479447 A7 五、發明說明（ 本發明關於用於形成圖案之積層體，其製造方法和使 用該積層體形成圖案之方法。 迄至目前，利用曝光技術之微影印刷術已被應用於如 電路板、顯示板、蝕刻等，作爲在塑膠、無機物質等之 上形成圖案之方法。 作爲形成圖案之方法爲已知方法，例如其中在基質表 面上塗複一種絕緣或導電之光敏感性組成物以形成一種 絕緣或導電性塗膜層之後，用電子束或熱輻射射線，經 過光罩之中介以射於表面，然後使該絕緣或導電性之光 敏性塗膜層顯影而獲得所需之圖案。然而，此種方法因 爲絕緣或導電性塗膜層並無充份之光敏感性，有不能形 成明銳圖案的問題。 經過反覆積極硏究謀求解決上述問題之結果，本發明 人等今已發現上述問題可以藉由具有特定熱敏感性塗膜 所層積之塗膜而獲得解決，並完成本發明。 因此，根據本發明而提供一種用於形成圖案之積層 體，其特徵在於在基質表面連續層積一種負型或正型熱 輻射-敏感性樹脂塗膜層（A)，一種熱輻射-透射性片層（B) 和一種遮蔽熱輻射而爲能量射線-敏感性塗膜層（C)而製 成。 然後，本發明用於形成圖案之積層體，其製法和利用 該積層體形成圖案之方法將作更爲詳細之說明。 用於本發明積層體之基質並無特別限制，只要迄至目 前已用於形成圖案者即可比照使用，其可述及者，例 (請先閱讀背面之注意事項再填寫本頁) 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 479447 A7 B7 五、發明說明（2 ) (請先閱讀背面之注意事項再填寫本頁) 如’電絕緣之玻璃-環氧樹脂板；塑膠片或塑膠板，其 如聚乙二醇對苯二酸酯片，聚醯亞胺片等；其上形成有 _電塗膜之塑膠板或塑膠片爲黏貼有諸如銅、鋁等之金 屬范者，或用諸如銅、鎳、銀等金屬，或如導電性氧化 物而以氧化銦錫（ITO)爲代表等以真空蒸鍍、化學蒸鍍、 ^鍍等方法形成者；具有穿孔部位之塑膠板或塑膠片而 在其上已有上述導電塑膠形成於表面和穿孔部位者；金 屬板如銅板等；形成圖紋由銅穿孔之印刷電路基板等。 ,線· 用本發明積層體中之負型或正型熱輻射-敏感性樹脂 塗膜層（A)無特別限制，只要是一種負型塗膜層（A-1)， 在塗膜層未受熱輻射照射之部位，在顯影溶液內因溶解 或擴散而被除去；而塗膜層經熱輻射線照射之部份，在 顯影溶液內不因溶解或擴散被除去而留下成爲光阻塗 者；或是一種正型塗膜層（A-2)，塗膜層未經熱輻射線照 射之部位’在顯影溶液內不因溶解或擴散被除去而留下 成爲光阻塗膜者，而塗膜層經熱輻射線照射之部位受熱 輻射線分解’在顯影溶液內因溶解或擴散被除去，而具 有.如此熱輻射-敏感性特質者。 經濟部智慧財產局員工消費合作社印製 .作爲形成負型熱輻射-敏感性樹脂塗膜層（A-1)之樹脂 組成物，可以用一種已知之形成塗膜之樹脂組成物，例 如，含有可交聯官能基之樹脂與熱輻射固化交聯劑之一 種結合物；熱輻射可固化（或可聚合）之樹脂或化合物 與熱模式反應起始劑（熱模式自由基聚合觸媒、熱模式 陽離子聚合觸媒等）所成之一種結合物等。 -4- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 479447 A7 __B7 五、發明說明（3 ) (請先閱讀背面之注意事項再填寫本頁) 作爲上述含有可交聯官能基之樹脂者，是使用一種具 有可交聯官能基之樹脂，其爲可與交聯劑因熱輻射之照 射而反應’並有足夠之可離子化基（可陰離子化基或可 陽離子化基）使在鹼顯影溶液或酸顯影溶液內溶解或擴 散樹脂。 作爲含於該樹脂內之可交聯官能基而可述及者，例 如’羥基、環氧基等；即作爲交聯劑之可述及者，例 如’胺基樹脂、嵌段聚異氰酸酯、羧酸（酐）、聚胺等。 作爲含可交聯官能基之樹脂與交聯劑之結合物而可述 及者’例如’含羥基樹脂/胺樹脂、含羧基樹脂/嵌段 聚異氰酸酯、環氧樹脂/酚樹脂、環氧樹脂/羧酸 (酐）、環氧樹脂/聚胺等結合物。 經濟部智慧財產局員工消費合作社印製 另一方面，作爲上述熱輻射可固化（或可聚合）之樹 脂或化合物，其可列示者，例如一種具有不飽和基或 熱-敏感性官能基之樹脂或化合物。其爲可藉熱輻射之 照射因交聯而固化之樹脂或因聚合而固化之化合物，並 有足夠之可離子化基（可陰離子化基或可陽離子化基） 使溶解或擴散該樹脂或化合物於鹼顯影溶液或酸顯影溶 液之。 作爲含於熱輻射-可固化樹脂中之熱敏感性不飽和 基，其可述及者，例如，丙烯醯基、甲基丙烯醯基、乙 烯基、苯乙烯基、烯丙基等。作爲可離子化基而可述及 者，例如以羧基作爲可陰離子化基之代表，該羧基含量 較佳通常在約10-700毫克KOH/克，特別是約20-600毫 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 479447 A7 ___ _ B7___ 五、發明說明（4 ) 克KOH/克作爲樹脂酸値之範圍內。作爲可陽離子化基 者，胺基可爲代表，且該胺基之含量較佳通常在約20-6*50，特別是約30-600毫克作爲樹脂胺値之範圍內。 作爲可陰離子化之熱輻射-可固化樹脂者，其可述及 者例如含羧基樹脂（聚羧酸樹脂），在其中之不飽和基 和羧基是以引入例如（甲基）丙烯酸液水甘油酯之不飽 和單體反應所獲得。 作爲可陽離子化之熱輻射可固化之樹脂，其可列示 者，例如，由含羥基與三級胺基之樹脂，與由含羥基不 飽和化合物與二異氰酸酯化合物之反應生成物，作加成 反應而製成之樹脂。 作爲上述可陰離子化和可陽離子化之熱輻射可固化之 樹脂，載於日本公開專利公告第223759/1 99 1號（=美 國專利第5,045，434號），其內容在此代替詳細說明。 作爲熱自由基聚合觸媒，其可述及者，例如，諸如二 笨甲酮、苯偶姻甲基醚、苯偶姻異丙基醚、芳基_酮、 9-氧二苯并硫哌喃蒽醌等之芳族羰基化合物；諸如乙醯 苯、丙醯苯、α-羥異丁醯苯、α，α’-二氯-4-苯氧乙醯 苯、1-羥-1-環己基乙醯苯、二乙醯苯乙醯苯等之醯苯 類；諸如過氧化苯醯、第三丁基過氧-2-乙基已酸酯、第 三·丁基過氧化氫、二第三丁基二過氧異苯二酸酯、 3,·3，，4,4’-四（第三丁基過氧羰基）二苯甲酮等之有機過 氧化物；諸如3-苯基-5-異得唑酮、2,4,6-三（三氯甲 基）-1，3,5-三畊、苯并蒽酮等之雜環和多環化合物；諸 -6- 本紙張尺度適用中國國家標準（CNS)A4規格mo X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ·. 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印制衣 479447 A7 ---B7 五、發明說明（5 ) 如2,2’-偶氮（2,4-二甲基戊腈）、2,2’-偶氮雙異丁腈、 1，1’_偶氮（環已烷-1_腈）、2,2’_偶氮（2_甲基丁腈）等 之偶氮化合物。其間各可單獨或以2或多種合倂使用。 :作爲熱模式之陽離子聚合觸媒者，可包括例如路易斯 酸鍺合物名、鐵鹽（毓鹽、銹鹽、鎖鹽等）和可特別述479447 A7 V. Description of the invention (The present invention relates to a laminated body for forming a pattern, a manufacturing method thereof, and a method for forming a pattern using the laminated body. So far, lithography using exposure technology has been applied to, for example, a circuit board , Display boards, etching, etc., as methods for forming patterns on plastics, inorganic substances, etc. As methods for forming patterns are known methods, for example, an insulating or conductive light-sensitive composition is coated on the surface of a substrate to form After an insulating or conductive coating film layer, an electron beam or heat radiation is radiated through the reticle to the surface, and then the insulating or conductive photosensitive coating film layer is developed to obtain the desired pattern. However, This method has the problem that the sharp or sharp pattern cannot be formed because the insulating or conductive coating film layer does not have sufficient light sensitivity. As a result of repeated active research to solve the above problems, the inventors have found the above problems today The present invention can be solved by a coating film laminated with a specific heat-sensitive coating film, and the present invention is completed. Therefore, according to the present invention Provided is a laminated body for forming a pattern, which is characterized in that a negative or positive heat radiation-sensitive resin coating film layer (A) and a heat radiation-transmissive sheet layer (B) are continuously laminated on the surface of a substrate. And an energy ray-sensitive coating film layer (C) for shielding heat radiation. Then, the method for forming a laminated body for forming a pattern according to the present invention and the method for forming a pattern using the laminated body will be described in more detail. The substrate used in the laminated body of the present invention is not particularly limited, as long as it has been used to form a pattern so far, it can be used in comparison. It can be mentioned, for example (please read the precautions on the back before filling this page) ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 479447 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling in this page) Such as' electrically insulated glass-epoxy board; plastic sheet or plastic Plate, such as polyethylene glycol terephthalate film, polyimide film, etc .; the plastic plate or plastic sheet on which the _electric coating film is formed is a metal plate such as copper, aluminum, etc., or Use such as copper, Metals such as nickel and silver, or conductive metal oxides such as indium tin oxide (ITO), etc., formed by vacuum evaporation, chemical evaporation, or metallization; plastic plates or sheets with perforations The above-mentioned conductive plastics are formed on the surface and perforated parts; metal plates such as copper plates, etc .; printed circuit substrates formed with copper perforations on the pattern, etc., using the negative or positive heat radiation in the laminated body of the present invention -The sensitive resin coating film layer (A) is not particularly limited, as long as it is a negative coating film layer (A-1), the portion of the coating film layer that is not exposed to heat radiation is removed by dissolution or diffusion in the developing solution; And the part of the coating film layer irradiated with heat radiation is not removed as a photoresist by being dissolved or diffused in the developing solution; or a positive coating film layer (A-2), the coating film layer The parts that are not irradiated by heat radiation are not left in the developing solution as a photoresist coating film due to dissolution or diffusion, and the parts of the coating film layer exposed to heat radiation are decomposed by heat radiation. Dissolution or diffusion is removed while having. Thermal radiation - sensitive nature of those. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. As a resin composition for forming a negative heat radiation-sensitive resin coating film layer (A-1), a known resin coating composition can be used, for example, containing A combination of crosslinkable functional group resin and thermal radiation curing crosslinker; thermal radiation curable (or polymerizable) resin or compound and thermal mode reaction initiator (thermal mode radical polymerization catalyst, thermal mode Cation polymerization catalyst, etc.). -4- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 479447 A7 __B7 V. Description of the invention (3) (Please read the precautions on the back before filling this page) As the above content can be delivered A resin having a cross-linkable functional group is a resin having a cross-linkable functional group, which is capable of reacting with the cross-linking agent due to the irradiation of heat radiation, and has sufficient ionizable groups (anionizable groups or cationizable groups) (Chemical group) to dissolve or diffuse the resin in the alkali developing solution or the acid developing solution. It can be mentioned as a crosslinkable functional group contained in the resin, such as 'hydroxyl, epoxy, etc .; that is, it can be mentioned as a crosslinking agent, such as' amino resin, block polyisocyanate, carboxylic acid, etc. Acid (anhydride), polyamine, etc. As a combination of a cross-linkable functional group-containing resin and a cross-linking agent, it can be mentioned, for example, a hydroxyl-containing resin / amine resin, a carboxyl-containing resin / block polyisocyanate, an epoxy resin / phenol resin, and an epoxy resin. / Carboxylic acid (anhydride), epoxy resin / polyamine and other combinations. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. On the other hand, as the above heat radiation curable (or polymerizable) resin or compound, it can be listed, for example, an unsaturated or heat-sensitive functional group. Resin or compound. It is a resin that can be cured by cross-linking or a compound that is cured by polymerization by the irradiation of heat radiation, and has sufficient ionizable groups (anionizable or cationizable groups) to dissolve or diffuse the resin or compound In alkali developing solution or acid developing solution. As the heat-sensitive unsaturated group contained in the heat radiation-curable resin, there can be mentioned, for example, acrylfluorenyl, methacrylfluorenyl, vinyl, styryl, allyl, and the like. It can be mentioned as an ionizable group, for example, a carboxyl group is used as a representative of an anionizable group. The content of the carboxyl group is preferably about 10-700 mgKOH / g, especially about 20-600 milligrams. This paper is suitable for China. National Standard (CNS) A4 specification (210 X 297 public love) 479447 A7 ___ _ B7___ 5. Description of the invention (4) Grams KOH / g is within the scope of resin acid rhenium. As the cationizable group, an amine group may be representative, and the content of the amine group is preferably in the range of about 20-6 * 50, especially about 30-600 mg as the resin amine. As an anionizable heat radiation-curable resin, it can be mentioned, for example, a carboxyl group-containing resin (polycarboxylic acid resin), in which unsaturated groups and carboxyl groups are introduced, for example, (meth) acrylic acid liquid water glyceride Obtained by the reaction of unsaturated monomers. As a cationizable heat radiation curable resin, it can be listed as, for example, addition of a reaction product containing a hydroxyl group and a tertiary amine group with a reaction product containing a hydroxyl group-containing unsaturated compound and a diisocyanate compound. Resin made by reaction. As the above-mentioned anionizable and cationizable heat radiation curable resin, it is described in Japanese Laid-Open Patent Publication No. 223759/1 99 1 (= U.S. Patent No. 5,045,434), the contents of which are described here instead of detailed description. As a thermal radical polymerization catalyst, it can be mentioned, for example, such as dibenzyl ketone, benzoin methyl ether, benzoin isopropyl ether, aryl_ketone, 9-oxodibenzothiopiper Aromatic carbonyl compounds such as anthraquinone; such as acetophenone, propenebenzene, α-hydroxyisobutyrenebenzene, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-ring Benzenes such as hexylacetophenone, diethylacetophenone, etc .; such as benzene peroxide, third butylperoxy-2-ethylhexanoate, third · butyl hydrogen peroxide, Organic peroxides such as tributyldiperoxyisophthalate, 3,3,4,4'-tetrakis (third butylperoxycarbonyl) benzophenone; such as 3-phenyl- Heterocyclic and polycyclic compounds such as 5-isodazolidone, 2,4,6-tris (trichloromethyl) -1,3,5-trigon, benzoxanthone; etc.-6- Applicable to China National Standard (CNS) A4 specification mo X 297 mm) (Please read the notes on the back before filling out this page) ·. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Clothing 479447 A7 --- B7 V. Description of the invention (5) Such as 2, 2 -Azo (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'_azo (cyclohexane-1_nitrile), 2,2'_couple Azo compounds such as nitrogen (2-methylbutyronitrile). Each of them may be used alone or in a combination of two or more. : As a cationic polymerization catalyst in thermal mode, it may include, for example, the name of a Lewis acid germanium compound, iron salts (yu salt, rust salt, lock salt, etc.) and special descriptions.
及之商品，例如 SAIRACURE UVI-6970 > S AIRACURE UVI-697 1、SAIRAUCRE UVI-6990、SAIRAUCRE UVI- 6950(Union Carbide，USA 製造，商品名）、Irgacure 261 (Ciba Specialty Chemicals 製造，商品名）、CP-66、CP- 77(均爲 Asahi Denka Ltd·製造，商品名，毓鹽）、CG- 24-61(Ciba Specialty Chemicals 製造，商品名）、 DAICAT-Π (Daicel Chemical Industries Co ·製造，商品 名）、CI-2734、CI-275 8、CI - 2 8 5 5 (均 N i p p ο n S o d a C o ·製 造，商品名）、PI-2074(Rhone-Poulenc Co. Ltd.製造，商 品名，五氟苯基硼酸酯甲苯甲醯基異丙苯基銚鹽）、FFC ♦ 509(3M Co.製造，商品名）、BBI 102(Midori Chemistry Co·製，商品名）、SAN-AID-SI(Sanshin Chemical Ind.And products such as SAIRACURE UVI-6970 > S AIRACURE UVI-697 1, SAIRAUCRE UVI-6990, SAIRAUCRE UVI- 6950 (Union Carbide, USA, trade name), Irgacure 261 (Ciba Specialty Chemicals, trade name), CP-66, CP-77 (all manufactured by Asahi Denka Ltd., trade name, Yuyan), CG- 24-61 (manufactured by Ciba Specialty Chemicals, trade name), DAICAT-Π (manufactured by Daicel Chemical Industries Co., product Name), CI-2734, CI-275 8, CI-2 8 5 5 (both N ipp ο n S oda Co. · product, trade name), PI-2074 (manufactured by Rhone-Poulenc Co. Ltd., trade name , Pentafluorophenylborate tolylmethylisopropylphenylsulfonium salt), FFC 509 (manufactured by 3M Co., trade name), BBI 102 (manufactured by Midori Chemistry Co., trade name), SAN-AID- SI (Sanshin Chemical Ind.
Co. Ltd.製，商品名，毓鹽）等。其間各可單獨或以2或 多種合倂使用。 在上述熱模式反應起始劑中，特別以毓鹽較佳，因其 易以加熱而產生陽離子，且對聚合反應有高度活性。 熱模式反應起始劑之配用比例，在每1 00重量份可熱 輻射固化之樹脂或化合物中用0.1-25重量份，較佳爲 0.2-10重量份之範圍。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂： 丨線. 經濟部智慧財產局員工消費合作社印制衣 479447 A7 ----- B7 五、發明說明（6 ) 若用熱模式-陽離子聚合觸媒，較佳倂用陽離子放大 劑，其爲因受熱輻射照射所產生之陽離子之催化而重又 產生陽離子者。如此之陽離子放大劑是一種化合物而具 有比較強的殘酸，其在有陽離子性觸媒存在時易於解離 並重又產生陽離子（酸）者。作爲如此之陽離子放大劑， 其可述及者，例如二氯乙酸、三氯乙酸、甲烷磺酸、乙 烷磺酸、苯磺酸、對甲苯磺酸、苯磺酸、苯基膦酸等。 作爲上述可熱輻射固化之樹脂或化合物與熱模式反應 起始劑之結合實例，其可述及者，例如，環氧樹脂/熱 模式陽離子聚合觸媒，含醚鍵之烯烴不飽和化合物/熱 模式陽離子聚合觸媒，不飽和樹脂/熱模式自由基聚合 觸媒等。 此外，作爲可用於形成負型熱輻射-敏感性樹脂塗膜 層（Α-1)之樹脂，例如，具有羧基及/或羥苯基和醚鍵兩 者之可自行交聯之烯烴不飽和化合物。 在上列形成負型熱輻射-敏感性樹脂塗膜層（Α-1)之樹 脂組成物中，特別以環氧樹脂/熱模式陽離子聚合觸 媒，和不飽和樹脂/熱模式自由基聚合觸媒之結合爲較 佳。 對於形成熱輻射-敏感性樹脂塗膜層（Α-1)之樹脂組成 物，若有需要，可以配入飽和樹脂。該飽和樹脂可用於 控制該樹脂組成物之溶解度（阻塗膜在鹼顯影溶液中之 溶解度，或例如用於除去熱固化塗膜之強鹼溶液之溶解 度），並且包括例如聚酯樹脂、醇酸樹脂、（甲基）丙嫌 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂---------線-- (請先閱讀背面之注意事項再填寫本頁) 479447 Λ7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（7 ) 酸樹脂、矽樹脂、氟樹脂、聚氨基甲酸酯樹脂等。此等 樹脂可以單獨或以2或多種合倂使用。 該樹脂組成物可以溶解或擴散於例如有機溶劑、水或 溶如其間之混合溶劑中而塗於基質表面。作爲有機溶劑 者，可述及如酮類、酯類、醚類、溶纖劑類、芳族烴、 醇類、鹵化烴類等。 溶解或擴散於溶劑中之該樹脂組成物可以用例如滾 筒、滾塗器、旋塗器、幕滾塗器、噴塗、靜電塗複、漆 塗、絲印、旋塗等方法予以塗複。然後將已形成之塗 膜，視需要靜置後，乾燥於例如約50-約130°C使獲得 負型熱輕射-敏感性樹脂塗fl吴（A - 1 )。 水性之負型熱輻射敏感性樹脂組成物可以獲自於溶解 或擴散上述負型熱輻射-敏感性樹脂組成物。 負型熱輻射-敏感性樹脂組合物之水溶解或水擴散可 以進行於用鹼（中和劑）中和在可熱輻射固化之樹脂中之 可陰離子化基（例如羧基），或用酸（中和劑）中和在可 熱輻射固化之樹脂中之可陽離子化基（例如胺基）。 除上述之外，已知水可顯影之熱輻射可固化之樹脂組 成物也可以用作負型熱輻射-敏感性樹脂組成物。作爲 此種物質而可述及者，例如，引入熱輻射可固化之不飽 和基和離子形成基至線性酚型環氧樹脂中而製成之水性 樹脂。該水性樹脂可以獲自例如經由加入（甲基）丙烯酸 至線性酚型環氧樹脂所具有之部份環氧基’並經由至少 使部份環氧基與例如三級胺化合物反應而形成水溶性鐵 (請先閱讀背面之注意事項再填寫本頁) · -1線· -· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印制衣 479447 A7 137 五、發明說明（8 ) 鹽基而給予熱可固化性至樹脂中。所得之水性樹脂曝於 熱輻射之部位因而被固化變成非水溶性，而未曝於熱輻 射之部位則被水顯影而除去。再者，塗膜在水顯影之後 可以藉由加熱（例如在約1 40-200°C歷10-30分鐘）使 留於已固化之塗膜內之可離子化基被揮發而成疏水性。 d此得以形成一種塗膜，其爲有優異之阻蝕特性而不具 有親水基（羧基、胺基等）或其鹽顯（與顯影溶液所成 之鹽），其爲形成自上述鹼可顯影和酸可顯影之熱敏感 性組成物之阻蝕塗膜在塗膜中所具有者。另外，除線性 辦型環氧樹脂外，也可以採用獲自如同上述之狀況，以 (甲基）丙烯酸和例如三級胺，與含環氧基而可由自由基 聚合之不飽和單體共聚物，諸如（甲基）丙烯酸縮水甘油 3，4-環氧環已基烷基（甲基）丙烯酸酯、乙烯基縮水 甘油基醚等；或一種共聚物，由一種以上之此等單體與 另一自由基可聚合之不飽和單體（例如碳數1-24之（甲 基）丙烯酸烷酯或環烷酯），自由基可聚合之不飽和芳 族化合物等所反應獲得。 負型熱輻射-敏感性樹脂塗膜層（A-1)之顯影之進行， 若形成塗膜層之負型熱輻射-敏感性樹脂組成物是可陰 離子化者，則用鹼顯影溶液；若爲可陽離子化者，則用 酸顯影溶液。如果樹脂本身爲水溶性（例如上述含鏺鹽 碁，之樹脂等）則可進行水顯影。 負型熱輻射-敏感性樹脂塗膜層（A-1 )本身可爲導電性 或絕緣性。因此，若有需要，可在熱輻射-敏感性樹脂 -10- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂： 丨線· 479447 A7 B7 五、發明說明（9 ) 組成物中配入一種導電材料（已知之導電顏料，例如， 各種金屬，其一種以上之合金及其氧化物，諸如銀、 銅、鐵、錳、鎳、鋁、鈷、鉻、鉛、鋅、鉍、IT〇等， 絕緣材料於其表面塗有或蒸鍍導電材料者等等），或一 種絕緣材料（塑膠細粉、絕緣性無機粉料等），使該塗 膜產生導電性或絕緣性。絕緣性塗膜較佳爲最後形成之 塗膜之體積固有電阻通常超過109Ω · cm，特別是在 1〇1()Ω · 〇ηι-1018Ω · cm範圍內。另一方面，導電性塗 膜在最後形成之塗膜，其體積固有電阻較佳通常是小於 109Ω · cm，特別是在 1Ω · cm-108Q · cm 範圍內。 另一方面，作爲形成正型熱輻射-敏感性樹脂塗膜層 (令-2)之樹脂組成物，其可用於之組成物包括例如一種熱 酸·產生劑成分和一種樹脂成分。作爲該樹脂成分可以用 一種形成塗膜之樹脂，其物性如極性、分子量等是因熱 酸產生劑成分發熱輻射照射所產生之酸使樹脂分解而改 變，結果表現出對諸如鹼或酸水性顯影溶液、水顯影溶 液、有機溶劑顯影溶液等之溶解度。再者，對於該樹脂 組成物中用於調整對顯影溶液之其他樹脂，可以另依需 要配用。 作爲用於正型熱輻射-敏感性樹脂組成物所用樹脂成 分，其可述及作爲代表者，例如，應用於如丙烯酸樹脂 等基本樹脂之正型光化能量射線-敏感性組成物，其因 力口熱至已交聯而不溶於鹼顯影溶液或酸顯影溶液之塗膜 所形成之一種機轉，使經熱輻射照射之部位，因熱酸產 -11 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂： 線· 經濟部智慧財產局員工消費合作社印制农 經濟部智慧財產局員工消費合作社印製 479447 A7 ____B7__ 五、發明說明（1〇 ) 生劑受熱輻射照射所產生之酸，剪斷已交聯之結構，變 成可溶於鹼顯影溶液或酸顯影溶液（參見日本公開專利 公告第295064/1 994號、日本公開專利公告第3 0873 3/ 1 9 94號、日本公開專利公告第3 1 3 1 3 4/ 1 994號（=美國專 利第5,527,65 6號）、日本公開專利公告第3 1 3 1 3 5/ 1 994 號（=美國專利第5,527,65 6和第5,702,8 72號）、日本公 開專利公告第3 1 3 1 3 6/ 1 994號（=美國專利第5,527,65 6 珀第5,702,872號）、曰本公開專利公告第1 465 52/ 1 995 號等）。作爲上述正型熱輻射-敏感性樹脂，載於上述 各公告，其內容在此代替詳細說明。 熱酸產生劑是一種在曝光時產生酸之化合物。所生之 酸依化樹脂之分解。一種已知可用之化合物，可特別提 示者，例如，諸如毓鹽、銨鹽、鳞鹽、鎭鹽、硒鹽、 鐵-丙二烯鍺合物、釕-丙二烯鍺合物、矽烷醇-金屬螫合 物鍺合物、三嗪化合物、二疊氮萘醌化合物、磺酸酯、 磺酸醯亞胺酯、鹵素型化合物等。除上述者之外，也可 用曰本公開專利公告第1 46552/1 995號和日本公開專利 公告第23 773 1 /1 999號所述之熱酸產生劑。此等熱酸產 生劑成分可以與上述樹脂成混合物或與其本身鍵結之形 式。熱酸產生劑之配用比例，以每1 00重量份樹脂成份 計，一般較佳在約〇.卜約40重量份之範圍內，特別是 在約0.2-約20重量份。 該樹脂組成物可以溶解或擴散於例如有機溶劑、水、 或於其混合物之溶劑中而塗於基質表面上。作爲有機溶 -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) .. 線· 479447 A7 ___B7______ 五、發明說明（Π ) 劑而可述及者，例如，酮類、酯類、醚類、溶纖劑類、 芳族烴類、醇類、鹵化烴類等。 ，溶於或擴散於溶劑之該樹脂組成物可以用例如滾筒、 滾塗器、旋塗器、導滾塗器、噴塗、靜電塗複、浸塗、 絲印、旋塗等方法塗用。