201219982 六、發明說明： 【發明所屬之技術領域】 本發明有關正型感光性樹脂組成物，詳言之，有關可 用爲半導體元件的層間絕緣膜、表面保護膜等之正型感光 性樹脂組成物。 【先前技術】 在來，爲電子儀器的半導體元件所用之層間絕緣膜 (innerlayer insulating film)、表面保護膜（surface protection film)等，廣泛使用耐熱性、機械性特性優異的聚醯亞胺系 樹脂》又’爲生產性的提升、膜形成精密度的提升等，亦 在進行賦與有感光性之感光性聚醯亞胺系樹脂（photosensitive polyimide series resins)的硏究。例如，於專利文獻 1、2 中’揭示有含有聚醯亞胺先質（polyimide precursor)及鄰醌二 疊氮基（ortho-quinon diazide)化合物之正型感光性組成物 (posi-type photo sensitive composition)。然而，此等正型 感光性組成物，在耐熱性、電絕緣特性、對基板的黏附性 等上，存有缺點。 於是，專利文獻3中，提案有：具有苯酚性羥基之鹼 可溶性樹脂、具有醌二疊氮基之化合物、交聯微粒子（cross-linked particle)、 分子中具有至少 2 個經烷基醚化 之胺基 之化合物、以及含有溶劑之正型感光性絕緣樹脂組成物。 如採用此種正型感光性絕緣樹脂組成物，則可製得解像度 (resolution)、電絕緣性、對基板的黏附性等良好的硬化物 -5- 201219982 。此種硬化物，可作爲例如，半導體元件上之永久絕緣膜 (permanent insulating film)使用 〇 [先前技術文獻] [專利文獻] 專利文獻1 :日本專利特開平5_5 996號公報 專利文獻2:日本專利特開2000-98601號公報 專利文獻3:日本專利特開2003-215789號公報 【發明內容】 [發明所欲解決之課題] 然而，隨著近年來的積體電路的微細化，積集電路中 之配線互相間的距離接近，因而需要開發一種能顯示更高 水準的解像度及電絕緣特性之感光性樹脂組成物以及其硬 化物。又，由上述各專利文獻中所記載之正型感光性樹脂 組成物所製作之硬化物，具有硬且脆的性質之故，欲作爲 半導體元件中之永久絕緣膜使用時，則尙有改良的餘地。 本發明係鑑於此種狀況下所開發者，其目的在於提供 一種能顯示良好的解像度、以及成爲其硬化物時之良好的 電絕緣特性及強度之正型感光性樹脂組成物。 [用以解決課題之手段] 本發明人等發現，如對含有具有苯酚性羥基之鹼可溶 性樹脂及具有醌二疊氮基之化合物之正型感光性樹脂組成 物，添加具有特定構造的構成單元之丙烯酸樹脂’則其組 -6 - 201219982 成物會顯示良好的解像度、且從其組成物所製作之硬化物 會顯示良好的電絕緣特性及強度之事實，終於完成本發明 0 本發明，係一種正型感光性樹脂組成物，其特徵爲含 有：（A)具有苯酚性羥基之鹼可溶性樹脂、（B)具有醌二疊 氮基之化合物、（C)分子中具有至少2個經烷基醚化之胺 基之化合物、（D)含有可以下述一般式（1)表示之構成單元 (dl)及從不飽和羧酸所衍生之構成單元（d2)，而質量平均 分子量爲2萬至50萬之丙.烯酸樹脂、以及（S)溶劑。201219982 VI. [Technical Field] The present invention relates to a positive photosensitive resin composition, and more particularly to a positive photosensitive resin composition which can be used as an interlayer insulating film or a surface protective film of a semiconductor element. . [Prior Art] A polyimide-based resin excellent in heat resistance and mechanical properties is widely used as an interlayer insulating film or a surface protection film for a semiconductor device of an electronic device. In addition, in order to improve the productivity, the precision of film formation, and the like, it is also carried out to impart photosensitive photosensitive polyimide series resins. For example, in Patent Documents 1 and 2, a positive photosensitive composition containing a polyimide precursor and an ortho-quinon diazide compound is disclosed (posi-type photo sensitive). Composition). However, these positive photosensitive compositions have disadvantages in heat resistance, electrical insulating properties, adhesion to substrates, and the like. Then, Patent Document 3 proposes an alkali-soluble resin having a phenolic hydroxyl group, a compound having a quinonediazide group, a cross-linked particle, and at least two alkyl etherified groups in the molecule. A compound of an amine group and a positive photosensitive insulating resin composition containing a solvent. When such a positive photosensitive insulating resin composition is used, a cured product having good resolution, electrical insulating properties, adhesion to a substrate, and the like can be obtained -5-201219982. Such a cured product can be used as, for example, a permanent insulating film on a semiconductor element. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Laid-Open Publication No. Hei No. 5_5 996 Patent Document 2: Japanese Patent [Problems to be Solved by the Invention] However, with the miniaturization of the integrated circuit in recent years, the circuit is accumulated in the circuit. Since the wirings are close to each other, it is necessary to develop a photosensitive resin composition capable of exhibiting a higher level of resolution and electrical insulating properties and a cured product thereof. Moreover, the cured product produced from the positive photosensitive resin composition described in each of the above-mentioned patent documents has a hard and brittle property, and is intended to be improved when used as a permanent insulating film in a semiconductor element. room. The present invention has been made in view of the above circumstances, and an object of the invention is to provide a positive photosensitive resin composition which exhibits good resolution and excellent electrical insulating properties and strength when it is cured. [Means for Solving the Problem] The present inventors have found that a constituent unit having a specific structure is added to a positive photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group and a compound having a quinonediazide group. The present invention is finally completed by the group of -6 - 201219982, which exhibits good resolution and the cured product produced from the composition exhibits good electrical insulation properties and strength. A positive photosensitive resin composition characterized by comprising: (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound having a quinonediazide group, and (C) having at least two alkyl groups in the molecule The etherified amine group-containing compound (D) contains a constituent unit (d1) represented by the following general formula (1) and a constituent unit (d2) derived from an unsaturated carboxylic acid, and has a mass average molecular weight of 20,000 to 500,000 C. Acrylic resin, and (S) solvent.
(上述一般式（1)中，R1表示氫原子或烷基，R2獨立表示烴 基，P表示〇至3)。 [發明之效果] 如採用本發明，則可提供一種能顯示良好的解像度， 以及成爲其硬化物時之良好的電絕緣特性及強度之正型感 光性樹脂組成物。 [發明之最佳實施形態] 201219982 以下，就本發明之正型感光性樹脂組成物的一實施形 態加以說明。 有關本實施形態之正型感光性樹脂組成物中，含有： (A)具有苯酚性羥基之鹼可溶性樹脂、（B)具有醌二疊氮基 之化合物、（C)分子中具有至少2個經烷基醚化之胺基之 化合物、（D)具有特定構造的構成單元，而質量平均分子 量爲2萬至50萬之丙烯酸樹脂、以及（S)溶劑。以下，就 有關本發明之正型感光性樹脂組成物中所含之各成分加以 詳細說明。 [(A)具有苯酚性羥基之鹼可溶性樹脂] 具有苯酚性羥基之鹼可溶性樹脂（以下，簡稱「（A)成 分」）而言’並不特別加以限定，惟較佳爲酚醛清漆樹脂 (novolac resin)。此種酚醛清漆樹脂，可由使苯酚類與醛 類在酸觸媒存在下進行加成縮合（addition condensation)而 製得。 上述苯酚類而言’可例舉：苯酚；鄰甲酚、間甲酚' 對甲酚等的甲酚類；2,3-二甲苯酚、2,4-二甲苯酌、2,5-二 甲苯酚、2,6-二甲苯酚、3，4-二甲苯酚、3,5-二甲苯酚等的 二甲苯酚類；鄰乙基苯酚、間乙基苯酚、對乙基苯酚、2_ 異丙基苯酚、3-異丙基苯酚、4-異丙基苯酚、鄰丁基苯酚 、間丁基苯酚、對丁基苯酚、對第三丁基苯酚等的烷基苯 酚類；2,3,5_三甲基苯酚、3,4,5-三甲基苯酚等的三胺基苯 酚類；間苯二酚、兒茶酚（catechol)、氫醌、氫醌單甲基 -8- 201219982 醚、五倍子酚（pyroSaUo1)、間苯三酚（Phloroglucinol)等的 多元苯酚類；烷基間苯二酚（alky1 resorcin)、烷基兒茶酚 、烷基氫醌等的烷基多元苯酚類（任何烷基均爲碳數1至 4); α-萘酚、萘酚、羥基二苯基、雙酚A等。此等苯 酚類，可以單獨使用，亦可以組合2種以上方式使用。 此等苯酚類之中，較佳爲間甲酚、對甲酚，更佳爲倂 用間甲酚與對甲酚。此時，如調整兩者的調配比例，則可 調整靈敏度（sensitivity)、耐熱性等的諸特性。 上述醛類而言，可例舉：甲醛、仲甲醛、糠醛（furfural) 、苯甲醛（benzaldehyde)、硝基苯甲醛、乙醛等。此等醛 類，可以單獨使用，亦可以組合2種以上方式使用。 上述酸觸媒而言，可例舉：鹽酸、硫酸、磷酸、亞磷 酸等的無機酸類；甲酸、草酸、醋酸、二乙基硫酸、對甲 苯基磺酸等的有機酸類；醋酸鋅等的金屬鹽類等。此等酸 觸媒，可以單獨使用，亦可以組合2種以上之方式使用。 如此方式所製得之酚醛清漆樹脂而言，可具體例舉： 苯酚/甲醛縮合酚醛清漆樹脂、甲酚/甲醛縮合酚醛清漆樹 脂、苯酚-萘酚/甲醛縮合酚醛清漆樹脂等。 又，具有酚醛清漆樹脂以外的苯酚性羥基之鹼可溶性 樹脂而言，可例舉：聚羥基苯乙烯及其共聚物、苯酚-茬 二醇縮合樹脂、甲酚-茬二醇縮合樹脂、苯酚-雙環戊二烯 縮合樹脂等。 此等樹脂的質量平均分子量，係從解像性、所得硬化 物的耐熱衝擊性（resistance to thermal shock)、耐熱性等 -9 - 201219982 的觀點來看，較佳爲1 000至50000。 (A)成分的含量，係對正型感光性樹脂組成物的固體 成分，較佳爲45至90質量％、更佳爲50至80質量％。 如將（A)成分的含量作成上述範圍，則可將正型感光性樹 脂組成物的顯像性（d e v e 1 o p i n g a b i 1 i t y)作成良好者。 又，（A)成分的含量，係如將（A)成分和後述之（D)成分 的合計作成1〇〇質量份時，較佳爲70至90質量份、更佳 爲80至88質量份。如在上述範圍內，則藥液耐性、解像 力（resolving power)會優異之故很合適。 [(B)具有醌二疊氮基之化合物] 具有醌二疊氮基之化合物（以下，簡稱「（B)成分」）而 言，並不特別加以限定，惟較佳爲具有苯酚性羥基1個以 上之化合物、與含醌二疊氮基之磺酸之間的完全酯化物或 部分酯化物。此種具有醌二疊氮基之化合物，如使具有苯 酚性羥基1個以上之化合物與具有醌二疊氮基之磺酸；在 二噚烷（dioxane)等適當的溶劑中，在三乙醇胺、碳酸鹽、 碳酸氫鹽等鹼化合物存在下進行縮合，以使其完全酯化或 部分酯化，則可製得。 具有上述苯酚性羥基1個以上之化合物而言’可例舉 :2,3,4-三羥基二苯基酮、2,3,4,4’-四羥基二苯基酮等的 聚羥基二苯基酮類； 參（4_羥基苯基）甲烷、雙（4_羥基-3-甲基苯基）-2-羥基 苯基甲烷、雙（4-羥基-2,3,5-三甲基苯基）-2·羥基苯基甲烷 -10- 201219982 、雙（4-羥基-3,5-二甲基苯基）-4-羥基苯基甲烷、雙（4-羥 基-3,5-二甲基苯基）-3-羥基苯基甲烷、雙（4-羥基-3,5-二甲 基苯基）-2-羥基苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-4-羥基苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-3-羥基苯基甲 烷、雙（4-羥基-2,5-二甲基苯基）-2-羥基苯基甲烷、雙（4-羥基-3,5-二甲基苯基）-3,4-二羥基苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-3,4-二羥基苯基甲烷、雙（4-羥基-2,5-二 甲基苯基）-2,4-二羥基苯基甲烷、雙（4-羥基苯基）-3-甲氧 基-4-羥基苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-4-羥基苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-3-羥基 苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-2-羥基苯基 甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-3,4-二羥基苯基 甲烷等的參苯酚型化合物； 2,4-雙（3,5-二甲基-4-羥基苄基）-5-羥基酚、2,6-雙 (2,5-二甲基-4-羥基苄基）-4-甲基酚等的線性3核種苯酚 (linear three nuclide phenol)化合物； 1，1-雙[3-(2-羥基-5-甲基苄基）-4-羥基-5-環己基苯基] 異丙烷、雙[2,5-二甲基-3-(4-羥基-5-甲基苄基）-4-羥基苯 基]甲烷、雙[2,5-二甲基-3-(4-羥基苄基）-4-羥基苯基]甲烷 、雙[3-(3,5-二甲基-4-羥基苄基）-4-羥基-5-甲基苯基]甲烷 、雙[3-(3,5-二甲基-4-羥基苄基）-4-羥基-5-乙基苯基]甲烷 、雙[3-(3,5-二乙基-4-羥基苄基）-4-羥基-5-甲基苯基]甲烷 、雙[3-(3，5-二乙基-4-羥基苄基）-4-羥基-5-乙基苯基]甲烷 、雙[2_羥基- 3-(3，5-二甲基-4-羥基苄基）-5-甲基苯基]甲烷 -11 - 201219982 、雙[2-羥基-3.