TWI352875B - Photosensitive transcription sheet, photosensitive - Google Patents

Photosensitive transcription sheet, photosensitive Download PDF

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TWI352875B
TWI352875B TW093124377A TW93124377A TWI352875B TW I352875 B TWI352875 B TW I352875B TW 093124377 A TW093124377 A TW 093124377A TW 93124377 A TW93124377 A TW 93124377A TW I352875 B TWI352875 B TW I352875B
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photosensitive
photosensitive layer
layer
transfer sheet
light
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TW093124377A
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TW200513796A (en
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Morimasa Sato
Yuichi Wakata
Masanobu Takashima
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/56—Organic absorbers, e.g. of photo-resists
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G03F7/07—Silver salts used for diffusion transfer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)

Description

1352875 九、發明說明： 【發明所屬之技術領域】 本發明係關於感光性轉印片、感光性積層體、影像圖 案形成方法、及配線圖案形成方法。本發明係特別有關於 作爲印刷配線板製造用之有用的感光性轉印片、積層體， 及使用該感光性轉印片或積層體來形成印刷配線板之配線 圖案形成方法。 【先前技術】 具有支持體與感光層之感光性轉印片，被廣泛地利用 作爲用於如印刷配線板、濾色器或柱形材、唇形材、間隔 片、間隔壁等顯示用構件、印刷版、全息照相、微型機械、 耐材等各種影像形成材料等製造之影像的圖案形成材料。 在印刷配線板之製造領域中，進行著藉由使用由透明 支持體（例如聚對苯二甲酸乙二酯）與形成於該支持體上之 感光層所構成之感光性轉印片（亦稱爲乾膜光阻）之光微影 技術來形成配線圖案。例如，在具有通孔之印刷配線板製 造的情況下，於印刷配線板形成用基板（例如鍍銅積層板） 形成通孔，並於通孔內側壁部分形成金屬鍍層後，於基板 表面重疊密著感光性轉印片之感光層，在配線圖案形成區 域與包含通孔開口部分之區域各別照射光成爲既定圖案形 狀來硬化感光層。其次，剝除感光性轉印片之支持體，利 用顯像液來溶解除去配線圖案形成區域上之未硬化區域及 通孔開口部分區域上之硬化區域（稱爲保護幕膜）以外之未 硬化區域後，蝕刻處理暴露之金屬層部分，然後藉由除去 硬化區域，進行於基板表面上生成配線圖案。 1352875 . 使用上述保護幕膜來保護通孔之金屬鎪層的方法，一 般被稱爲保護幕法。又在多層構成之印刷配線板中有設置 稱爲連接孔之層間接續用孔洞的情況，在該情況下亦同樣 地，在配線圖案形成時，有藉由保護幕膜保護連接孔部分 之必要。 近年來，對於印刷配線板之高密度化的要求提高，而 要求可具有較高解析度之光阻膜。由於提高光阻膜之解析 度，所以可有效地使其感光層膜厚變薄。然而如前述，感 光層硬化後之硬化層亦有保護形成於印刷配線板之通孔或 連接孔的功能，單純地使感光層的膜厚變薄時，則在溶解 除去感光性樹脂組成物之未硬化範圍之步驟或蝕刻處理已 暴露之金屬層部分之步驟中，發生所謂該保護幕膜破裂之 問題。 迄今正熱烈進行著可形成高解析度之圖案，並可形成 不易破裂之保護幕膜之感光性轉印片的開發，該結果揭示 如下》 於專利文獻1中，記載著具有由具有羧基之黏結劑成 分、特定乙烯基胺甲酸酯化合物與特定之丙烯酸酯化合物 的單體成分、及光聚合起始劑所構成之感光層的感光性轉 印片。 於專利文獻2中，記載著具有以於支持體之上設置其 爲鹼性可溶性、因加熱導致之流動性小、且對於活性能源 線感應之第一感光層’進一步於其上設置其爲鹼性可溶 性 '因加熱導致之流動性大、對於活性能源線感應之第二 感光層所構成之雙層感光層的感光性轉印片。於該專利文 1352875 獻中，說明可藉由將感光性轉印片之第二感光層埋入通孔 內來保護通孔之金屬層。 於專利文獻3中，記載著其爲於支持體之上具有第一 感光層與第二感光層之感光性樹脂積層體，該等二層具有 互不相同之乙烯共聚物，而且於兩層中包含特定單官能單 體之範例，並記載其效果爲提昇其密著與解析。 於專利文獻4中，記載著於支持體上具有非黏著性之 感光層與黏著性感光層之光阻、及使用它之印刷配線板之 形成方法，記載以伸張性與解析性提昇作爲其效果。 於專利文獻5中，揭示於基材上具有光聚合速度互不 相同之至少二層的光聚合性層（厚度爲25 y m〜2.5mm)、接 近基板側的聚合速度快之印刷凸版製造用的感光板，記載 形成印刷面之基部變得較頂部寬之凸版像的範例。 【專利文獻1】特開平10- 142789號公報 【專利文獻2】特開平8-54732號公報 【專利文獻3】特開平10-111573號公報 【專利文獻4】特開平3 - 1 7 6 5 0號公報 【專利文獻5】特公昭3 7 - 1 3 0 6號公報 【發明內容】 [發明所欲解決之課題] 本發明之課題係在於提供可容易地在影像內形成厚度 不同之所希望圖案的感光性轉印片及感光性積層體。 又本發明之課題亦在於提供可使用感光性轉印片或感 光性積層體，來對於工業上有利地於影像內形成厚度不同 之所希望圖案的方法。 1352875 . 特別地，本發明之課題在於提供對於印刷配線板之製 造爲有效、可藉由薄層化進行高解析度化、可形成破裂不 易之保護幕膜的感光性轉印片。 又本發明之課題亦在於提供可使用感光性轉印片，在 工業上有利地製造具有通孔或連接孔等孔洞部分之印刷配 線板的方法。 [解決課題的手段] 本發明第一在於在支持體上，依次積層由包含黏結 劑' 聚合性化合物、及光聚合起始劑之感光性樹脂組成物 所構成之第一感光層，障壁層，然後由包含黏結劑、聚合 性化合物、及光聚合起始劑之感光性樹脂組成物所構成、 顯示比第一感光層之光感度相對高之光感度的第二感光層 所構成之感光性轉印片。 上述第一發明之較佳實施態樣係如下所述。 (1) 障壁層係含有對水或碳原子數1~4的低級醇顯示有 親和性之樹脂爲主要成分。 (2) 障壁層係含有對水或碳原子數1~4的低級醇顯示可 溶性之樹脂爲主要成分。 (3) 障壁層係具有— 範圍的厚度。 (4) 障壁層具有聚合性化合物。 (5) 障壁層具有感光性、且障壁層的光感度比第一感光 層的光感度係相對低。 (6) 障壁層含有之聚合性化合物係具有聚合性基之聚 合物。 (7) 具有上述（6)聚合性基之聚合物係對水或碳原子數1 1352875 . 至4的低級醇顯示有親和性。 (8) 具有上述（7)聚合性差之聚合物係對水或碳原子數1 至4的低級醇有可溶性。 (9) 在以第一感光層之光感度爲1之情況下，第二感光 層之光感度在2~200的範圍。 (1 〇)以用來硬化第二感光層所必須之光能量A與用來 硬化第一感光層所必須之光能量B的A/B所表示之比例在 0.005〜0.5的範圍° (1 1)以用來硬化第二感光層所必須之光能量A與直到 開始硬化第一感光層所必須之光能量C的C/A所表示之比 例在1 ~ 1 0的範圍。 (12) 第一感光層與二感光層各別含有增感劑。 (13) 於第二光感層所含有之增感劑的量比於第一感光 層所含有之增感劑的量多。 (14) 於第二光感層所含有之光聚合起始劑的量比於第 一感光層所含有之光聚合起始劑的量多。 (15) 於第二光感層所含有之聚合性化合物的量比於第 一感光層所含有之聚合性化合物的量多。 (16) 第一感光層波長4〇5nm的吸光度爲0.1〜1.0之範 圍β (17) 在第一感光層及/或第二感光層中含有於 380~430nm具有極大吸收波長之化合物。 (18) 在第一感光層及/或第二感光層中含有於 3 80~4 3 0nm具有極大吸收波長之化合物係爲增感劑。 (19) 第一感光層具有1範圍之厚度’而且該厚 1352875 度比第二感光層的厚度大。 (20) 第二光感層具有0.1~15/zm範圍之厚度。 (21) 支持體爲合成樹脂製，而且透明。 (22) 支持體爲帶狀支持體。 (23) 於第二感光層上配置著保護膜。 (24) 其爲帶狀支持體，並捲取成滾筒狀。 (25) 其爲印刷配線板製造用。 本發明第二在於在基體上，依次積層由包含黏結劑、 聚合性化合物、及光聚合起始劑之感光性樹脂組成物所構 成之第二感光層，障壁層，然後由包含黏結劑、聚合性化 合物、及光聚合起始劑之感光性樹脂組成物所構成、顯示 比第二感光層之光感度相對低之光感度的第一感光層所構 成之感光性積層體。 上述第二發明之較佳實施態樣如下所述。 (1) 障壁層係含有對水或碳原子數1〜4的低級醇顯示有 親和性之樹脂爲主要成分。 (2) 障壁層係含有對水或碳原子數1~4的低級醇顯示可 溶性之樹脂爲主要成分。 (3) 障壁層係具有0.1~5//m範圍的厚度。 (4) 障壁層具有聚合性化合物。 (5) 障壁層具有感光性、且障壁層的光感度比第一感光 層的光感度係相對低。 (6) 障壁層含有之聚合性化合物係具有聚合性基之聚 合物。 (7) 具有上述（6)聚合性基之聚合物係對水或碳原子數1 -10- 1352875 至4的低級醇顯示有親和性。 (8) 具有上述（7)聚合性差之聚合物係對水或碳原子數1 至4的低級醇有可溶性。 (9) 在以第一感光層之光感度爲1之情況下，第二感光 層之光感度在2〜200的範圍。 (10) 以用來硬化第二感光層所必須之光能量A與用來 硬化第一感光層所必須之光能量B的A/B所表示之比例在 0.005〜(K5的範圍° (1 1 )以用來硬化第二感光層所必須之光能量A與直到 開始硬化第一感光層所必須之光能量C的C/A所表示之比 例在1〜1 0的範圍。 (12) 第一感光層與二感光層各別含有增感劑。 (13) 於第二光感層所含有之增感劑的量比於第—感光 層所含有之增感劑的量多。 (14) 於第二光感層所含有之光聚合起始劑的量比於第 一感光層所含有之光聚合起始劑的量多° (15) 於第二光感層所含有之聚合性化合物的量比於第 一感光層所含有之聚合性化合物的量多。 (16) 第一感光層波長4〇5nm的吸光度爲0·1"*1.0之範 圍。 (17) 在第一感光層及/或第二感光層中含有於 380~430nm具有極大吸收波長之化合物。 (18) 在第一感光層及/或第二感光層中含有於 3 80~4 3〇11111具有極大吸收波長之化合物係爲增感齊1° (19) 第一感光層具有1~1〇〇#111範圍之厚度’而且該厚 -11 - 1352875 度比第二感光層的厚度大。 (20)第二光感層具有0.1〜15/zm範圍之厚度。 (2 1)基體係爲印刷配線板形成用基板。 (22) 將第一感光層之上的支持體（特佳爲透明樹脂薄 膜）加以積層。 (23) 其爲帶狀支持體，並捲取成滾筒狀。 (24) 其爲印刷配線板製造用。 本發明第三係於基板上由經同時硬化第一感光層與第 二感光層所形成之硬化樹脂層存在之區域、與硬化樹脂層 不存在之區域所構成之影像圖案形成方法，其包含下述步 驟： (1) 於基板上，積層前述第一發明之感光性轉印片使得 感光性轉印片的第二感光層爲基板側之位置關係，以得到 積層體之步驟； (2) 從積層體之第一感光層側進行既定影像圖案之光 照射，同時硬化接受該光照射之區域的第一感光層與第二 感光層之步驟； (3) 從積層體除去支持體之步驟；然後 (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 本發明第四係於基板上由經同時硬化第一感光層與第 二感光層所形成之樹脂層存在的區域、藉由硬化第二感光 層所形成之樹脂層存在的區域、然後硬化樹脂層不存在之 區域所構成之影像圖案形成方法，其包含下述步驟： (1)於基板上，以該第二感光層爲基板側之關係位置來 積層前述第一發明之感光性轉印片而得到積層體之步驟； -12- 1352875 (2) 從積層體之第一感光層側，以規定照射互不相同之 至少二程度之照射能量光線之區域的影像圖案來進行光照 射，同時硬化接受光照射能量相對大之光照射區域的第一 層感光層與第二感光層，然後硬化接受光照射能量相對小 之光照射區域之第二感光層之步驟； (3) 從積層體除去支持體之步驟；然後， (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 於本發明之第三與第四發明中之較佳態樣係如下所 述。 (1) 從（3)積層體除去支持體之步驟，係由在步驟（2)與 步驟（4)之間進行，取代爲在步驟U)與步驟（2)之間進行。 (2) 藉由雷射光之照射進行步驟（2)中之光照射。 本發明第五係於印刷配線板形成用基板上，形成由以 藉由同時硬化第一感光層與第二感光層所形成之硬化樹脂 層所被覆之區域，與基板表面暴露之區域所構成之配線圖 案形成方法，其包含下述步驟：。 (1) 於基板上，積層前述第一發明之感光性轉印片使得 感光性轉印片的第二感光層爲基板側之位置關係，以得到 積層體之步驟； (2) 從積層體之第一感光層側進行既定配線圖案之光 照射，同時硬化接受該光照射區域之第一感光層與第二感 光層之步驟； (3) 從積層體除去支持體之步驟；然後， (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 本發明第六係在具有孔洞部分之印刷配線板形成用基 -13- 1352875 . 板上，形成由以藉由同時硬化第一感光層與第二感光層所 形成之硬化樹脂層所被覆之孔洞部分、以藉由硬化第二感 光層所形成之硬化樹脂層所被覆之區域、然後基板表面暴 露之區域所構成之配線圖案形成方法，其包含下述步驟： (1) 於基板上，積層前述第一發明之感光性轉印片使得 感光性轉印片的第二感光層爲基板側之位置關係，以得到 積層體之步驟； (2) 從積層體之第一感光層側，進行如在孔洞部分則賦 予光照射能量相對大之光照射來同時硬化第一感光層與第 二感光層，然後在配線形成區域則賦予光照射能量相對小 之光照射來硬化第二感光層之影像圖案光照射之步驟； (3) 從積層體除去支持體之步驟；然後， (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 於本發明之第五與第六發明中之較佳態樣係如下所 述。 (1) 從（3)積層體除去支持體之步驟，係由在步驟（2)與 步驟（4)之間進行，取代爲在步驟（1)與步驟（2)之間進行。 (2) 藉由雷射光之照射進行步驟（2)中之光照射。 【發明之效果】 本發明之感光性轉印片及感光性積層體係可藉由變化· 其光照射量（可換言之爲曝光量），而於任意之區域形成厚 度不同之硬化層。因此，使用本發明之感光性轉印片或感 光性積層體來進行影像形成時，則有可於每個所希望之區 域形成任意厚度之硬化層（可形成三次元之影像）、可於每 個所希望之區域變化光透過量（可變化影像之濃度）、可於 -14- 1352875 . 每個所希望之區域形成顯示所希望之膜強度的硬化層等許 多之優點。例如，在希望增強硬化層之膜強度的區域中， 可增厚硬化層之厚度，又在希望提高解析度之區域中，亦 可形成所謂使硬化層厚度變薄之圖案。 因此，本發明之感光性轉印片及感光性積層體係在使 用於印刷配線板之製造、特別在製造成具有通孔或連接孔 等孔洞部分之印刷配線板的情況下，在配線圖案形成區域 上係可形成相對厚度薄、高解析之硬化層，而在通孔或連 接孔上係可形成相對厚度厚、高強度之硬化層。因而，藉 由利用本發明，可由工業上有利之保護幕法製造高解析度 之印刷配線板。 [實施發明的最佳形態] 本發明感光性轉印片之一例，係如具有二層感光層構 成之模式截面圖之第1圖與第2圖所示。 在第1圖中，感光性轉印片10係依序積層著支持體 11、第一感光層12、障壁層13、第二感光層14。第一感 光層12及第二感光層14係各別由包含黏結劑 '聚合性化 合物、及光聚合起始劑之感光性樹脂組成物所構成，並藉 由光之照射來硬化。本發明之感光性轉印片係具有第二感 光層14比第一感光層12相對上光感度較高方面爲主要特 徵。其中，所謂光感度係相當於對於各別感光層硬化所必 須之光能量，所謂光感度高係表示以比第一感光層12較少 之光照射量開始第二感光層14之硬化’或以比第一感光層 12較少之光照射量結束第二感光層14之硬化的意思。 第2圖係於第1圖之感光性轉印片上’進一步積層保 -15- 1352875 . 護膜15之感光性轉印片。 第一感光層、障壁層而後第二感光層之厚度係各別可 針對目的來任意地設定。但是，第一感光層係以具有1〜100 ym範圍之厚度爲佳，以具有5〜80ym範圍之厚度爲更 佳，以具有l〇~50/zm範圍之厚度爲特佳。第一感光層厚 度較l/zm薄時，在增強膜強度方面有不適當之情況，厚度 超過100 時則有招致顯像殘渣變得容易殘留等之顯像 上問題的情況。第一感光層之厚度比第二感光層之厚度愈 大愈好。 障壁層係具有〇.1~5;/ m範圍的厚度爲佳、又具有〇.5~4 範圍的厚度爲佳、特別是具有l~3/zm範圍的厚度爲 佳。當障壁層的厚度比0.1# m薄時，會有無法得到充分障 壁性的情形，厚度超過5 /z m時顯像係需要較長的時間。第 二感光層係具有0.1〜15// m範圍的厚度爲佳、又具有1〜12 // m範圍的厚度爲佳、特佳爲具有3~10/i m範圍的厚度。第 二感光層的厚度比〇.l//m薄時，會容易有塗布時的厚不均 勻，厚度超過15;/m時會有解析性降低等的問題。 本發明之感光性轉印片之層構成並不限定於上述第1 圖及第2圖所示之層構成，亦可含有第1圖及第2圖所示 之層以外之層。例如，於支持體11與第一感光層12之間、 或於保護膜15與第二感光層14之間，亦可設置調整與支 持體或基板之剝離性或密著力之層、成暈現象防止層、或 障壁層等》該情況之障壁層係具有包含於感光層、支持體' 或保護膜之物質移動防止或移動之抑制、一方面防止一方 面抑制氧或溼度等外在影響的功能等。 -16- 1352875 . 其次參照第3圖並且說明在本發明之感光性轉印片及 感光性積層體中之光照射量與感光層之硬化量的關係。第 3圖係顯示例如在轉印已從示於第1圖之感光性轉印片、 或示於第2圖之感光性轉印片剝離保護膜之感光性轉印片 於基板上來形成積層體的情況下，對於該積層體，在從基 板與反面，於具有支持體的情況下通過支持體、或必要時 剝離支持體來照射光線於感光層之情況的光照射量、該照 射（曝光）、與接下來藉由顯像處理所生成之硬化層厚度的 關係曲線圖（感度曲線）。於第3圖中，橫軸表示光照射量， 縱軸表示藉由光之照射所硬化、於進行顯像處理後所得之 硬化層的厚度。縱軸D表示由第二感光層所形成之硬化層 厚度、E表示合計由第一感光層所形成之硬化層厚度與由 第二感光層所形成之硬化層厚度之厚度。 如第3圖所示，在本發明之感光性轉印片上，從支持 體側所照射之光線，在具有支持體之情況下，儘管依照支 持體、第一感光層、障壁層、然後第二感光層之順序進行， 第二感光層之硬化係較第一感光層爲先地以少的光能量開 始。然後，第二感光層全體硬化之後，增加光能量時，第 一感光層之硬化開始，進一步使光能量變多時，第—感光 層全體硬化。 針對第一感光層之感度與第二感光層之感度的關係’ 在以1爲第一感光層之光感度的情況時，以第二感光層之 光感度在2~200之範圍爲佳，以2.5~100之範圍爲更佳’ 以3~50之範圍爲特佳。 雖然直到第一感光層之硬化開始所必須之光能量C亦 -17- 1352875 . 可與用於硬化第二感光層所必須之光能量A同量，但以比 光能量A大者爲佳。 直至第一感光層之硬化開始所需之必須光能量C，係與 硬化第二感光層之必須光能量A同量爲佳，但是亦可比光能 量A大》 具有如上述般感度曲線之感光性轉印片，例如：第二 感光層的光聚合起始劑含量係比第一感光層多，或者第二 感光層中可藉由添加較多的增感劑而得到。 於感光層中添加増感劑之情形中曝光波長的吸光度 (或光學的濃度；0D)係爲重要，特別是積層感光層之情形 下，上層（本發明之情形爲第一感光層）的吸光度之設計係 爲非常重要。以下係記載其説明。 即，在曝光波長下的第一感光層之吸光度（光學的濃度） 高之情形中，由於達到第二感光層的光量減少，第二感光 層之硬化係非充分地增強，第一感光層與第二感光層的感 度差變大。例如，若在第一感光層之曝光波長下的吸收度 爲0.3的話，光透過率爲1/2、對第二感光層的曝光量係爲來 自光源的曝光量之1/2。同樣地，若在第一感光層之曝光波 長下的吸收度爲0.6的話，光透過率爲1/4,第二感光層的曝 光量係爲來自光源之曝光量的1/4。再者，吸光度爲超過1.〇 時，光透過率爲10%以下，光幾乎無法達到下層。 因此，積層感光層之感光性轉印片保持下層的感度， 在上層的曝光波長下之吸光度係爲非常重要。 本發明的感光性轉印片中，第一感光層的波長4〇5nm 之光吸光度爲0.1〜1.0範圍。第一感光層的波長405ηιτι之光 -18- 1352875 吸光度爲0.1〜0.8範圍爲更佳、0.1~0.6範圍爲最佳。 又，第二感光層之波長405nm的光吸光度爲〇.1~1.5範 圍爲佳、0.1〜1.0範圍爲更佳。吸光度大於1.5時，光的透過 率下降，係無法增強在基板附近的感光層硬化，基板黏著 性會有惡化的傾向。此外，吸光度低於0.1時會有無法得到 充分感度的情形。 感光層的吸光度，係大多以在一般曝光波長具有吸收 性之化合物的量來加以調節。調整感光層吸光度之化合物 以増感劑爲佳。第一感光層中亦可不使用増感劑，但是若 第一感光層的波長405nm之光吸光度爲0.6以下之範圍的 話，以添加增感劑爲佳。 増感劑係爲在380~430nm具有極大吸收波長之化合物 爲佳。 於第4圖及第5圖之感光性轉印片50中，以51表示支持 體，於該支持體51上，依次積層著第一感光層52、障壁層 53、第二感光層54、障壁層53、然後第三感光層55。第5 圖顯示著於第4圖之感光性轉印片上設置保護膜5 6的構成。 即使在該等之三層感光層構成的情況下，各感光層係 比較於接近於支持體側之感光層的感度，距離支持體較遠 側之感光層的感度相對地變高。即，感光層之感度係第三 感光層最高，第二感光層爲次高，第一感光層最低。 使用圖示於第4圖及第5圖所構成的感光性轉印片， 於必要之區域中針對使用於圖案形成用之光能量’藉由變 化僅硬化第三感光層之光能量X、硬化第三感光層及第二 感光層之光能量Y、硬化第三感光層、第二感光層、及第 -19- 1352875 —感光層全部之光能量Z與光照射量，如第6圖所示，於 基板57上，以單一種類感光性轉印片可形成所謂具有僅硬 化第三感光層55之厚度的區域、具有硬化第三感光層55 及第二感光層54之厚度的區域、具有硬化第三感光層55' 第二感光層54及第一感光層52全部之厚度的區域之具有 三階段不同厚度之圖案。 又同樣地感光層爲N層（感光層數爲N)，比較於接近 於支持體側之感光層的感度，如果使用距離支持體較遠側 之感光層感度相對高之感光性轉印片，以單一種類感光性 轉印片可形成具有N階段不同厚度之硬化層圖案。 如迄今所記載，本發明之感光性轉印片係針對其曝光 量（所謂光能量），可使藉由曝光及顯像處理所得之硬化層 厚度成爲所希望之厚度，必要時可藉由變更曝光量的圖 案，劃分從僅硬化最接近基板之感光層，依序改變厚度直 到硬化全部感光層之區域。因此，以單一種類感光性轉印 片可形成賦予在影像內部厚度不同之三次元造型、或僅使 所希望之區域的膜強度變強、或僅使所希望之區域的影像 濃度變高等特性之硬化樹脂影像等。 因此，在印刷配線板之製造、特別在具有通孔或連接 孔之印刷配線板的製造中使用本發明之感光性轉印片時， 於配線圖案形成區域中可形成相對厚度薄、高解析之硬化 層，於通孔或連接孔中可形成相對厚度厚、高強度之硬化 層。因此，藉由使用本發明之感光性轉印片，具有可利用 作爲保護幕法之充分的保護幕膜強度，而且在必須高解析 度之部分可容易地形成足夠解析度之硬化樹脂圖案。 -20- I352S75 藉由本發明，具有如前述之感度曲線的感光性轉印 片，係判斷可藉由依照從接近於支持體側朝向距離支持體 較遠側之順序相對地提高各感光層感度來實現。該感光層 爲二層以上，依序相對提高該等感光層之感度的方法，可 全部使用已知之高感度化技術。即，可藉由例如高感度起 始劑之使用、增感劑之使用、光聚合起始劑及/或增感劑含 有量之增加量、或者使感光層中之聚合性化合物含有量變 多、聚合抑制劑或聚合停止劑之比例變少等手法而得。特 別地如果感光層爲二層之情況下，例如除了使用高感度起 始劑，亦可藉由於第二感光層中添加增感劑、使第二感光 層中之光聚合起始劑及/或增感劑含有量變得較第一感光 層多、或者使第二感光層中之聚合性化合物含有率變得較 第一感光層多等之手法而得。 在本發明之支持體上，使用依序積層由包含黏結劑、 聚合性化合物、及光聚合起始劑之感光性樹脂組成物所構 成之第一感光層、障壁層，然後由包含黏結劑、聚合性化 合物、及光聚合起始劑之感光性樹脂組成物、顯示比第一 感光層之光感度相對高之光感度的二感光層所構成之感光 性轉印片來形成影像圖案（硬化樹脂圖案）的情況下，第二 感光層之硬化開始之光能量S係以在0.05〜lOmJ/cm2之範 圍爲佳，以在 0.1~5mJ/cm2之範圍爲更佳，以在 0.1 5 ~2.5 mJ/cm2之範圍爲特佳。又用來硬化第二感光層所 必須之光能量A係以在0.1 ~20mJ/cm2之範圍爲佳，以在 〇.2~15mJ/cm2之範圍爲更佳，以在0.4~10mJ/cm2之範圍爲 特佳。 -21- 1352875 . 用來硬化第二感光層所必須之光能量A與用來硬化第 一感光層所必須之光能量B之比（A/B)係以在0.005〜0.5之 範圍爲佳，以在〇.〇1~〇.4之範圍爲更佳，以在0.02~0.35 之範圍爲特佳。然後，用來硬化第二感光層所必須之光能 量A與直到第一感光層之硬化開始所必須之光能量C之比 (C/A)係以在卜10之範圍爲佳，以在1.1~9之範圍爲更佳， 以在 1.3~8之範圍爲特佳。又該光能量 C係以在 0.1~200mJ/cm2之範圍爲佳，以在l~l〇〇mJ/cm2之範圍爲更 佳，以在2~50mJ/Cm2之範圍爲特佳。 其次，說明用於本發明之感光性轉印片及感光性積層 體之感光層的各材料。 [黏結劑] 用於各感光層之黏結劑係以可溶於鹼性水溶液爲佳， 或以至少具有膨潤性爲佳。該等黏結劑之範例方面，雖可 利用具有酸性基（羧基、磺基、磷酸基等）者，但特別以具 有羧基之黏結劑爲代表，舉例有含有羧基之乙烯基共聚 物、含有羧基之聚胺甲酸酯樹脂 '聚醯胺酸樹脂、改質環 氧樹脂等’但從對於塗布溶劑之溶解性、對於鹼性顯像液 之溶解性、合成適性、膜物性之調整的難易等來看則以含 有羧基之乙烯基共聚物爲佳。 含有羧基之乙烯基共聚物係可藉由至少（1)含有羧基 之乙烯基單體及（2)可與該等共聚合之單體的共聚合而得。 含有羧基之乙烯基單體之範例方面，舉出有（甲基）丙 烯酸、乙烯基苯甲酸、順丁烯二酸、順丁烯二酸單烷基酯、 反丁烯二酸、衣康酸、巴豆酸、肉桂酸、丙.烯酸二聚物等。 -22- 1352875 . 又’亦可利用具有（甲基）丙稀酸-2-經基乙醋等之經基單體 與順丁烯二酸酐或如酞酐、環己基二羧酸酐之環狀無水物 的加成反應物 '單（甲基）丙烯酸-ω-羧基多己內醋等。又， 亦可利用順丁稀二酸酐、衣康酸野、檸康酸酐等之含有無 水物單體作爲殘基先質。還有於該等之內，從共聚合性或 成本、溶解性等觀點來看係以（甲基）丙烯酸爲特佳。 可使用於上述共聚物之合成的其他可共聚合單體方面 並無特別之限制，該等單體之範例方面，舉例以（甲基）丙 烯酸酯類 '巴豆酸酯類、乙烯酯類、順丁烯二酸二酯類' 反丁烯二酸二酯類、衣康酸二酯類、（甲基）丙烯醯胺類、 乙烯醚類' 乙烯醇之酯類、苯乙烯類、（甲基）丙烯腈等爲 佳。該等實例方面係舉例有如以下之化合物。 (甲基）丙烯酸酯類之範例方面，舉出有（甲基）丙烯酸甲 酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯 酸異丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲 基）丙烯酸第三丁酯 '(甲基）丙烯酸正己酯 '(甲基）丙烯酸 環己酯、（甲基）丙烯酸第三丁基環己酯、（甲基）丙烯酸- 2-乙基己酯、（甲基）丙烯酸第三辛酯、（甲基）丙烯酸癸酯、（甲 基）丙烯酸十八酯、（甲基）丙烯酸乙醯氧基乙酯、（甲基）丙 烯酸苯酯、（甲基）丙烯酸-2_羥基乙酯、（甲基）丙烯酸-2·甲 氧乙酯 '(甲基）丙烯酸-2-乙氧乙酯、（甲基）丙烯酸_2(2·甲 氧基乙氧基）乙酯、（甲基）丙烯酸-3-苯氧基-2-羥基丙酯、（甲 基）丙烯酸苄酯、（甲基）丙烯酸二乙二醇單甲基醚酯、（甲基） 丙烯酸二乙二醇單乙基醚酯、（甲基）丙烯酸二乙二醇單苯 基醚酯、（甲基）丙烯酸三乙二醇單甲基醚酯、（甲基）丙烯酸 •23- 1352875 三乙二醇單乙基醚酯、（甲基）丙烯酸多乙二醇單甲基醚 酯、（甲基）丙烯酸多乙二醇單乙基醚酯、丙烯酸苯氧基 乙氧基乙酯、（甲基）丙烯酸壬基苯氧基多乙二醇酯、（甲基） 丙烯酸二環庚酯 '(甲基）丙烯酸二環庚烯酯、（甲基）丙烯酸 二環庚烯氧基乙酯、（甲基）丙烯酸三氟乙酯、（甲基）丙烯酸 八氟庚酯、（甲基）丙烯酸過氟辛基乙酯、（甲基）丙烯酸三溴 苯酯、（甲基）丙烯酸三溴苯氧基乙酯等。 巴豆酸酯類之範例方面，舉出有巴豆酸丁酯、及巴豆 酸己酯等β乙烯酯類之範例方面，舉出有乙酸乙烯酯、丙 酸乙烯酯、丁酸乙烯酯、甲氧基乙酸乙烯酯、及苯甲酸乙 烯酯等。 順丁烯二酸二酯類之範例方面，舉出有順丁烯二酸二 甲酯 '順丁烯二酸二乙酯 ' 及順丁烯二酸二丁酯等。反丁 烯二酸二酯類之範例方面，舉出有反丁烯二酸二甲酯、反 丁烯二酸二乙酯、及反丁烯二酸二丁酯等。衣康酸二酯類 之範例方面，舉出有衣康酸二甲酯、衣康酸二乙酯、及衣 康酸二丁酯等。 (甲基）丙烯醯胺類方面，舉出有（甲基）丙烯醯胺、Ν-甲基（甲基）丙烯醯胺' Ν-乙基（甲基）丙烯醯胺、Ν-丙基（甲 基）丙烯醯胺、Ν-異丙基（甲基）丙烯醯胺、Ν-正丁基（甲基） 丙烯醯胺、Ν-第三丁基（甲基）丙烯醯胺、Ν-環己基（甲基） 丙烯醯胺、Ν-(2-甲氧乙基）（甲基）丙烯醯胺、Ν，Ν-二甲基（甲 基）丙烯醯胺、Ν，Ν，-二乙基（甲基）丙烯醯胺、Ν-苯基（甲基） 丙烯醯胺、Ν-苄基（甲基）丙烯醯胺、（甲基）丙烯腈嗎林、二 丙酮丙烯醯胺等。 -24- 1352875 苯乙烯類之範例方面，舉出有苯乙烯、甲基苯乙烯、 二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙 烯、丁基苯乙烯、羥基苯乙烯、甲氧基苯乙烯、丁氧基苯 乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙 烯、氯甲基苯乙烯、以可藉由酸性物質脫保護之官能基（例 如第三Boc等）所保護之羥基苯乙烯、乙烯基苯甲酸甲酯、 及甲基苯乙烯等。乙烯基醚類之範例方面，舉出有甲基 乙烯醚、丁基乙烯醚、己基乙烯醚、及甲氧乙基乙烯醚等。 在上述化合物之外，亦可使用（甲基）丙烯腈、乙烯基 取代之雜環型官能基（例如乙烯基吡啶、乙烯基四氫吡咯 酮、乙烯基咔唑等）、Ν-乙烯基甲醯胺、Ν-乙烯基乙醯胺、 Ν-乙烯基咪唑 '乙烯基己內酯等。 又，亦可利用 2-丙烯醯胺-2-甲基丙磺酸、磷酸單（2-丙烯腈氧基乙酯）、磷酸單（1-甲基-2-丙烯腈氧基乙酯）等。 在上述化合物之外，亦可使用具有例如胺甲酸酯基、 脲基、磺醯胺基、酚基、亞醯胺基等官能基之乙烯基單體。 該等具有胺甲酸酯基、或脲基之單體方面，可利用例如異 氰酸酯基與羥基、或胺基之加成反應來適宜地合成。具體 而言’可藉由含有異氰酸酯基單體與含有1個羥基之化合 物或含有1個1級或2級胺基之化合物的加成反應、或者 含有羥基單體或含有i級或2級胺基單體與單異氰酸酯之 加成反應來適宜地合成。 含有異氰酸酯基單體之具體實例方面，舉例有如下述 之化合物（R1表示氫原子或甲基）。 [化1] -25- 1352875 .[Technical Field] The present invention relates to a photosensitive transfer sheet, a photosensitive laminate, a method for forming an image pattern, and a method for forming a wiring pattern. In the present invention, a photosensitive transfer sheet, a laminate, and a wiring pattern forming method for forming a printed wiring board using the photosensitive transfer sheet or the laminate are particularly useful. [Prior Art] A photosensitive transfer sheet having a support and a photosensitive layer is widely used as a display member for use in, for example, a printed wiring board, a color filter or a column material, a lip material, a spacer, and a partition wall. Pattern forming materials for images produced by various image forming materials such as printing plates, holograms, micromachines, and refractory materials. In the field of manufacturing a printed wiring board, a photosensitive transfer sheet composed of a transparent support (for example, polyethylene terephthalate) and a photosensitive layer formed on the support is used (also referred to as a photosensitive transfer sheet). A wiring pattern is formed by photolithography of dry film photoresist. For example, in the case of manufacturing a printed wiring board having through holes, a through hole is formed in a printed wiring board forming substrate (for example, a copper plated laminated board), and a metal plating layer is formed on the inner side wall portion of the through hole, and then the substrate surface is densely laminated. The photosensitive layer of the photosensitive transfer sheet is cured in a predetermined pattern shape in the wiring pattern forming region and the region including the opening portion of the through hole to harden the photosensitive layer. Next, the support of the photosensitive transfer sheet is peeled off, and the developing solution is used to dissolve and remove the unhardened region on the wiring pattern forming region and the hardened region on the opening portion of the via hole (referred to as a protective curtain film). After the region, the exposed portion of the metal layer is etched, and then the wiring pattern is formed on the surface of the substrate by removing the hardened region. 1352875 .  The method of protecting the metal ruthenium of the via hole by using the above protective film is generally called a protective curtain method. Further, in the printed wiring board having a multilayer structure, a layer in which a layer called a connection hole is provided is used to indirectly continue the hole. In this case as well, it is necessary to protect the connection hole portion by the protective film during the formation of the wiring pattern. In recent years, there has been an increasing demand for higher density of printed wiring boards, and a photoresist film having a higher resolution has been demanded. Since the resolution of the photoresist film is improved, the thickness of the photosensitive layer can be effectively reduced. However, as described above, the hardened layer after the photosensitive layer is cured also functions to protect the through holes or the connection holes formed in the printed wiring board. When the thickness of the photosensitive layer is simply reduced, the photosensitive resin composition is dissolved and removed. In the step of the uncured range or the step of etching the exposed portion of the metal layer, a problem of so-called rupture of the protective film occurs. The development of a photosensitive transfer sheet which can form a high-resolution pattern and can form a protective film which is not easily broken has been actively carried out, and the results are disclosed as follows. In Patent Document 1, it is described that it has a bond having a carboxyl group. A photosensitive transfer sheet of a component, a specific vinyl urethane compound, a monomer component of a specific acrylate compound, and a photosensitive layer composed of a photopolymerization initiator. Patent Document 2 describes that the first photosensitive layer which is made to be alkaline-soluble on the support, which is small in fluidity due to heating, and which is induced to the active energy source is further provided as a base thereon. A photosensitive transfer sheet of a double-layer photosensitive layer composed of a second photosensitive layer which is highly fluid due to heating and which is induced by the active energy source. In the patent 1352875, it is explained that the metal layer of the via hole can be protected by embedding the second photosensitive layer of the photosensitive transfer sheet in the through hole. Patent Document 3 describes that it is a photosensitive resin laminate having a first photosensitive layer and a second photosensitive layer on a support, and the two layers have mutually different ethylene copolymers, and are in two layers. An example of a specific monofunctional monomer is included, and the effect is described to enhance its adhesion and resolution. Patent Document 4 describes a photoresist having a non-adhesive photosensitive layer and a photosensitive photosensitive layer on a support, and a method of forming a printed wiring board using the same, and describes the effect of the stretchability and the analytical improvement. . Patent Document 5 discloses a photopolymerizable layer having a photopolymerization rate different from each other on the substrate (having a thickness of 25 μm 2 . 5 mm), a photosensitive plate for printing a relief printing having a fast polymerization speed close to the substrate side, and an example of forming a relief image whose base portion of the printing surface is wider than the top is described. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 10- No. Hei. [Patent Document 5] Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. Photosensitive transfer sheet and photosensitive laminate. Further, another object of the present invention is to provide a method for forming a desired pattern having a different thickness in an image in an industrially advantageous manner by using a photosensitive transfer sheet or a photosensitive laminate. 1352875 .  In particular, an object of the present invention is to provide a photosensitive transfer sheet which is effective for the production of a printed wiring board and which can be formed into a high-resolution thin layer by a thin layer and which can form a protective curtain film which is not easily broken. Further, another object of the present invention is to provide a method of industrially advantageously producing a printed wiring board having a hole portion such as a through hole or a connecting hole by using a photosensitive transfer sheet. [Means for Solving the Problem] In the first aspect of the present invention, a first photosensitive layer composed of a photosensitive resin composition containing a binder 'polymerizable compound and a photopolymerization initiator, and a barrier layer are sequentially laminated on a support. Then, a photosensitive transfer sheet comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and having a second photosensitive layer having a light sensitivity higher than that of the first photosensitive layer . The preferred embodiment of the first invention described above is as follows. (1) The barrier layer contains a resin which exhibits affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. (2) The barrier layer contains a resin which exhibits solubility in water or a lower alcohol having 1 to 4 carbon atoms as a main component. (3) The barrier layer has a thickness of the range. (4) The barrier layer has a polymerizable compound. (5) The barrier layer is photosensitive, and the light sensitivity of the barrier layer is relatively lower than that of the first photosensitive layer. (6) The polymerizable compound contained in the barrier layer is a polymer having a polymerizable group. (7) The polymer having the above (6) polymerizable group is water or carbon atom number 1 1352875.  Lower alcohols up to 4 showed affinity. (8) The polymer having the above (7) poor polymerizability is soluble in water or a lower alcohol having 1 to 4 carbon atoms. (9) When the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is in the range of 2 to 200. (1 〇) The ratio of the light energy A necessary for hardening the second photosensitive layer to the A/B of the light energy B necessary for hardening the first photosensitive layer is 0. 005~0. The range of 5 (1 1) is the ratio of the light energy A necessary for hardening the second photosensitive layer to the C/A of the light energy C necessary to start hardening the first photosensitive layer at 1 to 10 range. (12) The first photosensitive layer and the second photosensitive layer each contain a sensitizer. (13) The amount of the sensitizer contained in the second photosensitive layer is larger than the amount of the sensitizer contained in the first photosensitive layer. (14) The amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer. (15) The amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer. (16) The absorbance of the first photosensitive layer having a wavelength of 4〇5 nm is 0. 1~1. The range of 0 (17) contains a compound having a maximum absorption wavelength at 380 to 430 nm in the first photosensitive layer and/or the second photosensitive layer. (18) A compound having a maximum absorption wavelength of 380 to 430 nm in the first photosensitive layer and/or the second photosensitive layer is a sensitizer. (19) The first photosensitive layer has a thickness of 1 range ' and the thickness of 1352875 is larger than the thickness of the second photosensitive layer. (20) The second photosensitive layer has 0. Thickness in the range of 1~15/zm. (21) The support is made of synthetic resin and is transparent. (22) The support is a strip support. (23) A protective film is disposed on the second photosensitive layer. (24) It is a belt-shaped support and is wound into a roll shape. (25) It is used for the manufacture of printed wiring boards. In the second aspect of the present invention, a second photosensitive layer composed of a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator is laminated on the substrate, and the barrier layer is then polymerized by a binder. A photosensitive laminate composed of a photosensitive resin composition of a compound and a photopolymerization initiator, and a first photosensitive layer having a light sensitivity lower than that of the second photosensitive layer. The preferred embodiment of the second invention described above is as follows. (1) The barrier layer contains a resin which exhibits affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. (2) The barrier layer contains a resin which exhibits solubility in water or a lower alcohol having 1 to 4 carbon atoms as a main component. (3) The barrier layer has 0. Thickness in the range of 1~5//m. (4) The barrier layer has a polymerizable compound. (5) The barrier layer is photosensitive, and the light sensitivity of the barrier layer is relatively lower than that of the first photosensitive layer. (6) The polymerizable compound contained in the barrier layer is a polymer having a polymerizable group. (7) The polymer having the above (6) polymerizable group exhibits affinity for water or a lower alcohol having 1 to 10,352,875 to 4 carbon atoms. (8) The polymer having the above (7) poor polymerizability is soluble in water or a lower alcohol having 1 to 4 carbon atoms. (9) When the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is in the range of 2 to 200. (10) The ratio of the light energy A necessary for hardening the second photosensitive layer to the A/B of the light energy B necessary for hardening the first photosensitive layer is 0. 005~(the range of K5° (1 1 ) is the ratio of the light energy A necessary for hardening the second photosensitive layer to the C/A of the light energy C necessary to start hardening the first photosensitive layer at 1~ The range of 10 (12) The first photosensitive layer and the second photosensitive layer each contain a sensitizing agent. (13) The amount of the sensitizing agent contained in the second photosensitive layer is greater than that of the first photosensitive layer. The amount of the sensate is large. (14) The amount of the photopolymerization initiator contained in the second photosensitive layer is more than the amount of the photopolymerization initiator contained in the first photosensitive layer (15) in the second light. The amount of the polymerizable compound contained in the photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer. (16) The absorbance of the first photosensitive layer having a wavelength of 4〇5 nm is 0·1"*1. The scope of 0. (17) A compound having a maximum absorption wavelength at 380 to 430 nm is contained in the first photosensitive layer and/or the second photosensitive layer. (18) The compound having a maximum absorption wavelength of 3 80~4 3〇11111 in the first photosensitive layer and/or the second photosensitive layer is sensitized by 1° (19) The first photosensitive layer has 1~1〇 〇#111 thickness> and the thickness -11 - 1352875 degrees is greater than the thickness of the second photosensitive layer. (20) The second photosensitive layer has 0. Thickness in the range of 1 to 15/zm. (2 1) The base system is a substrate for forming a printed wiring board. (22) A support (preferably a transparent resin film) on the first photosensitive layer is laminated. (23) It is a belt-shaped support and is wound into a roll shape. (24) It is used for the manufacture of printed wiring boards. The third aspect of the present invention is a method for forming an image pattern formed on a substrate by a region where a cured resin layer formed by simultaneously curing the first photosensitive layer and the second photosensitive layer and a region where the cured resin layer does not exist, which includes The steps of: (1) stacking the photosensitive transfer sheet of the first invention on the substrate such that the second photosensitive layer of the photosensitive transfer sheet is in the positional relationship on the substrate side to obtain a laminated body; a step of performing light irradiation of a predetermined image pattern on the first photosensitive layer side of the laminate while hardening the first photosensitive layer and the second photosensitive layer in the region irradiated with the light; (3) a step of removing the support from the laminated body; (4) The step of developing the laminated body and removing the unhardened portion of the laminated body. The fourth aspect of the present invention is a region on the substrate which is formed by a resin layer formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer, a region where the resin layer formed by hardening the second photosensitive layer exists, and then the resin layer is cured. The image pattern forming method of the non-existing region includes the following steps: (1) laminating the photosensitive transfer sheet of the first invention on the substrate with the second photosensitive layer as the substrate side relationship Step of obtaining a laminated body; -12- 1352875 (2) Light irradiation is performed from the side of the first photosensitive layer of the laminated body by an image pattern of a region irradiated with at least two different irradiation energy rays, and hardening is accepted Light illuminating the first photosensitive layer and the second photosensitive layer of the light-irradiated region with relatively large light, and then hardening the second photosensitive layer of the light-irradiated region receiving light with relatively small light irradiation; (3) removing the support from the laminated body And then, (4) developing the laminated body and removing the unhardened portion of the laminated body. The preferred aspects of the third and fourth inventions of the present invention are as follows. (1) The step of removing the support from the (3) laminate is carried out between steps (2) and (4) instead of between step U) and step (2). (2) The light in step (2) is irradiated by irradiation of laser light. The fifth aspect of the present invention is formed on a substrate for forming a printed wiring board, and is formed by a region covered with a cured resin layer formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer, and a region exposed to the surface of the substrate. A wiring pattern forming method comprising the following steps: (1) a step of laminating the photosensitive transfer sheet of the first invention on the substrate such that the second photosensitive layer of the photosensitive transfer sheet is in the positional relationship on the substrate side to obtain a laminated body; (2) from the laminated body a step of performing light irradiation of a predetermined wiring pattern on the first photosensitive layer side while hardening the first photosensitive layer and the second photosensitive layer receiving the light irradiation region; (3) a step of removing the support from the laminated body; and then, (4) The step of developing the laminated body and removing the unhardened portion of the laminated body. The sixth aspect of the present invention is a printed wiring board forming base having a hole portion - 13 - 1352875 .  On the plate, a region covered by a hardened resin layer formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer, and a region covered with a hardened resin layer formed by hardening the second photosensitive layer are formed, And a wiring pattern forming method formed by the exposed surface of the substrate, comprising the steps of: (1) laminating the photosensitive transfer sheet of the first invention on the substrate such that the second photosensitive layer of the photosensitive transfer sheet is a step of obtaining a laminated body on the side of the substrate; (2) from the side of the first photosensitive layer of the laminated body, performing light irradiation with a relatively large amount of light irradiation energy in the hole portion to simultaneously harden the first photosensitive layer and the first a second photosensitive layer, and then in the wiring forming region, a step of irradiating light having a relatively small light irradiation energy to harden the image pattern light of the second photosensitive layer; (3) a step of removing the support from the laminated body; and then, (4) The step of developing the laminated body and removing the unhardened portion of the laminated body. Preferred aspects of the fifth and sixth inventions of the present invention are as follows. (1) The step of removing the support from the (3) laminate is carried out between steps (2) and (4) instead of between step (1) and step (2). (2) The light in step (2) is irradiated by irradiation of laser light. [Effect of the Invention] The photosensitive transfer sheet and the photosensitive laminated system of the present invention can form a hardened layer having a different thickness in an arbitrary region by changing the amount of light irradiation (in other words, the amount of exposure). Therefore, when the image formation is carried out by using the photosensitive transfer sheet or the photosensitive laminate of the present invention, a hardened layer of any thickness (a three-dimensional image can be formed) can be formed in each desired region, and each can be formed. The area of light that is desired to change the amount of light transmission (the concentration of the image that can be changed) can be from -14 to 1352875.  Each of the desired regions forms a number of advantages such as a hardened layer exhibiting a desired film strength. For example, in a region where it is desired to enhance the film strength of the hardened layer, the thickness of the hardened layer can be thickened, and in a region where the resolution is desired to be improved, a pattern in which the thickness of the hardened layer is made thin can be formed. Therefore, the photosensitive transfer sheet and the photosensitive laminated system of the present invention are used in the production of a printed wiring board, particularly in the case of a printed wiring board having a hole portion such as a through hole or a connection hole, in the wiring pattern forming region. The upper layer can form a hard layer having a relatively thin thickness and a high resolution, and a hard layer having a relatively thick thickness and a high strength can be formed on the through hole or the connection hole. Thus, by utilizing the present invention, a high-resolution printed wiring board can be manufactured by an industrially advantageous protective curtain method. BEST MODE FOR CARRYING OUT THE INVENTION An example of the photosensitive transfer sheet of the present invention is shown in Figs. 1 and 2, which are schematic cross-sectional views of a two-layer photosensitive layer. In the first embodiment, the photosensitive transfer sheet 10 is sequentially laminated with a support 11, a first photosensitive layer 12, a barrier layer 13, and a second photosensitive layer 14. Each of the first photosensitive layer 12 and the second photosensitive layer 14 is composed of a photosensitive resin composition containing a binder 'polymerizable compound and a photopolymerization initiator, and is cured by irradiation with light. The photosensitive transfer sheet of the present invention has a main feature in that the second photosensitive layer 14 has a higher light sensitivity than the first photosensitive layer 12. Here, the light sensitivity corresponds to the light energy necessary for curing the respective photosensitive layers, and the high light sensitivity means that the second photosensitive layer 14 is hardened by a light irradiation amount smaller than that of the first photosensitive layer 12 or The amount of light irradiation less than the first photosensitive layer 12 ends the hardening of the second photosensitive layer 14. Figure 2 is attached to the photosensitive transfer sheet of Figure 1 to further laminate -15 - 1352875.  A photosensitive transfer sheet of the film 15. The thicknesses of the first photosensitive layer, the barrier layer and then the second photosensitive layer can be arbitrarily set for the purpose. However, the first photosensitive layer preferably has a thickness in the range of 1 to 100 μm, more preferably has a thickness in the range of 5 to 80 μm, and particularly preferably has a thickness in the range of 10 Å to 50/zm. When the thickness of the first photosensitive layer is thinner than l/zm, it may be inappropriate in terms of the strength of the reinforcing film. When the thickness exceeds 100, there is a problem in that the development residue of the developing residue is likely to remain. The thickness of the first photosensitive layer is preferably as large as the thickness of the second photosensitive layer. The barrier layer has a flaw. The thickness of 1~5; / m range is good, and has 〇. The thickness in the range of 5 to 4 is preferable, and in particular, the thickness in the range of 1 to 3/zm is preferable. When the thickness of the barrier layer is greater than 0. When 1# m is thin, there is a case where sufficient barrier properties are not obtained, and when the thickness exceeds 5 /z m, the imaging system takes a long time. The second photosensitive layer has 0. The thickness in the range of 1 to 15 // m is preferably in the range of 1 to 12 // m, and particularly preferably in the range of 3 to 10 / i m. The thickness of the second photosensitive layer is greater than 〇. When l//m is thin, it tends to have uneven thickness during coating, and when the thickness exceeds 15; /m, there is a problem that the resolution is lowered. The layer configuration of the photosensitive transfer sheet of the present invention is not limited to the layer configuration shown in Figs. 1 and 2, and may include layers other than the layers shown in Figs. 1 and 2 . For example, between the support 11 and the first photosensitive layer 12, or between the protective film 15 and the second photosensitive layer 14, a layer that adjusts the peeling or adhesion force with the support or the substrate, and a halo phenomenon may be provided. The barrier layer in this case, or the barrier layer in this case has a function of preventing the movement or movement of the substance contained in the photosensitive layer, the support or the protective film, and on the other hand, preventing the external influence such as oxygen or humidity from being suppressed on the one hand. Wait. -16- 1352875 .  Next, the relationship between the amount of light irradiation and the amount of hardening of the photosensitive layer in the photosensitive transfer sheet and the photosensitive laminate of the present invention will be described with reference to Fig. 3 . Fig. 3 is a view showing, for example, the formation of a laminate by transferring a photosensitive transfer sheet which has been peeled off from the photosensitive transfer sheet shown in Fig. 1 or the photosensitive transfer sheet shown in Fig. 2 onto the substrate. In the case of the laminated body, when the support body is provided with the support, the amount of light irradiation when the light is irradiated onto the photosensitive layer by the support or, if necessary, the support is removed, the irradiation (exposure) And a graph (sensitivity curve) of the relationship between the thickness of the hardened layer and the thickness of the hardened layer generated by the development process. In Fig. 3, the horizontal axis represents the amount of light irradiation, and the vertical axis represents the thickness of the hardened layer obtained by the irradiation of light and after the development process. The vertical axis D represents the thickness of the hardened layer formed by the second photosensitive layer, and E represents the thickness of the hardened layer formed by the first photosensitive layer in total and the thickness of the hardened layer formed by the second photosensitive layer. As shown in Fig. 3, in the photosensitive transfer sheet of the present invention, the light irradiated from the side of the support has a support, in accordance with the support, the first photosensitive layer, the barrier layer, and then the second The order of the photosensitive layers is performed, and the hardening of the second photosensitive layer starts with less light energy than the first photosensitive layer. Then, when the entire second photosensitive layer is hardened, when the light energy is increased, the curing of the first photosensitive layer is started, and when the light energy is further increased, the entire first photosensitive layer is hardened. For the relationship between the sensitivity of the first photosensitive layer and the sensitivity of the second photosensitive layer, when 1 is the light sensitivity of the first photosensitive layer, the light sensitivity of the second photosensitive layer is preferably in the range of 2 to 200, 2. The range of 5~100 is better. The range of 3~50 is especially good. Although the light energy C necessary until the hardening of the first photosensitive layer begins is also -17 - 1352875.  It may be the same amount as the light energy A necessary for hardening the second photosensitive layer, but it is preferably larger than the light energy A. The necessary light energy C required to start the hardening of the first photosensitive layer is preferably the same as the necessary light energy A for hardening the second photosensitive layer, but may also be larger than the light energy A" having the sensitivity of the sensitivity curve as described above. For the transfer sheet, for example, the photopolymerization initiator content of the second photosensitive layer is more than that of the first photosensitive layer, or the second photosensitive layer can be obtained by adding a large amount of the sensitizer. The absorbance (or optical concentration; 0D) of the exposure wavelength in the case where a sensitizer is added to the photosensitive layer is important, particularly in the case of a laminated photosensitive layer, the absorbance of the upper layer (in the case of the present invention, the first photosensitive layer) The design is very important. The description is described below. That is, in the case where the absorbance (optical concentration) of the first photosensitive layer at the exposure wavelength is high, since the amount of light reaching the second photosensitive layer is reduced, the hardening of the second photosensitive layer is not sufficiently enhanced, and the first photosensitive layer is The sensitivity difference of the second photosensitive layer becomes large. For example, if the absorbance at the exposure wavelength of the first photosensitive layer is 0. In the case of 3, the light transmittance is 1/2, and the exposure amount to the second photosensitive layer is 1/2 of the exposure amount from the light source. Similarly, if the absorbance at the exposure wavelength of the first photosensitive layer is 0. In the case of 6, the light transmittance is 1/4, and the exposure amount of the second photosensitive layer is 1/4 of the exposure amount from the light source. Furthermore, the absorbance is more than 1. At 〇, the light transmittance is 10% or less, and the light hardly reaches the lower layer. Therefore, the photosensitive transfer sheet of the laminated photosensitive layer maintains the sensitivity of the lower layer, and the absorbance at the exposure wavelength of the upper layer is very important. In the photosensitive transfer sheet of the present invention, the light absorption of the first photosensitive layer having a wavelength of 4 〇 5 nm is 0. 1~1. 0 range. The wavelength of the first photosensitive layer is 405ηιτι light -18- 1352875 The absorbance is 0. 1~0. 8 range is better, 0. 1~0. 6 range is the best. Moreover, the light absorption of the second photosensitive layer at a wavelength of 405 nm is 〇. 1~1. 5 range is better, 0. 1~1. The range of 0 is better. The absorbance is greater than 1. At 5 o'clock, the transmittance of light is lowered, and the photosensitive layer hardening in the vicinity of the substrate cannot be enhanced, and the substrate adhesion tends to be deteriorated. In addition, the absorbance is less than 0. At 1 o'clock, there will be a situation where you can't get enough sensitivity. The absorbance of the photosensitive layer is mostly adjusted by the amount of the compound having absorbency at a general exposure wavelength. A compound which adjusts the absorbance of the photosensitive layer is preferably a sensitizer. The sensitizer may not be used in the first photosensitive layer, but if the first photosensitive layer has a light absorption at a wavelength of 405 nm of 0. In the range of 6 or less, it is preferred to add a sensitizer. The sensitizer is preferably a compound having a maximum absorption wavelength at 380 to 430 nm. In the photosensitive transfer sheet 50 of FIGS. 4 and 5, a support is indicated by 51, and the first photosensitive layer 52, the barrier layer 53, the second photosensitive layer 54, and the barrier are sequentially laminated on the support 51. Layer 53, then third photosensitive layer 55. Fig. 5 is a view showing a configuration in which a protective film 56 is provided on the photosensitive transfer sheet of Fig. 4. Even in the case of the three photosensitive layers, the photosensitive layer is relatively sensitive to the photosensitive layer on the far side of the support, compared to the sensitivity of the photosensitive layer on the side closer to the support. That is, the sensitivity of the photosensitive layer is the highest in the third photosensitive layer, the second photosensitive layer is the second highest, and the first photosensitive layer is the lowest. Using the photosensitive transfer sheet formed in Figs. 4 and 5, the light energy used for pattern formation in the necessary region is hardened by hardening only the light energy X of the third photosensitive layer. The light energy Y of the third photosensitive layer and the second photosensitive layer, the hardened third photosensitive layer, the second photosensitive layer, and the photosensitive energy Z and the amount of light irradiation of the photosensitive layer -19-3522875, as shown in FIG. On the substrate 57, a single type of photosensitive transfer sheet can be formed into a region having a thickness only for hardening the third photosensitive layer 55, a region having a thickness of the cured third photosensitive layer 55 and the second photosensitive layer 54, and having hardening. The third photosensitive layer 55' has a pattern of three stages of different thicknesses in the entire thickness region of the second photosensitive layer 54 and the first photosensitive layer 52. Similarly, the photosensitive layer is N layer (the number of photosensitive layers is N), and the sensitivity is similar to that of the photosensitive layer on the side of the support, and if a photosensitive transfer sheet having a relatively high sensitivity to the photosensitive layer on the far side of the support is used, A hardened layer pattern having a different thickness of N stages can be formed by a single type of photosensitive transfer sheet. As described so far, the photosensitive transfer sheet of the present invention can make the thickness of the hardened layer obtained by the exposure and development processing into a desired thickness with respect to the exposure amount (so-called light energy), and can be changed if necessary. The pattern of the exposure amount is divided from the photosensitive layer which is only hardened closest to the substrate, and the thickness is sequentially changed until the entire photosensitive layer is hardened. Therefore, a single type of photosensitive transfer sheet can be formed to impart a three-dimensional shape having a different thickness inside the image, or to increase the film strength of only a desired region, or to increase the image density of only a desired region. Hardened resin image, etc. Therefore, when the photosensitive transfer sheet of the present invention is used in the production of a printed wiring board, particularly in the production of a printed wiring board having through holes or connection holes, a relatively thin thickness and a high resolution can be formed in the wiring pattern formation region. The hardened layer can form a hardened layer having a relatively thick thickness and high strength in the through hole or the connecting hole. Therefore, by using the photosensitive transfer sheet of the present invention, it is possible to use a sufficient protective film strength as a protective curtain method, and it is possible to easily form a cured resin pattern having a sufficient resolution in a portion having a high resolution. -20- I352S75 According to the present invention, the photosensitive transfer sheet having the sensitivity curve as described above is judged to be capable of relatively increasing the sensitivity of each photosensitive layer in order from the side close to the support toward the far side of the support. achieve. The photosensitive layer is two or more layers, and the sensitivity of the photosensitive layers is relatively increased in order, and all known high sensitivity techniques can be used. That is, for example, the use of a high-sensitivity initiator, use of a sensitizer, an increase in the amount of a photopolymerization initiator and/or a sensitizer, or a content of a polymerizable compound in a photosensitive layer can be increased. The ratio of the polymerization inhibitor or the polymerization stopper is reduced. In particular, if the photosensitive layer is a two-layer, for example, in addition to using a high-sensitivity initiator, a photo-polymerization initiator in the second photosensitive layer may be added by adding a sensitizer to the second photosensitive layer and/or The content of the sensitizer is increased as compared with the first photosensitive layer, or the content of the polymerizable compound in the second photosensitive layer is increased by more than the first photosensitive layer. In the support of the present invention, a first photosensitive layer and a barrier layer composed of a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator are sequentially laminated, and then a binder is contained, A photosensitive resin composition comprising a polymerizable compound and a photopolymerization initiator, and a photosensitive transfer sheet comprising a two-photosensitive layer having a light sensitivity higher than that of the first photosensitive layer to form an image pattern (cured resin pattern) In the case, the light energy S of the hardening of the second photosensitive layer is at 0. The range of 05~lOmJ/cm2 is better, at 0. The range of 1~5mJ/cm2 is better, at 0. 1 5 ~ 2. The range of 5 mJ/cm2 is particularly good. The light energy A required to harden the second photosensitive layer is also 0. The range of 1 ~ 20mJ / cm2 is better, in the 〇. The range of 2~15mJ/cm2 is better, at 0. The range of 4~10mJ/cm2 is especially good. -21- 1352875 .  The ratio (A/B) of the light energy A necessary for hardening the second photosensitive layer to the light energy B necessary for hardening the first photosensitive layer is 0. 005~0. The range of 5 is better, in the 〇. 〇1~〇. The range of 4 is better, at 0. 02~0. The range of 35 is particularly good. Then, the ratio (C/A) of the light energy A necessary for hardening the second photosensitive layer to the light energy C necessary until the first photosensitive layer is hardened is preferably in the range of 10, to be 1 . The range of 1~9 is better, in 1. The range of 3~8 is especially good. And the light energy C is at 0. The range of 1 to 200 mJ/cm 2 is preferably in the range of l to l 〇〇 mJ/cm 2 , and is particularly preferably in the range of 2 to 50 mJ/cm 2 . Next, each material used in the photosensitive transfer sheet of the present invention and the photosensitive layer of the photosensitive laminate will be described. [Binder] The binder used for each photosensitive layer is preferably soluble in an aqueous alkaline solution, or preferably at least swellable. In the case of the above-mentioned binders, those having an acidic group (carboxyl group, sulfo group, phosphoric acid group, etc.) may be used, but a binder having a carboxyl group is particularly exemplified, and a vinyl copolymer having a carboxyl group and a carboxyl group are exemplified. Polyurethane resin 'polyamide resin, modified epoxy resin, etc.' However, it is difficult to adjust the solubility in a coating solvent, solubility in an alkaline developing solution, synthetic suitability, and membrane physical properties. It is preferred to use a vinyl copolymer having a carboxyl group. The vinyl group containing a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group and (2) a monomer copolymerizable with the copolymer. Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid. , crotonic acid, cinnamic acid, C. An acid dimer or the like. -22- 1352875 .  Further, it is also possible to use an addition of a transbasic monomer having (meth)acrylic acid-2-acetic acid acetal or the like to maleic anhydride or a cyclic anhydrate such as phthalic anhydride or cyclohexyldicarboxylic anhydride. The reactant 'mono(meth)acrylic acid-ω-carboxypolyhexyl vinegar or the like. Further, an anhydrous monomer such as cis-succinic anhydride, itaconic acid or citraconic anhydride may be used as a residue precursor. Further, among these, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. The other copolymerizable monomers which can be used for the synthesis of the above copolymer are not particularly limited, and examples of the monomers are exemplified by (meth) acrylates such as crotonates, vinyl esters, and cis. Butenedioic acid diesters 'fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers 'vinyl alcohol esters, styrenes, (methyl Acrylonitrile or the like is preferred. Examples of such examples are compounds as below. Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (A) Base) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate 'n-hexyl (meth)acrylate 'cyclohexyl (meth)acrylate, third (meth)acrylate Butylcyclohexyl ester, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, decyl (meth)acrylate, octadecyl (meth)acrylate, (methyl) Ethyl ethoxide ethyl acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (2-) Oxyethyl ester, (2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, Diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monophenyl (meth)acrylate Ether ether ester, triethylene glycol monomethyl ether (meth)acrylate, (meth)acrylic acid • 23-1352875 triethylene glycol monoethyl ether ester, (meth)acrylic acid polyglycol monomethyl Ether ester, polyethylene glycol monoethyl ether (meth)acrylate, phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, (meth)acrylic acid Cycloheptyl ester 'bicycloheptenyl (meth) acrylate, dicycloheptenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoroheptyl (meth) acrylate, ( Methyl)perfluorooctylethyl acrylate, tribromophenyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, and the like. Examples of crotonates include exemplified β-vinyl esters such as butyl crotonate and hexyl crotonate, and examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, and methoxy group. Vinyl acetate, vinyl benzoate, and the like. Examples of the maleic acid diesters include dimethyl maleate 'diethyl maleate' and dibutyl maleate. Examples of the anti-butenedioic acid diesters include dimethyl fumarate, diethyl methacrylate, and dibutyl fumarate. Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the (meth) acrylamides include (meth) acrylamide, hydrazine-methyl (meth) acrylamide Ν-ethyl (meth) acrylamide, hydrazine-propyl ( Methyl) acrylamide, Ν-isopropyl (meth) acrylamide, Ν-n-butyl (meth) acrylamide, hydrazine-tert-butyl (meth) acrylamide, hydrazine-ring Hexyl (meth) acrylamide, Ν-(2-methoxyethyl)(meth) acrylamide, hydrazine, hydrazine-dimethyl(meth) acrylamide, hydrazine, hydrazine, -diethyl (Meth) acrylamide, fluorenyl-phenyl (meth) acrylamide, hydrazine-benzyl (meth) acrylamide, (meth) acrylonitrile, diacetone acrylamide, and the like. -24- 1352875 Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, Hydroxystyrene, methoxystyrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, deprotected by acidic substances A hydroxystyrene, methyl benzoate, methyl styrene or the like protected by a functional group (for example, a third Boc or the like). Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. In addition to the above compounds, (meth)acrylonitrile, vinyl-substituted heterocyclic functional groups (for example, vinyl pyridine, vinyl tetrahydropyrrolidone, vinyl carbazole, etc.), fluorene-vinyl ketone may also be used. Indoleamine, hydrazine-vinylacetamide, hydrazine-vinylimidazole, vinylcaprolactone, and the like. Further, 2-propenylamine-2-methylpropanesulfonic acid, mono(2-acrylonitrileoxyethyl phosphate), mono(1-methyl-2-acrylonitrileoxyethyl phosphate), or the like may be used. . In addition to the above compounds, a vinyl monomer having a functional group such as a carbamate group, a ureido group, a sulfonamide group, a phenol group or a sulfhydryl group can also be used. The monomer having a urethane group or a ureido group can be suitably synthesized by, for example, an addition reaction of an isocyanate group with a hydroxyl group or an amine group. Specifically, 'addition reaction by containing an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound having one or a second-order amine group, or containing a hydroxyl group monomer or containing an i- or 2-grade amine The base monomer is reacted with a monoisocyanate to be suitably synthesized. Specific examples of the isocyanate group-containing monomer include the following compounds (R1 represents a hydrogen atom or a methyl group). [Chem. 1] -25- 1352875 .

