200844655 九、發明說明 【發明所屬之技術領域】 本發明係關於一種可藉由曝光、顯像形成微細圖案之 感光性組成物，使用該等組成物之抗焊劑及感光性乾膜。 詳言之，本發明係關於可獲得難燃性、柔軟性、耐熱性、 與金屬之密著性以及電絕緣性優異之硬化物的感光性組成 物，使用該等組成物之抗焊劑及感光性乾膜。本發明之感 光性組成物可使用作爲光阻材料，尤其可使用作爲印刷配 線板之絕緣材料及抗焊劑材料，可使用於電氣、電子材料 領域。 【先前技術】 最近伴隨著對電子設備之多機能化、高積體化、薄型 化以及小型輕量化之要求，在印刷配線板中配線圖案進展 爲高密度化之同時，亦擴大需要薄且可彎曲之撓性配線板 (以下稱爲FPC )。伴隨於此，於配線板製造中所用之光 阻材料等’除了要求有更高之高解像度以及高信賴性以外 ，爲了對應於FPC，光阻劑本身具有柔軟性成爲必要。 再者電子設備中所用之零件大多爲了確保安全性而有 義務賦予符合UL規格之難燃性。尤其FPC時由於與印刷 配線板相較其基板之滅火作用較小，故於FPC中所用之光 阻劑本身要求有高的難燃性。 印刷配線板製造中所用之具有難燃性之抗焊劑迄今提 -4 - 200844655 出有溴化環氧化合物與銻化合物作爲難燃劑者（專利文獻1 )° 然而，含有溴等鹵素之組成物雖顯示高的難燃效果， 但另一方面，由於燃燒時有發生有害戴奧辛化合物之虞慮 ，因此近年來，要求有材料之非鹵素化。 作爲非鹵素系之難燃性組成物已知有無機氫氧化物（ 專利文獻2)、由磷酸酯所構成之磷系難燃劑（專利文獻3 )以及倂用水合金屬化合物及氮化合物（專利文獻4)。然 而，如無機氫氧化物（水合金屬化合物）般之無機塡料成 份其難燃效果比鹵素系難燃劑或磷系難燃劑等均爲低，若 調配可充分獲得難燃效果之量，則有絕緣信賴性降低之問 題。又，尤其是使用於FPC用途時，若塡料成份多則硬化 物失去柔軟性而發生基板彎曲。另一方面，由磷酸酯所構 成之磷系難燃劑之難燃效果比較高，一般以比無機氫氧化 物少之調配量可獲得充分的難燃性。然而，磷酸酯等之難 燃劑亦有耐熱性或絕緣信賴性降低之問題。又，尤其是曝 光顯像時之解像性有大爲降低的問題。 磷系難燃劑亦已知有膦酸鹽（專利文獻5 )。 專利文獻1 :特開平1 1 -24233 1號公報 專利文獻2 :特開2006- 1 94968號公報 專利文獻3 :特開2001 - 1 83 8 1 9號公報 專利文獻4 :特開2004- 1 28 1 0號公報 專利文獻5 :特開2003-3 0 1 0 1 3號公報 200844655 【發明內容】 〔發明欲解決的問題〕 如上述，過去之抗焊劑組成物於維持 於薄型印刷配線板或FPC方面仍有問題。 本發明人等爲了發現具有充分難燃性 存安定性優異、其硬化物之述及耐熱性及 抗焊劑所必須之特性得以維持同時進而柔 亦可使用於薄型印刷配線板或FPC基板之 燃劑之感光組成物而進行廣泛檢討。 〔用以解決問題之手段〕 爲解決上述問題，申請專利範圍第1 感光性組成物含有具有源自環氧化合物骨 及游離基聚合性基之化合物（A )、丙烯酉 )、具有游離基聚合性基之除（A )與（E 化合物（C )、含磷原子之塡料（D )以及 E )。 申請專利範圍第2項所述之本發明感 申請專利範圍第1項之發明，其中以成份 )之合計量100質量份爲基準，含有20〜 (A) ，10〜80質量份之成份（B) ，5〜50 C )。 難燃性同時適用 且解像性以及保 電絕緣性之作爲 軟性亦優異，而 含有非鹵素系難 項所述之本發明 架且具備羧基以 隻胺基甲酸酯（B 5 )以外之聚合性 光聚合起始劑（ 丨光性組成物爲如 (A )及成份（B 9〇質量份之成份 質量份之成份（ -6 - 200844655 申請專利範圍第3項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中以成份（A )、成份 (B)及成份（C)之合計量100質量份爲基準，含有 1〜1 5 0質量份之成份（D )。 申請專利範圍第4項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中具有源自環氧化合 物之骨架且具備羧基以及游離基聚合性基之化合物（A )係 使環氧化合物與不飽和單羧酸進行加成反應，並使所生成 之羥基與多元酸酐進行加成反應所得之化合物。 申請專利範圍第5項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中丙烯酸胺基甲酸酯 (B)爲具有聚碳酸酯多元醇骨架之化合物。 申請專利範圍第6項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中丙烯酸胺基甲酸酯 (B)爲具有不具有羧基之聚碳酸酯多元醇骨架之化合物。 申請專利範圍第7項所述之本發明感光性組成物爲如 申請專利範圍第6項所述之發明，其中具備不具有羧基之 聚碳酸酯多元醇骨架之化合物的丙烯酸胺基甲酸酯（B)之 質量平均分子量爲2,000〜50,000。 申請專利範圍第8項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中具有游離基聚合性 基之除（A )及（B )以外之聚合性化合物（C )爲1分子 中具有3個以上之（甲基）丙烯醯基之化合物。 200844655 申請專利範圍第9項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中含磷原子之塡料（D )爲磷之含氧酸類之金屬鹽。 申請專利範圍第1 〇項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中含磷原子之塡料（D )爲膦酸之金屬鹽。 • 申請專利範圍第1 1項所述之本發明感光性組成物爲如 申請專利範圍第丨項所述之發明，其中含磷原子之塡料（D )爲膦酸之鋁鹽。 申請專利範圍第1 2項所述之本發明感光性組成物爲如 申請專利範圍第1項所述之發明，其中亦含有含磷原子之 塡料（D )以外之磷化合物（F )。 申請專利範圍第1 3項所述之本發明抗焊劑之特徵爲含 有如申請專利範圍第1〜1 2項中任一項所述之感光性組成物 • 申請專利範圍第1 4項所述之本發明感光性乾膜之特徵 係在支撐薄膜上形成含有申請專利範圍第1〜；1 2項中任一項 之感光性組成物之被覆膜。 【實施方式】 以下詳細的說明本發明。 另外’本說明書中丙烯酸酯及甲基丙烯酸酯統稱爲（ 甲基）丙ϋ酸酯。又’丙烯基及甲基丙烯基統稱爲（甲基 冬 200844655 )丙烯基。 依據本發明，不使用含有鹵素原子之難燃劑’而獲得 可賦予硬化物優異難燃性、柔軟性、耐熱性、電絕緣性’ 且解像性及儲存安定性良好之感光性組成物。 另外，以成份（A )及成份（B )之總量100質量份爲 基準，於含有20〜90質量份之成份（A) 、10〜80質量份之 成份（B ) 、5〜50質量份之成份（C )時，可成爲藉由鹼性 水溶液之顯像性充分且硬化塗膜之柔軟性充分之感光性組 成物。 再者，以成份（A )、成份（B )及成份（C )之總量 1〇〇質量份爲基準，含有1〜150質量份之成份（D)時，可 成爲難燃性改善效果相當充分且硬化物被覆膜之柔軟性或 絕緣信賴性等物性不會降低之感光性組成物。 另外，具有源自環氧化合物之骨架且具備羧基以及游 離基聚合性基之化合物（A )，爲使環氧化合物與不飽和單 羧酸進行加成反應，且使產生之羥基與多元酸酐進行加成 反應所得之化合物時，可成爲解像性與硬化物之柔軟性優 異之感光性組成物。 再者，丙烯酸胺基甲酸酯（B)爲具有聚碳酸酯多元醇 骨架之化合物時，可成爲硬化物之絕緣信賴性優異之感光 性組成物。 另外，丙烯酸胺基甲酸酯（B )爲具備不具有羧基之聚 碳酸酯多元醇骨架之化合物時，可以成爲硬化物之耐水性 -9 - 200844655 以及絕緣信賴性優異之感光性組成物。 再者，具備不具有羧基之聚碳酸酯多元醇骨架之化合 物之丙烯酸胺基甲酸酯（B)之質量平均分子量爲 2,000〜5 0,000時，可成爲解像性與硬化物之柔軟性優異之 感光性組成物。 又，具有游離基之除（A )及（：8)以外之聚合性化合 物（C)爲每1分子中具有3個以上（甲基）丙烯醯基之化 合物時，可成爲其硬化物具有高的絕緣信賴性之感光性組 成物。 再者，若含有磷原子之塡料（D)爲磷之含氧酸之金屬 鹽時，可成爲解像性優異且硬化物具有高的難燃性以及絕 緣信賴性之感光組成物。 又，含磷原子之塡料（D)若爲膦酸類之金屬鹽時，可 成爲解像性更優異，且硬化物具有更高難燃性及絕緣信賴 性之感光性組成物。 再者，含磷原子之塡料（D)若爲膦酸類之鋁鹽時，可 成爲解像性特別優異且硬化物具有特別高的難燃性及絕緣 信賴性之感光性組成物。 另外，若含有除含磷原子之塡料（D )以外之磷化合物 (F )時，則可成爲可獲得更有效之難燃性高之硬化物之感 光性組成物。 本發明之抗焊劑可用於薄型印刷配線板或FPC基板之 加工。 -10· 200844655 本發明之感光性乾膜較好用作爲電子材料。 〔實施本發明之最佳形態〕 1 · ( A )成份 (A)成份爲具有源自ig興化合物骨架且具備殘基以及 游離基聚合性基之化合物。 作爲（A )成份，可使用各種化合物，較佳之具體例舉 例爲例如使環氧化合物（環氧樹脂）與不飽和單羧酸反應 製造具有羥基之化合物，使該具有羥基之化合物之經基一 部分或全部與飽和或不飽和多元酸酐（以下稱爲多元酸酐 )進行加成反應而成之反應物等。 該情況下使用之環氧樹脂之例舉例爲雙酚A型環氧樹 脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛型 環氧樹脂、甲酚酚醛型環氧樹脂以及多酚型環氧樹脂等。 不飽和單羧酸之例爲丙烯酸、甲基丙烯酸、巴豆酸及 桂皮酸等。 多元酸酐爲馬來酸酐、琥珀酸柑、衣康酸酐、苯二甲 酸酐、四氫苯二甲酸酐及偏苯三酸酐等。 多元酸酐相對於具有羥基之化合物之反應比例並無特 別限制，但相對於具有羥基之化合物之羥基1莫耳，多元 酸酐較好爲莫耳，更好爲0.2〜0.9莫耳。若該比例 未達0.1莫耳，則由於於鹼液之溶解性不足，導致感光性 組成物之鹼顯像性降低。另一方面，若該比例超過1 .0莫 -11 - 200844655 耳， 酐結 起殘 存安[Technical Field] The present invention relates to a photosensitive composition which can form a fine pattern by exposure and development, and uses a solder resist and a photosensitive dry film of the composition. In particular, the present invention relates to a photosensitive composition which can obtain a cured product excellent in flame retardancy, flexibility, heat resistance, adhesion to metal, and electrical insulation, and uses the solder resist and photosensitive of the compositions. Dry film. The photosensitive composition of the present invention can be used as a photoresist material, and particularly as an insulating material and a solder resist material for a printed wiring board, and can be used in the field of electrical and electronic materials. [Prior Art] Recently, with the demand for a large number of functions, high integration, thinning, and reduction in size and weight of electronic devices, wiring patterns have been increasing in density in printed wiring boards, and the need for expansion has been reduced. Curved flexible wiring board (hereinafter referred to as FPC). Along with this, in addition to the need for higher resolution and high reliability in the production of photoresist materials and the like used in the manufacture of wiring boards, it is necessary to have flexibility of the photoresist itself in accordance with FPC. Further, in order to ensure safety, most of the components used in electronic equipment are obligated to impart flame retardancy in accordance with UL specifications. In particular, in FPC, since the fire extinguishing effect of the substrate is small compared with the printed wiring board, the photoresist used in the FPC itself requires high flame retardancy. A solder resist which is flame retardant used in the manufacture of printed wiring boards has been proposed so far. - 200844655 A brominated epoxy compound and a ruthenium compound are used as a flame retardant (Patent Document 1). However, a composition containing a halogen such as bromine Although it exhibits a high flame retardant effect, on the other hand, since there is a concern that harmful dioxin compounds are generated during combustion, in recent years, non-halogenation of materials has been demanded. An inorganic hydroxide (Patent Document 2), a phosphorus-based flame retardant composed of a phosphate ester (Patent Document 3), and a hydrazine hydrated metal compound and a nitrogen compound (patent) are known as a non-halogen-based flame retardant composition. Document 4). However, the inorganic tanning component such as an inorganic hydroxide (hydrated metal compound) has a lower flame retarding effect than a halogen-based flame retardant or a phosphorus-based flame retardant, and if it is formulated, the amount of the flame retardant effect can be sufficiently obtained. There is a problem that the insulation reliability is lowered. Further, especially when used for FPC use, if a large amount of the raw material is used, the hardened material loses flexibility and the substrate is bent. On the other hand, the phosphorus-based flame retardant composed of a phosphate ester has a relatively high flame retarding effect, and generally, a sufficient flame retardancy can be obtained with a smaller amount than the inorganic hydroxide. However, a flame retardant such as a phosphate ester also has a problem of lowering heat resistance or insulation reliability. Further, in particular, the resolution at the time of exposure development is greatly degraded. Phosphonates are also known as phosphorus-based flame retardants (Patent Document 5). Patent Document 1: Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 5: JP-A-2003-3 0 1 0 1 No. 200844655 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] As described above, the conventional solder resist composition is maintained on a thin printed wiring board or FPC. There are still problems in the aspect. The inventors of the present invention have found that they have excellent flame retardancy and excellent stability, and the properties of the cured product and the heat resistance and the properties necessary for the solder resist are maintained while being soft and can also be used for the thin printed wiring board or the FPC substrate. The sensitizing composition was extensively reviewed. [Means for Solving the Problem] In order to solve the above problems, the first photosensitive composition of the patent application includes a compound (A) derived from an epoxy compound bone and a radical polymerizable group, propylene oxide, and has radical polymerization. The removal of the group (A) and (E compound (C), the phosphorus atom-containing material (D) and E). The invention of claim 1, wherein the invention contains 20 to (A) and 10 to 80 parts by mass based on 100 parts by mass of the total amount of the component (B). ), 5~50 C). The flame retardancy is applied at the same time, and the resolution and the electrical insulating property are excellent as softness, and the present invention having the non-halogen type and having a carboxyl group to be polymerized only by the urethane (B 5 ) The photopolymerization initiator (the photosynthetic composition is a photosensitive composition of the present invention as described in (A) and