-(2-羥基-5-甲基苄基）-5-甲基苯基]甲烷、雙 [4-羥基-3-(2-羥基-5-甲基苄基）-5-甲基苯基]甲烷、雙[2,5-二甲基- 3-(2 -羥基-5-甲基苄基）-4-羥基苯基]甲烷等的線性 4核種苯酚化合物； 2,4-雙[2-羥基-3-(4-羥基苄基）-5-甲基苄基]-6-環己基 苯酚、2,4-雙[4-羥基·3-(4-羥基苄基）-5-甲基苄基]-6-環己 基苯酚、2,6-雙[2,5-二甲基-3-(2-羥基-5-甲基苄基）-4-羥 基节基]-4 -甲基本酣等的線性5核種苯酣化合物： 雙（2,3,4-三羥基苯基）甲烷、雙（2,4_二羥基苯基）甲烷 、2,3,4-三羥基苯基-4，·羥基苯基甲烷、2-(2,3,4-三羥基苯 基）-2-(2’，3’，4’-三羥基苯基）丙烷、2-(2,4_二羥基苯基）-2· (2’，4’-二羥基苯基）丙烷、2-(4-羥基苯基）-2-(4，-羥基苯基） 丙烷、2-(3-氟代-4-羥基苯基）-2-(3，-氟代-4，-羥基苯基）丙 烷、2-(2,4-二羥基苯基）_2-(4，-羥基苯基）丙烷、2-(2,3,4-三羥基苯基）-2-(4’-羥基苯基）丙烷、2_(2,3,4_三羥基苯基 )-2-(4’-羥基 _3’，5’-二甲基苯基）丙烷、羥 基苯基）-1-甲基乙基]苯基]亞乙基]雙酚等的雙酚型化合物 » 1-[1-(4-經基苯基）異丙基]•4_[1，1_雙（4·羥基苯基）乙基 ]苯、1-[1-(3-甲基-4-羥基苯基）異丙基]·雙（3_甲基- 4-羥基苯基）乙基]苯等的多核支化型化合物（p〇iynuclean branching compound)； 1，1-雙（4-羥基苯基）環己烷等的縮合型苯酚化合物； 等。 -12- 201219982 此等化合物，可以單獨使用，亦可以組合2種以上之 方式使用。 上述含醌二疊氮基之磺酸而言，可例舉：萘醌-1，2-二 疊氮基-5-磺酸、萘醌-1，2·二疊氮基-4-磺酸、鄰蒽醌二疊 氮基磺酸等。 (Β)成分的含量，係對（Α)成分1〇〇質量份、較佳爲5 至5 0質量份、更佳爲5至25質量份。如將（Β)成分的含 量作成上述範圍時，則可使正型感光性樹脂組成物的靈敏 度作成良好者。 [(C)在分子中具有至少2個經烷基醚化之胺基之化合物] 分子中具有至少2個經烷基醚化之胺基之化合物（以 下，簡稱「（C)成分」），係在正型感光性樹脂組成物的顯 像後的熱處理時，作爲與上述（Α)成分反應之交聯劑作用 者。此種化合物而言，可例舉：（聚）羥甲基化蜜胺、（聚） 羥甲基化甘脲、（聚）羥甲基化苯并胍胺、（聚）羥甲基化脲 等的經使活性羥甲基的全部或一部分加以胺基醚化之含氮 化合物。胺基而言，可例舉：甲基、乙基、丁基、或經將 此等組合者，而亦可含有經部分自縮合（self-condensation) 所成之低聚物（oligomer)。可具體例舉：六甲氧甲基化蜜 胺、六丁氧甲基化蜜胺、四甲氧甲基化甘脲、四丁氧甲基 化甘脲等。此等化合物，可以單獨使用，亦可以組合2種 以上之方式使用。 (C)成分的含量，係對（A)成分100質量份，較佳爲5 -13- 201219982 至60質量份、更佳爲10至50質量份。如將（C)成分的含 量作成上述範圍時，則可使正型感光性樹脂組成物的硬化 性及解像度（圖型構成特性（patterning char act eristic)以及 硬化物的電絕緣特性及耐熱性作成良好者。 [(D)丙烯酸樹脂] ‘ 丙烯酸樹脂（以下，簡稱「（D)成分」），包含可以下 述一般式（1)表示之構成單元（dl)及由不飽和羧酸所衍生 之構成單元（d2)。（D)成分中所含之構成單元（dl)，係對 正型感光性樹脂組成物賦與良好的解像性，以使其硬化 物的強度（斷裂伸度（elongation at break)及電絕緣特性（ 介電常數（dielectric constant)提升。亦即，本發明，係根 據如對正型感光性組成物添加含有構成單元（dl)之丙烯酸 樹脂’即可良好平衡之方式改善正型感光性組成物或其硬 化物時之解像性、強度以及介電常數之心得所開發者。又 ’（D)成分中所含之構成單元（d2)，將對正型感光性樹脂組 成物賦與良好的解像性。(In the above general formula (1), R1 represents a hydrogen atom or an alkyl group, R2 independently represents a hydrocarbon group, and P represents 〇 to 3). [Effects of the Invention] According to the present invention, it is possible to provide a positive photosensitive resin composition which exhibits good resolution and good electrical insulating properties and strength when it is cured. [Best Mode for Carrying Out the Invention] 201219982 Hereinafter, an embodiment of the positive photosensitive resin composition of the present invention will be described. The positive photosensitive resin composition of the present embodiment contains: (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound having a quinonediazide group, and (C) having at least two molecules in the molecule. The alkyl etherified amine group compound, (D) has a specific structural unit, and the mass average molecular weight is 20,000 to 500,000 acrylic resin, and (S) solvent. Hereinafter, each component contained in the positive photosensitive resin composition of the present invention will be described in detail. [(A) Alkali-soluble resin having a phenolic hydroxyl group] The alkali-soluble resin having a phenolic hydroxyl group (hereinafter referred to as "(A) component") is not particularly limited, but is preferably a novolak resin (novolac). Resin). Such a novolak resin can be obtained by addition condensation of a phenol and an aldehyde in the presence of an acid catalyst. The above phenols may be exemplified by phenol, cresols such as o-cresol and m-cresol, p-cresol, 2,3-xylenol, 2,4-xylene, 2,5-di. a xylenol such as cresol, 2,6-xylenol, 3,4-xylenol or 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2_ different Alkyl phenols such as propyl phenol, 3-isopropyl phenol, 4-isopropyl phenol, o-butyl phenol, m-butyl phenol, p-butyl phenol, p-tert-butyl phenol, etc.; 2, 3, 5-aminophenols such as trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, hydroquinone monomethyl-8- 201219982 ether , polyphenols such as pyro-ca phenol (pyroSaUo1), phloroglucinol, etc.; alkyl polyphenols such as alkyl resorcin, alkyl catechol, alkyl hydroquinone (any The alkyl groups are all carbon to 1 to 4); α-naphthol, naphthol, hydroxydiphenyl, bisphenol A and the like. These phenols may be used singly or in combination of two or more. Among these phenols, m-cresol and p-cresol are preferred, and m-cresol and p-cresol are more preferred. At this time, if the ratio of the two is adjusted, the characteristics such as sensitivity and heat resistance can be adjusted. The aldehydes may, for example, be formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde or acetaldehyde. These aldehydes may be used singly or in combination of two or more. The acid catalyst may, for example, be an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or phosphorous acid; an organic acid such as formic acid, oxalic acid, acetic acid, diethylsulfonic acid or p-tolylsulfonic acid; or a metal such as zinc acetate. Salt and so on. These acid catalysts may be used singly or in combination of two or more. The novolac resin obtained in this manner may specifically be exemplified by a phenol/formaldehyde condensed novolac resin, a cresol/formaldehyde condensed novolac resin, a phenol-naphthol/formaldehyde condensed novolac resin, and the like. Further, the alkali-soluble resin having a phenolic hydroxyl group other than the novolak resin may, for example, be polyhydroxystyrene and a copolymer thereof, a phenol-nonanediol condensation resin, a cresol-nonanediol condensation resin, or a phenol- Dicyclopentadiene condensation resin and the like. The mass average molecular weight of these resins is preferably from 1,000 to 50,000 from the viewpoints of resolution, resistance to thermal shock of the obtained cured product, heat resistance, and the like. The content of the component (A) is preferably from 45 to 90% by mass, more preferably from 50 to 80% by mass, based on the solid content of the positive photosensitive resin composition. When the content of the component (A) is in the above range, the developability (d e v e 1 o p i n g a b i 1 i t y) of the positive photosensitive resin composition can be made good. In addition, when the total amount of the component (A) and the component (D) described later is 1 part by mass, it is preferably 70 to 90 parts by mass, more preferably 80 to 88 parts by mass. . If it is within the above range, the chemical liquid resistance and the resolving power will be excellent. [(B) Compound having a quinonediazide group] The compound having a quinonediazide group (hereinafter, abbreviated as "(B) component") is not particularly limited, but preferably has a phenolic hydroxyl group 1 A fully esterified or partially esterified compound of more than one compound with a sulfonic acid containing a quinonediazide group. Such a compound having a quinonediazide group, such as a compound having one or more phenolic hydroxyl groups and a sulfonic acid having a quinonediazide group; in a suitable solvent such as dioxane, in triethanolamine, It can be obtained by condensing in the presence of an alkali compound such as a carbonate or a hydrogencarbonate to completely esterify or partially esterify it. The compound having one or more of the above phenolic hydroxyl groups may be exemplified by a polyhydroxy group such as 2,3,4-trihydroxydiphenyl ketone or 2,3,4,4'-tetrahydroxydiphenyl ketone. Phenyl ketones; ginseng (4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethyl Phenyl)-2.hydroxyphenylmethane-10-201219982, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5- Dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethyl Phenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylbenzene 2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethyl Phenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)- 3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methyl 4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methyl a phenol type compound such as phenyl)-2-hydroxyphenylmethane or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane; 2,4 -Bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol, etc. Linear three nuclide phenol compound; 1,1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylphenyl]isopropane, double [ 2,5-Dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl) 4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5 -Dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5 -methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-( 3,5-dimethyl-4-hydroxyl ,5-methylphenyl]methane-11 - 201219982, bis[2-hydroxy-3.