HR1 HR1 6=0-000^^^° c=c-co-nco i Λ 單異氰酸酯之具體實例方面，舉例有異氰酸環己醋' 異氰酸正丁酯、異氰酸甲苯酯、異氰酸苄酯、異氰酸苯醋 等。 含有羥基單體之具體實例方面，舉例有如下述之化合 物（R1表示氫原子或甲基，η表示1以上整數）。 [化2] H R1HR1 HR1 6=0-000^^^° c=c-co-nco i 具体 Specific examples of monoisocyanate include, for example, n-butyl isocyanate, n-butyl isocyanate, toluene isocyanate, and Benzyl cyanate, phenyl isocyanate, and the like. Specific examples of the hydroxy group-containing monomer include the following compounds (R1 represents a hydrogen atom or a methyl group, and η represents an integer of 1 or more). [Chemical 2] H R1

C=C-COO I HC=C-COO I H

含有1個羥基之化合物方面，舉出有醇類（甲醇、乙醇、 正丙醇、異丙醇'正丁醇、第二丁醇、第三丁醇、正己醇、 2-乙基己醇、正癸醇、正十二醇、正十八醇、環戊醇、環 己醇、苄醇、苯基乙醇等）、酚類（酚、甲酚、萘酚等）；近 一步包含取代基者方面，氟乙醇、三氟乙醇' 甲氧基乙醇、 苯氧基乙醇、氯酚、二氯酚、甲氧基酚、乙醯氧基酚等。 含有1級或2級胺基單體之範例方面，舉例有乙烯基 苄基胺等。 含有1個1級或2級胺基之化合物的具體範例方面， 舉出有烷基胺（甲胺、乙胺、正丙胺 '異丙胺、正丁胺、第 -26- 1352875 . 二丁胺、第三丁胺、己胺、2-乙基己胺、癸胺、十二院基 胺、十八烷基胺、二甲胺 '二乙胺' 二丁胺、二辛胺）、環 狀烷基胺（環庚胺、環己胺等）、芳烷基胺（苄胺、苯乙胺等）、 芳基胺（苯胺、甲苯胺 '二甲苯胺、萘胺等）；進一步組合 該等（N -甲基-N-千胺等）、進一步包含取代基之胺（三氟乙 胺、六氟異丙胺、甲氧基苯胺、甲氧基丙胺等）等。 上述化合物可僅使用一種、或亦可倂用二種以上。特 佳之其他單體範例爲（甲基）丙烯酸甲酯、（甲基）丙烯酸乙 酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸苄酯、（甲基）丙稀酸 _2-乙基己酯、苯乙烯、氯苯乙烯、溴苯乙烯、及羥基苯乙 * 烯等。 該等乙烯基共聚物係依照其爲已知之方法的常法來共 聚合各別相當之單體而得。例如利用溶解該等單體於適當 溶劑中，並於其中添加自由基聚合起始劑而於溶液中聚合 的方法（溶液聚合法）而得。又亦可於水性溶劑中以分散上 述單體之狀態藉由所謂乳化聚合等來進行聚合。 於溶液聚合法所使用之適當溶劑範例方面，可針對所 使用之單體、及所生成之共聚物的溶解性來任意地選擇。· 舉例有甲醇、乙醇、丙醇、異丙醇、卜甲氧基_2_丙醇、丙 酮 '甲基乙基酮、甲基異丁基酮、乙酸甲氧基丙酯、乳酸 乙酯、乙酸乙酯、乙腈、四氫呋喃、二甲基甲醯胺、氯仿、 甲苯。該等溶劑亦可混合二種以上來使用。又，自由基聚 合起始劑方面，可利用如2,2，-偶氮雙（異丁腈）（AIBN)、 2，2’-偶氮雙（2，4，-二甲基戊腈）之偶氮化合物；如苯甲醯基 過氧化物之過氧化物；及如過硫酸鉀、過硫酸銨之過硫酸 -27- 1352875 鹽等。 從具有由該等單體所得之乙烯基共聚物中的羧基之聚 合性化合物而來的重複單位含有率，係在各感光層均以共 聚物之全部重複單位中的5~50莫耳％爲佳，以10〜40莫耳 %爲更佳，以15~35莫耳％爲特佳。該含有率低於5莫耳％ 時則有對於鹸性水之顯像性不足的情況，超過50莫耳％時 則有硬化部分（影像部分）之顯像液耐性不足的情況。 具有羧基之黏結劑分子量雖可任意地調整，各感光層 中均以2000-3 00000作爲質量分子量爲佳，以4000〜1 50000 爲特佳。質量平均分子量低於2000時則有膜強度容易不 足、又安定製造變得困難之傾向。又分子量超過300000時 則有顯像性降低之傾向。 又該等之具有羧基之黏結劑係各感光層爲一種或倂用 二種以上之黏結劑均可。倂用2種以上黏結劑之情況的範 例方面，舉出有由不同共聚合成分所構成之2種以上之黏 結劑、不同質量平均分子量之2種以上的黏結劑、不同分 散度之2種以上的黏結劑。 具有羧基之黏結劑係亦可以鹼性物質來中和該羧基之 一部分或全部。黏結劑亦可進一步倂用聚酯樹脂、聚醯胺 樹脂、聚胺甲酸酯樹脂、環氧樹脂、聚乙烯醇、明膠等構 造不同之樹脂。 又，黏結劑之範例方面，亦可舉出有記載於專利 2873889號等之可溶於鹼性水溶液之樹脂等。 感光層中之黏結劑含有量通常係各感光層均爲10〜9 0 重量％，以20~80重量％爲佳、以40~80重量％爲特佳。該具 -28- 1352875 · 有羧基之黏結劑（及必要時所倂用之聚合物結合劑）含有量 少時，則有鹼性顯像性或與印刷配線板形成用基板（例如， 鍍銅積層板）之密著性容易降低之傾向，變得過多時，則有 對於顯像時間之安定性或硬化膜（保護幕膜）之強度降低的 傾向。又爲了感度調整，亦可於上述範圍內進行使第二感 光層中所含有之黏結劑含有率比第一感光層中所含有之黏 結劑含有率低（提高聚合性化合物含有率）等之調整。 [聚合性化合物] 於感光層中’雖使用聚合性化合物（所謂單體），但以 使用含有2個以上聚合性基之單體、或寡聚物（多官能單 體、多官能寡聚物）爲特佳。聚合性基方面舉出有乙烯性不 飽和鍵（例如（甲基）丙烯腈基、（甲基）丙烯醯胺基、苯乙烯 基、乙烯酯或乙烯醚等乙烯基、烯丙醚或烯丙酯等之丙烯 基等）' 可聚合之環狀醚基（例如環氧基、氧雜環丁烷基等） 等。於該等之內則以乙烯性不飽和鍵結爲佳。 該等多官能單體之範例方面，舉出有不飽和羧酸（例 如’丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、 順丁烯二酸等）與脂肪族多元醇化合物之酯類、不飽和羧酸 與多元胺化合物之醯胺等》 脂肪族多元醇化合物方面與不飽和羧酸之酯類皐體的 具體範例方面，有二（甲基）丙烯酸乙二醇酯、乙烯基數爲 2〜18之二（甲基）丙烯酸多乙二醇酯（例如二（甲基）丙烯酸二 乙二醇酯、二（甲基）丙烯酸三乙二醇酯、二（甲基）丙烯酸四 乙二醇酯 '二（甲基）丙烯酸九乙二醇酯、二（甲基）丙烯酸十 二乙二醇酯、二（甲基）丙烯酸十四乙二醇酯等）、二（甲基） -29- 1352875 丙烯酸丙二醇酯、丙烯基數爲2~18之二（甲基）丙烯酸聚丙 二醇酯（例如二（甲基）丙烯酸二丙二醇酯、二（甲基）丙烯酸 三丙二醇酯、二（甲基）丙烯酸四丙二醇酯、二（甲基）丙烯酸 十二丙二醇酯等）、二（甲基）丙烯酸新戊二醇酯 '環氧乙烷 改質二（甲基）丙烯酸新戊二醇酯、環氧丙烷改質二（甲基） 丙烯酸新戊二醇酯、三（甲基）丙烯酸三羥甲基丙酯、二（甲 基）丙烯酸三羥甲基丙酯、三羥甲基丙基三（（甲基）丙烯腈氧 基丙基）醚、三（甲基）丙烯酸三羥甲基乙酯、二（甲基）丙烯 酸-1,3-丙二醇酯、二（甲基）丙烯酸-1,3-丁二醇酯、二（甲基） 丙烯酸- I，4-丁二醇酯、二（甲基）丙烯酸-1,6-己二醇酯、二 (甲基）丙烯酸四甲二醇酯、二（甲基）丙烯酸-1,4-環己二醇 酯、三（甲基）丙烯酸-1，2,4-丁三醇酯、（甲基）丙烯酸-1,5-戊二醇酯、二（甲基）丙烯酸異戊四醇酯、三（甲基）丙烯酸異 戊四醇酯、四（甲基）丙烯酸異戊四醇酯、五（甲基）丙烯酸二 異戊四醇酯、六（甲基）丙烯酸二異戊四醇酯、三（甲基）丙烯 酸山梨糖醇酯、四（甲基）丙烯酸山梨糖醇酯、五（甲基）丙烯 酸山梨糖醇酯、六（甲基）丙烯酸山梨糖醇酯、二（甲基）丙烯 酸二羥甲基二環戊酯、二（甲基）丙烯酸三環癸酯、二（甲基） 丙烯酸新戊二醇酯、新戊二醇改質二（甲基）丙烯酸三羥甲 基丙酯、具有各別平均至少1個乙二醇鏈/丙二醇鏈之亞烴 基二醇鏈之二（甲基）丙烯酸酯（例如記載於WO01/9 8832號 公報之化合物等）、已加成環氧乙烷及/或環氧丙烷之三羥 甲基丙烷之三（甲基）丙烯酸酯、二（甲基）丙烯酸多丁二醇 酯、二（甲基）丙烯酸丙三醇酯、三（甲基）丙烯酸丙三醇酯、 二（甲基）丙烯酸二甲苯酚酯等作爲（甲基）丙烯酸酯。 -30- 1352875 . 於上述（甲基）丙烯酸酯類中較佳之範例方面，從該等 取得之難易來看，可舉出二（甲基）丙烯酸乙二醇酯、二（甲 基）丙烯酸多乙二醇酯、二（甲基）丙烯酸丙二醇酯、二（甲基） 丙烯酸聚丙二醇酯、具有各別平均至少1個乙二醇鏈/丙二 醇鏈之亞烴基二醇鏈之二（甲基）丙烯酸酯、三（甲基）丙烯酸 三羥甲基丙酯、四（甲基）丙烯酸異戊四醇酯、三（甲基）丙燦 酸異戊四醇酯、二（甲基）丙烯酸異戊四醇酯、五（甲基）丙稀 酸二異戊四醇酯、六（甲基）丙烯酸二異戊四醇酯、三（甲基） 丙烯酸丙三醇酯、二（甲基）丙烯酸二丙三醇酯、二（甲基） 丙烯酸-1,3-丙二醇酯、三（甲基）丙烯酸-1,2,4-丁三醇酯、 二（甲基）丙烯酸-1,4-環己二醇酯、二（甲基）丙烯酸5-環 戊二醇酯、二（甲基）丙烯酸新戊二醇酯、已加成環氧乙烷 之三羥甲基丙烷之三（甲基）丙烯酸酯等。 衣康酸與脂肪族多元醇化合物之酯類（衣康酸酯）之範 例方面’有二衣康酸乙二醇酯、二衣康酸丙二醇酯、二衣 康酸-1,3-丁二醇酯、二衣康酸-1,4-丁二醇酯、二衣康酸四 甲二醇酯、二衣康酸異戊四醇酯、及四衣康酸山梨糖醇酯 等。 巴豆酸與脂肪族多元醇化合物之酯類（巴豆酸酯）之範 例方面’有二巴豆酸乙二醇酯、二巴豆酸四甲二醇酯、二 巴豆酸異戊四醇酯、及四巴豆酸山梨糖醇酯等。 異巴豆酸與脂肪族多元醇化合物之酯類（異巴豆酸酯） 之範例方面’有二異巴豆酸乙二醇酯、二異巴豆酸異戊四 醇酯、及四異巴豆酸山梨糖醇酯等。順丁烯二酸與脂肪族 多元醇化合物之酯類（順丁烯二酸酯）之範例方面，有二順 1352875 . 丁烯二酸乙二醇酯、二順丁烯二酸三甲二醇酯、二丁烯二 酸異戊四醇酯、及四順丁烯二酸山梨糖醇酯等。 又，從多元胺化合物與不飽和羧酸所衍生之醯胺的範 例方面’有亞甲基雙（甲基）丙烯醯胺、伸乙基雙（甲基）丙烯 醯胺' 1，6 -六亞甲基雙（甲基）丙烯醯胺、八亞甲基雙（甲基） 丙烯醯胺、二乙三胺三（甲基）丙烯醯胺、二乙三胺雙（甲基） 丙烯醯胺 '及二甲苯雙（甲基）丙烯醯胺等。 再者’亦可舉出具有雙酚骨架之2,2-雙[4-(3-(甲基）丙 烯酸基氧基-2-羥基丙氧基）苯基]丙烷、2，2_雙[4_(甲基）丙 烯酸基氧基乙氧基）苯基]丙烷、取代1個酚性之〇H基之環 氧乙基數目爲2~20之2,2-雙[4-(甲基）丙烯腈氧基多乙氧基） 苯基]丙烷（例如2，2-雙[4-(甲基）丙烯腈氧基二乙氧基）苯基] 丙烷、2，2-雙[4-(甲基）丙烯腈氧基四乙氧基）苯基]丙烷、 2,2-雙[4-(甲基）丙烯腈氧基五乙氧基）苯基]丙烷、2,2-雙 [4-(甲基）丙烯腈氧基十乙氧基）苯基]丙烷、2,2-雙[4-(甲基） 丙烯腈氧基十五乙氧基）苯基]丙烷等）、2,2·雙[4-(甲基）丙 烯腈氧基丙氧基）苯基]丙烷 '取代1個酚性之0H基之環氧 丙基數爲2~2〇之2,2-雙[4-(甲基）丙烯腈氧基多丙氧基）苯 基]丙烷（例如2,2-雙[4-(甲基）丙烯腈氧基二丙氧基）苯基] 丙烷、2,2_雙[4-(甲基）丙烯腈氧基四丙氧基）苯基]丙烷、 雙[4_(甲基）丙烯腈氧基五丙氧基）苯基]丙烷、2,2-雙 [4-(甲基）丙烯腈氧基十丙氧基）苯基]丙烷、2,2-雙[4-(甲基） 丙烯腈氧基十五丙氧基）苯基]丙烷等）或於同一分子中包含 聚環氧乙烷骨架與聚環氧丙烷骨架兩者作爲該等化合物之 多醚部位的化合物等。（例如記載於WO01/98832號公報之 -32- 1352875 . 化合物等）。該等化合物係可由 BPE-200、BPE-500、 ΒΡΕ- 1000(新中村化學工業股份有限公司製）等取得。 又，亦可如對於在所得作爲雙酚與環氧乙烷或環氧丙 烷等之加成物、重複加成物之末端具有羥基之化合物，而 具有異氰酸酯基與聚合基之化合物（（甲基）丙烯酸-2·異氰 酸酯基乙酯、異氰酸-α，α-二甲基-乙烯基苄酯等）之加成 物地利用具有雙酚骨架與胺甲酸酯基之聚合性化合物。 又，亦可利用加成α,θ-不飽和羧酸於酚醛樹脂型環 氧樹脂、丁二醇- I，4-二環氧丙基醚、環己二甲醇環氧丙基 醚、乙二醇二環氧丙基醚、二乙二醇二環氧丙基醚、二丙 二醇二環氧丙基醚、己二醇二環氧丙基醚、三羥甲基丙烷 三環氧丙基醚、異戊四醇四環氧丙烯基醚、雙酚Α二環氧 丙基醚 '丙三醇三環氧丙基醚等含有環氧丙基化合物而得 之化合物。 又，亦可利用含有聚合性基與胺甲酸酯基之化合物。 該等化合物之範例方面，舉出有記載於特公昭48-4 1 708、 特開昭51-37193、特公平5-50737、特公平7-7208、特開 2001-154346、特開2 00 1-356476號公報等、例如藉由加成 1分子中具有2個以上之異氰酸酯基之聚異氰酸酯化合物 (例如二異氰酸六亞甲酯、二異氰酸三甲基六亞甲酯、二異 氰酸異佛爾酮酯、二異氰酸二甲苯酯、二異氰酸甲苯酯、 二異氰酸伸苯酯、二異氰酸降冰片酯、二異氰酸二苯酯' 二異氰酸二苯基甲酯、二異氰酸- 3,3’-二甲基- 4,4’-二苯酯 或該等之二異氰酸酯的貳縮脲體或異三聚氰酸酯等之3聚 物、該等二異氰酸酯類與三亞甲基丙烷、異戊四醇、丙三 -33- 1352875 . 醇等多官能醇、或與該等之環氧乙烷加成物等所得之多官 能醇之加成物等）與於分子中含有羥基之乙烯基單體（例如 (甲基）丙烯酸-2-徑基乙酯、（甲基）丙烯酸-2-羥基丙酯、（甲 基）丙稀酸-4-徑基丁酯、單（甲基）丙烯酸二乙二醇酯 '單（甲 基）丙烯酸三乙二醇酯、單（甲基）丙烯酸多乙二醇酯、單（甲 基）丙稀酸二丙二醇酯、單（甲基）丙烯酸三丙二醇酯、單（甲 基）丙烯酸聚丙二醇酯 '二（甲基）丙烯酸三亞甲基丙酯、三 (甲基）丙烯酸異戊四醇酯等）而得之於分子中含有2個以上 之聚合性乙烯基的乙烯基胺甲酸酯化合物等。又，亦可利 用如三（（甲基）丙烯腈氧基乙基）異三聚氰酸酯 '二（甲基）丙 稀酸化異三聚氰酸酯、環氧乙烷改質異三聚氰酸之三（甲基） 丙烯酸酯等之具有異三聚氰酸酯環的化合物。 又’可舉出有如記載於特開昭48-64 1 83號、特公昭 49-43191號、待公昭52-304 90號公報之聚酯丙烯酸酯或聚 酯（甲基）丙烯酸酯寡聚物類、環氧化合物（酚醛樹脂型環氧 樹脂、丁二醇-1,4 -二環氧丙基醚、環己二甲醇環氧丙基醚、 二乙二醇二環氧丙基醚、二丙二醇二環氧丙基醚、己二醇 二環氧丙基醚 '三羥甲基丙基三環氧丙基醚、異戊四醇四 環氧丙基醚、雙酚Α二環氧丙基醚 '丙三醇三環氧丙基醚 等）與（甲基）丙烯酸反應之環氧丙烯酸酯類等之多官能基丙 烯酸酯或甲基丙烯酸酯。又亦舉出有由酞酸或偏苯三甲酸 等與於前述之分子中含有羥基之乙烯基單體所得之酯化物 等。再者亦可使用於日本接著協會誌vol.20、No.7、第 300~308頁（1984年）介紹作爲光硬化性單體及寡聚物者。 又’亦可使用烯丙酯（例如酞酸二烯丙酯、己二酸二烯 -34- 1352875 丙醋、丙一酸二烯丙酯、酞酸二烯丙酯、偏苯三甲酸三烯 丙酯、苯二磺酸二烯丙酯、異三聚氰酸三烯丙酯等）；及二 烯丙基醯胺（例如二烯丙基乙醯胺等）等。 又’亦可利用陽離子聚合性之二乙烯醚類（例如丁二醇 -1，4-_乙燒醒、環己—甲醇二乙稀酸、乙二醇二乙基酸、 二乙二醇二乙烯醚、二丙二醇二乙烯醚 '己二醇二乙烯醚' 三羥甲基丙基三乙烯醚、異戊四醇四乙烯醆 '雙酚A二乙 稀醚、丙三醇三乙烯醚等）、環氧化合物（酚醛樹脂型環氧 樹脂、丁二醇-1，4·二環氧丙基醚、環己二甲醇環氧丙基醚、 乙二醇二環氧丙基醚、二乙二醇二環氧丙基醚、二丙二醇 二環氧丙基醚 '己二醇二環氧丙基醚、三羥甲基丙基三環 氧丙基醚、異戊四醇四環氧丙基醚、雙酚A二環氧丙基醚、 丙三醇三環氧丙基醚等）、環氧丁烷類（例如丨，4-雙[(3_乙基 -3 -環氧丁基甲氧基）甲基]苯等）作爲聚合性化合物。又環氧 化合物、環氧丁院類方面，亦可使用記載於WO01/22165 之化合物。 乙烯酯類之範例方面，亦可利用琥珀酸二乙烯酯、己 二酸二乙烯酯、酞酸二乙烯酯、對苯二甲酸二乙烯酯、苯 •1，3-二磺酸二乙烯酯及丁 -丨，4-二磺酸二乙烯酯等。 苯乙烯化合物之範例方面，可舉出有二乙烯基苯、4-稀丙基苯乙烯及4-異丙烯基苯乙烯。 再者，上述化合物以外之化合物方面，亦可舉出丙烯 酸羥乙基-冷-(甲基丙烯醯胺）乙酯、N，N-雙（冷-甲基 丙烯酸氧乙基）丙烯醯胺、甲基丙烯酸烯丙酯等之具有2個 +同之乙烯性不飽和雙鍵之化合物作爲適宜地使用於本發 -35- 1352.875. 明的化合物。 該等多官能單體 '寡聚物係可單獨地或組合2種以上 來使用。 再者，必要時，亦可併用含有1個聚合性基於分子內 之聚合性化合物（單官能單體）》單官能單體之範例方面， 舉出有舉例說明作爲前述之黏結劑原料的化合物、揭示於 特開平6-236031號公報之如2鹼基的單（（甲基）丙烯腈氧烷 基酯）單（鹵化氧烷基酯）之單官能單體（例如鄰酞酸-r -氯_ 冷-羥丙基- 甲基丙烯腈氧乙酯等）等，或記載於專利 2744643號、WOOO/52529號、專利2548016號公報等之化 合物。 感光層之單體含有量係一般在各感光層中均爲5〜90 質量％之範圍，以15〜60質量％之範圍爲佳，以20~50質量 %之範圍爲特佳。單體含有量較上述範圍少時則保護幕膜 強度降低’較多時則有保存時之邊緣熔融（從輥終端部分之 滲出毛病）惡化之傾向。又含有2個以上全部單體內聚合性 基之多官能單體含有量，一般爲5~1〇〇質量％之範圍，以 20~100質量％之範圍爲佳，以40~100質量％之範圍爲更 佳。又爲了感度調整’亦可進行於上述範圍內提高第二感 光層之單體含有率等的調整。 [光聚合起始劑] 於本發明之感光性轉印片中所使用之光聚合起始劑方 面，可使用全部具有起始前述單體成分聚合之能力的化合 物，特別是如果對於從紫外線區域至可見光線具有感光性 者則可適合地使用。光聚合起始劑係以含有至少一種於約 -36- 1352875. 300~800nm(以330~500nm較佳）之範圍內具有至少約50之 分子吸光係數的成分爲佳。又光聚合起始劑亦可爲與經過 光激發之增感劑產生任何作用、並生成活性自由基之活性 劑，又亦可爲如針對單體種類來起始陽離子聚合之起始劑。 於感光層中所使用之較佳光聚合起始劑方面，可舉例 有鹵化烴衍生物（例如具有三阱骨架者、具有噁二唑骨架 者）、六芳基雙咪唑、肟衍生物、有機過氧化物 '硫基化合 物、酮化合物、芳香族鎗鹽、酮肟醚等。其中，特別是從 感光層之感度、保存性、及感光層與印刷配線板形成用基 板之密著性等觀點來看，以使用具有三阱骨架之鹵化烴、 肟衍生物、六芳基雙咪唑、酮化合物爲佳。 具有三阱骨架之鹵化烴方面，舉出如下之化合物^ 若林等著、Bull. Chem. Soc. Japan, 42，2924(1969)記 載之化合物，例如，2 -苯基-4,6 -雙（三氯甲基）-1,3,5 -三畊、 2-(4_氯苯基）-4,6-雙（三氯甲基）-1,3,5-三阱' 2-(4_甲苯 基）-4,6-雙（三氯甲基）-1,3,5-三畊、2-(4-甲氧苯基）-4,6-雙 (三氯甲基）-1，3,5-三阱、2-(2,4-二氯苯基）-4,6-雙（三氯甲 基）-1,3,5-三阱、2,4,6-三（三氯甲基）-1,3,5-三阱、2-甲基 _4,6-雙（三氯甲基）-1,3,5-三畊、2-正壬基-4,6-雙（三氯甲 基）-1，3,5-三阱、及2-(α，α，沒-三氯乙基）-4,6-雙（三氯甲 基）-1,3,5-三阱。 英國專利1 3 8 8492號說明書記載之化合物，例如，2-苯乙烯基-4,6·雙（三氯甲基）-1,3,5-三畊、2-(4-甲基苯乙烯 基）_4,6-雙（三氯甲基）-1,3,5-三阱、2-(4-甲氧基苯乙烯 基）-4,6-雙（三氯甲基）-1,3,5-三畊、及2-(4-甲氧基苯乙烯 -37- 1352875. 基）-4-胺基6-三氯甲基-1，3,5-三畊。 特開昭53 - 1 3 3 4 2 8號公報記載之化合物，例如，2-(4-甲氧基-萘-1-醯基）-4,6-雙（三氯甲基）-1,3,5-三阱、2-(4-乙 氧基-萘-卜醯基）-4,6-雙（三氯甲基）-1,3,5-三畊、2-[4-(2-乙 氧基乙基）-萘-卜醯基]-4,6-雙（三氯甲基）-1,3,5-三阱、 2-(4,7-二甲氧基-萘-1-醯基）-4,6-雙（三氯甲基）-1，3,5-三 阱 '及2-(噁萘-5-醯基）-4,6-雙（三氯甲基）-1,3,5-三阱。 德國專利33 3 7 024號說明書記載之化合物，例如，2-(4-苯乙烯基苯基）-4,6-雙（三氯甲基）-1,3，5-三畊、2-(4-(4-甲氧 基苯乙烯基）苯基）-4,6-雙（三氯甲基）-1，3,5-三哄、2-(1-萘 基亞乙烯基苯基）-4,6-雙（三氯甲基）-1，3,5-三畊、2-氯苯乙 烯基苯基-4,6-雙（三氯甲基）-1,3,5-三阱、2-(4-噻吩-2-亞乙 烯基苯基）-4,6-雙（三氯甲基）-1,3,5-三阱、2-(4-噻吩-3-亞乙 烯基苯基）-4,6-雙（三氯甲基）-1,3,5-三阱、2-(4-呋喃-2-亞乙 烯基苯基）-4,6-雙（三氯甲基）-1，3,5-三阱、及2-(4-苯并呋喃 -2-亞乙烯基苯基）-4,6-雙（三氯甲基）-1,3,5-三阱。 由 F.C. Schaefer 等之 J. Org. Chem.; 29, 1 527 ( 1 964) 記載之化合物，例如，2-甲基-4,6-雙（三溴甲基）-1,3,5-三 阱、2,4,6-三（三溴甲基）-1,3,5-三畊' 2,4,6-三（二溴甲 基）-1,3,5-三阱、2-胺基-4-甲基-6-三（溴甲基）-1,3,5-三畊、 及2-甲氧基-4-甲基-6-三氯甲基-1，3,5-三阱。 特開昭62-5 824 1號公報記載之化合物，例如，2-(4-苯基乙炔基苯基）-4,6-雙（三氯甲基）-1,3，5-三阱' 2-(4-萘基 -1-乙炔基苯基）-4,6-雙（三氯甲基）-1,3,5-三阱、2-(4-(4-甲 苯基乙炔基）苯基）-4,6-雙（三氯甲基）-1,3,5-三畊' 2-(4-(4- -38- 1352.875. 甲氧基苯基）乙炔基苯基）-4，6-雙（三氯甲基）-1，3,5-三阱、 2-(4-(4-異丙苯基乙炔基）苯基）-4,6-雙（三氯甲基）-1,3,5-三 哄、2-(4-(4_乙基苯基乙炔基）苯基）-4,6-雙（三氯甲 基）-1，3,5-三哄。 特開平5 -2 8 1 728號公報記載之化合物，例如2-(4-三 氟甲基苯基）-4,6-雙（三氯甲基）-1,3,5-三畊、2-(2,6-二氟苯 基）-4,6·雙（三氯甲基）-1,3,5-三畊、2-(2,6-二氯苯基）-4,6-雙（三氯甲基）-1,3，5-三畊、2-(2,6-二溴苯基）-4,6-雙（三氯甲 基）-1,3,5-三阱。 舉出有特開平5-34920號公報記載之2,4-雙（三氯甲 基）-6-[4-(N，N-二乙氧基羧基甲胺基）-3-溴苯基]-1，3,5-三 阱、記載於美國專利第4239 850號說明書之三鹵化甲基-s-三阱化合物、再者2,4,6-三（三氯甲基）-s-三阱、2-(4-氯苯 基）-4,6-雙（三溴甲基）-s-三阱等。 又，亦可舉出記載於美國專利第42 1 297 6號說明書之 具有噁二唑骨架之化合物等。具有噁二唑骨架之化合物方 面舉例有 2 -三氯甲基-5-苯基-1,3,4·噁二唑、2 -三氯甲基 -5-(4-氯苯基）-1，3，4-噁二唑、2-三氯甲基- 5-(1-萘基）-1,3,4-噁二唑、2-三氯甲基- 5-(2-萘基）-1，3，4-噁二唑、2-三溴甲基 -5 -苯基-1,3,4 -噁二唑、2-三溴甲基-5-(2-萘基）-1,3,4 -噁二 唑、2-三氯甲基-5-苯乙烯基-1，3，4-噁二唑、2-三氯甲基 -5-(4-氯苯乙烯基）-1,3，4-噁二唑' 2-三氯甲基- 5-(4-甲氧基 苯乙烯基）-1,3,4-噁二唑、2-三氯甲基-5-(1-萘基）-1,3,4-噁 二唑' 2 -三氯甲基-5-(4 -正丁氧基苯乙烯基）-1,3,4 -噁二 唑、2 -三溴甲基-5-苯乙烯基-1,3,4 -噁二唑等。 -39- 1352875 於本發明中所適宜地使用之肟衍生物方面，可舉出以 下述通式所示之化合物。Examples of the compound having one hydroxyl group include alcohols (methanol, ethanol, n-propanol, isopropanol 'n-butanol, second butanol, third butanol, n-hexanol, 2-ethylhexanol, N-nonanol, n-dodecyl alcohol, n-octadecyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethanol, etc.), phenols (phenol, cresol, naphthol, etc.); In terms of fluoroethanol, trifluoroethanol 'methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, ethoxylated phenol, and the like. As an exemplary aspect of the amine monomer having a grade 1 or 2, a vinylbenzylamine or the like is exemplified. Specific examples of the compound containing one of the first or second amine groups include alkylamines (methylamine, ethylamine, n-propylamine 'isopropylamine, n-butylamine, -26 to 1352875. dibutylamine, Third butylamine, hexylamine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine 'diethylamine' dibutylamine, dioctylamine), cyclic alkane Alkamine (cycloheptylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), arylamine (aniline, toluidine 'zylidine, naphthylamine, etc.); further combination of these ( N-methyl-N-benzylamine or the like), an amine further containing a substituent (trifluoroethylamine, hexafluoroisopropylamine, methoxyaniline, methoxypropylamine, etc.). These compounds may be used alone or in combination of two or more. Examples of other preferred monomers are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid_2-B Hexyl hexyl ester, styrene, chlorostyrene, bromostyrene, and hydroxyphenylethylene. These vinyl copolymers are obtained by copolymerizing different equivalent monomers in accordance with a conventional method known in the art. For example, it is obtained by a method (solution polymerization method) in which the monomers are dissolved in a suitable solvent and a radical polymerization initiator is added thereto to be polymerized in a solution. Further, the polymerization may be carried out by so-called emulsion polymerization or the like in the state of dispersing the above monomers in an aqueous solvent. The solvent example used in the solution polymerization method can be arbitrarily selected in view of the solubility of the monomer to be used and the copolymer to be produced. · Examples are methanol, ethanol, propanol, isopropanol, b-methoxy-2-propanol, acetone 'methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. These solvents may be used in combination of two or more kinds. Further, as the radical polymerization initiator, for example, 2,2,-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4,-dimethylvaleronitrile) can be used. An azo compound; a peroxide such as benzammonium peroxide; and a persulfate -27- 1352875 salt such as potassium persulfate or ammonium persulfate. The repeating unit content ratio from the polymerizable compound having a carboxyl group in the vinyl copolymer obtained from the monomers is 5 to 50 mol% in all the repeating units of the copolymer in each photosensitive layer. Good, with 10~40 mol% is better, and 15~35 mol% is especially good. When the content is less than 5 mol%, the development of the hydrophobic water may be insufficient. When the content is more than 50 mol%, the liquid resistance of the cured portion (image portion) may be insufficient. Although the molecular weight of the binder having a carboxyl group can be arbitrarily adjusted, it is preferable that the photosensitive layer has a mass molecular weight of from 2,000 to 30,000, and particularly preferably from 4,000 to 1,50,000. When the mass average molecular weight is less than 2,000, the film strength tends to be insufficient, and the production tends to be difficult. When the molecular weight exceeds 300,000, the developing property tends to decrease. Further, the binder having the carboxyl group may be one type or one or more types of binders. Examples of the case where two or more kinds of the binder are used include two or more kinds of binders composed of different copolymerization components, two or more kinds of binders having different mass average molecular weights, and two or more kinds of different dispersities. Adhesive. The binder having a carboxyl group may also neutralize a part or all of the carboxyl group with a basic substance. Further, the binder may be a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, a polyvinyl alcohol or a gelatin to form a different resin. Further, examples of the binder include resins which are soluble in an alkaline aqueous solution and the like which are described in Patent No. 2,873,889. The content of the binder in the photosensitive layer is usually 10 to 90% by weight of each photosensitive layer, preferably 20 to 80% by weight, particularly preferably 40 to 80% by weight. The -28- 1352875 carboxy group-containing binder (and polymer binder used when necessary) has a basic development property or a substrate for forming a printed wiring board (for example, copper plating) In the case where the adhesion is likely to be lowered, the stability of the development time or the strength of the cured film (protective film) tends to decrease. Further, in order to adjust the sensitivity, the content of the binder contained in the second photosensitive layer may be adjusted to be lower than the content of the binder contained in the first photosensitive layer (increasing the content of the polymerizable compound). . [Polymerizable compound] In the photosensitive layer, a polymerizable compound (so-called monomer) is used, but a monomer containing two or more polymerizable groups or an oligomer (polyfunctional monomer, polyfunctional oligomer) is used. ) is especially good. The polymerizable group is exemplified by an ethylenically unsaturated bond (for example, a vinyl group, an allyl ether or an allyl group such as a (meth)acrylonitrile group, a (meth)acrylamide group, a styryl group, a vinyl ester or a vinyl ether. A propylene group such as an ester, etc.) a polymerizable cyclic ether group (e.g., an epoxy group, an oxetanyl group, etc.). Within these, ethylenically unsaturated bonds are preferred. Examples of such polyfunctional monomers include unsaturated carboxylic acids (eg, 'acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyol compounds. Examples of esters, unsaturated carboxylic acids and polyamine compounds, guanamines, etc., and specific examples of aliphatic polyol compounds and ester steroids of unsaturated carboxylic acids, there are ethylene glycol di(meth)acrylate, a vinyl group having 2 to 18 bis (meth)acrylic acid polyglycol ester (for example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, di(meth)acrylic acid Tetraethylene glycol ester 'pentaethylene glycol di(meth)acrylate, dodecaethylene glycol di(meth)acrylate, tetradecyl glycol di(meth)acrylate, etc.), di(methyl) -29- 1352875 Propylene glycol acrylate, polypropylene glycol with 2 to 18 bis (meth) acrylate (such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, di (a) Base) tetrapropylene glycol acrylate, di(methyl) 12-propylene glycol acrylate, etc.), neopentyl glycol di(meth)acrylate, ethylene oxide modified neopentyl glycol di(meth)acrylate, propylene oxide modified di(meth)acrylic acid Pentyl glycol ester, trimethylolpropyl tri(meth)acrylate, trimethylolpropyl di(meth)acrylate, trimethylolpropyltris((meth)acrylonitrileoxypropyl) Ether, trimethylolethyl tris(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, di(methyl) Acrylic acid - I, 4-butylene glycol ester, 1,6-hexanediol di(meth)acrylate, tetramethyl glycol di(meth)acrylate, di-(meth)acrylic acid-1,4- Cyclohexanediol ester, 1,2,4-butane triol (meth)acrylate, 1,5-pentanediol (meth)acrylate, pentaerythritol di(meth)acrylate , Isoamyl tris(meth)acrylate, isoamyl tetra(meth)acrylate, diisopentyl pentate (meth)acrylate, diisoamyl pentoxide (hexa) Tris(methyl)-propyl Sorbitol ester, sorbitan tetra(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(meth)acrylate, dimethylol di(meth)acrylate Cyclopentyl ester, tricyclodecyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropyl bis(meth)acrylate, with individual average a di(meth)acrylate of at least one ethylene glycol chain/propylene glycol chain of a hydrocarbylene glycol chain (for example, a compound described in WO01/9 8832, etc.), an added ethylene oxide and/or a ring Trimethyl (meth) acrylate of trimethylolpropane of oxypropane, polybutylene glycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate And (meth) acrylate such as bis (meth) acrylate. -30- 1352875. In terms of preferred examples of the above (meth) acrylates, from the viewpoint of the difficulty in obtaining, it is exemplified by ethylene glycol di(meth)acrylate and di(meth)acrylic acid. Ethylene glycol ester, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, dialkyl (meth) group having an alkylene glycol chain having an average of at least one ethylene glycol chain/propylene glycol chain Acrylate, trimethylolpropyl tri(meth)acrylate, isoamyl tetra(meth)acrylate, isoamyl tris(meth)propionate, isoamyl di(meth)acrylate Tetraol ester, diisopentyl penta(methyl) acrylate, diisopentyl hexa(meth) acrylate, glycerol tri(meth) acrylate, di(meth) acrylate Glycerol ester, 1,3-propanediol di(meth)acrylate, 1,2,4-butanetriol tris(meth)acrylate, di(meth)acrylic acid-1,4-cyclohexane Glycol ester, 5-cyclopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trishydroxymethyl which has been added to ethylene oxide Propane tri (meth) acrylate. An exemplary aspect of an ester of itaconic acid and an aliphatic polyol compound (itaconate) is ethanoic acid ethylene glycol ester, diaconic acid propylene glycol ester, and itaconic acid-1,3-butane Alcohol esters, diitaconic acid-1,4-butanediol esters, tetraethanoic acid tetramethylene glycol ester, isaconic acid dipentyl glycolate, and sorbitan tetraisoate. Examples of esters of crotonic acid and aliphatic polyol compounds (crotonate) are ethylene glycol dicrotonate, tetramethyl glycol dicrotonate, pentaerythritol dicrotonate, and tetracrodo beans. Sorbitol ester and the like. Exemplary aspects of esters of isocrotonic acid with aliphatic polyol compounds (isocrotonate) are ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate Ester and the like. An example of an ester (maleate) of maleic acid and an aliphatic polyol compound is dicis 1352875. Ethylene phthalate, trimethyl glycol maleate And pentaerythritol dimaleate, and sorbitol tetramaleate. Further, from the exemplary aspect of the decylamine derived from the polyamine compound and the unsaturated carboxylic acid, there is methylene bis(meth) acrylamide, and ethyl bis(methyl) acrylamide 1, 1,6 -6 Methylene bis(meth) acrylamide, octamethylene bis(methyl) acrylamide, diethylene triamine tri (meth) acrylamide, diethylene triamine bis (meth) acrylamide 'and xylene bis(methyl) acrylamide and the like. Furthermore, 2,2-bis[4-(3-(methyl)acryloyloxy-2-hydroxypropoxy)phenyl]propane having a bisphenol skeleton, 2,2_double [ 4_(Meth)acryloxyethoxy)phenyl]propane, substituted by a phenolic oxime H group, the number of epoxy groups is 2-20, 2,2-bis[4-(methyl) Acrylonitrileoxypolyethoxy)phenyl]propane (eg 2,2-bis[4-(methyl)acrylonitrileoxydiethoxy)phenyl]propane, 2,2-bis[4-( Methyl)acrylonitrileoxytetraethoxy)phenyl]propane, 2,2-bis[4-(methyl)acrylonitrileoxypentaethoxy)phenyl]propane, 2,2-bis[4 -(Methyl)acrylonitrileoxydecaethoxy)phenyl]propane, 2,2-bis[4-(methyl)acrylonitrileoxypentadecyloxy)phenyl]propane, etc., 2, 2. Bis[4-(methyl)acrylonitrileoxypropoxy)phenyl]propane' substituted 1 phenolic 0H group has 2,2-bis[4-" (Meth)acrylonitrileoxypolypropoxy)phenyl]propane (for example, 2,2-bis[4-(methyl)acrylonitrileoxydipropoxy)phenyl]propane, 2,2_double [4-(Methyl)acrylonitrileoxytetrapropoxy)phenyl]propane, double [4_ (Meth)acrylonitrileoxypentapropoxy)phenyl]propane, 2,2-bis[4-(methyl)acrylonitrileoxydapoxy)phenyl]propane, 2,2-double [ 4-(Methyl)acrylonitrileoxypentadecapropoxy)phenyl]propane or the like) or both of a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule as a polyether moiety of the compound Compounds, etc. (For example, it is described in WO01/98832 -32- 1352875. Compounds, etc.). These compounds are available from BPE-200, BPE-500, ΒΡΕ-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like. Further, a compound having an isocyanate group and a polymerizable group ((methyl) may be used as a compound having a hydroxyl group at the terminal of the addition product of bisphenol and ethylene oxide or propylene oxide or a repeating adduct. A polymerizable compound having a bisphenol skeleton and a urethane group is used as an adduct of acrylic-2, isocyanate ethyl ester, isocyanate-α, α-dimethyl-vinylbenzyl ester or the like. Further, it is also possible to use an addition of α, θ-unsaturated carboxylic acid to a phenolic resin type epoxy resin, butanediol-I,4-diepoxypropyl ether, cyclohexanedimethanol epoxypropyl ether, and ethylene Alcohol diepoxypropyl ether, diethylene glycol diepoxypropyl ether, dipropylene glycol diepoxypropyl ether, hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, A compound containing an epoxy propyl compound such as isovalerol tetraethylene oxide propylene ether or bisphenol quinone diepoxypropyl ether glycerol triepoxypropyl ether. Further, a compound containing a polymerizable group and a carbamate group can also be used. Examples of such compounds are described in Japanese Patent Publication No. 48-4 1 708, Special Open No. 51-37193, Special Fair 5-50737, Special Fair 7-7208, Special Open 2001-154346, Special Open 2 00 1 -356476 or the like, for example, by adding a polyisocyanate compound having two or more isocyanate groups in one molecule (for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diiso) Isophorone cyanide, xylyl diisocyanate, toluene diisocyanate, phenyl diisocyanate, norbornyl diisocyanate, diphenyl diisocyanate diisocyanate Diphenyl methyl ester, 3,3'-dimethyl-4,4'-diphenyl diisocyanate or a urecure or isomeric cyanate of such diisocyanates Polymer, polyisocyanate, polyfunctional alcohol such as trimethylenepropane, isovaerythritol, propylene triene-33-1352875, alcohol, or polyfunctional alcohol obtained from such ethylene oxide adducts An adduct, etc.) and a vinyl monomer having a hydroxyl group in the molecule (for example, 2-methyl ethyl methacrylate, 2-hydroxypropyl (meth) acrylate, (meth) propylene -4-diabutyl butyl ester, diethylene glycol mono(meth)acrylate 'triethylene glycol mono(meth)acrylate, poly(ethylene glycol) mono(meth)acrylate, mono(methyl) propyl Dipropylene glycol diester, tripropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, trimethylene propyl di(meth)acrylate, pentaerythritol tris(meth)acrylate, etc. It is obtained from a vinyl urethane compound containing two or more polymerizable vinyl groups in the molecule. Further, it is also possible to use, for example, tris((meth)acrylonitrileoxyethyl)isocyanate 'di(meth)acrylic acid isomeric cyanurate, ethylene oxide modified heterotrimerization A compound having an iso-cyanate ring such as tris(meth) acrylate of cyanic acid. Further, a polyester acrylate or polyester (meth) acrylate oligomer which is described in JP-A-48-64 1 83, JP-A-49-43191, and Kokai No. 52-304 90 can be cited. Class, epoxy compound (phenolic resin type epoxy resin, butanediol-1,4-diepoxypropyl ether, cyclohexanedimethanol epoxypropyl ether, diethylene glycol diepoxypropyl ether, two Propylene glycol diepoxypropyl ether, hexanediol diepoxypropyl ether 'trimethylolpropyl triepoxypropyl ether, isopentenyl alcohol tetraepoxypropyl ether, bisphenol quinone diepoxypropyl A polyfunctional acrylate or methacrylate such as an epoxy acrylate which is reacted with (meth)acrylic acid, such as ether glycerol triepoxypropyl ether. Further, there are also esterified products obtained from a vinyl monomer having a hydroxyl group in the above-mentioned molecule, such as capric acid or trimellitic acid. Further, it can also be used as a photocurable monomer and oligomer in Japanese Society Association vol. 20, No. 7, pp. 300-308 (1984). Also, allyl esters can be used (for example, diallyl citrate, diene adipate-34- 1352875 propylene vinegar, diallyl propionate, diallyl citrate, trimellitic acid triene) Propyl ester, diallyl benzenedisulfonate, triallyl isocyanurate, etc.; and diallylamine (for example, diallylacetamide, etc.). Also, 'cationic polymerizable divinyl ethers can also be used (for example, butanediol-1,4-e b abbreviated, cyclohexan-methanol diethylene acid, ethylene glycol diethyl acid, diethylene glycol II) Vinyl ether, dipropylene glycol divinyl ether 'hexane diol divinyl ether' trimethylol propyl trivinyl ether, isovaerythritol tetravinyl hydrazine 'bisphenol A diethyl ether ether, glycerol trivinyl ether, etc.) Epoxy compound (phenolic resin type epoxy resin, butanediol-1,4·diepoxypropyl ether, cyclohexanedimethanol epoxypropyl ether, ethylene glycol diepoxypropyl ether, diethylene glycol) Alcohol diepoxypropyl ether, dipropylene glycol diepoxypropyl ether 'hexanediol diepoxypropyl ether, trimethylolpropyl triepoxypropyl ether, isopentaerythritol tetraepoxypropyl ether , bisphenol A diglycidyl ether, glycerol triepoxypropyl ether, etc.), butylene oxides (eg, hydrazine, 4-bis[(3-ethyl-3-epoxybutyl methoxy)) Methyl]benzene or the like) is a polymerizable compound. Further, in the case of an epoxy compound or a butyl epoxide, a compound described in WO01/22165 can also be used. Examples of vinyl esters may also utilize divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinyl benzene 1,3-disulfonate, and D-indole, 4-disulfonic acid divinyl ester, and the like. Examples of the styrene compound include divinylbenzene, 4-dipropylstyrene, and 4-isopropenylstyrene. Further, examples of the compound other than the above compound include hydroxyethyl-cold-(methacrylamide)ethyl acrylate and N,N-bis(cold-oxyethyl methacrylate) acrylamide. A compound having two + identical ethylenically unsaturated double bonds, such as allyl methacrylate, is suitably used as a compound of the present invention in 35- 1352.875. These polyfunctional monomer 'oligomer systems can be used singly or in combination of two or more. Further, if necessary, an example of a monofunctional monomer containing one polymerizable intramolecular polymerizable compound (monofunctional monomer) may be used in combination, and a compound exemplified as a raw material of the above-mentioned binder may be mentioned. A monofunctional monomer such as a 2 (base) (meth)acrylonitrile oxyalkyl ester mono (halogenated oxyalkyl ester) as disclosed in JP-A-6-236031 (for example, o-nonanoic acid-r-chloro) _Cold-hydroxypropyl-methacrylonitrile oxyethyl ester, etc., or a compound described in Patent No. 2744643, WOOO/52529, and Patent No. 2548016. The monomer content of the photosensitive layer is generally in the range of 5 to 90% by mass in each photosensitive layer, preferably in the range of 15 to 60% by mass, particularly preferably in the range of 20 to 50% by mass. When the amount of the monomer is less than the above range, the strength of the protective film is lowered. When there is a large amount of the film, the edge melts during storage (the bleeding from the end portion of the roll) tends to deteriorate. Further, the content of the polyfunctional monomer containing two or more polymerizable groups in the monomer is generally in the range of 5 to 1% by mass, preferably in the range of 20 to 100% by mass, and preferably in the range of 40 to 100% by mass. For better. Further, in order to adjust the sensitivity, it is also possible to adjust the monomer content and the like of the second photosensitive layer within the above range. [Photopolymerization initiator] In terms of the photopolymerization initiator used in the photosensitive transfer sheet of the present invention, all of the compounds having the ability to initiate polymerization of the aforementioned monomer components can be used, particularly if for the ultraviolet region If it is photosensitive to visible light, it can be suitably used. The photopolymerization initiator is preferably one having at least one molecular absorption coefficient of at least about 50 in the range of from about -36 to 1352875. 300 to 800 nm (preferably from 330 to 500 nm). Further, the photopolymerization initiator may be an active agent which exerts any action with a photo-excited sensitizer and generates an active radical, or may be an initiator which initiates cationic polymerization as for a monomer species. Preferred examples of the photopolymerization initiator used in the photosensitive layer include halogenated hydrocarbon derivatives (for example, those having a triple well skeleton and having a oxadiazole skeleton), hexaarylbisimidazole, anthracene derivatives, and organic groups. Peroxide 'sulfur compound, ketone compound, aromatic gun salt, ketoxime ether, and the like. Among them, in particular, from the viewpoints of the sensitivity and storage stability of the photosensitive layer, and the adhesion between the photosensitive layer and the substrate for forming a printed wiring board, a halogenated hydrocarbon, an anthracene derivative, or a hexaaryl double having a triple well skeleton is used. Imidazole and ketone compounds are preferred. In the case of a halogenated hydrocarbon having a triple well skeleton, the following compounds are exemplified by Ruolin et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis ( Trichloromethyl)-1,3,5-three tillage, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triso' 2-(4 _Tolyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1 , 3,5-tripper, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-trisole, 2,4,6-tri Trichloromethyl)-1,3,5-tri-trap, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-n-decyl-4,6 - bis(trichloromethyl)-1,3,5-tripper, and 2-(α,α, s-trichloroethyl)-4,6-bis(trichloromethyl)-1,3, 5-triple well. A compound described in the specification of British Patent No. 1 38 8492, for example, 2-styryl-4,6·bis(trichloromethyl)-1,3,5-three tillage, 2-(4-methylstyrene —4,6-bis(trichloromethyl)-1,3,5-tri-trap, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1, 3,5-three tillage, and 2-(4-methoxystyrene-37- 1352875.yl)-4-amino 6-trichloromethyl-1,3,5-three tillage. A compound described in JP-A-53-1353, No. 2, for example, 2-(4-methoxy-naphthalen-1-indolyl)-4,6-bis(trichloromethyl)-1, 3,5-tripper, 2-(4-ethoxy-naphthalene-didecyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[4-(2- Ethoxyethyl)-naphthalene-didecyl]-4,6-bis(trichloromethyl)-1,3,5-tri-trap, 2-(4,7-dimethoxy-naphthalene-1-anthracene -4,6-bis(trichloromethyl)-1,3,5-tritrap' and 2-(oxanaphthalen-5-fluorenyl)-4,6-bis(trichloromethyl)-1 , 3, 5 - triple well. A compound described in the specification of German Patent No. 33 3 7 024, for example, 2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-( 4-(4-methoxystyryl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(1-naphthylvinylenephenyl) -4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-chlorostyrylphenyl-4,6-bis(trichloromethyl)-1,3,5-three Trap, 2-(4-thiophene-2-vinylidenephenyl)-4,6-bis(trichloromethyl)-1,3,5-tri-trap, 2-(4-thiophene-3-tetramethylene Phenyl)-4,6-bis(trichloromethyl)-1,3,5-tri-trap, 2-(4-furan-2-vinylidenephenyl)-4,6-bis(trichloro) Methyl)-1,3,5-tripper, and 2-(4-benzofuran-2-vinylidenephenyl)-4,6-bis(trichloromethyl)-1,3,5- Three wells. A compound described by FC Schaefer et al., J. Org. Chem.; 29, 1 527 (1 964), for example, 2-methyl-4,6-bis(tribromomethyl)-1,3,5-three Trap, 2,4,6-tris(tribromomethyl)-1,3,5-trin' 2,4,6-tris(dibromomethyl)-1,3,5-tri-trap, 2- Amino-4-methyl-6-tris(bromomethyl)-1,3,5-three tillage, and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5 - Three wells. A compound described in JP-A-62-5 824 No. 1, for example, 2-(4-phenylethynylphenyl)-4,6-bis(trichloromethyl)-1,3,5-tritrap 2-(4-naphthyl-1-ethynylphenyl)-4,6-bis(trichloromethyl)-1,3,5-tri-trap, 2-(4-(4-methylphenylethynyl) Phenyl)-4,6-bis(trichloromethyl)-1,3,5-trin' 2-(4-(4- -38- 1352.875. methoxyphenyl)ethynylphenyl)- 4,6-bis(trichloromethyl)-1,3,5-tri-trap, 2-(4-(4-isopropylphenylethynyl)phenyl)-4,6-bis(trichloromethyl) )-1,3,5-triazine, 2-(4-(4-ethylphenylethynyl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine . A compound described in JP-A-5-2,728, for example, 2-(4-trifluoromethylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2 -(2,6-difluorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(2,6-dichlorophenyl)-4,6- Bis(trichloromethyl)-1,3,5-three tillage, 2-(2,6-dibromophenyl)-4,6-bis(trichloromethyl)-1,3,5-triad . 2,4-bis(trichloromethyl)-6-[4-(N,N-diethoxycarboxymethylamino)-3-bromophenyl] described in JP-A-H05-34920 -1,3,5-triple, a trihalogenated methyl-s-tripper compound described in U.S. Patent No. 4,239,850, and 2,4,6-tris(trichloromethyl)-s-three Well, 2-(4-chlorophenyl)-4,6-bis(tribromomethyl)-s-tripper, etc. Further, a compound having an oxadiazole skeleton or the like described in the specification of U.S. Patent No. 4,1,297,6 is also mentioned. Examples of the compound having a oxadiazole skeleton are 2-trichloromethyl-5-phenyl-1,3,4oxadiazole and 2-trichloromethyl-5-(4-chlorophenyl)-1. , 3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5-(2-naphthyl)-1 , 3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyryl)- 1,3,4-oxadiazole '2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-( 1-naphthyl)-1,3,4-oxadiazole '2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2 -three Bromomethyl-5-styryl-1,3,4-oxadiazole and the like. In the case of the anthracene derivative which is suitably used in the present invention, a compound represented by the following formula may be mentioned.