the component (B 9 parts by mass of the component parts by mass) ( -6 - 200844655 Patent Application No. 3) The invention according to claim 1, wherein the composition contains 1 to 150 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (C). The photosensitive composition of the present invention as described in claim 4, which has the skeleton derived from the epoxy compound and which has a carboxyl group and a radical polymerizable group. The compound (A) is a compound obtained by subjecting an epoxy compound to an unsaturated monocarboxylic acid, and reacting the resulting hydroxyl group with a polybasic acid anhydride. The photosensitive property of the present invention as recited in claim 5 The composition is as special as the application The invention of claim 1, wherein the urethane urethane (B) is a compound having a polycarbonate polyol skeleton. The photosensitive composition of the present invention described in claim 6 is as claimed in the patent application. The invention of claim 1, wherein the urethane urethane (B) is a compound having a polycarbonate polyol skeleton having no carboxyl group. The photosensitive composition of the present invention described in claim 7 is as The invention of claim 6, wherein the acrylamide urethane (B) having a compound having a polycarbonate polyol skeleton having no carboxyl group has a mass average molecular weight of 2,000 to 50,000. The photosensitive composition of the present invention is the invention according to the first aspect of the invention, wherein the polymerizable compound (C) other than (A) and (B) having a radical polymerizable group is in one molecule. A compound having three or more (meth) acryloyl fluorenyl groups. The method of claim 1, wherein the photosensitive composition of the present invention is the invention described in claim 1, wherein the phosphorus-containing The material (D) of the present invention is a metal salt of an oxyacid of phosphorus. The photosensitive composition of the present invention according to the first aspect of the invention is the invention of claim 1, wherein the phosphorus atom is contained. The material (D) is a metal salt of a phosphonic acid. The photosensitive composition of the present invention described in claim 1 is the invention described in the above-mentioned claim, wherein a phosphorus atom-containing material is used. (D) is an aluminum salt of a phosphonic acid. The photosensitive composition of the present invention described in claim 1 is the invention of claim 1, which also contains a phosphorus atom-containing material (D). The phosphorus compound (F) of the present invention is characterized in that the photosensitive composition of the present invention is characterized by containing the photosensitive composition according to any one of claims 1 to 12. The photosensitive dry film of the present invention according to the invention of claim 1 is characterized in that the coating film containing the photosensitive composition according to any one of the first to the first aspect of the invention is formed on the support film. [Embodiment] The present invention will be described in detail below. Further, in the present specification, acrylate and methacrylate are collectively referred to as (meth)propionate. Further, the propylene group and the methacryl group are collectively referred to as (methyl winter 200844655) propylene group. According to the present invention, a photosensitive composition which imparts excellent flame retardancy, flexibility, heat resistance and electrical insulating properties to a cured product, and which is excellent in resolution and storage stability can be obtained without using a flame retardant containing a halogen atom. Further, the component (B) and the component (B) in an amount of 20 to 90 parts by mass, based on 100 parts by mass of the total of the component (A) and the component (B), and 5 to 50 parts by mass. In the case of the component (C), it is possible to obtain a photosensitive composition having sufficient visibility of an aqueous alkaline solution and sufficient flexibility of the cured coating film. Further, when the component (D) is contained in an amount of from 1 to 150 parts by mass based on 1 part by mass of the total of the component (A), the component (B) and the component (C), the flame retardancy improving effect is equivalent. A photosensitive composition which is sufficiently resistant to physical properties such as flexibility or insulation reliability of the cured coating film. Further, the compound (A) having a carboxyl group derived from an epoxy compound and having a carboxyl group and a radical polymerizable group is subjected to an addition reaction of an epoxy compound and an unsaturated monocarboxylic acid, and the generated hydroxyl group and the polybasic acid anhydride are subjected to an addition reaction. When the compound obtained by the addition reaction is used, it is a photosensitive composition which is excellent in the resolvability and the softness of the cured product. Further, when the urethane urethane (B) is a compound having a polycarbonate polyol skeleton, it can be a photosensitive composition excellent in insulation reliability of a cured product. Further, when the urethane urethane (B) is a compound having a polycarbonate polyol skeleton having no carboxyl group, it can be a water-resistant -9 - 200844655 of a cured product and a photosensitive composition excellent in insulation reliability. In addition, when the mass average molecular weight of the urethane urethane (B) having a compound having a polycarbonate polyol skeleton having no carboxyl group is 2,000 to 500,000, the flexibility of the resolution and the cured product can be excellent. Photosensitive composition. In addition, when the polymerizable compound (C) other than (A) and (8) having a radical is a compound having three or more (meth)acryl fluorenyl groups per molecule, the cured product can be high. A photosensitive composition that is insulating and reliable. In addition, when the phosphorus (D) containing phosphorus atom is a metal salt of phosphorus oxyacid, it can be used as a photosensitive composition which is excellent in resolution and has high flame retardancy and excellent reliability. In addition, when the phosphorus atom-containing material (D) is a metal salt of a phosphonic acid, it is excellent in resolution, and the cured product has a higher flame retardancy and insulation reliability. In addition, when the phosphorus atom-containing material (D) is an aluminum salt of a phosphonic acid, it is a photosensitive composition which is particularly excellent in resolution and has a particularly high flame retardancy and insulation reliability. Further, when the phosphorus compound (F) other than the phosphorus atom-containing material (D) is contained, it is possible to obtain a photosensitive composition which is more effective and has a high flame retardancy. The solder resist of the present invention can be used for processing of a thin printed wiring board or an FPC board. -10· 200844655 The photosensitive dry film of the present invention is preferably used as an electronic material. [Best Mode for Carrying Out the Invention] 1 (A) Component The component (A) is a compound having a skeleton derived from an ig-forming compound and having a residue and a radical polymerizable group. As the component (A), various compounds can be used, and preferred examples are exemplified by, for example, reacting an epoxy compound (epoxy resin) with an unsaturated monocarboxylic acid to produce a compound having a hydroxyl group, and a part of a base group of the compound having a hydroxyl group. Or a reaction product obtained by performing an addition reaction with a saturated or unsaturated polybasic acid anhydride (hereinafter referred to as a polybasic acid anhydride). Examples of the epoxy resin used in this case are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and cresol novolac type epoxy resin. And polyphenol type epoxy resin and the like. Examples of the unsaturated monocarboxylic acid are acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. The polybasic acid anhydrides are maleic anhydride, succinoic acid, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride. The reaction ratio of the polybasic acid anhydride to the compound having a hydroxyl group is not particularly limited, but the polybasic acid anhydride is preferably mole, more preferably 0.2 to 0.9 mol, based on 1 mol of the hydroxyl group of the compound having a hydroxyl group. If the ratio is less than 0.1 mol, the solubility of the alkali solution is insufficient, and the alkali developability of the photosensitive composition is lowered. On the other hand, if the ratio exceeds 1.00 -11 - 200844655 ears, the anhydride will be remnant
之 丙 (甲 2. 多C (A 2. More