-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4 -hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl) Linear 4-nuclear phenolic compound such as 4-hydroxyphenyl]methane; 2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol , 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3 - Linear 5-nuclear benzoquinone compound of (2-hydroxy-5-methylbenzyl)-4-hydroxyl]-4-methylbenzhydrazine: bis(2,3,4-trihydroxyphenyl)methane, Bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4,hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-( 2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2·(2',4'-dihydroxyphenyl)propane, 2-(4- Hydroxyphenyl)-2-(4,-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3,-fluoro-4,-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)_2- (4,-Hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl) Bisphenol-type compound such as -2-(4'-hydroxy-3',5'-dimethylphenyl)propane, hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol » 1-[1-(4-Phenylphenyl)isopropyl]•4_[1,1_bis(4.hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4) a polynuclear branched compound (p〇iynuclean branching compound) such as -hydroxyphenyl)isopropyl]-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene; 1,1-bis(4- a condensed phenol compound such as hydroxyphenyl)cyclohexane; -12- 201219982 These compounds may be used singly or in combination of two or more. The above quinonediazide-containing sulfonic acid may, for example, be naphthoquinone-1,2-diazido-5-sulfonic acid or naphthoquinone-1,2·diazido-4-sulfonic acid. , o-quinonediazidesulfonic acid, and the like. The content of the (Β) component is 1 part by mass, preferably 5 to 50 parts by mass, more preferably 5 to 25 parts by mass. When the content of the (Β) component is in the above range, the sensitivity of the positive photosensitive resin composition can be made good. [(C) a compound having at least two alkyl etherified amine groups in a molecule] a compound having at least two alkyl etherified amine groups in the molecule (hereinafter, simply referred to as "(C) component"), In the heat treatment after development of the positive photosensitive resin composition, it acts as a crosslinking agent which reacts with the above (Α) component. Such a compound may, for example, be (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanamine, (poly)methylolated urea A nitrogen-containing compound which is amine-etherified by all or a part of the active methylol group. The amine group may, for example, be a methyl group, an ethyl group, a butyl group or a combination thereof, or may contain an oligomer formed by partial self-condensation. Specific examples thereof include hexamethoxymethylated melamine, hexaoxymethylated melamine, tetramethoxymethylated glycoluril, and tetrabutoxymethylated glycoluril. These compounds may be used singly or in combination of two or more. The content of the component (C) is 100 parts by mass of the component (A), preferably 5 -13 to 201219982 to 60 parts by mass, more preferably 10 to 50 parts by mass. When the content of the component (C) is in the above range, the curability and resolution of the positive photosensitive resin composition (patterning char act eristic) and electrical insulating properties and heat resistance of the cured product can be made. [(D) Acrylic resin] 'Acrylic resin (hereinafter, simply referred to as "(D) component)") includes a constituent unit (d1) represented by the following general formula (1) and derived from an unsaturated carboxylic acid. The constituent unit (d2) contained in the component (D) imparts good resolution to the positive photosensitive resin composition to increase the strength (elongation) of the cured product. At break) and electrical insulation properties (dielectric constant), that is, the present invention is based on the method of adding an acrylic resin containing a constituent unit (dl) to a positive photosensitive composition. The developer who has improved the resolution, strength, and dielectric constant of the positive photosensitive composition or its cured product. The constituent unit (d2) contained in the '(D) component will be positively photosensitive. Resin Imparting to the composition of good resolution.
上述一般式（1)中，R1爲氫原子或烷基、較佳爲氫原 -14- 201219982 子或甲基。又，上述一般式（1)中，R2爲烴基、較佳爲鏈 狀的脂肪族烴基，更佳爲碳數1至5的烷基、再佳爲甲基 、乙基、丙基或丁基、特佳爲乙基。p爲〇至3、較佳爲〇 至2。如p爲2或3時，R2可爲分別相異者。 將作爲可以上述一般式（1)表示之構成單元（dl)合適的 例’表示於下述中。再者，於下述例中，Ri爲與上述式 (1)中者同樣者。In the above general formula (1), R1 is a hydrogen atom or an alkyl group, preferably a hydrogen atom -14-201219982 or a methyl group. Further, in the above general formula (1), R2 is a hydrocarbon group, preferably a chain aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Particularly preferred is ethyl. p is 〇 to 3, preferably 〇 to 2. If p is 2 or 3, R2 may be different. An example of a suitable constituent unit (d1) which can be expressed by the above general formula (1) is shown below. Further, in the following examples, Ri is the same as in the above formula (1).
又’上述構成單元（dl)，較佳爲可以下述一般式（2)表 示之構成單元。Further, the above-mentioned constituent unit (d1) is preferably a constituent unit which can be expressed by the following general formula (2).
(2)(2)
-15 - 201219982 (上述一般式（2)中，R1及R2，爲與上述一般式（1)中者同 樣者）° 構成單元（d2)，可從不飽和羧酸衍生。由於（D)成分含 有此種構成單元（d2)之故，對（D)成分賦與鹼可溶性、並對 正型感光性樹脂組成物賦與良好的顯像性。在此，（D)成 分係如上所述，賦與有鹼可溶性之樹脂，惟並非相當於前 述中所說明之（A)成分。 如欲製得（D)成分時，並不特別加以限定，惟可例舉 :依常法使爲導入構成單元（dl)之用的單體成分、與爲導 入構成單元（d2)之用的單體成分、與需要時之其他單體成 分進行共聚合之方法。作爲此種共聚合的方法·，可例舉： 自由基聚合法（radical polymerization)。 爲導入構成單元（dl)之用的單體成分而言，可例舉：（ 甲基）丙烯酸的取代或非取代己基酯。此種化合物而言， 可例示：環己基（甲基）丙烯酸酯、1-甲基環己基（甲基）丙 烯酸酯、2-甲基環己基（甲基）丙烯酸酯、3-甲基環己基（甲 基）丙烯酸酯、4-甲基環己基（甲基）丙烯酸酯、1-乙基環己 基（甲基）丙烯酸酯、2-乙基環己基（甲基）丙烯酸酯、3-乙 基環己基（甲基）丙烯酸酯、4-乙基環己基（甲基）丙烯酸酯 、1-丙基環己基（甲基）丙烯酸酯' 2-丙基環己基（甲基）丙 烯酸酯、3-丙基環己基（甲基）丙烯酸酯、4-丙基環己基（甲 基）丙烯酸酯、1-異丙基環己基（甲基）丙烯酸酯、1，4_二甲 基環己基（甲基）丙烯酸酯、卜乙基-4-甲基環己基（甲基）丙 烯酸酯、4-第三丁基環己基（甲基）丙烯酸酯、3，4-二甲基 -16- 201219982 環己基（甲基）丙烯酸酯、2，4-二甲基環己基（甲基）丙烯酸酯 等。此等單體成分，可以單獨使用，亦可組合2種以上之 方式使用。 再者，本說明書中，如「（甲基）丙烯酸」或者「（甲基 )丙烯酸酯」之用語，係分別以「丙烯酸或甲基丙烯酸酯 」或者「丙烯酸酯或者甲基丙烯酸酯」之意義所使用者。 爲導入構成單元（d2)之用的單體成分而言，可例舉： 具有伸乙基性不飽和鍵結及羧基之化合物。此種化合物而 言，可例示：（甲基）丙烯酸、乙烯基安息香酸、乙烯基醋 酸、α-溴化（甲基）丙烯酸、/3-呋喃基（甲基）丙烯酸、巴 豆酸（erotonic acid)、丙炔酸（propiolic acid)、肉桂酸 (cinnamic acid)、α-氰基肉桂酸、馬來酸（maleic acid)、 馬來酸酐、馬來酸單甲酯、馬來酸單乙酯、馬來酸單異丙 醋、富馬酸（fumarie acid)、衣康酸（itaconic acid)、衣康 酸酐、檸康酸（citraconic acid)、檸康酸酐等。此等單體成 分，可以單獨使用，亦可組合2種以上之方式使用。 其他單體成分而言，可例舉：具有伸乙基性的不飽和 鍵結之化合物。此種化合物而言，可例舉：申基乙烯基醚 、乙基乙烯基醚等的乙烯基化合物：甲基（甲基）丙烯酸酯 、乙基（甲基）丙烯酸酯、正丙基（甲基）丙烯酸酯、異丙基（ 甲基）丙烯酸酯、正丁基（甲基）丙烯酸酯、異丁基（甲基）丙 烯酸酯、第二丁基（甲基）丙烯酸酯、第三丁基（甲基）丙烯 酸酯、2-羥基乙基（甲基）丙烯酸酯、2-甲氧乙基（甲基）丙 烯酸酯、2-羥基丙基（甲基）丙烯酸酯、3-羥基丙基（甲基） -17- 201219982 丙烯酸酯、2-羥基丁基（甲基）丙烯酸酯、3-羥基丁基（甲基 )丙烯酸酯、4-羥基丁基（甲基）丙烯酸酯、3-乙基己基（甲 基）丙烯酸酯、乙二醇單（甲基）丙烯酸酯、甘油（甲基）丙烯 酸酯、二異戊四醇單（甲基）丙烯酸酯、甲氧三乙二醇（甲基 )丙烯酸酯、二甲基胺基乙基（甲基）丙烯酸酯、二乙基胺基 乙基（甲基）丙烯酸酯、四氫呋喃基（甲基）丙烯酸酯、縮水 甘油基（甲基）丙烯酸酯、2,2,2-三氟代乙基（甲基）丙烯酸酯 、2,2,3,3-三氟代丙基（甲基）丙烯酸酯、二環戊烷烯（甲基） 丙烯酸酯、金剛烷基甲基丙烯酸酯等的（甲基）丙烯酸酯化 合物等。此等單體成分，可以單獨使用，亦可以組合2種 以上之方式使用。 再者，本發明中，（D)成分，較佳爲作爲單體而不含 有：苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙 烯、苄基（甲基）丙烯酸酯、苯氧乙基（甲基）丙烯酸酯、苯 氧聚乙二醇（甲基）丙烯酸酯、壬基苯氧聚乙二醇單（甲基） 丙烯酸酯、壬基苯氧聚丙烯單（甲基）丙烯酸酯、2-羥基-3-苯氧丙基丙烯酸酯、2-丙烯醯氧乙基酞酸酯、2-丙烯醯氧 乙基-2-羥基乙基酞酸酯、2-甲基丙烯醯氧乙基-2-羥基丙 基酞酸酯等的芳香族系化合物。 如（D)成分含有構成單元（dl)、構成單元（d2)、以及由 上述例示的其他單體成分（乙烯基化合物、（甲基）丙烯酸酯 化合物）所衍生之構成單元，則由於正型感光性樹脂組成 物的硬化物的電絕緣特性（介電係數）會成爲良好之故很合 適。 -18- 201219982 (D)成分中之構成單元（dl)與構成單元（d2)之比例’以 莫耳比計、較佳爲15/1至4/1、更佳爲10/1至4/1。又’ (D)成分中構成單元（dl)和構成單元（d2)的合計所佔比例’ 以莫耳計，較佳爲3 0%以上、更佳爲40%以上。莫耳比的 上限可爲1 0 〇 %、較佳爲8 5 %以下、再佳爲7 0 %以下。在 此，（D)成分中構成單元（dl)和構成單元（d2)的合計所佔比 例，係指相當於對爲導入構成單元（dl)之用的單體成分、 和爲導入構成單元（d 2)之用的單體成分、和適需要所使用 之其他單體成分的總量之’爲導入構成單元（dl)之用的單 體成分和爲導入構成單元（d2)之用的單體成分的合計之比 之意。 (D)成分的質量平均分子量，爲2萬至50萬。如（D) 成分的質量平均分子量在此數値的範圍時，則除能使正型 感光性樹脂組成物的硬化物的強度（斷裂伸度）及電絕緣特 性（介電常數）作成爲良好者之外，尙能使正型感光性樹脂 組成物的解像度（圖型構成特性）作成爲良好者。（D)成分的 質量平均分子量，較佳爲5萬至35萬、更佳爲8萬至25 萬。 (D)成分的玻璃化溫度（Tg)，較佳爲-60至25°C。如 (D)成分的玻璃化溫度在此數値的範圍，則能使正型感光 性樹脂組成物的硬化物的斷裂伸度（強度）作成爲良好者。 在此，上述的Tg的範圍，係較一般樹脂爲相當低的數値 。