TW200948891A - Resin composition for printed circuit board, dry film and printed circuit board - Google Patents

Resin composition for printed circuit board, dry film and printed circuit board Download PDF

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TW200948891A
TW200948891A TW98110131A TW98110131A TW200948891A TW 200948891 A TW200948891 A TW 200948891A TW 98110131 A TW98110131 A TW 98110131A TW 98110131 A TW98110131 A TW 98110131A TW 200948891 A TW200948891 A TW 200948891A
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Taiwan
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printed circuit
circuit board
resin
resin composition
pigment
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TW98110131A
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Chinese (zh)
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TWI441869B (en
Inventor
Touko Shiina
Masao Arima
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Taiyo Ink Mfg Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C09D167/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a resin composition for printed circuit concerning environment while maintaining enhancement characteristic of resin composition for printed circuit, a dry film and a printed circuit board using the same. The resin composition for printed circuit includes regenerated polyethylene glycol terephthalate.

Description

200948891 六、發明說明： 【發明所屬之技術領域】 本發明係關於考慮到環境，且絕緣性、耐熱性爲良好 之印刷電路板用樹脂組成物與使用此之乾膜及印刷電路板 【先前技術】 φ 近年來，環境問題之觀點，對於電子機器所使用之印 刷電路板也被要求使用有考慮到對環境影響的材料。例如 ，由於燃燒時之戴奧辛等有害氣體之發生的社會問題，對 於預浸體或防焊膜等所使用之難燃化材料或染色材料，被 要求從以往之含有溴等之鹵素系到無鹵素系之轉換。 例如，關於印刷電路板用組成物之難燃材料之無鹵素 化，至此進行了種種之檢討（例如參照專利文獻1等）。 但，由提高對環境問題的關心乃至更進一步考慮到環境的 〇 影響。 另一方面，因印刷電路板係使用於電子機器，而被要 求有絕緣性。又，對於印刷電路板之層間樹脂絕緣層，因 電子零件係在高溫下進行組裝，而被要求有耐熱性。 又，近年來，伴隨著形成於印刷電路板之最外層的防 焊膜之圖型的微細化，圖型形成則使用光微影法》此時， 由於係藉由透過光罩圖型照射活性能量線而形成圖型，對 於用以形成防焊膜之樹脂組成物，更被要求有光硬化性。 於此，如此般之感光性之樹脂組成物中，被提出有考慮到 -5- 200948891 環境的無鹵素形態之物（例如參照專利文獻2等）。 如此般，對於印刷電路板用樹脂組成物，被要求同時 有考慮到對環境的影響與維持提升特性。 另一方面，由於PET瓶近年來，輕量且透明性、阻氣 性優良，高強度其使用量急據增加，伴隨著此事，其廢棄 方法也漸漸地成爲社會問題。因此，進行種種檢討關於 PET瓶之回收利用（參照專利文獻3〜5等）。但，回收利 用過程中，有由於酯鍵結之加水分解造成PET之分子量減 少，且PET之熔融黏度與機械性強度減少之問題。接著， 如此之品質的降低則成爲PET瓶之回收利用障礙的原因。 因此，再生PET樹脂，其現狀，僅只被利用於纖維領域或 產業用資材領域中。伴隨著PET瓶廢棄量之增加，再生 PET樹脂之新式有效之活用法仍係被探索中。 〔專利文獻1〕W002/006399號公報（請求項1等） 〔專利文獻2〕特開2000-7974號公報（請求項！等 ) 〔專利文獻3〕特開平1 0-287844號公報（請求項1 等） 〔專利文獻4〕特開平1 1 -1 149 61號公報（請求項i 等） 〔專利文獻5〕特開2000-53892號公報（請求項i等 【發明內容】 -6- 200948891 〔發明所欲解決之課題〕 如上述，對於印刷電路板用樹脂組成物，被同時要求 有考慮到對環境的影響與維持提升特性。 於此，本發明係提供一種可同時考慮到對環境的影響 且維持提升特性之印刷電路板用樹脂組成物及使用此之乾 膜、印刷電路板作爲其目的者。 Φ 〔用以解決課題之手段〕 爲了解決上述課題，本發明之一種形態之印刷電路板 用樹脂組成物，其特徵爲含有再生聚對酞酸乙二酯（A) 者。 藉由此種構成，則可得到絕緣性、耐熱性、光透過性 優良，且考慮到環境的影響之印刷電路板用樹脂組成物。 又，對於如此般之印刷電路板用樹脂組成物，以混合 平均粒徑0.1〜15μιη之再生聚對酞酸乙二酯微粉末而調製 ❿ 爲佳。 藉由此種構成，可同時得到印刷電路板之良好平滑性 、絕緣性，且抑制圖型形成時之圖型缺陷。 又，如此般之印刷電路板用樹脂組成物，前述再生聚 對酞酸乙二酯（Α)係以全體量之0.1〜75 %爲佳。 藉由此種構成，可同時得到印刷電路板用樹脂組成物 之良好流動性、塗佈性、成形性’且抑制其硬化物之脆弱 性。 又，對於如此般之印刷電路板用樹脂組成物，以含有 200948891 熱硬化性樹脂（B)爲佳。 藉由含有熱硬化性樹脂（B)，可藉由加熱使其硬化 ，而可形成良好之永久被膜。 接著，對於如此般之印刷電路板用樹脂組成物，以感 光性樹脂（C )爲佳。 又，藉由使用感光性樹脂（C)，可藉由光照射使其 · 硬化，藉由光微影法之微細圖型之形成則成爲可能。 然後，本發明之一種形態之乾膜，其特徵爲在基材上 @ 具備有上述之印刷電路板用樹脂組成物之塗佈乾燥膜。 藉由此種構成，可得到絕緣性、耐熱性、光透過性優 良之乾膜，藉由轉印至印刷電路板，可在印刷電路板上形 成含有簡易之再生聚對酞酸乙二酯（A)之樹脂組成物層 〇 接著，本發明之一種形態之印刷電路板，其特徵爲具 備有，形成有電路之基板，與此基板上之至少一部份形成 有使上述之印刷電路板用樹脂組成物硬化後之永久被膜。 © 藉由此種構成，可得到絕緣性、耐熱性優良之印刷電 路板。 又，本發明之一種形態之印刷電路板，其特徵爲具備 有，形成有電路之基板，與此基板上之至少一部份’使藉 由上述之乾膜所轉印之印刷電路板用樹脂組成物之塗佈乾 燥膜硬化後之永久被膜。 藉由此種構成，可簡單得到絕緣性、耐熱性優良、且 考慮到對環境影響的印刷電路板。 -8 - 200948891 〔發明之效果〕 藉由本發明之印刷電路板用樹脂組成物及使用此之乾 膜、印刷電路板，可同時考慮到對環境的影響且維持提升 特性。 【實施方式】 φ 〔用以實施發明之最佳形態〕 以下，說明關於本發明之實施形態。 本實施形態之印刷電路板用樹脂組成物，其特徵爲含 有再生聚對酞酸乙二酯（A)。 本實施形態之再生聚對酞酸乙二酯（A)，只要係再 生聚對酞酸乙二酯則無特別限定。例如，將經使用之PET 瓶等予以回收、粉碎•破碎、洗淨之再生原料，或可使用 從在PET瓶或PET薄膜至製造步驟中所發生之不良品等 〇 所得之再生聚對酞酸乙二酯原料。 如此般之再生聚對酞酸乙二酯原料中，對酞酸乙二酯 單獨聚合物，或依據場合，以含有少量之共聚物之高結晶 性樹脂爲佳。此時，可藉由加熱處理使結晶性成爲例如 3 5 %以上。又，亦可將聚酯樹脂或變性聚酯樹脂等熔融混 合。然後，將如此般之再生聚對酞酸乙二酯原料藉由機械 粉碎或化學粉碎’將微粉碎後之微粉碎再生PET直接或漿 化後，藉由使用噴射式磨機等之各種粉碎及分散處理或各 種分級裝置進行處理’使平均粒徑作爲〇·1~15μιη使用爲 200948891 佳。若平均粒徑不滿〇·1 μιη，因其表面能量變高而變得容 易凝集，由於凝集物之影響有造成無法充分得到印刷電路 板之平滑性、絕緣性之虞。又，相反地若平均粒徑超過 15 μιη，印刷電路板之平滑性受損，於防焊膜形成時，有由 於圖型之缺陷所造成之不良產生之虞。更佳理想者爲，平 _ 均粒徑爲1〜12μιη。於此，爲防止因前述表面能量變高而 變得容易凝集一事，也可在有機溶劑預先分散後之漿狀態 下進行操作。此時之平均粒徑並無受限於上述，也可在更 @ 細微之狀態下使用。 藉由將如此般之微粉碎再生PET混合熱硬化性成分、 感光性成分等，形成印刷電路板用樹脂組成物。此時，再 生聚對酞酸乙二酯（A)之配合比爲，以組成物全體量之 0.1 ~75重量％爲佳。若考慮到對環境影響，其配合比以高 於1重量％以上爲佳。另一方面，若超過60重量％，絕緣 組成物之硬化物則變脆，絕緣組成物之流動性降低，有成 爲塗佈、成型障礙之虞。更理想者爲1~60重量％。 0 本實施形態之印刷電路板用樹脂組成物，除再生聚對 酞酸乙二酯（A)以外，可含有熱硬化性成分、感光性成 分等各種之構成成分。只要係絕緣性、耐熱性等、可適用 於印刷電路板者，並無限定特定其之構成成分，可適宜選 tm 擇。 基本而言，可提出含有熱硬化性成分或感光性成分又 或係其兩成分之各種形態。一般而言，熱硬化性樹脂組成 物之場合時，含有再生聚對酞酸乙二酯（A)、熱硬化性 -10- 200948891 樹脂（B):光硬化性樹脂組成物之場合時，含有再生聚 對酞酸乙二酯（A)、感光性樹脂（C)、光聚合起始劑（ D ):鹼顯像性之光硬化性熱硬化性樹脂組成物之場合時 ，含有再生聚對酞酸乙二酯（A)、熱硬化性樹脂（B)及 感光性樹脂（C)、光聚合起始劑（D)、含羧基之樹脂（ E)。接著·適當地選擇此些各成分的種類，藉有使用作 爲使配合比最佳化之印刷電路板用樹脂組成物，可得到所 ❹ 期望之特性的硬化物。 如此般之印刷電路板用樹脂組成物，更可依據需要， 可使其含有熱硬化觸媒（F)、塡充劑（G)、有機溶劑（ H)等。 本實施形態中，作爲熱硬化性樹脂（B )，只要係將 絕緣性等硬化物用於印刷電路板之場合時的諸特性爲優良 者則並不特別限定，具體而言可舉出，環氧樹脂、苯酚、 胺基甲酸乙酯樹脂、聚酯樹脂、羥基、胺基或含羧基之聚 © 胺基甲酸乙酯、聚酯、聚碳酸酯類、聚醇、苯氧樹脂、丙 烯酸系共聚合樹脂、乙烯樹脂、聚醯亞胺、聚醯胺醯亞胺 、噁嗪樹脂、氰酸鹽樹脂、氧環丁烷化合物、聚異氰酸酯 、嵌段異氰酸酯、碳二醯亞胺（化合物）樹脂、噁唑啉（ 化合物）樹脂等。此些可單獨或2種類以上混合使用。 如此般之熱硬化性樹脂（B )之配合比係’相對於再 生PET粉末（A) 100質量份，爲10〜100000質量份’更 佳爲30〜1〇〇〇質量份。若不滿10質量份，其流動性降低 ’塗佈或形成則變得困難，且機械性強度降低。另一方面 -11 - 200948891 ，若超過100000質量份，從考慮對環境影響的觀點來看 ，則無意義，且不理想。 作爲感光性樹脂（C )，只要係藉由活性能量線之照 射，乙烯性不飽和雙鍵會進行自由基聚合之化合物則無特 別限定，可舉出（甲基）丙烯酸酯系化合物、不飽和聚酯 系化合物、不飽和胺基甲酸乙酯系化合物、苯乙烯系化合 物、丁二烯系化合物等。如此般之乙烯性不飽和化合物之 中，以（甲基）丙烯酸酯系化合物爲特佳，此（甲基）丙 烯酸酯系化合物，只要係單官能、多官能及單體、寡聚物 (預聚物）之中任一即可，又，具有丙烯醯基（甲基丙烯 醯基）以外之官能基者亦可。具體而言，可舉出取代或非 取代之脂肪族丙烯酸酯、脂環族丙烯酸酯、芳香族丙烯酸 酯及此些之環氧乙烷變性丙烯酸酯等之單體，或環氧丙烯 酸酯、胺基甲酸乙酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯 酸酯、聚醇丙烯酸酯、醇酸丙烯酸酯、三聚氰胺丙烯酸酯 、聚矽氧丙烯酸酯、聚丁二烯丙烯酸酯等之寡聚物、以及 對應此些之甲基丙烯酸酯類等。此些可單獨或2種類以上 混合使用。 爲提高如此般之感光性樹脂（C)之反應性，也亦可 添加光反應性單體。具體而言，可舉出（甲基）丙烯酸丁 氧基甲酯、2-乙基己基（甲基）丙烯酸酯、（甲基）丙烯 酸十二酯、（甲基）丙烯酸羥乙酯、（甲基）丙烯酸羥丙 酯、（甲基）丙烯酸丙三醇酯、4-(甲基）芳氧基三環〔 5.2.1.02.6〕癸烷、（甲基）丙烯酸異崁酯、（甲基）丙 -12- 200948891 烯酸異癸酯、（甲基）丙烯酸苯氧乙酯、（甲基）丙烯酸 環己酯、（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）丙烯 酸苯酯、四氫糠基（甲基）丙烯酸酯、4-(甲基）芳氧基 烷基磷酸酯、r-(甲基）芳氧基烷基三烷氧基矽烷等之 單官能（甲基）丙烯酸酯類；丙烯醯基嗎啉、N-乙烯基吡 咯烷酮、N，N-二甲基丙烯醯胺、N-乙烯咔唑、苯乙烯、乙 φ 酸乙烯酯、丙烯腈、三烷氧基乙烯基矽烷等之單官能單體 類；雙酚-A-二（甲基）丙烯酸酯、環氧烷變性雙酚-A-二 (甲基）丙烯酸酯、1,4 -丁二醇二（甲基）丙烯酸酯、 1，6-己二醇二（甲基）丙烯酸酯、1,9·壬二醇二（甲基） 丙烯酸酯、乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲 基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、聚丙二醇 二（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯 、季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基） 〇 丙烯酸酯、雙〔4-(甲基）芳氧基甲基〕三環〔5.2.1.02.6 〕癸烷、雙〔4-(甲基）芳氧基-2-羥基丙氧基苯基〕丙烷 、異佛酮二異氰酸酯變性胺基甲酸乙酯二（甲基）丙烯酸 酯、環己烷二異氰酸酯變性胺基甲酸乙酯二（甲基）丙烯 酸酯、三甲基環己烷二異氰酸酯變性胺基甲酸乙酯（甲基 )丙烯酸酯、三甲基環己烷二異氰酸酯變性胺基甲酸乙酯 (甲基）丙烯酸酯、脂肪族環氧變性（甲基）丙烯酸酯、 寡矽氧烷基二（甲基）丙烯酸酯等之多官能（甲基）丙烯 酸酯類；三烯丙基異三聚氰酸酯、（甲基）丙烯酸乙烯酯 -13- 200948891 、（甲基）丙烯酸烯丙酯等之多官能單體類等。此些之乙 烯性不飽和化合物可單獨或2種以上混合使用。 如此般之感光性樹脂（C )之配合比係，相對於再生 PET粉末（A) 100質量份，爲10~1 00000質量份，更佳 爲30〜1 000質量份。若不滿10質量份，其流動性降低， 'The invention relates to a resin composition for a printed circuit board which is excellent in insulation and heat resistance, and a dry film and a printed circuit board using the same in consideration of the environment [Prior Art] φ In recent years, the viewpoint of environmental issues, and printed circuit boards used in electronic equipment are also required to use materials that have an environmental impact. For example, due to the social problem of the generation of harmful gases such as dioxin during combustion, it is required to use a halogen-based material such as bromine or the like to a halogen-free material or a dye-dye material used for a prepreg or a solder resist film. The conversion. For example, the halogen-free material of the flame-retardant material of the composition for a printed circuit board has been subjected to various reviews (see, for example, Patent Document 1). However, the concern for environmental issues is raised and the environmental impact is further taken into account. On the other hand, since printed circuit boards are used in electronic equipment, they are required to have insulation properties. Further, in the interlayer resin insulating layer of a printed circuit board, since the electronic component is assembled at a high temperature, heat resistance is required. Further, in recent years, with the miniaturization of the pattern of the solder resist film formed on the outermost layer of the printed circuit board, the pattern formation is performed by the photolithography method. At this time, the activity is irradiated by the pattern of the transmissive mask. The energy line forms a pattern, and the resin composition for forming the solder resist film is required to have photocurability. In the case of the photosensitive resin composition, a halogen-free form having an environment of -5 to 200948891 has been proposed (for example, see Patent Document 2). As such, the resin composition for printed circuit boards is required to have both environmental impact and maintenance improvement characteristics. On the other hand, in recent years, PET bottles have been light, transparent, and gas-blocking, and the use of high-strength has increased rapidly. With this, the disposal method has gradually become a social problem. Therefore, various kinds of reviews have been carried out regarding the recycling of PET bottles (see Patent Documents 3 to 5, etc.). However, during the recycling process, the molecular weight of PET is reduced due to the hydrolysis of the ester bond, and the melt viscosity and mechanical strength of PET are reduced. Then, such a decrease in quality is a cause of obstacles to the recycling of PET bottles. Therefore, the state of the recycled PET resin is only used in the field of fibers or industrial materials. Along with the increase in the waste of PET bottles, the new and effective use of recycled PET resin is still being explored. [Patent Document 1] (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. 2000-7974 (A. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei No. 2000-53892 (Patent Document 5) Japanese Patent Application Publication No. 2000-53892 (Summary of the Invention, etc.) -6- 200948891 OBJECTS TO BE SOLVED BY THE INVENTION As described above, the resin composition for a printed circuit board is required to have environmental impact and maintenance improvement characteristics at the same time. Here, the present invention provides an environmental impact that can be considered at the same time. In addition, a resin composition for a printed circuit board and a printed circuit board using the same are used as the object of the invention. Φ [Means for Solving the Problem] In order to solve the above problems, a printed circuit board of one form of the present invention is provided. A resin composition containing regenerated polyethylene terephthalate (A). With such a structure, insulation, heat resistance, and light transmittance are excellent, and environmental effects are considered. Further, it is preferable to prepare a resin composition for a printed circuit board by using a regenerated polyethylene terephthalate fine powder having a mixed average particle diameter of 0.1 to 15 μm as a resin composition for a printed circuit board. The composition can simultaneously obtain good smoothness and insulation of the printed circuit board, and suppress pattern defects in pattern formation. Further, the resin composition for a printed circuit board, the regenerated polyethylene terephthalate (Α) is preferably 0.1 to 75% of the total amount. With such a configuration, it is possible to simultaneously obtain good fluidity, coatability, and formability of the resin composition for a printed circuit board, and to suppress the fragility of the cured product. Further, it is preferable that the resin composition for a printed circuit board contains a thermosetting resin (B) of 200948891. The thermosetting resin (B) can be cured by heating. A good permanent film is formed. The resin composition for a printed circuit board is preferably a photosensitive resin (C). By using a photosensitive resin (C), it can be irradiated with light. hardening The formation of a fine pattern by the photolithography method is possible. Then, the dry film of one embodiment of the present invention is characterized in that it is coated on the substrate with the above-mentioned resin composition for a printed circuit board. Dry film. With such a structure, a dry film excellent in insulation, heat resistance, and light transmittance can be obtained, and by transfer to a printed circuit board, a simple regenerated polyparaic acid B can be formed on a printed circuit board. The resin composition layer of the diester (A) is characterized in that the printed circuit board according to one aspect of the present invention is characterized in that the substrate is formed with a circuit, and at least a portion of the substrate is formed to enable the printing A permanent film which is cured by a resin composition for a circuit board. © With such a configuration, a printed circuit board excellent in insulation and heat resistance can be obtained. Further, a printed circuit board according to one aspect of the present invention is characterized in that: a substrate on which a circuit is formed, and at least a portion of the substrate is provided with a resin for a printed circuit board transferred by the dry film described above The composition is coated with a permanent film after the dried film is hardened. According to this configuration, a printed circuit board having excellent insulation properties and heat resistance and having an environmental impact can be obtained. -8 - 200948891 [Effects of the Invention] The resin composition for a printed circuit board of the present invention and the dry film or printed circuit board using the same can simultaneously take into consideration the influence on the environment and maintain the lifting property. [Embodiment] φ [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described. The resin composition for a printed wiring board of the present embodiment is characterized by containing regenerated polyethylene terephthalate (A). The regenerated polyethylene terephthalate (A) of the present embodiment is not particularly limited as long as it is a polyethylene terephthalate. For example, recycled PET bottles, etc., recycled, crushed, washed, recycled raw materials, or regenerated polyparaic acid obtained from PET bottles or PET films to defective products such as those produced in the manufacturing process. Ethylene glycol raw material. In the thus-regenerated polyethylene terephthalate raw material, it is preferred to use a polymer of ethylene phthalate alone or, depending on the case, a highly crystalline resin containing a small amount of a copolymer. In this case, the crystallinity can be made, for example, 35% or more by heat treatment. Further, a polyester resin, a denatured polyester resin or the like may be melt-mixed. Then, the thus-regenerated polyethylene terephthalate raw material is directly pulverized or slurried by mechanical pulverization or chemical pulverization, and then pulverized by using a jet mill or the like. The dispersion treatment or various classification devices are carried out to make the average particle diameter as 〇·1~15μιη used as 200948891. When the average particle diameter is less than 〇·1 μιη, the surface energy becomes high and it becomes easy to aggregate, and the smoothness and insulation of the printed circuit board cannot be sufficiently obtained due to the influence of the aggregate. On the other hand, if the average particle diameter exceeds 15 μm, the smoothness of the printed circuit board is impaired, and when the solder resist film is formed, defects due to defects of the pattern are caused. More preferably, the average particle size is 1 to 12 μm. Here, in order to prevent the above surface energy from becoming high, it is easy to aggregate, and it is also possible to operate in a slurry state in which the organic solvent is dispersed in advance. The average particle diameter at this time is not limited to the above, and it can also be used in a more subtle state. By repeating such fine pulverization, the PET is mixed with a thermosetting component, a photosensitive component, or the like to form a resin composition for a printed circuit board. In this case, the mixing ratio of the regenerated polyethylene terephthalate (A) is preferably from 0.1 to 75% by weight based on the total amount of the composition. If the environmental impact is taken into consideration, the mixing ratio is preferably more than 1% by weight. On the other hand, when it exceeds 60% by weight, the cured product of the insulating composition becomes brittle, and the fluidity of the insulating composition is lowered, which may cause problems in coating and molding. More preferably, it is 1 to 60% by weight. In addition to the regenerated poly(ethylene terephthalate (A), the resin composition for a printed wiring board of the present embodiment may contain various components such as a thermosetting component and a photosensitive component. As long as it is suitable for a printed circuit board, such as insulation, heat resistance, etc., it is not limited to a specific component, and it is preferable to select tm. Basically, various forms containing a thermosetting component or a photosensitive component or both components can be proposed. In general, when the thermosetting resin composition contains regenerated polyethylene terephthalate (A) and thermosetting-10-200948891 resin (B): a photocurable resin composition, it contains When the regenerated polyethylene terephthalate (A), the photosensitive resin (C), and the photopolymerization initiator (D) are used as a photo-curable thermosetting resin composition, the regenerated poly-pair is contained. Ethylene phthalate (A), thermosetting resin (B), photosensitive resin (C), photopolymerization initiator (D), and carboxyl group-containing resin (E). Then, the type of each of these components is appropriately selected, and by using a resin composition for a printed circuit board which optimizes the blending ratio, a cured product having desired properties can be obtained. The resin composition for a printed circuit board can be made to contain a thermosetting catalyst (F), a chelating agent (G), an organic solvent (H), or the like as needed. In the present embodiment, the thermosetting resin (B) is not particularly limited as long as it is excellent in the case where a cured product such as insulating properties is used for a printed circuit board, and specifically, a ring is specifically mentioned. Oxygen resin, phenol, urethane resin, polyester resin, hydroxyl group, amine group or carboxyl group-containing polyethyl urethane, polyester, polycarbonate, polyalcohol, phenoxy resin, acrylic Polymer resin, vinyl resin, polyimine, polyamidimide, oxazine resin, cyanate resin, oxycyclobutane compound, polyisocyanate, blocked isocyanate, carbodiimide (compound) resin, Oxazoline (compound) resin and the like. These may be used alone or in combination of two or more types. The blending ratio of the thermosetting resin (B) is from 10 to 100,000 parts by mass, more preferably from 30 to 100 parts by mass, per 100 parts by mass of the recycled PET powder (A). If it is less than 10 parts by mass, the fluidity is lowered. 'Coating or forming becomes difficult, and the mechanical strength is lowered. On the other hand, -11 - 200948891, if it exceeds 100,000 parts by mass, it is meaningless and unsatisfactory from the viewpoint of considering environmental impact. The photosensitive resin (C) is not particularly limited as long as it is a compound which undergoes radical polymerization by an ethylenic unsaturated double bond by irradiation with an active energy ray, and examples thereof include a (meth) acrylate compound and an unsaturated group. A polyester-based compound, an unsaturated urethane-based compound, a styrene-based compound, a butadiene-based compound, or the like. Among such ethylenically unsaturated compounds, a (meth) acrylate type compound is particularly preferable, and the (meth) acrylate type compound is monofunctional, polyfunctional, and monomeric, oligomer (pre Any one of the polymers may have a functional group other than an acryloyl group (methacryloyl group). Specific examples thereof include a substituted or unsubstituted aliphatic acrylate, an alicyclic acrylate, an aromatic acrylate, and a monomer such as an ethylene oxide-modified acrylate, or an epoxy acrylate or an amine. Oligomers such as ethyl acrylate, polyester acrylate, polyether acrylate, polyalcohol acrylate, alkyd acrylate, melamine acrylate, polyoxy acrylate, polybutadiene acrylate, and the like, and Corresponding to such methacrylates and the like. These may be used alone or in combination of two or more types. In order to increase the reactivity of the photosensitive resin (C), a photoreactive monomer may be added. Specific examples thereof include butoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, and hydroxyethyl (meth)acrylate. Hydroxypropyl acrylate, glycerol (meth) acrylate, 4-(methyl) aryloxytricyclo [ 5.2.1.02.6] decane, isodecyl (meth) acrylate, (methyl )C-12- 200948891 Isodecyl enoate, phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) ) butyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 4-(methyl) aryloxy alkyl phosphate, r- (a Monofunctional (meth) acrylates such as aryloxyalkyltrialkoxydecane; acryloylmorpholine, N-vinylpyrrolidone, N,N-dimethylpropenamide, N-ethylene Monofunctional monomers such as carbazole, styrene, vinyl ethoxide, acrylonitrile, trialkoxyvinyl decane, etc.; bisphenol-A-di(meth)acrylic acid , alkylene oxide-denatured bisphenol-A-di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1, 9. decanediol di(meth) acrylate, ethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(methyl)decyl acrylate, bis[4-(methyl)aryl Oxymethylmethyl]tricyclo[5.2.1.02.6]decane, bis[4-(methyl)aryloxy-2-hydroxypropoxyphenyl]propane, isophorone diisocyanate denatured urethane Ester di(meth)acrylate, cyclohexane diisocyanate denatured urethane di(meth)acrylate, trimethylcyclohexane diisocyanate denatured urethane (meth)acrylate, three Methylcyclohexane diisocyanate denatured urethane (meth) acrylate, aliphatic epoxidized (meth) acrylate , polyfunctional (meth) acrylates such as oligooxyalkyl di(meth) acrylates; triallyl isocyanurate, vinyl (meth) acrylate-13- 200948891, (A A polyfunctional monomer such as allyl acrylate or the like. These ethylenically unsaturated compounds may be used singly or in combination of two or more kinds. The blending ratio of the photosensitive resin (C) is from 10 to 100,000 parts by mass, more preferably from 30 to 1,000 parts by mass, per 100 parts by mass of the recycled PET powder (A). If it is less than 10 parts by mass, its fluidity will decrease, '