-40- ⑴ (2) 1352875 ch3o i ch3 ch3 -U--N CH, CH3 ch3s ◎-40- (1) (2) 1352875 ch3o i ch3 ch3 -U--N CH, CH3 ch3s ◎

I -N 0 (3) 0CH2-<Q> (4) 〇c4h9 ch3s (5) (7)I -N 0 (3) 0CH2-<Q> (4) 〇c4h9 ch3s (5) (7)

CH3S (9)CH3S (9)

CH3S O T) ch3sCH3S O T) ch3s

•N O•N O

CH3S (6)CH3S (6)

JLJL

-N O-N O

OO

JL -N O CH30 pC2H4OC2H4OCH3JL -N O CH30 pC2H4OC2H4OCH3

II

och2co2ch3 NII ◎ pC12H25Och2co2ch3 NII ◎ pC12H25

JLJL

-N O (8)-N O (8)

CH3S ◎ (10) -N 0 ch3sCH3S ◎ (10) -N 0 ch3s

pCH2C02C4H9 r~\ N O 0CH2-<^>-C02CH3 N 0 och2co2c2h5 r~\ •N 0 -41 - -0· (13)1352875 Π 2) ch3s pC2H4C〇2C2H5 N 1 -N 0pCH2C02C4H9 r~\ N O 0CH2-<^>-C02CH3 N 0 och2co2c2h5 r~\ •N 0 -41 - -0· (13)1352875 Π 2) ch3s pC2H4C〇2C2H5 N 1 -N 0

CH3S O'CH3S O'

JL (1 4) ch3s och2co2ch2 N Π -N 0 (15) (16)JL (1 4) ch3s och2co2ch2 N Π -N 0 (15) (16)

〇 r -N O N-〇 r -N O N-

N © 修 (17) (18) OCO·N © Repair (17) (18) OCO·

CH3S 1CH3S 1

•N O ch3shQ>- 0S02 NII k (1 9) · ch3s [0 1. 1 4] "Ο•N O ch3shQ>- 0S02 NII k (1 9) · ch3s [0 1. 1 4] "Ο

-<D-<D

OCONH Γ N O -42- 1352875. (2 0)OCONH Γ N O -42- 1352875. (2 0)

(2 2) (2 1) Ν-0-S-^) ◦七 0 :N-0-C一CH3 .(2 3) 0 \ 〇 II n-o-c-c2h5 0=( =N~〇-C~CH3(2 2) (2 1) Ν-0-S-^) ◦7 0 :N-0-C-CH3 .(2 3) 0 \ 〇 II n-o-c-c2h5 0=( =N~〇-C~CH3

【0 115] -43- 1352875 (2 8)[0 115] -43- 1352875 (2 8)

