A-2 154 154 154 154 154 A-3*1 154 A - 4*2 154 Starting agent B-1*3 5 5 5 5 5 5 5 5 5 B-2*4 2 2 1 1 1 1 2 1 1 1 Styryl containing C-1*5 20 5 5 5 5 5 5 5 5 5 Compound C-2*' 20 D-1*7 20 5 10 Maleimine D-2*8 20 Compound D-3*9 5 5 5 5 5 D-4*'0 5 Hydrogenthio compound Ε -Γ11 1 1 1 1 1 E-2·'2 0.5 E-3*13 0.2 0.2 F-Γ'4 5 5 5 35 30 15 Thermal hardening component F-2*15 35 35 35 10 40 40 40 40 F-3*,s 5 5 F-4*17 10 10 Benzopyrene 2 2 1 1 1 1 3 3 Melamine 2 2 2 2 2 2 2 2 2 2 Phenolthiophene 0.2 0.2 0.2 0.2 1RGANOX1010*'9 1 1 1 2 2 Hydrotalcite 10 10 10 10 10 10 10 DPHA*'9 15 15 15 15 15 15 15 15 15 15 15 15 Barium sulfate &quot;° 100 100 100 100 100 100 100 100 100 100 100 100 G-1*2' 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 G-2*m 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Polyoxane defoamer 3 3 3 3 3 3 3 3 3 3 3 3 DPM*'3 3 3 3 3 3 3 3 3 3 3 3 3 Remarks* 1 : ZFR-1401H (solid content: 65.0%, solid content acid price: 100 manufactured by Nippon Kayaku Co., Ltd.) * 2 : ZCR_1601H (solid content: 65.0%, solid component acid price: 100 manufactured by Nippon Kayaku Co., Ltd.) -51 - 201116928 *3: 2-Methyl-1-(4-methylthiophenyl)-2-morpholine Propane-1-one (ICGACURE9 07, manufactured by Ciba-Japan) *4: Ethylketone-1 [9-ethyl-6-(2-methylbenzimidyl)-9H-carbitol-3 -Based] 1,1-(0-Ethyl hydrazine) (Ciba, IMGACURE, manufactured by Nippon Co., Ltd. OXE02) *5: Compound obtained by condensation reaction of bisphenol A with halogenated methyl styrene (made by Showa Polymer Co., Ltd.: RIPOKIN BPV-1X) *6: oligophenylene ether compound of terminal styrene (Mitsubishi Gas Chemical Co., Ltd.) * 7 : Bismaleimide compound (MIA-2〇〇 manufactured by DIC Corporation) *8: 4,4'-diphenylmethane bismaleimide (BMI-1 000H manufactured by Daiwa Kasei Kogyo Co., Ltd.) *9: 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) *10: 1 , 6-Bismaleimide-(2,2,4-trimethyl)hexane (BMI-TMH, manufactured by Daiwa Kasei Kogyo Co., Ltd.) * 1 1 : 2,4,6_trihydrothio-S- San Geng (ZISNET F, manufactured by Sankyo Chemical Co., Ltd.) *12: 1,4-bis(3-hydrothiobutoxy)butane (CURRANTS MTBD1, manufactured by Showa Denko) * 13 : 2-Hydroxythiobenzoquinone Thiazole (AKUSERU 制 manufactured by Kawaguchi Chemical Industry Co., Ltd.) *14: Polybutadiene skeleton epoxy resin (ΡΒ3600 manufactured by DAISEL Chemical Co., Ltd.) -52- 201116928 *15: Bisphenol type epoxy resin (YSLV- manufactured by Nippon Steel Chemical Co., Ltd.) 80XY) *16: Block isocyanate (Asahi Kasei Chemical Co., Ltd. TPA-B80E) * 17 : Methylated melamine resin (Mw-1 0 0 L 制 manufactured by Sanwa Chemical Co., Ltd.) *18: Antioxidant (made by Ciba-Japan) *19: Dipentaerythritol hexaacrylate (Japan) Pharmacopoeia) * 20 : Β-30 (manufactured by Sigma Chemical Co., Ltd.) 氺21 : CIPigment Blue 15:3 * 22 : CIPigment Yellow 147 * 23 : Dipropylene glycol monomethyl ether performance evaluation: &lt;Optimum exposure &gt; The composition of each of the examples and the comparative examples described in Table 1 was subjected to troweling by a polishing drum, water washing, and drying, and the copper-thick 35 μm circuit pattern substrate was completely coated by screen printing. Dry in a hot air circulating oven at 80 t for 60 minutes. After drying, exposure and development were carried out by a stepping machine (Kodak Νο. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) (30: (:, 〇 '2 MPa, 丨wt% Na 2 C03 aqueous solution) for 60 seconds. In the case where the pattern of the remaining stepper is 7 steps, the optimum exposure amount is obtained. <Developability> The compositions of the examples and comparative examples shown in Table 1 are dried, after -53-201116928 The method of forming about 25 μm was applied to the copper-clad substrate 8 by screen printing (the hot air circulating drying oven of TC was dried for 30 minutes. The drying was carried out with a 1% by mass aqueous solution of sodium carbonate, and the dryness was removed by a code table. The time required. Characteristic test: The composition of each of the examples and the comparative examples shown in Table 1 was formed into a pattern of copper foil substrate by screen printing by forming a film thickness of about 20 μm. Drying at 80 °C for 30 minutes, cold temperature. Exposure to the solder resist pattern on the substrate at the optimum exposure using an exposure equipped with a high-pressure mercury lamp (short-arc lamp), 1 wt% Na2C03 at 30 °C The aqueous solution is sprayed at a pressure