塗佈或形成則會變得困難，且機械性強度降低。另一方面 ，若超過1 00000質量份，從考慮到對環境的影響的觀點 來看，則無意義，且不理想。 Q 作爲光聚合起始劑（D)，可使用選自肟酯系光聚合 起始劑、α-胺苯乙酮系光聚合起始劑、及醯基滕氧化物 系光聚合起始劑所成群之1種或2種以上。 作爲肟酯系光聚合起始劑，具體而言，市販品中可舉 出 Ciba Specialty Chemicals 公司製之 CGI-325、Irgacure OXEOl、Irgacure OXE02 等、ADEKA 公司製 N-1919。 作爲α-胺苯乙酮系光聚合起始劑，具體而言，可舉 出2-甲基-1-〔4-(甲硫）苯基〕-2-嗎啉基丙酮-1、2-苄 0 基-2-二甲基胺-1-(4-嗎啉基苯基）-丁烷-1-酮、2-(二甲 基胺）-2-〔 （4-甲基苯基）甲基〕-l-〔 4-(4-嗎啉基）苯 基〕-1-丁酮、Ν,Ν·二甲基胺苯乙嗣等。作爲市販品，可 舉出 Ciba Specialty Chemicals 公司製之 Irgacure 907、 Irgacure369 、 Irgacure379 等 ° 作爲醯基膦氧化物系光聚合起始劑，具體而言，可舉 出2,4,6-三甲基苄醯基二苯基膦氧化物、雙（2,4,6-三甲 基苄醯基）-苯基膦氧化物、雙（2,6-二甲氧基苄醯基）- -14- 200948891 2，4,4-三甲基-戊基膦氧化物等。作爲市販品，可舉出 BASF 公司製之 Lucirin TPO、Ciba Specialty Chemicals 公 司製之Irgacure 819等。 此般之光聚合起始劑（D)之配合比爲，相對於感光 ' 性樹脂（C) 100質量份只要係〇.〇1 ~50質量份即可。若不 滿〇.〇1質量份，印刷電路板所用之銅上之光硬化性則不 足，因有塗膜剝離，耐藥品性等之塗膜特性降低等故不理 φ 想。另一方面，若超過50質量份，光聚合起始劑（D)之 阻焊塗膜表面下之光吸收變得激烈，而有深部硬化性降低 之傾向。更佳者爲〇.5~3 0質量份。 更進一步，對本實施形態之印刷電路板用樹脂組成物 ，可使用上述化合物以外之光聚合起始劑、光開始助劑及 增感劑等。例如，可舉出安息香化合物、苯乙酮化合物、 蒽醌化合物、噻噸酮化合物、縮酮化合物、二苯基酮化合 物、咕噸酮化合物、及3級胺化合物等。 〇 作爲安息香化合物，具體而言，可舉出安息香、安息 香甲醚、安息香乙醚、安息香異丙醚等。 作爲苯乙酮化合物，具體而言，可舉出苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、 1，1-二氯苯乙酮等。 作爲蒽醌化合物，具體而言，可舉出2-甲基蒽醒、2_ 乙基蒽醌、2-t-丁基蒽醌、1-氯蒽醌等。 作爲噻噸酮化合物，具體而言，可舉出2,4_二甲基唾 噸酮、2，4-二乙基噻噸酮、2-氯噻噸酮、2，4-二異丙基噻 -15- 200948891 噸酮等。 作爲縮酮化合物，具體而言，可舉出苯乙酮二乙基縮 酮、苄基二甲基縮酮等。 作爲二苯基酮化合物，具體而言，可舉出二苯基酮、 4-苄醯基二苯基硫化物、4-苄醯基-4’-甲基二苯基硫化物 、4-苄醯基-4，-乙基二苯基硫化物、4-苄醯基-4’·丙基二苯 基硫化物等。 作爲3級胺化合物，具體而言，可舉出乙醇胺化合物 、具有二烷基胺苯構造之化合物、例如，4,4’·二甲胺二苯 基酮（日本曹達公司製 NissoCure-MABP) 、4,4’-二乙胺 二苯基酮（保土谷化學公司製EAB )等之二烷基胺二苯基 酮、7-(二乙胺）-4-甲基-2H-1-苯併吡喃-2-酮（7-(二乙 胺）-4 _甲基薰草素）等之二烷基胺基含有薰草素化合物、 4 -二甲基胺安息香酸乙酯（日本化藥公司製Kayacure-EPA )、2-二甲基胺安息香酸乙醋 （Internati〇nalBio-Synthetics 公司製 Quantacure DMB) 、4 - 一 甲基胺安息香 酸（η-丁氧基）乙基（InternationalBio- Synthetics 公司 製Quantacure BEA) 、p-—甲基胺安息香酸異戊基乙基 酯（日本化藥公司製Kayacure 一 DMBI ) 、4_二甲基胺安 息香酸2 -乙基己酯（Van 公司製Es〇丨〇1 507) 、4,4’- 二乙胺二苯基酮（保土谷化學公司製EAB )等。 此些化合物之中，特別係以噻噸酮化合物及3級胺化 合物爲佳。含有噻噸酮化合物一事’從深部硬化性之面來 看係爲理想，其中以2,4_二甲基噻噸酮、2，4_二乙基噻噸 -16- 200948891 酮、2-氯噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮化合物 爲佳。 作爲3級胺化合物，以具有二烷基胺苯構造之化合物 爲佳，其中則以二烷基胺二苯基酮化合物，最大吸收波長 在3 50〜4 1 Onm之含二烷基胺基之薰草素化合物爲特佳。作 爲二烷基胺二苯基酮化合物，以4,4’-二乙胺二苯基酮， 其毒性低爲佳。最大吸收波長在350〜410nm之含二烷基胺 0 基之薰草素化合物，因其最大吸收波長在紫外線領域之中 ，不待言其染色爲少，爲無色透明之感光性組成物，使用 染色顏料，成爲可提供反映出染色顏料自身之顏色的染色 防焊膜。特別係以7-(二乙胺）-4-甲基-2H-1-苯倂吡喃-2-酮，相對於波長爲400〜41 Onm之雷射光，展現出優良之 增感效果而爲佳。 此些之光聚合起始劑、光開始助劑及增感劑可單獨或 2種類以上混合使用》 〇 又，作爲含羧基樹脂（E)，可使用於分子中具有羧 基之各種樹脂化合物，可賦予鹼顯像性。作爲此般之含羧 基樹脂（E)，特別係，以分子中具有乙烯性不飽和雙鍵 之含羧基之感光性樹脂（E -1 )，由光硬化性或耐顯像性 之面觀之更爲佳。接著，其不飽和雙鍵以丙烯酸或甲基丙 烯酸或其之源自衍生物者爲佳。 作爲含羧基樹脂（E )之具體例，以下所列舉之化合 物爲佳。尙，（甲基）丙烯酸酯係指，將丙烯酸酯、甲基 丙烯酸酯及其之混合物所總稱之用語，關於其他之類似的 -17- 200948891 表現也爲相同。 (1) 藉由（甲基）丙烯酸與不飽和基含有物之共聚 合所得之含羧基樹脂。 (2) 藉二異氰酸酯與含羧基之二醇（dialcohol)化 合物及二元醇（diol )化合物之加成聚合反應所成之含羧 酸之胺基甲酸乙酯樹脂。 (3) 藉二異氰酸酯與2官能環氧（甲基）丙烯酸酯 或其部分酸酐變性物及含羧基之二醇化合物及二元醇化合 魏 物之加成聚合反應所成之含感光性羧酸之胺基甲酸乙酯樹 脂。 (4) 添加了上述之（2)或（3)之樹脂的合成中於 分子内具有1個羥基與1個以上之（甲基）丙烯酸基之化 合物的在末端含有（甲基）丙烯酸化羧酸之胺基甲酸乙酯 樹脂。 (5) 添加了上述（2)或（3)之樹脂的合成中於分 子内具有異氰酸酯基與1個以上之（甲基）丙烯酸基之化 〇 合物的在末端含有（甲基）丙烯酸化羧酸之胺基甲酸乙酯 樹脂。 (6) 使2官能及多官能（固形）環氧樹脂與（甲基 )丙烯酸反應，存在於側鏈之羥基中添加二質子酸酐的含 感光性羧基樹脂。 (7) 使將2官能（固形）環氧樹脂之經基更進—步 以環氧氯丙烷進行環氧化之多官能環氧樹脂與（甲基）丙 烯酸反應，使生成之在羥基添加了二質子酸酐之含感光性 -18- 200948891 羧基樹脂。 (8) 使2官能氧環丁烷樹脂與二羧酸反應，使生成1 級之羥基添加了二質子酸酐之含羧酸聚酯樹脂。 (9) 對上述樹脂進而添加於1分子内具有1個之環 氧基與1個以上之（甲基）丙烯酸基的化合物而成之含感 ' 光性羧基樹脂。 藉由含有此些之含羧基樹脂（E)，由於主幹高分子 ❹ （backbone polymer)之側鏈具有多數的遊離殘基，而藉 由稀釋鹼水溶液的顯像則成爲可能。 又，含羧基樹脂（E)之酸價，以40〜2 0 0mgKOH/ g 爲佳。若含羧基樹脂之酸價不滿40mgKOH/ g則鹼顯像變 得困難，另一方面，若超過200mgKOH/ g，顯像液所造 成的曝光部之溶解則會進行，使線路成爲比必要以上還窄 ，根據情況，會無法區別曝光部與未曝光部，在顯像液中 溶解剝離，正常光阻圖型之描畫則變得困難。以 〇 45~120mgKOH/g 爲更佳。 又，含羧基樹脂（E)之重量平均分子量，雖依據樹 脂骨架而有所不同，一般而言以在2,000〜1 50,000、更進 一步在5,000~ 1 00,000之範圍者爲佳。若重量平均分子量 不滿2,000，有無黏性能拙劣之情形，曝光後之塗膜之耐 濕性變差，於顯像時產生膜減少，有解析度大幅變差之情 形。另一方面，若重量平均分子量超過150,000，有顯像 性顯著變差之情形，有儲藏安定性拙劣之情形。 此般之含羧基樹脂（E)之配合比爲，全組成物中， -19- 200948891 以20〜60質量％爲佳。比上述範圍爲少之情況，因塗膜強 度會降低故不理想。另一方面，若比上述範圍爲多時，黏 性變高塗佈性等則會降低。更佳爲3 0~5 0質量％。 此般之含羧基樹脂可單獨或2種類以上混合使用。 又，作爲熱硬化觸媒（F)，可使用熱硬化性樹脂之 可促進硬化之樹脂，作爲此般之熱硬化觸媒，具體而言可 舉出，咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪 唑、2-苯基咪唑、4-苯基咪唑、1-氰乙基-2-苯基咪唑、1-(2-氰乙基）-2-乙基-4-甲基咪唑等之咪唑衍生物；二氰 胺、苄基二甲胺、4-(二甲基胺）-Ν,Ν-二甲基苄基胺、4-甲氧基-Ν，Ν-二甲基苄基胺、4-甲基-Ν，Ν-二甲基苄基胺等 之胺化合物、已二酸二醯肼、癸二酸二醯肼等之肼化合物 ;三苯基膦等之磷化合物等，又作爲市售者，可舉出例如 四國化成工業公司製的 2ΜΖ-Α、2ΜΖ-ΟΚ、2ΡΗΖ、 2Ρ4ΒΗΖ、2Ρ4ΜΗΖ (任一皆爲咪唑系化合物之商品名）、 San-apro 公司製的 U-CAT3503N、U-CAT3502T (任一皆爲 二甲胺之嵌段異氰酸酯化合物之商品名）、DBU、DBN、 U-CATSA102、U-CAT5002 (任一皆爲二環式脒化合物及 其鹽）等。特別係’並限定於此些者，只要係促進環氧樹 脂或氧環丁烷化合物之熱硬化觸媒，或環氧基及/或氧環 丁烷基與羧基之反應者即可，此些可單獨或2種類以上混 合使用。 又，也可使用胍胺、乙胍胺、苯代胍胺、三聚氰胺、 2,4-二胺基-6-甲基丙烯醯基氧乙基-S-三嗪、2_乙烯基-4,6- -20- 200948891 二胺基-S-三嗪' 2-乙烯基-4,6-二胺基-S-三嗓.異三聚氰 酸加成物、2,4-二胺基-6-甲基丙烯醯基氧乙基-S-三嗪· 異三聚氰酸加成物等之S-三嗪衍生物，將此些也可作爲密 著性賦予劑運用之化合物與熱硬化觸媒倂用爲佳。 此些熱硬化觸媒之配合比，通常之量之比則足夠，例 如相對於熱硬化性成分（B)或含羧基樹脂（E) 100質量 份，以0.1-20質量份爲佳。更佳爲0.5〜15.0質量份。 〇 塡充劑（G)，爲提升其塗膜之物理性強度等可依據 需要使用。作爲此般之塡充劑（G)，可使用無機或有機 塡充劑，特別係硫酸鋇、球狀二氧化矽及滑石可適宜使用 。又，如使用於預浸體、絕緣薄片、附樹脂銅箔般之層間 絕緣層之場合時，可使用玻璃布或無機、有機纖維不織布 。更進一步，爲了得到白色之外觀或難燃性，也可將氧化 鈦或金屬氧化物、氫氧化鋁等之金屬氫氧化物作爲體質顏 料塡充劑使用。 ® 塡充劑（G )之配合比，以組成物全體量之75重量％ 以下爲佳。塡充劑之配合比，若超過組成物全體量75重 量％之情況時，絕緣組成物的黏度變高，而塗佈、成形性 降低，硬化物變脆。更佳爲0.1〜6 0重量％。 又，有機溶劑（Η )係用於，熱硬化性樹脂（B )、感 光性樹脂（C)、含羧基樹脂（Ε)之合成或組成物之調整 ’或絕緣組成物之成型、塗佈時之黏度調整而被使用。 作爲此般之有機溶劑，可舉出酮類、芳香族烴類、乙 二醇醚類、乙二醇醚乙酸鹽類、酯類、醇類、脂肪族烴、 -21 - 200948891 石油系溶劑等。更具體而言，可舉出甲基乙基酮、環 等之酮類；甲苯、茬、四甲基苯等之芳香族烴類；溶 、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、 卡必醇、丙二醇單甲基醚、二丙二醇單甲基醚、二丙 二乙基醚、三乙二醇單乙基醚等之乙二醇醚類；乙酸 、乙酸丁酯、二丙二醇甲基醚乙酸酯、丙二醇甲基醚 酯、丙二醇乙基醚乙酸酯、丙二醇丁基醚乙酸酯、乳 酯、乳酸乙酯、乳酸丁酯等之酯類；乙醇、丙醇、乙 、丙二醇等之醇類；辛烷、癸烷等之脂肪族烴；石油 石油腦、加氫石油腦、溶劑油等之石油系溶劑等。此 有機溶劑可單獨或2種類以上混合使用。 更可依據需要，可使用酞菁•藍、酞菁•綠、碘 、雙偶氮黃、結晶紫、氧化鈦、碳黑、萘黑等之公知 之染色劑（顏料、染料、色素之任一皆可）。 於以下例舉此些之染色劑。 〔青色染色劑〕 青色染色劑有酞菁系、蒽醌系，顏料系有分類於 (Pigment)之化合物，具體而言，如可舉出具有下 色指數（C.I. ; The Society of Dyers and Colourists 發行）號碼者。Coating or forming becomes difficult and the mechanical strength is lowered. On the other hand, if it exceeds 100,000 parts by mass, it is meaningless and unsatisfactory from the viewpoint of considering the influence on the environment. Q, as the photopolymerization initiator (D), a photopolymerization initiator selected from the group consisting of an oxime ester photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, and a thiophene oxide photopolymerization initiator can be used. One or two or more of the groups. Specific examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXEO1, Irgacure OXE02 manufactured by Ciba Specialty Chemicals Co., Ltd., and N-1919 manufactured by ADEKA Co., Ltd.. Specific examples of the α-aminoacetophenone photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2- Benzyl0-dimethylamine-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamine)-2-[(4-methylphenyl) Methyl]-l-[4-(4-morpholinyl)phenyl]-1-butanone, hydrazine, hydrazine dimethylamine phenethyl hydrazine and the like. As a commercially available product, Irgacure 907, Irgacure 369, Irgacure 379, etc., manufactured by Ciba Specialty Chemicals Co., Ltd., may be mentioned as a mercaptophosphine oxide photopolymerization initiator, and specific examples thereof include 2,4,6-trimethyl. Benzylidene diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)--14- 200948891 2,4,4-Trimethyl-pentylphosphine oxide, etc. As a commercial product, Lucirin TPO manufactured by BASF Corporation and Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. may be mentioned. The blending ratio of the photopolymerization initiator (D) is preferably from 1 to 50 parts by mass based on 100 parts by mass of the photosensitive resin (C). If it is less than 1 part by mass, the photocurability of the copper used for the printed circuit board is insufficient, and the film properties such as peeling of the coating film and chemical resistance are deteriorated. On the other hand, when it exceeds 50 parts by mass, the light absorption under the surface of the solder resist coating film of the photopolymerization initiator (D) becomes intense, and the deep hardenability tends to be lowered. More preferably, it is 55 to 30 parts by mass. Furthermore, as the resin composition for a printed wiring board of the present embodiment, a photopolymerization initiator, a photo-starting agent, a sensitizer, or the like other than the above compounds can be used. For example, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a diphenyl ketone compound, a xanthone compound, a tertiary amine compound, and the like can be given. 〇 Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone. 1,1-dichloroacetophenone and the like. Specific examples of the ruthenium compound include 2-methyl oxime, 2-ethyl oxime, 2-t-butyl fluorene, and 1-chloropurine. Specific examples of the thioxanthone compound include 2,4-dimethylstilbone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropyl. Thio-15- 200948891 tons of ketone and so on. Specific examples of the ketal compound include acetophenone diethyl ketal and benzyl dimethyl ketal. Specific examples of the diphenyl ketone compound include diphenyl ketone, 4-benzyl fluorenyl diphenyl sulfide, 4-benzyl fluorenyl 4'-methyl diphenyl sulfide, and 4-benzyl. Mercapto-4,-ethyldiphenyl sulfide, 4-benzylindolyl-4'-propyldiphenyl sulfide, and the like. Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylamine benzene structure, for example, 4,4′·dimethylamine diphenyl ketone (NissoCure-MABP manufactured by Nippon Soda Co., Ltd.). Dialkylamine diphenyl ketone, 7-(diethylamine)-4-methyl-2H-1-benzoate, etc., such as 4,4'-diethylamine diphenyl ketone (EAB manufactured by Hodogaya Chemical Co., Ltd.) A dialkylamine group such as pyran-2-one (7-(diethylamine)-4 _methylhumoxin) contains a xanthanin compound, 4-dimethylamine benzoic acid ethyl ester (Japanese chemical) Kayacure-EPA, 2-dimethylamine benzoic acid ethyl acetate (Quantacure DMB, manufactured by Internati〇nal Bio-Synthetics, Inc.), 4-methylamine benzoic acid (η-butoxy)ethyl (International Bio- Synthetics) Quantacure BEA), p-methylamine benzoate isoamylethyl ester (Kayacure-DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamine benzoate 2-ethylhexyl ester (Es manufactured by Van Co., Ltd.) 