優 丙 酯 價 香 則由於殘留未反應之多元酸酐，而有未反應之多元酸 晶化之顧慮，或者在大多情況下，由於保存期間會引 留羥基與未反應多元酸酐之反應，因此有組合物之保 定性降低之顧慮。 (A )成份，於上述中，爲了使之成爲解像性與硬化物 軟性優異者，較佳爲具有羧基之雙酚型環氧（甲基） 酸酯。環氧（甲基）丙烯酸酯爲具有使環氧化合物與 基）丙烯酸進行加成反應所得構造之化合物。 (B )成份 (B)成份爲（甲基）丙烯酸胺基甲酸酯化合物。 (B )成份亦可使用各種市售品，舉例爲例如多元醇與 異氰酸酯及含有羥基之（甲基）丙烯酸酯之反應物等 (B )成份，於上述中，爲使成爲硬化物之絕緣信賴性 t者，因此較好爲具有聚碳酸酯多元醇骨架之（甲基） ί酸胺基甲酸酯。 具有聚碳酸酯多元醇骨架之（甲基）丙烯酸胺基甲酸 ;可使用各種市售品，例如可使用聚碳酸酯多元醇與多 I氰酸酯及含有羥基之（甲基）丙烯酸酯之反應產物等 聚碳酸酯多元醇之例舉例爲使具有伸烷基、烷基、芳 I烴基、環鏈烷系烴基等之碳酸酯與具有伸烷基、烷基 -12- 200844655 、芳香族烴基、環鏈烷系烴基等之多元醇反應而獲得之聚 碳酸酯多元醇。 碳酸酯之較佳具體例爲例如碳酸二甲酯、碳酸二乙酯 、碳酸二苯酯、碳酸乙二酯、碳酸丙二酯以及碳酸二環己 酯等。 另外，多元醇之較佳具體例爲例如1，6-己二醇、1，4-環 己烷二甲醇、3-甲基-1，5-戊烷二醇、1，5-戊烷二醇、聚氧乙 二醇、聚氧丙二醇、聚氧丁二醇、聚己內酯二醇、三甲基 己烷二醇、以及1，4·丁二醇等。 此處，碳酸酯以及多元醇可使用1種或者亦可倂用2 種以上之分子量或組成不同者。 較佳之多價異氰酸酯爲甲苯二異氰酸酯、二苯基甲烷 二異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯 及氫化二苯基甲烷二異氰酸酯等。 較佳之含有羥基之（甲基）丙烯酸酯爲（甲基）丙烯 酸羥基乙酯及（甲基）丙烯酸羥基丙酯等（甲基）丙烯酸 羥基烷酯。 作爲（B )成份，於上述中，爲使硬化物之耐水性以及 絕緣信賴性優異，因此較好爲不具有羧基之（甲基）丙烯 酸胺基甲酸酯。 較佳之（B )成份’亦即不具有羧基之（甲基）丙烯酸 胺基甲酯，其質量平均分子量較好爲2,000〜50,000，更好 爲5,000〜20,000，若質量平均分子量未達2,〇〇〇，則有時硬 200844655 化物之柔軟性不足，另一方面，若超過50,000則由於解像 度降低因此較不佳。 (A )成份、（B )成份之較佳調配比例，以（A )成 份與（B )成份之合計作爲100質量份，（A )成份在 20〜90質量份之範圍內。未達2〇質量份時，藉由鹼性水溶 液之顯像性不足，超過90質量份時，則硬化物之柔軟性不 足而不佳。更好之範圍爲40〜80質量份。 3. ( C )成份 (C )成份爲具有游離聚合性基之除（A )及（B )以 外之聚合性化合物。 作爲（C )成份所具有之游離基聚合性基可舉例較佳者 爲游離基聚合性之碳-碳雙鍵，最佳者爲丙烯醯基、甲基丙 烯醯基、烯丙基或乙烯基等。 具有1個游離基聚合性基之聚合性化合物（C )之具體 例可舉例爲（甲基）丙緯酸甲酯、（甲基）丙烯酸丁酯、 (甲基）丙烯酸2 -乙基己酯、（甲基）丙烯酸羥基乙酯及 (甲基）丙烯酸羥基丙酯等之官能基（甲基）丙烯酸酯； 苯乙烯等具有乙烯基之化合物；以及烯丙基酚等具有烯丙 基之化合物等。 具有2個游離基聚合性基之聚合性化合物（^ )之具體 例可舉例爲丁烷二醇二（甲基）丙烯酸酯、二乙二醇 二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯及聚 -14 - 200844655 丙一醇一（甲基）丙細酸醋等二（甲基）丙嫌酸醋；二乙 烯基苯等之乙烯基化合物；以及苯二甲酸二烯丙酯等之稀 丙基化合物。 具有3個以上游離基聚合性基之聚合性化合物（c )之 具體例可舉例爲三羥甲基丙烷三（甲基）丙烯酸醋、季戊 四醇三（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸 酯及三烯丙基異尿氰酸酯等。 爲成爲硬化物爲具有較高絕緣信賴性者，較好使用具 有3個以上之游離基聚合性基之化合物作爲（C )成份。更 好爲1分子中具有3、個以上（甲基）丙烯醯基之化合物。 (C )成份之較佳調配比例，相對於以（A )成份及（ B)成份之合計爲100質量份，爲5〜50質量份，尤其是在 5〜20質量份之範圍內。若該比例未達5質量份，則硬化物 之交聯密度變得不足且焊料耐熱性或絕緣信賴性降低，若 超過5 0質量份則會使硬化物之柔軟性降低。 4 · ( D )成份 (D )成份爲含磷原子之塡料。本發明中，塡料意指無 法溶解於感光性組成物中而係經分散，亦即在常溫（1 0〜3 0 °C )下爲固體者。成份（D )係用以對組成物賦予難燃性之 成份。 作爲難燃成份之含磷原子之塡..料般之與組成物中之樹 脂成份、有機溶劑等不相溶而藉由以微粒子使用，對於源 -15- 200844655 自樹脂〔成份（A) 、 ( B ) 、 （C)〕之組成物或硬化物 之物性，尤其是感光性或對於顯像液之溶解性之不良影響 可變小，而使用作爲光阻劑時可展現高的解像性。再者含 碟原子者與無機氫氧化物般之塡料相比較，可以低調配量 獲得高的難燃性。 含磷原子之塡料之具體例可舉例爲膦酸鹽化合物、二 乙基膦酸鹽化合物、二丁基膦酸鹽化合物、二羥基甲基膦 酸鹽化合物、聚磷酸銨、聚磷酸三聚氰胺、磷酸胍等。 作爲（D )成份，爲使感光性組成物具有高的解像性且 使硬化物具有高的難燃性以及絕緣信賴性，較好使用磷之 含氧酸之金屬鹽類，更好使用膦酸類之金屬鹽。本發明中 ’膦酸類意指膦酸或與膦酸之磷原子鍵結之氫原子之】個 或2個經烷基、芳基或鹵素原子取代之化合物合稱之化合 物群。上述之烷基以及芳基亦可具有羥基、烷氧基等取代 基。 膦酸類之例可舉例爲膦酸、苯基膦酸、二苯基膦酸、 甲基膦酸、二甲基膦酸、乙基膦酸、二乙基膦酸、丁基膦 酸、二丁基膦酸、苯基氯膦酸、二羥基甲基膦酸等。 磷之含氧酸之例除上述膦酸類以外，可舉例爲次磷酸 、二次磷酸、磷酸、焦磷酸、偏磷酸、過氧磷酸、過氧二 磷酸、二磷酸、二硫代磷酸、苯基次磷酸、甲基次磷酸、 乙基次磷酸、羥基甲基次磷酸等。 另外，構成金屬鹽之元素可舉例爲鈉等鹼金屬、鎂等 -16- 200844655 鹼土類金屬、屬於週期表13族之鋁等金屬元素’以及屬於 週期表8族等之鐵等過渡金屬元素，作爲金屬尤其是錕鹽 ，由於可使組成物具有高的解像性，以及易成爲具有高的 難燃性、絕緣信賴性之硬化物故而較佳，且最好爲膦酸鋁 鹽 ° (D)成份較好爲平均粒徑0.5〜15μπι，尤其是1〜5μηι 者。若平均粒徑超過1 5 μπι則會有柔軟性變差之情況。又， 尤其是使用作爲膜厚5〇 μπι以下之薄膜之感光性乾膜時，有 薄膜之表面狀態惡化之情況。另一方面，若平均粒徑未達 0·5 μχη，由於含磷原子之薄膜之鬆密度變小，因此有將含磷 原子之塡料分散於其他成份中變困難之情況。 (D )成份之調配量，以（A )成份、（B )成份及（C )成份之合計100質量份爲基準，較好爲1〜150質量份， 更好爲10〜100質量份。若未達〗質量份，則有難燃性提高 效果變得不充分之情況，另一方面，若超過1 5 0質量份， 則有使硬化物之柔軟性或絕緣信賴性等物性降低之情況。 5. ( E )成份 (E)成份爲光聚合起始劑。 (E)成份爲可藉由紫外線等照射起始游離基聚合者， 具體而言舉例爲苯偶因、苯偶因甲基醚、苯偶因乙基酸、 苯偶因異丙基醚等苯偶因及苯偶因烷基醚類；苯乙酮、2,2· 二甲氧基-2-苯乙酮、2’2-二乙氧基-2-苯乙酮、15；U二氯苯 -17- 200844655 乙酮等之苯乙酮類；2-甲基蒽醌、2-乙基蒽酿、第三丁基 恩醌、1-氯恩醌、2 -戊基蒽醌等之蒽醌類；嘯噸酮、2 -氯噻 噸酮、2-烷硫基噻噸酮、2,4_二烷基噻噸酮等噻噸酮類；二 苯甲酮、4-氯二苯甲酮、4，4，-二氯二苯甲酮、4,4，·雙二甲 基胺基二苯甲酮等二苯甲酮類等。 (E)成份之g周配量，以（a)成份、（b)成份及（c )成份之合計作爲1〇〇質量份，爲0.5〜10質量份，較好爲 1〜5質量份。若未達〇·5質量份則反應無法充分起始，使經 由曝光獲得之塗膜之機械強度變弱，使顯像步驟中於硬化 塗膜剝離後造成圖案蛇行。另一方面，當超過1〇質量份時 ，則曝光時沒有被使用之光聚合起始劑會大量殘留在塗膜 中，導致硬化塗膜之耐熱性等物性降低。 本發明中，上述（E)成份較好與增感劑—起彳并用。 作爲增感劑可舉例爲N，N-二甲基胺基苯甲酸、N，N- = 甲基胺基苯甲酸異戊酯、三乙胺、二乙基嚷噸酮以及三乙 醇胺等。增感劑可爲市售者，例如新日曹化工公胃製之商 品名「Nissocure ΕΡΑ、ΕΜΑ、ΙΑΜΑ」等，臼本化藥公司製 之商品名「卡雅久雅EPA、DETX、DMBI」等，大阪有機 公司製之商品名^ DABA」等。 該等增感劑之調配量，以（A )成份、（B )成份及（ C)成份之合計作爲1〇〇質量份，較好爲0.5〜1〇質量份。 若未達〇 · 5質量份則無法充分的提升以紫外線等硬化之反 應速度，當超過1 0質量份時’會使反應加速造成感光性組 -18- 200844655 成物之儲存安定性惡化。 6. ( F)成份 本發明之感光性組成物亦可添加除含磷原子之塡料（D )以外之磷化合物（F )。該化合物與含磷原子之塡料（D )不同，係可溶解於組成物中而存在之磷化合物。 • ( F )成份調配之目的係提高難燃性，藉由與擔任賦予 難燃性之必要成份之（D )成份之相乘效果，可更有效地發 揮組成物難燃性之提高。 (F )成份之例可舉例爲磷酸三苯酯、磷酸三甲酚酯、 磷酸三（二甲苯）酯、磷酸三乙酯、磷酸甲酚苯酯、磷酸 二甲苯基二苯酯等磷酸酯類，間苯二酚雙（二苯基）磷酸 酯、雙酚A雙（二苯基）磷酸酯、雙酚A雙（二甲酚）磷 酸酯、間苯二酚雙（二-2，6-伸二甲苯）磷酸酯等縮合型磷 ♦ 酸酯類，以及丙氧基磷腈、苯氧基磷腈、胺基磷腈等磷腈 化合物等。 最佳之（F )成份爲縮合型磷酸酯類、磷腈化合物。 添加（F )成份時之調配量，以（a )成份、（B )成 份以及（C )成份之合計1 0 0質量份爲基準，較好爲卜5 0 質量份，更好爲1〜30質量份，最好爲I〜25質量份。若添 加未達1質量份則難燃性之提高效果不充分，另一方面， 若超過5 0質量份則有時造成塗膜曝光顯像而形成圖案時之 解像性或硬化塗膜之絕緣信賴性等物性降低。 200844655 爲了抑制對上述解像性或絕緣信賴性之不良影饗，（f )成份之調配量，較好與（D )成份之調配量相同量以下， 更好爲2/3以下，且最好爲1/2以下。 7. ( G )成份 本發明之感光性組成物亦可爲添加有經由加熱而產生 II 游離基之熱聚合起始劑（G )。 (G)成份可舉例爲例如有機過氧化物、具有偶氮雙結 構之起始劑等。若由由於分解開始溫度高故儲存安定性良 好之觀點，以及分解時低分子量揮發成份產生較少之觀點 ，則較好爲二烷基過氧化物，具體而言舉例爲二枯烯基過 氧化物、第三丁基枯烯基過氧化物、2,5-二甲基-2,5-二（ 第三丁基過氧基）己烷以及2,5·二甲基-2,5·(第三丁基過 氧基）己院等。The eutectic ester has a concern that the unreacted polybasic acid anhydride remains, but there is a concern that the unreacted polybasic acid is crystallized, or in most cases, since the reaction between the hydroxyl group and the unreacted polybasic acid anhydride is retained during storage, there is a composition. The concern of lowering the stability. In the above, the component (A) is preferably a bisphenol type epoxy (meth) acid ester having a carboxyl group in order to provide excellent resolution and softness of the cured product. The epoxy (meth) acrylate is a compound having a structure obtained by subjecting an epoxy compound to a acryl acid. (B) Component (B) The component is a (meth)acrylic acid urethane compound. As the component (B), various commercially available products can be used, and examples thereof include a component (B) such as a reaction product of a polyhydric alcohol with an isocyanate and a hydroxyl group-containing (meth) acrylate, and in the above, in order to make a hardened insulating material It is preferably a (meth) succinate having a polycarbonate polyol skeleton. A (meth)acrylic acid amide having a polycarbonate polyol skeleton; various commercially available products can be used, for example, a reaction of a polycarbonate polyol with a poly-cyanate and a hydroxyl group-containing (meth) acrylate can be used. Examples of the polycarbonate polyol such as a product include a carbonate having an alkylene group, an alkyl group, an aryl I hydrocarbon group, a cycloalkane hydrocarbon group, and the like, and an alkylene group, an alkyl group 12-200844655, an aromatic hydrocarbon group, A polycarbonate polyol obtained by reacting a polyol such as a cycloalkane hydrocarbon group. Preferable specific examples of the carbonate are, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, and dicyclohexyl carbonate. Further, preferred specific examples of the polyhydric alcohol are, for example, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,5-pentane 2 Alcohol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polycaprolactone diol, trimethyl hexane diol, and 1,4-butanediol. Here, the carbonate and the polyhydric alcohol may be used alone or in combination of two or more kinds of molecular weights or compositions. Preferred polyvalent isocyanates are toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like. Preferred (meth) acrylates having a hydroxyl group are hydroxyethyl (meth) acrylate and hydroxyalkyl (meth) acrylate such as hydroxypropyl (meth) acrylate. In the above, the (B) component is excellent in water resistance and insulating reliability of the cured product, and therefore it is preferably a (meth)acrylic acid urethane having no carboxyl group. Preferably, the component (B), that is, the aminomethyl (meth)acrylate having no carboxyl group, has a mass average molecular weight of preferably 2,000 to 50,000, more preferably 5,000 to 20,000, and if the mass average molecular weight is less than 2, 〇 〇〇, sometimes the hardness of the hard 200844655 compound is insufficient. On the other hand, if it exceeds 50,000, the resolution is lowered, which is not preferable. The preferred blending ratio of the component (A) and the component (B) is 100 parts by mass of the total of the components (A) and (B), and the component (A) is in the range of 20 to 90 parts by mass. When the amount is less than 2 parts by mass, the development performance of the alkaline aqueous solution is insufficient, and when it exceeds 90 parts by mass, the softness of the cured product is insufficient. A better range is 40 to 80 parts by mass. 3. (C) Component (C) The component is a polymerizable compound other than (A) and (B) having a free polymerizable group. The radical polymerizable group which the (C) component has is preferably exemplified by a radical polymerizable carbon-carbon double bond, and most preferably an acryl fluorenyl group, a methacryl fluorenyl group, an allyl group or a vinyl group. Wait. Specific examples of the polymerizable compound (C) having one radical polymerizable group are exemplified by methyl (meth)propionate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. a functional (meth) acrylate such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; a compound having a vinyl group such as styrene; and a compound having an allyl group such as allyl phenol Wait. Specific examples of the polymerizable compound (^) having two radical polymerizable groups are, for example, butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol II. (meth) acrylate and poly-14 - 200844655 propanol mono(methyl) propionate vinegar and other di(methyl) propyl vinegar; vinyl compound such as divinyl benzene; a propyl compound such as allyl ester. Specific examples of the polymerizable compound (c) having three or more radical polymerizable groups may, for example, be trimethylolpropane tri(meth)acrylate vinegar, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(methyl) ) acrylate and triallyl isocyanurate. In order to obtain a cured product having high insulation reliability, a compound having three or more radical polymerizable groups is preferably used as the component (C). More preferably, it is a compound having 3 or more (meth) acrylonitrile groups in one molecule. The ratio of the component (C) is preferably 5 to 50 parts by mass, particularly preferably 5 to 20 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When the ratio is less than 5 parts by mass, the crosslinking density of the cured product becomes insufficient, and solder heat resistance or insulation reliability is lowered. When the ratio exceeds 50 parts by mass, the softness of the cured product is lowered. 