of 2 kg/cm 2 for 6 seconds. The film is obtained in a UV cyclone furnace at a temperature of 1 000 mJ/cm 2 and then hardened at i7 (TC) for a minute. The resulting printed substrate (evaluation substrate) <Characteristics of the evaluation. &lt;Electroless electroless gold plating> Plating using a commercially available electroless nickel plating bath and an electroless gold plating bath under conditions of 0.5 μΐη, gold 0·03 μιη, and stripping through a tape Whether the agent layer is peeled off or whether plating is infiltrated or not. The evaluation criteria for peeling off the resist layer through the tape peeling test are as follows. On the top, after drying, the dry film is dried to form a shape to the chamber. The device was subjected to the measurement of the amount of light under 60 t or less in the nickel separation test. Judgment -54- 201116928 ◎: Infiltration and no peeling occurred. 〇: A little infiltration was observed after plating, and no peeling occurred after the tape peeling test Peeling: △: Only a little infiltration occurred after plating, and peeling was observed after the tape peeling test. X: Peeling occurred after plating. &lt;Insulation after humidification test (hast)> Each of the conditions described in Table 1 The composition of the examples and the comparative examples was applied to a substrate on which a gate electrode (line/space = 50 μm / 50 μπι) was formed, and after exposure and development, it was thermally hardened to prepare an evaluation substrate. The evaluation substrate was placed in 1 3 In a high-temperature and high-humidity bath at a humidity of 8 ° C and a humidity of 8 5 %, the voltage is 5 V and charged for 192 hours and HAST (Highly Accelerated Stress Test). The electrical insulation after HAST is measured. < TCT resistance > The compositions of the respective examples and comparative examples described in Table 1 were applied onto a substrate having a copper wire pattern of 2 mm, exposed to light, developed, and then thermally cured to form 3 mm on the copper wire. Evaluation substrate for the tetragonal resist pattern. The evaluation substrate was placed in a thermal cycler which was subjected to temperature cycling between -65 ° C and 150 ° C to carry out T C T (Thermal Cycle Test). Subsequently, the appearance at 600 cycles, 800 cycles, and 1000 cycles was observed. ◎ : No abnormality occurred after 1000 cycles. -55- 201116928 〇: No abnormality occurred in 800 cycles. Turtle occurred in the looo cycle. △: No abnormality occurred in 600 cycles, and crack occurred in 800 cycles. X : 600 cycles of cracking. &lt;PCT resistance&gt; The formation of the substrate is: (ESPEC, the coating film of the composition of each of the examples and the comparative examples described in Table 1 and the hardened film (hardened film) in the film form at 1 2 1 192 hours, using PCT 168, PCT (Pressure Cooker Test) under the conditions of °C, saturation, and 0.2 MPa manufactured by HIS SYSTEM TPC-412MD. Subsequently, the post-processing status is evaluated. The judgment criteria are as follows. ◎ : 1 92 hours without swelling, discoloration, discoloration, dissolution 〇: 1 68 hours without swelling, peeling, discoloration, dissolution △: Some swelling, peeling, discoloration, dissolution. X: There are many cases of swelling, peeling, discoloration, and dissolution. Evaluation of dry film: An evaluation substrate was prepared by the method shown in the photosensitive resin compositions of Example 1 and Comparative Example 1, and the same evaluation was carried out. &lt;Dry film production&gt; The film thickness FB-50 was separately obtained: The photocurable resin compositions of Example 1 and Comparative Example 1 were appropriately diluted with methyl ethyl ketone, and then dried by a coater. The film was applied to a PET film (manufactured by Toray Industries, Inc. - 56-201116928 1 6 μηι) in a manner of 20 μm, and dried at 80 ° C for 30 minutes to obtain a dry film. &lt;Substrate preparation&gt; After the substrate on which the circuit was formed was subjected to buffer honing, the dry film produced by the above method was vacuum laminated (MVLP (registered trademark)-500 manufactured by Nihon Seisakusho Co., Ltd.). A laminate having an unexposed solder resist layer (unexposed substrate) was prepared by heating lamination under conditions of 8 MPa, 70 ° C, 1 minute, and a vacuum of 133.3 Pa. The evaluation results are shown