本發明之（D)成分之所以能顯示如此低的Tg之理由，可 推測爲因（D)成分含有上述構成單元（dl)之故。 -19- 201219982 (D)成分的含量，係對（A)成分100質量份，較佳爲ι〇 至30質量份、更佳爲12至20質量份。如將（D)成分的含 量作成上述範圍，則除能使正型感光性樹脂組成物的硬化 物的強度（斷裂伸度）及電絕緣特性（介電常數）作成爲良好 者之外，尙能使正型感光性組成物的解像度（圖型構成特 性）作成爲良好者。 又，（D)成分的含量，如將（A)成分和（D)成分的合計作 成100質量份時，則較佳爲10至30質量份、更佳爲12 至20質量份。 如在上述.範圍內，則由於本發明之效果更優異，並且 藥液耐性、解像力優異之故很合適。 當製作（D)成分時，除如上所述，使用作爲構成單元 (dl)之單體及作爲構成單元（d2)之單體以作成共聚合物之 外，尙可採用例如，對含有構成單元（d2)之聚合物，使 1-乙基-1-環己醇等的醇進行反應，以變換該聚合物的構 成單元（d2)的一部分爲構成單元（dl)之方法。又’亦可按 相反方式，採用對含有構成單元（dl)之聚合物，藉由水 解（hydrolysis)而使該聚合物的構成單兀（dl)之一部分變換 爲構成單元（d2)之方法。 [(S)溶劑] 溶劑（以下，簡稱「（S)成分」）而言，並不特別加以限 定，而可採用本領域中所泛用之溶劑。可例舉：乙二醇單 甲基醚乙酸酯、乙二醇單乙基醚乙酸酯等的乙二醇單烷基 -20- 201219982 醚乙酸酯類；丙二醇單甲基醚、丙二醇單乙基醚、丙二醇 單丙基醚、丙二醇單丁基醚等的丙二醇單烷基醚類；丙二 醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、丙二醇 二丁基醚等的丙二醇二烷基醚類；丙二醇單甲基醚乙酸酯 、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、丙二 醇單丁基醚乙酸酯等的丙二醇單烷基醚乙酸酯類；乙基溶 纖劑（ethyl cellosolve)、丁基溶纖劑等的溶纖劑類；丁基 卡必醇（buthyl carbitol)等的卡必醇類；乳酸甲酯、乳酸乙 酯、乳酸正丙酯、乳酸異丙酯等的乳酸酯類；醋酸乙酯、 醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、醋 酸正戊酯、醋酸異戊酯、丙酸異丙酯、丙酸正丁酯、丙醇 異丁酯等的脂肪族羧酸酯類；3 -甲氧丙酸甲酯、3 -甲氧丙 酸乙酯、3-乙氧丙酸甲酯、3-乙氧丙酸乙酯、丙酮酸甲酯 、丙酮酸乙酯等的其他酯類；甲苯、茬（xylene)等的芳香 族烴類；2-庚酮、3-庚酮、4-庚酮、環己酮等的酮類；N-二甲基甲醯胺、N-甲基乙醯胺、N，N-二甲基乙醯胺、N-甲 基吡咯烷酮等的醯胺類；T-丁內酯等的內酯類等。此等 溶劑，可以單獨使用，亦可以組合2種以上之方式使用。 (S)成分的含量，並不特別加以限定，惟一般，較佳 爲正型感光性樹脂組成物的固體成分濃度能成爲10至60 質量％之量，更佳爲能成爲2 0至5 0質量％之量。 [(E)含氮鹼性化合物] 有關本實施形態之正型感光性樹脂組成物，較佳爲再 -21 - 201219982 含有（E)含氮鹼性化合物（以下，簡稱「（E)成分」）。（E)成分 ，係當顯像後的感光性樹脂組成物加熱以進行熱硬化處理時 ，發揮（A)成分藉由（C)成分而進行交聯之觸媒作用。由此， 可降低熱硬化處理時的加熱溫度，又，所得之硬化物，可獲 得與在高溫下進行熱硬化之硬化物同等的斷裂伸度，且亦可 提升耐藥品性。雖並不特別加以限定，惟具體上，利用對正 型感光性樹脂組成物中的（E)成分的添加，即可將正型感光 性樹脂組成物的熱硬化處理的加熱溫度降低至1 80°C以下的 程度。由於前述熱硬化處理的加熱溫度之降低，而可提升介 電係數及臨界解像度（critical resolution)之故很合適》 (E)成分，係含有鹼性的氮原子之化合物。（E)成分而 言，可舉：含氮有機化合物，雖不特別加以限定，惟可例 舉：己基胺、庚基胺、辛基胺、壬基胺、.癸基胺、苯胺、 2-甲基苯胺、3-甲基苯胺、4-甲基苯胺、4-硝基苯胺、伸 乙基二胺、四伸乙基二胺、六伸乙基二胺、二丁基胺、二 戊基胺、二己基胺、二庚基胺、二辛基胺、二壬基胺、二 癸基胺、三乙基胺、三甲基胺、三丙基胺、三丁基胺、三 戊基胺、三己基胺、三庚基胺、三辛基胺、三壬基胺、三 癸基胺、甲基二丁基胺、甲基二戊基胺、甲基二己基胺、 甲基二環己基胺、甲基二庚基胺、甲基二辛基胺、甲基二 壬基胺、甲基二癸基胺、乙基二丁基胺、乙基二戊基胺、 乙基二己基胺、.乙基二庚基胺、乙基二辛基胺、乙基二壬 基胺、乙基癸基胺、二環己基甲基胺、三乙醇胺、三異丙 醇胺等的脂肪族胺化合物；苯胺、N-甲基苯胺、二苯基胺 -22- 201219982 、N，N-二甲基苯胺、2,6-異丙基苯胺等的芳香族胺化合物 :哌陡（piperidine)、咪哩（imidazole)、哌陡、卩比 Π定（pyridine) 、4-甲基吡啶、2-羥基甲基吡啶、2-(2-羥基乙基）吡啶、2-(3-羥基丙基）吡啶、4-甲基咪啤、聯二吡啶（bipyridine)等 的以氮作爲雜原子（hetero atom)之雜環化合物（hetero ring compound)等。此等之中，如考慮正型感光性樹脂組成物 的保持穩定性時，較佳爲以氮作爲雜原子之雜環化合物、 更佳爲2 -羥基甲基吡啶、2 - (2 -羥基乙基）吡啶或2 - (3 -羥基 丙基）吡啶。此等含氮有機化合物，可以單獨使用，亦可 以組合2種以上之方式使用。 (E)成分的含量，係對（A)成分100質量份，較佳爲 0.1至10質量份、更佳爲0.1至5質量份。如（E)成分的含 量作成上述範圍，則可使正型感光性樹脂組成物的熱硬化 處理中之加熱溫度良好地降低，且可使正型感光性樹脂組 成物的儲存穩定性作成良好者。 [其他成分] 本實施形態之正型感光性樹脂組成物，需要時，亦可 含有其他單體、加成性樹脂、酸生成劑、可塑性、穩定劑 、著色劑、表面活性劑等。 例如，如對正型感光性樹脂組成物添加（甲基）丙烯酸 單體時，由於熱硬化後的硬化物中之殘餘應力（residual stress)會減低，可抑制硬化物的裂紋的生成、或使晶圓 (wafer)等的基板薄壁化時之基板及硬化物的翹曲彎曲之故 -23- 201219982 很合適。 又，如對正型感光性樹脂組成物中添加環氧樹脂時， 亦由於能降低熱硬化後的硬化物中之殘餘應力，因而可獲 得與添加（甲基）丙烯酸單體時同樣效果之故很合適。其他 ，再可獲得耐熱性的提升、耐藥品性的提升的效果之故很 合適。 其次，就使本實施形態的正型感光性樹脂組成物硬化 之硬化物加以說明。此種硬化物係能作爲永久絕緣膜使用 者，例如，很適合作爲半導體元件的層間絕緣膜或表面保 護膜等使用。 如欲形成此種硬化物時，首先，對矽晶圓等的基板塗 佈本實施形態的正型感光性樹脂組成物，並乾燥以形成塗 膜。塗佈方法而言，可例舉：浸漬（dipping)法、噴塗（spray coating)法、鑲條塗佈（bar coating)法、輕式塗佈（r〇il coating) 法、旋塗（spin coating)法、簾流塗佈（curtain coating)法等。 塗膜的厚度，則藉由塗佈方法 '正型感光性樹脂組成物的 固體成分濃度或黏度之調節，而可適當加以控制。 接著，介由所需之光罩圖型（mask pattern)而進行塗膜 之曝光。曝光所用之放射線而言，可例舉：從低壓水銀燈 、高壓水銀燈、金屬鹵化物燈（metal halide lamp)、g射線 步進式投影微影裝置（g-ray stepper)、i射線步進式投影微 影裝置（i-ray stepper)等所放射之紫外線、電子射線、雷射 光線等。曝光量而言，因使用之光線或塗膜的膜厚等而有 所不同，惟在膜厚ΙΟμηι之情形，爲500至1500mJ(微焦耳 -24- 201219982 )/cm2程度。 接著，使用鹼顯像液以進行塗膜之顯像，並溶解、去除 曝光部之結果，製得所需的樹脂圖型。顯像方法而言，可例 舉：噴淋式顯像（shower developing)法、噴霧式顯像（spray developing)法、浸漬顯像（dip developing)法、浸置式顯像 (puddle developing)法等《鹼顯像液而言，可例舉：經將 氫氧化鈉、氫氧化鉀、氨水、氫氧化四甲基胺、膽鹼 (choline)等的鹼性化合物按濃度能成爲1至10質量％程度 之方式溶解於水之鹼性水溶液。 然後，進行所得樹脂圖型之加熱（熱硬化處理），則可 製得硬化膜。加熱條件而言，並不特別加以限定，可在 100至250 °C的溫度下爲30分鐘至10小時程度。此時， 亦可依2階段進行加熱。例如，亦可作成作爲第1階段， 在50至100°C的溫度下加熱1〇分鐘至2小時，作爲第2 階段，在100至250 °C的溫度下加熱20分鐘至3小時之方 式。在此’如前所述，由於本實施形態的正型感光性組成 物中含有（E)成分之故’可將該加熱溫度作成較在來的正 型感光性樹脂組成物爲低之方式。例如，如使用本實施形 態之正型感光性樹脂組成物時，則上述加熱條件，可爲 1 0 0至2 0 0 °C程度’如在2階段加熱之情形，則可作成作 爲第1階段爲50至i〇〇°C，而作爲第2階段爲1〇〇至2〇〇 °C程度之方式。加熱條件’係觀察所製作之硬化物的狀態 後，適當加以設定即可。 -25- 201219982 【實施方式】 以下，將藉由實施例而更具體方式說明本發明內容， 惟本發明之範圍並不因下述之實施例而有所限定。 [實施例1至14、比較例1至1 1] 依照表1至表3所記載之配方（單位爲質量份），混合 :具有苯酚性羥基之鹼可溶性樹脂，具有醌二疊氮基之化 合物、交聯劑、丙烯酸樹脂、含氮之鹼性化合物、溶劑、 丙烯酸單體以及環氧樹脂，以調製實施例1至14及比較 例1至11的正型感光性樹脂組成物。在此，於表1至3 中，調配量成爲空欄之成分而言，表示在調製正型感光性 樹脂組成物時並未調配之意。又，表1至3中，爲簡化起 見，分別表記：具有苯酚性羥基之鹼可溶性樹脂爲「苯酚 類樹脂」，具有醌二疊氮基之化合物爲「醌二疊氮基化合 物」，將含氮之鹼基性化合物爲「鹼性化合物」。表1至 3中之各成分的詳細內容，係如下所述。 苯酚類樹脂A :於間甲酚中添加福爾馬林（formaiin)並 依常法進行加成縮合所得之甲酚清漆樹脂（cresol novolac resin)(質量平均分子量8000) 苯酚類樹脂B:將間甲酚與對甲酚按間甲酚/對甲酚 = 60/40(質量比）之方式混合，並添加福爾馬林依常法進行 加成縮合所得之甲酚清漆樹脂（質量平均分子量20000) 醌二疊氮基化合物A:將雙（5-環己基-4-羥基-2-甲基 苯基）-3,4-二羥基苯基甲烷的全羥基的2.0莫耳％的氫原子 -26 - 201219982 ，以1,2-萘醌二疊氮基-5-磺基取代之化合物 醌二疊氮基化合物B:將4,4’-[1-[4-[1-(4_羥基苯基）_ 1-甲基乙基]苯基]亞乙基]雙酚的全羥基的2.2莫耳％的氫 原子，以1，2-萘醌二疊氮基-4-磺基取代之化合物 交聯劑：2,4,6-參[雙（甲氧甲基胺基）]-1，3,5_三哄 (triazine)(三和化學（股）製，Mw-IOOLM) 丙烯酸樹脂A:將按1-乙基環己基丙烯酸酯/2-甲氧乙 基丙烯酸酯/正-丁基丙烯酸酯/丙烯酸=44.1 /3 6.8/12.3/6.8 的比例所混合之單體，依常法進行自由基聚合（radical polymerization)所得之丙嫌酸樹脂（質量平均分子量1〇〇〇〇〇 Tg = -14.2〇C ) 丙烯酸樹脂B:將按1-乙基環己基丙烯酸酯/2-甲氧乙 基丙烯酸酯/正-丁基丙烯酸酯/丙烯酸=4 4.1 /3 6.8/12.3/6.8 的比例所混合之單體，依常法進行自由基聚合所得之丙烯 酸樹脂（質量平均分子量22 0 0 00 Tg = -14.2 °C ) 丙烯酸樹脂C:將按1-乙基環己基丙烯酸酯/2-甲氧乙 基丙烯酸酯/甲基丙烯酸=43.5/48.3/8.2的比例所混合之單 體，依常法進行自由基聚合所得之丙烯酸樹脂（質量平均 分子量 200000 Tg = -ll.4°C ) 丙烯酸樹脂D:將按1-乙基環己基丙烯酸酯/2-甲氧乙基 丙烯酸酯/甲氧三乙二醇丙烯酸酯/丙烯酸=44.1/3 6.8/12.3/6.8 的比例所混合之單體，依常法進行自由基聚合所得之丙烯 酸樹脂（質量平均分子量220000 Tg = -14.4°C ) 丙烯酸樹脂E:將按2-乙基環己基丙烯酸酯/2-甲氧乙 -27- 201219982 基丙烯酸酯/正丁基丙烯酸酯/丙烯酸=44.1/3 6.8/12.3/6.8 的比例所混合之單體，依常法進行自由基聚合所得之丙烯 酸樹脂（質量平均分子量220000 18 = -14.21) 丙烯酸樹脂F:將按1-乙基環己基丙烯酸酯/2-甲氧乙 基丙烯酸酯/正-丁基丙烯酸酯/丙烯酸=44.1/3 6.8/12.3/6.8 的比例所混合之單體，依常法進行自由基聚合所得之丙烯 酸樹脂（質量平均分子量20000 Tg = -14.2°C) 丙烯酸樹脂G:將按1-乙基環己基丙烯酸酯/2-甲氧乙基 丙烯酸酯/甲氧三乙二醇丙烯酸酯/丙烯酸=44· 1/3 6.8/12.3/6.8 的比例所混合之單體，依常法進行自由基聚合所得之丙烯 酸樹脂（質量平均分子量8000 Tg = -14.4°C) 丙烯酸樹脂Η:將按苯乙烯/2-甲氧乙基丙烯酸酯/甲 氧三乙二醇丙烯酸酯/丙烯酸=44.1/36.8/1 2.3/6.8的比例所 混合之單體，依常法進行自由基聚合所得之丙烯酸樹脂（ 質量平均分子量220000 Tg = 6.6°C) 丙烯酸樹脂I:將按苄基甲基丙烯酸酯/2-甲氧乙基丙 烯酸酯/甲氧三乙二醇丙烯酸酯/丙烯酸=44.1/3 6.8/12.3/6.8 的比例所混合之單體，依常法進行自由基聚合所得之丙烯 酸樹脂（質量平均分子量220000 Tg = -5.8t ) 丙烯酸樹脂J:將按雙環戊二烯基甲基丙烯酸酯/2-羥 基乙基甲基丙烯酸酯/2-甲氧乙基丙烯酸酯/正丁基丙烯酸 酯/甲基丙烯酸=65/7/4M/20的比例所混合之單體，依常法 進行自由基聚合所得之丙烯酸樹脂（質量平均分子量20000 Tg= 1 2 9.8 °C ) -28- 201219982 丙烯酸樹脂K:將按金剛烷基甲基丙烯酸酯/2-羥基乙基 甲基丙烯酸酯/2-甲氧乙基丙烯酸酯/正丁基丙烯酸酯/甲基丙 烯酸=65/7/4/4/20的比例所混合之單體，依常法進行自由 基聚合所得之丙烯酸樹脂（質量平均分子量3 0000 Tg=135 °C ) 丙烯酸樹脂L:將按1-乙基環己基丙烯酸酯/2-甲氧乙 基丙烯酸酯/正丁基丙烯酸酯=44.1/36.8/1 9.1的比例所混 合之單體，依常法進行自由基聚合所得之丙烯酸樹脂（質 量平均分子量220000 Tg =-22.0 °C) 鹼性化合物A : 2-羥基甲基吡啶 鹼性化合物B : 2-(2-羥基乙基）吡啶 鹼性化合物C: 2-(3 -羥基丙基）吡啶 丙烯酸單體A:二異戊四醇六丙烯酸酯（曰本化藥（股） 製，DPHA) 丙烯酸單體B:異戊四醇四丙烯酸酯（東亞合成（股）製 ，阿羅尼克斯M-450) 丙烯酸單體C:氧化伸乙基改性三羥甲基三丙烯酸.酯（ 東亞合成（股）製，阿羅尼克斯M-3 50) 環氧樹脂：4官能環型環氧樹脂（黛色爾化學工業（股） 製，埃坡里特GT-401) 溶劑：丙二醇單甲基醚乙酸酯 [硬化物的強度之評價] 作爲硬化物的強度之評價，進行硬化物的斷裂伸度之 -29- 201219982 測定。 就實施例1至14及比較例1至11的各正型感光性樹 脂組成物，利用旋塗法而將正型感光性樹脂組成物塗佈於 6吋的矽晶圓表面，在120 °C下使其乾燥3分鐘，以製得 膜厚25μηι的塗膜。接著，將此塗膜在18(TC下加熱2小 時，以製得膜厚20μιη的硬化物。將所得硬化物裁切爲 8mmx5 cm大小，以製得短箋紙狀的試樣。將此試樣的斷裂 伸度（％)，使用 RTC-1210A TENDILON(ORIENTEC 社製） 加以評價。具體而言，試樣將因加重而切斷爲止對款樣以 5 mm/分鐘的速度施加朝上的負荷，並由[(試樣切斷時的長 度）-(試樣原來的長度）]/(試樣原來的長度）xl〇〇的式以算 出斷裂伸度（％)。將其結果表示於表1至3中。 [介電常數之測定] 作爲硬化物的電絕緣特性之評價，進行硬化物的介電 常數之測定。 •就實施例1至1 4及比較例1至1 1的各正型感光性樹 脂組成物，利用旋塗法而將正型感光性樹脂組成物塗佈於 6吋的矽晶圓表面，在120 °C下使其乾燥3分鐘，以製得 膜厚6μιη的塗膜。接著，將此塗膜在180°C下加熱2小時 ，以製得膜厚5 μιη的硬化物。就此硬化物，利用介電常數 測定裝置 SSM 495 CVSystem(Solid State Measurement 社製） ，以測定膜厚方向對真空之電容率（specific inductive capacity)。將其結果，表示於表1至3。 -30- 201219982 [解像性之評價] 就實施例1至14及比較例1至1 1的各正型感光性樹脂 組成物，利用旋塗法而將正型感光性樹脂組成物塗佈於6 吋的矽晶圓表面，在120°C下使其乾燥3分鐘，以製得膜厚 6μιη的塗膜。對此塗膜，使用Ultratech社製，Prismatic ghi stepped稜柱型g，h，i射線步進式投影微裝置），透過記錄 有1至20μηι爲止，按每Ιμιη大小的圓形圖型在混雜之測試 圖型（test pattern)之光罩（photomask)，以進行 1 000mJ/cm2 的 曝光。使用顯像液（東京應化工業（股）製，NMD-3)而使顯像曝 光後的塗膜顯像以形成樹脂圖型（resin pattern)，再將所得樹 脂圖型在180°C下加熱2小時（但，實施例12則在200°C下 2 小時）以製得硬化物。使用 SEM((Scanning Electron Microscope) 掃描式電子顯微鏡）觀察所得硬化物的剖面’以評價臨界 解像度（單位μπι)。將其結果，表示於表1至3。 -31 · 201219982 [表1] 實施例 2 3 4 5 6 7 8 苯酚樹脂A 100 100 100 100 100 100 100 苯酚樹脂B 100 醌二疊氮基化合物A 24 24 24 24 24 24 24 醌二疊氮基化合物B 24 交聯劑 20 20 20 20 20 50 20 30 丙烯酸樹脂A 18 18 18 18 18 丙烯酸樹脂B 18 丙烯酸樹脂C 18 丙烯酸樹脂D 18 鹼性化合物A 2 2 2 2 2 2 鹼性化合物B 2 鹼性化合物C 2 溶劑 300 300 300 300 300 300 300 300 丙烯酸單體A 10 丙烯酸單體B 10 環氧樹脂 10 斷裂伸度(％) 14 16 14 15 15 15 16 14 介電常數 3.6 3.6 3.5 3.6 3.5 3.5 3.6 3.6 臨界解像度（㈣） 3 3 3 3 3 3 3 3 丙烯酸樹脂之Tg -14.2 -14.2 -14.2 -11.4 -14.2 -14.2 -14.2 -14.2 丙烯酸樹脂之分子量（χιο” 10 22 20 22 10 10 10 10 [表2] 實挤 m 9 10 11 12 13 14 苯酚樹脂A 100 100 100 苯酚樹脂B 100 100 100 醌二疊氮基化合物A 24 24 24 24 24 醌二疊氮基化合物B 24 交聯劑 30 30 30 30 20 30 丙烯酸樹脂Λ 18 18 18 18 丙烯酸樹脂Ε 18 丙烯酸樹脂F 18 鹼性化合物A 2 2 2 溶劑 300 300 300 300 300 300 丙烯酸單體C 10 10 10 10 10 環氧樹脂 10 10 10 10 10 斷裂伸度(％) 16 14 14 16 14 12 介電常數 3.5 3.6 3.6 4.0 3.6 3.6 臨界解像度（"⑹ 3 3 3 6 3 4 丙烯酸樹脂之Tg -14.2 -14.2 -14.2 -14.2 -14.2 -14.2 丙烯酸樹脂之分子量（xi〇4) 10 10 10 10 22 2 -32- 201219982 [表3] 比較例 2 3 4 5 6 7 8 9 10 1f 苯酚樹脂A 100 100 too 100 100 100 100 100 100 100 100 —二昼氮基化合物A 24 24 24 24 24 24 24 24 24 24 24 交聯劑 20 50 20 20 20 20 20 20 20 丙烯酸樹脂G 18 丙烯酸樹脂Η 18 丙烯酸樹脂I 18 丙烯酸樹脂J 18 丙烯酸樹脂Κ 18 丙烯酸樹脂L 18 鹼性化細A 2 2 2 2 2 2 2 2 溶劑 300 300 300 300 300 300 300 300 300 300 300 斷裂伸摩⑹ 4 4 4 5 . 4 4 8 12 4 4 4 介電常數 4.3 4.2 4.2 4.2 4.3 4.3 4.7 4.7 3.6 3.6 3.6 臨界解像度（㈣） 10 10 10 10 10 20 10 10 8 8 >20 丙烯酸樹脂之Τε -14.4 6.6 -5.8 129.8 135 -22 丙烯酸樹脂之分子量(ΧΙΟ” 0.8 22 22 2 3 22 可從表1至表3瞭解於含有可以上述式（1)表示之構成 單元（dl)及可從不飽和羧酸衍生之構成單元（d2)，且含有 質量平均分子量在2萬至50萬之丙烯酸樹脂（丙烯酸樹脂 A至丙烯酸樹脂F)之實施例1至14的正型感光性樹脂組 成物中，按良好平衡之方式改善有正型感光性樹脂組成物 的解像度（臨界解像度），以及其硬化物的電絕緣特性（介電 係數）及強度（斷裂伸度）之情形。 相對於此，於丙烯酸樹脂不含有可以上述式（1)表示之 構成單元（dl)之比較例7至1.0，丙烯酸樹脂的質量平均分 子量在2萬以下之比較例6，以及丙烯酸樹脂不含有可從 不飽和羧酸衍生之構成單元（dl)之比較例11的正型感光性 樹脂組成物中，則正型感光性樹脂組成物的解像度（臨界 解像度），以及其硬化物的電絕緣特性（介電常數）及強度（ -33- 201219982 斷裂伸度）的全部或至少任一種性能爲較劣差之結果之情 形。 又，從實施例9、1 1以及12之對照，則可確認由於 含有（E)成分之結果，在維持正型感光性樹脂組成物的斷 裂伸度爲良好之下，可提升介電係數及臨界解像度之事實 。亦即，可瞭解經從實施例9的正型感光性樹脂組成物去 除（E)成分之實施例1 1的正型感光性樹脂組成物的硬化物 ，係較實施例9的正型感光性樹脂組成物的硬化物爲斷裂 伸度低，如欲將此作成與實施例9的正型感光性樹脂組成 物的硬化物同等程度時，則需要將熱硬化溫度作成較1 80 °C爲高2〇°C之200°c之事實（參照實施例12)。然而可瞭解 ’在此情形’如實施例1 2所示，即使能將斷裂伸度作成 與實施例9者同等程度，介電常數及臨界解像度仍然會降 低’以致不能維持此等特性爲良好的方式之事實。 -34--15 - 201219982 (In the above general formula (2), R1 and R2 are the same as those in the above general formula (1)). The constituent unit (d2) can be derived from an unsaturated carboxylic acid. Since the component (D) contains such a structural unit (d2), the component (D) is rendered alkali-soluble, and the positive photosensitive resin composition imparts good developability. Here, the component (D) is imparted with an alkali-soluble resin as described above, but does not correspond to the component (A) described above. When the component (D) is to be produced, it is not particularly limited, and examples thereof include a monomer component for introducing a constituent unit (d1) and a component for introducing the constituent unit (d2) by a usual method. A method of copolymerizing a monomer component and other monomer components as needed. As a method of such copolymerization, a radical polymerization method can be mentioned. The monomer component for introducing the constituent unit (d1) may, for example, be a substituted or unsubstituted hexyl ester of (meth)acrylic acid. Such a compound is exemplified by cyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 3-methylcyclohexyl (Meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 2-ethylcyclohexyl (meth) acrylate, 3-ethyl Cyclohexyl (meth) acrylate, 4-ethylcyclohexyl (meth) acrylate, 1-propylcyclohexyl (meth) acrylate '2-propylcyclohexyl (meth) acrylate, 3- Propylcyclohexyl (meth) acrylate, 4-propylcyclohexyl (meth) acrylate, 1-isopropylcyclohexyl (meth) acrylate, 1,4-dimethylcyclohexyl (methyl) Acrylate, ethyl 4-methylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, 3,4-dimethyl-16- 201219982 cyclohexyl (methyl) ) acrylate, 2,4-dimethylcyclohexyl (meth) acrylate, and the like. These monomer components may be used singly or in combination of two or more. In addition, in this specification, the term "(meth)acrylic acid" or "(meth)acrylate" means "acrylic acid or methacrylate" or "acrylate or methacrylate" respectively. User. The monomer component for introducing the constituent unit (d2) may, for example, be a compound having an ethylenically unsaturated bond and a carboxyl group. Such a compound can be exemplified by (meth)acrylic acid, vinylbenzoic acid, vinyl acetate, α-brominated (meth)acrylic acid, /3-furyl (meth)acrylic acid, or crotonic acid. ), propiolic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, Maleic acid monoisopropyl vinegar, fumarie acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and the like. These monomer components may be used singly or in combination of two or more. The other monomer component may, for example, be a compound having an ethylenically unsaturated bond. Such a compound may, for example, be a vinyl compound such as a vinyl ether or an ethyl vinyl ether: methyl (meth) acrylate, ethyl (meth) acrylate or n-propyl (a) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tbutyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Methyl) -17- 201219982 Acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-ethyl Hexyl (meth) acrylate, ethylene glycol mono (meth) acrylate, glycerol (meth) acrylate, diisopentaerythritol mono (meth) acrylate, methoxy triethylene glycol (methyl) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Hydrofuranyl (meth) acrylate, glycidyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-trifluoropropane A (meth) acrylate compound such as a base (meth) acrylate, dicyclopentene (meth) acrylate or adamantyl methacrylate. These monomer components may be used singly or in combination of two or more. Further, in the present invention, the component (D) is preferably as a monomer and does not contain: styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, benzyl (A) Acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol mono (meth) acrylate, nonyl phenyloxy polymer Propylene mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-propenyloxyethyl phthalate, 2-propenyloxyethyl-2-hydroxyethyl phthalate, An aromatic compound such as 2-methacryloyloxyethyl-2-hydroxypropyl phthalate. When the component (D) contains a constituent unit (d1), a constituent unit (d2), and a constituent unit derived from the other monomer components (vinyl compound or (meth) acrylate compound) exemplified above, It is suitable that the electrical insulating property (dielectric coefficient) of the cured product of the photosensitive resin composition is good. -18- 201219982 The ratio of the constituent unit (dl) to the constituent unit (d2) in the component (D) is, in terms of molar ratio, preferably 15/1 to 4/1, more preferably 10/1 to 4/ 1. Further, the ratio of the total of the constituent unit (d1) and the constituent unit (d2) in the component (D) is preferably 30% or more, and more preferably 40% or more in terms of moles. The upper limit of the molar ratio may be 10%, preferably 8.55% or less, and more preferably 70% or less. Here, the ratio of the total of the constituent unit (d1) and the constituent unit (d2) in the component (D) is equivalent to the monomer component for introducing the constituent unit (d1), and is the introduction constituent unit ( The monomer component used for d 2) and the total amount of other monomer components to be used are 'the monomer component for introducing the constituent unit (dl) and the single for the introduction of the constituent unit (d2) The ratio of the total composition of body components. The mass average molecular weight of the component (D) is from 20,000 to 500,000. When the mass average molecular weight of the component (D) is in the range of the number 値, the strength (elongation and elongation) and the electrical insulating property (dielectric constant) of the cured product of the positive photosensitive resin composition can be made good. In addition, 尙 can make the resolution (pattern configuration characteristic) of the positive photosensitive resin composition excellent. The mass average molecular weight of the component (D) is preferably from 50,000 to 350,000, more preferably from 80,000 to 250,000. The glass transition temperature (Tg) of the component (D) is preferably -60 to 25 °C. When the glass transition temperature of the component (D) is in the range of several 値, the elongation at break (strength) of the cured product of the positive photosensitive resin composition can be made good. Here, the range of the above Tg is a considerably lower number than the general resin. The reason why the component (D) of the present invention can exhibit such a low Tg is presumed to be that