〇丨〇1 507), 4,4'-diethylamine diphenyl ketone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like. Among these compounds, a thioxanthone compound and a tertiary amine compound are particularly preferred. The case of containing thioxanthone compounds is ideal from the point of deep hardenability, in which 2,4-dimethylthioxanthone, 2,4-diethylthioxene-16-200948891 ketone, 2-chloro A thioxanthone compound such as thioxanthone or 2,4-diisopropylthioxanthone is preferred. As the tertiary amine compound, a compound having a dialkylamine benzene structure is preferred, wherein a dialkylamine diphenyl ketone compound having a maximum absorption wavelength of 3 50 to 4 1 Onm containing a dialkylamine group is preferred. Kaempferol compounds are particularly good. As the dialkylamine diphenyl ketone compound, 4,4'-diethylamine diphenyl ketone is preferred, and its toxicity is low. A scopolamine compound containing a dialkylamine 0 group having a maximum absorption wavelength of 350 to 410 nm, because its maximum absorption wavelength is in the ultraviolet field, it is said that the dyeing is small, and it is a colorless and transparent photosensitive composition, and dyeing is used. The pigment becomes a dyed solder resist film that reflects the color of the dyed pigment itself. In particular, 7-(diethylamine)-4-methyl-2H-1-benzopyran-2-one exhibits excellent sensitizing effect with respect to laser light having a wavelength of 400 to 41 Onm. good. The photopolymerization initiator, the photoinitiator, and the sensitizer may be used alone or in combination of two or more kinds. Further, as the carboxyl group-containing resin (E), various resin compounds having a carboxyl group in the molecule may be used. Give alkali developability. In particular, the carboxyl group-containing resin (E) is a photosensitive resin (E -1 ) having a carboxyl group having an ethylenically unsaturated double bond in the molecule, and is photohardenable or developable. Better. Next, it is preferred that the unsaturated double bond is acrylic acid or methacrylic acid or a derivative thereof. As a specific example of the carboxyl group-containing resin (E), the compounds listed below are preferred.尙, (meth) acrylate means a term generally referred to as acrylate, methacrylate and mixtures thereof, and the same is true for other similar -17-200948891. (1) A carboxyl group-containing resin obtained by copolymerization of (meth)acrylic acid and an unsaturated group-containing material. (2) A carboxylic acid-containing urethane resin obtained by addition polymerization of a diisocyanate with a dialohol compound and a diol compound. (3) A photosensitive carboxylic acid formed by addition polymerization of a diisocyanate with a difunctional epoxy (meth) acrylate or a partial acid anhydride denature thereof, a carboxyl group-containing diol compound, and a diol compound A urethane resin. (4) In the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth)acrylic groups in the molecule is contained at the terminal (meth)acrylated carboxylate. Acid urethane resin. (5) In the synthesis of the resin of the above (2) or (3), the (meth)acrylic acid compound having an isocyanate group and one or more (meth)acrylic acid groups in the molecule is contained in the synthesis. Carbamate urethane resin. (6) A photosensitive carboxyl group-containing resin obtained by reacting a bifunctional and polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a diproton acid anhydride to a hydroxyl group of a side chain. (7) The polyfunctional epoxy resin which is epoxidized by epichlorohydrin is further reacted with (meth)acrylic acid to form a bifunctional (solid) epoxy resin, and the resulting hydroxyl group is added. The photoacid anhydride contains photosensitivity -18- 200948891 carboxyl resin. (8) A carboxylic acid-containing polyester resin obtained by reacting a bifunctional oxygen cyclobutane resin with a dicarboxylic acid to form a first-order hydroxyl group to which a diproton anhydride is added. (9) A photosensitive carboxy resin containing a compound having one epoxy group and one or more (meth)acrylic groups in one molecule. By containing such a carboxyl group-containing resin (E), since the side chain of the backbone polymer has a large number of free residues, it is possible to develop by diluting an aqueous alkali solution. Further, the acid value of the carboxyl group-containing resin (E) is preferably from 40 to 200 mgKOH/g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH/g, the dissolution of the exposed portion due to the developing solution proceeds, and the line becomes more than necessary. It is narrow, and depending on the situation, it is impossible to distinguish between the exposed portion and the unexposed portion, and it is dissolved and peeled off in the developing liquid, and the drawing of the normal photoresist pattern becomes difficult. It is preferably 〇45~120mgKOH/g. Further, the weight average molecular weight of the carboxyl group-containing resin (E) varies depending on the resin skeleton, and is generally preferably in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 1,000,000. If the weight average molecular weight is less than 2,000, there is a case where the viscosity is poor, and the moisture resistance of the coating film after exposure is deteriorated, and the film is reduced at the time of development, and the resolution is greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, there is a case where the visibility is remarkably deteriorated, and there is a case where the storage stability is poor. The compounding ratio of the carboxyl group-containing resin (E) is preferably 20 to 60% by mass in the total composition, -19 to 200948891. When the ratio is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when it is more than the above range, the viscosity becomes high and the coating property and the like are lowered. More preferably, it is 30 to 50% by mass. Such a carboxyl group-containing resin may be used singly or in combination of two or more kinds. In addition, as the thermosetting catalyst (F), a thermosetting resin which can promote curing can be used. As such a thermosetting catalyst, specifically, imidazole, 2-methylimidazole, and 2- are mentioned. Ethyl imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2 -imidazole derivatives such as ethyl-4-methylimidazole; dicyanamide, benzyldimethylamine, 4-(dimethylamine)-oxime, fluorene-dimethylbenzylamine, 4-methoxy - an anthracene compound such as hydrazine, hydrazine-dimethylbenzylamine, 4-methyl-hydrazine, hydrazine-dimethylbenzylamine or the like, adipic acid dihydrazine, azelaic acid diterpene or the like; For example, a product such as a triphenylphosphine compound or the like, which is a product of an imidazole compound, which is manufactured by Shikoku Kasei Kogyo Co., Ltd., is commercially available, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ. Name), U-CAT3503N, U-CAT3502T (any trade name of dimethylamine block isocyanate compound) manufactured by San-apro Co., Ltd., DBU, DBN, U-CATSA102, U-CAT5002 (all are Bicyclic guanidine compound and its salt)In particular, 'and limited to these, as long as it promotes the thermosetting catalyst of epoxy resin or oxycyclobutane compound, or the reaction of epoxy group and/or oxycyclobutane group with carboxyl group, such They may be used alone or in combination of two or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-4 can also be used. 6- -20- 200948891 Diamino-S-triazine '2-vinyl-4,6-diamino-S-triazine. Iso-cyanuric acid adduct, 2,4-diamino- An S-triazine derivative such as a 6-methacryl oxiranyloxyethyl-S-triazine·isocyanuric acid addition product, and a compound which can also be used as an adhesion imparting agent and thermosetting Catalyst is better. The mixing ratio of the thermosetting catalyst is usually a sufficient ratio, for example, 0.1 to 20 parts by mass based on 100 parts by mass of the thermosetting component (B) or the carboxyl group-containing resin (E). More preferably, it is 0.5 to 15.0 parts by mass.塡 The chelating agent (G) can be used as needed to increase the physical strength of the coating film. As such a chelating agent (G), an inorganic or organic chelating agent can be used, and in particular, barium sulfate, spheroidal cerium oxide and talc can be suitably used. Further, when it is used for a prepreg, an insulating sheet, or an interlayer insulating layer such as a resin-coated copper foil, a glass cloth or an inorganic or organic fiber nonwoven fabric can be used. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, a metal oxide or aluminum hydroxide may be used as a body pigment sizing agent. The compounding ratio of the filler (G) is preferably 75% by weight or less based on the total amount of the composition. When the blending ratio of the enthalpy is more than 75 wt% of the total amount of the composition, the viscosity of the insulating composition becomes high, and the coating and moldability are lowered, and the cured product becomes brittle. More preferably, it is 0.1 to 60% by weight. Further, the organic solvent (Η) is used for the synthesis of a thermosetting resin (B), a photosensitive resin (C), a carboxyl group-containing resin (Ε), or the composition of the composition or the molding of the insulating composition. The viscosity is adjusted and used. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and -21 - 200948891 petroleum solvents. . More specifically, ketones such as methyl ethyl ketone and ring; aromatic hydrocarbons such as toluene, hydrazine, and tetramethylbenzene; and soluble, methyl cellosolve, butyl cellosolve, and carbitol are mentioned. Glycol ethers such as methyl carbitol, carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene diethyl ether, triethylene glycol monoethyl ether; acetic acid, acetic acid Ester of butyl ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether ester, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, lactate, ethyl lactate, butyl lactate, etc.; An alcohol such as propanol, ethylene or propylene glycol; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum petroleum brain, hydrogenated petroleum brain or solvent oil. These organic solvents may be used singly or in combination of two or more kinds. Further, any known dye (pigment, dye, or pigment) such as phthalocyanine blue, phthalocyanine, green, iodine, bisazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, or the like can be used. Can be). These dyeing agents are exemplified below. [Cyan dye] Cyan dyes are phthalocyanines and anthraquinones, and pigments are classified into (Pigment) compounds. Specifically, they have a color index (CI; The Society of Dyers and Colourists ) number.