4 · (D) The component (D) is a phosphorus-containing material. In the present invention, the crucible means that it is not dissolved in the photosensitive composition and is dispersed, that is, it is solid at normal temperature (10 to 30 ° C). Ingredient (D) is a component which imparts flame retardancy to the composition. As a phosphorus-containing atom of a flame-retardant component, it is incompatible with the resin component, organic solvent, etc. in the composition, and is used as a microparticle, for the source -15-200844655 from the resin [ingredient (A), The physical properties of the composition or cured product of (B) and (C)], especially the photosensitivity or the adverse effect on the solubility of the developing solution, may be small, and high resolution can be exhibited when used as a photoresist. . Furthermore, those containing the atom of the dish can be compared with the inorganic hydroxide-like material to obtain a high flame retardancy with a low dosage. Specific examples of the phosphorus atom-containing material may be exemplified by a phosphonate compound, a diethylphosphonate compound, a dibutylphosphonate compound, a dihydroxymethylphosphonate compound, ammonium polyphosphate, and melamine polyphosphate. Barium phosphate and the like. As the component (D), in order to impart high resolution to the photosensitive composition and to have high flame retardancy and insulation reliability of the cured product, it is preferred to use a metal salt of phosphorus oxyacid, and it is preferable to use phosphine. A metal salt of an acid. In the present invention, the term "phosphonic acid" means a group of compounds in which a phosphonic acid or a hydrogen atom bonded to a phosphorus atom of a phosphonic acid or a compound substituted with an alkyl group, an aryl group or a halogen atom is collectively referred to. The above alkyl group and aryl group may have a substituent such as a hydroxyl group or an alkoxy group. Examples of the phosphonic acid are exemplified by phosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, methylphosphonic acid, dimethylphosphonic acid, ethylphosphonic acid, diethylphosphonic acid, butylphosphonic acid, and dibutyl. Phosphonic acid, phenylchlorophosphonic acid, dihydroxymethylphosphonic acid, and the like. Examples of the phosphorus oxyacid include, in addition to the above phosphonic acids, hypophosphorous acid, phosphoric acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, peroxyphosphoric acid, peroxydiphosphate, diphosphoric acid, dithiophosphoric acid, and phenyl. Hypophosphorous acid, methyl hypophosphorous acid, ethyl hypophosphorous acid, hydroxymethyl hypophosphorous acid, and the like. Further, the element constituting the metal salt may, for example, be an alkali metal such as sodium, a metal such as -16-200844655 alkaline earth metal, a metal element such as aluminum belonging to Group 13 of the periodic table, and a transition metal element such as iron belonging to Group 8 of the periodic table. The metal, particularly the onium salt, is preferred because it has a high resolution and can be a cured product having high flame retardancy and insulation reliability, and is preferably an aluminum phosphonate salt (D). The composition is preferably an average particle diameter of 0.5 to 15 μm, especially 1 to 5 μm. If the average particle diameter exceeds 15 μm, the softness may be deteriorated. Further, in particular, when a photosensitive dry film having a film thickness of 5 μm or less is used, the surface state of the film may be deteriorated. On the other hand, if the average particle diameter is less than 0.5 μm, the bulk density of the film containing the phosphorus atom becomes small, so that it is difficult to disperse the phosphorus atom-containing material in other components. The amount of the component (D) is preferably from 1 to 150 parts by mass, more preferably from 10 to 100 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C). In the case where the amount of the flame retardant is not sufficient, the effect of improving the flame retardancy may be insufficient. On the other hand, when it exceeds 150 parts by mass, physical properties such as flexibility of the cured product or insulation reliability may be lowered. 5. (E) Ingredient (E) The component is a photopolymerization initiator. (E) The component is a radical polymerization which can be initiated by irradiation with ultraviolet rays or the like, and specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl acid, benzoin isopropyl ether and the like. Occasion and benzoin alkyl ethers; acetophenone, 2,2. dimethoxy-2-acetophenone, 2'2-diethoxy-2-acetophenone, 15; U dichloride Benzene-17- 200844655 Ethyl ketones such as ethyl ketone; 2-methyl hydrazine, 2-ethyl hydrazine, tert-butyl hydrazine, 1-chloroenhydrazine, 2-pentyl hydrazine, etc. Terpenes; thioxanthone, 2-chlorothioxanthone, 2-alkylthiothioxanthone, 2,4-dialkylthioxanthone, etc.; benzophenone, 4-chlorobenzophenone A benzophenone such as a ketone, 4,4,-dichlorobenzophenone or 4,4,-bisdimethylaminobenzophenone. The weekly dosing amount of the component (E) is 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, based on the total of the components (a), (b) and (c). If it is less than 5 parts by mass, the reaction does not sufficiently start, and the mechanical strength of the coating film obtained by the exposure is weakened, so that the pattern is serrated after the hard coating film is peeled off in the developing step. On the other hand, when it exceeds 1 part by mass, the photopolymerization initiator which is not used at the time of exposure may remain in a large amount in the coating film, resulting in deterioration of physical properties such as heat resistance of the cured coating film. In the present invention, the above component (E) is preferably used in combination with a sensitizer. The sensitizer may, for example, be N,N-dimethylaminobenzoic acid, N,N- = isoamyl methylaminobenzoate, triethylamine, diethylxanthone or triethanolamine. The sensitizer may be a commercially available one, for example, the brand name "Nissocure ΕΡΑ, ΕΜΑ, ΙΑΜΑ", etc., which is manufactured by Sakamoto Chemical Co., Ltd., and the product name "Kayajaya EPA, DETX, DMBI" manufactured by Sakamoto Chemical Co., Ltd. , the product name of Osaka Organic Co., Ltd. ^ DABA". The blending amount of the sensitizer is 1 part by mass, preferably 0.5 to 1 part by mass, based on the total of the component (A), the component (B) and the component (C). If it is less than 5 parts by mass, the reaction speed of curing by ultraviolet rays or the like may not be sufficiently increased, and when it exceeds 10 parts by mass, the reaction may be accelerated to cause deterioration of the storage stability of the photosensitive group -18-200844655. 6. (F) Component The photosensitive composition of the present invention may also contain a phosphorus compound (F) other than the phosphorus atom-containing material (D). This compound is different from the phosphorus atom-containing material (D) in that it is a phosphorus compound which is soluble in the composition. • (F) The purpose of blending is to improve the flame retardancy. By multiplying the component (D) which is a necessary component for imparting flame retardancy, it is possible to more effectively improve the flame retardancy of the composition. Examples of the component (F) include phosphates such as triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, triethyl phosphate, cresyl phenyl phosphate, and xylylene diphenyl phosphate. Resorcinol bis(diphenyl)phosphate, bisphenol A bis(diphenyl)phosphate, bisphenol A bis(xylenol) phosphate, resorcinol bis (di-2,6-extension Condensation type phosphoric acid ester such as toluene phosphate, and phosphazene compound such as propoxyphosphazene, phenoxyphosphazene or aminophosphazene. The most preferred (F) component is a condensed phosphate or phosphazene compound. When the amount of the component (F) is added, based on the total of 100 parts by mass of the component (a), the component (B), and the component (C), it is preferably 50 mass parts, more preferably 1 to 30 parts. The mass part is preferably from 1 to 25 parts by mass. When the amount is less than 1 part by mass, the effect of improving the flame retardancy is insufficient. On the other hand, if it exceeds 50 parts by mass, the film may be exposed to light to form a pattern, and the resolution of the pattern or the insulation of the cured film may be formed. Physical properties such as reliability are reduced. 200844655 In order to suppress the adverse effect on the above resolution or insulation reliability, the amount of the component (f) is preferably equal to or less than the amount of the component (D), preferably 2/3 or less, and preferably It is 1/2 or less. 7. (G) Component The photosensitive composition of the present invention may be a thermal polymerization initiator (G) to which a II radical is generated by heating. The component (G) can be exemplified by, for example, an organic peroxide, an initiator having an azo double structure, or the like. It is preferably a dialkyl peroxide, specifically a di- cumenyl peroxidation, from the viewpoint that storage stability is high due to high decomposition initiation temperature and that low molecular weight volatile components are generated at the time of decomposition. , t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5·dimethyl-2,5· (Third butylperoxy) hexanthene and the like.