in Table 2. [Table 2] Characteristic Example Comparative Example 1 2 3 4 5 6 7 8 1 2 3 4 Solder Resist "D: Dry Film 1 LL: Liquid" LDLLLLLLLLDLLL Optimum Exposure (mJ/cm2) 80 70 80 80 90 90 90 80 90 110 100 100 90 100 Developability (seconds) 20 20 20 25 25 25 30 30 25 20 20 20 25 20 Resistance to electroless gold plating 〇 0 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ HAST (X108Q 1 2 2 0.3 0.2 Ot 5 2 6 0.08 0.1 0.01 0.1 0.3 TCT resistance 0 〇Ο 〇0 〇 ◎ ◎ ◎ X △ Δ △ Δ PCT resistance 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ X △ △ 〇〇 Table 2 As shown in the above, in the case of Examples 1 to 8 in which a styrene group-containing compound and a maleidinolide compound were used, it was found that the photocurability was not lowered and it was good when compared with Comparative Examples i to 4. HAST, TCT tolerance and PCT tolerance. In particular, the examples (Examples 1, 2, and 6 to 8) of a-1 containing a carboxyl group-containing resin are suitable as solder resists because of their excellent insulating reliability. Further, in Comparative Examples 2 to 4 in which no maleidin compound was used, the TCT resistance and PCT resistance were inferior, and the obtained cured coating film was also an embrittled coating film. Further, in the case of Comparative Example 1 in which a compound containing a styryl group and a maleidinide compound were not used, 'the result was that the sensitivity was not good and the electrical characteristics were lowered except for the 1' CT resistance and the PCT resistance. . -58-

Claims (1)

201116928 七、申請專利範圍： 1 · 一種光硬化性樹脂組成物，其特徵爲含有，含羧基 之樹脂、光聚合起始劑、含苯乙烯基之化合物，及馬來醯 亞胺化合物。 2 ·如申請專利範圍第1項之光硬化性樹脂組成物，其 爲含有氫硫基化合物。 3. —種乾薄膜，其特徵爲，使如申請專利範圍第1或 2項之光硬化性樹脂組成物塗佈於薄膜上並經乾燥而得。 4. 一種硬化物，其特徵爲，使如申請專利範圍第1或 2項之光硬化性樹脂組成物塗佈於基材上並經乾燥而得之 乾燥塗膜，或使前述光硬化性樹脂組成物塗佈於薄膜上並 經乾燥而得之乾薄膜層合於基材上所得之塗膜，經活性能 量線照射進行光硬化而得者。 5 . —種印刷電路板，其特徵爲，具有使如申請專利範 圍第1或2項之光硬化性樹脂組成物塗佈於基材上並經乾 燥而得之乾燥塗膜，或使前述光硬化性樹脂組成物塗佈於 薄膜上並經乾燥而得之乾薄膜層合於基材上所得之塗膜， 經活性能量線照射進行光硬化而得之硬化物的圖型。 -59- 201116928 四 指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明：無 201116928 五、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201116928 VII. Patent application scope: 1 . A photocurable resin composition characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, a styryl group-containing compound, and a maleic imine compound. 2. The photocurable resin composition of claim 1, which is a hydrogenthio group-containing compound. 3. A dry film obtained by applying a photocurable resin composition according to claim 1 or 2 to a film and drying it. A cured product obtained by applying a photocurable resin composition according to claim 1 or 2 to a substrate and drying the dried coating film, or the photocurable resin The coating film obtained by coating a composition on a film and drying the dried film to be laminated on a substrate is photocured by irradiation with an active energy ray. A printed circuit board comprising: a dried coating film obtained by applying a photocurable resin composition according to claim 1 or 2 to a substrate and dried, or the light A pattern of a cured product obtained by applying a curable resin composition to a film obtained by laminating a dry film obtained by laminating a dry film to a substrate, and photohardening by irradiation with an active energy ray. -59- 201116928 IV Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201116928 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none
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US11434313B2 (en) * 2020-12-16 2022-09-06 Canon Kabushiki Kaisha Curable composition for making cured layer with high thermal stability

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006285174A (en) * 2004-12-08 2006-10-19 Fuji Photo Film Co Ltd Photosensitive composition, photosensitive film, permanent pattern and method for forming same
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US7662906B2 (en) * 2006-03-10 2010-02-16 Mitsubishi Gas Chemical Company, Inc. Polyfunctional phenylene ether oligomer, derivative thereof, resin composition containing the same, and use thereof
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JP2008274003A (en) * 2007-04-25 2008-11-13 Hitachi Chem Co Ltd Phosphorus-containing compound, resin composition containing the same, photosensitive film by using resin composition, method for forming resist pattern and printed wiring board
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