Pigment Blue 15、Pigment Blue 15:1、Pigment Blue 、Pigment Blue 15:3、Pigment Blue 15:4、Pigment 15:6、Pigment Blue 16、Pigment Blue 60 ' 己酮 纖劑 丁基 二醇 乙酯 乙酸 酸甲 二醇 醚、 等之 •綠 慣用 顏料 述之 公司 15:2 Blue -22- 200948891 作爲染料系可使用Pigment Blue 15, Pigment Blue 15:1, Pigment Blue, Pigment Blue 15:3, Pigment Blue 15:4, Pigment 15:6, Pigment Blue 16, Pigment Blue 60 'hexanone fiber butyl glycol ethyl acetate acetic acid Methyl diol ether, etc. • Green Conventional Pigment Company 15:2 Blue -22- 200948891 Can be used as a dye system

Solvent Blue 35 、 Solvent Blue 45 、 Solvent Blue 63 、Solvent Blue 35, Solvent Blue 45, Solvent Blue 63,

Solvent Blue 68、Solvent Blue 70 、Solvent Blue 83、 Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、 Solvent Blue 101、Solvent Blue 104、Solvent Blue 122、 Solvent Blue 136、Solvent Blue 67、Solvent Blue 70 等。 上述以外也可使用以金屬取代或無取代之酞菁化合物。 〇 〔綠色染色劑〕 作爲綠色染色劑，同樣地有酞菁系、蒽醌系、茈系， 具體而言可使用 Pigment Green 7、Pigment Green 36、 Solvent Green 3 、 Solvent Green 5 、 Solvent Green 20 、 Solvent Green 28等。此些以外也可使用以金屬取代或無 取代之酞菁化合物。 © 〔黃色染色劑〕 作爲黃色染色劑，有單偶氮系、雙偶氮系、縮合偶氮 系、苯並咪唑酮系、異吲哚林酮系、蒽醌系等，具體而言 可舉出以下者。 系 醌 蒽Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 101, Solvent Blue 104, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, and the like. A phthalocyanine compound substituted with or without a metal may also be used in addition to the above. 〇 [Green dye] As a green dye, similarly, there are phthalocyanine, lanthanide, and lanthanide. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 and so on. A phthalocyanine compound substituted with or without a metal may also be used in addition to these. © [Yellow coloring agent] Examples of the yellow coloring agent include a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, and the like. The following are available. Department 醌 蒽

Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193 ' Pigment Yellow 147 ' Pigment Yellow 199、Pigment Yellow 202 -23- 200948891 (異吲哚林酮系）Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193 ' Pigment Yellow 147 ' Pigment Yellow 199, Pigment Yellow 202 -23- 200948891 (isoindolone)