(30) n-CgHiy (3 1 )樟腦基 (32) p-CH3C6H4(30) n-CgHiy (3 1 ) camphor (32) p-CH3C6H4

R (33) n-C3H7 (34) p-CH3C6H4 -44 1352875 可使用於本發明之六芳基雙咪唑方面，舉出有2,2’-雙（2-氯苯基卜4,4’，5,5’-四苯基雙咪唑、2,2’-雙（2·氟苯 基）-4,4’，5,5’-四苯基雙咪唑、2,2’-雙（2-溴苯基）-4,4’，5,5’-四苯基雙咪唑、2,2’-雙（2,4-二氯苯基）-4,4’，5,5’-四苯基雙 咪唑、2,2’-雙（2-氯苯基）-4,4’，5,5’-四（3-甲氧基苯基）雙咪 唑、2,2’-雙（2-氯苯基）-4,4’，5,5’-四（4-甲氧基苯基）雙咪 唑、2,2’-雙（4 -甲氧基苯基）-4,4’，5,5’-四苯基雙咪唑、2,2’-雙（2,4-二氯苯基）-4,4’，5,5’-四苯基雙咪唑、2,2’-雙（2-硝基 苯基）-4,4’，5,5’-四苯基雙咪唑、2,2’-雙（2-甲苯 基）-4,4’，5,5’-四苯基雙咪唑、2,2’-雙（2 -三氟甲基苯 基）-4,4’，5,5’-四苯基雙咪唑、記載於\¥〇00/5 2529號公報 之化合物等。 上述雙咪唑類，可藉由例如於Bull. Chem. Soc. Japan， 33，565(1960)、及 J. Org. Chem., 36(16)2262(1971)所揭示 之方法來容易地合成。 酮化合物方面，舉出有二苯基酮、2-甲基二苯基酮、 3-甲基二苯基酮、4-甲基二苯基酮、4-甲氧基二苯基酮、2-氯二苯基酮、4-氯二苯基酮、4-溴二苯基酮、2-羧基二苯基 酮、2-乙氧基羧基二苯基酮、二苯基酮四羧酸或其四甲基 酯、4,4’-雙（二烷基胺基）二苯基酮類（例如4,4’-雙（二甲胺 基）二苯基酮、4，4’-雙（二環己胺基）二苯基酮、4,4’-雙（二 乙胺基）二苯基酮、4，4’-雙（二羥乙胺基）二苯基酮' 4-甲氧 基-4’-二甲胺基二苯基酮、4，4’-二甲氧基二苯基酮' 4-二甲 胺基二苯基酮）、4-二甲胺基苯乙酮、苄、蒽醌' 2-第三丁 基蒽醌、2-甲基蒽醌 '菲二酮、咕噸酮、噻噸酮、2-苄基- -45- 1352.875. 二甲胺基-1-(4 -嗎林苯基）-1-丁酮、2 -甲基- l- [4-(甲基硫代） 苯基]-2-嗎林-1-丙酮、2-羥基-2-甲基-[4-(1-甲基乙烯基） 苯基]丙醇寡聚物、苯偶因、苯偶因醚類（例如苯偶因甲基 醚、苯偶因乙基醚、苯偶因丙基醚 '苯偶因異丙基醚、苯 偶因苯基醚 '苄基二甲基縮酮）、吖啶酮、氯吖啶酮、N-甲基吖啶酮、N -丁基吖啶酮等。 又其他亦舉出有吖啶衍生物（例如9-苯基吖啶、1，7-雙 (9,9，-吖啶）庚烷等）' N-苯基環胺乙酸等、多鹵化合物（例 如，四溴甲烷、苯基三溴甲颯、苯基三氯甲基酮等）、薰草 素類（舉例有.3-(2-苯并糠醯基）-7-二乙胺基薰草素、3-(2-苯并糠醯基）·7-(卜吡咯啶基）薰草素、3-苯甲醯基-7-二乙胺 基薰草素、3-(2-甲氧基苯甲醯基）-7-二乙胺基薰草素'3-(4-二甲胺基苯甲醯基）-7-二乙胺基薰草素、3,3’-羧基雙（5,7-二正丙氧基薰草素）、3,3’-羧基雙（7-二乙胺基薰草素）、3-苯甲醯基-7-甲氧基薰草素、3-(2-糠醯基）-7-二乙胺基薰草 素、3-(4·二乙胺基桂皮醯基）-7-二乙胺基薰草素、7-甲氧 基-3-(3-吡啶羧基）薰草素' 3-苯甲醯基-5,7-二丙氧基薰草 素、7-苯并三唑-2-醯基薰草素等，其他舉出有記載於特開 平5-19475號、特開平7-271028號公報、特開2002-363206 號、特開 200 2-363207號、特開2002-363208號、待開 2002-363209號公報等之薰草素化合物）、胺類（舉例有4_ 二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸正丁酯、4-二甲 胺基苯甲酸苯乙酯、4-二甲胺基苯甲酸-2-酞亞醯乙酯、4-二甲胺基苯甲酸-2·甲基丙烯腈氧基乙酯、五亞甲基雙（4-二甲胺基苯甲醯酯）、3-二甲胺基苯甲酸之苯乙酯及五亞甲 -46- 1352875. 基苯甲醛、4 -二甲胺基苯甲醛、2_氯-4_二甲胺苯甲醛、4-二甲胺基苄醇、乙基（4-二甲胺基苯甲醯）乙醯酯、4_N_六氫 吡啶基苯乙酮'4 -二甲胺基苯偶因、N，N_二甲基-4_甲苯胺、 N，N-二乙基-3-乙氧苯胺、三苄胺、二苄基苯胺、N_甲基·Ν· 苯基；胺' 4-溴-Ν，Ν·二甲基苯胺、十三烷基胺 '胺基氧雜 蒽類（ODB、ODBII等）' 結晶紫內酯、無色結晶紫等）、烯 丙基膦氧化物類（例如雙（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-戊苯基膦 氧化物、LucirinTPO等）、茂金屬類（例如雙（π 5_2,4-環戊 二烯-1-醯基）-雙（2,6 -二氟- 3_(1Η_吡咯-卜醯基苯基）鈦、 7/ 5 -環戊二稀-?7 6 -異丙苯基-鐵（1+)_六氟磷化物（1_)等）、 於特開昭53-133428號公報、特公昭57_1819號公報、 57-6096號公報、及美國專利第3615455號說明書所揭示之 化合物等。 再者亦可使用揭示於美國專利第2367660號說明書所 揭示之連位聚縮醛化合物 '記載於美國專利第2448828號 說明書之酮醇醚化合物、記載於美國專利第27225 1 2號說 明書之以α -碳氫化合物取代之芳香族酮醇化合物、記載於 美國專利第3046 1 27號說明書及第295 1 758號說明書之多 核醌化合物、記載於特開2〇〇2-：229194號公報之有機硼化 合物或其他範例說明之自由基產生劑等、又三芳基鑰鹽（所 謂六氟銻或六氟磷鹽之鹽）、如（苯基吩噻基）二苯基鎗鹽等 之鱗鹽化合物（作爲陽離子聚合起始劑有效）、WO01/71428 號公報之鑰鹽化合物等。 光聚合起始劑係可使用一種或倂用2種以上。該等組 -47- 1352875. 合方面，亦可利用例如記載於美國專利第3 5 4 9 3 6 7號說明 書之六芳基雙咪唑與4 -胺基酮類之組合、記載於特公昭 5148516號公報之苯并噻唑化合物與三鹵素甲基三阱 化合物之組合等，又硫代氧酮等之芳香族酮化合物與氫供 應體（例如含有二烷基胺基之化合物、酚化合物等）之組 合、六芳基雙咪唑與二茂鈦之組合、薰草素類與二茂鈦與 苯基胺乙酸類之組合。 光聚合起始劑之使用量係於各感光層中均針對感光層 之全部成分，一般爲0.1-30質量％之範圍，以0.5~20質量 %之範圍爲佳，以0.5~15質量％之範圍爲特佳。又在以光 聚合起始劑含有量調整各感光層之感度差的情況下，於第 二感光層所含有之光聚合起始劑量亦可比第一感光層所含 有之光聚合起始劑量多。第二感光層之光聚合起始劑含有 量係針對第一感光層之光聚合起始劑含有量而以1.5~100 倍之量爲佳，以1 .8~50倍爲更佳，以2~ 20倍之量爲特佳。 [增感劑] 爲了調整各感光層曝光中之感度或感光波長之目的而 可添加增感劑。在使用可見光線或紫外光•可見光雷射作 爲曝光光線（活性能量線束）的情況等之下，增感劑係藉由 活性能量線束成爲激發狀態，並與其他物質（例如自由基產 生劑、氧產生劑等）相互作用（例如能量移動、電子移動等）， 可產生自由基或氧等之有用官能基。 增感劑方面’亦可利用已知之多核芳香族類（例如，焦 油腦、茈、聯三伸苯）、咕噸類（例如，螢光黃、曙紅、原 藻紅、玫瑰紅、玫瑰樹膠）、賽安寧類（例如，吲哚碳賽安 -48- 1352875. 寧、噻碳賽安寧、草酸碳賽安寧）、部花青類（例如，部花 青、碳部花青）、噻阱類（例如，硫堇、亞甲基藍、甲苯胺 藍）、吖啶類（例如，吖啶橙' 氯黃素、吖啶黃素）、蒽輥類（例 如’蒽醌）、角鯊鎗類（例如，角鯊鎗）、吖啶酮類（例如，吖 啶酮、氯吖啶酮、N -甲基吖啶酮' N - 丁基吖啶酮、N - 丁基-氯吖啶酮等）、薰草素類（例如，舉出有3-(2 -苯并糠醯基）_7-二乙胺基薰草素、3-(2-苯并糠基）-7-(1-吡咯啶基）薰草素' 3-苯甲醯基-7-二乙胺基薰草素、3-(2-甲氧基苯甲醯基）-7-二乙胺基薰草素、3-(4-二甲胺基苯甲醯基）-7-二乙胺基薰 草素、3,3’-羧基雙（5,7-二正丙氧基薰草素）、3,3’-羧基雙（7· 二乙胺基薰草素）' 3-苯甲醯基-7-甲氧基薰草素、3-(2-糠 醯基）-7-二乙胺基薰草素、3-(4-二乙胺基桂皮醯基）-7-二乙 胺基薰草素、7 -甲氧基- 3- (3 -吡啶羧基）薰草素、3 -苯甲醯 基-5,7-二丙氧基薰草素等，其他舉出有記載於特開平 5- 1 9475 號' 特開平 7-27 1 028 號、特開 2002-363206 號、 特開 2002-363207 號、特開 2002-363208 號、特開 20〇2-3632〇9號等各公報之薰草素化合物）等。 聚合起始劑與增感劑之組合方面，舉例有記載於特開 2001-305734號公報之記載於電子移動型起始系[(1)電子供 給型起始劑及增感色素、（2)電子接受型起始劑及增感色 素、（3)電子供給型起始劑、增感色素及電子接受型起始劑 (三元起始系）]等之範例等。 第一感光層與第二感光層各別亦可包含增感劑。增感 劑之添加量係相對於感光性樹脂組成物之全部成分，一般 在0.05〜30質量％之範圍，以0.1~20質量％之範圍爲佳，以 -49- 1352875. 0.2~ 10質量％之範圍爲特佳。增感劑添加量多時則於保存 時會從感光層析出，過少時則對於活性能量線束之感度降 低，在曝光步驟中花費時間，生產性降低。 在以增感劑調整各感光層之感度差的情況下，於第二 感光層所含有之增感劑量可較於第一感光層所含有之增感 劑量多。第二感光層之增感劑含有量係相對於第一感光層 之增感劑含有量而以1.5~100倍之量爲佳，以1.8~50倍之 量爲更佳，以2~ 20倍爲特佳。又於第一感光層中亦可進行 未含有增感劑等之調整。 [其他成分] 感光層係於必要時可倂用熱聚合抑制劑、可塑劑、發 色劑、著色劑、再者對於基體表面之密著促進劑及其他助 劑類（例如顏料、導電性粒子、塡充劑、消泡劑、難燃劑、 勻塗劑、剝離促進劑、抗氧化劑、香料、熱交聯劑、表面 張力調整劑、鏈轉移劑等），因而可調整其爲目的之感光性 轉印片之安定性、照相性、燒出性、膜物性等性質。前述 成分均可添加於第一感光層及第二感光層，該添加量係可 隨目的來決定，又對於各別之感光層之添加量係可相同或 亦可不同。 [熱聚合抑制劑] 熱聚合抑制劑係亦可爲了防止感光層聚合性化合物之 熱聚合或長時間之聚合來添加。熱聚合抑制劑方面，舉例 有甲氧基酚、氫醌、烷基或芳基取代之氫醌、第三丁基 鄰苯二酚、五倍子酚、2 -羥基二苯基酮、4 -甲氧基-2-羥基 二苯基嗣、氯化銅、啡噻畊、四氯醌、萘胺、萘酚'2,6- -50- 1352875. 二第三丁基―4-甲酚、2,2’_亞甲基雙（4-甲基-6-第三丁基 酚）、吡啶、硝基苯、二硝基苯、苦味酸、4-甲苯胺、亞甲 基藍 '銅與有機螯合劑反應物、柳酸甲酯、及啡噻哄、亞 硝基化合物、亞硝基化合物與鋁之螯合物等。 熱聚合抑制劑添加量係相對於感光層聚合性化合物而 以在0.001~5質量％之範圍爲佳，以〇.〇〇5~2質量％之範圍 爲較佳’以0.01〜1質量％之範圍爲特佳。熱聚合抑制劑之 添加量超過該範圍爲多時則有對於活性能量線束之感度降 低的傾向，超過該區域爲少時則有保存時之安定性降低的 傾向。 [可塑劑] 可塑劑係亦可爲了控制感光性膜悟物（可撓性）來添 加。可塑劑之範例方面，舉出有酞酸二甲酯、酞酸二丁酯、 酞酸二異丁酯、酞酸二庚酯、酞酸二辛酯、酞酸二環己酯、 酞酸二-十三酯、酞酸丁基苄酯、酞酸二異癸酯、酞酸二苯 酯、酞酸二丙烯酯 '酞酸辛基辛酯等之酞酸酯類；二乙酸 三乙二醇酯、二乙酸四乙二醇酯、酞酸二甲基乙二醇酯、 乙基乙二醇酸乙基酞酯、乙基乙二醇酸甲基酞酯、丁基乙 二醇酸丁基酞酯、三乙二醇二辛酸酯等二醇酯類；三甲酚 磷酸酯、三苯基磷酸酯等磷酸酯類；4-甲苯磺醯胺、苯磺 醯胺、N-正丁基苯磺醯胺、N-正丁基乙醯胺等醯胺類；己 二酸二異丁酯 '己二酸二辛酯、庚二酸二甲酯、庚二酸二 丁酯、庚二酸二辛酯、辛二酸二辛酯、壬二酸二丁酯等脂 肪族二鹼基酸酯類；檸檬酸三乙酯、檸檬酸三丁酯、丙三 醇三乙醯酯、月桂酸丁酯、4,5-二環氧環己-1,2-二羧酸二 -51- 1352875. 辛酯等 '多乙二醇、聚丙二醇等二醇類β 可塑劑之添加量係相對於感光層之全部成分而以在 0.1-50質量％範圍爲佳，以0·5〜4〇質量％之範圍爲較佳， 以1~30質量％之範圍爲特佳。 [發色劑] 發色劑係亦可爲了在曝光後之感光層賦予可見影像 (燒出機能）來添加。發色劑方面，可舉例有三（4_二甲胺基 苯基）甲烷（無色結晶紫）、三（4 —二乙胺基苯基）甲烷、三（4_ 二甲胺基-2-甲苯基）甲烷 '三（4_二乙胺基_2_甲苯基）甲烷、 雙（4~二丁胺基苯基）-[4-(2 -氰基乙基）甲胺基苯基]甲烷、雙 (4-二甲胺基苯基）-2 -喹啉基甲烷 '三（4-丙胺基苯基）甲烷等 胺基三芳基甲烷類；3,6 -雙（二甲胺基）-9 -苯基黃嘌呤、3-肢基-6-二甲胺基-2 -甲基-9-(2 -氯苯基）黃嘌呤等胺基黃嘌 呤類；3,6-雙（二乙胺基）-9-(2-乙氧羧苯基）噻噸、3,6-雙（二 甲胺基）噻噸等胺基噻噸類；3,6-雙（二乙胺基）-9,10-二氫 -9 -苯基吖啶' 3,6-雙（苄胺基）-9,10 -二氫-9-甲基吖啶等胺 基·9，10-二氫吖啶類；3,7-雙（二乙胺基）吩噁畊等胺基吩噁 畊類；3,7-雙（乙胺基）啡噻哄等胺基啡噻阱類；3，7-雙（二乙 胺基）-5-己基·5,10-二氫二苯駢吡阱等胺基二氫二苯駢吡 畊類；雙（4-二甲胺基苯基）苯胺基甲烷等胺苯基甲烷類；4-胺基-4’-二甲胺基二苯基胺、4-胺基-α，沒-二氰基氫化肉桂 酸甲基酯等胺基氫化肉桂酸類；1-(2-萘基）-2-苯基阱聯胺 等哄聯胺類；1,4-雙（乙胺基）-2,3-二氫化蒽醌等之胺基 -2，3-二氫化蒽醌類；N，N-二乙基-4-苯乙基苯胺等之苯乙基 苯胺類；10-乙醯基-3，7-雙（二甲胺基）啡噻畊等之包含鹼性 -52- 1352875. NH之無色色素的醯基衍生物；三（4-二乙胺基-2-甲苯基） 乙氧羧基蓋烷等之不具有能氧化之氫者，如於發色化合物 中能氧化之無色化合物；無色靛藍色素；如記載於美國專 利3,042,5 1 5號及第3,042,5 1 7號之於發色形能中氧化的有 機胺類（例如，4,4’-乙二胺、二苯胺、Ν,Ν-二甲基苯胺、4,4’-甲二胺三苯胺、Ν -乙烯基甲酚）。特別以無色結晶紫等之三 芳基甲烷系化合物爲佳。 再者，爲了使該等無色體發色等之目的，已知有與鹵 化合物組合者。鹵化合物之範例方面舉出有鹵化烴（例如四 g 溴甲烷、碘仿、溴乙烯、二溴甲烷、溴戊烷 '溴異戊烷、 碘戊烷、二溴丁烷、碘丁烷、溴二苯甲烷、六氯乙烷、1，2-二溴乙烷' 1，1，2,2-四溴乙烷' 1，2-二溴-1,1，2-三氯乙烷、 1，2,3-三溴丙烷、1-溴-4_氯丁烷、ι，2,3,4 -四溴丁烷、四氯 環丙烯、六氯環戊二烯、二溴環己烷' 1,1，1-三氯- 2,2-雙（4-氯苯基）乙烷等）；鹵化醇化合物（例如，2,2,2 -三氯乙醇、 三溴乙醇、1,3-二氯-2-丙醇、1，1，1_三氯-2-丙醇、二（碘六 亞甲基）胺基異丙醇、三溴-第三丁醇、2,2，3-三氯丁 -1,4- φ 二醇等）；鹵化羰基化合物（例如1,1-二氯丙酮、1，3-二氯丙 酮、六氯丙酮 '六溴丙酮、1，1，3,3-四氯丙酮、ΐ，ι，ι_三氯 丙酮、3，4 -二溴-2-丁酮、1,4 -二氯-2-丁酮' 二溴環己酮等）； 鹵化醚化合物（例如2-溴乙基甲基醚' 2_溴乙基乙基酸、二 (2_溴乙基）醚、1,2-二氯乙基乙基醚等）；鹵化酯化合物（例 如乙酸溴乙酯 '三氯乙酸乙酯、三氯乙酸三氯乙酯、丙烯 酸-2,3 -二溴丙酯之同元聚合物及共聚物、二溴丙酸三氯乙 •53- I352875 酷、二氯丙烯酸乙酯等）；鹵化醯胺化合物（例如氯乙 酸胺、漠乙酸胺'二氯乙醯胺、三氯乙薩胺、三溴乙藤胺、 Η氯乙基三氯乙醯胺、2_溴異丙醯胺、2,2,2-三氯丙醯胺' 氯丁二醯胺、Ν-溴丁二醯胺等）；具有硫或磷之化合物（例 如三溴甲苯颯、心硝基苯基三溴甲碾、4_氯苯基三溴甲碾、 Η(2,3-二溴丙基）磷酸鹽等）；2,4·雙（三氯甲基）-6-苯三唑 等。在有機鹵化合物中係以具有二個以上鍵結於一個碳原 子之鹵素原子的_化合物爲佳’以於一個碳原子具有三個 鹵素原子爲特佳°有機鹵化合物係可單獨地使用’亦可並 用二種以上。該等之中特佳之有機鹵化合物有三溴甲基苯 楓、2,4-雙（三氯甲基）-6-苯三哩。 發色劑之添加量係相對於感光層全成分而以〇·〇1 ~20 質量％之範圍爲佳，以〇·〇5~ 10質量％之範圍爲較佳，以 0.1 ~2質量％之範圍爲特佳。又鹵化合物量係相對於感光層 之全成分而一般爲〇.〇〇1~5質量％之範圍’以0.005〜1質量 %爲佳。 [染料] 於感光層中，一方面爲了處理性提昇而著色感光性樹 脂組成物，一方面以賦予保存安定性爲目的而可使用染 料。適當之染料範例方面，可舉出孔雀綠（例如其硫酸鹽）、 曙紅、乙基紫、原藻紅Β、甲基綠、結晶紫、鹼性洋紅、 酚酞、1,3-二苯基三哄' 茜素紅S、瑞香草酚酞、甲基紫 2Β、喹哪啶紅、玫瑰樹膠、胺苯磺酸黃、瑞香草磺基酚酞、 二甲苯酚藍、甲基橙、橙IV、二苯基酪卡巴胂、2,7-二氯 螢光黃、對甲基紅、剛果紅、本佐紅紫4Β ' α -萘基紅、 -54- 1352875. 萘鹵藍A、非那西塔林、甲基紫、孔雀綠、對洋紅、油藍 #6 0 3 (東方化學工業股份有限公司製）、鹼性蕊香紅B、及鹼 性蕊香紅6G '維多利亞純藍ΒΟΗ等。陽離子染料之相對 陰離子方面’如爲有機酸或無機酸之殘留官能基即可，舉 例有溴酸、碘酸、硫酸 '磷酸、甲酸、甲磺酸 '甲苯磺酸 等之殘留官能基（陰離子）。較佳之染料爲陽離子染料，舉 例有孔雀綠甲酸鹽、孔雀綠硫酸鹽等。 染料之較佳添加量係相對於感光層之全成分而爲 0.00 1~10質量％之範圍，以0.01~5質量％之範圍爲較佳， 以0.1~2質量％之範圍爲特佳。 [密著促進劑] 爲了提昇各層間之密著性、或感光性轉印片與基體之 密著性，於各層中可使用已知之所謂密著促進劑。 密著促進劑方面可適當地使用記載於特開平5-11439 號公報、特開平5-341532號公報、及特開平6-43638號公 報等之密著促進劑。具體來說，可舉出有苯并咪唑、苯醯 噁唑、苯醯噻唑、2-硫醇基苯并咪唑、2-硫醇基苯醯噁唑、 2 -硫醇基苯醯噻唑、3 -嗎林甲基-1 -苯三唑-2 -硫、3 -嗎林甲 基-5-苯基噁二唑-2-硫、5 -胺基-3-嗎林甲基噻二唑-2-硫、 及2-硫醇基-5-甲基硫代噻二唑、三唑、四唑、苯并三唑、 羧基苯并三唑 '含有胺基之苯并三唑、矽烷偶合劑等。 密著促進劑之較佳添加量係相對於感光層之全成分而 在0.001質量％~20質量％之範圍。以0_01~10質量％之範圍 爲較佳、以0.1質量％~5質量％之範圍爲特佳。 感光層亦可包含例如如記載於J.科沙著「光感系統」 1352875. (「Light Sensitive Systems」）第五章之有機硫化合物、過 氧化物、氧化還原系化合物、偶氮及二偶氮化合物、光還 原性色素、及有機鹵化合物等。有機硫化合物之範例方面， 可舉出有二正丁基二硫化物、二苄基二硫化物、2 -硫醇基 苯醯噻唑、2-硫醇基苯醯噁唑、苯硫酚、乙基三氯甲烷次 磺酸酯、2 -硫醇基苯并咪唑。過氧化物之範例方面，可舉 出有過氧化二第三丁烷' 過氧化苯甲醯、過氧化甲基乙基 酮。氧化還原化合物係由過氧化物與還原劑之組合所構成 者’可舉出有亞鐵離子與過硫酸離子、鐵離子與過氧化物 等。偶氮及二偶氮化合物方面，可舉出有α,α’-偶氮雙異 丁腈、2-偶氮雙·2_甲基丁腈、4-胺基二苯胺之二偶氮鑰類。 光還原性色素方面，可舉出有玫瑰樹膠、原藻紅、吖啶黃 素、核糖黃素、硫堇。 [界面活性劑] 爲了改善於製造感光性轉印片時所產生之平面狀不 均、可添加已知之界面活性劑。界面活性劑之範例方面， 可適宜選自陰離子系及陽離子系界面活性劑或非離子系界 面活性劑、兩性界面活性劑、含氟界面活性劑等。添加量 係相對於感光性樹脂組成物之固體成分而以0.001〜10質量 %爲佳，低於0.001質量％時則不能得到平面狀改良效果， 超過10質量％時則容易發生所謂密著性降低之問題。氟系 之界面活性劑方面，以於3~20碳鏈上含有40質量％以上氟 原子，而且以具有含有鍵結於從非鍵結末端起計數至少3 個碳原子之氫原子被氟取代之氟化脂肪族基的丙烯酸酯或 甲基丙烯酸酯作爲共聚合成分之聚合物界面活性劑等爲 -56- 1352875. 佳c [障壁層] 本發明的感光性轉印片或感光性積層體係在第一感光 層與第二感光層之間配置障壁層。障壁層係具有防止或抑 制感光層、支持體、保護薄膜內所含有物質的遷移，防止、 抑制氧或濕度等以外的影響的功能》 例如、障壁層的設置，係有防止各感光層之成分遷移至 其他層而改變感度或膜物性等的效果。 障壁層係含有樹脂爲佳，且以含有對水或碳原子數1〜4 的低級醇顯示有親和性之樹脂爲主要成分爲佳。親和性係 代表對上述溶劑具有乳化.、分散、膨潤、一部分溶解、濕 潤性。又障壁層係含有對水或碳原子數1~4的低級醇之可溶 性樹脂爲主要成分爲佳。 障壁層可含有聚合性化合物。聚合性化合物係爲具有 聚合性官能碁之化合物，除了低分子化合物（單體）以外， 亦含有高分子化合物（寡聚物、聚合物）。障壁層較佳係含 有具有低分子聚合性化合物與黏結劑機能之聚合物（樹脂） 兩者，或者含有具有黏結劑機能之高分子聚合性化合物（樹 脂）兩者。 障壁層中所含有的聚合性化合物係藉由第一感光層與 第二感光層所含有的光聚合起始劑、或任意障壁層中所含 有的光聚合起始劑之作用，進行光聚合。障壁層內所含有 光聚合起始劑於製造感光性轉印片時，第一感光層或第二 感光層內所含有的光聚合起始劑的一部份爲在障壁層中移 動者亦佳。因此，障壁層亦可含有感光性。但是，障壁層 -57- Ϊ352875. 的光感度比第一感光層的光感度相對低（感度的順存係爲 第二感光層/第一磁光屑/障壁層）係爲所期望的。 聚合性化合物的聚合性官能基以開環聚合性基或加成 聚合佳基爲佳，加成聚合性基爲更佳。加成聚合性基以乙 烯性不飽和基爲特佳。 聚合性化合物係一分子中含有複數個的聚合性官能基 爲佳。 低分子的聚合性化合物係與上述感光層中含有的聚合 性化合物相同。但是，障壁層內含有的低分子聚合性化合 物係對水或碳原子數1至4的低級醇顯示有親和性爲佳、對 水或碳原子數1至4的低級醇有可溶性爲更佳。 與低分子的聚合性化合物倂用的黏結劑，係爲對溶劑 (水或碳原子數1至4的低級醇）顯示有親和性爲佳。親和性 係意味者對上述溶劑具有乳化、分散、膨糊、溶解（包括部 分溶解）、濕潤性。障壁層內含有的黏結劑係對溶劑（水或 低碳原子數1至4的低級醇）有可溶性爲更佳。 低分子的聚合性化合物與黏結劑（樹脂）的質量比，聚 合性化合物：黏結劑以90 : 10~1 : 99爲佳、70 : 30~5 : 95 爲更佳、60 : 40~5 ·· 95爲最佳。 低分子的聚合性化合物亦可倂用二種類以上。亦可倂 用低分子的聚合性樹脂化合物與高分子的聚合性化合物 (下述）。 具有黏結劑機能之高分子聚合性化合物（樹脂），可藉 由導入具有黏結劑機能之聚合性官能基而得到。具有黏結 劑機能之聚合物的實例’係包括後述感光層含有的黏結劑 -58- 1352875. 之例。但是’障壁層含有的黏結劑係與感光層含有的黏結 劑不同’以對溶劑（水或碳原子數1至4的低級醇）顯示有親 和性爲佳。關於親合性方面’其與低分子的聚合性化合物 倂用之黏結劑係說明如下。 咼分子聚合性化合物的分子量係以500以上烏佳，1〇〇〇 以上爲更佳。 對水或碳原子數1至4的低級醇顯示親合性的聚合物之 例’係包括聚乙烯醇、改質聚乙烯醇、聚乙烯吡咯啶酮、 水溶性聚醯胺 '明膠、纖維素。以聚乙烯醇及改質聚乙烯 醇爲特佳。 爲了使聚合性基導入聚合物，其亦可與含有對聚合物 的官能基（例如：羥基、胺基）具有反應性之官能基（例如： 翔基、擴基、殘基、醒鹵基、酸野構造、經甲基、異氰酸 酯基）及具有聚合性基之化合物進行反應。 具有羧基（即對聚合物的官能基具有反應性之官能 基’以下省略）與聚合性基的化合物實例，係包括（甲基）丙 烯酸、衣康酸、肉桂酸、丙烯酸二聚物 '乙烯基苯甲酸、 乙烯氧基苯甲酸。 具有磺基與聚合性基的化合物之例係包括2 -丙烯醯胺 -2-甲基丙烷磺酸、苯乙烯磺酸。 具有羥基與聚合性基的化合物之例係包括羥乙基（甲 基）丙烯酸酯。 具有聚合性基的（環状）酸酐之例係包括馬來酸酐、衣 康酸酐。在其他的酸酐（例如：苯二酸酐、丁二酸酐）中所 導入乙烯性不飽和基之化合物，亦可使用具有聚合性基之 -59- 1352875. 羧基。 具有羥甲基與聚合性基的化合物之例係包括羥甲基 (甲基）丙烯醯胺。 具有異氰酸酯基與聚合性基的化合物之例，包括2-(甲 基）丙烯醯氧基乙基異氰酸酯、（甲基）丙烯醯基異氰酸酯、 1-(4·乙烯苯基）-卜甲基乙基異氰酸酯、1-(4-異丙烯基苯 基）-1-甲基乙基異氰酸酯。 具有黏結劑機能之高分子聚合性化合物（樹脂），亦可 使用具有聚合性基之水溶性聚胺甲酸酯樹脂（特開平 3-168209號、同7-25958號的各公報記載）。具有聚合性基之 水溶性聚胺甲酸酯樹脂係藉由與具有羧基之二醇及聚環氧 烷二醇和聚異氰酸酯進行反應，反應生成物反應具有羥基 之（甲基）丙烯酸酯，所得樹脂中的羧基以胺進行中和而得 到。又，反應具有4級銨鹽之多元醇與聚異氰酸酯，藉由使 反應生成物中具有羥基之（甲基）丙烯酸酯進行反應，可製 造具有聚合性基之水溶性聚胺甲酸酯樹脂。 具有聚合性基之環氧樹脂（特開平4-211413號公報中 所記載），亦可利用具有黏結劑機能的高分子聚合性化合物 (樹脂具有聚合性基之環氧樹脂，環氧可藉由反應丙烯 酸酯中的酸酐，以胺中和而得到。 具有對水或碳原子數至4的低級醇顯示有親和性之官 能基的單體（例如：乙烯吡咯啶酮）與具有複數個的聚合性 基之單體（例如：烯丙基（甲基）丙烯酸酯）進行共聚合，後者 單體中所含有的聚合性基之一部份亦可殘留爲聚合物的聚 合性基。 -60- 1352875. 在丙燒醯基嗎啉與具有經基之（甲基）丙稀酸醋的共聚 物中，反應甲基丙烯醯基乙基異氰酸酯所得之聚合物（特開 平9-1 4627 0號公報記載），亦可使用具有黏結劑機能之高分 子聚合性化合物（樹脂）。 亦可倂用二種類以上的高分子聚合性化合物。亦可併 用高分子聚合性化合物與其他的（不含有聚合性基）聚合物 (例如聚（甲基）丙烯酸酯、聚醯胺 '聚酯）。倂用的聚合物與 高分子聚合性化合物相同，其對水或碳原子數1〜4的低級醇 顯示有親和性（或可溶性）爲佳。 製造上述障壁層時，亦可使用與感光層同様的黏結 劑，亦可與其不同之黏結劑所成之層。這樣的聚合物係可 使用例如各種的醇可溶性.水溶性聚合物、醇分散性、水 分散性、乳化性或鹼可溶性聚合物，係舉例例如聚乙稀醇 (亦包括改質聚乙烯醇類）、聚乙烯吡咯啶酮、水溶性聚醯 胺、明膠、纖維素等及此等之衍生物等。此等聚合物可單 獨使用，亦可二種以上倂用。又在不損及水溶性、鹼水可 溶性之範圍內，亦可添加丙烯系聚合物 '醯胺系聚合物、 酯系聚合物等的各種聚合物。障壁層亦可使用在專利 2<794242號中記載的熱塑性樹脂或中間層所使用之化合物。 [感光性轉印片之製造] 本發明之感光性轉印片係例如可如以下所述來製造。 首先，溶解、乳化或分散上述各種材料於水或溶劑中， 各別調製第一感光層形成用之第一感光性樹脂組成物溶液 與第二感光層形成用之第二感光性樹脂組成物溶液。 第一感光性樹脂組成物溶液、及第二感光性樹脂組成 -61 - 1352875. 物溶液之溶劑方面，舉例有甲醇'乙醇、正丙醇、異丙醇、 正丁醇 '第二丁醇、正己醇等醇類；丙酮、甲基乙基酮、 甲基異丁基酮、環己酮、二異丁基酮等酮類；乙酸乙酯、 乙酸丁酯、乙酸正戊酯、硫酸甲酯、丙酸乙酯、酞酸二甲 酯 '苯甲酸乙酯、及乙酸甲氧基丙酯等酯類；甲苯、二甲 苯、苯、乙苯等芳香族碳氫化合物類；四氯甲烷、三氯乙 烯、氯仿、1,1，1-三氯乙烷、二氯甲烷、單氯苯等之鹵化烴 類：四氫呋喃、乙醚、乙二醇單甲基醚、乙二醇單乙基醚、 1-甲氧基-2-丙醇等之醚類；二甲基甲醯胺、二甲基乙醯胺、 二甲基亞颯、四氫噻吩-1，1-二氧化物等，亦可混合該等來 使用。於第一感光性樹脂組成物溶液、及第二感光性樹脂 組成物溶液中亦可添加已知之界面活性劑。 障壁層形成用的聚合物溶液溶劑亦可使用與感光層同 樣地塗布溶劑，亦可使用水、或水與溶劑之混合溶劑。溶 劑係可使用甲醇、乙醇、正丙純、異丙醇、正丁醇等的醇 類等之上述親水性溶劑等。溶劑的使用係使固形分成爲 10%~90%的塗布液爲佳。 接著，將第一感光性樹脂組成物溶液塗布至支持體 上’藉由乾燥以形成第一感光層。然後將障壁層形成用的 塗布液塗布至第一感光層上，加以乾燥。於其上塗布第二 感光性樹脂組成物溶液、藉由乾燥，以形成第二感光層。 塗布多層時，可如前述般逐次塗布，亦可同時多層塗布。 感光性樹脂組成物溶液的塗布方法係沒有特別地限制，可 採用例如：噴塗法、輥塗法、回轉塗布法、棒塗法、擠壓 塗布法·簾塗法、口膜塗布法、凹槽塗布法、漆包線塗布 -62- 1352875. 法、及刮刀塗布法等的各種方法。乾燥的條件係因各成分、 溶劑的種類、使用比例等而有所不同，通常爲60~1 10°C的 温度、3 0秒~ 1 5分鐘左右^ 即使在感光層較二層多之情況下，亦可藉由重複同樣 之操作來製造所希望之感光性轉印片。由於感光層爲二層 以上，亦可使感光層厚度總合在10私m~ 10mm之範圍。 [支持體及保護膜] 支持體係希望可剝離感光層，而且光透過性良好，又 表面平滑性良好。支持體係以合成樹脂製、且爲透明者爲 佳。支持體之範例方面，可舉出有聚對苯二甲酸乙二酯、 聚萘二乙酯、聚丙烯、聚乙烯、三乙酸纖維素、二乙酸纖 維素、聚（甲基）丙烯酸烷基酯、聚（甲基）丙烯酸酯共聚物、 聚氯乙烯、聚乙烯醇、聚碳酸酯、聚苯乙烯、賽珞凡、聚 偏二氯乙烯共聚物' 聚醯胺、聚亞醯胺、氯乙烯·乙酸乙 烯酯共聚物、聚四氟乙烯、聚三氟乙烯、纖維素系膜、耐 綸膜等各種塑膠膜。再者亦可使用由該等二種以上所構成 之複合材料。於上述之中以聚對苯二甲酸乙二酯爲特佳。 支持體之厚度係以2〜150 # m爲佳，以5~ 100 v m爲較佳， 以8~50以m爲特佳。支持體係以帶狀支持體爲佳。於製造 本發明之感光性轉印片時所使用之帶狀支持體的長度雖可 任意地決定，但是亦可使用例如l〇m~20000m之長度者。 本發明之感光性轉印片係可於第二感光層之上配置保 護膜。上述保護膜之範例方面，可舉出有使用於前述支持 體者、及紙，或者已積層聚乙烯、聚丙烯之紙等。以聚乙 烯膜、聚丙烯膜爲特佳。保護膜之厚度係以5〜10ym之範 -63- 1352875. 圍爲佳，以8~l5//m之範圍爲更佳，以i〇〜30#m之範圍 爲特佳。此時，感光層與支持體之接著力A和感光層與保 護膜之接著力B有形成爲接著力A>接著力B之關係的必 要。支持體/保護膜之組合範例方面，可舉出有聚對苯二甲 酸乙二酯/聚丙烯 '聚對苯二甲酸乙二酯/聚乙烯 '聚氯乙 烯/賽珞凡、聚亞醯胺/聚丙烯、聚對苯二甲酸乙二酯/聚對 苯二甲酸乙二酯等。又，藉由表面處理支持體及保護膜至 少一者，可滿足如前述接著力之關係。爲了提高與感光層 之接著力亦可實施支持體之表面處理，可舉例有下塗層之 塗設、電暈放電處理、火焰處理、紫外線照射處理、高周 波照射處理、輝光放電照射處理 '活性電漿照射處理、雷 射光線.照射處理等。又，支持體與保護膜之靜摩擦係數亦 重要。該等之靜摩擦係數係以〇·3~1·4爲佳、以0.5〜1.2爲 特佳。由於低於0.3會過滑，則發生形成滾筒狀時捲曲不 齊。又，在超過1.4之情況下，則難以捲曲成良好之滾筒 狀。 本發明之感光性轉印片係以例如圓筒狀之卷芯捲曲， 並以帶狀捲成滾筒狀來保管。該帶狀之長度係可任意地決 定，例如可在l〇m ~ 2 0000m之範圍內選擇。亦可縱切加工 成使用者容易使用並在l〇〇m~1000m之範圍中形成其爲帶 狀之滾筒狀。還有在此時係以捲曲成爲支持體在最外側爲 佳。又亦可縱切前述滾筒狀之感光性轉印片成爲片狀。從 保管時、終端面之保護、防止邊緣熔融之觀點來看，在終 端面係以設置分離器（特別是防濕性者、加入乾燥劑者）爲 佳，又以使用捆包或透濕性低之材料爲佳。 -64- 1352875. 亦可表面處理保護膜。表面處理係進行用來調整保護 膜與感光層之接著性。例如，於保護膜表面，設置由聚有 機矽氧烷、氟化聚烯烴、聚氟乙烯、及聚乙烯醇等聚合物 所構成之下塗層。下塗層之形成係一般在塗布上述聚合物 塗布液於保護膜表面之後，藉由在30~150°C (特別是50~12〇 °C)下乾燥1~30分鐘來進行》又，除了感光層、支持體、保 護膜之外，亦可具有緩衝層、剝離層、接著層、光吸收層、 表面保護層等。 [基體] 轉印本發明之感光性轉印片的基體方面，可從表面平 滑性高者至具有其爲凹凸之表面者中任意地選擇。以使用 板狀之基體、所謂基板爲佳。具體而言，舉出有已知之印 刷配線板製造用之基板、玻璃板（鈉玻璃板等）、合成樹脂 性之薄膜、紙、金屬板等。 於基體上，形成依序積層由包含黏結劑、聚合性化合 物、及光聚合起始劑之感光性樹脂組成物所構成之第二感 光層、然後由包含黏結劑、聚合性化合物、及光聚合起始 劑之感光性樹脂組成物所構成、顯示較第二感光層之光感 度相對低之光感度的第一感光層而成之感光性積層體。又 亦可在上述第一感光層與第二感光層之間配置障壁層，而 形成感光性積層體。 本發明之感光性轉印片係可廣泛地利用作爲印刷配線 板、濾色器或柱形材、唇形材、間隔片、間隔壁等之顯示 用構件、全息照相、微型機械、耐材等各種影像形成材料、 圖案形成材料。其中，以對於印刷配線板、顯示構件之應 -65- 1352875. 用爲佳，以對於印刷配線板之應用爲特佳。 [圖案形成方法] 本發明之感光性轉印片係包含（1)於基板上，以該第二 感光層爲基板側之位置關係來積層而得到積層體之步驟； (2)從積層體之第_感光層側進行既定影像圖案之光照 射，同時硬化接受該光照射區域之第一感光層與第二感光 層之步驟；（3)從積層體除去支持體之步驟；然後，（4)顯像 積層體、並除去積層體中未硬化部分之步驟，於基板上， 藉由形成以同時硬化第一感光層與第二感光層所形成之硬 化樹脂存在之區域與硬化樹脂不存在之區域所構成之影像 圖案形成方法，可形成所希望之圖案。 又，本發明之感光性轉印片係包含（1)於基板上，以該 第二感光層爲基板側之位置關係來積層而得到積層體之步 驟；（2)從積層體之第一感光層側，以規定照射互不相同之 至少二程度之照射能量光線之區域的映像圖案來進行光照 射，而同時硬化接受光照射能量相對大之光照射區域的第 一感光層與第二感光層，然後硬化接受光照射能量相對小 之光照射區域之第二感光層之步驟；（3)從積層體除去支持 體之步驟；然後，（4)顯像積層體、並除去積層體中未硬化 部分之步驟，於基板上，藉由形成由以同時硬化第一感光 層與第二感光層所形成之樹脂存在的區域、以硬化第二感 光層所形成之樹脂存在的區域、然後硬化樹脂不存在之區 域所構成的影像圖案方法，亦可形成所希望之圖案。 但是，於上述方法中’於步驟（2)與步驟（4)之間取代進 行（3)之從積層體除去支持體之步驟，亦可於步驟（1)與步驟 -66- 1352875. (2)之間進行》 步驟（2)中之光照射的光源方面，在經由支持體來進行 光照射的情況下，使用透過支持體而且活性化所使用之光 聚合起始劑或增感劑的電磁波、產生波長爲300~1500nm、 以3 20〜8 OOnm之範圍爲佳之紫外線~可見光之光源、以 3 3〇nm~650nm範圍爲特佳之光源。例如，可使用（超）高壓水 銀燈' 氙氣燈、碳電弧燈、鹵素燈、複印機用等之螢光燈、 LED、半導體雷射等之已知光源。此外，亦可使用電子射 線或X射線等。又即使在由剝離支持體到進行光照射的情況 下，亦可使用同樣之光源。其中，以雷射光之照射來進行 光照射爲佳，雷射波長係以200〜15 OOnm之範圍爲佳，以 300~800nm之範圍爲更佳，以370nm~650nm之範圍爲特佳， 以400nm~450nm之範圍爲最佳。 [印刷配線板之製造方法] 本發明之感光性轉印片係可適當地使用於印刷配線板 之製造、特別是具有通孔或連接孔等之孔洞部分的印刷配 線板之製造。 本發明之感光性轉印片係包含（1)於基板上，以該第二 感光層爲基板側之位置關係來積層而得到積層體之步驟； (2)從積層體之第一感光層側進行既定配線圖案之光照 射，同時硬化接受該光照射區域之第一感光層與第二感光 層之步驟；（3)從積層體除去支持體之步驟；然後，（4)顯像 積層體、並除去積層體中未硬化部分之步驟，於印刷配線 板形成用基板上，藉由形成由以同時硬化第一感光層與第 二感光層所形成之硬化樹脂所被覆之區域與基板表面暴露 •67- 1352875. 之區域所構成的配線圖案方法，可形成所希望之圖案。 又，本發明之感光性轉印片係包含（1)於基板上，以該 第二感光層爲基板側之位置關係來積層而得到積層體之步 驟；（2)從積層體之第一感光層側，在孔洞部分中，賦予光 照射能量相對大之光照射來同時硬化第一感光層與第二感 光層，然後在配線形成區域中，賦予光照射能量相對小之 光照射來硬化第二感光層地進行影像圖案之光照射之步 驟；（3)從積層體除去支持體之步驟：然後，（4)顯像積層體、 並除去積層體中未硬化部分之步驟，於具有孔洞部分之印 刷配線板形成用基板上，藉由形成由以同時硬化第一感光 層與第二感光層所形成之硬化樹脂所被覆之孔洞部分、由 以硬化第二感光層所形成之硬化樹脂所被覆的區域，然後 基板表面暴露之區域所構成的配線圖案方法，亦可形成所 希望之圖案。 於上述方法中，於步驟（2)與步驟（4)之間取代進行（3) 之從積層體除去支持體之步驟，亦可於步驟（1)與步驟（2) 之間進行。 於步驟（2)中之光照射光源方面，在經由支持體來進行 光照射之情況下，使用透過支持體並與前述同樣之光源》 光源方面係以藉由雷射光照射進行爲佳。 之後，在得到印刷配線板中，可藉由進行蝕刻或電鍍 步驟之方法、例如以已知之減式法或加式法（半加式法、全 加式法）處理已形成上述配線圖案之印刷配線板形成用基 板。爲了以工業上有利之保護幕法形印刷配線板之目的係 以使用藉由蝕刻之減式法爲佳。可剝離殘存於上述處理後 -68- 1352875. 印刷配線板形成用基板之硬化樹脂，又，在半加式法之情 況下，剝離後可再進一步蝕刻銅薄膜部分，可形成所希望 之印刷配線板。又，亦可與上述印刷配線板之製造法同樣 地製造多層印刷配線板。 其次，參照附加圖式之第7圖同時說明具有使用本發 明感光性轉印片之印刷配線板之製造方法。第7圖係顯示 使用示於第1圖之感光性轉印片，或示於第2圖之感光性 轉印片之情況。 首先，如第7(A)圖所示，預備具有通孔22、以金屬度 曾被覆表面之印刷配線板用基板2 1。印刷配線板形成用基 板21方面，可使用已形成銅鍍層於鍍銅積層板及玻璃-環 氧樹脂等之絕緣基材的基板，或積層層間絕緣膜於該等基 板上並形成銅鍍層的基板（積層基板）。 其次，如第7(B)所示，在具有保護膜之情況下，剝離 該保護膜並成爲如使該第二感光層14鄰接於印刷配線板形 成用基板21表面地使用加壓輥31來壓著感光性轉印片 1 〇(積層步驟）。因此，得到依序積層印刷配線板形成用基 板21、第二感光層14'障壁層13、第一感光層12'然後支 持體η之積層體。感光性轉印片之積層係可於室溫（15~30 °C )或加熱下（30〜180°C )進行。特別地，以於60~140°C之加 熱下進行爲佳。壓著輥之輥壓係以於l~l〇kg/cm2之範圍爲 佳。壓著速度係以l~3m/分鐘之速度爲佳。又亦可預先加熱 印刷配線板形成用基板21。又’亦可於減壓下積層。 取代使用感光性轉印片’藉由依序直接塗布、乾燥感 光性轉印片製造用之第二感光性樹脂組成物溶液、障壁層 -69- 1352875. 溶液、第一感光性樹脂組成物溶液於印刷配線板形 板表面，亦可得到依序積層印刷配線板形成用基板 感光層、障壁層、然後第一感光層之積層體《 其次，如第7(C)圖所示，從積層體之支持體11 照射光來硬化積層體。還有此時，於必要時（例如在 之光透過性不足的情況等）亦可剝離支持體後進 射。在印刷配線板形成用基板21之配線圖案形成區 照射爲了硬化第二感光層14所必須之光能量之光 既定的圖案狀，而形成配線圖案形成用之硬化層16 (配線部分曝光步驟）。於印刷配線板形成用基板之3 的開口部分及其周圍，照射爲了各別硬化第一感光开 第二感光層1 4所必須之光能量之光線，而形成通孔 層保護用硬化層17的區域（孔洞部分曝光步驟）。配 曝光步驟與孔洞部分曝光步驟，雖亦可各別獨立來 但以並行爲佳。曝光係藉由經由光遮罩來照射光線 或藉由使用雷射曝光裝置照射雷射光來進行。特別 用後者之雷射曝光裝置的方法，由於可不使用高價 地進行圖案形成，因爲無起因於遮罩之步驟上的問 於少量多種類之製品製造。 在經由光遮罩來照射光之情況下，亦可利用如 線圖案形成用之硬化層16區域形成用的光遮罩來 硬化第二感光層之光能量，並經由通孔之金屬層保 硬化層17區域形成用的光遮罩來照射硬化第一感 第二感光層兩層的光能量地進行曝光2次的方法。 可使用製成爲對應於配線圖案形成用之硬化層16 成用基 、第二 側面， 支持體 行光照 :域中， 線成爲 的區域 匿孔2 2 I 12與 之金屬 線部分 進行， 進行， 地，使 光遮罩 題，適 經由配 照射僅 護用之 光層與 或者亦 區域部 -70- 1352875 分的光透過率低、對應於通孔之金屬層保護用之硬化層17 區域部分的光透過率高之光遮罩來一起進行曝光。另外在 使用雷射曝光裝置來照射雷射光的情況下，以各別之必要 區域變更光照射量同時進行掃描曝光爲佳。 在尙未剝離支持體之情況下，如第7(D)圖所示，從積 層體剝離支持體1 1 (支持體剝離步驟）。 其次，如第7(E)圖所示，以適當之顯像液溶解除去印 刷配線板形成用基板21之第一感光層12、障壁層13及第二 感光層14的未硬化區域，形成配線圖案形成用之硬化層16 與通孔之金屬層保護用硬化層17的圖案，並暴露基板表面 之金屬層23 (顯像步驟）。顯像液係可使用鹼性水溶液、水 系顯像液、有機溶劑等對應於感光性樹脂組成物的顯像 液。顯像液方面係以弱鹼性水溶液爲佳。該弱鹼性水溶液 之鹼基成分方面，舉出有氫氧化鋰、氫氧化鈉、氫氧化鉀、 碳酸鋰、碳酸鈉、碳酸鉀、碳酸氫鋰、碳酸氫鈉、碳酸氫 鉀、磷酸鈉、磷酸鉀、焦磷酸鈉 '、焦磷酸鉀、硼砂等。又 用於顯像之鹼性水容易的pH値約爲8~ 12，特別以約9~11爲 佳。具體而言，可使用〇.1~5質量％之碳酸鈉水溶液、碳酸 鉀水溶液等。又顯像液之溫度雖可配合感光層之顯像性來 調整，一般以約25 °C ~40°C爲佳。又於現象液中，亦可併用 界面活性劑、消泡劑、有機鹼基（例如乙二胺、乙醇胺、氫 氧化四甲基銨、二伸乙基三胺、三伸乙基五胺、嗎林、三 乙醇胺等）或用於促進顯像之有機溶劑（醇類、酮類、酯類、 醚類、醯胺類、內酯類等）。顯像液係可使用混合有水或鹼 性水溶液與有機溶劑之水系顯像液，單獨有機溶劑亦可。 -71 - 1352875 又，顯像後於必要時亦可藉由後加熱處理或後曝光處 理，來進行更爲促進硬化部分之硬化反應。顯像係可藉由 如上述之濕式顯像法、亦可藉由乾式顯像法來進行。 其次，如第7(F)圖所示，以蝕刻液溶解除去基板表面 之已暴露的金屬層23 (蝕刻步驟）。由於通孔22之開口部分 係以硬化樹脂組成物（保護幕膜）1 7覆蓋著，不會因爲蝕刻 液進入通孔內而腐蝕通孔內之鍍金屬物，通孔之鍍金屬物 係以既定之形狀殘留。因而於印刷配線板形成用基板21形 成有配線圖案24。在以銅形成金屬層23之情況下，蝕刻 液方面可使用氯化銅溶液、氯化鐵溶液、鹼性蝕刻溶液、 過氧化氫系蝕刻液等。即使在該等之中，從蝕刻因素之觀 點來看，特別以氯化鐵溶液爲佳。 其次，如第7(G)圖所示，以強鹼水溶液等，以硬化層 1 6、1 7爲剝離片1 8，而從印刷配線板形成用基板除去（硬 化物除去步驟）。強鹼水溶液之鹼基成分方面舉出有氫氧化 鈉、氫氧化鉀等。又所使用之強鹼水溶液的pH値約爲 12~14，特別以約13~14爲佳。具體而言，可使用卜10質 量％之氫氧化鈉水溶液、氫氧化鉀水溶液等。 又，印刷配線板亦可爲多層構造之印刷配線板。又本 發明之感光性轉印片，不僅使用於上述之蝕刻製程，亦可 使用於電鍍製程。電鍍法方面，有例如硫酸銅電鍍、焦磷 酸銅電鍍等銅電鍍；髙電鍍能力軟焊條電鍍等之軟焊條電 鍍；濕式浸浴（硫酸鎳-氯化鎳）電鍍、磺胺酸鎳電鍍等鎳電 鍍；硬金電鍍、軟金電鍍等之金電鍍等。 【實施方式】 -72- 1352875. 【實例1】 於20"m厚之聚對苯二甲酸乙二酯薄膜上，塗布、乾 燥由下述組成所構成之第一感光性樹脂組成物溶液，形成 25 β m厚之感光層（第一感光層）。_ [第一感光性樹脂組成物溶液之組成] •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙15質量份 烯酸共聚物(共聚物組成(莫耳比）：55/11.7/4.5/28.8、質量平均分 子量：90000、Tg : 70°C ) •十二聚丙二醇二丙烯酸酯 6.5質量份 •四乙二醇二甲基丙烯酸酯 1.5質量份 • 4,4’-雙（二乙胺)二苯基酮 0.04質量份 •二苯基酮 1.0質量份 • 4-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 0.02質量份 • 1,2,4-三唑 〇.〇1質量份 •無色結晶紫 0.2質量份 •三溴甲基苯碾 0.1質量份 •甲基乙基酮 30質量份 接者，在第一感光層上塗布由下述組成所構成的水溶 性聚合物溶液，乾燥以形成1.6/zm厚的障壁層。 -73- 1352875R (33) n-C3H7 (34) p-CH3C6H4 -44 1352875 The hexaarylbisimidazole which can be used in the present invention is exemplified by 2,2'-bis(2-chlorophenylbu 4,4', 5,5'-tetraphenylbisimidazole, 2,2'-bis(2.fluorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2- Bromophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl Bis-imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)bisimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetrakis(4-methoxyphenyl)bisimidazole, 2,2'-bis(4-methoxyphenyl)-4,4',5 , 5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis ( 2-nitrophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-tolyl)-4,4',5,5'-tetraphenyl Bisimidazole, 2,2'-bis(2-trifluoromethylphenyl)-4,4',5,5'-tetraphenylbisimidazole, a compound described in \¥〇00/5 2529, etc. The above biimidazoles can be obtained, for example, by Bull. Chem. Soc. Japa. n, 33, 565 (1960), and J. Org. Chem., 36 (16) 2262 (1971) for easy synthesis. For ketone compounds, there are diphenyl ketone, 2-methyl Diphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 4-methoxydiphenyl ketone, 2-chlorodiphenyl ketone, 4-chlorodiphenyl ketone, 4 -bromodiphenyl ketone, 2-carboxydiphenyl ketone, 2-ethoxycarboxydiphenyl ketone, diphenyl ketone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dialkyl Amino)diphenyl ketones (eg 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(dicyclohexylamino)diphenyl ketone, 4,4'- Bis(diethylamino)diphenyl ketone, 4,4'-bis(dihydroxyethylamino)diphenyl ketone '4-methoxy-4'-dimethylaminodiphenyl ketone, 4, 4'-dimethoxydiphenyl ketone '4-dimethylaminodiphenyl ketone), 4-dimethylaminoacetophenone, benzyl, 蒽醌'2-tert-butyl fluorene, 2- Methyl 蒽醌 phenanthrene, xanthone, thioxanthone, 2-benzyl- -45- 1352.875. dimethylamino-1-(4-morphinyl)-1-butanone, 2 - Methyl-l-[4-(methylthio)phenyl]-2-morphin-1-propanone, 2- Hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzoin, benzoin ether (eg benzoin methyl ether, benzoin ethyl) Ether, benzoin propyl ether 'benzoin isopropyl ether, benzoin phenyl ether 'benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butyl acridone and the like. Other examples include acridine derivatives (for example, 9-phenyl acridine, 1,7-bis(9,9,-acridine)heptane, etc.), N-phenylcycloamine acetic acid, etc., polyhalogen compounds (for example, tetrabromomethane, phenyltribromoformamidine, phenyltrichloromethyl ketone, etc.), oxacillin (for example, .3-(2-benzomercapto)-7-diethylamine Oxalate, 3-(2-benzofluorenyl)·7-(pyrrolidyl)-hydrogenin, 3-benzylidene-7-diethylaminosulphate, 3-(2-A Oxylbenzylidene)-7-diethylaminosulphate '3-(4-dimethylaminobenzimidyl)-7-diethylaminosulphate, 3,3'-carboxyl double (5,7-di-n-propoxy-oxacin), 3,3'-carboxybis(7-diethylaminosulphate), 3-benzylidene-7-methoxyloxacin, 3-(2-mercapto)-7-diethylaminosporin, 3-(4·diethylamino cinnamate)-7-diethylaminosporin, 7-methoxy- 3-(3-pyridylcarboxy)-oxacin' 3-benzhydryl-5,7-dipropoxysulphate, 7-benzotriazol-2-mercaptosin, etc. It is described in JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, and JP-A-200 2-36320 No. 7, JP-A-2002-363208, to-be-examined compounds such as JP-A-2002-363209, and amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid n-butyl) Ester, phenylethyl 4-dimethylaminobenzoate, 2-pyridinium 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid-2·methacrylonitrileoxyethyl ester , pentamethylene bis(4-dimethylaminobenzamide), phenylethyl 3-dimethylaminobenzoic acid and penta-46- 1352875. Benzoaldehyde, 4-dimethylamino Benzaldehyde, 2-chloro-4-dimethylamine benzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzamide) acetamyl ester, 4_N_hexahydropyridylacetophenone '4-dimethylaminobenzine, N,N-dimethyl-4-toluidine, N,N-diethyl-3-ethoxyaniline, tribenzylamine, dibenzylaniline, N-A Base·Ν·phenyl; amine '4-bromo-indole, Ν·dimethylaniline, tridecylamine 'amino oxaxanthene (ODB, ODBII, etc.)' Crystal violet lactone, colorless crystal violet, etc. ), allylphosphine oxides (eg bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzamide) Base) 2,4,4_trimethyl-pentylphosphine oxide, LucirinTPO, etc.), metallocenes (eg bis(π 5 2 ,4-cyclopentadien-1-yl)-bis (2, 6-difluoro-3_(1Η_pyrrole-diphenylphenyl)titanium, 7/5-cyclopentadienyl-?7 6-isopropylphenyl-iron (1+)_hexafluorophosphide (1_), etc.) The compounds disclosed in JP-A-53-133428, JP-A-57_1819, 57-6096, and US Pat. No. 3,615,455. Further, a ketal ether compound disclosed in the specification of U.S. Patent No. 2,448,828, which is described in the specification of U.S. Patent No. 2,367, 660, which is described in the specification of U.S. Patent No. 2,725,512, - a hydrocarbon-substituted aromatic keto alcohol compound, a polynuclear ruthenium compound described in the specification of U.S. Patent No. 3,046,1, and the specification of No. 2,591,758, and the organic boron described in JP-A-2-222-194194 a compound or other exemplified radical generator or the like, a triaryl aryl salt (so-called hexafluoroantimony or a salt of a hexafluorophosphate salt), a scaly salt compound such as a (phenylphenothiyl)diphenyl gun salt ( It is effective as a cationic polymerization initiator, and a key salt compound of WO01/71428. The photopolymerization initiator may be used alone or in combination of two or more. The combination of the hexaarylbisimidazole and the 4-aminoketone described in the specification of U.S. Patent No. 3 5 4 3 3 7 is described in Japanese Patent Publication No. 4,451,516. a combination of a benzothiazole compound and a trihalomethyltrim compound, and an aromatic ketone compound such as a thiooxone and a hydrogen donor (for example, a compound containing a dialkylamine group, a phenol compound, etc.) Combination, combination of hexaarylbisimidazole and titanocene, combination of oxalicin and ferrocene and phenylamine acetic acid. The amount of the photopolymerization initiator used is generally in the range of 0.1 to 30% by mass, preferably 0.5 to 20% by mass, and 0.5 to 15% by mass, based on the total composition of the photosensitive layer in each photosensitive layer. The range is particularly good. Further, in the case where the sensitivity of each photosensitive layer is adjusted by the amount of the photopolymerization initiator, the photopolymerization starting dose contained in the second photosensitive layer may be larger than the photopolymerization starting dose contained in the first photosensitive layer. The photopolymerization initiator content of the second photosensitive layer is preferably 1.5 to 100 times the amount of the photopolymerization initiator of the first photosensitive layer, more preferably 1.8 to 50 times, and more preferably 2 ~ 20 times the amount is especially good. [Sensitizer] A sensitizer may be added for the purpose of adjusting the sensitivity or the photosensitive wavelength in exposure of each photosensitive layer. Under the condition of using visible light or ultraviolet light/visible laser light as exposure light (active energy beam), the sensitizer is excited by the active energy beam and is combined with other substances (such as a radical generator, oxygen). A generator (such as an energy shift, an electron shift, etc.) can generate a useful functional group such as a radical or oxygen. In terms of sensitizers, it is also possible to use known polynuclear aromatics (for example, tar brain, bismuth, bismuth benzene), xanthene (for example, fluorescent yellow, blush, diatom red, rose, rose gum) ), Saianning (for example, 吲哚Carbon-An-48- 1352875. Ning, thiapine, oxalic acid, and cycline), florets (for example, merocyanine, carbon, cyanine), tweezers Classes (eg, thioindigo, methylene blue, toluidine blue), acridines (eg, acridine orange 'chloroflavin, acridine flavin), enamel rolls (eg '蒽醌'), horn sharks (eg , squalane gun), acridone (for example, acridone, chloroacridone, N-methylacridone 'N-butylacridone, N-butyl-chloroacridone, etc.), Kaempferols (for example, 3-(2-benzopyryl)-7-diethylaminosporin, 3-(2-benzomercapto)-7-(1-pyrrolidinyl) ) Kaempferin' 3-Benzylmercapto-7-diethylaminosporin, 3-(2-methoxybenzimidyl)-7-diethylaminosulphate, 3-(4) -dimethylaminobenzhydryl)-7-diethylaminosporin, 3,3'-carboxybis(5,7-di-n-propyl薰草草素), 3,3'-carboxybis(7·diethylaminosulphate)' 3-Benzylmercapto-7-methoxyloxacin, 3-(2-indenyl) -7-diethylaminosporin, 3-(4-diethylamino cinnamate)-7-diethylaminosporin, 7-methoxy-3-(3-pyridinecarboxy) Oxalate, 3-benzylidenyl-5,7-dipropoxysulphate, etc., other examples are described in JP-A No. 5 - 1 9475 'Special Kaiping 7-27 1 028, Special Opening 2002- No. 363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-20-2-3632-9, etc. The combination of a polymerization initiator and a sensitizer is described in JP-A-2001-305734, which is described in JP-A-2001-305734. Examples of electron-accepting initiators and sensitizing dyes, (3) electron-donating initiators, sensitizing dyes, and electron-accepting initiators (ternary starting systems). The first photosensitive layer and the second photosensitive layer may each further comprise a sensitizer. The amount of the sensitizer added is generally in the range of 0.05 to 30% by mass, preferably in the range of 0.1 to 20% by mass, and -49 to 1352875. 0.2 to 10% by mass based on the total amount of the photosensitive resin composition. The range is particularly good. When the amount of the sensitizer added is large, it is detected by photoreceptor during storage. When the amount of the sensitizer is too small, the sensitivity to the active energy ray is lowered, and time is taken in the exposure step, and productivity is lowered. In the case where the sensitivity of each photosensitive layer is adjusted by the sensitizer, the sensitizing dose contained in the second photosensitive layer may be more than the sensitizing dose contained in the first photosensitive layer. The sensitizer content of the second photosensitive layer is preferably 1.5 to 100 times the amount of the sensitizer of the first photosensitive layer, more preferably 1.8 to 50 times, more preferably 2 to 20 times. It is especially good. Further, adjustment of the sensitizer or the like may be performed in the first photosensitive layer. [Other Ingredients] The photosensitive layer may be a thermal polymerization inhibitor, a plasticizer, a color former, a colorant, a adhesion promoter for the surface of the substrate, and other auxiliary agents (for example, pigments, conductive particles). , squeezing agent, defoaming agent, flame retardant, leveling agent, peeling accelerator, antioxidant, perfume, thermal crosslinking agent, surface tension adjuster, chain transfer agent, etc., so that it can be adjusted for the purpose of sensitization Properties such as stability, photographic properties, burnout properties, and film properties of the transfer sheet. The above components may be added to the first photosensitive layer and the second photosensitive layer. The amount of addition may be determined depending on the purpose, and the amount of addition to the respective photosensitive layers may be the same or different. [Thermal polymerization inhibitor] The thermal polymerization inhibitor may be added in order to prevent thermal polymerization of the photosensitive layer polymerizable compound or polymerization for a long period of time. Examples of thermal polymerization inhibitors include methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, tert-butyl catechol, gallic phenol, 2-hydroxydiphenyl ketone, 4-methoxy 2-hydroxydiphenyl hydrazine, copper chloride, thiophene, tetrachloroguanidine, naphthylamine, naphthol '2,6- -50- 1352875. di-tert-butyl- 4-cresol, 2,2 '_Methylene bis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue 'copper and organic chelating agent reactant, Methyl salicylate, morphiathene, nitroso compound, chelating compound of nitroso compound and aluminum, and the like. The amount of the thermal polymerization inhibitor added is preferably in the range of 0.001 to 5% by mass based on the photosensitive layer polymerizable compound, and preferably in the range of 5% to 5% by mass in terms of 5% to 5% by mass. The range is particularly good. When the amount of the thermal polymerization inhibitor added is more than the above range, the sensitivity to the active energy ray bundle tends to decrease, and when the amount is less than this region, the stability at the time of storage tends to decrease. [Plasticizer] The plasticizer can also be added to control the photosensitive film (flexibility). Examples of plasticizers include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and decanoic acid. - decyl ester, butyl benzyl phthalate, diisononyl phthalate, diphenyl phthalate, dipropenyl citrate, octyl octyl phthalate, etc.; triethylene glycol diacetate , tetraethylene glycol diacetate, dimethyl glycol phthalate, ethyl decyl ethyl glycolate, methyl decyl glycolate, butyl butyl ethate Glycol esters such as ester and triethylene glycol dicaprylate; phosphates such as tricresol phosphate and triphenyl phosphate; 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonate Indoleamines such as decylamine and N-n-butylethylamine; diisobutyl adipate dioctyl adipate, dimethyl pimelate, dibutyl pimelate, dioctyl pimelate Aliphatic dibasic acid esters such as esters, dioctyl suberate and dibutyl sebacate; triethyl citrate, tributyl citrate, glycerol triacetate, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid di-51- 1352875. Xin The addition amount of the diol-based β plasticizer such as polyglycol or polypropylene glycol is preferably in the range of 0.1 to 50% by mass, and in the range of 0.5 to 4% by mass based on the total composition of the photosensitive layer. Preferably, it is particularly preferably in the range of 1 to 30% by mass. [Color Reagent] The color former can also be added in order to impart a visible image (burning function) to the photosensitive layer after exposure. As the color former, there may be exemplified three (4-dimethylaminophenyl)methane (colorless crystal violet), tris(4-diethylaminophenyl)methane, and tris(4-dimethylamino-2-methylphenyl). Methane 'tris(4-diethylamino)-2-tolyl)methane, bis(4-dibutylaminophenyl)-[4-(2-cyanoethyl)methylaminophenyl]methane, Aminotriarylmethanes such as bis(4-dimethylaminophenyl)-2-quinolinylmethane tris(4-propylaminophenyl)methane; 3,6-bis(dimethylamino)-9 -Phenylxanthine, 3-arm exo-6-dimethylamino-2-methyl-9-(2-chlorophenyl)xanthine and other amine xanthine; 3,6-bis(diethylamine) Amino-thioxanthene such as 9-(2-ethoxycarboxyphenyl)thioxanthene, 3,6-bis(dimethylamino)thioxanthene; 3,6-bis(diethylamino)-9 , 10-dihydro-9-phenyl acridine '3,6-bis(benzylamino)-9,10-dihydro-9-methyl acridine, etc. Amine·9,10-dihydroacridine 3,7-bis(diethylamino) phenanthrene and other amine-based argon farming; 3,7-bis(ethylamino) phenothiaquinone and other aminophenthiophenes; 3,7-double ( Aminodihydrodiphenylhydrazine such as diethylamino)-5-hexyl·5,10-dihydrodiphenylpyrazole Pyridin; amine phenylmethane such as bis(4-dimethylaminophenyl)anilinomethyl; 4-amino-4'-dimethylaminodiphenylamine, 4-amino-α, no -Aminohydrocinnamic acid such as methyl dicyanohydrocinnamate; hydrazine amine such as 1-(2-naphthyl)-2-phenyl hydrazine; 1,4-bis(ethylamino)- Amino-2,3-indanes such as 2,3-dihydroanthracene; phenethylaniline such as N,N-diethyl-4-phenylethylaniline; 10-ethylenyl -3,7-bis(dimethylamino) phenyl sulfonate, etc., containing a basic -52-1352875. NH colorless pigment sulfhydryl derivative; tris(4-diethylamino-2-methylphenyl) An oxycarboxycapane or the like which does not have oxidizable hydrogen, such as a colorless compound which can be oxidized in a chromophoric compound; a colorless indigo blue pigment; as described in U.S. Patents 3,042, 5 1 5 and 3,042,5 1 7 An organic amine oxidized in the chromonic energy (for example, 4,4'-ethylenediamine, diphenylamine, hydrazine, hydrazine-dimethylaniline, 4,4'-methyldiaminetriphenylamine, hydrazine-vinyl Cresol). In particular, a triarylmethane-based compound such as a colorless crystal violet is preferred. Further, in combination with a halogen compound, for the purpose of coloring or the like of the colorless body, it is known. Exemplary examples of halogen compounds include halogenated hydrocarbons (eg, tetra g bromide, iodoform, vinyl bromide, dibromomethane, bromopentane 'bromoisopentane, iodopentane, dibromobutane, iodine butane, bromine diphenyl) Methane, hexachloroethane, 1,2-dibromoethane ' 1,1,2,2-tetrabromoethane ' 1,2-dibromo-1,1,2-trichloroethane, 1,2 , 3-tribromopropane, 1-bromo-4-chlorobutane, iota, 2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane' 1, 1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, etc.; halogenated alcohol compound (for example, 2,2,2-trichloroethanol, tribromoethanol, 1,3-dichloro 2-propanol, 1,1,1-trichloro-2-propanol, di(iodohexamethylene)aminoisopropanol, tribromo-butanol, 2,2,3-trichloro Butyl-1,4-φdiol, etc.; halogenated carbonyl compounds (eg 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetra Chloroacetone, hydrazine, ι,ι_trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone's dibromocyclohexanone, etc.; halogenated ether compounds (eg 2-bromoethyl methyl ether ' 2_bromoethyl ethyl acid, two (2-bromoethyl)ether, 1,2-dichloroethylethyl ether, etc.; halogenated ester compound (for example, ethyl bromoacetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, acrylic acid-2) , terpolymers and copolymers of 3-dibromopropyl ester, trichloroethylene 53- I352875, ethyl dichloroacrylate, etc.; halogenated guanamine compounds (such as chloroacetic acid amine, methyl acetate) 'Dichloroacetamide, trichloroethamide, tribendazim, chloroethyltrichloroacetamide, 2_bromoisopropylamine, 2,2,2-trichloropropionamide' chlorine Butane amine, bismuth-bromobutylamine, etc.; compounds with sulfur or phosphorus (eg, tribromotoluene, heart nitrophenyl tribromo, 4 chlorophenyl tribromo, Η ( 2,3-dibromopropyl)phosphate, etc.; 2,4·bis(trichloromethyl)-6-benzenetriazole, and the like. It is preferable to use a compound having two or more halogen atoms bonded to one carbon atom in the organic halogen compound. It is particularly preferable to have three halogen atoms in one carbon atom. The organic halogen compound can be used alone. Two or more types can be used in combination. Among the preferred organic halogen compounds are tribromomethylbenzamine and 2,4-bis(trichloromethyl)-6-benzenetriazole. The amount of the coloring agent to be added is preferably in the range of ~·〇1 to 20% by mass based on the total composition of the photosensitive layer, and preferably in the range of ~·〇5 to 10% by mass, and preferably 0.1 to 2% by mass. The range is particularly good. The amount of the halogen compound is generally in the range of ~1 to 5 mass% with respect to the total composition of the photosensitive layer, and is preferably 0.005 to 1 mass%. [Dye] In the photosensitive layer, the photosensitive resin composition is colored for the purpose of improving the handleability, and the dye can be used for the purpose of imparting stability to the storage. Examples of suitable dyes include malachite green (such as its sulfate), eosin, ethyl violet, protocorrim, methyl green, crystal violet, basic magenta, phenolphthalein, and 1,3-diphenyl.三哄' Alizarin Red S, Resveratrol, Methyl Violet 2, Quinidine Red, Rose Gum, Aminobenzene Sulfonate, Resveratrol, Glycerol Blue, Methyl Orange, Orange IV, II Phenyl tyrosin, 2,7-dichlorofluorescein, p-methyl red, Congo red, Benzo red purple 4Β 'α-naphthyl red, -54- 1352875. Naphthalene blue A, phenacetin, Methyl violet, malachite green, pair of magenta, oil blue #6 0 3 (made by Oriental Chemical Industry Co., Ltd.), alkaline ruthenium red B, and basic ruthenium red 6G 'Victoria pure blue ΒΟΗ. The relative anionic aspect of the cationic dye may be a residual functional group of an organic acid or an inorganic acid, and examples thereof include residual functional groups (anions) of bromic acid, iodic acid, sulfuric acid 'phosphoric acid, formic acid, methanesulfonic acid 'toluenesulfonic acid, and the like. . Preferred dyes are cationic dyes, exemplified by malachite green formate, malachite green sulfate, and the like. The amount of the dye to be added is preferably in the range of 0.001 to 10% by mass based on the total composition of the photosensitive layer, preferably in the range of 0.01 to 5% by mass, particularly preferably in the range of 0.1 to 2% by mass. [Adhesion Promoter] In order to improve the adhesion between the layers or the adhesion between the photosensitive transfer sheet and the substrate, a known so-called adhesion promoter can be used for each layer. As the adhesion promoter, a adhesion promoter such as that disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei 5- No. Hei No. Hei. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-thiol benzimidazole, 2-thiol benzoxazole, 2-thiol benzothiazole, and 3 - morphin methyl-1 - benzotriazole-2 - sulfur, 3-morphinyl-5-phenyloxadiazole-2-sulfo, 5-amino-3-morphinylthiathiazol-2-sulfate, and 2 - thiol-5-methylthiothiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole 'amino-containing benzotriazole, decane coupling agent, and the like. The adhesion amount of the adhesion promoter is preferably in the range of 0.001% by mass to 20% by mass based on the total amount of the photosensitive layer. It is preferably in the range of 0_01 to 10% by mass, and particularly preferably in the range of 0.1% by mass to 5% by mass. The photosensitive layer may also contain, for example, an organic sulfur compound, a peroxide, a redox compound, an azo, and a dimer, as described in J. Kosa's "Light Sensitive Systems" 1352875. ("Light Sensitive Systems"). A nitrogen compound, a photoreducible dye, an organic halogen compound, or the like. Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-thiol benzothiazole, 2-thiol benzoxazole, thiophenol, and B. Trichloromethane sulfenate, 2-thiol benzimidazole. Examples of the peroxide include ditributor peroxide, benzammonium peroxide, and methyl ethyl ketone peroxide. The redox compound is composed of a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, iron ions and peroxides. Examples of the azo and diazo compounds include diazogens of α,α'-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, and 4-aminodiphenylamine. . Examples of the photoreducible pigment include rose gum, protamine, acriflavine, riboflavin, and thioindigo. [Surfactant] In order to improve the planar unevenness which occurs when the photosensitive transfer sheet is produced, a known surfactant can be added. Examples of the surfactant are suitably selected from the group consisting of anionic and cationic surfactants, nonionic surfactants, amphoteric surfactants, and fluorine-containing surfactants. The amount of addition is preferably 0.001 to 10% by mass based on the solid content of the photosensitive resin composition, and when it is less than 0.001% by mass, the planar improvement effect is not obtained, and when it exceeds 10% by mass, the adhesion is likely to occur. The problem. In the fluorine-based surfactant, 40% by mass or more of fluorine atoms are contained in the 3-20 carbon chain, and the hydrogen atom having a bond containing at least 3 carbon atoms counted from the non-bonded terminal is replaced by fluorine. A fluoroacrylate-based acrylate or methacrylate polymer-polymerizing agent or the like as a copolymerization component is -56 to 1352875. Preferably, the barrier layer is a photosensitive transfer sheet or a photosensitive laminate system of the present invention. A barrier layer is disposed between the first photosensitive layer and the second photosensitive layer. The barrier layer has a function of preventing or suppressing migration of a substance contained in the photosensitive layer, the support, and the protective film, and preventing or suppressing effects other than oxygen or humidity. For example, the barrier layer is provided, and the components of each photosensitive layer are prevented. Migration to other layers changes the effect of sensitivity or film properties. The barrier layer is preferably a resin, and preferably contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. The affinity means that the above solvent has emulsification, dispersion, swelling, partial dissolution, and wettability. Further, the barrier layer contains a soluble resin having a water or a lower alcohol having 1 to 4 carbon atoms as a main component. The barrier layer may contain a polymerizable compound. The polymerizable compound is a compound having a polymerizable functional oxime, and also contains a polymer compound (oligomer or polymer) in addition to the low molecular compound (monomer). The barrier layer preferably contains both a polymer (resin) having a low molecular polymerizable compound and a binder function, or a polymerizable compound (resin) having a binder function. The polymerizable compound contained in the barrier layer is photopolymerized by the action of the photopolymerization initiator contained in the first photosensitive layer and the second photosensitive layer, or a photopolymerization initiator contained in any barrier layer. When the photosensitive polymerization transfer sheet is contained in the barrier layer, a part of the photopolymerization initiator contained in the first photosensitive layer or the second photosensitive layer is preferably moved in the barrier layer. . Therefore, the barrier layer may also contain photosensitivity. However, the light sensitivity of the barrier layer -57-Ϊ352875. is relatively lower than that of the first photosensitive layer (the sensitivity of the second photosensitive layer/first magneto-optical/male layer) is desirable. The polymerizable functional group of the polymerizable compound is preferably a ring-opening polymerizable group or an addition polymerization group, and an addition polymerizable group is more preferable. The addition polymerizable group is particularly preferably an ethylenically unsaturated group. The polymerizable compound preferably contains a plurality of polymerizable functional groups in one molecule. The low molecular polymerizable compound is the same as the polymerizable compound contained in the above photosensitive layer. However, the low molecular polymerizable compound contained in the barrier layer exhibits an affinity for water or a lower alcohol having 1 to 4 carbon atoms, and is more preferably soluble in water or a lower alcohol having 1 to 4 carbon atoms. The binder used for the low molecular weight polymerizable compound is preferably an affinity for a solvent (water or a lower alcohol having 1 to 4 carbon atoms). Affinity means that the above solvent has emulsification, dispersion, swell, dissolution (including partial dissolution), and wettability. The binder contained in the barrier layer is more soluble in a solvent (water or a lower alcohol having a low carbon number of 1 to 4). The mass ratio of the low molecular polymerizable compound to the binder (resin), the polymerizable compound: the binder is preferably 90:10 to 1:99, and the 70:30 to 5:95 is more preferable, 60:40 to 5 · 95 is the best. The low molecular weight polymerizable compound may be used in two or more types. A polymerizable compound of a low molecular weight polymerizable resin compound and a polymer (described below) can also be used. A polymerizable compound (resin) having a binder function can be obtained by introducing a polymerizable functional group having a binder function. An example of a polymer having a binder function includes an example of a binder - 58 - 1352875. which is contained in a photosensitive layer to be described later. However, the "barrier layer contains a binder which is different from the binder contained in the photosensitive layer", and it is preferred to exhibit affinity for a solvent (water or a lower alcohol having 1 to 4 carbon atoms). Regarding the affinity, the binder which is used for the polymerizable compound with a low molecular weight is described below. The molecular weight of the fluorene molecular polymerizable compound is preferably 500 or more, more preferably 1 Å or more. Examples of polymers which exhibit affinity for water or a lower alcohol having 1 to 4 carbon atoms include polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyamide amine gelatin, cellulose . Polyvinyl alcohol and modified polyvinyl alcohol are particularly preferred. In order to introduce a polymerizable group into a polymer, it may also be a functional group having a reactivity with a functional group (for example, a hydroxyl group or an amine group) of the polymer (for example, a base group, a base group, a residue group, a wake-up group, The acid field structure, a methyl group, an isocyanate group, and a compound having a polymerizable group are reacted. Examples of the compound having a carboxyl group (that is, a functional group reactive with a functional group of a polymer 'to be omitted hereinafter) and a polymerizable group include (meth)acrylic acid, itaconic acid, cinnamic acid, and acrylic acid dimer 'vinyl Benzoic acid, vinyloxybenzoic acid. Examples of the compound having a sulfo group and a polymerizable group include 2-propenylamine-2-methylpropanesulfonic acid and styrenesulfonic acid. Examples of the compound having a hydroxyl group and a polymerizable group include hydroxyethyl (meth) acrylate. Examples of the (cyclic) acid anhydride having a polymerizable group include maleic anhydride and itaconic anhydride. A compound having an ethylenically unsaturated group introduced into another acid anhydride (e.g., phthalic anhydride or succinic anhydride) may be a carboxyl group having a polymerizable group of -59 to 1352875. Examples of the compound having a methylol group and a polymerizable group include hydroxymethyl (meth) acrylamide. Examples of the compound having an isocyanate group and a polymerizable group include 2-(meth)acryloxyethyl isocyanate, (meth)acryl decyl isocyanate, 1-(4·vinylphenyl)-methylethyl isocyanate , 1-(4-isopropenylphenyl)-1-methylethyl isocyanate. A polymerizable compound (resin) having a binder function, or a water-soluble polyurethane resin having a polymerizable group (described in each of JP-A-3-168209 and No. 7-25958) can also be used. The water-soluble polyurethane resin having a polymerizable group is reacted with a diol having a carboxyl group and a polyalkylene oxide diol and a polyisocyanate, and the reaction product is reacted with a (meth) acrylate having a hydroxyl group, and the obtained resin The carboxyl group in the middle is obtained by neutralizing with an amine. Further, by reacting a polyhydric alcohol having a quaternary ammonium salt with a polyisocyanate, a water-soluble polyurethane resin having a polymerizable group can be produced by reacting a (meth) acrylate having a hydroxyl group in the reaction product. An epoxy resin having a polymerizable group (described in JP-A-4-211413) may be a polymerizable compound having a binder function (a resin having a polymerizable group, and an epoxy resin may be used) The acid anhydride in the reaction acrylate is obtained by neutralizing with an amine. A monomer having a functional group having an affinity for water or a lower alcohol having a carbon number of 4 (for example, vinylpyrrolidone) and having a plurality of polymerizations The monomer of the group (for example, allyl (meth) acrylate) is copolymerized, and a part of the polymerizable group contained in the latter monomer may remain as a polymerizable group of the polymer. 1352875. A polymer obtained by reacting methacryl oxiranyl ethyl isocyanate in a copolymer of propyl morphyl morpholine and a methacrylic acid having a transalkyl group (Japanese Unexamined Patent Publication No. Hei 9-1 4627 0) It is also possible to use a polymerizable compound (resin) having a binder function. Two or more types of polymerizable compounds may be used. Polymerizable compounds and other polymers may be used in combination (without polymerizability). base a polymer (for example, poly(meth)acrylate, polyamine' polyester). The polymer used for the same is the same as the polymerizable compound, and exhibits affinity for water or a lower alcohol having 1 to 4 carbon atoms. (or soluble) is preferable. When the barrier layer is produced, a binder which is the same as the photosensitive layer or a layer different from the binder may be used. Such a polymer may be, for example, various alcohol soluble and water soluble. Polymers, alcohol dispersibility, water dispersibility, emulsifying or alkali-soluble polymers, for example, polyethylene glycol (also including modified polyvinyl alcohol), polyvinylpyrrolidone, water-soluble polyamine, Gelatin, cellulose, etc., and the like, etc. These polymers may be used singly or in combination of two or more kinds, and propylene polymerization may be added insofar as the water solubility and alkali water solubility are not impaired. Various polymers such as amide-based polymers and ester-based polymers. The barrier layer can also be used in patent 2 <A compound of the thermoplastic resin or intermediate layer described in No. 794242. [Production of Photosensitive Transfer Sheet] The photosensitive transfer sheet of the present invention can be produced, for example, as described below. First, dissolving, emulsifying or dispersing the above various materials in water or a solvent, separately preparing a first photosensitive resin composition solution for forming a first photosensitive layer and a second photosensitive resin composition solution for forming a second photosensitive layer . The first photosensitive resin composition solution and the second photosensitive resin composition -61 - 1352875. Examples of the solvent of the solution include methanol 'ethanol, n-propanol, isopropanol, n-butanol' second butanol, Alcohols such as n-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate , esters of ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; tetrachloromethane, three Halogenated hydrocarbons such as vinyl chloride, chloroform, 1,1,1-trichloroethane, dichloromethane, monochlorobenzene, etc.: tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1 An ether such as methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylhydrazine, tetrahydrothiophene-1,1-dioxide, etc., may also be mixed These are used. A known surfactant may be added to the first photosensitive resin composition solution and the second photosensitive resin composition solution. The solvent solution for forming the barrier layer may be the same as the photosensitive layer, and water or a mixed solvent of water and a solvent may be used. As the solvent, the above hydrophilic solvent such as methanol, ethanol, n-propyl acetate, isopropanol or n-butanol can be used. The use of the solvent is preferably a coating liquid having a solid content of 10% to 90%. Next, the first photosensitive resin composition solution is applied onto the support by drying to form a first photosensitive layer. Then, a coating liquid for forming a barrier layer is applied onto the first photosensitive layer and dried. A second photosensitive resin composition solution is applied thereon by drying to form a second photosensitive layer. When the plurality of layers are coated, they may be applied one by one as described above, or may be applied in multiple layers at the same time. The coating method of the photosensitive resin composition solution is not particularly limited, and for example, a spray coating method, a roll coating method, a rotary coating method, a bar coating method, an extrusion coating method, a curtain coating method, a film coating method, and a groove can be employed. Various methods such as coating method, enameled wire coating-62- 1352875. method, and doctor blade coating method. The drying conditions vary depending on the components, the type of solvent, the ratio of use, etc., and are usually 60 to 1 10 ° C, 30 seconds to 15 minutes or so. ^ Even when the photosensitive layer is more than the second layer. The desired photosensitive transfer sheet can also be produced by repeating the same operation. Since the photosensitive layer is two or more layers, the thickness of the photosensitive layer can also be in the range of 10 private m to 10 mm. [Support and Protective Film] The support system is expected to be able to peel off the photosensitive layer, and has good light transmittance and good surface smoothness. The support system is made of synthetic resin and is transparent. Examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, and alkyl poly(meth)acrylate. , poly(meth)acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, celecoxib, polyvinylidene chloride copolymer 'polyamide, polyamine, vinyl chloride - Various plastic films such as vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, and nylon film. Further, a composite material composed of two or more of these may be used. Among them, polyethylene terephthalate is particularly preferred. The thickness of the support body is preferably 2 to 150 #m, preferably 5 to 100 v m, and particularly preferably 8 to 50 m. The support system is preferably a ribbon support. The length of the belt-shaped support used in the production of the photosensitive transfer sheet of the present invention can be arbitrarily determined, but it is also possible to use, for example, a length of from 10 m to 20,000 m. In the photosensitive transfer sheet of the present invention, a protective film can be disposed on the second photosensitive layer. Examples of the protective film include those used for the above-mentioned support, paper, or paper having laminated polyethylene or polypropylene. Polyethylene film and polypropylene film are particularly preferred. The thickness of the protective film is preferably in the range of 5 to 10 μm -63 to 1352875. It is preferably in the range of 8 to 15/m, and particularly preferably in the range of i 〇 30 30 m. At this time, the adhesion force A between the photosensitive layer and the support and the adhesion force B between the photosensitive layer and the protective film are formed to be in the relationship of the force A > the force B. Examples of the combination of the support/protective film include polyethylene terephthalate/polypropylene' polyethylene terephthalate/polyethylene' polyvinyl chloride/ceaphan, polyamidamine. / Polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. Further, at least one of the surface treatment support and the protective film can satisfy the relationship of the above-described adhesive force. In order to improve the adhesion to the photosensitive layer, the surface treatment of the support may be carried out, and examples thereof include coating of the undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, and glow discharge irradiation treatment. Slurry irradiation treatment, laser light irradiation treatment, and the like. Also, the static friction coefficient of the support and the protective film is also important. These static friction coefficients are preferably 〇·3~1·4, and particularly preferably 0.5 to 1.2. Since the slip is less than 0.3, the curling occurs when the roll is formed. Further, in the case of more than 1.4, it is difficult to curl into a good roll shape. The photosensitive transfer sheet of the present invention is, for example, crimped in a cylindrical core, and is wound in a roll shape in a roll shape. The length of the strip can be arbitrarily determined, for example, it can be selected from the range of l 〇 m to 20,000 m. It can also be slit into a drum shape which is easy for the user to use and which is formed in a strip shape in the range of l〇〇m to 1000m. Also at this time, it is preferable that the curl is the support on the outermost side. Further, the photosensitive transfer sheet having the above-described roll shape may be cut into a sheet shape. From the viewpoints of storage, protection of the terminal surface, and prevention of edge melting, it is preferable to provide a separator (especially a moisture-proof person or a desiccant) on the end surface, and to use a bale or a moisture permeability. Low materials are preferred. -64- 1352875. The protective film can also be surface treated. The surface treatment is performed to adjust the adhesion of the protective film to the photosensitive layer. For example, on the surface of the protective film, a coating layer composed of a polymer such as a polysiloxane, a fluorinated polyolefin, a polyvinyl fluoride, or a polyvinyl alcohol is provided. The formation of the undercoat layer is generally carried out by drying the polymer coating liquid on the surface of the protective film by drying at 30 to 150 ° C (especially 50 to 12 ° C) for 1 to 30 minutes. In addition to the photosensitive layer, the support, and the protective film, a buffer layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, and the like may be provided. [Base] The base of the photosensitive transfer sheet of the present invention can be arbitrarily selected from those having a high surface smoothness to a surface having irregularities. It is preferable to use a plate-shaped substrate or a so-called substrate. Specifically, a substrate for producing a known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, a metal plate, or the like can be given. Forming, on the substrate, a second photosensitive layer composed of a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and then comprising a binder, a polymerizable compound, and photopolymerization A photosensitive laminate formed of a photosensitive resin composition of a starter and having a first photosensitive layer having a light sensitivity lower than that of the second photosensitive layer. Further, a barrier layer may be disposed between the first photosensitive layer and the second photosensitive layer to form a photosensitive laminate. The photosensitive transfer sheet of the present invention can be widely used as a display member such as a printed wiring board, a color filter or a columnar material, a lip material, a spacer, a partition, etc., a hologram, a micromachine, a refractory material, or the like. Various image forming materials and pattern forming materials. Among them, it is preferable to use it for the printed wiring board and the display member, and it is particularly preferable for the application to the printed wiring board. [Pattern forming method] The photosensitive transfer sheet of the present invention comprises the steps of: (1) laminating the substrate on the substrate, and laminating the second photosensitive layer on the substrate side; (2) from the laminated body a step of irradiating light of a predetermined image pattern on the first photosensitive layer side while hardening the first photosensitive layer and the second photosensitive layer receiving the light irradiation region; (3) a step of removing the support from the laminated body; and then, (4) a step of developing the laminated body and removing the uncured portion of the laminated body, on the substrate, by forming a region where the hardened resin formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer exists and a region where the hardened resin does not exist The image pattern forming method formed can form a desired pattern. Further, the photosensitive transfer sheet of the present invention comprises (1) a step of laminating the substrate on the substrate with the second photosensitive layer as a positional relationship on the substrate side, and (2) a first photosensitive layer from the laminated body. On the layer side, the light is irradiated with a map pattern of a region of the irradiation energy ray that is different in illumination from each other, and at the same time, the first photosensitive layer and the second photosensitive layer that lightly receive the light irradiation region having a relatively large light irradiation energy are hardened. And then hardening the step of receiving the second photosensitive layer in the light-irradiated region where the light is irradiated with relatively small light; (3) removing the support from the laminated body; and then, (4) developing the laminated body and removing the unhardened layered body a partial step of forming a region where the resin is formed by hardening the region where the resin formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer is formed by hardening the second photosensitive layer, and then hardening the resin on the substrate. The image pattern method formed by the existing region can also form a desired pattern. However, in the above method, the step of removing the support from the laminate by the step (3) and the step (4) may be carried out in the step (1) and the step -66 to 1352875. In the case of the light source irradiated with light in the step (2), when the light is irradiated through the support, the electromagnetic wave of the photopolymerization initiator or the sensitizer used for the activation and the activation is used. It is a light source with a wavelength of 300 to 1500 nm, a range of 3 20 to 800 nm, preferably a source of ultraviolet light to visible light, and a light source of 3 3 〇 nm to 650 nm. For example, a known light source such as a (ultra) high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a fluorescent lamp for a copying machine, an LED, a semiconductor laser, or the like can be used. In addition, electron rays or X-rays or the like can also be used. Further, even in the case where the support is peeled off and light is irradiated, the same light source can be used. Among them, it is preferable to irradiate with laser light, and the laser wavelength is preferably in the range of 200 to 1,500 nm, more preferably in the range of 300 to 800 nm, and particularly preferably in the range of 370 nm to 650 nm, and 400 nm. The range of ~450nm is optimal. [Manufacturing Method of Printed Wiring Board] The photosensitive transfer sheet of the present invention can be suitably used for the production of a printed wiring board, particularly a printed wiring board having a hole portion such as a through hole or a connecting hole. The photosensitive transfer sheet of the present invention comprises (1) a step of laminating the substrate on the substrate in a positional relationship of the second photosensitive layer on the substrate side; (2) from the side of the first photosensitive layer of the laminated body a step of irradiating light of a predetermined wiring pattern while hardening the first photosensitive layer and the second photosensitive layer receiving the light irradiation region; (3) a step of removing the support from the laminated body; and then, (4) developing the laminated body, And removing the uncured portion of the laminated body on the substrate for forming a printed wiring board by exposing the region covered by the hardened resin formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer to the surface of the substrate. 67- 1352875. The wiring pattern method formed by the region can form a desired pattern. Further, the photosensitive transfer sheet of the present invention comprises (1) a step of laminating the substrate on the substrate with the second photosensitive layer as a positional relationship on the substrate side, and (2) a first photosensitive layer from the laminated body. On the layer side, in the hole portion, light having a relatively large light irradiation energy is applied to simultaneously harden the first photosensitive layer and the second photosensitive layer, and then in the wiring forming region, light irradiation light is applied to the light to harden the second light. a step of irradiating light of the image pattern on the photosensitive layer; (3) a step of removing the support from the laminated body: (4) a step of developing the laminated body and removing the uncured portion of the laminated body, having a hole portion a printed wiring board forming substrate which is covered by a hardened resin formed by hardening a second photosensitive layer by forming a hole portion covered with a hardening resin formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer The wiring pattern method formed by the region and then the exposed surface of the substrate may also form a desired pattern. In the above method, the step of removing the support from the laminate by the step (3) may be carried out between the step (2) and the step (4), or may be carried out between the step (1) and the step (2). In the case of the light-irradiating light source in the step (2), it is preferable to use the light-transmitting light source in the case where the light is irradiated through the support, and the light source is the same as the light source described above. Thereafter, in the obtained printed wiring board, the printing which has formed the above wiring pattern can be processed by a method of performing an etching or plating step, for example, by a known subtractive method or an additive method (semi-additive method, full addition method) A board for forming a wiring board. The purpose of printing the wiring board in an industrially advantageous protective screen shape is preferably to use a subtractive method by etching. The hardened resin remaining on the substrate for forming a printed wiring board can be peeled off after the above-mentioned treatment, and in the case of the semi-additive method, the copper thin film portion can be further etched after peeling to form a desired printed wiring. board. Further, a multilayer printed wiring board can be manufactured in the same manner as the above-described method of manufacturing a printed wiring board. Next, a method of manufacturing a printed wiring board using the photosensitive transfer sheet of the present invention will be described with reference to Fig. 7 of the additional drawings. Fig. 7 shows the case where the photosensitive transfer sheet shown in Fig. 1 or the photosensitive transfer sheet shown in Fig. 2 is used. First, as shown in Fig. 7(A), a substrate 2 1 for a printed wiring board having a through hole 22 and having a metal surface coated thereon is prepared. In the printed wiring board forming substrate 21, a substrate on which a copper plating layer is formed on a copper-clad laminate and an insulating substrate such as a glass-epoxy resin or a substrate in which an interlayer insulating film is laminated on the substrates to form a copper plating layer can be used. (Laminated substrate). Next, as shown in the seventh (B), when the protective film is provided, the protective film is peeled off, and the pressure roller 31 is used so that the second photosensitive layer 14 is adjacent to the surface of the printed wiring board forming substrate 21. The photosensitive transfer sheet 1 is pressed (layering step). Therefore, a laminated body for sequentially laminating the printed wiring board forming substrate 21, the second photosensitive layer 14' barrier layer 13, and the first photosensitive layer 12' and then supporting the body η is obtained. The laminate of the photosensitive transfer sheet can be carried out at room temperature (15 to 30 ° C) or under heating (30 to 180 ° C). In particular, it is preferably carried out under heating at 60 to 140 °C. The roll pressure of the pressing roll is preferably in the range of l to l 〇 kg/cm 2 . The pressing speed is preferably at a speed of 1 to 3 m/min. Further, the printed wiring board forming substrate 21 may be heated in advance. Also, it can be laminated under reduced pressure. Instead of using the photosensitive transfer sheet, the second photosensitive resin composition solution for the production of the photosensitive transfer sheet, the barrier layer-69-1352875 is directly applied and dried, and the solution of the first photosensitive resin composition is applied thereto. On the surface of the printed wiring board, a laminated layer of the substrate printed wiring board forming substrate, the barrier layer, and then the first photosensitive layer can be obtained. Next, as shown in Fig. 7(C), the laminated body is The support 11 irradiates light to harden the laminate. Further, at this time, when necessary (for example, when the light transmittance is insufficient), the support may be peeled off and then injected. The wiring pattern forming region of the printed wiring board forming substrate 21 is irradiated with a predetermined pattern of light for curing the light energy necessary for the second photosensitive layer 14, and a hardened layer 16 for wiring pattern formation is formed (wiring portion exposure step). The opening portion of the printed wiring board forming substrate 3 and the periphery thereof are irradiated with light rays for hardening the light energy necessary for the first photosensitive opening of the second photosensitive layer 14 to form the hard coat layer for the via layer protection. Area (hole part exposure step). The exposure step and the partial exposure step of the hole may be independent, but the behavior is good. The exposure is performed by irradiating light through a light mask or by irradiating laser light using a laser exposure device. In particular, the latter method of laser exposure apparatus can be used for pattern formation without expensive use because there is no manufacturing of a small variety of articles due to the steps of the mask. In the case where the light is irradiated through the light mask, the light energy of the second photosensitive layer may be hardened by using a light mask such as a region for forming the hardened layer 16 for forming a line pattern, and hardened by the metal layer of the through hole. A method in which the light mask for forming the layer 17 region is irradiated and the light energy of the two layers of the first photosensitive layer is hardened is irradiated twice. The base layer and the second side surface which are formed to correspond to the formation of the wiring pattern can be used, and the support body is illuminated in the field: the region is formed by the hole 2 2 I 12 and the metal wire portion. , to make the light mask problem, suitable for the light layer which is only protected by the irradiation, or the light of the region portion -70 - 1352875, which has a low light transmittance, and corresponds to the region of the hardened layer 17 for protecting the metal layer of the through hole Exposure is performed together with a high transmittance light mask. Further, in the case where a laser exposure apparatus is used to illuminate the laser beam, it is preferable to change the amount of light irradiation in each of the necessary regions while performing scanning exposure. When the support is not peeled off, as shown in Fig. 7(D), the support 1 1 is peeled off from the laminate (support peeling step). Next, as shown in Fig. 7(E), the uncured regions of the first photosensitive layer 12, the barrier layer 13, and the second photosensitive layer 14 of the printed wiring board forming substrate 21 are dissolved and removed by a suitable developing solution to form wiring. The hardened layer 16 for pattern formation and the metal layer of the via hole protect the pattern of the hardened layer 17 and expose the metal layer 23 on the surface of the substrate (development step). As the developing solution, a developing solution corresponding to a photosensitive resin composition such as an aqueous alkaline solution, a water-based developing solution or an organic solvent can be used. In terms of the developing solution, a weakly alkaline aqueous solution is preferred. Examples of the base component of the weakly alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and sodium phosphate. Potassium phosphate, sodium pyrophosphate', potassium pyrophosphate, borax, and the like. Further, the pH of the alkaline water used for development is about 8 to 12, and particularly preferably about 9 to 11. Specifically, an aqueous solution of sodium carbonate of 11 to 5% by mass, an aqueous solution of potassium carbonate or the like can be used. Further, although the temperature of the developing liquid can be adjusted in accordance with the developing property of the photosensitive layer, it is preferably about 25 ° C to 40 ° C. Further, in the phenomenon liquid, a surfactant, an antifoaming agent, or an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triamethyleneethylamine, or the like) may be used in combination. Lin, triethanolamine, etc.) or organic solvents (alcohols, ketones, esters, ethers, guanamines, lactones, etc.) used to promote imaging. As the developing liquid, an aqueous developing solution in which water or an aqueous alkali solution and an organic solvent are mixed may be used, and an organic solvent may be used alone. -71 - 1352875 Further, after the development, if necessary, the hardening reaction of the hardened portion can be further promoted by post-heat treatment or post-exposure treatment. The imaging system can be carried out by a wet development method as described above or by a dry development method. Next, as shown in Fig. 7(F), the exposed metal layer 23 on the surface of the substrate is removed by etching (etching step). Since the opening portion of the through hole 22 is covered with the hardened resin composition (protective curtain film) 17 , the metal plating in the through hole is not corroded by the etching liquid entering the through hole, and the metal plating of the through hole is The established shape remains. Therefore, the wiring pattern 24 is formed on the printed wiring board forming substrate 21. In the case where the metal layer 23 is formed of copper, a copper chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used as the etching liquid. Even among these, from the viewpoint of etching factors, a ferric chloride solution is particularly preferable. Then, as shown in Fig. 7(G), the hardened layers 16 and 17 are removed from the printed wiring board forming substrate by a strong alkali aqueous solution or the like (the hardened material removing step). The base component of the strong alkali aqueous solution is exemplified by sodium hydroxide or potassium hydroxide. Further, the aqueous alkali solution used has a pH of about 12 to 14, particularly preferably about 13 to 14. Specifically, a 10% by mass aqueous sodium hydroxide solution, a potassium hydroxide aqueous solution or the like can be used. Further, the printed wiring board may be a printed wiring board having a multilayer structure. Further, the photosensitive transfer sheet of the present invention can be used not only in the above etching process but also in an electroplating process. In the electroplating method, there are copper plating such as copper sulfate plating or copper pyrophosphate plating; soft electrode plating such as electroplating capability soft electrode plating; wet type bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, etc. Electroplating; gold plating such as hard gold plating, soft gold plating, etc. [Embodiment] -72-1352875. [Example 1] A first photosensitive resin composition solution composed of the following composition was applied and dried on a 20"m thick polyethylene terephthalate film to form a solution; 25 β m thick photosensitive layer (first photosensitive layer). _ [Composition of the first photosensitive resin composition solution] • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl propyl 15 parts by weight of olefinic acid copolymer (copolymer composition ( Mohrby): 55/11.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 70 ° C) • 126 parts by mass of dodecapropanediol diacrylate • 1.5 parts by mass of tetraethylene glycol dimethacrylate 4,4'-bis(diethylamine)diphenyl ketone 0.04 parts by mass • Diphenyl ketone 1.0 parts by mass • 4-toluenesulfonamide 0.5 parts by mass • Peacock oxalate 0.02 parts by mass • 1,2, 4-triazolium. 〇1 parts by mass • Colorless crystal violet 0.2 parts by mass • Tribromomethylbenzene mill 0.1 parts by mass • Methyl ethyl ketone 30 parts by weight, coated on the first photosensitive layer consisting of the following composition The resulting water-soluble polymer solution was dried to form a 1.6/zm thick barrier layer. -73- 1352875