the component (D) is contained in the component (D). -19- 201219982 The content of the component (D) is 100 parts by mass of the component (A), preferably 10 to 30 parts by mass, more preferably 12 to 20 parts by mass. When the content of the component (D) is in the above range, the strength (breaking elongation) and the electrical insulating property (dielectric constant) of the cured product of the positive photosensitive resin composition can be made good. The resolution (pattern configuration characteristic) of the positive photosensitive composition can be made good. In addition, when the total of the components (A) and (D) is 100 parts by mass, the content of the component (D) is preferably 10 to 30 parts by mass, more preferably 12 to 20 parts by mass. In the above range, the effect of the present invention is more excellent, and the chemical liquid resistance and the resolution are excellent. When the component (D) is produced, in addition to the monomer as the constituent unit (d1) and the monomer as the constituent unit (d2) as a copolymer as described above, for example, the constituent unit may be used. The polymer of (d2) is obtained by reacting an alcohol such as 1-ethyl-1-cyclohexanol to convert a part of the structural unit (d2) of the polymer into a constituent unit (d1). Further, a method of converting a part of the constituent unit (d) of the polymer into a constituent unit (d2) by hydrolysis of the polymer containing the constituent unit (d1) may be employed in the opposite manner. [(S) Solvent] The solvent (hereinafter, simply referred to as "(S) component") is not particularly limited, and a solvent widely used in the art can be used. Ethylene glycol monoalkyl-20-201219982 ether acetate such as ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol single Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether Dialkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. Type; cellosolve such as ethyl cellosolve or butyl cellosolve; carbitol such as buthyl carbitol; methyl lactate, ethyl lactate, n-propyl lactate , lactate such as isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate , an aliphatic carboxylic acid ester such as n-butyl propionate or isobutyl propionate; 3-methoxypropionic acid Other esters of methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; toluene, xylene Or an aromatic hydrocarbon; a ketone such as 2-heptanone, 3-heptanone, 4-heptanone or cyclohexanone; N-dimethylformamide, N-methylacetamide, N, A phthalamide such as N-dimethylacetamide or N-methylpyrrolidone; a lactone such as T-butyrolactone. These solvents may be used singly or in combination of two or more. The content of the component (S) is not particularly limited. However, it is preferred that the positive photosensitive resin composition has a solid content concentration of 10 to 60% by mass, more preferably 20 to 50. The amount of mass %. [(E) Nitrogen-containing basic compound] The positive-type photosensitive resin composition of the present embodiment preferably contains (E) a nitrogen-containing basic compound (hereinafter referred to as "(E) component"). ). (E) Component: When the photosensitive resin composition after development is heated to perform heat curing treatment, the catalyst component (A) is crosslinked by the component (C). Thereby, the heating temperature at the time of the thermosetting treatment can be lowered, and the obtained cured product can obtain the same elongation at break as the cured product which is thermally hardened at a high temperature, and can also improve the chemical resistance. Although it is not particularly limited, the heating temperature of the thermosetting treatment of the positive photosensitive resin composition can be reduced to 180 by the addition of the component (E) in the positive photosensitive resin composition. The degree below °C. It is suitable because of the decrease in the heating temperature of the above-mentioned thermosetting treatment, and it is suitable for improving the dielectric constant and the critical resolution (E) component, which is a compound containing a basic nitrogen atom. The component (E) may, for example, be a nitrogen-containing organic compound, and is not particularly limited, and may, for example, be hexylamine, heptylamine, octylamine, decylamine, decylamine, aniline or 2- Methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, ethylidene diamine, tetraethylidene diamine, hexamethylenediamine, dibutylamine, dipentyl Amine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine , trihexylamine, triheptylamine, trioctylamine, tridecylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexyl Amine, methyl diheptylamine, methyldioctylamine, methyldidecylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, An aliphatic amine compound such as ethyl diheptylamine, ethyl dioctylamine, ethyl dimethyl decylamine, ethyl decylamine, dicyclohexylmethylamine, triethanolamine or triisopropanolamine; Aniline, N-methylaniline, diphenylamine -22- 201219982, Aromatic amine compounds such as N,N-dimethylaniline and 2,6-isopropylaniline: piperidine, imidazole, piperazine, pyridine , 4-methylpyridine, 2-hydroxymethylpyridine, 2-(2-hydroxyethyl)pyridine, 2-(3-hydroxypropyl)pyridine, 4-methylimiene, bipyridine A heterocyclic compound (hetero ring compound) or the like which uses nitrogen as a hetero atom. Among these, when considering the retention stability of the positive photosensitive resin composition, a heterocyclic compound containing nitrogen as a hetero atom, more preferably 2-hydroxymethylpyridine or 2-(2-hydroxyethyl) is preferable. Pyridine or 2-(3-hydroxypropyl)pyridine. These nitrogen-containing organic compounds may be used singly or in combination of two or more. The content of the component (E) is 100 parts by mass of the component (A), preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the content of the component (E) is in the above range, the heating temperature in the thermosetting treatment of the positive photosensitive resin composition can be favorably lowered, and the storage stability of the positive photosensitive resin composition can be improved. . [Other components] The positive photosensitive resin composition of the present embodiment may contain other monomers, an addition resin, an acid generator, a mold, a stabilizer, a colorant, a surfactant, and the like, as necessary. For example, when a (meth)acrylic monomer is added to a positive photosensitive resin composition, the residual stress in the cured product after thermal curing is reduced, and generation of cracks in the cured product can be suppressed or caused. When the substrate such as a wafer is thinned, the substrate and the cured product are warped and bent. -23- 201219982 is suitable. Further, when an epoxy resin is added to the positive photosensitive resin composition, since the residual stress in the cured product after the heat curing can be reduced, the same effect as when the (meth)acrylic monomer is added can be obtained. very suitable. Others are suitable for the improvement of heat resistance and the improvement of chemical resistance. Next, a cured product obtained by curing the positive photosensitive resin composition of the present embodiment will be described. Such a cured product can be used as a permanent insulating film, and is preferably used as an interlayer insulating film or a surface protective film of a semiconductor element, for example. When such a cured product is to be formed, first, a positive photosensitive resin composition of the present embodiment is applied to a substrate such as a tantalum wafer, and dried to form a coating film. The coating method may, for example, be a dipping method, a spray coating method, a bar coating method, a light coating method, or a spin coating method. ) method, curtain coating method, and the like. The thickness of the coating film can be appropriately controlled by adjusting the solid content concentration or viscosity of the positive photosensitive resin composition by the coating method. Next, the exposure of the coating film is carried out through a desired mask pattern. For the radiation used for exposure, it can be exemplified by a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a g-ray step projection lithography device (g-ray stepper), an i-ray step projection. Ultraviolet rays, electron beams, laser rays, etc. emitted by a lithography apparatus (i-ray stepper). The amount of exposure varies depending on the light used or the film thickness of the coating film, and is about 500 to 1500 mJ (microjoules -24 to 201219982)/cm2 in the case of the film thickness ΙΟμηι. Next, an alkali developing solution is used to develop the coating film, and the result of the exposed portion is dissolved and removed to obtain a desired resin pattern. The development method may, for example, be a shower developing method, a spray developing method, a dip developing method, a puddle developing method, or the like. In the case of the alkali imaging liquid, a basic compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylamine hydroxide or choline can be used in an amount of 1 to 10% by mass. The solution is dissolved in an alkaline aqueous solution of water. Then, heating (thermosetting treatment) of the obtained resin pattern is carried out to obtain a cured film. The heating conditions are not particularly limited and may be from about 30 minutes to 10 hours at a temperature of from 100 to 250 °C. At this time, it is also possible to perform heating in two stages. For example, it can be used as the first stage, heating at a temperature of 50 to 100 ° C for 1 minute to 2 hours, and as a second stage, heating at a temperature of 100 to 250 ° C for 20 minutes to 3 hours. Here, as described above, since the positive photosensitive composition of the present embodiment contains the component (E), the heating temperature can be made lower than that of the positive photosensitive resin composition. For example, when the positive photosensitive resin composition of the present embodiment is used, the heating condition can be about 100 to 200 ° C. If it is heated in two stages, it can be used as the first stage. It is 50 to i 〇〇 ° C, and the second stage is a mode of 1 〇〇 to 2 〇〇 ° C. The heating condition is determined by observing the state of the cured product to be produced. [Embodiment] The present invention will be described in more detail by way of examples, but the scope of the invention is not limited by the embodiments described below. [Examples 1 to 14 and Comparative Examples 1 to 1 1] According to the formulations (in parts by mass) described in Tables 1 to 3, mixed: an alkali-soluble resin having a phenolic hydroxyl group, a compound having a quinonediazide group A crosslinking agent, an acrylic resin, a nitrogen-containing basic compound, a solvent, an acrylic monomer, and an epoxy resin were used to prepare the positive photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 11. Here, in Tables 1 to 3, the blending amount is a component of the blank, and it means that it is not formulated when the positive photosensitive resin composition is prepared. Further, in Tables 1 to 3, for the sake of simplification, it is noted that the alkali-soluble resin having a phenolic hydroxyl group is a "phenolic resin", and the compound having a quinonediazide group is a "quinonediazide compound". The nitrogen-containing base compound is a "basic compound". The details of the components in Tables 1 to 3 are as follows. Phenol resin A: cresol novolac resin (mass average molecular weight 8000) obtained by adding formalin to m-cresol and adding and condensing according to a usual method. Phenolic resin B: The cresol and p-cresol are mixed in the form of m-cresol/p-cresol = 60/40 (mass ratio), and the cresol varnish resin obtained by the addition condensation of formalin according to the usual method is added (mass average molecular weight 20000) Bismuth azide compound A: 2.0 mol% hydrogen atom of the entire hydroxyl group of bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane - 26 - 201219982, a compound substituted with 1,2-naphthoquinonediazide-5-sulfo group, quinonediazide compound B: 4,4'-[1-[4-[1-(4-hydroxyl) a 2.2 mol% hydrogen atom of the entire hydroxyl group of phenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, substituted with 1,2-naphthoquinonediazide-4-sulfo Compound crosslinker: 2,4,6-gin[bis(methoxymethylamino)]-1,3,5_triazine (manufactured by Sanwa Chemical Co., Ltd., Mw-IOOLM) Acrylic resin A: Will be 1-ethylcyclohexyl acrylate/2-methoxyethyl acrylate / n-butyl Acrylate/acrylic acid=44.1 /3 6.8/12.3/6.8 ratio of the monomer mixed, the radical polymerization of the acrylic acid obtained by radical polymerization (mass average molecular weight 1 〇〇〇〇〇 Tg = -14.2〇C) Acrylic resin B: will be in the ratio of 1-ethylcyclohexyl acrylate / 2-methoxyethyl acrylate / n-butyl acrylate / acrylic acid = 4 4.1 / 3 6.8 / 12.3 / 6.8 Mixed monomer, acrylic resin obtained by radical polymerization according to the usual method (mass average molecular weight 22 0 00 Tg = -14.2 °C) Acrylic resin C: 1-ethylcyclohexyl acrylate/2-methoxy Acrylate resin obtained by radical polymerization of a monomer mixed with a ratio of ethyl acrylate/methacrylic acid = 43.5/48.3/8.2 (mass average molecular weight 200000 Tg = -11.4 ° C) Acrylic resin D : a monomer mixed in the ratio of 1-ethylcyclohexyl acrylate / 2-methoxyethyl acrylate / methoxy triethylene glycol acrylate / acrylic acid = 44.1/3 6.8 / 12.3 / 6.8, as usual Acrylic resin obtained by radical polymerization (mass average molecular weight 220000 Tg = -14.4 ° C Acrylic resin E: mixed in the ratio of 2-ethylcyclohexyl acrylate/2-methoxyethane-27- 201219982 acrylate/n-butyl acrylate/acrylic acid = 44.1/3 6.8/12.3/6.8 Monomer, acrylic resin obtained by radical polymerization according to the usual method (mass average molecular weight 220000 18 = -14.21) Acrylic resin F: 1-ethylcyclohexyl acrylate/2-methoxyethyl acrylate / positive - Butyl acrylate/acrylic acid = 44.1/3 6.8/12.3/6.8 ratio of the monomer mixed, the acrylic resin obtained by radical polymerization according to the usual method (mass average molecular weight 20000 Tg = -14.2 ° C) Acrylic resin G: Monomer mixed according to the ratio of 1-ethylcyclohexyl acrylate / 2-methoxyethyl acrylate / methoxy triethylene glycol acrylate / acrylic acid = 44 · 1/3 6.8 / 12.3 / 6.8 Acrylic resin obtained by free radical polymerization (mass average molecular weight 8000 Tg = -14.4 ° C) Acrylic resin Η: will be styrene/2-methoxyethyl acrylate / methoxy triethylene glycol acrylate / acrylic acid =44.1/36.8/1 The ratio of 2.3/6.8 mixed monomers, free radical polymerization according to the usual method Acrylic resin (mass average molecular weight 220000 Tg = 6.6 ° C) Acrylic resin I: will be benzyl methacrylate / 2 - methoxyethyl acrylate / methoxy triethylene glycol acrylate / acrylic = 44.1/ 3 The monomer mixed in the ratio of 6.8/12.3/6.8, the acrylic resin obtained by radical polymerization according to the usual method (mass average molecular weight: 220000 Tg = -5.8t) Acrylic resin J: biscyclopentadienyl methacrylate Monomer mixed in the ratio of ester/2-hydroxyethyl methacrylate/2-methoxyethyl acrylate/n-butyl acrylate/methacrylic acid=65/7/4M/20, according to the usual method Acrylic resin obtained by radical polymerization (mass average molecular weight 20000 Tg = 1 2 9.8 °C) -28- 201219982 Acrylic resin K: Will be adamantyl methacrylate/2-hydroxyethyl methacrylate/2- Acrylic resin obtained by radical polymerization of a monomer mixed with a ratio of methoxyethyl acrylate / n-butyl acrylate / methacrylic acid = 65 / 7 / 4 / 4 / 20 (mass average molecular weight 3 0000 Tg=135 °C) Acrylic resin L: will be 1-ethylcyclohexyl acrylate / 2 -Methoxyethyl acrylate / n-butyl acrylate = 44.1/36.8 / 1 9.1 ratio of the monomer mixed, the acrylic resin obtained by free radical polymerization according to the usual method (mass average molecular weight 220000 Tg = -22.0 ° C Basic compound A: 2-hydroxymethylpyridine basic compound B: 2-(2-hydroxyethyl)pyridine basic compound C: 2-(3-hydroxypropyl)pyridine acrylic acid monomer A: diisoprene Tetrahydrin hexaacrylate (DPHA), acrylic acid monomer B: isopentanic acid tetraacrylate (Aramid product, Aronix M-450) Acrylic monomer C: Oxidation-extended ethyl modified trimethylol triacrylate. (East Asia Synthetic Co., Aronix M-3 50) Epoxy Resin: 4-functional cyclic epoxy resin (黛色化学工业(股股) ), Epollite GT-401) Solvent: propylene glycol monomethyl ether acetate [Evaluation of the strength of the cured product] As the evaluation of the strength of the cured product, the elongation at break of the hardened material was measured -29-201219982 . With respect to each of the positive photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 11, a positive photosensitive resin composition was applied onto a 6-inch tantalum wafer surface by a spin coating method at 120 ° C. It was allowed to dry for 3 minutes to obtain a coating film having a film thickness of 25 μm. Next, this coating film was heated at 18 (TC for 2 hours to obtain a cured product having a film thickness of 20 μm. The obtained cured product was cut into a size of 8 mm x 5 cm to prepare a sample in the form of a short crepe paper. The elongation at break (%) was evaluated using RTC-1210A TENDILON (manufactured by ORIENTEC Co., Ltd.). Specifically, the sample was cut by weighting, and the upward load was applied to the sample at a speed of 5 mm/min. And the elongation at break (%) is calculated from the formula of [(the length at the time of sample cutting) - (the original length of the sample)] / (the original length of the sample) xl 。. The result is shown in the table. 1 to 3. [Measurement of Dielectric Constant] The dielectric constant of the cured product was measured as an evaluation of the electrical insulating properties of the cured product. • For each of Examples 1 to 14 and Comparative Examples 1 to 1 The photosensitive resin composition was applied onto the surface of a 6-inch tantalum wafer by a spin coating method, and dried at 120 ° C for 3 minutes to obtain a coating having a film thickness of 6 μm. Then, the coating film was heated at 180 ° C for 2 hours to obtain a cured product having a film thickness of 5 μm. The dielectric constant measuring device SSM 495 CVSystem (manufactured by Solid State Measurement Co., Ltd.) was used to measure the specific inductive capacity of the film in the film thickness direction. The results are shown in Tables 1 to 3. -30- 201219982 [Resolution Evaluation of properties] For each of the positive photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 1, a positive photosensitive resin composition was applied onto a 6 Å 矽 wafer surface by a spin coating method. The film was dried at 120 ° C for 3 minutes to obtain a film having a film thickness of 6 μm. The film was made of Ultratech, Prismatic ghi stepped prism type g, h, i-ray stepwise projection micro device. By recording 1 to 20 μm, a circular pattern of each Ιμη size is used in a photomask of a test pattern to perform exposure of 1 000 mJ/cm 2 . The development film after development exposure was developed using a developing solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., NMD-3) to form a resin pattern, and the resulting resin pattern was at 180 ° C. Heating was carried out for 2 hours (however, Example 12 was at 200 ° C for 2 hours) to obtain a cured product. The cross section of the obtained cured product was observed by SEM (Scanning Electron Microscope) to evaluate the critical resolution (unit: μπι). The results are shown in Tables 1 to 3. -31 · 201219982 [Table 1] Example 2 3 4 5 6 7 8 Phenol Resin A 100 100 100 100 100 100 100 100 Phenol Resin B 100 Osmium Diazide Compound A 24 24 24 24 24 24 24 Bismuth Azide Compound B 24 Crosslinking agent 20 20 20 20 20 50 20 30 Acrylic resin A 18 18 18 18 18 Acrylic resin B 18 Acrylic resin C 18 Acrylic resin D 18 Basic compound A 2 2 2 2 2 2 Basic compound B 2 Alkali Compound C 2 Solvent 300 300 300 300 300 300 300 300 Acrylic monomer A 10 Acrylic monomer B 10 Epoxy resin 10 Elongation at break (%) 14 16 14 15 15 15 16 14 Dielectric constant 3.6 3.6 3.5 3.6 3.5 3.5 3.6 3.6 Critical resolution ((iv)) 3 3 3 3 3 3 3 3 Tg of acrylic resin -14.2 -14.2 -14.2 -11.4 -14.2 -14.2 -14.2 -14.2 Molecular weight of acrylic resin (χιο" 10 22 20 22 10 10 10 10 [Table 2] squeezing m 9 10 11 12 13 14 phenol resin A 100 100 100 phenol resin B 100 100 100 醌 diazide compound A 24 24 24 24 24 醌 diazide compound B 24 Crosslinking agent 30 30 30 30 20 30 Acrylic resin Λ 18 18 18 18 Acrylic resin Ε 18 Acrylic resin F 18 Basic compound A 2 2 2 Solvent 300 300 300 300 300 300 Acrylic monomer C 10 10 10 10 10 Ring Oxygen resin 10 10 10 10 10 Breaking elongation (%) 16 14 14 16 14 12 Dielectric constant 3.5 3.6 3.6 4.0 3.6 3.6 Critical resolution ("(6) 3 3 3 6 3 4 Acrylic resin Tg -14.2 -14.2 -14.2 -14.2 -14.2 -14.2 Molecular weight of acrylic resin (xi〇4) 10 10 10 10 22 2 -32- 201219982 [Table 3] Comparative Example 2 3 4 5 6 7 8 9 10 1f Phenolic resin A 100 100 too 100 100 100 100 100 100 100 100 — Diazide nitrogen compound A 24 24 24 24 24 24 24 24 24 24 24 Crosslinking agent 20 50 20 20 20 20 20 20 20 Acrylic resin G 18 Acrylic resin Η 18 Acrylic resin I 18 Acrylic resin J 18 Acrylic resin Κ 18 Acrylic resin L 18 Alkaline fine A 2 2 2 2 2 2 2 2 Solvent 300 300 300 300 300 300 300 300 300 300 300 Breaking and stretching (6) 4 4 4 5 . 4 4 8 12 4 4 4 Dielectric constant 4.3 4.2 4.2 4.2 4.3 4.3 4.7 4.7 3.6 3.6 3.6 Critical resolution ((iv)) 10 10 10 10 10 20 10 10 8 8 >20 Acrylic resin Τε -14.4 6.6 -5.8 129.8 135 - 22 The molecular weight of the acrylic resin (ΧΙΟ) 0.8 22 22 2 3 22 It can be understood from Table 1 to Table 3 that the constituent unit (dl) which can be represented by the above formula (1) and the constituent unit which can be derived from the unsaturated carboxylic acid (d2) And the positive photosensitive resin composition of Examples 1 to 14 containing an acrylic resin (acrylic resin A to acrylic resin F) having a mass average molecular weight of 20,000 to 500,000, which has a positive balance in a well-balanced manner The resolution (critical resolution) of the photosensitive resin composition, and the electrical insulating properties (dielectric coefficient) and strength (breaking elongation) of the cured product. On the other hand, in Comparative Example 7 to 1.0 in which the acrylic resin does not contain the constituent unit (d1) represented by the above formula (1), Comparative Example 6 in which the mass average molecular weight of the acrylic resin is 20,000 or less, and the acrylic resin does not contain In the positive photosensitive resin composition of Comparative Example 11 in which the structural unit (dl) derived from the unsaturated carboxylic acid is derived, the resolution (critical resolution) of the positive photosensitive resin composition and the electrical insulating properties of the cured product ( The dielectric constant) and the strength (-33-201219982 elongation at break) of all or at least one of the properties are the result of poorer results. Further, from the comparison of Examples 9, 11 and 12, it was confirmed that the dielectric constant was improved while maintaining the elongation at break of the positive photosensitive resin composition as a result of the content of the component (E). The fact of critical resolution. In other words, the cured product of the positive photosensitive resin composition of Example 1 which was subjected to the removal of the component (E) from the positive photosensitive resin composition of Example 9 was found to be positive photosensitive of Example 9. The cured product of the resin composition has a low elongation at break, and if it is to be formed to the same level as the cured product of the positive photosensitive resin composition of Example 9, it is necessary to set the heat curing temperature to be higher than 180 °C. The fact that 200 ° C of 2 ° C (refer to Example 12). However, it can be understood that 'in this case', as shown in Example 12, even if the elongation at break can be made to be equivalent to that of Example 9, the dielectric constant and the critical resolution are lowered, so that it is not possible to maintain such characteristics. The fact of the way. -34-