然後依需要靜置後乾燥於例如 約50-約13(TC之溫度以獲得正型熱輻射-敏感性樹脂塗 膜層（A-2)。 一種水性正型熱輻射-敏感性樹脂組成物可以獲自於 溶解或擴散上述正型熱輻射-敏感性樹脂組成物於水 中〇 正型熱輻射-敏感性樹脂組成物之水溶解或水擴散可 以進行於用鹼（中和劑）中和在樹脂中之可陰離子化基 (例如羧基），或用酸（中和劑）中和在樹脂中之可陽 離子化基（例如胺基）。 正型熱輻射-敏感性樹脂塗膜層（A-2)之顯影，當形成 塗膜層之正型熱輻射-敏感性樹脂組成物爲可陰離子化 時，則進行於用鹼顯影溶液；若其爲可陽離子化時’則 用酸顯影溶液。如果樹脂本身爲水溶液（例如含鏺鹽之 樹脂等），可行水顯影。 正型熱輻射-敏感性樹脂塗膜層（A-2)本身可爲導電性 或絕緣性。因此，若有需要，可以於熱輻射·敏感性樹 脂.組成物中配入一種導電材料（已知之導電顏料’例 如，各種金屬，其一種以上之合金和其氧化物’諸如 ·· 銀、銅、鐵、錳、鎳、鋁、鈷、鉻、鉛、鋅、鉍、IT0 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) · -丨線_ 經濟部智慧財產局員工消費合作社印製 479447 A7 B7 五、發明說明（12 ) (請先閱讀背面之注意事項再填寫本頁) 等’絕緣材料之表面塗有或蒸鍍此等導電材料者）；或 一種絕緣材料（塑膠細粉、絕緣無機粉等）以使該塗膜 產生導電性或絕緣性。絕緣塗膜在最後形成塗膜時之體 鐵:固有電阻，通常較佳超過1 〇9 Ω · Cm，特別是在1 0 10 Ω · cm-1018Q · cm範圍內。另一方面，導電塗膜在最 後形成之塗膜之體積固有電阻較佳通常小於1 〇9 Ω · cm，特別是在 1Ω · cm-108Q . cm。 上述負型或正型熱輻射-敏感性樹脂塗膜層（A)之厚度 並無嚴格限制，但可依最後積層體之用途等作適當選 擇，而較佳通常在約1微米-約5毫米之範圍內，特別 是約2微米-約5 0 0微米。 經濟部智慧財產局員工消費合作社印製 作爲本發明積層體內所用之熱輻射-透射性片層（B) 者，已知可用之產品對其材料無特別限制，只要樹脂片 至少透射約90%，較佳約99%或更高之所照熱輻射。可 用之片爲聚合物構成，例如，聚乙二醇對苯二酸酯、聚 氯乙烯、聚乙酸乙烯酯、聚乙烯醇縮丁醛、纖維素類、 聚氨基甲酸酯、聚丙烯酸酯、芳醯胺、Capton、聚甲基 戍烯、聚乙烯、聚丙烯等。特別以採用聚乙二醇對苯二 酸酯爲佳。片層（B)之厚度通常較佳爲約1〇微米-約5毫 米之範圍內，特別是約15微米-約5 00微米。 用於本發明積層體遮蔽熱輻射之能量射線-敏感性塗 膜層（C)是形成於片層（B)表面上最上一層，其設置使光 化能量射線從該塗膜層（C)之上層表面照射至本發明之 積層體，然後被顯影而形成塗膜層（C)中之圖案，然後 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 479447 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（13 ) 因爲塗膜層（c)遮蔽（吸收及/或反射）熱輻射’熱輻 射從已有圖案之塗膜層（C)之表面和對應形成於塗膜層 (C)中所成圖案而照射而至底層之熱輻射-敏感性樹脂塗 膜層（A)。 能量射線-敏感性塗膜層（C)是扮演防止在較低層之塗 膜層（A)因熱輻射照射而生實質之變化（固化或分解） 之角色，其爲因上述塗膜層（C)上層表面遮蔽（吸收及 /或反射）熱輻射之照射；同時，因爲塗膜層（C)本身 在處理溶液如水、有機溶劑。鹼、酸等之中因光化能量 射線之照射而變成可溶解或可擴散，可以形成塗膜層（A) 所需之相同圖案；或是因爲塗膜層（C)本身由於光化能 量射線之照射在諸如水、有機溶劑、鹼、酸等處理溶液 中變成爲不可溶性或非可擴散性。 作爲能量射線-敏感性塗膜層（C)，可用一種產物，含 有吸收熱輻射之物質，例如熱輻射吸收劑、著色劑（著 色顏料、著色染料等）、塡料等於塗膜層之中。 作爲上述熱輻射吸收劑者可以特別列示例如花青、噁 考鐵、嗤B惡英鏺、司快利萬（Squarylium)、節苯胺、偶 氮蒽醌、萘醌、鋁自由基鹽、酞花青、萘二甲花青，雙 (二噻戊烯）以及其間之錯合物等。 作爲上述著色劑之可列示者，例如，諸如氧化鈦、鋅 白、鉛白、鹼性硫酸鉛、硫酸鉛、鋅鋇白、硫化鋅、銻 白等白色顏料；如碳黑、乙炔黑、燈黑、骨碳、石墨、 鐵黑、苯胺黑等黑色顏料；如萘酚黃S、漢撒黃10G、 -15- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------!*--------^---------f-· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 9447 A7 ----____ B7 五、發明說明（14 ) 永久黃、永久橙等橙色顏料；如氧化鐵、琥珀等棕色顏 料；如氧化鐵紅、鉛紅、永久紅、喹吖啶類紅類料等紅 色劑料；如鈷紫、錳紫、堅牢紫B、甲基紫沈澱色料等 紫色顏料；如群青、普魯士藍、鈷藍、Cerulean藍、酞 花青藍、堅牢天藍等藍色顏料；如鉻綠、酞花青綠等綠 色顏料。 作爲上述塡料之可列示者，例如，氧化鋇粉、Blunc fixe、碳酸鋇、石青、黏土、矽石、白碳、矽藻土、滑 石、碳酸鎂、礬土白、雲母粉等。 熱輻射吸收劑、著色劑和塡料之配用比例是依所照射 之熱輻射線強度、能量射線-敏感性塗膜層（C)之厚度等 作適當選擇，但對熱輻射吸收劑可在塗膜層（C)之0.01 重量％ - 5 0重量％之一般範圍，較佳爲0 · 0 2重量％ - 3 0重 量％ ;對於著色劑和塡料則可在塗膜層（C)之0.5重量 90重量％，較佳爲1重量％-50重量％。 作爲遮蔽熱輻射之能量射線-敏感性塗膜層（C)，也可 用含有反射熱輻射之反射劑（片狀金屬顏料等）。 作爲上述反射劑之可列示者，例如（片狀）鋁粉、青 銅粉、銅粉、錫粉、鉛粉、鋅粉、磷化碳、似珍珠之金 屬鍍雲母粉、似雲母之氧化鐵等。 所用反射劑之配用比例可依能量射線-敏感性塗膜層 厚度、所照射之熱輻射強度等作適當選擇’但一般可望 在塗膜層（C)之0.5重量％-90重量°/〇之範圍內’較佳爲1 重量％ - 5 0重量％。 -16- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） --------^----------- (請先閱讀背面之注意事項再填寫本頁) 479447 A7 B7 五、發明說明（15 ) 上述熱輻射吸收劑和反射劑可以合倂使用。 ---------— If — (請先閱讀背面之注意事項再填寫本頁) 形成能量射線-敏感性塗膜層（C)之樹脂可爲負型或正 型’且所照能量射線可爲熱輻射、可見光或電子束之任 一種。 作爲負型或正型熱輻射-敏感型產物，可用與形成上 述塗膜層（A)是樹脂組成物相似之產物。 -丨線· 經濟部智慧財產局員工消費合作社印製 另外，作爲負型和正型之可見光-敏感型產物者，可 用配入光敏感劑至形成上述塗膜層（A)上前述樹脂組成 物內而製成之產物。作爲該光敏感劑之已知可用光敏感 性染料，其可述及者例如，噻咕噸型、咕噸型、酮型、 噻螺基鏺鹽型、鹼苯乙烯基型、部花青型、3 -取代之香 豆型、3，4-取代之香豆型、花青型、吖啶型、噻嗪型、 酚噻嗪型、蒽型、天苯並苯型、苯並蒽型、二 萘嵌苯 型、酮基香豆型、富馬鹼型、硼酸鹽型等。其間可單獨 或以二或多種合倂使用。作爲硼酸鹽型光敏感性染料， 可列示者，例如載於日本公開專利公告第2 4 1 3 3 8 /1 9 9 3 號、日本公開專利公告第5 6 8 5/ 1 995號（=美國專利第 S，498,64 1號）、日本公開專利公告第225474/ 1 995號 (=美國專利第5,498,64 1號）。光敏感劑之配用比例可 在塗膜層（C)中約爲0.1-20重量％，較佳約0.2-10重量％ 範圍內（固含量）。 熱輻射-敏感性樹脂組成物是一種含有被諸如紅外光 等熱射線所交聯或分解之樹脂而成之組成物。作爲該樹 脂組成物者可用一種已知之產物，其可列示者，例如， -17- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 479447 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（16 ) 含羥基之樹脂/胺樹脂之結合物、含羥基之樹脂/嵌段 之異氰酸酯、三聚氰醯胺樹脂、矽樹脂或丙烯酸樹脂等 之含可水解基者（例如，院氧基甲砂院基、經甲砂院基 等）之結合物、環氧樹脂/酚樹脂之結合物、環氧樹脂 /羧酸（酐）之結合物、環氧樹脂/聚胺之結合物、不飽 和樹脂/自由基聚合觸媒（例如過氧化物等）之結合 物、含羧基及/或羥苯基與醚鍵之烯鍵不飽和化合物 等。再如另外，可以用其與熱酸產生劑配合而作爲正 型。 ，該用以形成能量射線-敏感性塗膜層（C)之樹脂可以溶 解或擴散於例如有機溶劑、水或其混合物中而塗於片層 (B)之表面上。 作爲上述有機溶劑之可列示者，例如，酮類、酯類、 醚類、溶纖劑類、芳族烴、醇類、鹵化烴類等，且該樹 脂組成物之塗用可進行於例如用諸如滾輪、滾塗器、旋 塗器、幕滾塗器、噴塗、靜電塗複、浸塗、絲印、旋塗 等方法。然後在視需要靜置之後乾燥於例如約50-約 1 3 (TC之溫度而獲得能量射線-敏感性塗膜層（C)。 能量射線-敏感性塗膜層（C)之厚度較佳通常爲約在1 微米-約500微米之範圍內，較佳約2微米·約10〇微 米。 在如此所成積層體之能量射線-敏感性塗膜層（C)表面 如有需要可以設置一面層，而塗層可以藉由攔截空氣中 之氧而有效防止曝於射線所產生之自由基因氧而生之鈍 -18- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------丨-!-書———II訂---------線—丨 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印制农 9447 A7 _— B7 五、發明說明（17 ) 化，並以曝於射線固化光敏感性材料而順利進行。 如此之面塗層可以形成於例如用諸如聚乙二醇對苯二 酸酯等之聚酯、丙烯酸樹脂、聚乙烯、聚氯乙烯樹脂等 之樹脂膜（厚度約1-約70微米）覆蓋於積層體表面； 或用諸如聚乙烯醇、局部皂化之聚乙酸乙烯酯、聚乙烯 醇/乙酸乙烯酯共聚物、局部皂化之聚乙酸乙烯酯/乙 酸乙烯酯共聚物、聚乙烯基吡咯烷酮、水溶性多醣質聚 合物如黏稠性多糖、丙烯酸樹脂、聚酯樹脂、乙烯基樹 月旨、環氧樹脂等之含鹼基、酸基或鹽基者等水性樹脂之 水溶液或水擴散液予以塗複（乾膜厚度：約0.5-約5微 ^ )於積層體表面，然後予以乾燥。 本發明用於形成圖案之積層體可以製自例如如下1-4 各方法之一。 1.一種在基質上形成負型或正型熱輻射-敏感性樹脂塗 膜層（A)，然後形成一熱輻射-透射之片層（B)和進一步層 積一遮蔽熱輻射之能量射線-敏感性塗膜層（C)之方法： 塗膜層（A)可以形成於塗覆或層積上述形成塗膜層（A) 之樹脂組成物於基質表面；或將製自該樹脂組成物之塗 膜經過光敏感性或熱敏感性黏著劑（接著劑）層黏於一 基質表面上。層片（B)可以形成於以上述之片熱積於塗 膜層（A)上；或經由壓力敏感性或熱敏感性黏著劑（接 著劑）層而黏著於塗膜層（A)上。另外，能量射線-敏感 性塗膜層（C)可用塗覆或層積將形成能量射線-敏感性塗 膜層（C)之樹脂組成物至片層（B)表面上而積成；或經過 -19- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） AW--------tT---------線— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印制衣 479447 A7 B7 五、發明說明（18 ) 光敏感性或熱敏感性黏著劑（接著劑）層而黏合於片層 (B)上而成。 .2.—種形成負型或正型熱輻射-敏感性樹脂塗膜層（A) 於基質表面上，然後層積一預先形成包含一熱輻射-透 射片層（B)和-遮蔽熱輻射之能量射線-敏感性塗膜層（C) 之2層積層體至該塗膜（A)之表面上，使該片層（B)例之 表面與上述塗膜層（A)接觸之方法： 塗膜層（A)可用如上述方法1之情形形成於基質表面 上。設置於塗膜層（A)上之2層積層體可以獲自於在層 片（B)之表面上塗複或積合將形成能量射線-敏感性塗膜 層（C)之樹脂組成物；或將製自該樹脂組成物之膜經過 光敏感性或熱敏感黏著劑（接著劑）層之中介而黏著。 另外，該積層體之片層（B)側表面對塗膜層（A)之積合可 進行於例如利用熱積法或用壓力敏感性或熱敏感性之黏 著劑（接著劑）層之方法。 3.—種在基質表面積合一種預先由負型或正型熱輻射-敏感性樹脂塗膜層（A)、熱輻射-透射之片層（B)和遮蔽熱 輻射之能量射線-敏感性塗膜層（C)等所形成之3層積層 體，使該塗膜層（A)側表面與基質表面接觸之方法： 4 該包含一負型或正型熱輻射-敏感性樹脂塗膜層（A)、 熱輻射-透射之片層（B)和遮蔽熱輻射之能量射線-敏感性 塗膜層（C)等之三層積層體可以製自例如在片層（B)之表 面塗覆一種形成塗膜層（A)之樹脂組成物，然後在需要 時予乾燥之後，塗覆一種用於形成塗膜層（C)之樹脂組 -20- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ·- --線· 479447 經濟部智慧財產局員工消費合作社印制衣 A7 ______B7___ 五、發明說明（19 ) 成物至片層（B)之另一表面（塗膜層（A)與塗膜層（C)之塗 覆次序可以反轉）。另外，該3層積層體之塗膜層（A) 側於基質表面之積合可以以例如熱積層法進行。 4. 一種在基質表面積合一包括負型或正型熱輻射-敏感 性樹脂塗膜層（A)和熱輻射-透射之片層（B)所預成之2層 積層體，使該塗膜層（A)側之表面接觸於基質表面，然 後形成一如上所述之遮蔽熱輻射之能量射線-敏感性塗 膜層（C)於所得3層積層體片層（B)側表面之方法： _負型或正型之熱輻射-敏感性樹脂塗膜層（A)和熱輻射-透射之片層（B)所成之2層積層體可以獲自於例如塗覆 一種將形成塗膜層（A)之樹脂組成物至片層（B)之一表面 上。該2層積層體之塗膜層（A)側在基質表面上之積合 可以進行於用例如熱積之方法。再者，塗膜層（C)之形 成可以進行於用將形成該塗膜層之樹脂組成物予以塗覆 或層合，或經由光敏感性或熱敏感性黏著劑（接著劑） 層之中介而黏著製自該樹脂組成物之塗膜。 用上述所製成本發明積層體形成圖案，可以進行於例 如如下之各步驟： (i)經由阻罩之中介或直接依圖案照射光化能量射線至 用於形成圖案之積層體之能量射線-敏感性塗膜層（C) 上， • (ii)經由塗膜層（C)之顯影除去能量射線-敏感性塗膜 層（C)中已照射或未照射之部位， (iii)然後，在以熱輻射照射整個表面之後， -21- (請先閱讀背面之注意事項再填寫本頁) - «- --線. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 479447 A7 ____B7 經濟部智慧財產局員工消費合作社印制衣 五、發明說明（2()) (iv) 自積層體之熱輻射-敏感性樹脂塗膜層（A)除去熱 輻射-透射之片層（B)和能量射線-敏感性塗膜層（C)，露 出熱輻射-敏感性樹脂塗膜層（A)， (v) 然後，用顯影溶液使塗膜層（A)顯影。 作爲用於光化能量射線照射之光源，其可述及者，例 如，超高張力、高壓、中度張力或低壓之水銀燈、化學 燈、碳弧燈、氙燈、金屬鹵化物燈、鎢燈等；或諸如氬 雷射（ 48 8nm(奈米））、YAG-SHG 雷射（5 3 2nm)、U V 雷 射（3 5 1 - 3 6 4 n m)等雷射（括符內數字表示振盪曲線之波 長）。作爲熱輻射源之可述及者，例如，半導體雷射 (8 3 0nm)、YAG雷射（1.06微米）、紅外線等。 塗膜層（A)和塗膜層（C)之顯影，若塗膜爲陰離子性， 則可進行於鹼顯影溶液；若爲陽離子性’則用酸顯影溶 液。依據塗膜之性質，其亦可能用有機溶劑或水顯影。 顯影可用噴液或浸入顯影溶液於約10-約80°C之溫 度，較佳約15-約50°C，經約10秒至約60分鐘，較佳 紂30秒-約30分鐘。 可以述及之鹼顯影溶液，例如，單甲基胺、二甲基 胺、三甲基胺、單乙基胺、二乙基胺、三乙基胺、單異 丙基胺、二異丙基胺、三異丙基胺、單丁基胺、二丁基 胺、三丁基胺、單乙醇胺、二乙醇胺、三乙醇胺、二甲 基胺基乙醇、二乙基胺基乙醇、氨、苛性鈉、苛性鉀、 偏砂酸鈉、偏砂酸鉀、碳酸鈉、四乙基氫氧化錢等之各 A 種水溶液。 -22- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) # · -丨線· 479447 A7 Γ37 經濟部智慧財產局員工消費合作社印制衣 五、發明說明（21 ) 作爲酸性顯影溶液而可列示者，例如甲酸、巴豆酸、 乙酸、丙酸、乳酸、鹽酸、硫酸、硝酸、磷酸等之水溶 液。 •作爲有機溶劑之可述及者，例如，諸如已烷、庚烷、 ·· 辛烷、甲苯、二甲苯、二氯甲烷、三氯甲烷、四氯化 碳、三氯乙烯等烴類；諸如二乙基醚、二丙基醚、二丁 基醚、乙基乙儲基醚、二噁院、氧化丙烯、四氫呋喃、 溶纖劑、甲基溶纖劑、丁基溶纖劑、甲基卡必醇、二乙 二醇甲乙基醚等之醚類；諸如丙酮、甲基乙基酮、甲基 異丁基酮、異佛爾酮、環已酮等酮類；諸如乙酸甲酯、 乙酸乙酯、乙酸丙酯、乙酸丁酯等酯類；諸如吡啶、甲 ϋ胺、N，N-二甲基甲醯胺等之他類等溶劑。 本發明用於形成圖案之積層體可以應用於，例如，形 成於基質上之圖案，諸如黑色陣列圖案、用作濾色器之 圖案、用於覆蓋電子零件之圖案（用作焊料之塗膜）、 陶瓷或燐光體的圖案、顯示板之畫區圖案等；或應用於 絕緣基質，諸如佈線用之塑膠基質，用於組合之塑膠基 質等或設於其上之導電圖案。 本發明以實施例作更爲詳細之說明。份與％以重量 計，除另有說明。 食g·.量射線··敏感件組成物U)之製備例 於10 0份（固含量）之熱輻射-可固化樹脂（樹脂固 含量5 5 %，丙二醇單甲苯醚有機溶劑，樹脂酸値5 0毫 克KOH/克，數平均分子量約20, 〇〇〇)，製自以24份甲 -23- (請先閱讀背面之注咅？事項再填寫本頁) # 一·°J·' -丨線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印剩衣 479447 A7 _ B7 五、發明說明（22 ) 基丙烯酸液水甘油脂與60份丙烯酸樹脂（樹脂酸値1 5 5 毫克KOH/克，甲基丙烯酸甲酯/丙烯酸丁酯/丙烯酸 = 40/40/20重量比）而作爲能量射線可固化之樹脂（高 分子膠合劑），1份熱自由基聚合起始劑（CGI 784，商 品名，Ciba-Geigy製，二茂鉍化合物），和5分紅外線 吸收齊!l (NK-2268，商品名，Hayashibara Biochemical Labs·，Inc.製造，3-乙基-2-{2-[2-二苯基胺基-3-[2-(l-乙 基-2-苯并噻唑啉亞基）亞乙基]環戊烯基]乙烯基}苯并噻 唑啉鏺過氯酸酯）等被配入以獲得組成物（a)(固含量 15%)。 熱輻射-敏感件組成物（b)之製備例 對100份（固含量）由24份甲基丙烯酸液水甘油酯 咢60份丙烯酸樹脂（樹脂酸値155毫克KOH/克，甲基 丙烯酸甲酯/丙烯酸丁酯/丙烯酸=40/40/20重量比） 製成而作爲熱輻射可固化樹脂（高分子膠合劑）之光可 固化樹脂（樹脂固含量55%，丙二醇單甲基醚有機溶 劑、樹脂酸値 55毫克 KOH/克，數平均分子量約 20,000 )，配入5份熱陽離子聚合觸媒（SAN-AID-SIA ’ 商品名，SANSHIN CHEMICAL IND. CO., LTD·， 毓鹽），以所配成之生成物，與1份酞花青綠，5 0份滑 石和20份環氧樹月旨（Epikoto 828，商品名，Yuka Shell Epoxy Co.，Ltd.，製，雙酚A型液體環氧樹脂）同溶於 二乙二醇二甲基醚溶劑中而獲得組成物（b)(固含量 3 0%)。 -24- 本纸張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂： ;線· 479447 經，濟部智慧財彥扃員工消費合作社印製 Λ7 B7 -----—-- 五、發明說明（23 ) 眚施例1 (1) 在一銅箔（ 200 x 2 00 x 1.1毫米）上用棒塗層器塗 上熱輻射-敏感性組成物（b)，並初步乾燥於8 0 °C 1 0分鐘 而形成約3 0微米厚之熱輻射-敏感性樹脂塗膜層（I )。 然後在所形成塗膜表面上粘上一聚乙二醇對苯二甲酸酯 片（3 8微米）而獲得片層（Π)。然後用滾筒在片層（Π)上 塗覆能量射線-敏感性組成物（a)，使乾膜厚度爲6微 米，並乾燥於65 °C歷1〇分鐘而形成一種能量射線-敏感 性塗膜層（ΠΙ )。 (2) 然後使塗膜層（瓜）依圖案曝於氬離子雷射（5 mj/cm2) 之直接照射。然後使浸入於鹼顯影溶液（碳酸鈉水溶 液，0.25%)於25 t歷60秒而除去在曝光部位之塗膜層 (瓜）。 (3) 然後在塗膜之整個表面上用近紅外光雷射（1 J/cm2) 照射。 (4) 然後將能量射線-敏感性塗膜層（瓜）和片層（Π )經熱 輻射-敏感性樹脂塗膜層（I )剝去而獲得由銅箔和熱輻 射-敏感性樹脂塗膜層（I )所成之積層體。 (5) 然後將未固化（未曝光部位）之熱輻射-敏感性樹 脂塗膜層（I)以使該積層體浸入於25°C之0.75%碳酸鈉 水溶液6 0秒而除去。 所得圖案是線（圖紋寬）/間隔圖紋=1 0 0微米/ 2 0 微米之條形圖形，且爲良好。Co. Ltd. System, trade name, Yuyan) and so on. Each of them may be used alone or in a combination of two or more. Among the above-mentioned thermal mode reaction initiators, it is particularly preferable to use a salt, because it is easy to generate cations by heating, and has high activity for polymerization. The proportion of the thermal mode reaction initiator is 0. 1 per 100 parts by weight of heat radiation-curable resin or compound. 1-25 parts by weight, preferably 0. A range of 2-10 parts by weight. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Order: 丨 Line. Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 479447 A7 ----- B7 V. Description of the invention (6) If a thermal mode-cation polymerization catalyst is used, a cationic amplifying agent is preferred, which is exposed to heat radiation The cations produced are catalyzed and re-produced. Such a cationic amplifying agent is a compound with relatively strong residual acid, and it is easy to dissociate in the presence of a cationic catalyst and generate cations (acids). As such a cationic amplifying agent, there can be mentioned, for example, dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, phenylphosphonic acid, and the like. As an example of the combination of the above heat radiation-curable resin or compound and a thermal mode reaction initiator, it can be mentioned, for example, epoxy resin / thermal mode cationic polymerization catalyst, ether-containing olefin unsaturated compound / heat Mode cationic polymerization catalyst, unsaturated resin / thermal mode radical polymerization catalyst, etc. In addition, as a resin that can be used to form a negative heat radiation-sensitive resin coating film layer (A-1), for example, a self-crosslinkable olefin unsaturated compound having both a carboxyl group and / or a hydroxyphenyl group and an ether bond . Among the resin compositions forming the negative heat radiation-sensitive resin coating film layer (A-1) listed above, the epoxy resin / thermal mode cationic polymerization catalyst and the unsaturated resin / thermal mode radical polymerization catalyst are particularly used. The combination of media is preferred. For the resin composition forming the heat radiation-sensitive resin coating film layer (A-1), a saturated resin may be blended if necessary. The saturated resin can be used to control the solubility of the resin composition (the solubility of the barrier coating film in an alkali developing solution, or, for example, the solubility of a strong alkali solution used to remove a thermosetting coating film), and includes, for example, a polyester resin, an alkyd Resin, (meth) acrylic acid This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------- Order --------- Line-- (Please (Please read the notes on the back before filling this page) 479447 Λ7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (7) Acid resin, silicone resin, fluororesin, polyurethane resin, etc. These resins may be used alone or in a combination of two or more. The resin composition may be applied to the surface of a substrate by dissolving or diffusing in an organic solvent, water, or a mixed solvent therebetween, for example. Examples of the organic solvent include ketones, esters, ethers, cellulolytic agents, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, and the like. The resin composition dissolved or diffused in the solvent can be applied by, for example, a roller, a roll coater, a spin coater, a curtain roll coater, spray coating, electrostatic coating, lacquer coating, silk screen printing, spin coating, or the like. Then, the formed coating film is allowed to stand as necessary, and then dried at, for example, about 50 to about 130 ° C to obtain a negative thermal light-sensitive resin coating FL (A-1). The water-based negative heat radiation-sensitive resin composition can be obtained by dissolving or diffusing the above-mentioned negative heat radiation-sensitive resin composition. The water dissolution or water diffusion of the negative heat radiation-sensitive resin composition can be performed by neutralizing an anionizable group (such as a carboxyl group) in a heat radiation-curable resin with an alkali (neutralizing agent), or using an acid ( Neutralizer) to neutralize cationizable groups (such as amine groups) in heat radiation curable resins. In addition to the above, it is known that a water-developable heat radiation-curable resin composition can also be used as a negative heat radiation-sensitive resin composition. As such a substance, for example, an aqueous resin prepared by introducing a heat radiation-curable unsaturated group and an ion-forming group into a novolac epoxy resin. The water-based resin can be obtained, for example, by adding (meth) acrylic acid to a part of epoxy groups of a novolac epoxy resin and forming water solubility by reacting at least part of the epoxy groups with, for example, a tertiary amine compound. Iron (Please read the precautions on the back before filling out this page) · -1 line ·-· This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Clothing 479447 A7 137 V. Description of the invention (8) The base is given to heat curability to the resin. The part of the obtained water-based resin exposed to heat radiation is cured to become water-insoluble, while the part not exposed to heat radiation is developed and removed by water. Furthermore, after the water-developed film is heated, the ionizable groups remaining in the cured film can be made hydrophobic by heating (for example, at about 1 40-200 ° C for 10-30 minutes). d This can form a coating film which has excellent corrosion resistance characteristics without hydrophilic groups (carboxyl group, amine group, etc.) or its salt (salt formed with the developing solution), which is formed from the above-mentioned alkali developable The corrosion-resistant coating film of an acid-developable heat-sensitive composition has the coating film. In addition, in addition to linear epoxy resins, it is also possible to use (meth) acrylic acid and, for example, tertiary amines, and unsaturated monomer copolymers which can be radically polymerized with epoxy groups, as described above , Such as glycidyl (meth) acrylate 3,4-epoxycyclohexylalkyl (meth) acrylate, vinyl glycidyl ether, etc .; or a copolymer consisting of more than one of these monomers and another A radically polymerizable unsaturated monomer (such as alkyl (meth) acrylates or naphthenes having 1 to 24 carbon atoms), a radically polymerizable unsaturated aromatic compound, etc. are obtained by reaction. The development of the negative heat radiation-sensitive resin coating film layer (A-1) is performed. If the negative heat radiation-sensitive resin composition forming the coating film layer is anionizable, an alkali developing solution is used; For those that can be cationized, the solution is developed with acid. If the resin itself is water-soluble (such as the above-mentioned resins containing osmium salt, etc.), water development can be performed. The negative heat radiation-sensitive resin coating film layer (A-1) itself may be conductive or insulating. Therefore, if necessary, the thermal radiation-sensitive resin-10- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Order : 丨 line · 479447 A7 B7 V. Description of the invention (9) The composition is compounded with a conductive material (known conductive pigments, for example, various metals, more than one alloy thereof and its oxides, such as silver, copper, iron, Manganese, nickel, aluminum, cobalt, chromium, lead, zinc, bismuth, IT0, etc., whose surface is coated or vapor-deposited with a conductive material, or an insulating material (fine plastic powder, insulating inorganic powder) Materials, etc.) to make the coating film conductive or insulating. The insulating coating film preferably has a volume intrinsic resistance of the finally formed coating film which usually exceeds 109 Ω · cm, especially in the range of 10 (Ω) 〇ηι-1018Ω · cm. On the other hand, the coating film formed at the end of the conductive coating film preferably has a volume intrinsic resistance of usually less than 109Ω · cm, especially in the range of 1Ω · cm-108Q · cm. On the other hand, as the resin composition forming the positive heat radiation-sensitive resin coating film layer (Ling-2), the composition which can be used includes, for example, a thermal acid generator component and a resin component. As the resin