# 又，添加（G )成份時之調配量，以（A )成份、（B )成份及（C )成份之合計1 〇〇質量份爲基準’較好爲 0.5〜1 0質量份。若未達〇 · 5質量份則添加效果不足’若超 過1 〇質量份則組成物之儲存安定性易變差’同時由於發& 大量之起始劑分解物，因而有損及硬化物耐熱性之顧慮° 本發明之感光性組成物較好爲實質上不含具有環氧基 之化合物（以下稱爲環氧化合物）者。若組成物含有環氧 化合物，則有組成物儲存安定性劣化之情況’故用途受到 限制。 -20- 200844655 但，在沒有要求高度儲存安定性之下，若有必要進一 步提高硬化物之耐熱性以及耐藥品性時，亦可依據需要於 感光性組成物中添加環氧化合物。該情況下，推薦利用使 用前才混合之二液型組成物。 環氧化合物之具體例可舉例爲甲酚酚醛環氧樹脂、苯 酚酚醛環氧樹脂、聚有異尿氰酸酯骨架之環氧樹脂以及雙 酚A型環氧樹脂等。 至於環氧化合物，較好爲具有2個以上環氧基之化合 物。 使用環氧化合物時，通常較好倂用胺系硬化劑、酸系 硬化劑以及酸酐系硬化劑等。 8.感光性組成物 本發明之感光性組成物可藉由使上述必要成份（A )〜 (E )成份以及視需要之（F ) 、（ G )成份、其他成份依據 慣用方法攪拌、混合而製造。 至於本發明之感光性組成物之使用方法，在作爲塗佈 劑、接著劑或光阻劑等使用之情況下，可舉例爲例如在基 材上塗佈組成物後，照射活性能量線，隨後加熱之方法等 〇 至於基材可舉例爲聚碳酸酯、聚甲基丙烯酸甲酯以及 聚氯乙烯等之成形樹脂加工品（塑膠）、金屬、玻璃、陶 瓷、混凝土、天然木材以及合成木材等木材、石材以及紙 -21” 200844655 等。 $ μ '活性能量線可舉例爲電子線、紫外線以及可見光 ’ u可μ光及紫外線照射時之光源，雖可依據所用之光聚 t ® ^齊！1適當的選擇，但較佳者爲高壓水銀燈以及金屬鹵 Λ物1¾ ° '活性能量線照射之條件可依據所使用成份以及目 的適當設定。 上述加熱中’加熱方法及條件可依據一般方法。 Ψ胃Η月2感光性組成物可用於各種用途。具體而言可 舉例爲塗料等之塗佈劑、油墨、光阻劑以及成形材等，較 好作爲光阻劑使用，更好作爲抗焊劑使用。 Τ說明使用本發明之組成物作爲光阻劑使用之情況 〇 使用本發明之感光性組成物作爲光阻劑之情況，可對 應需要添加光阻劑中通常所調配之無機塡充劑、平流劑、 • 消泡劑、顏料以及離子捕捉劑等添加劑。至於無機塡充劑 可舉例爲滑石、黏土、無機氫氧化物以及氧化矽等。至於 顏料可舉例爲酞花青、酞花綠以及碳黑等。該等調配量可 在不損及組成物之解像性以及儲存安定性、硬化物之耐熱 性、柔軟性以及電絕緣性等性能之範圍內調整。 使用本發明之感光性組成物作爲光阻劑時，可以液態 光阻劑之形態，亦可以乾膜光阻劑之形態使用。 作爲液狀光阻劑使用時，亦可視情況於本發明之感光 性組成物中添加高沸點溶劑。該情況下所用之高沸點溶劑 -22- 200844655 之例可舉例爲乙基溶纖素、丁基溶纖速、丁基卡必醇、乙 基溶纖素乙酸酯、丁基溶纖素乙酸酯、乙基卡必醇乙酸酯 以及丁基卡必醇乙酸酯等。 本發明之感光性組成物作爲液狀光阻劑使用時之使用 方法可舉例爲將組成物塗佈或印刷在基材上，以加熱使塗 膜乾燥’接著照射紫外線等活性能量線，再經加熱之方法 等。 將組成物塗佈在基材上時之塗佈裝置可舉例爲旋塗器 、輥塗器以及簾幕式塗佈器等。至於膜厚亦可依目的適當 設定，但較好爲1〜ΙΟΟμιη，最好爲5〜50μιη。 至於基材可舉例爲矽、鋁、鐵、鎳及銅等金屬·，玻璃 ;聚對苯二甲酸乙二醇酯、聚醯亞胺以及聚碳酸酯等塑膠 等基材，以及玻璃環氧基材等複合基材等。 在印刷配線板上形成光阻劑時，銅表面經硏磨後，若 在不形成氧化皮膜之銅箔表面上形成光阻劑時，由於可獲 得更高之密著性因而較佳。又，在進行銅表面之氧化處理 或粗糙面處理而形成凹凸後若形成光阻劑則密著性變得更 良好。 感光性組成物含有溶劑時，塗佈或印刷組成物後，係 藉由加熱使組成物中之溶劑蒸發。該情況下之加熱裝置可 舉例爲烘箱及加熱板等。至於加熱條件，可依據所用之組 成物種類及目的適當的設定，較佳之加熱溫度爲7〇t〜12〇 °C，較佳之加熱時間爲5〜30分鐘。 -23- 200844655 以上述獲得之塗膜上通過形成有特定圖案之光罩以活 性能量線照射。 至於組成物硬化所用之活性能量線可舉例爲電子線及 紫外線等，由可使用便宜裝置之觀點，較好使用紫外線。 至於活性能量線之照射條件亦可依據慣用之方法。至 於照射條件，可依據所使用之感光性組成物種類及目的適 當的使用，較好爲1 0〜5,000mJ/cm2，更好爲50〜50〇mj/cm2 〇 上述活性能量線照射之後，使未硬化部份驗性顯像。 至於顯像所使用之稀鹼性水溶液，亦可依據所用感光 性組成物之種類及目的適當的選擇，舉例例如〇·5〜2%之碳 酸鈉水溶液等。 至於顯像條件可依所用之感光性組成物種類以及目的 適S δ又疋’作爲顯像溫度爲15〜50C ’最好是2 0〜4 0 °C，顯 像時間爲15〜180杪，最好爲30〜120秒。 本發明之感光性組成物可使用作爲抗焊劑，最好是作 爲鹼性顯像型之照相法抗焊劑。 該情況下，經照射活性能量線、顯像後，爲了進一步 提升各種物性，因此可經加熱或活性能量線照射進行充分 的硬化。至於該加熱方法以及條件，亦可依據所用組成物 之種類及目的適當設定，至於加熱溫度爲100〜250 °C，最 好爲130〜2 3 0°C，加熱時間爲5分鐘〜5小時，最好爲30分 鐘〜2小時。活性能量線之照射條件可依據慣用之方法。照 -24- 200844655 射條件亦可依據所用組成物之種類及目的適當選擇，較好 爲 10〜5,000mJ/cm2，更好爲 500〜3,000mJ/cm2。 本發明之感光性組成物作爲乾膜之感光層使用時，乾 膜之製造方法可舉例爲將本發明之組成物塗佈在聚對苯二 甲酸乙二醇酯等支撐薄膜上，經由加熱乾燥去除溶劑後， 使聚丙烯等聚烯烴薄膜等作爲覆蓋薄膜加以重疊之方法等 。至於組成物塗膜（光阻層）之厚度爲1〜200 μιη，最好爲 5 〜5 0 μιη 〇 該情況下，亦可在所用支撐薄膜之塗佈中加入適當溶 劑。組成物中之溶劑必須在塗佈薄膜後在不使該組成物聚 合程度之加熱溫度與時間下揮發，因此該溶劑可舉例爲甲 基乙基酮、乙酸乙酯、乙酸丁酯、甲醇以及乙醇等沸點較 低者。 〔實施例〕 以下顯示實施例及比較例以更具體說明本發明。 以下實施例及比較例中，「份」意指質量份，「％」意 指質量％。 〇合成例1〔 （ A )成份之製造〕 於配置有溫度計、攪拌機及冷卻器之4頸瓶中注入950 克（5 · 0環氧當量）雙酚A型環氧樹脂〔油化峴殼環氧公司 製’商品名「Epicot 828」〕與450克作爲溶劑之甲苯，加 -25- 200844655 熱至1 10°C獲得均勻溶液。於該溶液中添加0.50克作 合抑制劑之吩噻嗪、1 〇克作爲觸媒之溴化四丁基銨 3 6 0克（5.0羧基當量）丙烯酸，一面吹入空氣一面在 °C下反應製造含有丙烯醯基及羥基之化合物（環氧丙 酯）。由酸價計算之丙烯酸消耗率接近1 〇〇%。 於上述產物之溶液中添加220克（1.5莫耳）之苯 酸酐，加熱至1 1 〇°C使苯二甲酸酐完全溶解後，再反應 時。於該溶液中添加1 040克丁基溶纖素後，減壓去除 克甲苯，獲得固成份60%之具有羧基之環氧丙烯酸酯 )溶液。 〇合成例2〔 （ B )成份之製造〕 於配置有溫度計、攪拌機及冷卻器之4頸瓶中注 克甲苯二異氰酸酯及2 0 Oppm之二月桂酸二丁基錫，一 持在70 °C，一面於攪拌下緩慢加入3 90克聚碳酸酯二 東亞合成公司製，碳酸二乙酯與1，6 -己二醇之反應產 碳酸二醇〕，攪拌1小時使之反應。於該溶液中 5 Oppm之二月桂酸二丁基錫，接著在攪拌下且維持在 下緩慢添加48克丙烯酸2-羥基乙酯而進行反應，以糸] 吸收光譜分析反應產物，繼續反應直到確定-N C Ο基；2 吸收消失爲止。 結果獲得500克不具有羧基之聚碳酸酯多元醇， 丙烯酸胺基甲酸酯（b -1 )之橡膠狀固形物。 爲聚 以及 110 烯酸 二甲 3小 3 00 入64 -面維 :醇〔 i物之 添加 7 0°C [外線 :特性 t架之 -26- 200844655 〇合成例3〔 （ B )成份之製造〕 於配置有溫度計、攪拌機及冷卻器之4頸瓶中注入72 克甲苯二異氰酸酯及5 Oppm之二月桂酸二丁基錫，一面維 持在70 °C，一面於攪拌下緩慢加入2 80克聚碳酸酯二醇〔 旭化成化學公司製，商品名「PCDL T6001」〕及12克二 羥甲基丙酸，攪拌1小時使之反應。於該溶液中添加 5 Oppm之二月桂酸二丁基錫，接著在攪拌下且維持在70°C 下緩慢添加1 7克丙烯酸2-羥基乙酯進行反應，以紅外線吸 收光譜分析反應產物，繼續反應直到確定-NCO基之特性吸 收消失爲止。 結果獲得3 8 0克具有羧基之聚碳酸酯多元醇骨架之丙 烯酸胺基甲酸酯（b-3 )之橡膠狀固形物。 〇合成例4〔 （B)成份之製造〕 於配置有溫度計、攪拌機及冷卻器之4頸瓶中注入3 3 克六亞甲基二異氰酸酯及50ppm之二月桂酸二丁基錫，一 面維持在，一面於攪拌下緩慢加入100克聚碳酸酯二 醇〔旭化成化學公司製，商品名「PCDL T5650J」〕，攪拌 3〇分鐘使之反應。於該溶液中添加50ppm之二月桂酸二丁 基錫，接著在攪拌下且維持在7〇t下緩慢添加24克丙烯酸 2-羥基乙酯進行反應，以紅外線吸收光譜分析反應產物， 繼續反應直到確定-NCO基之特性吸收消失爲止。 -27- 200844655 結果獲得156克不具有羧基之聚碳酸酯多元醇骨架之 丙烯酸胺基甲酸酯（b-4 )之橡膠狀固形物。 〇合成例5〔 （ B )成份之製造〕 於配置有溫度§十、擾拌機及冷卻器之4頸瓶中注入3 4 克六亞甲基二異氰酸酯及5 Oppm之二月桂酸二丁基錫，一 面維持在70 °C，一面於攪拌下緩慢加入1 000克聚碳酸酯二 醇〔東亞合成公司製，商品名「PES-3 60」〕及200克聚碳 酸酯二醇〔旭化成化學公司製，商品名「PCDL T5652」〕 ，攪拌1小時使之反應。於該溶液中添加50PPm之二月桂 酸二丁基錫，接著在攪拌下且維持在7〇°C下緩慢添加1 3克 丙烯酸2-羥基乙酯進行反應，以紅外線吸收光譜分析反應 產物，繼續反應直到確定-NCO基之特性吸收消失爲止。 結果獲得1 246克不具有羧基之聚碳酸酯多元醇骨架之 丙烯酸胺基甲酸酯（b-5 )之橡膠狀固形物。 〇實施例1〜11，比較例1〜7 使用1份之2,4-二乙基塞噸酮（增感劑）及甲基乙基 酮（溶劑）以及分別以固形分比例依據下表1及表2中所 示之調配比例之下列所示之（A )成份〜（J )成份，該等成 份以三軸輥混練，調配固成份65%之組成物。 -28- 200844655# Further, the amount of the (G) component to be added is preferably from 0.5 to 10 parts by mass based on 1 part by mass of the total of the components (A), (B) and (C). If it is less than 5 parts by mass, the effect of addition is insufficient. If it exceeds 1 part by mass, the storage stability of the composition may be deteriorated. At the same time, due to the large amount of the initiator decomposition product, the heat resistance of the cured product is impaired. The photosensitive composition of the present invention is preferably one which does not substantially contain a compound having an epoxy group (hereinafter referred to as an epoxy compound). When the composition contains an epoxy compound, there is a case where the storage stability of the composition is deteriorated, and the use is limited. -20- 200844655 However, if it is not necessary to have high storage stability, if it is necessary to further improve the heat resistance and chemical resistance of the cured product, an epoxy compound may be added to the photosensitive composition as needed. In this case, it is recommended to use a two-liquid type composition which is mixed before use. Specific examples of the epoxy compound are cresol novolac epoxy resin, phenol novolac epoxy resin, epoxy resin having an isocyanurate skeleton, and bisphenol A epoxy resin. As the epoxy compound, a compound having two or more epoxy groups is preferred. When an epoxy compound is used, an amine-based curing agent, an acid-based curing agent, an acid anhydride-based curing agent or the like is usually preferably used. 8. Photosensitive Composition The photosensitive composition of the present invention can be stirred and mixed according to a conventional method by subjecting the above-mentioned essential components (A) to (E) and optionally (F), (G) components and other components. Manufacturing. As a method of using the photosensitive composition of the present invention, when it is used as a coating agent, an adhesive, a photoresist, or the like, for example, after coating a composition on a substrate, the active energy ray is irradiated, followed by The heating method is equivalent to the substrate, which may be exemplified by polycarbonate, polymethyl methacrylate, polyvinyl chloride, polyvinyl chloride, etc., such as processed resin (plastic), metal, glass, ceramic, concrete, natural wood, and synthetic wood. , stone and paper - 21" 200844655, etc. $ μ 'active energy line can be exemplified by electron beam, ultraviolet light and visible light. u can be used for light and ultraviolet light, although it can be used according to the light used. Appropriate choice, but preferably high pressure mercury lamp and metal halides 13⁄4 ° 'The conditions of active energy line irradiation can be set according to the ingredients and purpose used. The heating method and conditions can be based on the general method. The photosensitive composition of the month 2 can be used for various purposes, and specific examples thereof include a coating agent such as a paint, an ink, a photoresist, and a molded material. It is used as a photoresist, and it is more preferably used as a solder resist. ΤWhen the composition of the present invention is used as a photoresist, when a photosensitive composition of the present invention is used as a photoresist, a photoresist may be added correspondingly. Additives such as inorganic chelating agents, admixtures, defoamers, pigments, and ion scavengers are usually formulated in the agent. As the inorganic chelating agent, talc, clay, inorganic hydroxide, cerium oxide, etc. can be exemplified. Examples thereof include phthalocyanine, phthalocyanine, and carbon black, etc. These blending amounts can be used without impairing the resolution of the composition, storage stability, heat resistance, softness, and electrical insulating properties of the cured product. When the photosensitive composition of the present invention is used as a photoresist, it can be used in the form of a liquid photoresist or a dry film photoresist. When used as a liquid photoresist, it can also be used as a case. A high boiling point solvent is added to the photosensitive composition of the present invention. Examples of the high boiling point solvent-22-200844655 used in this case are exemplified by ethyl cellosolve, butyl solvolysis, and butyl. Alcohol, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, etc. The photosensitive composition of the present invention is used as a liquid photoresist The method of use of the agent can be exemplified by coating or printing a composition on a substrate, heating to dry the coating film, followed by irradiation with an active energy ray such as ultraviolet rays, heating, etc. The composition is coated on the substrate. The coating device on the material can be