[水溶性聚合物溶液的組成] •聚乙烯醇（PVA205 可樂麗（股）製） 13質量份 •聚乙烯吡咯啶酮 6質量份 .水 200質量份 •甲醇 180質量份 其次，於該第一 感光層之上，塗布、 乾燥由下述組成 所構成之第二感光性樹脂組成物溶液，形成 5 // m厚之感光 層（第二感光層）。 [第二感光性樹脂組成物溶液之組成] •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸；酯/甲基丙15質量份 烯酸共聚物（共聚物組成(莫耳比） 40/26.7/4.5/28.8、質量平均 分子量：90000、Tg : 50°C) •十二聚丙二醇二丙烯酸酯 6.5質量份 •四乙二醇二甲基丙烯酸酯 1.5質量份 • 4,4’-雙(二乙胺)二苯基酮 0.4質量份 •二苯基酮 3.0質量份 • 4-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 〇·〇2質量份 • 1，2,4-三唑 〇·〇1質量份 •無色結晶紫 0.2質量份 •三溴甲基苯碉 0.1質量份 •甲基乙基酮 10質量份 • 1-甲氧基-2-丙醇 20質量份[Composition of water-soluble polymer solution] • Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd.) 13 parts by mass • 6 parts by mass of polyvinylpyrrolidone. 200 parts by mass of water • 180 parts by mass of methanol, followed by On the photosensitive layer, a second photosensitive resin composition solution composed of the following composition was applied and dried to form a photosensitive layer (second photosensitive layer) having a thickness of 5 // m. [Composition of second photosensitive resin composition solution] • Methyl methacrylate/2-ethylhexyl acrylate/methacrylic acid; ester/methyl propyl 15 parts by weight of enoic acid copolymer (copolymer composition (Mo Ear ratio) 40/26.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 50 ° C) • 126 parts by mass of dodecanediol diacrylate • 1.5 parts by mass of tetraethylene glycol dimethacrylate • 4, 4'-bis(diethylamine)diphenyl ketone 0.4 parts by mass • Diphenyl ketone 3.0 parts by mass • 4-toluene sulfonamide 0.5 parts by mass • Peacock oxalate 〇·〇 2 parts by mass • 1,2 , 4-triazolium·〇1 parts by mass • Colorless crystal violet 0.2 parts by mass • Tribromomethylphenylhydrazine 0.1 parts by mass • Methyl ethyl ketone 10 parts by mass • 1-methoxy-2-propanol 20 mass Share

最後於第二感光層上，積層12/zm厚之聚丙烯薄膜而 得到感光性轉印片。接在捲曲的芯之上述感光性轉印片以 -74- 1352875. 寬5 50mm、長度200m由支持體側外側捲取以得到輥狀物。 藉由後述之方法測定如此所得之感光性轉印片的感度時， 最短顯像時間爲30秒’用於硬化第二感光層所必要之光能 量A爲4mJ/crn2，用於硬化第二感光層所必要之光能量B爲 4 0mJ/cm2，直到第一感光層之硬化開始所必要之光能量C 爲14mJ/cm2(光能量C與光能量A之比例C/A爲3.5，光能量A 與光能量B之比例A/B爲0.1)。又’在第一感光層之光感度 爲1之情況下，第二感光層之光感度爲10 ° 【實例2】 除了變更實例1中之第二感光性樹脂組成物溶液之〇-4 質量份4，4’-雙（二乙胺）二苯基酮、3.0質量份二苯基酮成爲 0.16質量份N-甲基吖啶酮、1.04質量份2,2’-雙（2-氯苯 基）-4,4’，5,5，-四苯基雙咪唑以外，與實例1同樣地進行而得 到感光性轉印片。任何層層厚誤差均在±5 %以內。藉由後 述之方法測定如此所得之感光性轉印片的感度時’最短顯 像時間爲25秒，用於硬化第二感光層所必要之光能量A爲 2 mJ/c in2，用於硬化第二感光層所必要之光能量B爲 40mJ/cm2，直到第一感光層之硬化開始所必要之光能量C 爲14mJ/cm2(光能量C與光能量A之比例C/A爲7，光能量A與 光能量B之比例A/B爲〇_〇5)。又’在第一感光層之光感度爲 1之情況下，第二感光層之光感度爲20。 【實例3】 除了變更實例1中之第二感光性樹脂組成物溶液之15 質量份甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄 酯/甲基丙烯酸共聚物成爲13質量份'6.5質量份十二聚丙二 -75- 1352875. 醇二丙烯酸酯成爲8.1質量份、1.5質量份四乙二醇二甲基丙 烯酸酯成爲1.9質量份以外，與實例1同樣地進行而得到感 光性轉印片。任何層層厚誤差均在±5 %以內。藉由後述之 方法測定如此所得之感光性轉印片的感度時，最短顯像時 間爲30秒，用於硬化第二感光層所必要之光能量A爲 2mJ/Cm2，用於硬化第二感光層所必要之光能量B爲 40mJ/cm2，直到第一感光層之硬化開始所必要之光能量C 爲14mJ/cm2(光能量C與光能量A之比例C/A爲7，光能量A與 光能量B之比例A/B爲0.05)。又，在第一感光層之光感度爲 1之情況下，第二感光層之光感度爲20。 【實例4】 除了變更實例3中之第二感光性樹脂組成物溶液之 〇·4質量份4,4’-雙（二乙胺）二苯基酮、3.0質量份二苯基酮 成爲0.16質量份N-甲基吖啶酮、1.04質量份2,2’-雙（2-氯 苯基）-4,4’，5,5’-四苯基雙咪唑，並變更第一感光性樹脂組 成物溶液爲下述以外，與實例1同樣地進行而得到感光性 轉印片。任何層層厚誤差均在±5 %以內。藉由後述之方法 測定如此所得之感光性轉印片的感度時，最短顯像時間爲 30秒，用於硬化第二感光層所必要之光能量A爲lmJ/cm2, 用於硬化第二感光層所必要之光能量B爲l〇m J/crn2，直到 第一感光層之硬化開始所必要之光能量C爲3mJ/Cm2(光能 量C與光能量A之比例C/A爲3’光能量A與光能量B之 比例A/B爲0.1)。又，在第一感光層之光感度爲1之情況 下，第二感光層之光感度爲10。 -76- 1352875 [第一感光性樹脂組成物溶液之組成]_ •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙24質量份 烯酸共聚物（共聚物組成(莫耳比）：55/11.7/4.5/28.8 '質量平均 分子量：90000 ' Tg : 70°C) •六亞甲基二異氰酸酯與八環氧乙烷單（甲基)丙烯酸酯之1/2 12質量份 莫耳比加成物 N-甲基吖啶酮 0.2質量份 2,2’-雙(鄰氯苯基)-4,4’，5,5’-四苯基雙咪唑 0.8質量份 2-硫醇基苯并咪唑 0.2質量份 4-甲苯磺醯胺 0.8質量份 孔雀綠草酸鹽 〇.〇3質量份 1,2,4-三唑 〇.〇3質量份 無色結晶紫 0.32質量份 三溴甲基苯颯 0.25質量份 甲基乙基酮 55質量份 1-甲氧基-2-丙醇 8質量份 【比較例1】 除了變更實例1中之第一感光層膜厚成爲30"m，且不 塗布障壁層及第二感光層以外，與實例1同樣地進行而製成 感光性轉印片。藉由後述之方法測定如此所得之感光性轉 印片的感度時，最短顯像時間爲25秒，用於硬化感光層所 必要之光能量B爲40mJ/cm2,直到第一感光層之硬化開始所 必要之光能量C爲14mJ/cm 。 【比較例2】 未塗布實例1中之第一感光層及障壁層，並製成僅由5 -77- 1352875 // m層厚之第二感光層所構成之感光性轉印片，而藉由後述 之方法測定如此所得之感光性轉印片的感度時，最短顯像 時間爲1 0秒以下，用於硬化第二感光層所必要之光能量B 爲 4m J/c m2 〇 [感度之測定方法] (1)最短顯像時間之測定方法 於經過研磨、水洗、乾燥表面之鍍銅積層板（無通孔） 的表面上，剝離感光性轉印片之保護膜，並且使用積層機 (8B-7 20-PH型、大成積層機股份有限公司製）來壓著感光性 $ 轉印片成爲感光性轉印片之第二感光層鄰接於基板，製成 依序積層有鍍銅積層板、第二感光層、障壁層、第一感光 層、然後聚對苯二甲酸乙二酯膜之積層體。壓著條件爲1〇5 °C壓著輥溫度、3kg/cm2壓著輥壓力、然後lm/分鐘壓著速 度。從積層體剝取聚對苯二甲酸乙二酯膜，以0.15 Mpa壓 力噴灑30°C之1質量％碳酸鈉水溶液於鍍銅積層板上之感 光層全面。測定從碳酸鈉水溶液之噴灑開始至溶解除去鍍 銅積層板上的感光層所需要之時間，以其爲最短顯像時間。 φ (2 )感度之測定 於最短顯像時間測定同樣地進行來積層感光性轉印片 於基板上。於感光性轉印片之感光層上，使用具有405 nm 之雷射光源之曝光裝置，從聚對苯二甲酸乙二酯膜側照射 從0.1mJ/cm2以21/2倍間隔至100 mJ/cm2光能量不同之光 線，來硬化感光層。以室溫靜置1〇分鐘後，從積層體剝取 聚對苯二甲酸乙二酯膜。於鍍銅積層板上之樹脂組成物層 全面上，以〇.15MPa噴壓噴灑30°C之1質量％碳酸鈉水溶液 -78- 1352875. 以上述（1)求得之最短顯像時間2倍的時間，溶解除去未硬 化之樹脂組成物，測定殘存之硬化層厚度。其次，作圖光 照射量與硬化層厚度的關係而得到感度曲線。從如此所得 之感度曲線讀取硬化層厚度爲5/z m時之光能量（光能量 A)、硬化層厚度爲31.6 μ m時之光能量（光能量b)、及硬化 層厚度超過5 e m時之光能量（光能量C)。 [解析度之測定方法] 以與上述（1)之最短顯像時間評估方法相同的條件，製 成依序積層有鍍銅積層板、第二感光層 '障壁層、第一感 光層、然後聚對苯二甲酸乙二酯膜，並以室溫（23。〇、55 % RH) 靜置10分鐘。從所得之積層體的聚對苯二甲酸乙二酯膜 上，使用具有4〇5nm之雷射光源的曝光裝置，以線/幅= 進行l〇Aim~50/zm線寬而以5；^m爲刻度來進行各線寬之 曝光。此時之曝光量爲各感光性轉印片之第二感光層硬化 之光能量。以室溫靜置10分鐘後，從積層體剝取聚對苯二 甲酸乙二酯膜。於鍍銅積層板上之樹脂組成物層全面上， 以0.15MPa噴壓噴灑30°C之1質量％碳酸鈉水溶液於前述 求得之最短顯像時間2.倍的時間，溶解除去未硬化之樹脂 組成物。以光學顯微鏡觀察附著如此所得之硬化樹脂圖案 的鍍銅積層板表面，於硬化樹脂圖案之線上測定無終端、 扭曲等異常的最小線寬，以其爲解析度。解析度係數値愈 小愈好。 [印刷配線板之製.造以及評估] 在具有於內壁形成銅鍍層、3mm直徑之通孔，表面經 過硏磨 '水洗、乾燥之鍍銅積層板上，重疊並積層已剝離 -79- 1352875 保護膜之感光性轉印片的第二感光層，於前述同樣地進行 來製成依序積層有鍍銅積層板、第二感光層、障壁層、第 一感光層、然後聚對苯二甲酸乙二酯膜之積層體，並以室 溫（23°C、55%RH)靜置10分鐘》從所得之積層體的聚對苯 二甲酸乙二酯膜上，使用具有40 5ππι之雷射光源的曝光裝 置，於鍍銅積層板之配線圖案形成區域中，照射各感光性 轉印片之第二感光層硬化之光能量的光線成爲既定之圖案 狀，另外，在鍍銅積層板之通孔開口部分及其周圍區域， 照射各感光性轉印片之第一感光層的光能量光線，來曝光 感光層。曝光後，從積層體剝取聚對苯二甲酸乙二酯膜， 其次與前述評估方法同樣地噴灑碳酸鈉水溶液於感光層表 面，溶解除去第一感光層及第二感光層之未硬化區域，而 得到硬化層浮刻。以顯微鏡觀察所得之硬化層圖案，觀察 有無於配線圖案形成區域上之硬化層、及通孔開口部分上 之硬化層剝離或保護幕膜之破裂（保護幕性）等之缺陷〃 還有，以雷射顯微鏡（VK-95 00、其恩斯股份有限公司 製）測定此時硬化層之厚度時，配線圖案形成區域上之硬化 層厚度爲5/zm，通孔開口部分上之硬化層厚度爲31.6/im。 其次，於鍍銅積層板表面上，噴灑氯化鐵蝕刻劑（含有 氯化鐵蝕刻溶液），溶解除去未以硬化層覆蓋之暴露區域的' 銅層。其次噴灑2質量％之氫氧化鈉水溶液來除去硬化物 浮刻’而得到具有通孔、並於表面具備配線圖案狀之銅層 的印刷配線板。以目視觀察有無所得之印刷電路配線板的 通孔內壁銅鑛層之異常。 於表1顯示針對感光性轉印片評估解析度、硬化層剝 -80- 1352875 離、保護幕破裂、通孔內鍍銅物異常之有無的結果。 表1 _ 解析度硬化層之剝離保護幕破裂通孔內 銅鍍體異常 實例1 20 β m Μ 姐 /1\\ 無 實例2 2d β m Μ 姐 姐 實例3 20 β τη Μ 無 Μ 〆》、、 實例4 20 β m 無 無 姐 /»w 比較例1 40 β m 4rrr Till: Μ ΛττΤ. m 比較例2 20 β m 姐 全部發生破裂 有 (無殘存銅） [實施例5] 在20 // m的聚對苯二甲酸乙 二酯薄膜上 ，塗布由下述 組成所構成的第一感光性樹脂組成物溶液、乾燥，以形成 20# m厚的感光層（第一感光層）。Finally, a 12/zm thick polypropylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet. The photosensitive transfer sheet attached to the crimped core was taken up from the side of the support side at -74 to 1352875. Width 5 50 mm and length 200 m to obtain a roll. When the sensitivity of the thus obtained photosensitive transfer sheet is measured by the method described later, the shortest development time is 30 seconds. The light energy A necessary for hardening the second photosensitive layer is 4 mJ/crn2 for hardening the second photosensitive layer. The light energy B necessary for the layer is 40 mJ/cm 2 until the light energy C necessary for the start of hardening of the first photosensitive layer is 14 mJ/cm 2 (the ratio of the light energy C to the light energy A is C/A of 3.5, the light energy A The ratio A/B to the light energy B is 0.1). Further, in the case where the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is 10 ° [Example 2] In addition to the modification of the second photosensitive resin composition solution of Example 1, 质量-4 parts by mass 4,4'-bis(diethylamine)diphenyl ketone, 3.0 parts by mass of diphenyl ketone, 0.16 parts by mass of N-methylacridone, 1.04 parts by mass of 2,2'-bis(2-chlorophenyl group) A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that -4,4',5,5,-tetraphenylbisimidazole was used. Any layer thickness error is within ±5 %. When the sensitivity of the thus obtained photosensitive transfer sheet is measured by the method described later, the shortest development time is 25 seconds, and the light energy A necessary for curing the second photosensitive layer is 2 mJ/c in2 for hardening. The light energy B necessary for the two photosensitive layers is 40 mJ/cm 2 until the light energy C necessary for the hardening of the first photosensitive layer is 14 mJ/cm 2 (the ratio of the light energy C to the light energy A is C/A of 7, light energy) The ratio A/B of A to light energy B is 〇_〇5). Further, in the case where the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is 20. [Example 3] In addition to the modification of the second photosensitive resin composition solution of Example 1, 15 parts by mass of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer became 13 The mass fraction was obtained in the same manner as in Example 1 except that the amount of the mixture was 6.5 parts by mass of the propylene diacrylate-75-1352875. The alcohol diacrylate was 8.1 parts by mass and the 1.5 parts by mass of the tetraethylene glycol dimethacrylate was 1.9 parts by mass. Photosensitive transfer sheet. Any layer thickness error is within ±5 %. When the sensitivity of the thus obtained photosensitive transfer sheet is measured by the method described later, the shortest development time is 30 seconds, and the light energy A necessary for curing the second photosensitive layer is 2 mJ/cm 2 for hardening the second photosensitive layer. The light energy B necessary for the layer is 40 mJ/cm 2 until the light energy C necessary for the hardening of the first photosensitive layer is 14 mJ/cm 2 (the ratio of the light energy C to the light energy A is C/A is 7, the light energy A and The ratio A/B of the light energy B is 0.05). Further, in the case where the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is 20. [Example 4] In addition to the modification of the second photosensitive resin composition solution of Example 3, 4 parts by mass of 4,4'-bis(diethylamine) diphenyl ketone and 3.0 parts by mass of diphenyl ketone were 0.16 mass. Parts N-methyl acridone, 1.04 parts by mass of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, and changing the composition of the first photosensitive resin The photosensitive transfer sheet was obtained in the same manner as in Example 1 except that the solution was the following. Any layer thickness error is within ±5 %. When the sensitivity of the thus obtained photosensitive transfer sheet is measured by the method described later, the shortest development time is 30 seconds, and the light energy A necessary for hardening the second photosensitive layer is lmJ/cm 2 for hardening the second photosensitive layer. The light energy B necessary for the layer is l〇m J/crn2, and the light energy C necessary for the start of hardening of the first photosensitive layer is 3 mJ/cm 2 (the ratio of the light energy C to the light energy A is C'A 3' light) The ratio A/B of energy A to light energy B is 0.1). Further, in the case where the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is 10. -76- 1352875 [Composition of the first photosensitive resin composition solution]_•Methyl methacrylate/2-ethylhexyl acrylate/benzyl methacrylate/methyl propyl 24 parts by weight olefinic acid copolymer ( Copolymer composition (mol ratio): 55/11.7/4.5/28.8 'mass average molecular weight: 90,000 'Tg: 70 ° C) • Hexamethylene diisocyanate and octaethylene oxide mono (meth) acrylate 1/2 12 parts by mass of molar ratio adduct N-methylacridone 0.2 parts by mass of 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole 0.8 parts by mass of 2-thiol benzimidazole 0.2 parts by mass of 4-toluenesulfonamide 0.8 parts by mass of peacock green grass 〇. 〇 3 parts by mass of 1,2,4-triazolium. 〇 3 parts by mass of colorless crystals Purple 0.32 parts by mass of tribromomethylphenylhydrazine 0.25 parts by mass of methyl ethyl ketone 55 parts by mass of 1-methoxy-2-propanol 8 parts by mass [Comparative Example 1] The first photosensitive layer film of Example 1 was changed. A photosensitive transfer sheet was produced in the same manner as in Example 1 except that the barrier layer and the second photosensitive layer were not applied. When the sensitivity of the thus obtained photosensitive transfer sheet is measured by the method described later, the shortest development time is 25 seconds, and the light energy B necessary for hardening the photosensitive layer is 40 mJ/cm 2 until the hardening of the first photosensitive layer is started. The necessary light energy C is 14 mJ/cm. [Comparative Example 2] The first photosensitive layer and the barrier layer in Example 1 were not coated, and a photosensitive transfer sheet composed of only a second photosensitive layer having a thickness of 5 - 77 - 1352875 / m was formed. When the sensitivity of the photosensitive transfer sheet thus obtained is measured by the method described later, the shortest development time is 10 seconds or less, and the light energy B necessary for curing the second photosensitive layer is 4 m J/cm 2 〇 [Measurement of sensitivity) (1) Method for measuring the shortest development time On the surface of a copper-clad laminate (without via) which has been ground, washed, and dried, the protective film of the photosensitive transfer sheet is peeled off, and a laminator (8B) is used. -7 20-PH type, manufactured by Dacheng Laminated Machine Co., Ltd.) The photosensitive layer is pressed to form a photosensitive transfer sheet, and the second photosensitive layer is adjacent to the substrate, and a copper-clad laminate is sequentially laminated. a laminate of the second photosensitive layer, the barrier layer, the first photosensitive layer, and then the polyethylene terephthalate film. The pressing conditions were 1 〇 5 ° C pressing roller temperature, 3 kg/cm 2 pressing roller pressure, and then lm / minute pressing speed. The polyethylene terephthalate film was peeled off from the laminate, and a photosensitive liquid layer of 1% by mass of sodium carbonate at 30 ° C was sprayed at a pressure of 0.15 MPa on the copper-clad laminate. The time required from the spraying of the aqueous sodium carbonate solution to the dissolution of the photosensitive layer on the copper-clad laminate was measured, which was the shortest development time. Measurement of φ (2 ) sensitivity The measurement of the shortest development time was carried out in the same manner to laminate the photosensitive transfer sheet on the substrate. On the photosensitive layer of the photosensitive transfer sheet, an exposure apparatus having a laser light source of 405 nm was used, and the side of the polyethylene terephthalate film was irradiated from 0.1 mJ/cm 2 at intervals of 2 1/2 to 100 mJ/ The light of different light energy of cm2 is used to harden the photosensitive layer. After standing at room temperature for 1 minute, the polyethylene terephthalate film was peeled off from the laminate. The resin composition layer on the copper-plated laminate board is sprayed at a pressure of 1515 mesh to spray a 1% by mass aqueous sodium carbonate solution of -78-1352875 at 30 ° C. The shortest development time obtained by the above (1) is 2 times. At the time, the uncured resin composition was dissolved and removed, and the thickness of the remaining hardened layer was measured. Next, the sensitivity curve is obtained by plotting the relationship between the amount of light to be irradiated and the thickness of the hardened layer. From the sensitivity curve thus obtained, the light energy (light energy A) when the thickness of the hardened layer is 5/zm, the light energy (light energy b) when the thickness of the hardened layer is 31.6 μm, and the thickness of the hardened layer exceed 5 em Light energy (light energy C). [Method for Measuring Resolution] A copper-clad laminate, a second photosensitive layer, a barrier layer, a first photosensitive layer, and then a layer are sequentially formed under the same conditions as the shortest development time evaluation method of (1) above. The ethylene terephthalate film was allowed to stand at room temperature (23. Torr, 55 % RH) for 10 minutes. From the obtained polyethylene terephthalate film of the laminate, an exposure apparatus having a laser light source of 4 〇 5 nm was used, and the line width/width = line width of l〇Aim~50/zm was 5; m is a scale for exposure of each line width. The exposure amount at this time is the light energy hardened by the second photosensitive layer of each photosensitive transfer sheet. After standing at room temperature for 10 minutes, a polyethylene terephthalate film was peeled off from the laminate. The resin composition layer on the copper-plated laminate board is sprayed at a pressure of 0.15 MPa to spray a 1% by mass sodium carbonate aqueous solution at 30 ° C for 2 times of the shortest development time as described above, and is dissolved and removed without being hardened. Resin composition. The surface of the copper-clad laminate to which the hardened resin pattern thus obtained was attached was observed with an optical microscope, and the minimum line width of no abnormality such as termination or distortion was measured on the line of the cured resin pattern, which was used as the resolution. The resolution coefficient is as small as possible. [Manufacturing and evaluation of printed wiring board] On a copper-plated laminate with a copper-plated layer on the inner wall and a diameter of 3 mm, the surface is honed and washed and dried, and the layers are peeled off -79- 1352875 The second photosensitive layer of the photosensitive transfer sheet of the protective film is formed in the same manner as described above to form a copper-clad laminate, a second photosensitive layer, a barrier layer, a first photosensitive layer, and then polyterephthalic acid. a laminate of an ethylene glycol film and allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. From the obtained laminate polyethylene terephthalate film, a laser having 40 5ππι was used. In the exposure device of the light source, in the wiring pattern formation region of the copper-clad laminate, the light energy that illuminates the light energy of the second photosensitive layer of each photosensitive transfer sheet is formed into a predetermined pattern, and is also in the copper-plated laminate. The aperture opening portion and its surrounding area illuminate the photosensitive layer by irradiating light energy rays of the first photosensitive layer of each photosensitive transfer sheet. After the exposure, the polyethylene terephthalate film is peeled off from the laminate, and then an aqueous solution of sodium carbonate is sprayed on the surface of the photosensitive layer in the same manner as the above evaluation method to dissolve and remove the unhardened region of the first photosensitive layer and the second photosensitive layer. The hardened layer is obtained by embossing. Observing the obtained hardened layer pattern by a microscope, observing whether or not there is a defect in the hardened layer on the wiring pattern forming region, the peeling of the hardened layer on the opening portion of the through hole, or the cracking of the protective film (protective curtain property), etc. When the thickness of the hardened layer at this time was measured by a laser microscope (VK-95 00, manufactured by Enns Co., Ltd.), the thickness of the hardened layer on the wiring pattern forming region was 5/zm, and the thickness of the hardened layer on the opening portion of the through hole was 31.6/im. Next, on the surface of the copper-clad laminate, a ferric chloride etchant (containing a ferric chloride etching solution) was sprayed to dissolve the 'copper layer' of the exposed region not covered by the hardened layer. Then, a 2% by mass aqueous sodium hydroxide solution was sprayed to remove the cured product, and a printed wiring board having a through hole and having a wiring pattern on the surface thereof was obtained. The abnormality of the copper ore layer on the inner wall of the through hole of the obtained printed circuit board was visually observed. Table 1 shows the results of evaluating the resolution of the photosensitive transfer sheet, the peeling of the hardened layer -80 - 1352875, the crack of the protective curtain, and the presence or absence of abnormal copper plating in the through hole. Table 1 _ Resolution hardening layer peeling protection curtain rupture through-hole copper plating abnormal example 1 20 β m Μ sister / 1 \\ no instance 2 2d β m 姐 sister example 3 20 β τη Μ no Μ 〆 》, Example 4 20 β m No sister/»w Comparative Example 1 40 β m 4rrr Till: Μ ΛττΤ. m Comparative Example 2 20 β m Sister all cracked (no residual copper) [Example 5] at 20 // m On the polyethylene terephthalate film, a solution of the first photosensitive resin composition composed of the following composition was applied and dried to form a photosensitive layer (first photosensitive layer) having a thickness of 20 # m.

• 81 - 1352875 [第一感光性樹脂組成物溶液之組成]_ •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙15質量份 烯酸共聚物(共聚物組成(莫耳比）：55/11.7/4.5/28.8、質量平均 分子量：90000、Tg : 70°C) •十二聚丙二醇二丙烯酸酯 6.5質量份 •四乙二醇二甲基丙烯酸酯 1.5質量份 • 4,4’-雙(二乙胺)二苯基酮 0.04質量份 •二苯基酮 1.0質量份 • 4-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 0.02質量份 • 1，2,4·三唑 0.01質量份 •無色結晶紫 0.2質量份 •三溴甲基苯颯 0.1質量份 •甲基乙基酮 30質量份 接者，在第一感光層上塗布由下述組成所構成的水溶 性聚合物溶液，乾燥以形成1 . 6 // m厚的障壁層。 [水溶性聚合物溶液的組成] •聚乙烯醇（PVA205可樂麗（股）製） 13質量份 •聚乙烯吡咯啶酮 6質量份 .水 200質量份 •甲醇 1 80質量份 其次，於該第一感光層之上，塗布、 乾燥由下述組成 所構成之第二感光性樹脂組成物溶液，形成10 A/m厚之感光 層（第二感光層）。 -82- 1352875 [第二感光性樹脂組成物溶液之組成] •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙24質量份 烯酸共聚物(共聚物組成(莫耳比）：55/11.7/4.5/28.8、質量平 均分子量：90000、Tg : 70°C) •六亞甲基二異氰酸酯與八環氧乙烷單（甲基）丙烯酸酯之 莫耳比加成物 1/2 12質量份 • N-甲基吖啶酮 0.2質量份 • 2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑 0.8質量份 • 2-硫醇基苯并咪唑 0.2質量份 • 4-甲苯磺醯胺 0.8質量份 •孔雀綠草酸鹽 〇.〇3質量份 • 1，2,4-三唑 〇.〇3質量份 •無色結晶紫 0.32質量份 •三溴甲基苯颯 0.25質量份 •甲基乙基酮 55質量份 •卜甲氧基-2-丙醇 8質量份 接者，在第二感光層上塗布由下述組成所構成的水溶 性聚合物溶液，乾燥以形成1.6/2 m厚的障壁層。 其次，於該障壁層之上，塗布、乾燥由下述組成所構 成之第二感光性樹脂組成物溶液，形成5 v m厚之感光層（第 三感光層）。 -83- 1352875.• 81 - 1352875 [Composition of the first photosensitive resin composition solution] _ • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl propyl 15 parts by weight of enoic acid copolymer ( Copolymer composition (mole ratio): 55/11.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 70 ° C) • Doppler polypropylene diacrylate 6.5 parts by mass • Tetraethylene glycol dimethacrylate 1.5 parts by mass • 4,4'-bis(diethylamine)diphenyl ketone 0.04 parts by mass • Diphenyl ketone 1.0 parts by mass • 4-toluenesulfonamide 0.5 parts by mass • Peacock oxalate 0.02 parts by mass • 1,2,4·triazole 0.01 parts by mass • Colorless crystal violet 0.2 parts by mass • Tribromomethylphenylhydrazine 0.1 parts by mass • Methyl ethyl ketone 30 parts by weight, coated on the first photosensitive layer by the following The water-soluble polymer solution composed of the composition was dried to form a barrier layer of 1.6 Ω thick. [Composition of water-soluble polymer solution] • Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd.) 13 parts by mass • 6 parts by mass of polyvinylpyrrolidone. 200 parts by mass of water • 1 80 parts by mass of methanol, followed by On the photosensitive layer, a second photosensitive resin composition solution composed of the following composition was applied and dried to form a photosensitive layer (second photosensitive layer) having a thickness of 10 A/m. -82- 1352875 [Composition of second photosensitive resin composition solution] • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl propyl 24 parts by weight of enoic acid copolymer (copolymerization Composition (Morby): 55/11.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 70 ° C) • Hexamethylene diisocyanate and octaethylene oxide mono (meth) acrylate Ear to adduct 1/2 12 parts by mass • N-methyl acridone 0.2 parts by mass • 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl Bis-imidazole 0.8 parts by mass • 2-thiol-based benzimidazole 0.2 parts by mass • 4-toluenesulfonamide 0.8 parts by mass • Peacock oxalate 〇. 〇 3 parts by mass • 1,2,4-triazolium. 〇3 parts by mass • Colorless crystal violet 0.32 parts by mass • Tribromomethylphenylhydrazine 0.25 parts by mass • Methyl ethyl ketone 55 parts by mass • Bumethoxy-2-propanol 8 mass parts, in the second photosensitive A water-soluble polymer solution composed of the following composition was applied to the layer and dried to form a 1.6/2 m thick barrier layer. Next, a second photosensitive resin composition solution composed of the following composition was applied and dried on the barrier layer to form a 5 m thick photosensitive layer (third photosensitive layer). -83- 1352875.

[第三感光性樹脂組成物溶液之組成]_ •甲基丙烯酸甲酯/丙烯酸-2·乙基己酯/甲基丙烯酸苄酯/甲基13質量份 丙烯酸共聚物(共聚物組成(莫耳比）：40/26.7/4.5/28.8、質量平 均分子量：90000、Tg : 50°C) 十二聚丙二醇二丙烯酸酯 8.1質量份 四乙二醇二甲基丙烯酸酯 1.9質量份 N-甲基吖啶酮 0.16質量份 2,2’-雙(2-氯苯基)-4,4’，5,5’-四苯基雙咪唑 ΐ·〇4質量份 4-甲苯磺醯胺 0.5質量份 孔雀綠草酸鹽 0.02質量份 1，2,4-三唑 〇.〇1質量份 無色結晶紫 0.2質量份 三溴甲基苯礪 0.1質量份 甲基乙基酮 10質量份 1-甲氧基-2-丙醇 20質量份 最後於第三感光層上，積層12ym厚之聚丙烯薄膜而 得到感光性轉印片。任何層層厚誤差均在±5%以內。藉由 後述之方法測定如此所得之感光性轉印片的感度時，用於 硬化第三感光層所必要之光能量爲lmJ/cm2,用於硬化第二 感光層所必要之光能量爲8m J/cm2，用於硬化第一感光層所 必要之光能量爲35mJ/Cm2，直到第一感光層之硬化開始所 必要之光能量爲14mJ/cm2。第三感光層與第二感光層之 間，C/A = 8/3、A/B = 3/14、第二感光層與第一感光層之間， C/A=1.75、A/B = 8/35。 -84- 1352875 以與上述之最短顯像時間評估方法相同的條件，製成 依序積層有鍍銅積層板、第三感光層、障壁層 '第二感光 層、然後聚對苯二甲酸乙二酯膜，並以室溫（23 °C、55 %RH) 靜置10分鐘。從所得之積層體的聚對苯二甲酸乙二酯膜 上，使用具有405η m之雷射光源的曝光裝置，邊改變曝光量 邊照射圖案。之後，與實施例1同樣地剝離聚對苯二甲酸乙 二酯膜、以進行顯像處理。其結果、如第6圖所示以低能量 照射的部分厚度5 y m、以中能量照射的部分係厚度爲16.6 # m、以高能量照射的部分係厚度爲38.2 /z m時，係形成厚 度不同的圖案。 [實施例6] (第一感光層的形成） 在20ym的聚對苯二甲酸乙二酯薄膜上，塗布由下述 組成所構成的第一感光性樹脂組成物溶液、乾燥，以形成 25/im厚的第一感光層》[Composition of the third photosensitive resin composition solution]_•Methyl methacrylate/acrylic acid-2·ethylhexyl ester/benzyl methacrylate/methyl 13 parts by mass of acrylic acid copolymer (copolymer composition (mole) Ratio: 40/26.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 50 ° C) Dodecapropanediol diacrylate 8.1 parts by mass of tetraethylene glycol dimethacrylate 1.9 parts by mass of N-methyl hydrazine 0.16 parts by mass of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazolium·〇4 parts by mass of 4-toluenesulfonamide 0.5 parts by mass of peacock Oxalic acid salt 0.02 parts by mass of 1,2,4-triazolium. 1 part by mass of colorless crystal violet 0.2 parts by mass of tribromomethylphenylhydrazine 0.1 parts by mass of methyl ethyl ketone 10 parts by mass of 1-methoxy- 20 parts by mass of 2-propanol was finally applied to the third photosensitive layer, and a polypropylene film of 12 μm thick was laminated to obtain a photosensitive transfer sheet. Any layer thickness error is within ±5%. When the sensitivity of the photosensitive transfer sheet thus obtained is measured by the method described later, the light energy necessary for curing the third photosensitive layer is lmJ/cm 2 , and the light energy necessary for hardening the second photosensitive layer is 8 m J . /cm2, the light energy necessary for hardening the first photosensitive layer is 35 mJ/cm 2 until the light energy necessary for the start of hardening of the first photosensitive layer is 14 mJ/cm 2 . Between the third photosensitive layer and the second photosensitive layer, C/A = 8/3, A/B = 3/14, between the second photosensitive layer and the first photosensitive layer, C/A = 1.75, A/B = 8/35. -84- 1352875 In the same conditions as the shortest development time evaluation method described above, a copper-clad laminate, a third photosensitive layer, a barrier layer 'second photosensitive layer, and then polyethylene terephthalate are sequentially laminated. The ester film was allowed to stand at room temperature (23 ° C, 55 % RH) for 10 minutes. From the obtained polyethylene terephthalate film of the laminate, an exposure apparatus having a laser light source of 405 η m was used, and the pattern was irradiated while changing the exposure amount. Thereafter, the polyethylene terephthalate film was peeled off in the same manner as in Example 1 to carry out a development treatment. As a result, as shown in Fig. 6, a portion having a thickness of 5 μm irradiated with low energy, a thickness of a portion irradiated with medium energy of 16.6 #m, and a thickness of a portion irradiated with high energy of 38.2 /zm are different in thickness. picture of. [Example 6] (Formation of First Photosensitive Layer) A solution of a first photosensitive resin composition composed of the following composition was applied onto a 20 μm polyethylene terephthalate film and dried to form 25/. Im thick first photosensitive layer》

-85- 1352875 第一感光性樹脂組成物溶液 •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基15質量份 丙烯酸共聚物(共聚物組成(莫耳比）：55/11.7/4.5/28.8、質量 平均分子量：卯〇〇〇、Tg : 70°C) •六亞甲基二異氰酸酯與八環氧乙烷單（甲基)丙烯酸酯之1/28質量份 莫耳比加成物 • 4,4’-雙(二乙胺)二苯基嗣 〇.〇4質量份 •二苯基酮 1.0質量份 • 4-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 0.02質量份 • 1,2,4-三唑 0.01質量份 •無色結晶紫 0.02質量份 •三溴甲基苯碾 0.1質量份 •甲基乙基酮 30質量份 (障壁層之形成） 在第一感光層上塗布由下述組成所構成的水溶性聚合 物溶液，乾燥以形成厚的障壁層。 障壁層溶液 •下述構造體所示之聚乙烯醇衍生物 13質量份 •聚乙烯吡咯啶酮 6質量份 .水 200質量份 •甲醇 180質量份 聚乙烯醇衍生物 (聚合性基的導入率爲2莫耳％) -86- 1352875 [化i] CHgCH— CH2CH— OH / OCOCHa 一OCONH/S.^^ (第二感光層的形成） 在障壁層上塗布由下述組成所構成的第二感光1性樹脂 組成物溶液，乾燥以形成厚的第二感光層：_ 第二感光性樹脂組成物溶液 •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基 丙烯酸共聚物(共聚物組成(莫耳比）：40/26.7Μ·5/28·8、質量平 均分子量：90000、Tg : 70°C) 15質量份 •聚丙二醇二丙烯酸酯 6.5質量份 •四乙二醇二甲基丙烯酸酯 1.5質量份 • 4,4’-雙（二乙胺）二苯基酮 0.4質量份 •二苯基酮 3.0質量份 • 4-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 〇.〇2質量份 • 1，2,4-三唑 0.01質量份 •無色結晶紫 0.2質量份 •三溴甲基苯碾 0.1質量份 •甲基乙基酮 10質量份 •卜甲氧基-2-丙醇 20質量份 (感光性轉印片的製作） 最後於第二感光層上，積層12/zm厚之聚丙烯薄膜而 得到感光性轉印片。任一層的層或膜厚不均勻均在±5 %以 -87- 1352875 內。藉由上述之方法測定如此所得之感光性轉印片的感度 時，最短顯像時間爲30秒，用於硬化第二感光層所必要之 光能量A爲4 mJ/cm2，用於硬化第一感光層所必要之光能量 B爲40mJ/cm2,直到第一感光層之硬化開始所必要之光能量 C爲14mJ/cm2(光能量C與光能量A之比例C/A爲3.5，光能量 A與光能量B之比例A/B爲0.1)。又，在第一感光層之光感度 爲1之情況下，第二.感光層之光感度爲10。 [實施例7] (聚乙烯醇衍生物的合成例） 將聚乙烯醇衍生物（PVA205 可樂麗（股）製）10質量份 溶解於90質量份的水中。把羥甲基丙烯醯胺2.3質量份溶解 於永20.7質量份之溶液，且添加對苯二酚0.002質量份。於 其中加入硫酸0.04質量份於40°C下反應4小間，以得到在側 鎖具有丙烯醯胺基之聚乙烯醇10質量％的水溶液。 (感光捜轉印片的製作） 下述除了改變實施例6的障壁層溶液以外，係與實施例 6同樣地進行以得到感光性轉印片。 _ · 障壁層溶液____ •合成聚乙烯醇衍生物的10%水溶液 130質量份 •聚乙烯吡咯啶酮 6質量份 •水 83質量份 •甲醇 _180質量份 任一層的層或膜厚不均勻均在±5 %以內。藉由上述之 方法測定如此所得之感光性轉印片的感度時’最短顯像時 間爲3 0秒，用於硬化第二感光層所必要之光能量A爲 -88- 1352875. 4m J/cm2，用於硬化第一感光層所必要之光能量B爲 40mJ/cm2 ’直到第一感光層之硬化開始所必要之光能量C 爲l4mJ/cm2(光能量C與光能量A之比例C/A爲3.5，光能量A 與光能量B之比例A/B爲0.1)。 [實施例8] (感光性轉印片的製作） 下述除了改變實施例6的障壁層溶液以外 6同樣地進行以得到感光性轉印片。 ，係與實施例 障壁層溶液 •聚乙烯醇（PVA205、可樂麗（股）製） 13質量份 •聚乙烯吡咯啶酮 3質量份 •九丙二醇二丙烯酸酯 3質量份 •水 200質量份 •甲醇 1 80質量份 任一層的層或膜厚不均勻均在±5%以內。藉由上述之 方法測定如此所得之感光性轉印片的感度時，最短顯像時 間爲3 0秒，用於硬化第二感光層所必要之光能量A爲 4mJ/cm2，用於硬化第一感光層所必要之光能量B爲 40mJ/cm2，直到第一感光層之硬化開始所必要之光能量C 爲14mJ/cm2(光能量C與光能量A之比例C/A爲3.5，光能量A 與光能量B之比例A/B爲0.1)。又’第一感光層的光感度爲1 時，第二感光層的光感度係爲1〇。 [比較例3 ] 除了將實施例6中的第一感光層膜厚改成30//m、障壁 層、不塗布第二感光層之事以外’與實施例1同様地製作感 -89- 135.2875 光性轉印片。藉由上述之方法測定如此所得之感光性轉印 片的感度時’最短顯像時間爲2 5秒，用於硬化感光層所必 要之光能量B爲40mJ/cm2,直到第一感光層之硬化開始所必 要之光能量C爲14mJ/cm2。 [比較例4] 僅由實施例6中的第一感光層、不塗布障壁層、膜厚5 /z m的第二感光層所構成的感光性轉印片做成所得之感光 性轉印片的感度，藉由上述方法測定的結果，最短顯像時 間爲1 〇秒以下，用於硬化第二感光層所必要的光能量B爲 4mJ/cm2。 關於評價如此所得之感光性轉印片的解析度、保護幕 比較例4 20〆 全部破裂全部破裂 有 破裂（直徑3mm部、 及0 _ 2mm部） 、通孔內銅鍍有無異常 '保 存安定性之結果， 係如表2所示 〇 表2 感光性轉印 破古ίί密 保護幕破裂 通孔內銅鍵 保存安定性 片 酔饥反 3mm 0.2mm 有無異吊 實施例6 20/2 m jfrrr. 無 無 Λπτ. m 良好 實施例7 20^ m 無 無 無 良好 實施例8 20# m /fnT- 無 無 良好 比較例3 40// m 無 (註）-：由於沒有不同之感光層而未評價感度 -90- 1352875 [實施例9] (第一感光層的形成） 將20/zm厚的聚對苯二甲酸乙二醇酯膜，塗布由下述組 成所構成之第一癩光桂樹脂組成物溶液、乾煥，以形成20 〆m厚的第一感光層。_ 第一感光性樹脂組成物溶液_ •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙15質量份 烯酸共聚物(共聚物組成(莫耳比）：55/11.7/4.5/28.8、質量平均分 子量：90000、Tg : 70°C) •十二聚丙二醇二丙烯酸酯 6.5質量份 •四乙二醇二甲基丙烯酸酯 1.5質量份 • 4,4’-雙(二乙胺)二苯基酮 〇.〇4質量份 •二苯基酮. 1.0質量份 • 4-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 0.02質量份 • 1，2,4-三唑 〇.〇1質量份 •無色結晶紫 0.2質量份 •三溴甲基苯砸 0.1質量份 •甲基乙基酮 3〇質量份 (障壁層的形成） 在第一感光層上塗布由下述組成所構成的水溶性聚合 物溶液，乾燥以形成i.6^m厚的障壁層。__ 水溶性聚合物溶液 _ 13質量份 •下述構造式所示之聚乙烯醇衍生物 Ϊ352875 •聚乙烯吡咯啶酮 6質量份 •水 200質量份 _180 質量份 聚乙烯醇衍生物 [化2] -CH2CH — / in / —CH2CH— OCOCH3 ch2ch— OCONH/^^ (第二感光層的形成） 在障壁層上塗布由下述組成所構成的第二感光性樹脂 組成物溶液，乾燥以形成l〇#m厚的第二感光層。-85- 1352875 First photosensitive resin composition solution • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl 15 parts by mass of acrylic copolymer (copolymer composition (Mo Erbi ): 55/11.7/4.5/28.8, mass average molecular weight: 卯〇〇〇, Tg: 70 ° C) • 1/28 mass of hexamethylene diisocyanate and octaethylene oxide mono (meth) acrylate Momo ratio adducts • 4,4'-bis(diethylamine)diphenyl hydrazine. 4 parts by mass • Diphenyl ketone 1.0 parts by mass • 4-toluene sulfonamide 0.5 parts by mass • Peacock green grass Acid salt 0.02 parts by mass • 1,2,4-triazole 0.01 parts by mass • Colorless crystal violet 0.02 parts by mass • Tribromomethylbenzene mill 0.1 parts by mass • Methyl ethyl ketone 30 parts by mass (formation of barrier layer) A water-soluble polymer solution composed of the following composition was applied onto the first photosensitive layer, and dried to form a thick barrier layer. Barrier layer solution • 13 parts by mass of polyvinyl alcohol derivative shown in the following structure • 6 parts by mass of polyvinylpyrrolidone; 200 parts by mass of water • 180 parts by mass of methanol, polyvinyl alcohol derivative (introduction rate of polymerizable group) 2 mol%) -86-1352875 [chemical i] CHgCH-CH2CH-OH / OCOCHa-OCONH/S.^^ (formation of the second photosensitive layer) The second layer composed of the following composition is coated on the barrier layer A photosensitive resin composition solution is dried to form a thick second photosensitive layer: _ Second photosensitive resin composition solution • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / A Acrylic copolymer (copolymer composition (mole ratio): 40/26.7Μ·5/28·8, mass average molecular weight: 90,000, Tg: 70 ° C) 15 parts by mass • Polypropylene glycol diacrylate 6.5 parts by mass • Tetraethylene glycol dimethacrylate 1.5 parts by mass • 4,4'-bis(diethylamine) diphenyl ketone 0.4 parts by mass • Diphenyl ketone 3.0 parts by mass • 4-toluenesulfonamide 0.5 parts by mass • Peacock oxalate 〇. 〇 2 parts by mass • 1,2,4-triazole 0.01 parts by mass • Colorless crystal 0.2 parts by mass of purple • 0.1 parts by mass of tribromomethylbenzene; 10 parts by mass of methyl ethyl ketone • 20 parts by mass of methoxy-2-propanol (manufactured by photosensitive transfer sheet) On the layer, a 12/zm thick polypropylene film was laminated to obtain a photosensitive transfer sheet. The layer or film thickness unevenness of either layer is within ±5 % to -87 - 1352875. When the sensitivity of the thus obtained photosensitive transfer sheet was measured by the above method, the shortest development time was 30 seconds, and the light energy A necessary for hardening the second photosensitive layer was 4 mJ/cm 2 for hardening first. The light energy B necessary for the photosensitive layer is 40 mJ/cm 2 until the light energy C necessary for the start of hardening of the first photosensitive layer is 14 mJ/cm 2 (the ratio of the light energy C to the light energy A is C/A of 3.5, the light energy A The ratio A/B to the light energy B is 0.1). Further, in the case where the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is 10. [Example 7] (Synthesis Example of Polyvinyl Alcohol Derivative) 10 parts by mass of a polyvinyl alcohol derivative (manufactured by PVA205 Co., Ltd.) was dissolved in 90 parts by mass of water. 2.3 parts by mass of methylol acrylamide was dissolved in a solution of 20.7 parts by mass, and 0.002 parts by mass of hydroquinone was added. Thereto, 0.04 parts by mass of sulfuric acid was added and reacted at 40 ° C for 4 hours to obtain an aqueous solution in which 10% by mass of polyvinyl alcohol having a acrylamide group was locked. (Production of Photosensitive Release Transfer Sheet) A photosensitive transfer sheet was obtained in the same manner as in Example 6 except that the barrier layer solution of Example 6 was changed. _ · Barrier layer solution ____ • 10% aqueous solution of synthetic polyvinyl alcohol derivative 130 parts by mass • Polyvinylpyrrolidone 6 parts by mass • 83 parts by mass of water • Methanol _180 parts by mass of layer or film thickness uneven Both are within ±5 %. When the sensitivity of the thus obtained photosensitive transfer sheet is measured by the above method, the shortest development time is 30 seconds, and the light energy A necessary for hardening the second photosensitive layer is -88 to 1352875. 4m J/cm 2 The light energy B necessary for hardening the first photosensitive layer is 40 mJ/cm 2 ' until the light energy C necessary for the start of hardening of the first photosensitive layer is 14 mJ/cm 2 (the ratio of the light energy C to the light energy A C/A) As for 3.5, the ratio A/B of the light energy A to the light energy B is 0.1). [Example 8] (Production of photosensitive transfer sheet) The photosensitive transfer sheet was obtained in the same manner as in the following except that the barrier layer solution of Example 6 was changed. , Example and barrier layer solution • Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.) 13 parts by mass • 3 parts by mass of polyvinylpyrrolidone • 3 parts by mass of nona-propylene glycol diacrylate • 200 parts by mass of water • Methanol 1 80 parts by mass of any layer or film thickness unevenness within ± 5%. When the sensitivity of the thus obtained photosensitive transfer sheet was measured by the above method, the shortest development time was 30 seconds, and the light energy A necessary for hardening the second photosensitive layer was 4 mJ/cm 2 for hardening first. The light energy B necessary for the photosensitive layer is 40 mJ/cm 2 until the light energy C necessary for the start of hardening of the first photosensitive layer is 14 mJ/cm 2 (the ratio of the light energy C to the light energy A is C/A of 3.5, the light energy A The ratio A/B to the light energy B is 0.1). Further, when the light sensitivity of the first photosensitive layer is 1, the light sensitivity of the second photosensitive layer is 1 Å. [Comparative Example 3] A feeling was produced in the same manner as in Example 1 except that the film thickness of the first photosensitive layer in Example 6 was changed to 30 / / m, the barrier layer, and the second photosensitive layer were not applied. -89 - 135.2875 Light transfer sheet. When the sensitivity of the thus obtained photosensitive transfer sheet is measured by the above method, the shortest development time is 25 seconds, and the light energy B necessary for hardening the photosensitive layer is 40 mJ/cm 2 until the first photosensitive layer is hardened. The light energy C necessary for the start is 14 mJ/cm2. [Comparative Example 4] The photosensitive transfer sheet composed of the first photosensitive layer, the non-coated barrier layer, and the second photosensitive layer having a film thickness of 5 /zm was used as the photosensitive transfer sheet obtained. Sensitivity, as a result of the measurement by the above method, the shortest development time is 1 sec or less, and the light energy B necessary for hardening the second photosensitive layer is 4 mJ/cm 2 . Evaluation of the resolution of the photosensitive transfer sheet thus obtained and the protective screen Comparative Example 4 20 rupture, all cracks were broken (diameter: 3 mm, and 0 _ 2 mm), and copper plating in the through hole was abnormal "preservation stability" The results are shown in Table 2. 2 Table 2 Photosensitive transfer breaks the ancient 保护 保护 保护 破裂 破裂 破裂 破裂 通 铜 铜 铜 铜 铜 铜 铜 铜 铜 3 3 3 3 3 3 3 3 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 20 No Λπτ. m Good Example 7 20^m No or no good Example 8 20# m /fnT- No good Comparative Example 3 40// m No (Note)-: Not evaluated because there is no different photosensitive layer Sensitivity - 90 - 1352875 [Example 9] (Formation of first photosensitive layer) A 20/zm thick polyethylene terephthalate film was coated with the first glare resin composed of the following composition The solution was dried and dried to form a 20 μm thick first photosensitive layer. _ First photosensitive resin composition solution _ • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl propyl 15 parts by weight of enoic acid copolymer (copolymer composition (Mo Erbi ): 55/11.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 70 ° C) • 126 parts by mass of dipropylene glycol diacrylate • 1.5 parts by mass of tetraethylene glycol dimethacrylate • 4, 4 '-Bis(diethylamine)diphenyl ketone oxime. 4 parts by mass • Diphenyl ketone. 1.0 parts by mass • 4-toluenesulfonamide 0.5 parts by mass • Peacock oxalate 0.02 parts by mass • 1,2 , 4-triazolium. 〇1 parts by mass • Colorless crystal violet 0.2 parts by mass • Tribromomethylphenylhydrazine 0.1 parts by mass • Methyl ethyl ketone 3 〇 by mass (formation of barrier layer) on the first photosensitive layer A water-soluble polymer solution composed of the following composition was applied and dried to form a barrier layer having an i.6 μm thickness. __ Water-soluble polymer solution _ 13 parts by mass • Polyvinyl alcohol derivative Ϊ 352875 shown in the following structural formula • Polyvinylpyrrolidone 6 parts by mass • Water 200 parts by mass _180 parts by mass of polyvinyl alcohol derivative [Chemical 2 -CH2CH - / in / -CH2CH - OCOCH3 ch2ch - OCONH / ^^ (Formation of second photosensitive layer) A second photosensitive resin composition solution composed of the following composition is applied onto the barrier layer and dried to form 〇#m thick second photosensitive layer.