component, a coating film-forming resin can be used, and its physical properties such as polarity and molecular weight are changed by decomposition of the resin due to the acid generated by the thermal acid generator component due to heat radiation and radiation. Solubility of solution, water developing solution, organic solvent developing solution, etc. In addition, other resins for adjusting the developing solution in the resin composition may be formulated as needed. As the resin component used in the positive heat radiation-sensitive resin composition, it can be mentioned as a representative, for example, a positive actinic energy ray-sensitive composition applied to a basic resin such as an acrylic resin, and its reason It is heated by heat to a mechanism formed by the coating film that has been cross-linked and is not soluble in the alkali developing solution or the acid developing solution, so that the parts exposed to heat radiation are produced by thermal acid-11-This paper size applies to Chinese national standards ( CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page) Order: Printed by the line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Agriculture and Economy 479447 A7 ____B7__ 5. Description of the invention (1) The acid produced by the irradiation of the biocide by the radiation cuts the cross-linked structure and becomes soluble in an alkali developing solution or an acid developing solution (see Japanese Laid-Open Patent Publication No. 295064/1 994 No. 3, Japanese Patent Publication No. 3 0873 3/1 9 94, Japanese Patent Publication No. 3 1 3 1 3 4/1 994 (= US Patent No. 5,527,65 6), Japanese Patent Publication No. 3 1 3 1 3 5/1 994 (= US Patent Nos. 5,527,65 6 and 5,702,8 72), Japanese Published Patent Publication No. 3 1 3 1 3 6/1 994 (= US Patent No. 5,527,65 6 No. 5,702,872), Japanese Patent Publication No. 1 465 52/1995, etc.). As the above-mentioned positive heat radiation-sensitive resin, it is contained in each of the above-mentioned bulletins, and its content is replaced here with a detailed description. A thermal acid generator is a compound that generates an acid upon exposure. The resulting acid decomposes the resin. A compound that is known to be useful, and may be particularly reminded, for example, such as salt, ammonium, scale, osmium, selenium, iron-propadiene germanium, ruthenium-propadiene germanate, silanol -A metal adduct germanium, a triazine compound, a diazonaphthoquinone compound, a sulfonate, a sulfonium imine sulfonate, a halogen compound, and the like. In addition to the above, thermal acid generators described in Japanese Laid-Open Patent Publication No. 1 46552/1 995 and Japanese Laid-Open Patent Publication No. 23 773 1/1 999 can also be used. These thermal acid generator components may be in the form of a mixture with the above resin or a bond with itself. The mixing ratio of the hot acid generator is generally preferably about 0.000 per 100 parts by weight of the resin component. Bu in the range of about 40 parts by weight, especially in about 0. 2- about 20 parts by weight. The resin composition can be dissolved or diffused in a solvent such as an organic solvent, water, or a mixture thereof, and applied to the surface of the substrate. As an organic solvent -12- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page). . Line · 479447 A7 ___B7______ V. Inventive (Π) agents that can be mentioned, for example, ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, etc. The resin composition dissolved or diffused in a solvent can be applied by, for example, a roller, a roll coater, a spin coater, a guide roll coater, spray coating, electrostatic coating, dip coating, screen printing, spin coating, or the like. Then, it is allowed to stand and then dried at a temperature of, for example, about 50 to about 13 ° C. to obtain a positive heat radiation-sensitive resin coating film layer (A-2). An aqueous positive heat radiation-sensitive resin composition may be Obtained from dissolving or diffusing the positive heat radiation-sensitive resin composition described above in water. The water dissolution or water diffusion of the positive heat radiation-sensitive resin composition can be performed by neutralizing the resin with an alkali (neutralizing agent). The neutralizable anionizable group (such as carboxyl group), or the acid (neutralizing agent) to neutralize the cationizable group (such as amine group) in the resin. Positive heat radiation-sensitive resin coating film layer (A-2 ) Development, when the positive heat radiation-sensitive resin composition forming the coating film layer is anionizable, it is carried out with an alkali developing solution; if it is cationizable, then an acid developing solution is used. If the resin It is an aqueous solution (such as a resin containing osmium salt, etc.), which can be developed by water. The positive heat radiation-sensitive resin coating film layer (A-2) itself can be conductive or insulating. Therefore, if necessary, Heat radiation sensitive resin. A conductive material (known conductive pigments such as various metals, one or more alloys and oxides thereof) such as silver, copper, iron, manganese, nickel, aluminum, cobalt, chromium, lead, Zinc, bismuth, IT0 -13- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ·-_ Line _ Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the employee consumer cooperative 479447 A7 B7 V. Description of the invention (12) (Please read the precautions on the back before filling out this page) etc. The surface of the insulating material is coated or vapor-deposited with such conductive materials; or an insulating material (Plastic fine powder, insulating inorganic powder, etc.) to make the coating film conductive or insulating. The body of the insulating coating film when the coating film is finally formed. Iron: inherent resistance, which usually preferably exceeds 109 Ω · Cm, especially in the range of 10 10 Ω · cm-1018Q · cm. On the other hand, the volume inherent resistance of the final coating film formed by the conductive coating film is preferably generally less than 109 Ω · cm, especially 1Ω · cm-108Q. cm. The thickness of the above-mentioned negative or positive heat radiation-sensitive resin coating layer (A) is not strictly limited, but may be appropriately selected according to the purpose of the final laminated body, etc., and it is usually preferably about 1 micrometer to about 5 mm. Within this range, in particular from about 2 microns to about 500 microns. If the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the thermal radiation-transmissive sheet (B) used in the laminated body of the present invention, it is known that the available products have no particular restrictions on its material, as long as the resin sheet transmits at least about 90%, Preferably, about 99% or more of the radiated heat radiation. Useful tablets are made of polymers such as polyethylene glycol terephthalate, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, celluloses, polyurethanes, polyacrylates, Arylamine, Capton, polymethylpinene, polyethylene, polypropylene, etc. Particularly preferred is the use of polyethylene glycol terephthalate. The thickness of the sheet layer (B) is usually preferably in the range of about 10 micrometers to about 5 millimeters, particularly about 15 micrometers to about 500 micrometers. The energy ray-sensitive coating film layer (C) used for shielding the heat radiation of the laminated body of the present invention is the uppermost layer formed on the surface of the sheet layer (B), and is provided to enable actinic energy rays to pass from the coating film layer (C). The upper surface is irradiated to the laminated body of the present invention, and then developed to form the pattern in the coating film layer (C), and then -14- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 479447 Economy Printed by A7 B7, Consumer Cooperatives of the Ministry of Intellectual Property Bureau. 