exemplified by a spin coater, a roll coater, a curtain coater, etc. The film thickness can also be appropriately set according to the purpose, but is preferably 1 to ΙΟΟμιη, preferably 5 to 50 μm. The substrate may be exemplified by metals such as ruthenium, aluminum, iron, nickel, and copper, glass, plastics such as polyethylene terephthalate, polyimide, and polycarbonate, and glass epoxy. When a photoresist is formed on a printed wiring board, when a copper surface is honed, if a photoresist is formed on the surface of the copper foil on which the oxide film is not formed, a higher density can be obtained. The sex is thus better. Further, when the copper surface is oxidized or roughened to form irregularities, the adhesion is further improved when a photoresist is formed. When the photosensitive composition contains a solvent, after coating or printing the composition, the solvent in the composition is evaporated by heating. The heating device in this case can be exemplified by an oven, a heating plate, or the like. The heating conditions may be appropriately set depending on the type and purpose of the composition to be used, and the heating temperature is preferably 7 Torr to 12 Torr °C, and preferably the heating time is 5 to 30 minutes. -23- 200844655 The film obtained by the above is irradiated with a vibrating line by a photomask formed with a specific pattern. As the active energy ray used for hardening the composition, for example, an electron beam and an ultraviolet ray can be exemplified, and from the viewpoint of using an inexpensive device, ultraviolet rays are preferably used. The irradiation conditions of the active energy rays can also be based on conventional methods. The irradiation conditions may be appropriately used depending on the type and purpose of the photosensitive composition to be used, preferably from 10 to 5,000 mJ/cm 2 , more preferably from 50 to 50 μm/cm 2 , after the above-mentioned active energy ray irradiation. Unhardened partial immunographic imaging. The dilute alkaline aqueous solution used for the development may be appropriately selected depending on the type and purpose of the photosensitive composition to be used, and for example, a sodium carbonate aqueous solution of 5 to 2% is used. As for the development conditions, depending on the type of photosensitive composition used and the purpose, the appropriate S δ 疋 ' as the development temperature is 15 to 50 C ', preferably 2 0 to 4 0 ° C, and the development time is 15 to 180 杪, It is preferably 30 to 120 seconds. The photosensitive composition of the present invention can be used as a solder resist, and is preferably a photographic solder resist which is an alkaline development type. In this case, after the active energy ray is irradiated and developed, in order to further enhance various physical properties, it can be sufficiently cured by heating or active energy ray irradiation. The heating method and conditions may be appropriately set depending on the type and purpose of the composition to be used, and the heating temperature is 100 to 250 ° C, preferably 130 to 2 30 ° C, and the heating time is 5 minutes to 5 hours. It is best for 30 minutes to 2 hours. The irradiation conditions of the active energy rays can be determined according to a conventional method. The irradiation condition may be appropriately selected depending on the type and purpose of the composition to be used, and is preferably from 10 to 5,000 mJ/cm 2 , more preferably from 500 to 3,000 mJ/cm 2 . When the photosensitive composition of the present invention is used as a photosensitive layer of a dry film, the method for producing a dry film can be exemplified by applying the composition of the present invention to a support film such as polyethylene terephthalate and drying it by heating. After the solvent is removed, a polyolefin film such as polypropylene or the like is laminated as a cover film. The thickness of the composition coating film (photoresist layer) is 1 to 200 μm, preferably 5 to 50 μm. In this case, an appropriate solvent may be added to the coating of the support film to be used. The solvent in the composition must be volatilized after coating the film at a heating temperature and time which does not allow polymerization of the composition, and thus the solvent can be exemplified by methyl ethyl ketone, ethyl acetate, butyl acetate, methanol, and ethanol. The lower boiling point. [Examples] The examples and comparative examples are shown below to more specifically explain the present invention. In the following examples and comparative examples, "parts" means parts by mass, and "%" means mass%. 〇Synthesis Example 1 [Production of (A) component] Into a 4-neck bottle equipped with a thermometer, a stirrer, and a cooler, 950 g (5·0 epoxy equivalent) of bisphenol A type epoxy resin (oiled clam shell ring) was injected. Oxygen Company's 'product name "Epicot 828"] and 450 g of toluene as a solvent, plus -25 - 200844655 heat to 1 10 ° C to obtain a homogeneous solution. To the solution, 0.50 g of phenothiazine as a combination inhibitor and 1 gram of tetrabutylammonium bromide as a catalyst were added to 605 g (5.0 carboxy equivalent) of acrylic acid, and the reaction was carried out at ° C while blowing air. A compound (glycidyl ester) containing an acryloyl group and a hydroxyl group is produced. The acrylic acid consumption rate calculated from the acid value is close to 1%. To the solution of the above product, 220 g (1.5 mol) of phthalic anhydride was added, and the mixture was heated to 110 ° C to completely dissolve the phthalic anhydride, and then reacted. After adding 1,040 g of butyl cellosolve to the solution, gram of toluene was removed under reduced pressure to obtain a 60% solid epoxy acrylate solution having a carboxyl group. 〇Synthesis Example 2 [Production of (B) component] In a 4-neck bottle equipped with a thermometer, a stirrer, and a cooler, gram of toluene diisocyanate and 20 Oppm of dibutyltin dilaurate were held at 70 ° C. 3,90 g of a polycarbonate, manufactured by Toagosei Co., Ltd., and a reaction of diethyl carbonate and 1,6-hexanediol to produce a carbonate diol was slowly added under stirring, and the mixture was stirred for 1 hour to cause a reaction. In this solution, 5 Oppm of dibutyltin dilaurate was added, followed by slowly adding 48 g of 2-hydroxyethyl acrylate under stirring to maintain the reaction, and the reaction product was analyzed by absorption spectroscopy, and the reaction was continued until the -NC 确定 was determined. Base; 2 absorption disappears. As a result, 500 g of a polycarbonate polyol having no carboxyl group and a rubbery solid of urethane acrylate (b-1) were obtained. For poly and 110 olefinic acid dimethyl 3 small 3 00 into 64-face dimension: alcohol [i addition of 7 0 ° C [external line: characteristic t-frame -26- 200844655 〇 synthesis example 3 [ (B) component manufacturing 〕 Inject 72 g of toluene diisocyanate and 5 Oppm of dibutyltin dilaurate in a 4-neck bottle equipped with a thermometer, a stirrer and a cooler, while slowly maintaining 2 80 g of polycarbonate while stirring at 70 ° C A diol (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "PCDL T6001") and 12 g of dimethylolpropionic acid were stirred for 1 hour to cause a reaction. To the solution, 5 Oppm of dibutyltin dilaurate was added, followed by slowly adding 17 g of 2-hydroxyethyl acrylate with stirring at 70 ° C to carry out a reaction, and the reaction product was analyzed by infrared absorption spectroscopy, and the reaction was continued until It is determined that the absorption of the characteristic of the -NCO group disappears. As a result, a rubbery solid of 380 g of a acrylic acid urethane (b-3) having a carboxyl group-containing polycarbonate polyol skeleton was obtained. 〇Synthesis Example 4 [Production of (B) component] Into a four-necked flask equipped with a thermometer, a stirrer, and a cooler, 33 g of hexamethylene diisocyanate and 50 ppm of dibutyltin dilaurate were injected while maintaining 100 g of polycarbonate diol (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "PCDL T5650J") was slowly added under stirring, and the mixture was stirred for 3 minutes to cause a reaction. 50 ppm of dibutyltin dilaurate was added to the solution, followed by slowly adding 24 g of 2-hydroxyethyl acrylate with stirring at 7 Torr, and the reaction product was analyzed by infrared absorption spectroscopy, and the reaction was continued until it was determined - The absorption of the characteristics of the NCO group disappears. -27- 200844655 As a result, 156 g of a rubbery solid of acrylamide (b-4) having a polycarbonate polyol skeleton having no carboxyl group was obtained. 〇Synthesis Example 5 [Production of (B) component] Into a 4-neck bottle equipped with a temperature §10, a scrambler and a cooler, 34 g of hexamethylene diisocyanate and 5 Oppm of dibutyltin dilaurate were injected. While maintaining the temperature at 70 ° C, 1 000 g of polycarbonate diol (manufactured by Toagosei Co., Ltd., trade name "PES-3 60") and 200 g of polycarbonate diol (manufactured by Asahi Kasei Chemicals Co., Ltd.) were slowly added under stirring. The product name "PCDL T5652"] was stirred for 1 hour to react. 