1352875 第二感光性樹脂組成物溶液_ •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙24質量份 烯酸共聚物(共聚物組成(莫耳比）：55/11.7/4.5/28.8、質量平均 分子量：90000、Tg : 70°C) •六亞甲基二異氰酸酯與八環氧乙烷單（甲基）丙烯酸酯之 莫耳比加成物 1/2 12質量份 • N-甲基吖啶酮 0.2質量份 • 2,2’-雙(2-氯苯基)-4,4’，5,5’-四苯基雙咪唑 0.8質量份 • 2-硫醇基苯并咪唑 0.2質量份 • 4-甲苯磺醯胺 0.8質量份 •孔雀綠草酸鹽 〇.〇3質量份 • 1，2,4-三唑 〇.〇3質量份 •無色結晶紫 0.32質量份 •三溴甲基苯碾 0.25質量份 •甲基乙基酮 55質量份 • 1-甲氧基-2-丙醇 8質量份 (障壁層之形成） 在第二感光層上塗布由下述組成所構成的水溶性聚合 物溶液，乾燥以形成1.6/zm厚的障壁層。 (第三感光層之形成） 在障壁層上塗布由下述組成所構成的第三感光性樹脂 組成物溶液，乾燥以形成5 m厚的第二感光層。 -93- 135.2875 第三感光性樹脂組成物溶液_ •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙13質量份 烯酸共聚物(共聚物組成(莫耳比）：40/26.7/4.5/28.8、質量平均 分子量：90000、Tg : 50°C) •十二聚丙二醇二丙烯酸酯 8.1質量份 •四乙二醇二甲基丙烯酸酯 1.9質量份 • N-甲基吖啶酮 0.16質量份 • 2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑 1.04質量份 • 4-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 0.02質量份 • 1，2,4-三唑 0.01質量份 •無色結晶紫 0.2質量份 •三溴甲基苯颯 0.1質量份 •甲基乙基酮 10質量份 • 1-甲氧基-2-丙醇 20質量份 (感光性轉印片的製作） 在第三感光層上積層12μ m的聚丙烯薄膜（保趨薄膜） 以形成感光性轉印片。任一層的層或膜厚不均勻均在±5 % 以內。藉由上述之方法測定如此所得之感光性轉印片的感 度時，用於硬化第三感光層所必要之光能量爲lmJ/cm2，用 於硬化第二感光層所必要之光能量爲8mJ/cm2，直到第二感 光層之硬化開始所必要之光能量爲3mJ/cm2。用於硬化第一 感光層所必要之光能量爲35mJ/cm2，直到第一感光層之硬 -94- 1352875 化開始所必要之光能量爲14m J/cm2。第三感光層與第二感 光層之間’ C/A = 8/ 3、A/B = 3/14，第二感光層與第一感光層 之間，C/A=1.75' A/B = 8/35。 以與上述之最短顯像時間評估方法相同的條件，製成 依序積層有鍍銅積層板、第三感光層、障壁層、第二感光 層、障壁層、第一感光層，然後聚對苯二甲酸乙二酯膜， 並以室溫（23 °C、55 %RH)靜置10分鐘。從所得之積層體的 聚對苯二甲酸乙二酯膜上，使用具有405nm之雷射光源的曝 光裝置，邊改變曝光量邊照射圖案。之後，與實施例1同樣 地剝離聚對苯二甲酸乙二酯膜、以進行顯像處理。其結果、 如第6圖所示以低能量照射的部分厚度5 # m、以中能量照射 的部分係厚度爲16.6# m、以高能量照射的部分係厚度爲 38.2 μ m時’係形成厚度不同的圖案。 [實施例10] 在20//m厚的聚對苯二甲酸乙二酯薄膜上，塗布由下 述組成所構成之第一感光性樹脂組成物溶液、乾燥，以形 成20// m厚的感光層（第一感光層）。第—感光層的波長 405nm的光吸光度爲0.3、透過率爲50%(參考：波長36511111的 光吸光度爲低於〇 . 2 )。 -95- 135.2875 [第一感光性樹脂組成物溶液之組成] •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸；酯/甲基15質量份 丙烯酸共聚物(共聚物組成(莫耳比）： 55/11.7M.5/28.8、質量平 均分子量：90000、Tg : 70°C) •十二聚丙二醇二丙烯酸酯 6.5質量份 •四乙二醇二甲基丙烯酸酯 1.5質量份 • N-甲基吖啶嗣 〇·〇8質量份 •二苯基嗣 1.0質量份 • p-甲苯磺醯胺 0.5質量份 •孔雀綠草酸鹽 〇.〇2質量份 • 3-嗎啉代甲基-1-苯基三唑-2-硫 〇.〇1質量份 •無色結晶紫 0.2質量份 •三溴甲基苯颯 0.1質量份 •甲基乙基酮 30質量份 接著，在第一感光層上 多層塗布下述之障壁層塗布 液，乾燥以形成1.6/zm厚的障壁層。 [障壁層塗布液之組成] .聚乙烯醇衍生物（PVA205: 可樂麗公司製造）13質量份 •聚乙烯吡咯啶酮（PVPK30: GAF公司製造）6質量份 •水 200質量份 •甲醇 180質量份1352875 Second photosensitive resin composition solution _ • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl propyl 24 parts by weight of enoic acid copolymer (copolymer composition (Moerby ): 55/11.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 70 ° C) • Molybdenum adduct of hexamethylene diisocyanate and octaethylene oxide mono (meth) acrylate 1 /2 12 parts by mass • N-methyl acridone 0.2 parts by mass • 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole 0.8 parts by mass • 2-thiol benzimidazole 0.2 parts by mass • 4-toluenesulfonamide 0.8 parts by mass • Peacock oxalate 〇. 〇 3 parts by mass • 1,2,4-triazole oxime. 〇 3 parts by mass • Colorless Crystal violet 0.32 parts by mass • Tribromomethylbenzene 0.25 parts by mass • Methyl ethyl ketone 55 parts by mass • 1-methoxy-2-propanol 8 parts by mass (formation of barrier layer) on the second photosensitive layer A water-soluble polymer solution composed of the following composition was applied and dried to form a 1.6/zm thick barrier layer. (Formation of Third Photosensitive Layer) A third photosensitive resin composition solution composed of the following composition was applied onto the barrier layer and dried to form a second photosensitive layer having a thickness of 5 m. -93- 135.2875 Third photosensitive resin composition solution _ • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl propyl 13 parts by weight of enoic acid copolymer (copolymer composition ( Moerby): 40/26.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 50 ° C) • DD parts by weight of propylene glycol diacrylate • 1.9 parts by mass of tetraethylene glycol dimethacrylate • N-methylacridone 0.16 parts by mass • 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole 1.04 parts by mass • 4-toluenesulfonamide 0.5 parts by mass • peas oxalate 0.02 parts by mass • 1,2,4-triazole 0.01 parts by mass • colorless crystal violet 0.2 parts by mass • tribromomethylphenylhydrazine 0.1 parts by mass • methyl ethyl ketone 10 parts by mass • 20 parts by mass of 1-methoxy-2-propanol (manufacture of photosensitive transfer sheet) A 12 μm polypropylene film (film) was laminated on the third photosensitive layer to form a photosensitive transfer sheet. The layer or film thickness unevenness of any layer is within ±5 %. When the sensitivity of the photosensitive transfer sheet thus obtained is measured by the above method, the light energy necessary for curing the third photosensitive layer is lmJ/cm2, and the light energy necessary for hardening the second photosensitive layer is 8 mJ/ Cm2, the light energy necessary until the hardening of the second photosensitive layer starts is 3 mJ/cm2. The light energy necessary for hardening the first photosensitive layer was 35 mJ/cm 2 until the light energy necessary for the start of hard -94 - 1352875 of the first photosensitive layer was 14 m J/cm 2 . Between the third photosensitive layer and the second photosensitive layer 'C/A = 8/3, A/B = 3/14, between the second photosensitive layer and the first photosensitive layer, C/A = 1.75' A/B = 8/35. The copper-clad laminate, the third photosensitive layer, the barrier layer, the second photosensitive layer, the barrier layer, the first photosensitive layer, and then the polyphenylene oxide are sequentially formed under the same conditions as the shortest development time evaluation method described above. The ethylene dicarboxylate film was allowed to stand at room temperature (23 ° C, 55 % RH) for 10 minutes. From the obtained polyethylene terephthalate film of the laminate, an exposure device having a laser light source of 405 nm was used, and the pattern was irradiated while changing the exposure amount. Thereafter, the polyethylene terephthalate film was peeled off in the same manner as in Example 1 to carry out a development treatment. As a result, as shown in Fig. 6, the partial thickness of 5 # m irradiated with low energy, the thickness of the partial system irradiated with medium energy is 16.6# m, and the thickness of the partial system irradiated with high energy is 38.2 μm. Different patterns. [Example 10] A solution of a first photosensitive resin composition composed of the following composition was applied onto a 20//m thick polyethylene terephthalate film, and dried to form a 20//m thick film. Photosensitive layer (first photosensitive layer). The wavelength of the first photosensitive layer has a light absorbance of 405 nm of 0.3 and a transmittance of 50% (reference: the light absorbance of the wavelength of 35,511,111 is lower than 〇. 2 ). -95- 135.2875 [Composition of the first photosensitive resin composition solution] • Methyl methacrylate/2-ethylhexyl acrylate/methacrylic acid; ester/methyl 15 parts by mass of acrylic copolymer (copolymer composition) (Morby): 55/11.7M.5/28.8, mass average molecular weight: 90,000, Tg: 70 ° C) • Doppler polypropylene diacrylate 6.5 parts by mass • Tetraethylene glycol dimethacrylate 1.5 mass • N-methyl acridine 嗣〇·〇 8 parts by mass • Diphenyl hydrazine 1.0 parts by mass • p-toluene sulfonamide 0.5 parts by mass • Peacock oxalate 〇. 〇 2 parts by mass • 3-morpholino Methyl-1-phenyltriazole-2-thioindole. 〇1 parts by mass • Colorless crystal violet 0.2 parts by mass • Tribromomethylphenylhydrazine 0.1 parts by mass • Methyl ethyl ketone 30 parts by mass, followed by The following barrier layer coating liquid was applied to the photosensitive layer in multiple layers, and dried to form a 1.6/zm thick barrier layer. [Composition of barrier layer coating liquid] Polyvinyl alcohol derivative (PVA205: manufactured by Kuraray Co., Ltd.) 13 parts by mass • Polyvinylpyrrolidone (PVPK30: manufactured by GAF) 6 parts by mass • 200 parts by mass • Methanol 180 mass Share

在障壁層上，塗布由下述組成所構成之第二感光性樹 脂組成物溶液、乾燥，以形成5 a m厚的感光層（第二感光 -96- 135.2875 層）。第二感光層的波長405nm的光吸光度爲0.3、透過率爲 50 % (參考：波長365nm的光吸光度爲低於0.2)。_ [第一感光性樹脂組成物溶液之組成]_ •甲基丙烯酸甲酯/丙烯酸-2-乙基己酯/甲基丙烯酸苄酯/甲基丙15質量份 烯酸共聚物(共聚物組成(莫耳比）：55/11.7/4.5/28.8、質量平均 分子量：90000、Tg : 70°C) 十二聚丙二醇二丙烯酸酯 6.5質量份 四乙二醇二甲基丙烯酸酯 1.5質量份 N-甲基吖啶酮 0.16質量份 二苯基酮 3.0質量份 P-甲苯磺醯胺 0.5質量份 孔雀綠草酸鹽 〇.〇2質量份 3-嗎啉代甲基-1-苯基三唑-2-硫 〇.〇1質量份 無色結晶紫 0.2質量份 三溴甲基苯颯 0.1質量份 甲基乙基酮 30質量份 [實施例11 ] 除了將實施例10的第一感光性樹脂組成物溶液之N-甲 基丙烯酸甲酯0.08質量份改成爲0.12質量份以外，與實施例 1 〇同樣地進行，以製作實施例1 1的感光性轉印片。第一感 光層的波長405nm之光吸光度爲0.45，透過率爲36 %。 [實施例1 2 ] 除了將實施例10的第一感光性樹脂組成物溶液之N-甲 基丙烯酸甲酯0.08質量份改成爲0.20質量份以外，與實施例 10同樣地進行，以製作實施例12的感光性轉印片。第一感 -97- 135.2875 光層的波長405nm之光吸光度爲〇.75，透過率爲18%。 [評價] 實施例1〇~12製造的感光性轉印片之感度，係以下述之 方法加以評價。其結果如表3所示。 [感度的測定方法] 在鍍銅積層板上，感光性轉印片係其第二感光層連接 至鍍銅積層板表面般而壓著。感光性轉印片的感光層上， 使用從聚對苯二甲酸乙二酯膜側具有波長405nm雷射光源 之雷射曝光裝置，照射從〇.lmJ/cm2以21/2倍的間隔直至 100mJ/cm2的不同光量之光，以硬化感光層。在室温靜置10 分鐘後，剝取感光性轉印片的聚對苯二甲酸乙二酯膜。在 鍍銅積層板上感光層的全面上，以30 °C的1質量％碳酸鈉水 溶液用噴射壓力〇.15MPa進行噴射，且溶解除去未硬化的感 光層，以測定該硬化屑的厚度。接著，將光的照射量與硬 化層厚度的關係做圖以得到感度曲線。從如此所得之感度 曲線讀取硬化第二感光層之全體時的光量（光量A)、硬化第 一感光層與第二感光層時的光量（光量B)、及直至第一感光 層開始硬化時的光量（光量C)。 -98 - 135.2875 表3_ 第一感光第二感光 層波長 4 05 n m 的 光吸光度 (-) 層波長 405 nm的 光吸光度 (%) 光量 A(m J) 光量 B (m J ) 光量 C (m J ) C-A (mJ) 實施例1 0 0.3 50 4 20 10 6 實施例1 1 0.45 36 5.5 15 8 2.5 實施例1 2 0.75 18 6 15 8 2 根據表 3之結果 ，調整第一 感光層波長405nm的光吸 光度至1.0 以下的實施例10~12 之感光性轉印片，硬化第 二感光層所 必須的光 量A與直至第一感光層開始硬化所必 須的光量c 之差C-A 大，由於曝光量， 同時硬化第一感光 層及第二感光層兩層時，得知可能僅有第二感光層殘留。 【圖式簡單說明】 第1圖係依照本發明之感光性轉印片之一範例的模式 截面圖。 第2圖係依照本發明之感光性轉印片之其他範例的模 式截面圖。 第3圖係顯示表示從支持體側照射光於本發明感光性 轉印片時，光照射量與硬化層厚度關係之感度曲線的曲線 圖。 第4圖係依照本發明之感光性轉印片之一範例的模式 截面圖。 第5圖係依照本發明之感光性轉印片之其他範例的模 •99- 1352875 式截面圖。 第ό圖係顯示使用依照本發明之感光層爲三層之感光 性轉印片而可形成之影像範例（硬化層圖案）的模式圖。 第7圖係顯示具有依照本發明通孔之印刷配線板之製 造步驟之步驟圖。 【主要元件符號說明】 10 感光性轉印片 11 支持體 12 第一感光層 13障壁層 籲 14 第二感光層 15 保護膜 16 薄膜硬化層 1 7 厚膜硬化層 18 剝離片 21 印刷配線板形成用基板 22 通孔 23 金屬鍍層 0 2 4 配線圖案 3 1 加壓輥 50 感光性轉印片 51 支持體 5 2 第一感光層 5 3 障壁層 54 第二感光層 55 第三感光層 56 保護膜 -100-On the barrier layer, a solution of a second photosensitive resin composition composed of the following composition was applied and dried to form a 5 mm thick photosensitive layer (second photosensitive layer - 96 - 135.2875 layer). The light absorption at a wavelength of 405 nm of the second photosensitive layer was 0.3, and the transmittance was 50% (Reference: the light absorbance at a wavelength of 365 nm was less than 0.2). _ [Composition of the first photosensitive resin composition solution]_•Methyl methacrylate/2-ethylhexyl acrylate/benzyl methacrylate/methyl propyl 15 parts by weight olefinic acid copolymer (copolymer composition) (Morby): 55/11.7/4.5/28.8, mass average molecular weight: 90,000, Tg: 70 ° C) Dodecapropanediol diacrylate 6.5 parts by mass of tetraethylene glycol dimethacrylate 1.5 parts by mass N- Methyl acridone 0.16 parts by mass of diphenyl ketone 3.0 parts by mass of P-toluene sulfonamide 0.5 parts by mass of peacock green grass 〇. 〇 2 parts by mass of 3-morpholinomethyl-1-phenyltriazole- 2- thioindole. 〇 1 part by mass of colorless crystal violet 0.2 part by mass of tribromomethylphenylhydrazine 0.1 part by mass of methyl ethyl ketone 30 parts by mass [Example 11] The first photosensitive resin composition of Example 10 was used. The photosensitive transfer sheet of Example 11 was produced in the same manner as in Example 1 except that 0.08 parts by mass of the solution of N-methyl methacrylate was changed to 0.12 parts by mass. The light absorption at a wavelength of 405 nm of the first photosensitive layer was 0.45, and the transmittance was 36%. [Example 1 2] The same procedure as in Example 10 was carried out except that 0.08 parts by mass of N-methyl methacrylate of the first photosensitive resin composition solution of Example 10 was changed to 0.20 parts by mass. 12 photosensitive transfer sheet. First sense -97- 135.2875 The optical layer has a light absorption of 〇.75 at a wavelength of 405 nm and a transmittance of 18%. [Evaluation] The sensitivity of the photosensitive transfer sheet produced in Example 1 to 12 was evaluated by the following method. The results are shown in Table 3. [Method for Measuring Sensitivity] On the copper-clad laminate, the photosensitive transfer sheet was pressed while the second photosensitive layer was attached to the surface of the copper-clad laminate. On the photosensitive layer of the photosensitive transfer sheet, a laser exposure apparatus having a laser light source having a wavelength of 405 nm from the polyethylene terephthalate film side was used, and the irradiation was performed from 〇.lmJ/cm 2 at intervals of 2 1/2 times up to 100 mJ. /cm2 of different amounts of light to harden the photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film of the photosensitive transfer sheet was peeled off. On the entire surface of the photosensitive layer of the copper-clad laminate, a 1 mass% sodium carbonate aqueous solution at 30 °C was sprayed with a spray pressure of 1515 MPa, and the uncured photosensitive layer was dissolved to remove the thickness of the hardened swarf. Next, the relationship between the amount of irradiation of light and the thickness of the hardened layer is plotted to obtain a sensitivity curve. The amount of light (light amount A) when the entire second photosensitive layer is hardened, the amount of light (light amount B) when the first photosensitive layer and the second photosensitive layer are cured, and the first photosensitive layer start to harden are read from the sensitivity curve thus obtained. The amount of light (light quantity C). -98 - 135.2875 Table 3_ First photosensitive second photosensitive layer wavelength 4 05 nm light absorbance (-) layer wavelength 405 nm light absorbance (%) light amount A (m J) light amount B (m J ) light amount C (m J CA (mJ) Example 1 0 0.3 50 4 20 10 6 Example 1 1 0.45 36 5.5 15 8 2.5 Example 1 2 0.75 18 6 15 8 2 According to the results of Table 3, the light of the first photosensitive layer having a wavelength of 405 nm was adjusted. In the photosensitive transfer sheets of Examples 10 to 12 having an absorbance of 1.0 or less, the difference A between the amount of light A necessary for curing the second photosensitive layer and the amount of light c necessary until the first photosensitive layer starts to harden is large, due to the amount of exposure, When the first photosensitive layer and the second photosensitive layer are hardened, it is known that only the second photosensitive layer may remain. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive transfer sheet according to the present invention. Fig. 2 is a schematic cross-sectional view showing another example of the photosensitive transfer sheet according to the present invention. Fig. 3 is a graph showing a sensitivity curve showing the relationship between the amount of light irradiation and the thickness of the hardened layer when the photosensitive body of the present invention is irradiated with light from the support side. Fig. 4 is a schematic cross-sectional view showing an example of a photosensitive transfer sheet according to the present invention. Fig. 5 is a cross-sectional view of a mold of the other embodiment of the photosensitive transfer sheet according to the present invention. The figure is a schematic view showing an image example (hardened layer pattern) which can be formed by using the photosensitive transfer sheet of the present invention as a three-layer photosensitive transfer sheet. Fig. 7 is a view showing the steps of a manufacturing step of a printed wiring board having through holes in accordance with the present invention. [Main component symbol description] 10 Photosensitive transfer sheet 11 Support 12 First photosensitive layer 13 Barrier layer 14 Second photosensitive layer 15 Protective film 16 Thin film hardened layer 1 7 Thick film hardened layer 18 Release sheet 21 Printed wiring board formation Substrate 22 Via 23 Metal plating 0 2 4 Wiring pattern 3 1 Pressure roller 50 Photosensitive transfer sheet 51 Support 5 2 First photosensitive layer 5 3 Barrier layer 54 Second photosensitive layer 55 Third photosensitive layer 56 Protective film -100-

Claims (1)

申請專利範圍： 一種感光性轉印片，其係於支持體上，依序積層下列 者而成： 第一感光層：由包含黏結劑、聚合性化合物、及光聚合起 始劑之感光性樹脂組成物所構成； 障壁層；及 第二感光層：由包含黏結劑、聚合性化合物、及光聚合起 始劑之感光性樹脂組成物所構成，且其顯示出比第一感光 層之光感度相對高之光感度。 2 ·如申請專利範圍第1項之感光性轉印片，其中障壁層係 含有對水或碳原子數1~4的低級醇顯示有親和性之樹脂爲 主要成分。 3.如申請專利範圍第1項之感光性轉印片，其中障壁層係 含有對水或碳原子數1〜4的低級醇有可溶性之樹脂爲主要 成分。 4 ·如申請專利範圍第1項之感光性轉印片，其中障壁層係 具有0.1~5ym範圍的厚度。 5. 如申請專利範圍第1項之感光性轉印片，其中障壁層具 有聚合性化合物。 6. 如申請專利範圍第5項之感光性轉印片，其中障壁層具 有感光性、且障壁層的光感度比第一感光層的光感度係相 對低。 7. 如申請專利範圍第5項之感光性轉印片，其中障壁層含 有之聚合性化合物係具有聚合性基之聚合物。 8. 如申請專利範圍第7項之感光性轉印片，其中具有聚合 -101 - 1352875 性基之聚合物係對水或碳原子數1至4的低級醇顯示有親 和性。 9. 如申請專利範圍第8項之感光性轉印片，其中具有對水 或碳原子數1至4的低級醇顯示有親和性之聚合性基的聚 合物，其對水或碳原子數1至4的低級醇有可溶性。 10. 如申請專利範圍第1項之感光性轉印片，其中第一感光 層的光感度爲1時，第二感光層的光感度爲2〜200之範圍。 1 1 ·如申請專利範圍第1項之感光性轉印片，其中以用來硬 化第二感光層所必須之光能量A與用來硬化第一感光層所 必須之光能量B的A/B所表示之比例在0.005~0.5的範圍。 12. 如申請專利範圍第1項之感光性轉印片，其中以用來硬 化第二感光層所必須之光能量A與直到第一感光層之硬化 開始所必須之光能量C之C/A所表示之比例在1〜1 〇的範 圍。 13. 如申請專利範圍第1項之感光性轉印片’其中第一感光 層與第二感光層係各別包含增感劑。 14. 如申請專利範圍第13項之感光性轉印片’其中於第二感 光層所含有之增感劑量較於第一感光層所含有之增感劑 量多。 15 .如申請專利範圍第1項之感光性轉印片’其中於第二光 感層所含有之光聚合起始劑的量比於第一感光層所含有 之光聚合起始劑的量多" 16.如申請專利範圍第1項之感光性轉印片，其中於第一光 感層所含有之聚合性化合物的量比於第一感光層所含有 之聚合性化合物的量多。 -102- 1352875 17·如申請專利範圍第丨項之感光性轉印片，其中第一感光 層波長4〇5nm的吸光度爲〇.1~1.0之範圍。 18. 如申i靑專利範圍第1項之感光性轉印片，其中在第一感 光層及/或第二感光層中含有於380~43〇nm具有極大吸收 波長之化合物。 19. 如申請專利範圍第18項之感光性轉印片，其中在第一感 光層及，或第二感光層中含有於380〜4 3 0n m具有極大吸收 波長之化合物係爲增感劑。 20. 如申請專利範圍第1項之感光性轉印片，其中第一感光 鲁 層具有l-lOO^m範圍之厚度，而且該厚度比第三感光層 的厚度大。 21. 如申請專利範圍第1項之感光性轉印片’其中第二光感 層具有0.1〜15ym範圍之厚度。 22. 如申請專利範圍第1項之感光性轉印片’其中支持體爲 合成樹脂製，而且透明》 23·如申請專利範圍第1項之感光性轉印片’其中支持體爲 帶狀支持體。 籲 24·如申請專利範圍第1項之感光性轉印片，其係於第二感 光層上配置著保護膜。 25. 如申請專利範圍第1項之感光性轉印片’其係爲帶狀 體’並捲取成滾筒狀。 26. 如申請專利範圍第1至25項中任一項之感光性轉印片’ 其係印刷配線板製造用。 27. 一種感光性積層體，其係於基體上，依序積層下列者 而成： • 103- 135.2875 第二感光層：由包含黏結劑、聚合性化合物、及光聚合起 始劑之感光性樹脂組成物所構成； 障壁層；及 第一感光層：由包含黏結劑、聚合性化合物、及光聚合起 始劑之感光性樹脂組成物所構成，且其顯示出比第二感光 層之光感度相對低之光感度。 2 8.如申請專利範圍第27項之感光性積層體，其中障壁層係 含有對水或碳原子數1〜4的低級醇顯示有親和性之樹脂爲 主要成分。 2 9.如申請專利範圍第27項之感光性積層體，其中障壁層係 含有對水或碳原子數1〜4的低級醇有可溶性之樹脂爲主要 成分。 3 0.如申請專利範圍第27項之感光性積層體，其中障壁層具 有聚合性化合物。 3 1 .如申請專利範圍第30項之感光性積層體，其中障壁層具 有感光性，且障壁層的光感度比第一感光層的光感度係相 對低。 32.如申請專利範圍第30項之感光性積層體，其中障壁層含 有之聚合性化合物係具有聚合性基之聚合物。 3 3.如申請專利範圍第32項之感光性積層體，其中具有聚合 性基之聚合物係對水或碳原子數1至4的低級醇顯示有親 和性。 3 4.如申請專利範圍第33項之感光性積層體，其中具有對水 或碳原子數1至4的低級醇顯示有親和性之聚合性基的聚 合物，其對水或碳原子數1至4的低級醇有可溶性。 -104- 1352875 35.如申請專利範圍第27項之感光性積層體，其中第一感光 層波長4〇5nm的吸光度爲0.1~1.〇之範圍。 3 6.如申請專利範圍第27項之感光性積層體，其中在第一感 光層及/或第二感光層中含有於380~430nm具有極大吸收 波長之化合物。 37. 如申請專利範圍第36項之感光性積層體，其中在第一感 光層及/或第二感光層中含有於380~430nm具有極大吸收 波長之化合物係爲增感劑。 38. 如申請專利範圍第27項之感光性積層體，其中基體係爲 印刷配線板形成用基板。 3 9.如申請專利範圍第27至38項中任一項之感光性積層 體，其係於第一感光層上積層支持體。 4 0. —種影像圖案形成方法，其係於基板上形成由經同時硬 化第一感光層與第二感光層所形成之硬化樹脂層存在 之區域、與硬化樹脂層不存在之區域所構成，其包括以 下步驟： (1) 於基板上，積層如申請專利範圍第1項之感光性轉印 片使得感光性轉印片的第二感光層爲基板側之位置 關係，以得到積層體之步驟； (2) 從積層體之第一感光層側進行既定影像圖案之光照 射，同時硬化接受該光照射之區域的第一感光層與第 二感光層之步驟； (3) 從積層體除去支持體之步驟；然後 (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 41.—種影像圖案形成方法，其係於基板上形成由經同時硬 -105- 1352875 化第一感光層與第二感光層所形成之樹脂層存在的區 域、藉由硬化第二感光層所形成之樹脂層存在的區域、 然後硬化樹脂層不存在之區域所構成，其包括以下步驟： (1) 於基板上，積層如申請專利範圍第1項之感光性轉印 片使得感光性轉印片的第二感光層爲基板側之位置關 係，以得到積層體之步驟； (2) 從積層體之第一感光層側，以規定照射互不相同之至 少二程度的照射能量光線之區域的影像圖案來進行光 照射，同時硬化接受光照射能量相對大之光照射區域 的第一層感光層與第二感光層，然後硬化接受光照射 能量相對小之光照射區域之第二感光層之步驟； (3) 從積層體除去支持體之步驟；然後， (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 42.如申請專利範圍第40或41項之方法，其中（3)從積層體除 去支持體之步驟，係由在步驟（2)與步驟（4)之間進行，取 代爲在步驟（1)與步驟（2)之間進行。 4 3.如申請專利範圍第40或41項之方法，其中步驟（2)中的光 照射係藉由雷射光的照射而進行。 44. 一種配線圖案形成方法，其係於印刷配線板形成用基板 上，形成由以藉由同時硬化第一感光層與第二感光層所 形成之硬化樹脂層所被覆之區域，與基板表面暴露之區 域所構成，其包括以下步驟： (1)於基板上，積層如申請專利範圍第1項之感光性轉印 片使得感光性轉印片的第二感光層爲基板側之位置關 係，以得到積層體之步驟； -106- 1352875 (2) 從積層體之第一感光層側進行既定配線圖案之光照 射，同時硬化接受該光照射區域之第一感光層與第二 感光層之步驟； (3) 從積層體除去支持體之步驟；然後， (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 45. —種配線圖案形成方法，其係在具有孔洞部分之印刷配 線板形成用基板上，形成由以藉由同時硬化第一感光層 與第二感光層所形成之硬化樹脂層所被覆之孔洞部分、 以藉由硬化第二感光層所形成之硬化樹脂層所被覆之區 域、然後基板表面暴露之區域所構成，其包括以下步驟： (1) 於基板上，積層如申請專利範圍第1項之感光性轉印 片使得感光性轉印片的第二感光層爲基板側之位置關 係，以得到積層體之步驟； (2) 從積層體之第一感光層側，進行如在孔洞部分則賦予 光照射能量相對大之光照射來同時硬化第一感光層 與第二感光層，然後在配線形成區域則賦予光照射能 量相對小之光照射來硬化第二感光層之影像圖案光 照射之步驟； (3) 從積層體除去支持體之步驟；然後， (4) 顯像積層體，並除去積層體中未硬化部分之步驟。 4 6.如申請專利範圍第44或45項之方法，其中（3)從積層體除 去支持體之步驟，係由在步驟（2)與步驟（4)之間進行，取 代爲在步驟（1)與步驟（2)之間進行。 47·如申請專利範圍第44或45項之方法，其中步驟（2)中的 光照射係藉由雷射光的照射而進行》 -107-Patent application range: A photosensitive transfer sheet which is attached to a support and sequentially laminated to the following: First photosensitive layer: photosensitive resin containing a binder, a polymerizable compound, and a photopolymerization initiator a composition comprising: a barrier layer; and a second photosensitive layer: comprising a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator, and exhibiting a light sensitivity to the first photosensitive layer Relatively high light sensitivity. 2. The photosensitive transfer sheet of claim 1, wherein the barrier layer contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. 3. The photosensitive transfer sheet of claim 1, wherein the barrier layer contains a resin which is soluble in water or a lower alcohol having 1 to 4 carbon atoms as a main component. 4. The photosensitive transfer sheet of claim 1, wherein the barrier layer has a thickness in the range of 0.1 to 5 μm. 5. The photosensitive transfer sheet of claim 1, wherein the barrier layer has a polymerizable compound. 6. The photosensitive transfer sheet of claim 5, wherein the barrier layer has photosensitivity, and the light sensitivity of the barrier layer is relatively lower than that of the first photosensitive layer. 7. The photosensitive transfer sheet of claim 5, wherein the barrier layer contains a polymerizable compound which is a polymer having a polymerizable group. 8. The photosensitive transfer sheet of claim 7, wherein the polymer having a polymerization group of -101 - 1352875 exhibits affinity for water or a lower alcohol having 1 to 4 carbon atoms. 9. The photosensitive transfer sheet of claim 8 which has a polymerizable group having an affinity for water or a lower alcohol having 1 to 4 carbon atoms, which has a water or carbon number of 1 The lower alcohols up to 4 are soluble. 10. The photosensitive transfer sheet of claim 1, wherein the light sensitivity of the first photosensitive layer is 1 and the light sensitivity of the second photosensitive layer is in the range of 2 to 200. 1 1 . The photosensitive transfer sheet of claim 1, wherein the light energy A necessary for hardening the second photosensitive layer and the A/B of the light energy B necessary for hardening the first photosensitive layer are used. The ratio indicated is in the range of 0.005 to 0.5. 12. The photosensitive transfer sheet of claim 1, wherein the light energy A necessary for hardening the second photosensitive layer and the C/A of the light energy C necessary until the hardening of the first photosensitive layer starts The ratio indicated is in the range of 1 to 1 〇. 13. The photosensitive transfer sheet of claim 1, wherein the first photosensitive layer and the second photosensitive layer each comprise a sensitizer. 14. The photosensitive transfer sheet of claim 13 wherein the sensitizing amount contained in the second photosensitive layer is larger than the amount of the sensitizing agent contained in the first photosensitive layer. 15. The photosensitive transfer sheet of claim 1, wherein the amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer. The photosensitive transfer sheet of the first aspect of the invention, wherein the amount of the polymerizable compound contained in the first photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer. The photosensitive transfer sheet of the invention of claim 1, wherein the absorbance of the first photosensitive layer having a wavelength of 4 〇 5 nm is in the range of 〇.1 to 1.0. 18. The photosensitive transfer sheet of claim 1, wherein the first photosensitive layer and/or the second photosensitive layer contains a compound having a maximum absorption wavelength at 380 to 43 Å. 19. The photosensitive transfer sheet of claim 18, wherein the compound having a maximum absorption wavelength of 380 to 430 nm in the first photosensitive layer and or the second photosensitive layer is a sensitizer. 20. The photosensitive transfer sheet of claim 1, wherein the first photosensitive layer has a thickness in the range of from 1 to 100 μm, and the thickness is greater than the thickness of the third photosensitive layer. 21. The photosensitive transfer sheet of claim 1, wherein the second photosensitive layer has a thickness in the range of 0.1 to 15 μm. 22. The photosensitive transfer sheet of claim 1 wherein the support is made of a synthetic resin and is transparent. 23. The photosensitive transfer sheet of claim 1 wherein the support is strip-shaped support body. The photosensitive transfer sheet of claim 1, wherein a protective film is disposed on the second photosensitive layer. 25. The photosensitive transfer sheet as described in claim 1 is a strip-shaped body and is wound into a roll shape. 26. The photosensitive transfer sheet of any one of claims 1 to 25, which is used for the manufacture of a printed wiring board. 27. A photosensitive laminate which is attached to a substrate and sequentially laminated: • 103- 135.2875 Second photosensitive layer: photosensitive resin containing a binder, a polymerizable compound, and a photopolymerization initiator a composition comprising: a barrier layer; and a first photosensitive layer: comprising a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator, and exhibiting a light sensitivity to the second photosensitive layer Relatively low light sensitivity. 2. The photosensitive laminate of claim 27, wherein the barrier layer contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. 2. The photosensitive laminate according to claim 27, wherein the barrier layer contains a resin which is soluble in water or a lower alcohol having 1 to 4 carbon atoms as a main component. The photosensitive laminate of claim 27, wherein the barrier layer has a polymerizable compound. The photosensitive laminate of claim 30, wherein the barrier layer has photosensitivity, and the light sensitivity of the barrier layer is relatively lower than that of the first photosensitive layer. The photosensitive laminate according to claim 30, wherein the barrier layer contains a polymerizable compound which is a polymer having a polymerizable group. 3. The photosensitive laminate according to claim 32, wherein the polymer having a polymerizable group exhibits affinity for water or a lower alcohol having 1 to 4 carbon atoms. 3. The photosensitive laminate according to claim 33, which has a polymerizable group having an affinity for water or a lower alcohol having 1 to 4 carbon atoms, which has a water or carbon number of 1 The lower alcohols up to 4 are soluble. -104- 1352875 35. The photosensitive laminate of claim 27, wherein the absorbance of the first photosensitive layer having a wavelength of 4 〇 5 nm is in the range of 0.1 to 1. 3. The photosensitive laminate according to claim 27, wherein the first photosensitive layer and/or the second photosensitive layer contains a compound having a maximum absorption wavelength at 380 to 430 nm. 37. The photosensitive laminate according to claim 36, wherein the compound having a maximum absorption wavelength at 380 to 430 nm in the first photosensitive layer and/or the second photosensitive layer is a sensitizer. 38. The photosensitive laminate according to claim 27, wherein the base system is a substrate for forming a printed wiring board. The photosensitive laminate according to any one of claims 27 to 38, which is a laminated support on the first photosensitive layer. 40. A method for forming an image pattern, which is formed on a substrate by a region where a hardened resin layer formed by simultaneously curing the first photosensitive layer and the second photosensitive layer exists, and a region where the hardened resin layer does not exist, The method comprises the following steps: (1) stacking the photosensitive transfer sheet of the first application of the patent application range on the substrate such that the second photosensitive layer of the photosensitive transfer sheet has a positional relationship on the substrate side to obtain a laminated body (2) a step of irradiating light of a predetermined image pattern from the side of the first photosensitive layer of the laminated body while hardening the first photosensitive layer and the second photosensitive layer in the region irradiated with the light; (3) removing support from the laminated body a step of the body; then (4) developing the layered body and removing the unhardened portion of the layered body. 41. A method for forming an image pattern by forming a region on a substrate from a resin layer formed by simultaneously hard-105- 1352875 first photosensitive layer and second photosensitive layer, by hardening the second photosensitive layer The region where the resin layer is formed and then the region where the hardened resin layer is not present is composed of the following steps: (1) On the substrate, the photosensitive transfer sheet of the first application of the patent application is laminated to make the photosensitive transfer The second photosensitive layer of the sheet is a positional relationship on the substrate side to obtain a laminated body; (2) from the side of the first photosensitive layer of the laminated body, at least two regions of the irradiation energy ray which are different from each other are specified to be irradiated The image pattern is irradiated with light, and at the same time, the first photosensitive layer and the second photosensitive layer which receive the light irradiation region having a relatively large light irradiation energy are hardened, and then the second photosensitive layer of the light irradiation region having a relatively small light irradiation energy is hardened. (3) a step of removing the support from the laminate; then, (4) developing the laminate and removing the unhardened portion of the laminate. 42. The method of claim 40 or 41, wherein (3) the step of removing the support from the laminate is performed between step (2) and step (4), and is replaced by the step (1) It is carried out with step (2). 4. The method of claim 40 or 41, wherein the light irradiation in the step (2) is performed by irradiation of laser light. 44. A wiring pattern forming method for forming a region covered with a cured resin layer formed by simultaneously hardening a first photosensitive layer and a second photosensitive layer on a substrate for forming a printed wiring board, and exposing the surface of the substrate The composition includes the following steps: (1) laminating the photosensitive transfer sheet of the first application of the patent application on the substrate such that the second photosensitive layer of the photosensitive transfer sheet is on the substrate side, a step of obtaining a laminate; -106- 1352875 (2) a step of irradiating light of a predetermined wiring pattern from the side of the first photosensitive layer of the laminate while hardening the first photosensitive layer and the second photosensitive layer receiving the light-irradiated region; (3) a step of removing the support from the laminate; then, (4) developing the laminate and removing the unhardened portion of the laminate. 45. A method of forming a wiring pattern formed on a substrate for forming a printed wiring board having a hole portion, wherein a hole covered by a hardened resin layer formed by simultaneously hardening the first photosensitive layer and the second photosensitive layer is formed And comprising: a region covered by the hardened resin layer formed by hardening the second photosensitive layer, and then a region exposed by the surface of the substrate, comprising the following steps: (1) on the substrate, stacking as in claim 1 The photosensitive transfer sheet is such that the second photosensitive layer of the photosensitive transfer sheet has a positional relationship on the substrate side to obtain a laminated body; (2) from the side of the first photosensitive layer of the laminated body, as in the case of the hole portion The step of irradiating the light of the relatively large light irradiation light to simultaneously harden the first photosensitive layer and the second photosensitive layer, and then irradiating the light of the light irradiation energy with a relatively small light irradiation to harden the image pattern light of the second photosensitive layer in the wiring forming region (3) a step of removing the support from the laminate; then, (4) developing the laminate and removing the unhardened portion of the laminate. 4. The method of claim 44 or 45, wherein (3) the step of removing the support from the laminate is carried out between steps (2) and (4), and is replaced by the step (1). ) is carried out with step (2). 47. The method of claim 44, wherein the light illumination in step (2) is performed by irradiation of laser light. -107-
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JP4711862B2 (en) * 2006-03-08 2011-06-29 富士フイルム株式会社 Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board
KR101338110B1 (en) * 2006-12-29 2013-12-06 엘지디스플레이 주식회사 Dry film flim and method of forming liquid crystal display panel using it
JP4902369B2 (en) * 2007-01-25 2012-03-21 富士フイルム株式会社 Curable composition, color filter and method for producing the same
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