5. Description of the invention (13) Because the coating layer (c) shields (absorbs and / or reflects) thermal radiation. The thermal radiation from the existing pattern of the coating layer (C). The surface and the heat radiation-sensitive resin coating film layer (A) irradiated to the bottom layer corresponding to the pattern formed in the coating film layer (C). The energy ray-sensitive coating film layer (C) plays a role in preventing the coating film layer (A) in the lower layer from being substantially changed (cured or decomposed) due to heat radiation. C) The surface of the upper layer is shielded (absorbed and / or reflected) by heat radiation; at the same time, because the coating film layer (C) itself is in a processing solution such as water and organic solvents. The alkali, acid, etc. become soluble or diffusible due to the irradiation of actinic energy rays, and can form the same pattern required by the coating film layer (A); or because the coating film layer (C) itself is due to actinic energy rays The irradiation becomes insoluble or non-diffusible in treatment solutions such as water, organic solvents, alkalis, acids, etc. As the energy-ray-sensitive coating film layer (C), a product can be used that contains a substance that absorbs thermal radiation, such as a heat radiation absorbent, a colorant (coloring pigment, coloring dye, etc.), and a material equal to the coating film layer. As the above heat radiation absorber, there can be listed specifically examples such as cyanine, oxacoside, 嗤 Boxin 鏺, Squarylium, benzidine, azoanthraquinone, naphthoquinone, aluminum radical salt, phthalocyanine Cyanine, naphthalene cyanine, bis (dithiapentene), and complexes in between. As examples of the above-mentioned colorants, for example, white pigments such as titanium oxide, zinc white, lead white, basic lead sulfate, lead sulfate, zinc barium white, zinc sulfide, antimony white, and the like; such as carbon black, acetylene black, Lamp black, bone carbon, graphite, iron black, aniline black and other black pigments; such as naphthol yellow S, Hansa yellow 10G, -15- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ---------! * -------- ^ --------- f- · (Please read the notes on the back before filling out this page) Intellectual Property Bureau, Ministry of Economic Affairs Printed by employee consumer cooperatives 9447 A7 ----____ B7 V. Description of the invention (14) Orange pigments such as permanent yellow and orange; brown pigments such as iron oxide and amber; iron oxide red, lead red, permanent red, quine Red materials such as acridine red materials; purple pigments such as cobalt violet, manganese violet, fast violet B, and methyl violet precipitation pigments; such as ultramarine blue, Prussian blue, cobalt blue, Cerulean blue, phthalocyanine blue, fast Blue pigments such as sky blue; green pigments such as chrome green and phthalocyanine green. Illustrative examples of the aforementioned materials include barium oxide powder, Blunc fixe, barium carbonate, azurite, clay, silica, white carbon, diatomite, talc, magnesium carbonate, alumina white, mica powder, and the like. The proportion of the heat radiation absorber, colorant and filler is appropriately selected according to the intensity of the heat radiation irradiated, the thickness of the energy ray-sensitive coating layer (C), etc., but the heat radiation absorber can be used in Coating layer (C) of 0. 01% by weight-50% by weight in the general range, preferably 0. 02% by weight-30% by weight; for colorants and materials can be in the coating film layer (C) of 0. 5 weight to 90 weight%, preferably 1 to 50 weight%. As the energy ray-sensitive coating film layer (C) that shields heat radiation, a reflective agent (a sheet-like metallic pigment, etc.) containing heat radiation can also be used. Examples of the above-mentioned reflectors include (flake) aluminum powder, bronze powder, copper powder, tin powder, lead powder, zinc powder, phosphorous carbon, pearl-like metal-plated mica powder, and mica-like iron oxide. Wait. The proportion of the reflecting agent used can be appropriately selected according to the thickness of the energy ray-sensitive coating film layer and the intensity of the radiated heat radiation, etc., but it is generally expected to be 0 in the coating film layer (C). Within the range of 5% by weight to 90% by weight / ° ', it is preferably 1% by weight to 50% by weight. -16- This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) -------- ^ ----------- (Please read the precautions on the back first (Fill in this page again) 479447 A7 B7 V. Description of the invention (15) The above heat radiation absorber and reflector can be used in combination. ---------— If — (Please read the precautions on the back before filling this page) The resin that forms the energy ray-sensitive coating layer (C) can be negative or positive. The energy ray may be any of thermal radiation, visible light, or an electron beam. As a negative-type or positive-type heat radiation-sensitive product, a product similar to that in which the above-mentioned coating film layer (A) is a resin composition can be used. -丨 Line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, as negative and positive visible light-sensitive products, a photosensitizer can be blended into the aforementioned resin composition on the coating layer (A) And made product. Known usable light-sensitive dyes as the light-sensitive agent, which can be mentioned, for example, thioxanthan type, gluttonyl type, ketone type, thiospironium salt type, basic styryl type, merocyanine type , 3-substituted coumarin type, 3,4-substituted coumarin type, cyanine type, acridine type, thiazine type, phenothiazine type, anthracene type, benzobenzone type, benzoanthracene type, Perylene type, keto-coumar type, fumarine type, borate type, etc. It may be used alone or in a combination of two or more. As borate-type light-sensitive dyes, those listed can be listed in, for example, Japanese Patent Publication No. 2 4 1 3 3 8/1 9 93, Japanese Patent Publication No. 5 6 8 5/1 995 (= US Patent No. S, 498,64 1), Japanese Laid-Open Patent Publication No. 225474 / 1,995 (= US Patent No. 5,498,64 1). The proportion of the photosensitizer can be about 0 in the coating layer (C). 1-20% by weight, preferably about 0. In the range of 2-10% by weight (solid content). The heat radiation-sensitive resin composition is a composition containing a resin crosslinked or decomposed by heat rays such as infrared light. As the resin composition, a known product can be used, and it can be listed, for example, -17- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 479447 Employees of the Intellectual Property Bureau of the Ministry of Economy Consumption Printed by the cooperative A7 B7 V. Description of the invention (16) Hydrolyzable resin / amine resin combination, hydroxyl-containing resin / block isocyanate, melamine resin, silicone resin or acrylic resin, etc. Bases (for example, oxymethane bases, methanosyl bases, etc.) combinations, epoxy resin / phenol resin combinations, epoxy resin / carboxylic acid (anhydride) combinations, epoxy resins / Polyamine combination, unsaturated resin / radical polymerization catalyst (such as peroxides) combination, ethylenically unsaturated compounds containing carboxyl and / or hydroxyphenyl and ether bonds, etc. As another example, it can be used as a positive type in combination with a thermal acid generator. The resin used to form the energy ray-sensitive coating film layer (C) can be dissolved or diffused in, for example, an organic solvent, water, or a mixture thereof, and applied to the surface of the sheet layer (B). As examples of the organic solvents mentioned above, for example, ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, etc., and the application of the resin composition can be performed, for example, in Use methods such as rollers, roll coaters, spin coaters, curtain roll coaters, spray coating, electrostatic coating, dip coating, screen printing, spin coating, etc. Then, after standing still as necessary, it is dried at a temperature of, for example, about 50 to about 1 3 (TC) to obtain the energy ray-sensitive coating film layer (C). The thickness of the energy ray-sensitive coating film layer (C) is preferably usually In the range of about 1 micrometer to about 500 micrometers, preferably about 2 micrometers to about 10 micrometers. A surface layer can be provided on the surface of the energy ray-sensitive coating film layer (C) of the laminated body thus formed if necessary. And the coating can effectively prevent the bluntness caused by exposure to the free genetic oxygen produced by the rays by intercepting the oxygen in the air -18- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------- 丨-!-Books ———— Order II --------- Line— 丨 (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Cooperative printed agricultural 9447 A7 _ — B7 V. Description of the invention (17), and the light-sensitive material is cured by exposure to radiation. Such a surface coating can be formed, for example, with polyethylene glycol terephthalate Polyester, acrylic resin, polyethylene, polyvinyl chloride resin and other resin films (thickness about 1 to about 70 micrometers) ) Cover the surface of the laminate; or use materials such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl alcohol / vinyl acetate copolymer, partially saponified polyvinyl acetate / vinyl acetate copolymer, polyvinylpyrrolidone Water-soluble polysaccharide polymers such as viscous polysaccharides, acrylic resins, polyester resins, vinyl resins, epoxy resins, and other base resins, acid or salt-based aqueous solutions or aqueous dispersions Complex (dry film thickness: about 0. 