50 ppm of dibutyltin dilaurate was added to the solution, followed by slowly adding 13 g of 2-hydroxyethyl acrylate with stirring at 7 ° C to carry out the reaction, and the reaction product was analyzed by infrared absorption spectroscopy, and the reaction was continued until It is determined that the absorption of the characteristic of the -NCO group disappears. As a result, 1 246 g of a rubbery solid of acrylamide (b-5) having a polycarbonate polyol skeleton having no carboxyl group was obtained. 〇Examples 1 to 11, Comparative Examples 1 to 7 1 part of 2,4-diethyl ketoxime (sensitizer) and methyl ethyl ketone (solvent) and solid content ratios according to the following Table 1 And the blending ratios shown in Table 2 are the components (A) to (J) shown below, which are kneaded by a triaxial roll to prepare a composition of 65% solid content. -28- 200844655
1 1 1 i o o 1 o 1 1 1 1 1 1 ο 1 1 1 o 1 o 1 o 1 1 m 1 (N 1 1 i ΟΝ 1 1 o 1 1 o 1 o 1 1 m i (N 1 1 I οο 〇 1 I i i o i 1 1 m i (N I i i 卜 〇 1 1 1 1 o 1 1 1 m 1 ! ^ (N 1 1 1 νο 1 1 1 1 o 1 o i 1 m 1 (N ! ! 1 〇 1 1 1 1 o 1 o 1 1 m 宕 1 <N 1 1 1 寸 〇 1 i 1 1 o ! 沄 i m 1 I (M 1 1 1 ΓΛ 〇 1 1 1 1 1 o o 1 1 m 1 :1 <N 1 1 1 (Ν 1 o I 1 1 o 1 o i 1 m 1 1 (N 1 1 1 竇施例 1 ι 〇 1 1 1 1 o 1 o i 1 m 1 1 (N 1 1 1 ψ^ί /^S Τ·»Η Μ Z^-N (N e /^N m w irT 0 /^s 3 ό 1 3 /^N 也 Vm 1 4 (Ν' ^ ' /^N e f—H /^N H 1 •o 一、 /^s m g £ O g ζ^\ -29- .2008446551 1 1 ioo 1 o 1 1 1 1 1 1 ο 1 1 1 o 1 o 1 o 1 1 m 1 (N 1 1 i ΟΝ 1 1 o 1 1 o 1 o 1 1 mi (N 1 1 I οο 〇1 I iioi 1 1 mi (NI ii 〇 1 1 1 1 o 1 1 1 m 1 ! ^ (N 1 1 1 νο 1 1 1 1 o 1 oi 1 m 1 (N ! ! 1 〇1 1 1 1 o 1 o 1 1 m 宕1 <N 1 1 1 inch 〇1 i 1 1 o ! 沄im 1 I (M 1 1 1 ΓΛ 〇1 1 1 1 1 oo 1 1 m 1 :1 <N 1 1 1 ( Ν 1 o I 1 1 o 1 oi 1 m 1 1 (N 1 1 1 sinus example 1 ι 〇1 1 1 1 o 1 oi 1 m 1 1 (N 1 1 1 ψ^ί /^S Τ·»Η Μ Z^-N (N e /^N mw irT 0 /^s 3 ό 1 3 /^N Also Vm 1 4 (Ν' ^ ' /^N ef-H /^NH 1 •o I, /^smg £ O g ζ^\ -29- .200844655
卜 Ο 1 o ：1 i i 1 m 〇 i 1 1 1 1 i o r—H 1 I 1 i o m 1 1 (N O 寸 1 〇 1 1 o f—H 1 I 1 1 m o 1 (N 1 寸 1 1 1 1 1 1 1 ΓΠ 1 o (N 1 1 1 m 1 1 〇 f—1 1 I 1 I m o 1 (N 1 I 1 CM 1 1 o T 一 1 1 1 1 m 1 1 (N 1 1 o r—t 1 i 1 o ▼—H 1 i 1 1 1 <N i i o 實施例 /^N y_ < N r^H (b-2) ( ό ό /^s ▼—H rjT 3 /—*N r^l /—N /^s t—4 r—H -s r 4 去 /—N 1 *v3? g gv g o g /^\ -30- 200844655 表1與表2中各成份欄中之數値意指質量份。又，各 成份之簡寫符號意義如下： (a-Ι ):以合成例1製備之具有羧基之環氧丙烯酸酯 (b-1):以合成例2製備之不具有羧基之聚碳酸酯多 元醇骨架之丙烯酸胺基甲酸酯（質量平均分子量8000 ) (b-2 ):聚酯多元醇型丙烯酸胺基甲酸酯〔新中村化 學（股）製「U-200AX」，數平均分子量13000〕 (b-3 ):以合成例3製備之具有羧基之聚碳酸酯多元 醇骨架之丙烯酸胺基甲酸酯（質量平均分子量1 0000 ) (b-4):以合成例4製備之不具有羧基之聚碳酸酯多 元醇骨架之丙烯酸胺基甲酸酯（質量平均分子量1800) (b-5 ):以合成例5製備之不具有羧基之聚碳酸酯多 元醇骨架之丙烯酸胺基甲酸酯（質量平均分子量60000 ) (c-1 ):二季戊四醇〔由丙烯酸戊酯與二季戊四醇六 丙烯酸酯構成之組成物（東亞合成公司製，商品名「 ARONIX M-400」)〕 (c-2 ):季戊四醇二丙烯酸酯單硬脂酸酯〔東亞合成 公司製，商品名「ARONIX M-23 3」〕 (d-1 ):二乙基膦酸鋁〔日本Claimant’s公司製，商 品名「EXOLIT OP-930」，平均粒徑5μηι’ P含量23%〕 (d-2 ):聚磷酸三聚氰胺〔三和化學公司製’商品名 「MPP-B」，平均粒徑1 2μιη，P含量1 3%〕 (d-3 ):聚磷酸銨〔鈴祐化學公司製，商品名「FCp- -31 - 200844655 720」，平均粒徑20μΐΒ，P含量13%〕 (e·〗）：光聚合起始劑，2-甲基-〔4-(甲硫基） 〕-2-嗎啉基-1-丙酮〔汽巴特用化學品公司製造，商品 Iregacure 907」〕 (f-1 ):芳香族縮合磷酸酯〔大八化學公司製造 品名「PX-2 00」，P含量14%〕 • ( f-2 ):聚磷腈〔大塚化學公司製，商品名^ 10 0」，P含量1 3 %〕 (g-1 ):熱聚合觸媒，二枯烯過氧化物〔日本油 司製，商品名「Polkmil D」〕 (h-1 ):雙酚A型環氧樹脂〔油化蜆殻環氧公司 商品名「Epicot 828」〕 (i-1 ):三聚氰胺〔上述（h-1 )環氧樹脂之硬化: (j-1 ):氫氧化鎂〔無機氫氧化物系難燃劑，協 # 學工業公司製，商品名「Kisma 5A」，平均粒徑1 μηι〕 將上述感光性組成物塗佈於厚度25 μιη之聚對苯二 乙二醇酯製之薄膜（基底薄膜）上，於100 °C下加熱： 鐘，蒸發揮發性成份，形成感光性組成物之被覆膜（ 約30μηι)。隨後，於該被覆膜上貼合厚度2 5 μιη之聚 製薄膜（覆蓋薄膜）而製成乾膜。 爲了評價乾膜而將覆蓋薄膜剝除。一面使剝除覆 膜之乾膜加溫至7〇 °C，——面使感光性組成物之被覆膜 下稱爲感光層）附著於後述基板上之方式，使用層合 苯基 名「 ，商 SPB- 脂公 製， 劑〕 和化 甲酸 I 〇分 厚度 乙烯 蓋薄 (以 機加 •32- 200844655 以層合。如此獲得之附有感光層之基板係在基板上形成感 光層，於其上被覆基底薄膜者。 依據以下之方法評價該附有感光層基板之解像度、儲 存安定性、難燃性、基板彎曲、耐彎曲性、焊料耐熱性以 及絕緣信賴性。評價結果列於表3及表4中。 (解像度，儲存安定性） 使用FR-4基板〔住友背光板公司製，銅箔厚度ΐ8μιη 〕做爲基板。於所製成之附有感光層基板之感光層上，使 用具有 6 0 μ m、8 0 μ m、1 0 0 μ m及2 0 0 μ m線路寬度之圖案之 光罩，以25 0mJ/cm2之光量曝光。上述光罩係置於基底薄 膜上，對感光層之曝光係通過光罩及基底薄膜進行。曝光 後，剝離基底薄膜，以1 .5kg/cm2之壓力噴佈液溫30°C之 濃度1 %之碳酸鈉水溶液歷時6 0秒’藉由去除感光層之未 曝光部分，進行鹼顯像獲得試驗片。以顯微鏡觀察所得之 試驗片，對感光層之硬化膜狀態進行下列3階段評價。 〇…沒有異常 △…觀察到一部份異常（殘渣、剝離、蛇行等） X…觀察到全部異常（殘澄、剝離、蛇行等） 儲存安定性之評價係使乾膜在1 5 °C下儲存1個月後’ 與上述相同作成附有感光層之基板，對曝光、顯像後之試 驗片進行解像度評估者。 -33- 200844655 (難燃性） 使用25 μηι厚之聚亞醯胺薄膜〔東麗杜邦公司製，商品 名「Capton」做爲基板。對附有感光層之基板以 1 000mJ/cm2之光量曝光。隨後剝離基底薄膜，在160°C下 後硬化3 0分鐘獲得試驗片。 使用上述試驗片’以UL-94規格之薄材料垂直燃燒試 驗方法爲準評價難燃性。 (基板彎曲） 使用2 5 μιη厚之聚亞醯胺薄膜〔東麗杜邦公司製，商品 名「Capton」作爲基板。對附有感光層之基板以 1 000mJ/cm2之光量曝光。隨後剝離基底薄膜，在160°C下 後硬化30分鐘，切成邊長100mm獲得試驗片。 將試驗片放置在水平地板上，以mm單位測定各試驗 片之角距離地板之高度’以其平均値做爲彎曲大小之評價 〇 X…由於完全捲曲因此無法測定彎曲度 (耐彎曲性） 使用25 μιη厚之聚亞醯胺薄膜〔東麗杜邦公司製，商品 名「Capton」作爲基板。對附有感光層之基板以 1 000m]/cm2之光量曝光。隨後剝離基底薄膜，在160°C下 後硬化30分鐘’切成】〇〇mm邊長獲得試驗片。 -34- 200844655 使試驗片之感光層成爲外側彎曲90°或180° ’以目視觀 察感光層之裂痕等損傷’且以下列3階段評價： 〇...感光層沒有異常 △ ...感光層表面異常（裂痕等） X...裂痕到達感光層下面 ·(焊料耐熱性） 使用FR-4基板〔住友背光板公司製，銅箔厚度18μιη 〕作爲基板。對附有感光層之基板以1 0 0 0 m JT / c m2之光量曝 光。隨後剝離基底薄膜，在160 °C下後硬化30分鐘，獲得 試驗片。使試驗片浸漬在280°C之熔融焊料浴中歷時10秒 作爲1次循環’以目視觀察經過5次循環後之硬化膜狀態 ，且以下列3階段評價： 〇...感光層沒有剝離 φ △..·感光層一部份剝離 x…感光層大部份剝離或完全剝離 (絕緣信賴性） 使用由FR_4基板〔住友背光板公司製，銅箔厚度 18μπι〕作成之梳型試驗圖案（線路寬度1〇〇μπι，線路間距 ΙΟΟμηι )基板，對附有感光層之基板以〗〇 〇 〇 m j / c m 2之光量 曝光。隨後剝離基底薄膜，在1 6 01：下後硬化3 〇分鐘，獲 得試驗片。使所得試驗片在溫度85°C、相對濕度85%之氛 -35- 200844655 圍中測定施加直流電50V之狀態放置25 0小時、5 00小時 、：I 0 0 0小時後之絕緣電阻値。 X ...配線間短路，無法測得電阻値Ο 1 o :1 ii 1 m 〇i 1 1 1 1 ior—H 1 I 1 iom 1 1 (NO inch 1 〇1 1 of—H 1 I 1 1 mo 1 (N 1 inch 1 1 1 1 1 1 1 ΓΠ 1 o (N 1 1 1 m 1 1 〇f -1 1 I 1 I mo 1 (N 1 I 1 CM 1 1 o T -1 1 1 1 m 1 1 (N 1 1 or-t 1 i 1 o ▼—H 1 i 1 1 1 <N iio Example /^N y_ < N r^H (b-2) ( ό ό /^s ▼—H rjT 3 /—*N r^l /— N /^st—4 r—H -sr 4 to /—N 1 *v3? g gv gog /^\ -30- 200844655 The number in the column of each component in Table 1 and Table 2 means the mass. The abbreviated symbols of the respective components have the following meanings: (a-Ι): an epoxy acrylate having a carboxyl group (b-1) prepared in Synthesis Example 1: a polycarbonate polyol skeleton having no carboxyl group prepared in Synthesis Example 2 Amino acrylate (mass average molecular weight 8000) (b-2): polyester polyol type urethane urethane [U-200AX, manufactured by Shin-Nakamura Chemical Co., Ltd., number average molecular weight 13000] (b -3 ): Acrylic urethane having a carboxyl group-containing polycarbonate polyol skeleton prepared by Synthesis Example 3 (mass average molecular weight: 1 0000 ) (b-4): Acrylic urethane having a polycarbonate polyol skeleton having no carboxyl group prepared by Synthesis Example 4 (mass average molecular weight: 1800) (b-5): polycarbonate polyol skeleton having no carboxyl group prepared in Synthesis Example 5 Acrylic urethane (mass average molecular weight 60000) (c-1): dipentaerythritol [composition composed of amyl acrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name "ARONIX M-400") )] (c-2): pentaerythritol diacrylate monostearate [manufactured by Toagosei Co., Ltd., trade name "ARONIX M-23 3") (d-1): aluminum diethylphosphonate (manufactured by Claimant's, Japan) , the product name "EXOLIT OP-930", the average particle size of 5μηι' P content 23%] (d-2): melamine polyphosphate [Mr. Chemical Co., Ltd.'s trade name "MPP-B", average particle size 1 2μιη, P content: 1 3%] (d-3): Ammonium polyphosphate (manufactured by Suzuka Chemical Co., Ltd., trade name "FCp- -31 - 200844655 720", average particle size 20 μΐΒ, P content 13%] (e·): Photopolymerization initiator, 2-methyl-[4-(methylthio)]-2-morpholinyl-1-propanone Manufactured by the company, Iregacure 907" (f-1): Aromatic condensed phosphate ester [Da-8 Chemical Company's product name "PX-2 00", P content 14%] • (f-2): Polyphosphazene [大冢Chemical company, trade name ^ 10 0", P content 13%] (g-1): thermal polymerization catalyst, dicumyl peroxide [manufactured by Nippon Oil Co., Ltd., trade name "Polkmil D"] (h- 1): bisphenol A type epoxy resin [oily clam shell epoxy company trade name "Epicot 828"] (i-1): melamine [hardening of (h-1) epoxy resin: (j-1) : Magnesium hydroxide [Inorganic hydroxide-based flame retardant, manufactured by Kosei Kogyo Co., Ltd., trade name "Kisma 5A", average particle diameter 1 μηι]. The photosensitive composition is applied to a polyphenylene terephthalate having a thickness of 25 μm. On a film made of diethylene glycol ester (base film), it was heated at 100 ° C for a clock to evaporate volatile components to form a coating film of a photosensitive composition (about 30 μm). Subsequently, a polymer film (cover film) having a thickness of 25 μm was applied to the film to form a dry film. The cover film was peeled off in order to evaluate the dry film. The method of laminating the dry film of the peeling film to 7 ° C, and the surface of the coating of the photosensitive composition is referred to as a photosensitive layer) is attached to a substrate to be described later, and the laminated phenyl name is used. , Shang SPB-fat metric, agent] and formic acid I 〇 厚度 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 The base film was coated thereon. The resolution, storage stability, flame retardancy, substrate bending, bending resistance, solder heat resistance, and insulation reliability of the photosensitive layer substrate were evaluated according to the following methods. The evaluation results are shown in Table 3. And Table 4. (Resolution, storage stability) Using a FR-4 substrate [manufactured by Sumitomo Backlight Co., Ltd., copper foil thickness μ8μιη] as a substrate. On the photosensitive layer with the photosensitive layer substrate produced, A mask of a line width of 60 μm, 80 μm, 100 μm, and 200 μm is exposed at a light amount of 25 0 mJ/cm 2 . The mask is placed on a base film to be photosensitive. The