Pigment Yellow 110 、 Pigment Yellow 10 9 、 Pigment Yellow 139 ' Pigment Yellow 179 ' Pigment Yellow 185 (縮合偶氮系）Pigment Yellow 110 , Pigment Yellow 10 9 , Pigment Yellow 139 ' Pigment Yellow 179 ' Pigment Yellow 185 (condensed azo)

Pigment Yellow 93 ' Pigment Yellow 94 ' Pigment Yellow 95、Pigment Yellow 128 ' Pigment Yellow 155 ' Pigment Yellow 166、Pigment Yellow 180 (苯並咪唑酮系）Pigment Yellow 93 ' Pigment Yellow 94 ' Pigment Yellow 95, Pigment Yellow 128 ' Pigment Yellow 155 ' Pigment Yellow 166, Pigment Yellow 180 (benzimidazolone)

Pigment Yellow 120 、 Pigment Yellow 151 、 PigmentPigment Yellow 120 , Pigment Yellow 151 , Pigment

Yellow 154、Pigment Yellow 156、Pigment Yellow 175、 Pigment Yellow 181Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181

(單偶氮系）(monoazo)

PigmentYellowl，2,3,4,5,6,9，10，12,61，62,62:l，65,73,74,75, 97，100,104，105，111 ,116,167,168,169,182，183， (雙偶氮系）PigmentYellowl, 2,3,4,5,6,9,10,12,61,62,62:l,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183, (bisazo system)

PigmentYellowl2,13，14，16，17,55,63,81,83,87，126，127，152, 170,172,174,176,188,198 〔紅色染色劑〕 -24- 200948891 作爲紅色染色劑，有單偶氮系、雙偶氮系、偶氮色澱 系、苯並咪唑酮系、茈系、二酮吡咯並吡咯（diket〇-pyrrolo-pyrrole )系、縮合偶氮系、惠醒系、喹町陡酮（ q u i n a c r i d 〇 n e )系等，具體而言可舉出以下者。 (單偶氮系）PigmentYellowl2,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198 [Red stain] -24- 200948891 As a red stain, there are monoazo and disazo , azo lake system, benzimidazolone, lanthanide, diket〇-pyrrolo-pyrrole, condensed azo, awake, quinacrid 〇ne Specifically, the following may be mentioned. (monoazo)

Pigment Red ❹ 1 ,2,3,4,5,6,8,9,12,14,15,1 6,17,21,22,23,3 1,32,1 12,1 14,146 ，147,151,170,184,187,188,193,210,245,253,258,266,267,26 8,269, (雙偶氮系）Pigment Red ❹ 1 , 2,3,4,5,6,8,9,12,14,15,1 6,17,21,22,23,3 1,32,1 12,1 14,146,147,151,170,184,187,188,193,210,245,253,258,266,267,26 8,269, (double azo)

Pigment Red 3 7,3 8,4 1 (單偶氮色澱系） ❿ Pigment Red 48:1，48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1，53:2,57 :1,58:4,63:1,63:2,64:1,68 (苯並咪唑酮系）Pigment Red 3 7,3 8,4 1 (single azo lake system) ❿ Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52 :1,52:2,53:1,53:2,57 :1,58:4,63:1,63:2,64:1,68 (benzimidazolone)

Pigment Red 171、Pigment Red 175、Pigment Red 176、 Pigment Red 185、Pigment Red 208 (茈系） -25- 200948891Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208 (茈) -25- 200948891

Solvent Red 135 、 Solvent Red 179 、 Pigment Red 123 、Solvent Red 135, Solvent Red 179, Pigment Red 123,

Pigment Red 149、Pigment Red 166、Pigment Red 17 8、Pigment Red 149, Pigment Red 166, Pigment Red 17 8,

Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 179, Pigment Red 190, Pigment Red 194,

Pigment Red 224 (二酮吡咯並吡咯系）Pigment Red 224 (diketopyrrolopyrrole)

Pigment Red 254、Pigment Red 25 5、Pigment Red 264、 Pigment Red 270、Pigment Red 272 (縮合偶氮系）Pigment Red 254, Pigment Red 25 5, Pigment Red 264, Pigment Red 270, Pigment Red 272 (condensed azo)

Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 220, Pigment Red 144, Pigment Red 166,

Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 214, Pigment Red 220, Pigment Red 221,

Pigment Red 242 系 0 恵Pigment Red 242 Series 0 恵

Pigment Red 168、Pigment Red 177、Pigment Red 216、 Solvent Red 149、Solvent Red 150、Solvent Red 52、 Solvent Red 207 (喹吖啶酮系）Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207 (quinacridone)

Pigment Red 122、Pigment Red 202、Pigment Red 206、 Pigment Red 207、Pigment Red 209 其他，以調整色調爲目的，也可加入紫、菊色、茶色 、黑等之染色劑。具體而言，可舉出Pigment Violet 19、 -26- 200948891 23、29、32 ' 3 6' 38、42、Solvent Violet 13' 36' C.I. Pigment Orange 1、C.I. Pigment Orange 5、C.I. Pigment Orange 13、C.I. Pigment Orange 14、C.I. Pigment Orange 16、C.I. Pigment Orange 17、C.I. Pigment Orange 24、 C.I. Pigment Orange 34、C.I. Pigment Orange 36、C.I.Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 Others, for the purpose of adjusting the color tone, it is also possible to add a coloring agent such as purple, chrysanthemum, brown or black. Specifically, Pigment Violet 19, -26- 200948891 23, 29, 32 ' 3 6' 38, 42, Solvent Violet 13' 36' CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI

Pigment Orange 3 8 ' C.I. Pigment Orange 40 ' C.I Pigment Orange 4 3 、 C.I. Pigment Orange 4 6 、 C.I Pigment Orange 4 9 、 C.I. Pigment Orange 5 1 、 C.I Pigment Orange 6 1 、 C.I. Pigment Orange 63 、 C.I Pigment Orange 64 、 C.I. Pigment Orange 7 1 、 C.IPigment Orange 3 8 ' CI Pigment Orange 40 ' CI Pigment Orange 4 3 , CI Pigment Orange 4 6 , CI Pigment Orange 4 9 , CI Pigment Orange 5 1 , CI Pigment Orange 6 1 , CI Pigment Orange 63 , CI Pigment Orange 64 , CI Pigment Orange 7 1 , CI

Pigment Orange 73、C.I. Pigment Brown 23、C.I. Pigment Brown 2 5； C.I. P igm en t B1 ac k 1、C . I · P i gm ent B1 ack 7 等 o 其他，也可配合氫餛、氫醌單甲基醚、t-丁基兒茶 酚、五倍子酚、吩噻嗪等之熱聚合禁止劑、微粉二氧化矽 φ 、有機膨土、微晶高嶺石等之增黏劑、聚矽氧系、氟系、 高分子系等之消泡劑及/或調平劑、咪唑系、噻唑系、三 唑系等之密著性賦予劑或矽烷耦合劑等之添加劑類。 如此般之本實施形態的印刷電路板用樹脂組成物，可 爲單體或具有一定分子量之低分子量的聚合物分散於有機 溶劑中且未硬化狀態使用，或成形爲樹脂薄片（薄膜）使 用亦可。 未硬化狀態之場合時，例如可以將上述之有機溶劑調 整成爲適合塗佈方法之黏度，藉由浸塗法、淋塗法、輥塗 -27- 200948891 抹法、輥塗法、網板印染法、簾塗佈法等之方法塗佈於基 材上，藉由在約60~ 100°C之溫度下使含於組成物中之有機 溶劑揮發乾燥（預乾燥），形成無黏（tack_free )之塗膜 〇 此時，作爲揮發乾燥，熱風循環式乾燥爐、IR爐、加 熱板、對流烘箱等，使用具備有由蒸氣所產生之空氣加熱 方式的熱源者，可使用使乾燥機内之熱風向流接觸之方法 及藉由噴嘴吹向支持體之方法。 又，對於樹脂薄片之場合時、可藉由塗佈於載體膜上 ，將乾燥後之作爲薄膜捲取之乾膜貼於基材上，而形成樹 脂層。又，亦可爲於銅箔上形成有乾燥塗膜之附樹脂銅箔 或含浸於玻璃布中之半硬化狀態之預浸體。具體而言可舉 出，阻焊劑、預浸體、附樹脂銅箔、built-up材料、印刷 電路板用接著劑、印刷電路板用面塗、印刷電路板用底塗 、記號油墨等。 又，含有感光性樹脂（C)等之光硬化性的印刷電路 板用樹脂組成物，藉由光硬化而成爲硬化物。光硬化可使 用各種之紫外線硬化裝置、紫外線曝光裝置或雷射發信光 源，特別係波長爲3 5 0〜41 Onm之雷射光所成之光硬化裝置 使其硬化。更進一步，含有熱硬化樹脂（B)之光硬化性 熱硬化性的印刷電路板用樹脂組成物，可藉由此般之光硬 化後進行熱硬化而使其硬化。 然後，含有含羧基樹脂（E)的鹼顯像性之絕緣組成 物，可藉上述之光硬化裝置進行圖型曝光後，將未曝光部 -28- 200948891 藉由稀釋鹼水溶液進行顯像而形成圖型。 此時，作爲顯像方法，可藉由浸漬法、噴淋法、噴霧 法、刷法等，作爲顯像液，可使用氫氧化鉀、氫氧化鈉、 碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶 液。 ' 以下，藉由實施例具體說明本發明。 φ 〔實施例〕 以下，藉由實施例更進一步具體說明本發明，但本發 明並不係受限於下述實施例者。例中，份及％如無特別指 定則係爲質量基準。 〔微粉碎再生PET漿體之調製〕 (A-1之調製） 將宜興企業製微粉碎再生PET (平均粒徑25μιη)放 φ .入噴射式磨機粉碎機中，粉碎壓力爲〇.6MPa之條件下進 行2次，得到微粉碎再生pet (平均粒徑Ι2μπι) ( Α-0) 。將所得之微粉碎再生PET(A-O) 200g在丙二醇單甲基 醚乙酸酯200g中使其分散後，以SUS製120x1000斜紋織 網（公稱濾過精度：約30μιη )之篩目進行過濾，得到微 粉碎再生PET漿體（Α-1)。此時，平均粒徑無發現變化 (A-2之調製） -29- 200948891 除了在2-羥乙基甲基丙烯酸酯200g中使微粉碎再生 PET200g ( A-0 )分散後外，其他與製造例1中以同樣的方 法得到微粉碎再生PET漿體（A-2 )。此時’平均粒徑無 發現變化。 〔樹脂之合成〕 對具備有攪拌機、溫度計、環流冷卻管、滴下漏斗及 氮氣導入管之2公升之可拆式燒瓶導入甲酚醛型環氧樹脂 (日本化藥公司製、EOCN-104S、軟化點92°C、環氧當量 220 ) 660g、卡必醇乙酸酯 421.3g、及溶劑油 180.6g， 加熱至90 °C ·進行了攪拌、溶解。其次，冷卻至60 °C， 加入丙烯酸216g、三苯基膦4.0 g、甲基氫醌1.3g，在 l〇〇°C下使其反應12時間，得到酸價爲0.2mgKOH/g之 反應生成物。對此加入四氫酞酐241.7g，加熱至90°C， 使其反應6小時。藉此，得到酸價50mgKOH/g、雙鍵當 量（不飽和基每1莫耳之樹脂的g重量）400、重量平均 分子量7,000的羧基含有感光性樹脂（E-1)溶液" 〔樹脂組成物之調製〕 進行配合如表1所示之各成分，於攪拌機中進行預先 混合後，使用3支輥磨機進行混練，調製了實施例1〜5的 樹脂組成物。將於此所得之樹脂組成物的分散度以 Erichsen公司製粒度測定儀進行粒度測定而進行評價，爲 3 Ομπι以下。 200948891 〔表1〕Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 2 5; CI P igm en t B1 ac k 1 , C . I · P i gm ent B1 ack 7 etc. Others, can also be combined with hydroquinone, hydroquinone Thermal polymerization inhibitors such as base ether, t-butylcatechol, gallic phenol, phenothiazine, fine powder of cerium oxide φ, organic bentonite, microcrystalline kaolinite, polyfluorene, fluorine An antifoaming agent such as a polymer or a polymer, a leveling agent, an imidazole imparting agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, or an additive such as a decane coupling agent. In the resin composition for a printed wiring board of the present embodiment, the monomer or a low molecular weight polymer having a certain molecular weight may be dispersed in an organic solvent and used in an uncured state, or may be formed into a resin sheet (film). can. In the case of the unhardened state, for example, the above organic solvent can be adjusted to a viscosity suitable for the coating method, by dip coating, shower coating, roll coating -27-200948891 smearing, roll coating, screen printing A method such as a curtain coating method is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (pre-dried) at a temperature of about 60 to 100 ° C to form a tack-free type. At this time, as a volatile drying, hot air circulating drying oven, IR furnace, heating plate, convection oven, etc., a heat source having a heating method by air generated by steam can be used, and a hot air flow in the dryer can be used. The method of contacting and the method of blowing the nozzle toward the support. Further, in the case of a resin sheet, it can be applied onto a carrier film, and a dry film which is taken up as a film after drying can be applied to a substrate to form a resin layer. Further, it may be a resin-coated copper foil having a dried coating film formed on a copper foil or a semi-hardened prepreg impregnated in a glass cloth. Specific examples thereof include a solder resist, a prepreg, a resin-coated copper foil, a built-up material, an adhesive for a printed circuit board, a top coat for a printed circuit board, a primer for a printed circuit board, and a marking ink. In addition, a resin composition for a photocurable printed circuit board containing a photosensitive resin (C) or the like is cured by light curing. The photohardening can be hardened by various ultraviolet curing devices, ultraviolet exposure devices, or laser light sources, especially light curing devices made of laser light having a wavelength of 550 to 41 Onm. Furthermore, the resin composition for a photocurable thermosetting printed circuit board containing the thermosetting resin (B) can be hardened by heat hardening and hardening. Then, the alkali-developing insulating composition containing the carboxyl group-containing resin (E) can be formed by patterning the light-curing device and then developing the unexposed portion -28-200948891 by diluting an aqueous alkali solution. Graphic type. In this case, as a developing method, a dip method, a shower method, a spray method, a brush method, or the like can be used as the developing liquid, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, or cesium can be used. An aqueous solution of an alkali such as sodium, ammonia or an amine. Hereinafter, the present invention will be specifically described by way of examples. φ [Examples] Hereinafter, the present invention will be further specifically described by examples, but the present invention is not limited to the following examples. In the examples, parts and % are based on quality unless otherwise specified. [Preparation of finely pulverized recycled PET slurry] (Preparation of A-1) The finely pulverized recycled PET (average particle size 25 μmη) produced by Yixing Enterprise was placed in φ. In a jet mill pulverizer, the pulverization pressure was 〇.6 MPa. The condition was carried out twice to obtain a finely pulverized regenerated pet (average particle diameter Ι2 μm) (Α-0). 200 g of the obtained finely pulverized recycled PET (AO) was dispersed in 200 g of propylene glycol monomethyl ether acetate, and then filtered through a mesh of 120×1000 twill weave (nominal filtration precision: about 30 μmη) made of SUS. The regenerated PET slurry (Α-1) was pulverized. At this time, no change was observed in the average particle diameter (modulation of A-2) -29- 200948891 Other than the dispersion of 200 g of finely pulverized recycled PET (A-0) in 200 g of 2-hydroxyethyl methacrylate In the same manner as in Example 1, the finely pulverized recycled PET slurry (A-2) was obtained. At this time, no change was observed in the average particle diameter. [Synthesis of Resin] A cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point) was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a circulation cooling tube, a dropping funnel, and a nitrogen introduction tube. 92 ° C, epoxy equivalent 220 ) 660 g, carbitol acetate 421.3 g, and solvent oil 180.6 g, heated to 90 ° C · stirred and dissolved. Next, after cooling to 60 ° C, 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added, and the mixture was reacted at 10 ° C for 12 hours to obtain an acid value of 0.2 mg KOH / g. Things. To this, 241.7 g of tetrahydrophthalic anhydride was added, and the mixture was heated to 90 ° C to cause a reaction for 6 hours. Thereby, an acid value of 50 mgKOH/g, a double bond equivalent (g weight of the unsaturated group per 1 mol of the resin) 400, a carboxyl group having a weight average molecular weight of 7,000, and a photosensitive resin (E-1) solution were obtained. Preparation of the components The components shown in Table 1 were mixed, premixed in a blender, and kneaded by using three roll mills to prepare the resin compositions of Examples 1 to 5. The degree of dispersion of the resin composition obtained herein was measured by particle size measurement by a particle size analyzer manufactured by Erichsen Co., Ltd., and was evaluated to be 3 μm or less. 200948891 [Table 1]