5-about 5 micrometers) on the surface of the laminate, and then dried. The laminated body for forming a pattern of the present invention can be produced by, for example, one of the following methods 1-4. 1. A method for forming a negative or positive thermal radiation-sensitive resin coating layer (A) on a substrate, and then forming a thermal radiation-transmissive sheet (B) and further laminating an energy ray-sensitivity for shielding thermal radiation Method for coating film layer (C): The coating film layer (A) may be formed by coating or laminating the resin composition forming the coating film layer (A) on the surface of a substrate; or applying a coating film made from the resin composition A layer of light-sensitive or heat-sensitive adhesive (adhesive) is adhered to a substrate surface. The layer sheet (B) may be formed on the coating film layer (A) by thermally accumulating the above sheet, or may be adhered to the coating film layer (A) through a pressure-sensitive or heat-sensitive adhesive (adhesive) layer. In addition, the energy ray-sensitive coating film layer (C) can be coated or laminated to deposit the resin composition forming the energy ray-sensitive coating film layer (C) on the surface of the sheet (B); or -19- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) AW -------- tT --------- line— (Please read the note on the back first Please fill in this page again) Printed clothing 479447 A7 B7, Employee Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) Light-sensitive or heat-sensitive adhesive (adhesive) layer and adhered to the sheet (B) Made. . 2. -Forming a negative or positive heat radiation-sensitive resin coating layer (A) on the surface of the substrate, and then laminating a pre-formed energy ray including a heat radiation-transmissive sheet (B) and-shielding heat radiation -A method for making a two-layer laminate of the sensitive coating film layer (C) onto the surface of the coating film (A), and contacting the surface of the sheet layer (B) with the above-mentioned coating film layer (A): (A) can be formed on the surface of the substrate as in the case of the above method 1. The two-layer laminate provided on the coating film layer (A) can be obtained from a resin composition that is coated or laminated on the surface of the ply (B) to form an energy ray-sensitive coating film layer (C); or The film made from the resin composition is adhered through a layer of a light-sensitive or heat-sensitive adhesive (adhesive). In addition, the lamination of the layer (B) side surface of the laminate to the coating film layer (A) can be performed, for example, by a thermal deposition method or a pressure-sensitive or heat-sensitive adhesive (adhesive) layer method. . 3. -A kind of a negative or positive heat radiation-sensitive resin coating layer (A), a heat radiation-transmitting sheet (B) and an energy ray-sensitive coating layer that shields heat radiation in advance on the surface area of the substrate (C) The method of forming a three-layer laminated body such that the side surface of the coating layer (A) is in contact with the surface of the substrate: 4 The negative- or positive-type heat radiation-sensitive resin coating layer (A) The three-layer laminate of thermal radiation-transmissive sheet (B) and energy ray-sensitive coating film layer (C) that shields thermal radiation can be produced by, for example, applying a coating on the surface of sheet (B) to form a coating. The resin composition of the film layer (A) is then dried when necessary, and then a resin group for forming the coating film layer (C) is applied. -20- This paper is in accordance with China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) · --- Line · 479447 Printed clothing A7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (19) Finished product to sheet (B) the other surface (the coating order of the coating film layer (A) and the coating film layer (C) can be reversed). The coating of the coating layer (A) on the substrate surface of the three-layer laminate can be performed, for example, by a thermal lamination method. 4. A pre-formed two-layer laminate comprising a negative or positive heat radiation-sensitive resin coating film layer (A) and a heat radiation-transmitting sheet layer (B) combined on a surface area of a substrate so that the coating film layer ( A) The surface on the side is in contact with the surface of the substrate, and then an energy ray-sensitive coating film layer (C) for shielding heat radiation as described above is formed on the side surface of the obtained 3-layer laminate sheet (B): _ negative The two-layer laminate formed of the heat radiation-sensitive resin coating film layer (A) and the heat radiation-transmitting sheet layer (B) of the positive or positive type can be obtained, for example, by applying a coating film layer (A ) Onto the surface of one of the sheets (B). The accumulation of the coating layer (A) side of the two-layer laminate on the surface of the substrate can be performed by, for example, a thermal deposition method. Furthermore, the formation of the coating film layer (C) may be performed by coating or laminating the resin composition forming the coating film layer, or via an intermediate layer of a light-sensitive or heat-sensitive adhesive (adhesive). A coating film made from the resin composition is adhered. The formation of a pattern using the laminated body of the present invention made as described above can be performed, for example, in the following steps: (i) irradiating actinic energy rays through a mask intermediary or directly according to the pattern to the energy rays of the laminated body for pattern formation-sensitive On the coating film layer (C), • (ii) remove the irradiated or unirradiated parts of the energy ray-sensitive coating film layer (C) through the development of the coating film layer (C), (iii) then, After the heat radiation irradiates the entire surface, -21- (Please read the precautions on the back before filling this page)-«---- line. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 479447 A7 ____B7 Printing of clothing by employees' consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2 ()) (iv) Heat of self-laminated bodies The radiation-sensitive resin coating layer (A) removes the thermal radiation-transmitting sheet layer (B) and the energy ray-sensitive coating layer (C), exposing the thermal radiation-sensitive resin coating layer (A), ( v) Then, the coating film layer (A) is developed with a developing solution. As a light source for actinic energy ray irradiation, it can be mentioned, for example, ultra-high tension, high pressure, medium tension or low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, tungsten lamp, etc. ; Or lasers such as argon laser (48 8nm (nanometer)), YAG-SHG laser (5 3 2nm), UV laser (3 5 1-3 6 4 nm), etc. (the numbers in parentheses indicate the oscillation curve Its wavelength). As a source of thermal radiation, for example, semiconductor laser (830 nm), YAG laser (1. 06 microns), infrared and so on. For the development of the coating film layer (A) and the coating film layer (C), if the coating film is anionic, it can be performed in an alkaline developing solution; if it is cationic, the solution is developed with an acid. Depending on the nature of the coating film, it may also be developed with organic solvents or water. The development can be carried out by spraying or immersing the developing solution at a temperature of about 10 to about 80 ° C, preferably about 15 to about 50 ° C, for about 10 seconds to about 60 minutes, preferably 纣 30 seconds to about 30 minutes. Alkali developing solutions that can be mentioned, for example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Amine, triisopropylamine, monobutylamine, dibutylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, ammonia, caustic soda , Caustic Potassium, Sodium Metasalvate, Potassium Metasalvate, Sodium Carbonate, Tetraethyl Hydroxide, etc. -22- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) # ·-丨 Line · 479447 A7 Γ37 Staff of Intellectual Property Bureau, Ministry of Economic Affairs Consumption Cooperative Printed Clothing 5. Description of the Invention (21) As an acidic developing solution, for example, formic acid, crotonic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like can be listed. • As organic solvents, for example, hydrocarbons such as hexane, heptane, octane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, etc. Diethyl ether, dipropyl ether, dibutyl ether, ethyl ethyl ether, dioxin, propylene oxide, tetrahydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methylcarbitol , Diethylene glycol methyl ethyl ether and other ethers; such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone and other ketones; such as methyl acetate, ethyl acetate, Ester such as propyl acetate, butyl acetate; other solvents such as pyridine, formamidine, N, N-dimethylformamide and the like. The laminated body for pattern formation of the present invention can be applied to, for example, a pattern formed on a substrate such as a black array pattern, a pattern used as a color filter, a pattern for covering electronic parts (a coating film used as a solder) , Patterns of ceramics or phosphors, patterns of display areas of display boards, etc .; Or applied to insulating substrates, such as plastic substrates for wiring, plastic substrates for assembly, etc., or conductive patterns provided on them. The present invention will be described in more detail with examples. Parts and% are by weight unless otherwise stated.