exposure of the layer is performed through the mask and the base film. After the exposure, the base film was peeled off, and the solution was sprayed at a pressure of 1.5 kg/cm 2 at a temperature of 30 ° C at a concentration of 1% sodium carbonate aqueous solution for 60 seconds. The alkali exposure was obtained by removing the unexposed portion of the photosensitive layer. The test piece was observed under a microscope, and the state of the cured film of the photosensitive layer was evaluated in the following three stages: 〇...no abnormality Δ...a part of abnormality was observed (residue, peeling, meandering, etc.) X...all abnormalities were observed. (Residual, peeling, serpentine, etc.) The evaluation of storage stability is such that after the dry film is stored at 15 ° C for 1 month, the substrate with the photosensitive layer is formed in the same manner as above, and the test piece after exposure and development is performed. For the resolution evaluator -33- 200844655 (flammability) A 25 μη thick polyimide film (manufactured by Toray DuPont, trade name "Capton" as a substrate. The substrate with the photosensitive layer is 1 000 mJ. The amount of light was exposed to /cm 2 , and then the base film was peeled off, and post-hardened at 160 ° C for 30 minutes to obtain a test piece. The above test piece was used to evaluate the flame retardancy based on the UL-94 standard thin material vertical burning test method. Substrate bend A film of 2 5 μm thick polytheneamine film (manufactured by Toray DuPont Co., Ltd., trade name "Capton") was used as a substrate. The substrate with the photosensitive layer was exposed to light at a rate of 1 000 mJ/cm 2 , and then the base film was peeled off at 160 After hardening for 30 minutes at ° C, the test piece was obtained by cutting into a side length of 100 mm. The test piece was placed on a horizontal floor, and the height of each test piece was measured in mm units from the height of the floor, and the average 値 was used as the bending size. 〇X... The degree of curvature (bending resistance) could not be measured due to complete curling. A 25 μm thick polyimide film (manufactured by Toray DuPont, trade name "Capton") was used as the substrate. The substrate with the photosensitive layer was exposed to light of 1 000 m]/cm 2 . Subsequently, the base film was peeled off, and post-hardened at 160 ° C for 30 minutes to cut into a side length to obtain a test piece. -34- 200844655 The photosensitive layer of the test piece was bent to the outside by 90° or 180° 'to visually observe the damage such as cracks in the photosensitive layer' and evaluated in the following three stages: 〇...the photosensitive layer has no abnormality Δ...photosensitive layer Surface abnormalities (cracks, etc.) X... Cracks reached the bottom of the photosensitive layer. (Solder heat resistance) A FR-4 substrate (manufactured by Sumitomo Backlight Co., Ltd., copper foil thickness: 18 μm) was used as the substrate. The substrate with the photosensitive layer was exposed to light of 1 000 m JT / c m2. Subsequently, the base film was peeled off and post-hardened at 160 ° C for 30 minutes to obtain a test piece. The test piece was immersed in a molten solder bath at 280 ° C for 10 seconds as a single cycle'. The cured film state after 5 cycles was visually observed, and evaluated in the following three stages: 〇...the photosensitive layer was not peeled off φ △..· Partially peeled off the photosensitive layer... Most of the photosensitive layer is peeled off or completely peeled off (insulation reliability) A comb type test pattern (line) made of FR_4 substrate [manufactured by Sumitomo Backlight Co., Ltd., copper foil thickness 18 μm] A substrate having a width of 1 μm μm and a line pitch of ημηι is exposed to a substrate having a photosensitive layer at a light amount of 〇〇〇mj / cm 2 . Subsequently, the base film was peeled off, and after 6 6 01:, it was hardened for 3 Torr to obtain a test piece. The obtained test piece was placed in a state of a temperature of 85 ° C and a relative humidity of 85% -35 - 200844655, and a DC resistance of 50 V was applied for 25 hours, 500 hours, and an insulation resistance 后 after I 0 0 hours. X ... short circuit between wirings, the resistance cannot be measured値
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= X X <3 〇 X X <3 〇 相當於 ! VTM=0 〇 〇 〇 >10,2 >1012 〇 ο 〇 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 ο 0 X 〇 >1012 >10 丨2 ο 一Ο On 〇 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 〇 〇 〇 >10,2 〇〇 〇 〇 〇 〇 〇 〇 〇 〇 I相當於 丨 VTM-0 〇 <] 〇 >1012 >10,2 ο 卜 〇 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 〇 〇 〇 >10,2 >1012 ο ο VO 〇 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 <!0 〇 〇 〇 >10 丨2 >1012 >1012 〇 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 <10 〇 〇 〇 >1012 >1012 >1012 寸 〇 〇 〇 〇 〇 〇 Ο 〇 相當於 VTM-0 κη (Ν 〇 〇 〇 >1012 >10 丨2 >1012 m 〇 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 〇 〇 <3 >10,2 >!012 "ο <N 〇 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 〇 〇 〇 >10,2 >1012 Ο "ο 實施例 I l 〇 1 〇 〇 〇 〇 〇 〇 〇 相當於 VTM-0 〇 〇 〇 >10,2 >1012 >10,2 80μιη ΙΟΟμπι 200μιη 60μΐΉ 丨 80μηι ΙΟΟμπι 200μΓη 難燃性 基板彎曲(mm) ο 1 焊料耐熱性 1 250h 500h 1 lOOOh 解像度 解像度 (1個月後） 耐彎曲性 絕緣信賴性 (Ω) -37- 200844655= XX <3 〇XX <3 〇 is equivalent! VTM=0 〇〇〇>10,2 >1012 〇ο 〇〇〇〇〇〇〇〇equivalent to VTM-0 ο 0 X 〇>1012 >10 丨2 ο One Ο On 〇〇〇〇〇〇〇〇 is equivalent to VTM-0 〇〇〇>10,2 〇〇〇〇〇〇〇〇〇〇I is equivalent to 丨VTM-0 〇< ] 〇>1012 >10,2 ο Divination is equivalent to VTM-0 〇〇〇>10,2 >1012 ο ο VO 〇〇〇〇〇〇〇〇 is equivalent to VTM -0 <!0 〇〇〇>10 丨2 >1012 >1012 〇〇〇〇〇〇〇〇 is equivalent to VTM-0 <10 〇〇〇>1012 >1012 >1012 inch 〇 〇〇〇〇〇Ο 〇 is equivalent to VTM-0 κη (Ν 〇〇〇 >1012 >10 丨2 >1012 m 〇〇〇〇〇〇〇〇 is equivalent to VTM-0 〇〇<3 > 10,2 >!012 "ο <N 〇〇〇〇〇〇〇〇 is equivalent to VTM-0 〇〇〇>10,2 >1012 Ο "ο Example I l 〇1 〇〇〇 〇〇〇〇 is equivalent to VTM-0 〇 〇〇>10,2 >1012 >10,2 80μιη ΙΟΟμπι 200μιη 60μΐΉ 丨80μηι ΙΟΟμπι 200μΓη Flame retardant substrate bending (mm) ο 1 Solder heat resistance 1 250h 500h 1 lOOOh Resolution resolution (after 1 month) Flexural insulation reliability (Ω) -37- 200844655
卜 X X X 〇 X X X 〇 相當於 VTM-0 〇 〇 < CN Id η Λ "ο X X 〇 〇 〇 X X X < !相當於 VTM-0 X 〇 <3 Ο 一〇> co_^ r—4 X X X X X X X X 相當於 VTM-0 〇 < X 〇 Id t A Λ *〇 X 寸 X X X <3 X X X < 相當於 VTM-0 〇 < <] o X m X X X 〇 X X X 〇 相當於 VTM-0 〇 <3 〇 rsj T—H Λ 〇 Id X (N X X 〇 〇 X X 〇 〇 相當於 VTM-0 X X X < o τ*·Η X X 實施例 1 1 X S <3 ε 〇〇 〇 1 〇 〇 X 〇 〇 規格外 〇 〇 X 〇 Id t—t Λ H X ε 1 ε § 1 00 lOOum ε 1 (Ν 難燃性 基板彎曲(mm) 〇 〇 § f—Η 焊料耐熱性 宕 CN 〇 1 lOOOh 1 解像度 侧nc _奧 鑒C 耐彎曲性 絕緣信賴 性(Ω) -38- 200844655 依據表3，實施例1〜8中之解像度、儲存安定性、難 燃性、基板彎曲、耐彎曲性及焊料耐熱性之任何結果均良 好，雖然絕緣信賴性在儲存1 000小時後之電阻稍有降低’ 但可了解爲實用上沒有任何問題之範圍內而爲優異者。又 ，使用具有羧基之聚碳酸酯多元醇骨架之丙烯酸胺基甲酸 酯之實施例9，其絕緣信賴性有稍微降低之傾向。另外’儘 B 管使用不具有羧基之聚碳酸酯多元醇骨架之丙烯酸胺基甲 酸酯，但質量平均分子量較小之實施例1 〇中，基板彎曲及 耐彎曲性稍有降低，但質量平均分子量較大之實施例1 1則 有解像度降低之傾向。 另一方面，依據表4，可了解比較例1〜7中複數種評 價項目均不良。尤其，全部比較例中之解像度均不良，絕 緣信賴性除比較例6以外均相當的差，但比較例6之絕緣 信賴性亦無法稱之爲優良。 〔產業利用性〕 本發明之感光性組成物爲例如在薄膜支撐材上形成被 覆膜，而可提供感光性乾膜，可較好使用作爲光阻劑尤其 作爲抗焊劑等之電子材料，亦可使用於薄型印刷配線板或 FPC基板之加工。 另外，亦可作爲塗料等之塗覆劑、油墨而使用。 -39-卜 〇 XXX 〇 is equivalent to VTM-0 〇〇< CN Id η Λ "ο XX 〇〇〇XXX < ! is equivalent to VTM-0 X 〇<3 Ο一〇> co_^ r-4 XXXXXXXX Equivalent to VTM-0 〇< X 〇Id t A Λ *〇X 寸 XXX <3 XXX < Equivalent to VTM-0 〇<<] o X m XXX 〇XXX 〇 Equivalent to VTM-0 〇< ;3 〇rsj T—H Λ 〇Id X (NXX 〇〇XX 〇〇 is equivalent to VTM-0 XXX < o τ*·Η XX Example 1 1 XS <3 ε 〇〇〇1 〇〇X 〇〇 Specification 〇〇X 〇Id t—t Λ HX ε 1 ε § 1 00 lOOum ε 1 (Ν Flame retardant substrate bending (mm) 〇〇§ f—Η Solder heat resistance 宕CN 〇1 lOOOh 1 Resolution side nc _ AO Jian C Bending resistance reliability (Ω) -38- 200844655 According to Table 3, any results of resolution, storage stability, flame retardancy, substrate bending, bending resistance and solder heat resistance in Examples 1 to 8 Both are good, although the insulation reliability is slightly reduced after storage for 1 000 hours, but it can be understood that there is no problem in practical use. Further, in Example 9, which uses an acrylic urethane having a carboxyl group of a polycarbonate polyol, the insulating reliability tends to be slightly lowered. In addition, the use of a polycarbonic acid having no carboxyl group is used for the B tube. The urethane urethane of the ester polyol skeleton, but in Example 1 in which the mass average molecular weight is small, the substrate bending and the bending resistance are slightly lowered, but in Example 1 which has a large mass average molecular weight, the resolution is lowered. On the other hand, according to Table 4, it can be understood that the plurality of evaluation items in Comparative Examples 1 to 7 are all inferior. In particular, the resolutions in all of the comparative examples were poor, and the insulation reliability was inferior except for Comparative Example 6. However, the insulating property of Comparative Example 6 cannot be said to be excellent. [Industrial Applicability] The photosensitive composition of the present invention is, for example, a coating film formed on a film supporting member, and a photosensitive dry film can be provided, which is preferable. An electronic material which is used as a photoresist, in particular, as a solder resist, can be used for processing a thin printed wiring board or an FPC board, and can also be used as a coating agent for paints and the like. Ink used. -39-