實施例1 實施例2 實施例3 實施例4 實施例5 A成分 Α-1 40 30 40 30 Α-2 40 B成分 JER828 *1 100 ΕΡΡΝ-201 *2 15 15 ΥΧ-4000 *3 30 30 HP4032D *4 140 TD-2106 *5 100 ΥΡ-50 *6 10 C成分 DPHA *7 20 20 D成分 Irg907 *8 10 10 DETX *9 1 1 EAB *10 0.1 E成分 E-1 154 154 F成分 2PHZ-PW *11 1 二氰胺 3 0.3 0.3 2MZ-A *12 3 三聚氰胺 3 3 G成分 B-30 *13 20 50 滑石 10 二氧化矽 10 微粉二氧化矽 3 3 3 UVR-150G *14 100 Η成分 DPM *15 染色顏料 酞花青藍 0.5 0.5 0.5 染色顏料 AGR *16 0.3 0.3 0.3 消泡劑 聚矽氧系消泡劑 3 3 3 Σ 169 140 316.4 286.3 291 備考 *1 雙酸A型環氧樹脂（Japan Epoxy Resin製） *2 苯酚酚醛清漆型環氧樹脂（日本化藥製） *3 聯若酌型環氧樹脂（Japan^)〇xyResin製） *4 環氧樹脂，環氧當量145 (大日本油墨化學工業製） *5 苯酚酚醛清漆樹脂（大日本油墨化學工業製） *6 苯氧樹脂（東都化成製） *7 二季戊四醇六丙烯酸酯（曰本化藥製） *8 2-甲基-1-〔 4-(甲硫）苯基〕-2-嗎啉基丙酮-1 *9 2,4-二乙基噻噸酮 *10 二乙基胺二苯基酮 * 11 2-苯基*4,5_二羥基甲基咪唑（四國化成製） * 12 2,4-二胺基-6-〔 2’-甲基咪唑〕-(Γ )〕-乙基-s-三嗪（四國化成製） *13 硫酸鋇（堺化學公司製） *14 紫外線硬化性抗焊油墨（太陽油墨製） *15 二丙二醇甲基酸乙酸醋 *16 黃色顏料（ChlomophthalAGR:商品名)_ -31 - 200948891 〔樹脂組成物之評價1〕 (試驗片之製作） 關於如此所得之實施例1~4之各樹脂組成物，使用各 自有形成電路形成之貼銅層合板FR-4基板作爲基板（焊 劑耐熱性評價用）、形成有IPC B-25梳型電極B試樣之 貼銅層合板（電絕緣性評價用），如以下般製成試驗片。 實施例1之樹脂組成物：以PET 150篩目之網篩於各 基板上塗怖膜厚20μιη之厚度，藉由熱風循環式乾燥爐， 在150 °C下加熱30分使其熱硬化，製成試驗片。 實施例2之樹脂組成物：以PET225篩目之網篩於各 基板上塗佈膜厚15 μιη之厚度，一邊以輸送機於速度4m/ min下進行移送，一邊藉由空冷式的8 0 W/ cm的3燈式高 壓水銀燈進行照射紫外線而製成試驗片。 實施例3、4的樹脂組成物：以PET 100篩目之網篩於 各基板上塗佈膜厚20 μιη之厚度，藉由熱風循環式乾燥爐 ，在80°C下乾燥30分鐘，形成無黏的塗膜。將此基板貼 靠於負片，如所希望之圖型般進行曝光，以沖壓2kg/cm2 的lwt%Na2C03水溶液進行顯像而形成光阻圖型。將此基 板在1 50°C下加熱60分使其熱硬化，製成試驗片。 (性能評價） 關於如此般所製作之試驗片，進行評價了有關以下之 項目。 -32- 200948891 〈焊劑耐熱性〉 將實施例1〜4的樹脂組成物，於使用有電路形成之貼 銅層合板FR-4基板而製成之各試驗片上塗佈松香系焊劑 ，在預先加熱至260°C之焊劑槽中浸漬30秒，以丙二醇單 甲基醚將焊劑洗淨後，以目視評價關於光阻層之膨漲•剝 離·變色。 於表2表示評價結果。尙，如以下、 n 〇：完全無變化者 △:些微變化者 X:塗膜有膨漲、剝離者 作爲評價基準。 〈電絕緣性〉 將實施例1~4之樹脂組成物，對使用有IP C B-2 5梳 型電極B試樣形成之貼銅層合板所製成之各試驗片的梳型 φ 電極，施加DC5.5V之偏電壓，測量其在濕度85%、溫度 1 3 0 °C下放置1 5 0小時後之絕緣電阻値。 在表2中將其評價結果合倂表示。 〔表2〕 實施例1 實施例2 實施例3 實施例4 焊劑耐熱性 〇 〇 〇 〇 電絕緣性 1χ1012Ω 以上 lxlOuQ以上 1χ1012Ω 以上 1χ1012Ω 以上 如表2所示般，得知除了可得到良好焊劑耐熱性，也 -33- 200948891 可得到高電絕緣性。 〔樹脂組成物之評價2〕 (評價用樣品之製作） 對表1所示之實施例5的配合成分’更添加爲丙二醇 單甲基醚乙酸酯、微紛二氧化矽之AER0SIL #972作爲有 機溶劑，在3支輕磨機中混練分散’得到黏度調整爲 40dPa.s±10dPa.s (回轉黏度計5rpm、25°C)的熱硬化性 樹脂組成物。接著，將所得之熱硬化性樹脂組成物更使用 甲基乙基酮調整爲黏度1〜2dPa_s，而調製成塗佈用清漆。 將所得之塗佈用清漆各自分別使用染料槽塗佈於 18μιη厚之銅箔的粗面上（F3-WS:古河CIRCUIT FOIL公 司製）使乾燥塗膜之膜厚成爲60μπι，在40〜12CTC下乾燥 得到附樹脂銅箔。此時之附樹脂銅箔在1 70 °C下膠化時間 爲60秒至90秒。 接著，將如此所得之附樹脂銅箔2枚，就直接那樣使 樹脂面成爲内側相黏貼’.以熱壓機在120°C，5kgf/cm2之 條件下30分，且進而在170 °C下2小時使其熱硬化，一體 成形。然後將此就這樣直接，或將銅箔蝕刻，製成物性測 定用之硬化皮膜樣品。 又，由銅箔18μπι厚之玻璃環氧兩面貼銅層合板形成 内層電路，將附樹脂銅箔對進而使用 Mec公司的 MECetchBOND處理過之基板的兩面與樹脂面黏著，使用 熱壓機’在 5kgf/cm2、120°C 下 20 分，接著 25kgf/cm2、 200948891 1 70°C下2小時之條件中硬化，製成層合板。 更進一步，於此層合板之所定位置上，藉由鑽頭開洞 ，形成通孔部。又，首先使用抗蝕劑將洞位置選擇性地將 銅箔除去後設置向導，藉由以雷射加工機進行開洞而形成 雷射穿孔部。 接著，通孔部與雷射穿孔部之鑽污以去鑽污處理進行 除去後，藉由無電解銅電鍍及電解銅電鍍，導通洞部’藉 〇 由透過市售之抗蝕劑的蝕刻形成圖型，製成多層印刷電路 板樣品。 (性能評價） 關於如此般所製成之評價用樣品，進行評價以下2 ¥ 目。 〈剝離強度〉 ❹ 遵循JIS C648 1進行測定。 〈焊劑耐熱性〉 在288t：±3t：之焊劑層中，將完成之印刷電路板（ lOcmxlOcm)浸漬10秒。接著，重複此操作5次後’進 行確認銅箔與樹脂之剝離。 尙，如以下 〇：無剝離 X :有剝離 -35- 200948891 作爲評價標準。 〈圖型形成性〉 以目視檢查線與空間75μιη/75μιη之電路的剝離。尙 ，如以下 〇：無剝離 X :有剝離 作爲評價標準。 〔表3〕 實施例5 剝離強度 10.2N/cm 焊劑耐熱性 〇 圖型形成性 〇 如表3所示般，得知除了高剝離強度，也可得到良好 之焊劑耐熱性、圖型形成性。 猶，本發明並不係受限於上述之實施形態者。其他僅 不脫離其要旨範圍可改變其各種形態而實施。 -36-Example 1 Example 2 Example 3 Example 4 Example 5 A component Α-1 40 30 40 30 Α-2 40 B component JER828 *1 100 ΕΡΡΝ-201 *2 15 15 ΥΧ-4000 *3 30 30 HP4032D * 4 140 TD-2106 *5 100 ΥΡ-50 *6 10 C component DPHA *7 20 20 D component Irg907 *8 10 10 DETX *9 1 1 EAB *10 0.1 E component E-1 154 154 F component 2PHZ-PW * 11 1 dicyanamide 3 0.3 0.3 2MZ-A *12 3 melamine 3 3 G component B-30 *13 20 50 talc 10 cerium oxide 10 micro powder cerium oxide 3 3 3 UVR-150G *14 100 Η component DPM *15 Dyeing pigment phthalocyanine blue 0.5 0.5 0.5 Dyeing pigment AGR *16 0.3 0.3 0.3 Defoamer polyfluorene defoamer 3 3 3 Σ 169 140 316.4 286.3 291 Remarks *1 Double acid A type epoxy resin (Japan Epoxy Resin *2 Phenolic novolac type epoxy resin (manufactured by Nippon Kasei Co., Ltd.) *3 Epoxy resin (Japan^) 〇xyResin) *4 Epoxy resin, epoxy equivalent 145 (Daily Ink Chemical Industry) )) *5 phenol novolac resin (large Japanese ink Industrial Co., Ltd. *6 phenoxy resin (manufactured by Tohto Kasei Co., Ltd.) *7 Dipentaerythritol hexaacrylate (manufactured by Sakamoto Chemical Co., Ltd.) *8 2-Methyl-1-[4-(methylthio)phenyl]-2- Morpholinylacetone-1 *9 2,4-diethylthioxanthone*10 Diethylamine diphenyl ketone* 11 2-phenyl*4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei) * 12 2,4-Diamino-6-[ 2'-methylimidazolyl]-(Γ )]-ethyl-s-triazine (manufactured by Shikoku Chemicals Co., Ltd.) *13 Barium sulfate (manufactured by Nippon Chemical Co., Ltd.) * 14 UV curable solder resist ink (made by Sun Ink) *15 Dipropylene glycol methyl acid acetate vinegar *16 Yellow pigment (Chlomophthal AGR: trade name) _ -31 - 200948891 [Evaluation of resin composition 1] (Production of test piece) With respect to each of the resin compositions of Examples 1 to 4 thus obtained, a copper-clad laminate FR-4 substrate each having a circuit formation was used as a substrate (for evaluation of solder heat resistance), and an IPC B-25 comb-type electrode B was formed. A copper-clad laminate (for electrical insulation evaluation) of the sample was prepared as follows. The resin composition of Example 1 was formed by coating a mesh of a PET 150 mesh on a thickness of 20 μm on each substrate, and thermally hardening it by heating at 150 ° C for 30 minutes in a hot air circulating drying oven. Test piece. The resin composition of Example 2: a thickness of 15 μm was applied to each substrate by a mesh screen of PET225 mesh, and transferred by a conveyor at a speed of 4 m/min while being air-cooled by 80 W. A 3 mm high-pressure mercury lamp of /cm was irradiated with ultraviolet rays to prepare a test piece. The resin compositions of Examples 3 and 4 were coated with a PET 100 mesh screen on each substrate to a thickness of 20 μm, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes to form no Sticky film. The substrate was placed on a negative film, exposed as in the desired pattern, and developed by punching 2 kg/cm 2 of an aqueous solution of 1 wt% Na 2 CO 3 to form a photoresist pattern. This substrate was heated and cured at 150 ° C for 60 minutes to prepare a test piece. (Performance evaluation) The test piece produced in this way was evaluated for the following items. -32-200948891 <Pressure heat resistance> The resin composition of Examples 1 to 4 was coated with a rosin-based flux on each test piece prepared by using a circuit-formed copper-clad laminate FR-4 substrate, and heated in advance. After immersing in a flux bath of 260 ° C for 30 seconds, the flux was washed with propylene glycol monomethyl ether, and the swelling, peeling, and discoloration of the photoresist layer were visually evaluated. The evaluation results are shown in Table 2.尙, as follows, n 〇: No change at all △: Some slight change X: The film is swollen and peeled off. <Electrical Insulation> The comb-shaped φ electrode of each of the test pieces prepared by using the resin composition of Examples 1 to 4 and the copper-clad laminate formed using the IP C B-2 5 comb-type electrode B sample was A bias voltage of DC 5.5 V was applied, and the insulation resistance 后 after being placed at a humidity of 85% and a temperature of 130 ° C for 150 hours was measured. The evaluation results are collectively shown in Table 2. [Table 2] Example 1 Example 2 Example 3 Example 4 Heat resistance of solder 〇〇〇〇 Electrical insulating property 1 χ 1012 Ω or more lxlOuQ or more 1 χ 1012 Ω or more 1 χ 1012 Ω or more As shown in Table 2, it was found that good solder heat resistance was obtained. , also -33- 200948891 can obtain high electrical insulation. [Evaluation 2 of Resin Composition] (Production of Sample for Evaluation) The compounding component of Example 5 shown in Table 1 was further added with propylene glycol monomethyl ether acetate and AER0SIL #972 of bismuth dioxide. The organic solvent was kneaded and dispersed in three light mills to obtain a thermosetting resin composition having a viscosity adjusted to 40 dPa·s ± 10 dPa·s (rotational viscometer 5 rpm, 25 ° C). Next, the obtained thermosetting resin composition was adjusted to a viscosity of 1 to 2 dPa_s using methyl ethyl ketone to prepare a coating varnish. Each of the obtained coating varnishes was applied to a rough surface of a 18 μm thick copper foil (F3-WS: manufactured by Furukawa CIRCUIT FOIL Co., Ltd.) using a dye tank, and the film thickness of the dried coating film was 60 μm, at 40 to 12 CTC. Drying to obtain a resin-attached copper foil. The resin copper foil at this time has a gelation time of 60 seconds to 90 seconds at 1 70 °C. Next, the two resin-attached copper foils thus obtained were directly pasted so that the resin surface became the inner side. The hot press was subjected to a hot press at 120 ° C, 5 kgf/cm 2 for 30 minutes, and further at 170 ° C. It is thermohardened in 2 hours and is integrally formed. Then, this is done directly, or the copper foil is etched to prepare a hardened film sample for physical property measurement. Further, an inner layer circuit was formed by a copper foil 18 μm thick glass epoxy double-sided copper-clad laminate, and the resin-coated copper foil was adhered to both sides of the substrate treated with MECetch BOND of Mec Corporation, and the hot press was used at 5 kgf. /cm2, 20 minutes at 120 ° C, followed by hardening under conditions of 25 kgf / cm 2 , 2009 48891 1 70 ° C for 2 hours to form a laminate. Further, at a predetermined position of the laminate, the through hole portion is formed by opening the drill bit. Further, first, a resist is used to selectively remove the copper foil from the hole position, and then a guide is provided, and a laser perforated portion is formed by opening a hole by a laser processing machine. Then, after the through hole portion and the laser perforated portion are removed by the desmear treatment, the conductive hole portion is formed by etching through a commercially available resist by electroless copper plating and electrolytic copper plating. The pattern is made into a multilayer printed circuit board sample. (Performance evaluation) For the evaluation samples prepared in this way, the following two items were evaluated. <Peel strength> 测定 Measurement was carried out in accordance with JIS C648 1. <Solder Heat Resistance> The completed printed circuit board (10 cm x 10 cm) was immersed in a solder layer of 288 t: ± 3 t: for 10 seconds. Then, after repeating this operation five times, the peeling of the copper foil and the resin was confirmed.尙, such as the following 〇: no peeling X: peeling -35- 200948891 as the evaluation standard. <Pattern Formability> The peeling of the circuit of the line and the space of 75 μm / 75 μm was visually inspected.尙 , such as the following 无: no peeling X: peeling is used as the evaluation standard. [Table 3] Example 5 Peel strength 10.2 N/cm Flux heat resistance 〇 Pattern formation property 〇 As shown in Table 3, it was found that good solder heat resistance and pattern formation properties were obtained in addition to high peel strength. Still, the present invention is not limited to the above embodiments. Others may be implemented without departing from the scope of the gist thereof. -36-

Claims (1)

200948891 七、申請專利範圍： 1. 一種印刷電路板用樹脂組成物，其特徵爲含有再 生聚對酞酸乙二酯（A)。 2 ·如申請專利範圍第1項記載之印刷電路板用樹脂 ' 組成物，其係將平均粒徑0.1~15μιη之再生聚對酞酸乙二 ' 酯微粉末混合而調製。 3 .如申請專利範圍第1項記載之印刷電路板用樹脂 H 組成物，其中前述再生聚對酞酸乙二酯（Α)爲全體量的 0 · 1 〜7 5 %。 4.如申請專利範圍第1項記載之印刷電路板用樹脂 組成物，其中含有熱硬化性樹脂（Β)。 5 .如申請專利範圍第1項記載之印刷電路板用樹脂 組成物，其中含有感光性樹脂（C )。 6. —種乾膜，其特徵爲在基材上具備有如申請專利 範圍第1項至第5項中任一項記載之印刷電路板用樹脂組 φ 成物之塗佈乾燥膜。 7. ~種印刷電路板，其特徵爲，具備有 形成有電路之基板，與 在此基板上之至少一部份形成有使申請專利範圍第1 項至第5項中任一項所記載之印刷電路板用樹脂組成物硬 化後之永久被膜。 8. —種印刷電路板’其特徵爲，具備有 形成有電路之基板，與 在此基板上之至少一部份’使藉由申請專利範圍第6 -37- 200948891 項所記載之乾膜所轉印之該塗佈乾燥膜硬化後之永久被膜 -38- 200948891 四、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明··無200948891 VII. Patent application scope: 1. A resin composition for a printed circuit board, characterized in that it contains regenerated polyethylene terephthalate (A). (2) The resin composition for a printed circuit board according to the first aspect of the invention, which is prepared by mixing a regenerated poly(p-citric acid) ethylene phthalate fine powder having an average particle diameter of 0.1 to 15 μm. 3. The resin H composition for a printed circuit board according to the first aspect of the invention, wherein the regenerated polyethylene terephthalate (Α) is 0·1 to 7 5 % of the total amount. 4. The resin composition for a printed circuit board according to the first aspect of the invention, which contains a thermosetting resin. 5. The resin composition for a printed circuit board according to claim 1, wherein the photosensitive resin (C) is contained. A dry film comprising a coated resin film of a resin composition for a printed circuit board according to any one of the first to fifth aspects of the invention. 7. A printed circuit board comprising: a substrate on which a circuit is formed, and at least a portion of the substrate is formed in any one of claims 1 to 5; A permanent film of a printed circuit board hardened with a resin composition. 8. A printed circuit board characterized by having a substrate on which a circuit is formed, and at least a portion of the substrate on the substrate is made by the dry film described in the patent application No. 6-37-200948891 Transfer of the coated film after hardening of the permanent film -38- 200948891 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure·· -3- 200948891 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無-3- 200948891 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none
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JP2009239181A (en) 2009-10-15
CN101544863A (en) 2009-09-30

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