食 g ·. Measuring rays ·· Sensitive component composition U) Preparation example Heat radiation-curable resin (solid content: 55%, propylene glycol monotoluene organic solvent, resin acid: 50 mg KOH) / Gram, number average molecular weight about 20, 00)), made from 24 parts of A-23- (Please read the note on the back? Matters before filling out this page) # 一 · ° J · '-丨 Line · This Paper size applies to China National Standard (CNS) A4 (210 X 297 mm). The Intellectual Property Bureau, Ministry of Economic Affairs, Employees' Cooperatives, Printed Clothes 479447 A7 _ B7 V. Description of the invention (22) Acrylic liquid water glycerol and 60 parts of acrylic acid Resin (resin acid 155 mg KOH / g, methyl methacrylate / butyl acrylate / acrylic acid = 40/40/20 weight ratio) and energy ray curable resin (polymer adhesive), 1 part Thermal radical polymerization initiator (CGI 784, trade name, manufactured by Ciba-Geigy, bismuthcene compound), and 5 minutes infrared absorption! (NK-2268, trade name, Hayashibara Biochemical Labs, Inc. Manufacture, 3-ethyl-2- {2- [2-diphenylamino group 3- [2- (l-ethyl-2-benzothiazolinylidene) ethylene] cyclopentenyl] Vinyl} benzothiazolinium sulfonium perchlorate) and the like are compounded to obtain a composition (a) (solid content: 15%). Preparation example of heat radiation-sensitive component composition (b): 100 parts (solid content) of 24 parts of methacrylic acid liquid water glyceride; 60 parts of acrylic resin (resin acid: 155 mg KOH / g, methyl methacrylate) / Butyl acrylate / acrylic acid = 40/40/20 weight ratio) light curable resin (resin solid content 55%, propylene glycol monomethyl ether organic solvent, Resin acid 55 mg KOH / g, number average molecular weight about 20,000), compounded with 5 parts of thermal cationic polymerization catalyst (SAN-AID-SIA 'trade name, SANSHIN CHEMICAL IND. CO. , LTD., Yu salt), with the prepared product, and 1 part of phthalocyanine green, 50 parts of talc and 20 parts of epoxy tree moon purpose (Epikoto 828, trade name, Yuka Shell Epoxy Co. , Ltd. , Made, bisphenol A liquid epoxy resin) were dissolved in diethylene glycol dimethyl ether solvent to obtain composition (b) (solid content 30%). -24- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back before filling out this page) Order:; line · 479447 warp Printed by employee consumer cooperative Λ7 B7 --------- V. Description of invention (23) 眚 Example 1 (1) In a copper foil (200 x 2 00 x 1. 1 mm) with a bar coater to apply the heat radiation-sensitive composition (b), and preliminary drying at 80 ° C for 10 minutes to form a heat radiation-sensitive resin coating layer of about 30 microns thick (I). Then, a polyethylene glycol terephthalate sheet (38 m) was adhered to the surface of the formed coating film to obtain a sheet layer (Π). Then apply the energy ray-sensitive composition (a) to the sheet layer (Π) with a roller, so that the dry film thickness is 6 microns, and dry at 65 ° C for 10 minutes to form an energy ray-sensitive coating film. Layer (II). (2) The patterned layer (melon) is then directly exposed to an argon ion laser (5 mj / cm2) in a pattern. Then immersed in an alkali developing solution (aqueous sodium carbonate solution, 0. 25%) at 25 t for 60 seconds to remove the coating film layer (melon) on the exposed area. (3) Then irradiate the entire surface of the coating film with a near-infrared laser (1 J / cm2). (4) The energy ray-sensitive coating film layer (melon) and the sheet layer (Π) are then peeled off by the heat radiation-sensitive resin coating film layer (I) to obtain a copper foil and a heat radiation-sensitive resin coating. The laminated body formed by the film layer (I). (5) The uncured (unexposed area) heat-sensitive resin coating film layer (I) is then immersed in the laminate at 25 ° C to 0. The 75% sodium carbonate aqueous solution was removed in 60 seconds. The obtained pattern was a stripe pattern of line (pattern width) / space pattern = 100 μm / 20 μm, and was good.
%MMJL 0 * -25- 1紙^^用中國國家標準（CNS)A4規格（210 X 297公釐） ---------iii (請先閱讀背面之注意事項再填寫本頁) · --線· 經濟部智慧財產局員工消費合作社印製 479447 A7 --—__ B7 五、發明說明（24 ) 進行如同實施例1之處理，但以能量射線-敏感性塗 膜層（ΠΙ )和片層（II )預先層合之產物層積於熱輻射-敏感 性樹脂塗膜層（I )。所得圖案是線（圖紋寬度）/間隔 = 1·00微米/ 20微米成條狀圖形而且良好。 實施例3 進行如同實施例1之處理，但以熱輻射-敏感性樹脂 塗膜層（I )和片層（Π)預先層合產物層積於基質上，然 後形成能量射線-敏感性塗膜層（ΠΙ )。所得圖案成爲線 (圖紋寬度）/間隔=100微米/ 20微米之條狀圖形， 且爲良好。 實施例1 4 進行如同實施例1之處理，但以由熱輻射-敏感性樹 脂塗膜層（I )、片層（π )和能量射線-敏感性塗膜層（m ) 所預先層合之產物層積至基質上。所得圖案成爲線（圖 拳. 紋寬度）/間隔=100微米/ 20微米之條狀圖形，且爲 良好。 比較例1 在實施例1內，積層體之形成和顯影仍如同實施例 1，但塗膜層（m )不含熱輻射吸收劑。結果，所有所得之 膜因線之殘餘性質和間隔解析性質低劣而爲不良。 比較例2 如實施例2，積層體之形成和顯影仍如同實施例2， 但塗膜層（ΠΙ )不含熱輻射吸收劑。結果，所得之膜因線 之殘餘性質和間隔之解析性質低劣而不良。 -26- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------!——#------- —訂--------- 線丨Λ (請先閱讀背面之注意事項再填寫本頁) 479447 A7 ___ B7___ 五、發明說明（25 ) 比較例3 如實施例3，積層體之形成和顯影仍如同實施例3， 但塗膜層（ΠΙ )不含熱輻射吸收劑。結果，所得之膜因線 之殘餘性質和間隔之解析性質低劣而不良。 比較例4 如貫施例4，積層體之形成和顯影仍如同實施例4， 但塗膜層（m )不含熱輻射吸收劑。結果，所得之膜因線 之殘餘性質和間隔之解析性質低劣而不良。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）% MMJL 0 * -25- 1 paper ^^ Chinese National Standard (CNS) A4 (210 X 297 mm) --------- iii (Please read the precautions on the back before filling this page) · --Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 479447 A7 ---__ B7 V. Description of Invention (24) The treatment as in Example 1 was performed, but the energy ray-sensitive coating film layer (ΠΙ) The product previously laminated with the sheet layer (II) is laminated on the heat radiation-sensitive resin coating film layer (I). The obtained pattern is a line (pattern width) / space = 1.00 micrometers / 20 micrometers into a stripe pattern and is good. Example 3 A treatment similar to that in Example 1 was performed, but a heat radiation-sensitive resin coating film layer (I) and a sheet layer (Π) were laminated in advance on a substrate, and then an energy ray-sensitive coating film was formed. Layer (II). The obtained pattern was a stripe pattern of line (pattern width) / space = 100 micrometers / 20 micrometers, and was good. Example 14 The same treatment as in Example 1 was performed, but pre-laminated with a heat radiation-sensitive resin coating film layer (I), a sheet layer (π), and an energy ray-sensitive coating film layer (m). The product is laminated onto the substrate. The obtained pattern became a stripe pattern with a line (figure width) / space = 100 micrometers / 20 micrometers, and was good. Comparative Example 1 In Example 1, the laminated body was formed and developed as in Example 1, but the coating film layer (m) did not contain a heat radiation absorbent. As a result, all the obtained films were inferior due to the inferior residual properties of the wires and the properties of space analysis. Comparative Example 2 As in Example 2, the laminated body was formed and developed as in Example 2, but the coating film layer (II) did not contain a heat radiation absorbent. As a result, the obtained film was inferior due to the poor residual properties and analytical properties of the spaces. -26- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --------! —— # ------- —Order ------- -Line 丨 Λ (Please read the precautions on the back before filling this page) 479447 A7 ___ B7___ V. Description of the Invention (25) Comparative Example 3 As in Example 3, the formation and development of the laminated body is still the same as in Example 3, but The coating film layer (III) does not contain a heat radiation absorbent. As a result, the obtained film was inferior due to the poor residual properties and analytical properties of the spaces. Comparative Example 4 As in Example 4, the laminated body was formed and developed as in Example 4, but the coating film layer (m) did not contain a heat radiation absorbent. As a result, the obtained film was inferior due to the poor residual properties and analytical properties of the spaces. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm)