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TW201142515A - Positive-type radiation-sensitive composition, interlayer insulating film and method for forming same - Google Patents

Positive-type radiation-sensitive composition, interlayer insulating film and method for forming same Download PDF

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TW201142515A
TW201142515A TW100113093A TW100113093A TW201142515A TW 201142515 A TW201142515 A TW 201142515A TW 100113093 A TW100113093 A TW 100113093A TW 100113093 A TW100113093 A TW 100113093A TW 201142515 A TW201142515 A TW 201142515A
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mass
compound
positive
methyl
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TW100113093A
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Daigo Ichinohe
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Jsr Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0047Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention provides a positive-type radiation-sensitive composition being able to form interlayer insulating film in which degradation of transmittance, heat-resistant transparency and voltage retention are suppressed, and have excellent light resistance and heat resistance because of keeping radiation sensitivity of radiation-sensitive composition in high level and suppressing generation of radicals and peroxides. The positive-type radiation-sensitive composition comprises [A] polymer which has structure unit containing epoxy groups and structure unit containing groups represented by formula (1) in the same or different polymer compound, [B] photoacid generator and [C] at least one compound selected from the group consisting of compounds containing hindered phenol structure, compounds containing hindered amine structure, compounds containing alkyl phosphite structure and compounds containing thioether structure.

Description

201142515 六、發明說明: 【發明所屬之技術領域】 本發明關於正型感放射線性組成物、由該組成物形成 的層間絕緣膜以及該層間絕緣膜的形成方法,該正型感放 射線性組成物適合作爲液晶顯示元件(LCD)、有機EL顯示 元件(OLED)等顯示元件用的層間絕緣膜形成材料。 【先前技術】 在顯示元件中一般基於使層狀地配置的佈線間絕緣的 目的而設置層間絕緣膜。就層間絕緣膜的形成材料而言, 廣泛使用正型感放射線性組成物,這是因爲得到必要的圖 案形狀的步驟數少,而且具有足夠平整性是較佳的。形成 這種層間絕緣膜時使用的正型感放射線性組成物要求良好 的放射線靈敏度和保存穩定性,對由此得到的層間絕緣膜 要求優異的耐熱性和透明性等。 作爲上述正型感放射線性組成物的成分廣泛採用丙烯 酸類樹脂,例如在日本特開20〇4-4669號公報中提出了一 種正型化學增幅光阻劑組成物,其特徵在於:具有交聯劑、 酸產生劑及一種樹脂’該樹脂本身是不溶或難溶於鹼水溶 液’但是具有能夠由於酸的作用而裂解的保護基,該保護 基裂解後能溶於鹼水溶液。另外,在日本特開2004-264623 號公報中提出了一種感放射線性組成物,其特徵在於:含 有樹脂和酸產生劑,該樹脂含有縮醛和/或縮酮結構以及環 氧基。 201142515 但是,在上述那樣以前的感放射線性組成物中,曝光 時或加熱時,所含有的化合物的鍵被切斷,會產生自由基, 或會因氧化生成過氧化物。該自由基或過氧化物會導致聚 合物分子的鍵裂解,由此,會導致由組成物得到的硬化膜 的耐光性以及耐熱性低下的不佳狀況。 爲了解決該不佳狀況,比如在日本特開2002 -2 2 92 5號 公報中提出了一種在感放射線性組成物中添加受阻酚類化 合物的方法。但是,僅僅添加這種化合物,則感放射線性 組成物的感放射線度以及由感放射線性組成物得到的硬化 膜的透光率以及電壓保持率有降低的危險。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2004-4669號公報 [專利文獻2]日本特開2004-264623號公報 [專利文獻3]日本特開2002-22925號公報 【發明內容】 本發明是基於該等問題而提出者,其目的在於提供一 種正型感放射線性組成物,該正型感放射線性組成物可以 高水準地保持感放射線性組成物的感放射線度,同時抑制 自由基或過氧化物的產生,由此可形成具有優異的耐光性 以及耐熱性,而且抑制透光率、耐熱透明性以及電壓保持 率降低的層間絕緣膜等。 201142515 [用於解決課題的手段] 爲解決上述課題而達成的本發明爲—種正型感放射.線 性組成物,其含有: [A]在同一或不同聚合物分子中具有包含下述式(1)所 示的基的結構單元和含環氧基的結構單元的聚合物; [B ]光酸產生劑;以及 [C]從含受阻酚結構的化合物、含受阻胺結構的化合 物、含亞磷酸院基酯結構的化合物以及含硫醚結構的化合 物構成的群組中選出的一種或兩種以上化合物。 R1 —〇 —C—OR3 ⑴ R2 (式(1)中,R1和R2各自獨立地是氫原子、烷基、環烷 基或芳基’這些烷基、環烷基或芳基的氫原子的一部分或 全部可以被取代基取代(其中,不包括Ri和R2都是氫原子 的情形)。R3是烷基、環烷基、芳烷基、芳基或-M(R3m)3 所示的基(Μ是Si、Ge或Sn,R3m是烷基),這些的氫原子 的一部分或全部可以被取代基取代。Ri和R3可以連接形成 環狀醚。) 在該正型感放射線性組成物中,除了上述特定結構的 [A]聚合物以及[B]光酸產生劑,還含有[C]從含受阻酚結構 的化合物、含受阻胺結構的化合物、含亞磷酸烷基酯結構 的化合物以及含硫醚結構的化合物構成的群組中選出的一 201142515 種或兩種以上的化合物(以下,也稱爲[C]化合物),由此, 曝光時專加熱時產生的自由基的捕獲或因氧化生成的過氧 化物的分解變成可能,因此能夠防止該自由基或過氧化物 導致的聚合物分子的鍵的裂解。其結果,由該組成物得到 的層間絕緣膜等,能夠發揮優異的耐光性以及耐熱性。另 外’該組成物採用了具有上述特定的構造的[C]化合物,因 此即使加入了這些,該組成物的感放射線度仍保持在高水 準’同時能夠防止由該組成物得到的層間絕緣膜等的透光 率以及電壓保持率的降低。 [B]光酸產生劑較佳係含有包括下式(2)表示的肟磺酸 酯基的化合物。 Ο \ I βί ^C=N—〇 —S —Rb, (2) Ο (式(2)中’ RB1表示烷基' 環烷基或芳基,這些基的氬 原子的一部分或全部可以被取代基取代) 該組成物中’藉由含有具有上述結構的化合物作爲[B ] 光酸產生劑,能夠進一步提高感放射線度,從該組成物得 到的層間絕緣膜等能夠發揮優異的透光率、耐熱.透明性以 及電壓保持率。 該正型感放射線性組成物,相對於1〇〇質量份[A]聚合 物’ [C]化合物的含量在0.1質量份以上' 10質量份以下爲 較佳。 201142515 相對於100質量份[A]聚合物的[C]化合物的含量在上 述範圍內,由此,在保持該組成物的感放射線度的同時, 由組成物得到的層間絕緣膜等的透光率、電壓保持率、耐 光性以及耐熱性能夠進一步提高。 另外,本發明的顯示元件用的層間絕緣膜等的形成方 法具有下述步驟。 (1) 將該正型感放射線性組成物的塗膜形成在基板上 的步驟; (2) 對在步驟(1)形成的塗膜的至少一部分照射放射線 的步驟; (3 )對在步驟(2)中經照射放射線的塗膜進行顯影的步 驟;以及 (4)對在步驟(3)中經顯影的塗膜進行加熱的步驟。 在該方法中,採用具有優異的感放射線度的上述正型 感放射線性組成物,藉由利用感放射線性的曝光、顯影、 加熱來形成圖案’由此能夠容易地形成具有精細而且精巧 的圖案的顯示元件用的層間絕緣膜等。進而,如此形成的 層間絕緣膜等,平衡性優異地具有一般的要求特性,即耐 光性、耐熱性、透光率、耐熱透明性以及電壓保持率。 本說明書所述的放射線是指包括可見光線、紫外線、 遠紅外線、X光線、帶電粒子線等的槪念。 [發明的效果] 如上說明的那樣,本發明的正型感放射線性組成物藉 201142515 由含有上述[A]、[B]以及[C]成分,可以高水準地保持感放 射線性組成物的感放射線度,同時抑制自由基或過氧化物 的產生,由此可形成具有優異的耐光性以及耐熱性,而且 抑制透光率以及電壓保持率降低的層間絕緣膜等。 【實施方式】 [用於實施發明的形態] 本發明的正型感放射線性組成物含有:[A ]特定的聚合 物(以下,僅稱爲「[A]聚合物」)、[B]光酸產生劑以及[C] 化合物,此外,還可以含有其他任意成分。 < [A ]聚合物> [A]聚合物是在相同或不同聚合物分子中具有含有上 述式(1 )所表示基的結構單元(以下僅稱爲「結構單元(1 )」) 和含環氧基的結構單元’根據需要也可以具有其他結構單 元。對[A ]聚合物的形態沒有特別的限定,可以列舉出: (i) 在相同聚合物分子中具有結構單元(1)和含環氧基 的結構單元兩者’在[A]聚合物中存在一種聚合物分子的情 形; (ii) 具有在一個聚合物分子中具有結構單元(丨),與在 和其不同的聚合物分子中具有含環氧基的結構單元兩者, 在[A]聚合物中存在兩種聚合物分子的情形; (iii) 在一個聚合物分子中具有結構單元(1)和含環氧基 的結構單元兩者,在和其不同的聚合物分子中具有結構單 元(1),在和它們都不同的聚合物分子中具有含環氧基的結 構單兀’在[A]聚合物中存在三種聚合物分子的情形; 201142515 (iv)除了(i)〜(iii)規定的聚合物分子以外,在[A]聚合物 中進一步包含其他一種或兩種以上的聚合物分子的情形等 <結構單元(1 ) > 結構單元(1)中’上述式(1)所示的基以在酸存在下分解 產生極性基的基(以下,僅稱爲「酸分解性基」)的形式存 在’所以藉由照射放射線而由光酸產生劑產生的酸,將酸 分解性基分解’從而使鹼不溶性的[A ]聚合物成爲鹼可溶 性。上述酸分解性基具有對鹼相對上穩定的縮醛結構或縮 酮結構,它們可以藉由酸的作用分解。 上述式(1)中’就R1和R2所示的烷基而言,較佳爲碳 原子數爲1〜3 0的直鏈和支鏈的烷基,該烷基鏈中可以具有 氧原子、硫原子、氮原子。就上述烷基的具體例子而言, 可以列舉出例如甲基、乙基、正丙基、正丁基、正戊基、 正己基、正辛基、正十二烷基、正十四烷基、正十八烷基 等直鏈烷基、異丙基、異丁基、第三丁基、新戊基、2 -己 基、3-己基等支鏈烷基。 上述式(1)中’就R1和R2所示的環烷基而言,較佳爲 碳原子數爲3~20的環烷基,可以是多環,亦可以在環內具 有氧原子。就上述環烷基的具體例子而言,可以列舉出例 如環丙基、環戊基、環己基、環庚基、環辛基、萡基、降 萡基、金剛烷基等。 上述式(1)中’就R1和R2所示的芳基而言,較佳係碳 原子數爲6〜14的芳基’可以是單環,也可以是單環連接的 -10- 201142515 結構,也可以是稠環。就上述芳基的具體例子而言 列舉出例如苯基、萘基等。 上述R1和R2的氫原子的一部分或全部可以被 取代。就這種取代基而言,可以列舉出例如鹵原子、 硝基、氰基、羧基、羰基、環烷基(就該環烷基而言 於使用上述環烷基的說明)、芳基(就該芳基而言’ 使用上述芳基的說明)、烷氧基(較佳爲碳原子數爲] 烷氧基,可以列舉出例如甲氧基、乙氧基、丙氧基 氧基、戊氧基、己氧基、庚氧基、辛氧基等)、醯3 係碳原子數爲2~20的醯基,可以列舉出例如乙醯基 基、丁醯基、異丁醯基等)、醯氧基(較佳係碳原子數; 的醯氧基,可以列舉出例如乙醯氧基、丙醯氧基、 基、第三丁醯氧基、第三戊醯氧基等)、烷氧基羰3 係碳原子數爲2〜20的烷氧基羰基,可以列舉出例如 羰基、乙氧基羰基、丙氧基羰基等)、鹵烷基(上述 環烷基的氫原子的一部分或全部被鹵原子取代的基 列舉出例如全氟甲基、全氟乙基、全氟丙基、氟環 氟環丁基等)等。對於芳基、環烷基等中的環狀結構 列舉出上述烷基作爲進一步的取代基。 在上述式(1 )中,R3所示的烷基、環烷基和芳基 用R1和R2中的說明。在上述式(1)中,R3所示的芳 較佳係列舉出碳原子數爲7〜20的芳烷基,可以列舉 苄基、苯乙基、萘甲基、萘乙基等。上述式(1)中1 ,可以 取代基 羥基、 ,適合 適合於 卜20的 、正丁 Μ較佳 、丙醯 爲2〜10 丁醯氧 g (較佳 甲氧基 烷基或 ,可以 丙基、 ,可以 可以使 烷基, 出例如 ,就R3 -11- 201142515 的-M(R3m)3所示的基而言,可以列舉出例如三甲基矽烷 基、三甲基甲鍺烷基等。就可以取代該r3所示的芳烷基或 -M(R3mh所示的基的氫原子的—部分或全部的取代基而 言,適合採用上述取代基。 R1和R3可以連接形成環狀醚。就這種環狀醚而言’可 以列舉出例如2 -氧環丁烷基、2 -四氫呋喃基、2 -四氫哌喃 基、2-二噚烷基等。該環狀醚的氫原子的—部分或全部可 以被上述取代基取代》 結構單元(1 )藉由具有利用鍵結到其他碳原子上而能 夠具有縮醛結構或縮酮結構的官能基,可以具有該縮醛結 構或縮酮結構。 就上述藉由鍵結到其他碳原子上能夠具有縮醛結構的 官能基而言’可以列舉出例如1-甲氧基乙氧基、1·乙氧基 乙氧基、卜正丙氧基乙氧基、1-異丙氧基乙氧基、1_正丁氧 基乙氧基、1-異丁氧基乙氧基、1-第二丁氧基乙氧基、1-第三丁氧基乙氧基、1-環戊氧基乙氧基、1-環己氧基乙氧 基、1-降萡氧基乙氧基、1-萡氧基乙氧基、苯基氧基乙氧 基' 1-(1-萘基氧基)乙氧基、1-苄基氧基乙氧基、1·苯乙基 氧基乙氧基、(環己基)(甲氧基)甲氧基、(環己基)(乙氧基) 甲氧基、(環己基)(正丙氧基)甲氧基、(環己基)(異丙氧基) 甲氧基、(環己基)(環己基氧基)甲氧基、(環己基)(苯氧基) 甲氧基、(環己基)(苄基氧基)甲氧基、(苯基)(甲氧基)甲氧 基、(苯基)(乙氧基)甲氧基、(苯基)(正丙氧基)甲氧基、(苯 201142515 基)(異丙氧基)甲氧基、(苯基)(環己基氧基)甲氧基、(苯 基)(苯氧基)甲氧基、(苯基)(苄基氧基)甲氧基、(节基)(甲 氧基)甲氧基、(苄基)(乙氧基)甲氧基、(苄基)(正丙氧基) 甲氧基、(苄基)(異丙氧基)甲氧基、(苄基)(環己基氧基)甲 氧基、(苄基)(苯氧基)甲氧基、(苄基)(苄基氧基)甲氧基、 2 -四氫呋喃基氧基、2 -四氫哌喃基氧基、1-三甲基矽烷基氧 基乙氧基、1-三甲基甲鍺烷基氧基乙氧基等。 它們之中,較佳係列舉出1-乙氧基乙氧基、1-環己基 氧基乙氧基、2-四氫哌喃基氧基、1-正丙氧基乙氧基。 就上述藉由鍵結到其他碳原子上而能夠成爲具有縮酮 結構的官能基而言,可以列舉出例如1 -甲基-1 -甲氧基乙氧 基、1-甲基-1-乙氧基乙氧基、1-甲基-1-正丙氧基乙氧基、 b甲基-1 —異丙氧基乙氧基、1-甲基-1-正丁氧基乙氧基、1-甲基-丨_異丁氧基乙氧基、1-甲基-1-第二丁氧基乙氧基、1-甲基-1-第三丁氧基乙氧基、丨-甲基-丨-環戊氧基乙氧基、1_ 甲基-1-環己基氧基乙氧基、甲基-丨-降萡基氧基乙氧基、 1-甲基-1-萡基氧基乙氧基、1-甲基-卜苯基氧基乙氧基、1· 甲基_1_(1·萘基氧基)乙氧基、1-甲基-1-苄基氧基乙氧基、 1-甲基-1-苯乙基氧基乙氧基、1-環己基-1-甲氧基乙氧基、 1-環己基-1-乙氧基乙氧基、丨-環己基-1-正丙氧基乙氧基、 1-環己基-1-異丙氧基乙氧基、丨-環己基-1-環己基氧基乙氧 基、1-環己基-1-苯氧基乙氧基、1-環己基-1-苄基氧基乙氧 基、1-苯基-1-甲氧基乙氧基、1-苯基-1-乙氧基乙氧基、1- -13- 201142515 苯基-1-正丙氧基乙氧基、1-苯基-1_異丙氧基乙氧基、苯 基-1-環己基氧基乙氧基、1-苯基-1-苯基氧基乙氧基、1-苯 基-1-节基氧基乙氧基、1-节基-1_甲氧基乙氧基、1-节基-1-乙氧基乙氧基、1-苄基-1-正丙氧基乙氧基、1-苄基-1-異丙 氧基乙氧基、1-苄基-1-環己基氧基乙氧基、1-苄基-1-苯基 氧基乙氧基、1-苄基-1-苄基氧基乙氧基、2-(2 -甲基-四氫 呋喃基)氧基、2_(2 -甲基-四氫哌喃基)氧基、1-甲氧基-環戊 基氧基、1-甲氧基-環己基氧基等。 它們之中,較佳係列舉出1-甲基-丨-甲氧基乙氧基、1_ 甲基-1-環己基氧基乙氧基。 就具有上述縮醛或縮酮結構的結構單元(1)的具體例 子而言,可以列舉出例如下述式(1-1 )〜(1_ 3)所示的結構單[Technical Field] The present invention relates to a positive radiation sensitive composition, an interlayer insulating film formed of the composition, and a method of forming the interlayer insulating film, the positive type radiation linear composition It is suitable as an interlayer insulating film forming material for a display element such as a liquid crystal display element (LCD) or an organic EL display element (OLED). [Prior Art] In the display element, an interlayer insulating film is generally provided for the purpose of insulating between wirings arranged in a layer. As the material for forming the interlayer insulating film, a positive-type radiation-sensitive composition is widely used because the number of steps for obtaining a necessary pattern shape is small, and it is preferable to have sufficient flatness. The positive-type radiation-sensitive composition used in the formation of such an interlayer insulating film requires good radiation sensitivity and storage stability, and excellent heat resistance, transparency, and the like are required for the interlayer insulating film thus obtained. An acrylic resin is widely used as a component of the positive-type radiation-sensitive linear composition. For example, a positive-type chemically amplified photoresist composition is proposed in Japanese Patent Laid-Open Publication No. Hei 20-4-4669, which is characterized in that it has cross-linking. The agent, the acid generator and a resin 'the resin itself is insoluble or poorly soluble in an aqueous alkali solution' but has a protecting group capable of being cleaved by the action of an acid, and the protecting group is soluble in an aqueous alkali solution after being cleaved. Further, Japanese Laid-Open Patent Publication No. 2004-264623 proposes a radiation sensitive composition comprising a resin and an acid generator containing an acetal and/or ketal structure and an epoxy group. 201142515 However, in the conventional radiation sensitive composition as described above, the bond of the compound contained during the exposure or heating is cleaved, and radicals are generated or peroxide is generated by oxidation. The radical or peroxide causes cracking of the bond of the polymer molecule, whereby the cured film obtained from the composition is inferior in light resistance and heat resistance. In order to solve the problem, a method of adding a hindered phenol compound to a radiation sensitive composition is proposed, for example, in Japanese Laid-Open Patent Publication No. 2002-2292. However, when only such a compound is added, the radiation sensitivity of the radiation-sensitive composition and the light transmittance and voltage holding ratio of the cured film obtained from the radiation-sensitive composition are lowered. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-264623 [Patent Document 3] JP-A-2002-264623 The present invention has been made in view of such problems, and an object thereof is to provide a positive-type radiation-radiating composition capable of maintaining the sensitivities of a radiation-sensitive composition at a high level while simultaneously By suppressing the generation of radicals or peroxides, it is possible to form an interlayer insulating film or the like which has excellent light resistance and heat resistance, and which suppresses light transmittance, heat-resistant transparency, and voltage holding ratio. 201142515 [Means for Solving the Problems] The present invention achieved by solving the above problems is a positive-type radiation-radiating linear composition containing: [A] having the following formula in the same or different polymer molecules ( 1) a polymer having a base structural unit and an epoxy group-containing structural unit; [B] a photoacid generator; and [C] a compound having a hindered phenol structure, a compound having a hindered amine structure, and a sub One or two or more compounds selected from the group consisting of a compound of a phosphate ester structure and a compound containing a thioether structure. R1 - 〇 - C - OR3 (1) R2 (in the formula (1), R1 and R2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the hydrogen atom of the alkyl group, the cycloalkyl group or the aryl group Some or all of them may be substituted by a substituent (wherein, excluding the case where both Ri and R2 are a hydrogen atom). R3 is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group represented by -M(R3m)3. (Μ is Si, Ge or Sn, R3m is an alkyl group), and some or all of these hydrogen atoms may be substituted by a substituent. Ri and R3 may be bonded to form a cyclic ether.) In the positive-type radiation linear composition In addition to the above-mentioned specific structure of [A] polymer and [B] photoacid generator, [C] a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and A 201142515 or two or more compounds (hereinafter, also referred to as [C] compounds) selected from the group consisting of compounds containing a thioether structure, thereby capturing or causing free radicals generated during heating upon exposure The decomposition of the peroxide formed by oxidation becomes possible, so the free radical can be prevented Cleavage of the peroxide bond of the resulting polymer molecules. As a result, the interlayer insulating film or the like obtained from the composition can exhibit excellent light resistance and heat resistance. Further, the composition [C] having the specific structure described above is used, and therefore, even if these are added, the radiation sensitivity of the composition is maintained at a high level, and the interlayer insulating film obtained from the composition can be prevented. The light transmittance and the voltage retention rate are lowered. The [B] photoacid generator preferably contains a compound including an anthracenesulfonate group represented by the following formula (2). Ο \ I βί ^C=N—〇—S—Rb, (2) Ο (In the formula (2), RB1 represents an alkyl group, a cycloalkyl group or an aryl group, and some or all of the argon atoms of these groups may be substituted. In the composition, the compound having the above-described structure is used as the [B] photoacid generator, and the radiation sensitivity can be further improved, and the interlayer insulating film obtained from the composition can exhibit excellent light transmittance. Heat resistance, transparency and voltage retention. The positive-type radiation-sensitive composition is preferably contained in an amount of 0.1 part by mass or more and 10 parts by mass or less based on 1 part by mass of the [A] polymer '[C] compound. 201142515 The content of the [C] compound with respect to 100 parts by mass of the [A] polymer is within the above range, whereby the interlayer insulating film or the like obtained from the composition is transmitted while maintaining the radiation sensitivity of the composition. The rate, voltage holding ratio, light resistance, and heat resistance can be further improved. Further, the method of forming an interlayer insulating film or the like for a display element of the present invention has the following steps. (1) a step of forming a coating film of the positive-type radiation-sensitive composition on a substrate; (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation; (3) a step in the step ( 2) a step of developing a coating film irradiated with radiation; and (4) a step of heating the coating film developed in the step (3). In this method, the positive-type radiation-sensitive linear composition having excellent sensitivities is used, and the pattern is formed by radiation-sensitive exposure, development, and heating, whereby a fine and delicate pattern can be easily formed. An interlayer insulating film or the like for a display element. Further, the interlayer insulating film or the like thus formed has excellent required properties such as light resistance, heat resistance, light transmittance, heat-resistant transparency, and voltage holding ratio, which are excellent in balance. The radiation described in the present specification refers to a concept including visible rays, ultraviolet rays, far infrared rays, X-rays, charged particle rays, and the like. [Effects of the Invention] As described above, the positive-type radiation-sensitive composition of the present invention can hold the sense of the radiation-sensitive linear composition at a high level by containing the above-mentioned components [A], [B], and [C] by 201142515. The radiation is suppressed while the generation of radicals or peroxides is suppressed, whereby an interlayer insulating film or the like which has excellent light resistance and heat resistance and which suppresses light transmittance and voltage holding ratio can be formed. [Embodiment] The form of the positive radiation sensitive composition of the present invention contains: [A] a specific polymer (hereinafter, simply referred to as "[A] polymer"), [B] light. The acid generator and the [C] compound may further contain other optional components. < [A] Polymer> [A] The polymer has a structural unit containing the group represented by the above formula (1) in the same or different polymer molecules (hereinafter simply referred to as "structural unit (1)") and The structural unit containing an epoxy group may have other structural units as needed. The form of the [A] polymer is not particularly limited, and examples thereof include: (i) having both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule 'in the [A] polymer There is a case of a polymer molecule; (ii) having both a structural unit (丨) in one polymer molecule and a structural unit having an epoxy group in a polymer molecule different therefrom, in [A] a case where two polymer molecules are present in a polymer; (iii) having both a structural unit (1) and an epoxy group-containing structural unit in one polymer molecule, and having a structural unit in a polymer molecule different therefrom (1) A case where an epoxy group-containing structure monoterpene 'in the [A] polymer is present in three polymer molecules in a polymer molecule different from them; 201142515 (iv) except (i) to (iii) In the case where the [A] polymer further contains one or two or more kinds of polymer molecules in addition to the predetermined polymer molecule, <Structure unit (1) > Structural unit (1) in the above formula (1) ) the base shown decomposes in the presence of an acid to produce a polarity In the form of a group (hereinafter, simply referred to as "acid-decomposable group"), "the acid generated by the photo-acid generator by irradiation with radiation, and the acid-decomposable group is decomposed" to make the alkali insoluble [A] The polymer becomes alkali soluble. The above acid-decomposable group has an acetal structure or a ketal structure which is relatively stable to a base, and which can be decomposed by the action of an acid. In the above formula (1), the alkyl group represented by R1 and R2 is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and the alkyl chain may have an oxygen atom. Sulfur atom, nitrogen atom. Specific examples of the above alkyl group include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl. a branched alkyl group such as a linear alkyl group such as n-octadecyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a 2-hexyl group or a 3-hexyl group. In the above formula (1), the cycloalkyl group represented by R1 and R2 is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have a polycyclic ring or an oxygen atom in the ring. Specific examples of the above cycloalkyl group include, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decyl group, a decyl group, an adamantyl group and the like. In the above formula (1), 'in the case of the aryl group represented by R1 and R2, preferably the aryl group having 6 to 14 carbon atoms' may be a single ring or a single ring-bonded-10-201142515 structure. It can also be a fused ring. Specific examples of the above aryl group include, for example, a phenyl group, a naphthyl group and the like. Some or all of the hydrogen atoms of the above R1 and R2 may be substituted. Examples of such a substituent include a halogen atom, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (in the case of using the above cycloalkyl group as the cycloalkyl group), and an aryl group (in terms of The aryl group is 'the description of the above aryl group', the alkoxy group (preferably having a carbon number) alkoxy group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a pentyloxy group. Examples of the fluorenyl group having 2 to 20 carbon atoms and a fluorenyl group having 2 to 20 carbon atoms include, for example, an ethyl fluorenyl group, a butyl group, an isobutyl group, etc., and a decyloxy group (for example, an ethyl group, a hexyl group, a heptyl group, and an isobutyl group). Preferred examples of the decyloxy group include an ethoxy group, a propyloxy group, a benzyloxy group, a third pentyloxy group, and the like, and an alkoxycarbonyl group. The alkoxycarbonyl group having 2 to 20 carbon atoms may, for example, be a carbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group, or a haloalkyl group (a part or all of the hydrogen atom of the above cycloalkyl group may be substituted by a halogen atom) Examples of the group include, for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a fluorocyclofluorocyclobutyl group, and the like. For the cyclic structure in the aryl group, the cycloalkyl group or the like, the above alkyl group is exemplified as a further substituent. In the above formula (1), the alkyl group, the cycloalkyl group and the aryl group represented by R3 are as defined in R1 and R2. In the above formula (1), the aryl group represented by R3 is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. In the above formula (1), 1 may be a substituted hydroxy group, preferably suitable for the oxime 20, preferably n-butyl fluorene, and the propyl hydrazine is 2 to 10 butyl fluorenyl g (preferably a methoxyalkyl group or a propyl group). For example, the alkyl group may be, for example, a group represented by -M(R3m)3 of R3-11-201142515, and examples thereof include a trimethyldecyl group and a trimethylmethane group. The above-mentioned substituent may be suitably used in place of the aralkyl group represented by r3 or the substituent of -M (a hydrogen atom of the group represented by R3mh). R1 and R3 may be bonded to form a cyclic ether. Examples of such a cyclic ether include, for example, a 2-oxocyclobutane group, a 2-tetrahydrofuranyl group, a 2-tetrahydropiperidyl group, a 2-dialkylalkyl group, etc. The hydrogen atom of the cyclic ether - part or all may be substituted by the above substituents. The structural unit (1) may have the acetal structure or ketal by having a functional group capable of having an acetal structure or a ketal structure by bonding to other carbon atoms. In the above-mentioned functional group capable of having an acetal structure by bonding to other carbon atoms For example, 1-methoxyethoxy, 1-ethoxyethoxy, bupropoxyethoxy, 1-isopropoxyethoxy, 1-n-butoxyethoxy, 1-isobutoxyethoxy, 1-second butoxyethoxy, 1-tert-butoxyethoxy, 1-cyclopentyloxyethoxy, 1-cyclohexyloxyethoxy , 1-norbornoxyethoxy, 1-decyloxyethoxy, phenyloxyethoxy ' 1-(1-naphthyloxy)ethoxy, 1-benzyloxy B Oxyl, 1, phenethyloxyethoxy, (cyclohexyl)(methoxy)methoxy, (cyclohexyl)(ethoxy)methoxy, (cyclohexyl)(n-propoxy) Methoxy, (cyclohexyl)(isopropoxy)methoxy, (cyclohexyl)(cyclohexyloxy)methoxy, (cyclohexyl)(phenoxy)methoxy, (cyclohexyl) ( Benzyloxy)methoxy, (phenyl)(methoxy)methoxy, (phenyl)(ethoxy)methoxy, (phenyl)(n-propoxy)methoxy, Benzene 201142515-based (isopropoxy)methoxy, (phenyl)(cyclohexyloxy)methoxy, (phenyl) (phenoxy) ) methoxy, (phenyl) (benzyloxy) methoxy, (nod) (methoxy) methoxy, (benzyl) (ethoxy) methoxy, (benzyl) ( N-propoxy) methoxy, (benzyl)(isopropoxy)methoxy, (benzyl)(cyclohexyloxy)methoxy, (benzyl)(phenoxy)methoxy, (benzyl)(benzyloxy)methoxy, 2-tetrahydrofuranyloxy, 2-tetrahydropentanyloxy, 1-trimethyldecyloxyethoxy, 1-trimethylmethyl A decyloxyethoxy group, etc. Among them, a preferred series is 1-ethoxyethoxy, 1-cyclohexyloxyethoxy, 2-tetrahydropyranyloxy, 1- The n-propoxyethoxy group. The functional group having a ketal structure by bonding to another carbon atom as described above may, for example, be 1-methyl-1-methoxyethoxy. 1-methyl-1-ethoxyethoxy, 1-methyl-1-n-propoxyethoxy, b-methyl-1-isopropoxyethoxy, 1-methyl-1- n-Butoxyethoxy, 1-methyl-indole-isobutoxyethoxy, 1-methyl-1-butoxyethoxy, 1-methyl -1-t-butoxyethoxy, fluorenyl-methyl-hydrazine-cyclopentyloxyethoxy, 1-methyl-1-cyclohexyloxyethoxy, methyl-hydrazine-norbornyloxy Ethyloxy, 1-methyl-1-indolyloxyethoxy, 1-methyl-buphenyloxyethoxy, 1·methyl-1_(1·naphthyloxy)ethoxy , 1-methyl-1-benzyloxyethoxy, 1-methyl-1-phenylethyloxyethoxy, 1-cyclohexyl-1-methoxyethoxy, 1-ring Hexyl-1-ethoxyethoxy, fluorenyl-cyclohexyl-1-n-propoxyethoxy, 1-cyclohexyl-1-isopropoxyethoxy, fluorene-cyclohexyl-1-cyclohexyl Oxyethoxyethoxy, 1-cyclohexyl-1-phenoxyethoxy, 1-cyclohexyl-1-benzyloxyethoxy, 1-phenyl-1-methoxyethoxy, 1 -Phenyl-1-ethoxyethoxy, 1- 13-201142515 Phenyl-1-n-propoxyethoxy, 1-phenyl-1-isopropoxyethoxy, phenyl- 1-cyclohexyloxyethoxy, 1-phenyl-1-phenyloxyethoxy, 1-phenyl-1-phenyloxyethoxy, 1-pyryl-1_methoxy Ethoxy, 1-pyryl-1-ethoxyethoxy, 1-benzyl-1-n-propoxyethoxy, 1-benzyl-1-isopropoxyethoxy, 1 -benzyl-1-cyclohexyloxyethoxy, 1-benzyl-1-phenyloxyethoxy, 1-benzyl-1-benzyloxyethoxy, 2-(2-A A benzyl-tetrahydrofuranyloxy group, a 2-(2-methyl-tetrahydropyranyl)oxy group, a 1-methoxy-cyclopentyloxy group, a 1-methoxy-cyclohexyloxy group, and the like. Among them, a preferred series is 1-methyl-indole-methoxyethoxy, 1-methyl-1-cyclohexyloxyethoxy. Specific examples of the structural unit (1) having the above acetal or ketal structure include, for example, a structure list represented by the following formulas (1-1) to (1_3).

(式(1-1)和(1-3)中,R·是氫原子或甲基。r1、R2和R3 與上述式(1)的說明相同。) 就提供上述式(1-1)〜(I-3)所示的結構單元(1)的具有自 由基聚合性的單體(以下,僅稱爲「含縮醛結構的單體」) 而言,可以列舉出例如: -14- 201142515 (甲基)丙烯酸i-烷氧基烷基酯、(甲基)丙烯酸ι-(環烷 基氧基)烷基酯、(甲基)丙烯酸1-(鹵烷氧基)烷基酯、(甲基) 丙烯酸1-(芳烷基氧基)烷基酯、(甲基)丙烯酸四氫哌喃基酯 等(甲基)丙烯酸酯類含縮醛結構的單體; 2,3-二(1-(三烷基矽烷基氧基)烷氧基)羰基)-5-降萡 烯、2,3-二(1-(三烷基甲鍺烷基氧基)烷氧基)羰基)-5-降萡 烯、2,3-二(1-烷氧基烷氧基羰基)-5-降萡烯、2,3-二(1·(環 烷基氧基)烷氧基羰基)-5-降萡烯、2,3-二(1-(芳烷基氧基) 烷氧基羰基)-5-降萡烯等降萡烯類含縮醛結構的單體 卜烷氧基烷氧基苯乙烯、1-(鹵烷氧基)烷氧基苯乙烯、 1-(芳烷基氧基)烷氧基苯乙烯、四氫哌喃基氧基苯乙烯等苯 乙烯類含縮醛結構的單體。 它們之中,較佳係(甲基)丙烯酸1-烷氧基烷基酯、(甲 基)丙烯酸四氫哌喃基酯、1-烷氧基烷氧基苯乙烯、四氫哌 喃基氧基苯乙烯,更佳係(甲基)丙烯酸1-烷氧基烷基酯。 +就提供上述結構單元(1)的含縮醛結構的單體的具體 例子而言,可以列舉出例如: 甲基丙烯酸1-乙氧基乙基酯、甲基丙烯酸1-甲氧基乙 基酯、甲基丙烯酸1-正丁氧基乙基酯、甲基丙烯酸1-異丁 氧基乙基酯、甲基丙烯酸1-第三丁氧基乙基酯、甲基丙烯酸 1-(2-氯乙氧基)乙基酯、甲基丙烯酸1-(2·乙基己基氧基)乙 基酯、甲基丙烯酸1-正丙氧基乙基酯、甲基丙烯酸1-環己 基氧基乙基酯、甲基丙烯酸1-(2-環己基乙氧基)乙基酯、甲 基丙烯酸1-苄基氧基乙基酯、甲基丙烯酸2·四氫哌喃基酯, -15- 201142515 丙烯酸1-乙氧基乙基酯、丙烯酸1-甲氧基乙基酯、丙 烯酸1-正丁氧基乙基酯、丙烯酸1-異丁氧基乙基酯、丙烯 酸1-第三丁氧基乙基酯、丙烯酸1-(2-氯乙氧基)乙基酯、 丙烯酸1-(2-乙基己基氧基)乙基酯、丙烯酸丨-正丙氧基乙 基酯、丙烯酸1_環己基氧基乙基酯、丙烯酸1-(2-環己基乙 氧基)乙基酯、丙烯酸1-苄基氧基乙基酯、丙烯酸2 -四氫哌 喃基酯、 2,3-二(1-(三甲基矽烷基氧基)乙氧基)羰基)-5-降萡 烯、2,3-二(1-(三甲基甲鍺烷基氧基)乙氧基)羰基)_5_降萡 烯、2,3-二(1-甲氧基乙氧基羰基)-5-降萡烯、2,3-二(1-(環 己基氧基)乙氧基羰基)-5-降萡烯、2,3-二(1-(苄基氧基)乙 氧基羰基)-5-降萡烯, 對或間-1-乙氧基乙氧基苯乙烯、對或間-1-甲氧基乙氧 基苯乙烯、對或間-1-正丁氧基乙氧基苯乙烯、對或間-1-異丁氧基乙氧基苯乙烯、對或間-1-(1,1-二甲基乙氧基)乙 氧基苯乙烯、對或間-1-(2-氯乙氧基)乙氧基苯乙烯、對或 間-1-(2_乙基己基氧基)乙氧基苯乙烯、對或間-1-正丙氧基 乙氧基苯乙烯、對或間-1-環己基氧基乙氧基苯乙烯、對或 間-1_(2-環己基乙氧基)乙氧基苯乙烯、對或間-卜苄基氧基 乙氧基苯乙烯等。上述結構單元(1)可以使用—種或組合兩 種以上使用。 在提供上述結構單元(1)的含縮醛結構的單體中’較佳 係甲基丙烯酸1-乙氧基乙基酯、甲基丙嫌酸b正丁氧基乙 -16 - 201142515 基酯、甲基丙烯酸2-四氫哌喃基酯、甲基丙烯酸丨_节基氧 基乙基醋。 提供結構單元(1)的含縮醛結構的單體可以使用市售 者,也可以使用公知的方法合成者。例如,提供上述式d」〕 所示的結構單元(1)的含縮醛結構的單體可以如下述所 示,藉由在酸催化劑的存在下,使(甲基)丙烯酸和乙締基 醚反應合成。(In the formulae (1-1) and (1-3), R· is a hydrogen atom or a methyl group. r1, R2 and R3 are the same as those described in the above formula (1).) The above formula (1-1) is provided. The monomer having a radical polymerizable property (hereinafter referred to simply as "a monomer having an acetal structure") of the structural unit (1) represented by (I-3) may, for example, be: -14- 201142515 I-alkoxyalkyl (meth)acrylate, i-(cycloalkyloxy)alkyl (meth)acrylate, 1-(haloalkoxy)alkyl (meth)acrylate, ( Methyl) 1-(aralkyloxy)alkyl acrylate, (meth) acrylate (meth) acrylate-based (meth) acrylate-containing acetal structure-containing monomer; 2,3-di ( 1-(Trialkyldecyloxy)alkoxy)carbonyl)-5-nordecene, 2,3-bis(1-(trialkylcarbinyloxy)alkoxy)carbonyl)- 5-northene, 2,3-bis(1-alkoxyalkoxycarbonyl)-5-nordecene, 2,3-di(1.(cycloalkyloxy)alkoxycarbonyl)- 5-northene, 2,3-bis(1-(aralkyloxy)alkoxycarbonyl)-5-nordecene and the like decene acetal-containing monomer Alkyl styrene, 1-(haloalkoxy)alkoxystyrene, 1-(aralkyloxy)alkoxystyrene, tetrahydropyranyloxystyrene, etc. Monomer of aldehyde structure. Among them, preferred are 1-alkoxyalkyl (meth)acrylate, tetrahydrobenzylidene (meth)acrylate, 1-alkoxyalkoxystyrene, tetrahydropyranyloxyl The styrene is more preferably a 1-alkoxyalkyl (meth)acrylate. + Specific examples of the acetal structure-containing monomer which provides the above structural unit (1) include, for example, 1-ethoxyethyl methacrylate and 1-methoxyethyl methacrylate. Ester, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1-(2-methacrylate) Chloroethoxy)ethyl ester, 1-(2-ethylhexyloxy)ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate Base ester, 1-(2-cyclohexylethoxy)ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2·tetrahydropyranyl methacrylate, -15- 201142515 1-Ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-tert-butoxy acrylate Ethyl ester, 1-(2-chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, hydrazine-n-propoxyethyl acrylate, 1 ring of acrylic acid Hexyloxyethyl ester, propylene 1-(2-cyclohexylethoxy)ethyl ester, 1-benzyloxyethyl acrylate, 2-tetrahydrobenzylidene acrylate, 2,3-bis(1-(trimethyldecyl)alkyl Oxy)ethoxy)carbonyl)-5-nordecene, 2,3-bis(1-(trimethylmethylindenyloxy)ethoxy)carbonyl)_5_norbornene, 2,3 - bis(1-methoxyethoxycarbonyl)-5-nordecene, 2,3-bis(1-(cyclohexyloxy)ethoxycarbonyl)-5-northene, 2,3- Bis(1-(benzyloxy)ethoxycarbonyl)-5-nordecene, p- or m-ethoxyethoxystyrene, p- or m-methoxyethoxybenzene Ethylene, p- or m--1-n-butoxyethoxystyrene, p- or m--1-isobutoxyethoxystyrene, p- or m-(1,1-dimethylethoxyl) Ethyl styrene, p- or m-(2-chloroethoxy)ethoxystyrene, p- or m-(2-ethylhexyloxy)ethoxystyrene, Or m-n-propoxy ethoxystyrene, p- or m-cyclohexyloxyethoxystyrene, p- or m-(_cyclohexylethoxy)ethoxystyrene , p- or m-benzyloxyethoxystyrene, and the like. The above structural unit (1) may be used in combination of two or more kinds. In the acetal-containing monomer which provides the above structural unit (1), 'preferably 1-ethoxyethyl methacrylate, methyl propylene acid b-butoxyethyl-16 - 201142515-based ester , 2-tetrahydropyranyl methacrylate, 丨 节 氧基 ethoxyethyl methacrylate. The acetal structure-containing monomer which provides the structural unit (1) can be used commercially or by a known method. For example, the acetal structure-containing monomer of the structural unit (1) represented by the above formula d"] can be obtained by using (meth)acrylic acid and ethyl phenyl ether in the presence of an acid catalyst as shown below. Reaction synthesis.

(式中’ R’、R1和R3分別和上述式(1-1)中的R,、和 R3對應’ R21和R22以-CH(R21)(R22)的方式和上述式(1·η 中的R2對應。) 就[A ]聚合物中的結構單元(1 )的含量而言,只要是[a ] 聚合物藉由酸顯示出鹼可溶性,發揮出硬化膜所希望的耐 熱性,就沒有特別的限定,在一個聚合物分子中含有結構 單元(1)與含環氧基的結構單元這兩者的情況下,相對於[A] 聚合物中含有的全部的結構單元,以單體的加入比計,較 佳爲5質量%〜7 0質量%,更佳爲1 〇質量。〜6 0質量%,特 佳爲20質量〜50質量%。 另一方面,在一個聚合物分子中具有結構單元(1),而 且在其他另一聚合物分子中具有含環氧基的結構單元的情 況下’就具有結構單元(1)的一個聚合物分子中的結構單元 -17- 201142515 (1)的含量而言,相對於該聚合物分子中含有的全部的結構 單元’以單體的加入比計’較佳爲40質量%〜99質量% ’ 更佳爲5 0質量% ~ 9 8質量% ’特佳爲5 5質量%〜9 5質量%。 <含環氧基的結構單元> [A]聚合物在具有上述結構單元(1)的同時,還具有含 環氧基的結構單元。含環氧基的結構單元是來自具有自由 基聚合性的含環氧基的單體的結構單元。就該環氧基而 言,可以列舉出環氧乙烷基(1,2-環氧結構)、氧環丁烷基 (1,3-環氧結構)。[A]聚合物藉由在分子中具有含環氧乙烷 基或氧環丁烷基等的結構單元,可以提高由該正型感放射 線性組成物得到的硬也膜的硬度,進一步提高耐熱性。 就提供上述含環氧基的結構單元的含環氧基的單體的 具體例子而言,可以列舉出例如: 丙烯酸縮水甘油基酯、甲基丙烯酸縮水甘油基酯、丙 烯酸-3,4-環氧丁基酯、甲基丙烯酸-3,4-環氧丁基酯、丙烯 酸3-甲基-3,4-環氧丁基酯、甲基丙烯酸-3-乙基-3,4-環氧丁 基酯、丙烯酸-5,6-環氧己基酯、甲基丙烯酸-5,6-環氧己基 酯、甲基丙烯酸-5-甲基-5,6-環氧己基酯、甲基丙烯酸- 5-乙基·5,6-環氧己基酯、丙烯酸-6,7-環氧庚基酯、甲基丙烯 酸-6,7-環氧庚基酯’ 甲基丙烯酸3,4-環氧環己基酯、甲基丙烯酸3,4_環氧 環己基甲基酯、甲基丙烯酸3,4-環氧環己基乙基酯、甲基 丙烯酸3,4-環氧環己基丙基酯、甲基丙烯酸3,4-環氧環己 -18- 201142515 基丁基酯、甲基丙烯酸3,4-環氧環己基己基酯、丙烯酸 環氧環己基酯、丙烯酸3,4-環氧環己基甲基酯、丙烯酸 環氧環己基乙基酯、丙烯酸3,4-環氧環己基丙基酯、 酸3,4-環氧環己基丁基酯、丙烯酸3,4-環氧環己基己 等含環氧乙烷基的(甲基)丙烯酸類化合物; 鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水 基醚、對乙烯基苄基縮水甘油基醚、α-甲基-鄰乙烯基 縮水甘油基醚、α-甲基-間乙烯基苄基縮水甘油基醚、 基-對乙烯基苄基縮水甘油基醚等乙烯基苄基縮水甘 醚類;鄰乙烯基苯基縮水甘油基醚、間乙烯基苯基縮 油基醚、對乙烯基苯基縮水甘油基醚等乙烯基苯基縮 油基醚類; 3-(丙烯醯氧基甲基)氧環丁烷、3-(丙烯醯氧基甲I 甲基氧環丁烷、3-(丙烯醯氧基甲基)-3-乙基氧環丁 3-(丙烯醯氧基甲基)-3-苯基氧環丁烷、3-(2-丙烯醯氧 基)氧環丁烷、3_(2-丙烯醯氧基乙基)-3-乙基氧環丁 3-(2-丙烯醯氧基乙基)-3-乙基氧環丁烷、3-(2-丙烯醯 乙基)-3-苯基氧環丁烷, 3-(甲基丙烯醯氧基甲基)氧環丁烷、3-(甲基丙嫌 基甲基)-3-甲基氧環丁烷、3-(甲基丙烯醯氧基甲基)-3 氧環丁烷、3-(甲基丙烯醯氧基甲基)-3-苯基氧環丁烷、 甲基丙烯醯氧基乙基)氧環丁烷、3-(2-甲基丙烯醯氧 基)-3-乙基氧環丁烷、3-(2-甲基丙烯醯氧基乙基)-3-乙 環丁烷、3-(2 -甲基丙烯醯氧基乙基)-3-苯基氧環丁烷 3.4- 3.4-丙烯 基酯 甘油 苄基 α -甲 油基 水甘 水甘 I )-3-烷、 基乙 烷、 氧基 醯氧 -乙基 3-(2- 基乙 基氧 -19- 201142515 2-(丙烯醯氧基甲基)氧環丁烷、2-(丙烯醯氧基甲基)-2-甲基氧環丁烷、2-(丙烯醯氧基甲基)-2 -乙基氧環丁烷、 2-(丙烯醯氧基甲基)-2-苯基氧環丁烷、2-(2-丙烯醯氧基乙 基)氧環丁烷、2-(2-丙烯醯氧基乙基)-2 -乙基氧環丁烷、 2-(2-丙烯醯氧基乙基)-2-乙基氧環丁烷、2-(2-丙烯醯氧基 乙基)-2-苯基氧環丁烷, 2-(甲基丙烯醯氧基甲基)氧環丁烷、2-(甲基丙烯醯氧 基甲基)-2-甲基氧環丁烷、2-(甲基丙烯醯氧基甲基)-2-乙基 氧環丁烷、2-(甲基丙烯醯氧基甲基)-2-苯基氧環丁烷、2-(2-甲基丙烯醯氧基乙基)氧環丁烷、.2-(2-甲基丙烯醯氧基乙 基)-2-乙基氧環丁烷、2-(2-甲基丙烯醯氧基乙基)-2-乙基氧 環丁烷、2-(2-甲基丙烯醯氧基乙基)-2-苯基氧環丁烷等含 有氧環丁烷基的(甲基)丙烯酸類化合物等。上述含環氧基 的結構單元可以單獨或組合兩種以上使用。 上述含環氧基的單體中,從和其他自由基聚合性單體 的共聚反應性以及正型感放射線性組成物的顯影性的觀點 來看,較佳係甲基丙嫌酸縮水甘油基醋、甲基丙燒酸-2-甲 基縮水甘油基酯、甲基丙烯酸-3,4-環氧環己基酯、甲基丙 酸 酯 基 甲 基 己 環 氧 環Wherein 'R', R1 and R3 correspond to R, and R3 in the above formula (1-1), respectively, and 'R21 and R22 are in the form of -CH(R21)(R22) and in the above formula (1·η R2 corresponds to.) In terms of the content of the structural unit (1) in the [A] polymer, as long as the [a] polymer exhibits alkali solubility by an acid and exhibits desired heat resistance of the cured film, there is no In particular, in the case where both of the structural unit (1) and the epoxy group-containing structural unit are contained in one polymer molecule, the monomer is contained in all the structural units contained in the [A] polymer. The addition ratio is preferably 5% by mass to 70% by mass, more preferably 1 〇 by mass, ~60% by mass, particularly preferably 20% by mass to 50% by mass. On the other hand, it has a polymer molecule Structural unit (1), and in the case of a structural unit containing an epoxy group in another polymer molecule, 'the structural unit in a polymer molecule having the structural unit (1)-17- 201142515 (1) In terms of the content, the total structural unit contained in the polymer molecule is compared with the monomer addition ratio. Preferably, it is 40% by mass to 99% by mass. More preferably, it is 50% by mass to 9.8 % by mass. It is particularly preferably 55% by mass to 9.55% by mass. <The structural unit containing an epoxy group> [A] The polymer has the above structural unit (1) and also has an epoxy group-containing structural unit. The epoxy group-containing structural unit is a structural unit derived from a radical polymerizable epoxy group-containing monomer. The epoxy group may, for example, be an oxiranyl group (1,2-epoxy structure) or an oxycyclobutane group (1,3-epoxy structure). [A] a polymer in a molecule By having a structural unit containing an oxiranyl group or an oxycyclobutane group, the hardness of the hard film obtained from the positive-type radiation-sensitive composition can be improved, and the heat resistance can be further improved. Specific examples of the epoxy group-containing monomer of the structural unit include, for example, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, and methacrylic acid. -3,4-epoxybutyl ester, 3-methyl-3,4-epoxybutyl acrylate, 3-ethyl-3,4-methacrylic acid Oxybutyl acrylate, 5,6-epoxyhexyl acrylate, 5,6-epoxyhexyl methacrylate, 5-methyl-5,6-epoxyhexyl methacrylate, methacrylic acid - 5-ethyl·5,6-epoxyhexyl ester, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate-3,4-epoxy methacrylate Cyclohexyl ester, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexyl propyl methacrylate, A 3,4-epoxycyclohexyl-18- 201142515 butyl acrylate, 3,4-epoxycyclohexyl methacrylate, epoxy cyclohexyl acrylate, 3,4-epoxycyclohexyl acrylate Base ester, epoxy cyclohexylethyl acrylate, 3,4-epoxycyclohexyl propyl acrylate, 3,4-epoxycyclohexyl butyl acid, 3,4-epoxycyclohexyl acrylate, etc. Ethylene oxide-based (meth)acrylic compound; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-ethylene Glycidyl ether, α-methyl-inter-B Vinylbenzyl glycidyl ethers such as benzyl glycidyl ether, benzyl-p-vinylbenzyl glycidyl ether; o-vinylphenyl glycidyl ether, m-vinylphenyl ketal ether, Vinylphenyl condensed ethers such as vinyl phenyl glycidyl ether; 3-(acryloxymethyl)oxycyclobutane, 3-(acryloxymethoxymethyloxybutane, 3-(Allyloxymethyl)-3-ethyloxocyclobutene 3-(acryloxymethyl)-3-phenyloxycyclobutane, 3-(2-propenyloxy)oxy ring Butane, 3-(2-propenyloxyethyl)-3-ethyloxocyclobutene 3-(2-propenyloxyethyl)-3-ethyloxycyclobutane, 3-(2-propene醯ethyl)-3-phenyloxycyclobutane, 3-(methacryloxymethyl)oxycyclobutane, 3-(methylpropionylmethyl)-3-methyloxetane Alkane, 3-(methacryloxymethyl)-3oxycyclobutane, 3-(methacryloxymethyl)-3-phenyloxycyclobutane, methacryloxyloxy Oxycyclobutane, 3-(2-methylpropenyloxy)-3-ethyloxycyclobutane, 3-(2-methylpropenyloxyethyl)-3-ethenebutane , 3-(2 - A Propylene methoxyethyl)-3-phenyloxocyclobutane 3.4- 3.4-propenyl glyceryl benzyl α-methyl oleyl glycyrrhizin I )-3-alkane, ethane ethane, oxy oxime -ethyl 3-(2-ylethyloxy-19- 201142515 2-(acryloxymethyl)oxycyclobutane, 2-(acryloxymethyl)-2-methyloxetane , 2-(acryloxymethyl)-2-ethylcyclobutane, 2-(acryloxymethyl)-2-phenyloxycyclobutane, 2-(2-propenyloxy) Ethyl)oxycyclobutane, 2-(2-propenyloxyethyl)-2-ethylcyclobutane, 2-(2-propenyloxyethyl)-2-ethyloxetane Alkane, 2-(2-propenyloxyethyl)-2-phenyloxycyclobutane, 2-(methacryloxymethyl)oxycyclobutane, 2-(methacryloxyloxy) Methyl)-2-methyloxocyclobutane, 2-(methacryloxymethyl)-2-ethyloxycyclobutane, 2-(methacryloxymethyl)-2- Phenyloxycyclobutane, 2-(2-methylpropenyloxyethyl)oxycyclobutane, .2-(2-methylpropenyloxyethyl)-2-ethyloxycyclobutane , 2-(2-methylpropenyloxyethyl)-2-ethyloxocyclobutane, 2-(2- An (oxy)cycloalkyl group-containing (meth)acrylic compound such as methacryloxyethyl)-2-phenyloxycyclobutane or the like. The above epoxy group-containing structural unit may be used singly or in combination of two or more. Among the above epoxy group-containing monomers, from the viewpoints of copolymerization reactivity with other radical polymerizable monomers and developability of a positive-type radiation-linear composition, methyl propyl sulphonate is preferred. Vinegar, methylpropionic acid-2-methylglycidyl ester, methacrylic acid-3,4-epoxycyclohexyl ester, methyl propionate methyl hexyl epoxy ring

基 甲 基 氧 醯 烯 丙 基 甲 /(V 基 甲 基 氧 醯 烯 丙 基 甲 /IV - 3 、 烷 丁 環 氧 基 甲 烷 丁 環 氧 基 乙 只 言 而 量 含 的 元 單 構 結 的 基 氧 環 含 的 中 物 合 聚 TJ A rL 就 性 孰? 耐 的 望 希 所 等 膜 緣 絕 間 層 出 pa 擇 發 匕匕 厶目 是 要 元 單 構 結 有 含 中 子 分 物 合 聚 個 1 在 定 限 的 別基 特氧 有環 沒含 就與 -20- 201142515 的結構單元的情況下,相對於[A]聚合物中含有的全部的結 構單元’以單體的加入比計’較佳爲1 〇質量% ~ 6 〇質量% ’ 更佳爲1 5質量。〜5 5質量%,特佳爲2 〇質量5 〇質量%。 另一方面,在一個聚合物分子中具有結構單元(1),而 且在其他一個聚合物分子中具有含環氧基的結構單元的情 況下,就相對於具有含環氧基的結構單元的一個聚合物分 子中含有的全部結構單元之含環氧基的結構單元的含量而 言,以單體的加入比計’較佳爲1 〇質量%以上、8 0質量% 以下,更佳爲20質量%以上、70質量。以下,特佳爲25 質量%以上、60質量%以下。 &lt;其他結構單元&gt; 就提供其他結構單元的自由基聚合性單體而言,可以 列舉出具有羧基或其衍生物、羥基的自由基聚合性單體等。 就上述具有羧基或其衍生物的自由基聚合性單體而 言,可以列舉出丙烯酸、甲基丙烯酸、巴豆酸、2-丙烯醯 氧基乙基琥珀酸、2-甲基丙烯醯氧基乙基琥珀酸、2-丙烯 醯氧基乙基六氫鄰苯二甲酸、2-甲基丙烯醯氧基六氫鄰苯 二甲酸等一元羧酸; 馬來酸、富馬酸、檸康酸、中康酸、衣康酸等二元羧 酸; 上述二元羧酸的酸酐等。 ' 就上述具有羥基的自由基聚合性單體的例子而言,可 以列舉出: -21 - 201142515 丙烯酸-2-羥基乙基酯、丙烯酸-3-羥基丙基酯、丙烯酸 -4 -羥基丁基酯、丙烯酸-4-羥基甲基環己基甲基酯等丙烯酸 羥基烷基酯; 甲基丙烯酸_2-羥基乙基酯、甲基丙烯酸-3-羥基丙基 酯、甲基丙烯酸-4-羥基丁.基酯、甲基丙烯酸-5-羥基戊基 酯、甲基丙烯酸-6-羥基己基酯、甲基丙烯酸-4-羥基甲基-環己基甲基酯等甲基丙烯酸羥基烷基酯等。 這些具有羥基的自由基聚合性單體中,從和其他自由 基聚合性單體的共聚反應性以及得到的層間絕緣膜等的耐 熱性的觀點來看,較佳係丙烯酸-2-羥基乙基酯、丙烯酸-3-羥基丙基酯、丙烯酸_4_羥基丁基酯、甲基丙烯酸-2-羥基乙 基酯、甲基丙烯酸-4-羥基丁基酯、丙烯酸-4-羥基甲基-環 己基甲基酯、甲基丙烯酸-4-羥基甲基-環己基甲基酯。 就其他自由基聚合性單體的例子而言,可以列舉出·· 丙烯酸甲酯、丙烯酸異丙酯等丙烯酸烷基酯; 甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁 酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯等甲基丙 烯酸烷基酯; 丙烯酸環己酯、丙烯酸-2-甲基環己酯、丙烯酸三環 [5.2.1.02’6]癸-8·基酯、丙烯酸-2-(三環[5.2.1.02’6]癸-8-基 氧基)乙基酯、丙烯酸異萡基酯等丙烯酸脂環式烷基酯: 甲基丙烯酸環己酯、甲基丙烯酸-2-甲基環己酯、甲基 丙烯酸三環[5.2.1.02,0]癸-8-基酯、甲基丙烯酸-2-(三環 -22- 201142515 [5.2.1.02’6]癸-8-基氧基)乙基酯、甲基丙烯酸異萡基酯等甲 基丙烯酸脂環式烷基酯; 丙烯酸苯基酯、丙烯酸苄基酯等丙烯酸芳基酯和丙烯 酸芳烷基酯; 甲基丙烯酸苯基酯、甲基丙烯酸苄基酯等甲基丙烯酸 的芳基酯和甲基丙烯酸的芳烷基酯; 馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等二元 羧酸二烷基酯; 甲基丙烯酸四氫糠基酯、甲基丙烯酸四氫呋喃基酯、 甲基丙烯酸四氫哌喃-2-甲基酯等含有1個氧原子的5元雜 環的甲基丙烯酸酯和不飽和6元雜環的甲基丙烯酸酯; 4 -甲基丙烯醯氧基甲基-2 -甲基-2 -乙基-1,3-二氧戊 環、4 -甲基丙烯醯氧基甲基-2-甲基-2 -異丁基-1,3 -二氧k 環、4_甲基丙烯醯氧基甲基-2-環己基-1,3-二氧戊環等含有 兩個氧原子的不飽和5元雜環的甲基丙烯酸酯; 4-丙烯醯氧基甲基-2,2-二甲基-1,3-二氧戊環、4-丙烯 醯氧基甲基-2-甲基-2-乙基-1,3-二氧戊環、4-丙烯醯氧基甲 基-2,2-二乙基-1,3-二氧戊環、4-丙烯醯氧基甲基-2-甲基- 2-異丁基-1,3-二氧戊環、4-丙烯醯氧基甲基-2-環戊基-1,3-二 氧戊環、4_丙烯醯氧基甲基-2-環己基-1,3-二氧戊環、4-丙 烯酿氧基乙基-2-甲基-2-乙基-1,3-二氧戊環、4-丙烯醯氧基 丙基-2-甲基-2-乙基-1,3-二氧戊環、4-丙烯醯氧基丁基_2· 甲基-2-乙基-1,3-二氧戊環等含有兩個氧原子的不飽和5元 雜環的丙烯酸酯; -23- 201142515 苯乙烯、α_甲基苯乙烯、間甲基苯乙烯、對甲基苯乙 烯、對甲氧基苯乙烯、4_異丙烯基苯酚等乙烯基芳香族化 合物; Ν-苯基馬來醯亞胺、Ν_環己基馬來醯亞胺、Ν-苄基馬 來醯亞胺、Ν-琥珀醯亞胺基-3-馬來醯亞胺苯甲酸酯' Ν-琥 珀醯亞胺基-4-馬來醯亞胺丁酸酯、Ν-琥珀醯亞胺基-6-馬來 醯亞胺己酸酯、Ν -琥珀醯亞胺基-3-馬來醯亞胺丙酸酯、 Ν-(9-吖啶基)馬來醯亞胺等Ν-位取代的馬來醯亞胺; 1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等共軛 二烯類化合物; 丙烯腈、甲基丙烯腈、丙烯醯胺、甲基丙烯醯胺、氯 乙烯、氯化亞乙烯、乙酸乙烯酯等其他不飽和化合物。 從和具有上述反應官能基的自由基聚合性單體的共聚 反應性以及該正型感放射線性組成物的顯影性的方面來 看,這些其他自由基聚合性單體中,較佳係苯乙烯、4·異 丙烯基苯酚、甲基丙烯酸三環[5·2·1·02’6]癸_8·基酯、甲基 丙烯酸四氫糠基酯、i,3-丁二烯、4·丙烯醯氧基甲基-2_甲 基-2 -乙基-1,3 -二氧戊環、N -環己基馬來醯亞胺、N -苯基馬 來醯亞胺、甲基丙嫌酸节基醋等。 [A]聚合物的GPC(凝膠滲透色譜法)得到的聚苯乙烯換 算的質量平均分子量(以下,也稱作「Mw」)較佳爲 2.0χ103〜l.〇xl〇5,更佳爲 5.〇xl〇3〜5·〇χ1〇4° 藉由使[A]聚 合物的Mw爲上述範圍’可以提高該正型感放射線性組成 物的放射線靈敏度和鹼顯影性。 -24- 201142515 另外,[A]聚合物的GPC (凝膠滲透色譜法)得到的聚苯 乙烯換算的數量平均分子量(以下,也稱作「Μη」)較佳爲 2.〇xl〇3〜l_〇xl〇5’更佳爲5.0Χ103〜5.0χ104。藉由使共聚物 的Μη爲上述範圍,可以提高該正型感放射線性組成物的 塗膜硬化時的硬化反應性。 此外,[Α]聚合物的分子量分佈「Mw/Mn」較佳爲3.0 以下’更佳爲2.6以下。藉由使[A]聚合物的Mw/Mn爲3.0 以下’可以提高得到的層間絕緣膜的顯影性。含有[A]聚合 物的該正型感放射線性組成物在顯影時,沒有產生顯影殘 留’可以容易地形成所希望的圖案形狀。 ΙΑ]聚合物的製造方法&gt; [Α]聚合物可以藉由含縮醛結構的單體、含環氧基的單 體、提供其他結構單元的單體的自由基共聚而製造。在製 造在同一聚合物分子中包含結構單元(1)和含環氧基的結 構單兀這兩者的[Α]聚合物時,使用至少包含含縮醛結構的 單體和含環氧基的單體的混合物共聚即可。另一方面,在 製造在一個聚合物分子中具有結構單元(1),而在和其不同 的聚合物分子中具有含環氧基的結構單元的[Α]聚合物 時,使至少包含含縮醛結構的單體的聚合性溶液自由基聚 合’得到具有結構單元(丨)的聚合物分子,另外使至少包含 含環氧基單體的聚合性溶液自由基聚合,得到具有含環氧 基的結構單元的聚合物分子,最後將兩者混合形成聚合 物即可。 -25- 201142515 就在製造[A]聚合物的聚合反應中使用的溶劑 以列舉出例如醇類、醚類、二醇醚、乙二醇烷基醚 二乙二醇烷基醚、丙二醇單烷基醚、丙二醇單烷 酷、丙二醇單烷基醚丙酸酯、芳烴類、酮類、其他 就這些溶劑而言,分別可以列舉出: 作爲醇類是例如甲醇、乙醇、苄醇、2 -苯基 苯基· 1 -丙醇等; 作爲醚類是例如四氫呋喃等; 作爲二醇醚是例如乙二醇單甲基醚、乙二醇 等; 作爲乙二醇烷基醚乙酸酯是例如甲基溶纖素 乙基溶纖素乙酸酯、乙二醇單丁基醚乙酸酯、乙 基醚乙酸酯等; 作爲二乙二醇烷基醚是例如二乙二醇單甲基 二醇單乙基醚、二乙二醇二甲基醚、二乙二醇二 二乙二醇乙基甲基醚等; 作爲丙二醇單烷基醚是例如丙二醇單甲基醚 單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等 作爲丙二醇單烷基醚乙酸酯是例如丙二醇單 酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚 丙二醇單丁基醚乙酸酯等; 作爲丙二醇單烷基醚丙酸酯是例如丙二醇單 酸酯、丙二醇單乙基醚丙酸酯、丙二醇單丙基醚 丙二醇單丁基醚丙酸酯等; 而言,可 乙酸酯、 基醚乙酸 酯類等。 乙醇、3- 單乙基醚 乙酸酯、 二醇單乙 醚、二乙 乙基醚、 甲基醚乙 乙酸酯、 甲基醚丙 丙酸酯、 -26- 201142515 作爲芳香族烴類是例如甲苯、二甲苯等; 作爲酮類是例如甲基乙基酮、環己酮、4 -羥基-4-甲基 -2-戊酮等; 作爲其他酯類是例如乙酸甲酯、乙酸乙酯、乙酸丙酯、 乙酸丁酯、2 -羥基丙酸乙酯、2 -羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥 基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、 3 -羥基丙酸甲酯、3·羥基丙酸乙酯、3 -羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、 甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙 氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧 基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基 乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙 酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙 酸甲酯、2 -甲氧基丙酸乙酯、2 -甲氧基丙酸丙酯、2 -甲氧基 丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2_乙氧 基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、 3-甲氧基丙酸甲酯、3 -甲氧基丙酸乙酯、3-甲氧基丙酸丙 酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸 乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙 酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基 丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧 基丙酸丙酯、3-丁氧基丙酸丁酯等酯類。 -27- 201142515 在這些溶劑中,較佳係乙二醇烷基醚乙酸酯、二乙二 醇烷基醚、丙二醇單烷基醚、丙二醇單烷基醚乙酸酯、甲 氧基乙酸丁酯,特佳係二乙二醇二甲基醚、二乙二醇乙基 甲基醚、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、甲氧 基乙酸丁酯。 就製造[A]聚合物的聚合反應中使用的聚合引發劑而 言,可以使用一般作爲自由基聚合引發劑之已知者。就自 由基聚合引發劑而言,可以列舉出例如: 2,2’-偶氮雙異丁腈、2,2'-偶氮雙-(2-甲基丙酸甲酯)、 2,2·-偶氮雙-(2,4-二甲基戊腈)、2,2’-偶氮雙- (4-甲氧基-2,4-二甲基戊腈)等偶氮化合物; 過氧化苯甲醯、過氧化月桂醯、過氧化三甲基乙酸第 三丁基酯、1,Γ-雙(第三丁基過氧化)環己烷等有機過氧化 物以及過氧化氫。 在使用過氧化物作爲自由基聚合引發劑時,可以將過 氧化物和還原劑一起形成氧化還原型引發劑。 在用於製造[Α]聚合物的聚合反應中’可以使用分子量 調節劑調節分子量。就分子量調節劑的具體例子而言,可 以列舉出: 氯仿、四溴化碳等鹵化烴類; 正己基硫醇、正辛基硫醇、正十二烷基硫醇、第三(十 二烷基)硫醇、锍基乙酸等硫醇類; 硫化二甲基黃原酸酯、二硫化二異丙基黃原酸酯等黃 原酸酯類; -28- 201142515 對蓋二烯、α-甲基苯乙烯二聚物等。 &lt;[Β]光酸產生劑&gt; [Β]光酸產生劑是藉由照射放射線產生酸的化合物。這 裏,就放射線而言,可以使用例如可見光線、紫外線、遠 紫外線、電子束、X放射線等。該正型感放射線性組成物 藉由含有[Β]光酸產生劑,可以發揮出正型的感放射線特 性。[Β]光酸產生劑只要是藉由照射放射線產生酸(例如, 羧酸、磺酸等)的化合物,就沒有特別的限定。就[Β]光酸 產生劑在該組成物中的含有形態而言,可以是後述這樣的 化合物的光酸產生劑(以下也稱爲[Β ]光酸產生劑)的形態, 也可以是以[Α]聚合物或其他聚合物的一部分而組合的光 酸產生基的形態,還可以是這兩種形態。 作爲[Β]光酸產生劑,可以列舉出肟磺酸酯化合物、鑰 鹽、磺醯亞胺化合物、含鹵化合物、二偶氮甲烷化合物、 颯化合物、磺酸酯化合物、羧酸酯化合物等,其中較佳係 肟磺酸酯化合物。 &lt;肟磺酸酯化合物&gt; •就上述聘擴酸醋化合物而言,較佳係含下述式(2)所示 的照磺酸酯基的化合物。 〇Methyl methoxy allylyl group / (V-methyl methallyl propyl group / IV - 3 , alkane butyl oxymethane butyl epoxide ethoxylate The TQ A rL of the nucleus contained in the ring is 孰 孰 望 望 所 所 所 等 等 等 等 等 等 pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa In the case of a structural unit of -20-201142515, the ratio of the monomeric ratio of the monomeric components contained in the [A] polymer is preferably 1 〇 mass% ~ 6 〇 mass% ' More preferably 1 5 mass. ~ 5 5 mass%, particularly preferably 2 〇 mass 5 〇 mass%. On the other hand, having a structural unit in one polymer molecule (1) And in the case where the other structural unit has an epoxy group-containing structural unit, the epoxy group-containing structure of all the structural units contained in one polymer molecule having the epoxy group-containing structural unit In terms of the content of the unit, the addition of the monomer The ratio is preferably 1% by mass or more and 80% by mass or less, more preferably 20% by mass or more, and 70% by mass. More preferably, it is preferably 25% by mass or more and 60% by mass or less. <Other structural units> The radically polymerizable monomer which provides another structural unit may, for example, be a radical polymerizable monomer having a carboxyl group or a derivative thereof, a hydroxyl group, etc. The above-mentioned radical polymerizable single having a carboxyl group or a derivative thereof The main body can be exemplified by acrylic acid, methacrylic acid, crotonic acid, 2-propenylmethoxyethyl succinic acid, 2-methylpropenyloxyethyl succinic acid, 2-propenyl methoxyethyl hexahydro a monocarboxylic acid such as phthalic acid or 2-methylpropenyloxy hexahydrophthalic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; An acid anhydride of a dicarboxylic acid, etc. ' As an example of the above-mentioned radical polymerizable monomer having a hydroxyl group, -21 - 201142515 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate , 4-hydroxybutyl acrylate, 4-hydroxymethylcyclohexyl acrylate Hydroxyalkyl acrylate such as ester; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxy methacrylate a hydroxyalkyl methacrylate such as amyl ester, -6-hydroxyhexyl methacrylate or 4-hydroxymethyl-cyclohexylmethyl methacrylate, etc. Among these radically polymerizable monomers having a hydroxyl group From the viewpoints of copolymerization reactivity with other radical polymerizable monomers and heat resistance of the obtained interlayer insulating film, etc., 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate are preferable. _4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, methacrylic acid-4 -Hydroxymethyl-cyclohexylmethyl ester. Examples of other radical polymerizable monomers include alkyl acrylates such as methyl acrylate and isopropyl acrylate; methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; , alkyl methacrylate such as dibutyl methacrylate or t-butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.02'6]癸-8-yl acrylate, acrylate alicyclic alkyl ester such as 2-(tricyclo[5.2.1.02'6] fluoren-8-yloxy)ethyl acrylate or isodecyl acrylate: methacrylic acid ring Hexyl ester, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.02,0]non-8-yl methacrylate, methacrylic acid-2-(tricyclic-22-201142515 [5.2. 1.02'6] 癸-8-yloxy)ethyl ester, isopropyl methacrylate such as isodecyl methacrylate; aryl acrylate such as phenyl acrylate or benzyl acrylate and acrylic acid Aralkyl ester; aryl ester of methacrylic acid such as phenyl methacrylate or benzyl methacrylate; and aralkyl ester of methacrylic acid; maleic acid a dicarboxylic acid dialkyl ester such as ethyl ester, diethyl fumarate or diethyl itaconate; tetrahydrofurfuryl methacrylate, tetrahydrofuranyl methacrylate, tetrahydropyran methacrylate - a 5-membered heterocyclic methacrylate containing 1 oxygen atom such as 2-methyl ester and an unsaturated 6-membered heterocyclic methacrylate; 4-methylpropenyloxymethyl-2-methyl- 2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxyk-cyclo, 4-methacryl Oxyloxymethyl-2-cyclohexyl-1,3-dioxolan and the like - dimethyl-1,3-dioxolane, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxymethyl -2,2-diethyl-1,3-dioxolane, 4-propenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-propene醯oxymethyl-2-cyclopentyl-1,3-dioxolan, 4-propenyloxymethyl-2-cyclohexyl-1,3-dioxolan, 4-propene oxy Ethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propane Iridinyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxybutyl-2-methyl-2-ethyl-1,3-di An acrylate having two oxygen atoms and an unsaturated 5-membered heterocyclic ring such as oxylan; -23- 201142515 styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxy a vinyl aromatic compound such as styrene or 4-propenylphenol; Ν-phenyl maleimide, Ν-cyclohexylmaleimide, Ν-benzyl maleimide, Ν-amber Imino-3-maleimide benzoate' Ν-amber quinone imido-4-maleimine butyrate, hydrazine-amber quinone imine-6-maleimide Anthracene-substituted maleimine such as hexanoate, hydrazone-amber quinone imine-3-maleimide propionate, Ν-(9-acridinyl)maleimide; a conjugated diene compound such as 3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene; acrylonitrile, methacrylonitrile, acrylamide, methacryl Other unsaturated compounds such as decylamine, vinyl chloride, vinylidene chloride, and vinyl acetate. Among these other radically polymerizable monomers, styrene is preferred from the viewpoints of copolymerization reactivity with the radical polymerizable monomer having the above reactive functional group and developability of the positive-type radiation-sensitive composition. 4·isopropenylphenol, tricyclo[5·2·1·02'6]癸_8·yl ester, tetrahydrofurfuryl methacrylate, i,3-butadiene, 4· Propylene methoxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, methyl propylene Acid-based vinegar and so on. The polystyrene-equivalent mass average molecular weight (hereinafter, also referred to as "Mw") obtained by GPC (gel permeation chromatography) of [A] polymer is preferably 2.0 χ 103 〜 l. 〇 xl 〇 5, more preferably 5. 〇xl〇3 to 5·〇χ1〇4° The radiation sensitivity and alkali developability of the positive-type radiation-sensitive composition can be improved by making the Mw of the [A] polymer into the above range. In addition, the polystyrene-equivalent number average molecular weight (hereinafter, also referred to as "Μη") obtained by GPC (gel permeation chromatography) of [A] polymer is preferably 2. 〇xl 〇 3~ L_〇xl〇5' is preferably 5.0Χ103~5.0χ104. By setting the Μη of the copolymer to the above range, the curing reactivity at the time of hardening of the coating film of the positive-type radiation-sensitive composition can be improved. Further, the molecular weight distribution "Mw/Mn" of the [Α] polymer is preferably 3.0 or less', more preferably 2.6 or less. The developability of the obtained interlayer insulating film can be improved by making the Mw/Mn of the [A] polymer 3.0 or less. The positive-type radiation-sensitive composition containing the [A] polymer can be easily formed into a desired pattern shape at the time of development. ΙΑ]Method for Producing Polymer&gt; [Α] The polymer can be produced by radical copolymerization of a monomer having an acetal structure, an epoxy group-containing monomer, and a monomer providing another structural unit. In the case of producing a [Α] polymer comprising both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule, a monomer containing at least an acetal structure and an epoxy group-containing polymer are used. The mixture of monomers can be copolymerized. On the other hand, when a [Α] polymer having a structural unit (1) in one polymer molecule and having an epoxy group-containing structural unit in a polymer molecule different therefrom is used, at least a shrinkage-containing polymer is included. Polymerizable solution radical polymerization of a monomer having an aldehyde structure to obtain a polymer molecule having a structural unit (丨), and further radical polymerization of a polymerizable solution containing at least an epoxy group-containing monomer to obtain an epoxy group-containing polymer The polymer molecules of the structural unit are finally mixed to form a polymer. -25- 201142515 The solvent used in the polymerization for producing the [A] polymer is exemplified by, for example, an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether diethylene glycol alkyl ether, a propylene glycol monoalkane. Examples of the solvent include, for example, methanol, ethanol, benzyl alcohol, and 2-benzene. The alcohols are, for example, methanol, ethanol, benzyl alcohol, and 2-benzene. Examples of the ether are, for example, tetrahydrofuran; the glycol ether is, for example, ethylene glycol monomethyl ether, ethylene glycol or the like; and the ethylene glycol alkyl ether acetate is, for example, a Base cellosolve ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethyl ether acetate, etc.; as diethylene glycol alkyl ether is, for example, diethylene glycol monomethyl Alcohol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethylene glycol ethyl methyl ether, etc.; as propylene glycol monoalkyl ether is, for example, propylene glycol monomethyl ether monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, etc. as propylene glycol monoalkyl ether acetate are, for example, propylene glycol monoester, C Glycol monoethyl ether acetate, propylene glycol monopropyl ether propylene glycol monobutyl ether acetate, etc.; as propylene glycol monoalkyl ether propionate, for example, propylene glycol monoester, propylene glycol monoethyl ether propionate, Propylene glycol monopropyl ether propylene glycol monobutyl ether propionate or the like; in terms of, it may be an acetate, a vinyl acetate or the like. Ethanol, 3-monoethyl ether acetate, diol monoethyl ether, diethyl ether, methyl ether acetic acid acetate, methyl ether propyl propionate, -26- 201142515 as aromatic hydrocarbons, for example Toluene, xylene, etc.; as a ketone, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.; as other esters, for example, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, glycolic acid Ester, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxyl Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid Methyl ester, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, propyl acetoxyacetate Ester, methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, Butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, Esters such as 3-butoxypropionic acid butyl ester. -27- 201142515 Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, methoxyacetate are preferred. Ester, particularly preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl methoxyacetate. As the polymerization initiator used in the polymerization for producing the [A] polymer, those generally known as radical polymerization initiators can be used. The radical polymerization initiator may, for example, be: 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2-methylpropionate), 2,2· -Azo compound such as azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); An organic peroxide such as benzamidine, lauric acid peroxide, tributyl butyl peroxyacetate, 1, bismuth-bis(t-butylperoxy)cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide and the reducing agent may be combined to form a redox type initiator. In the polymerization for producing a [Α] polymer, a molecular weight regulator can be used to adjust the molecular weight. Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and third (dodecane); Mercaptans such as mercaptan, mercaptoacetic acid; xanthates such as dimethyl xanthate sulfide and diisopropyl xanthate disulfide; -28- 201142515 for capadiene, α- Methylstyrene dimer, and the like. &lt;[Β] Photoacid generator&gt; [Β] The photoacid generator is a compound which generates an acid by irradiation with radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray radiation or the like can be used. The positive-type radiation-radiating composition can exhibit a positive radiation-sensing property by containing a [Β] photo-acid generator. [Β] The photoacid generator is not particularly limited as long as it is a compound which generates an acid (for example, a carboxylic acid, a sulfonic acid, or the like) by irradiation with radiation. The form of the photoacid generator in the composition may be in the form of a photoacid generator (hereinafter also referred to as a [Β] photoacid generator) of a compound described later, or may be [Α] The form of the photoacid generating group combined with a part of the polymer or other polymer may also be the two forms. Examples of the [Β] photoacid generator include an oxime sulfonate compound, a key salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a ruthenium compound, a sulfonate compound, a carboxylic acid ester compound, and the like. Among them, a sulfonate compound is preferred. &lt;Anthracene sulfonate compound&gt; The compound of the above-mentioned formula (2) is preferably a compound containing a sulfonate group represented by the following formula (2). 〇

\ II Ο — Ν— Ο — S — R Βΐ\ II Ο — Ν — Ο — S — R Βΐ

/ II (2) 基或芳基,這些基的氫 〇 (在式(2)中,RB1是烷基、 原子的一部分或全部可以被取代基取代) •29- 201142515 就RB1的烷基而言’較佳爲碳原子數爲1〜10的直鏈或 支鏈的烷基。RB1的烷基可以被碳原子數爲1〜10的烷氧基 或脂環基(包括7,7-二甲基-2-氧合降萡基等包含橋鍵的脂 環基,較佳係雙環烷基等)取代。就RB1的芳基而言,較佳 係碳原子數爲6〜11的芳基,更佳爲苯基或萘基。RB1的芳 基可以被碳原子數爲1〜5的烷基、烷氧基或鹵原子取代。 含有上述式(2)所示的肟磺酸酯基的上述化合物更佳 爲下述式(3)所示的肟磺酸酯化合物。 &lt;X)m/ II (2) aryl or aryl, hydroquinone of these groups (in formula (2), RB1 is an alkyl group, a part or all of an atom may be substituted by a substituent) • 29- 201142515 For the alkyl group of RB1 'It is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of RB1 may be an alkoxy group or an alicyclic group having a carbon number of 1 to 10 (including an alicyclic group containing a bridge bond such as a 7,7-dimethyl-2-oxoanthracene group, preferably a system Substituted by a bicycloalkyl group or the like. The aryl group of RB1 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of RB1 may be substituted with an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms. The above compound containing the oxime sulfonate group represented by the above formula (2) is more preferably an oxime sulfonate compound represented by the following formula (3). &lt;X)m

B1 Ο (3) 在上述式(3)中,RB1和上述式(2)中的RB1的說明的定 義相同。X是烷基、烷氧基或鹵原子。m是0〜3的整數。m 爲2或3時,多個X可以相同,也可以不同。作爲X的烷 基較佳爲碳原子數爲1~4的直鏈或支鏈的烷基。 作爲X的院氧基較佳爲碳原子數爲1〜4的直鏈或支鏈 的烷氧基。作爲x的鹵原子較佳爲氯原子或氟原子。m較 佳爲0或1。尤其,在上述式(3)中,較佳係m是1,X是 甲基,X的取代位置是鄰位的化合物。 就肟磺酸酯化合物的具體例子而言,可以列舉出例如 下述式(3-i)〜(3-v)分別表示的化合物(3-i)、化合物(3_ii)、 化合物(3-iii)、化合物(3_iv)和化合物O-v)等。 -30- 201142515B1 Ο (3) In the above formula (3), the definitions of RB1 and RB1 in the above formula (2) are the same. X is an alkyl group, an alkoxy group or a halogen atom. m is an integer of 0 to 3. When m is 2 or 3, multiple Xs may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group of X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as x is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. Particularly, in the above formula (3), it is preferred that the compound m is 1, X is a methyl group, and the substitution position of X is an ortho-position compound. Specific examples of the oxime sulfonate compound include, for example, a compound (3-i), a compound (3_ii), and a compound (3-iii) represented by the following formulas (3-i) to (3-v), respectively. ), the compound (3_iv) and the compound Ov) and the like. -30- 201142515

SS

O N—O—S —n-C3H7 II (3]) oO N—O—S —n-C3H7 II (3]) o

N—O —— S —— CH2 II o s oN-O —— S —— CH2 II o s o

s N—O — S —n-C8Hv (3-ii) II os N—O — S —n-C8Hv (3-ii) II o

(3-iv)(3-iv)

N—-0 — S — n_C8H CH-, CN 〇N—-0 — S — n_C8H CH-, CN 〇

II (3-v)II (3-v)

O 它們可以單獨或組合兩種以上使用’也可以和作爲 成分的其他光酸產生劑組合使用。上述化合物(3_i)[(5_g 擴醯氧亞胺基- 5H-噻吩_2·亞基)-(2_甲基苯)乙腈]、化2 (3-ii)[(5H-辛基磺醯氧亞胺基·5η_噻吩.2_ 迎基)-(2 -甲_ 乙腈]、化合物(3 - i i i)[(樟腦磺酿氧亞晚甘 此妝基-5H -噻吩-2 基)-(2-甲基苯)乙腈]、化合物(3_iv) 對甲苯磺醯氧3 -31- 201142515 基- 5H-噻吩-2-亞基)-(2-甲基苯)乙腈]以及化合物(3-v)[(5_ 辛基磺醯氧亞胺基-(4-甲氧基苯)乙腈]均可藉由市售商品 而得到。 &lt;鑰鹽&gt; 就鍮鹽而言,可以例舉二苯基碘鎗鹽、三苯基鏑鹽、 鏑鹽、苯并噻唑鐺鹽、四氫噻吩鑰鹽。 就二苯基碘鑰鹽而言,可以列舉例如二苯基碘鑰四氟 硼酸鹽、二苯基碘鑰六氟磷酸鹽、二苯基碘鑰六氟砷酸鹽、 二苯基碘鑰三氟甲磺酸鹽、二苯基碘鑰三氟乙酸鹽、二苯 基碘鍮-對甲苯磺酸鹽、二苯基碘鑰丁基參(2,6-二氟苯基) 硼酸鹽、4-甲氧基苯基-苯基碘鑰四氟硼酸鹽、雙(4-第三丁 基苯基)碘鑰四氟硼酸鹽、雙(4-第三丁基苯基)碘鑰六氟砷 酸鹽、雙(4_第三丁基苯基)碘鎗三氟甲磺酸鹽、雙(4-第三 丁基苯基)碘鎗三氟乙酸鹽、雙(4-第三丁基苯基)碘鑰-對甲 苯磺酸鹽、雙(4-第三丁基苯基)碘鐺樟腦磺酸鹽等。 就三苯基毓鹽而言,可以列舉例如三苯基毓三氟甲磺 酸鹽、三苯基毓樟腦磺酸鹽、三苯基鏑四氟硼酸鹽、三苯 基毓三氟乙酸鹽、三苯基锍-對甲苯磺酸鹽、三苯基鏑丁基 參(2,6-二氟苯基)硼酸鹽等。 就锍鹽而言,可以列舉例如烷基鏑鹽、苄基鏑鹽、二 苄基锍鹽、經取代的苄基锍鹽等。 ‘就烷基鏑鹽而言,可以列舉例如4-乙醯氧基苯基二甲 基锍六氟銻酸鹽、4-乙醯氧基苯基二甲基锍六氟砷酸鹽、 -32- 201142515 二甲基-4-(苄氧羰基氧基)苯基锍六氟銻酸鹽、二甲基 -4-(苯甲醯氧基)苯基毓六氟銻酸鹽、二甲基- 4-(苯甲醯基 氧基)苯基锍六氟砷酸鹽、二甲基-3-氯-4-乙醯氧基苯基锍 六氟銻酸鹽等; 就苄基锍鹽而言,可以列舉例$苄基-4-羥基苯基甲基 锍六氟銻酸鹽、苄基-4-羥基苯基甲基鏟六氟磷酸鹽、4-乙 醯氧基苯基苄基甲基鏑六氟銻酸鹽、苄基-4-甲氧基苯基甲 基锍六氟銻酸鹽、苄基-2-甲基-4-羥基苯基甲基锍六氟銻酸 鹽、苄基-3-氯-4-羥基苯基甲基锍六氟砷酸鹽、4-甲氧基苄 基-4-羥基苯基甲基锍六氟磷酸鹽等; 就二苄基毓鹽而言,可以列舉例如二苄基-4-羥基苯基 锍六氟銻酸鹽、二苄基-4-羥基苯基锍六氟磷酸鹽、4-乙醯 氧基苯基二苄基毓六氟銻酸鹽、二苄基-4-甲氧基苯基锍六 氟銻酸鹽、二苄基-3-氯-4-羥基苯基锍六氟砷酸鹽、二苄基 _3_甲基-4-羥基-5-第三丁基苯基锍六氟銻酸鹽、苄基-4-甲 氧基苄基-4-羥基苯基锍六氟磷酸鹽等; 就經取代的苄基锍鹽而言,可以列舉例如對氯苄基-4-羥基苯基甲基毓六氟銻酸鹽、對硝基苄基-4-羥基苯基甲基 锍六氟銻酸鹽、對氯苄基-4-羥基苯基甲基锍六氟磷酸鹽、 對硝基苄基-3-甲基-4-羥基苯基甲基锍六氟銻酸鹽、3,5-二 氯苄基-4-羥基苯基甲基锍六氟銻酸鹽、鄰氯苄基-3-氯-4-羥基苯基甲基毓六氟銻酸鹽等。 -33- 201142515 就苯并噻唑鑰鹽而言,可以列舉例如3 -苄基苯并噻唑 鑰六氟銻酸鹽、3-苄基苯并噻唑鑰六氟磷酸鹽、3-苄基苯 并噻唑鑰四氟硼酸鹽、3-(對甲氧基苄基)苯并噻唑鏺六氟銻 酸鹽、3-苄基-2-甲基硫苯并噻唑鑰六氟銻酸鹽、3-苄基- 5-氯苯并噻唑鑰六氟銻酸鹽等。 就四氫噻吩鏺鹽而言,可以列舉例如4,7-二-正丁氧基 -萘四氫噻吩鎩三氟甲磺酸鹽、1_(4-正丁氧基萘-1-基)四氫 噻吩.鑰三氟甲磺酸鹽、1-(4-正丁氧基萘-1-基)四氫噻吩鑰 九氟正丁磺酸鹽、1-(4 -正丁氧基萘-1-基)四氫噻吩鑰 -1,1,2,2-四氟-2-(降萡烯-2-基)乙磺酸鹽、1-(4-正丁氧基萘 -1-基)四氫噻吩鎗- 2-(5-第三丁氧基羰基氧基雙環[2.2.1]庚 _2_基)-1,1,2,2-四氟乙磺酸鹽、1-(4-正丁氧基萘-1-基)四氫 噻吩鑰-2-(6-第三丁氧基羰基氧基雙環[2·2.1]庚-2-基)-1,1,2,2-四氟乙磺酸鹽。 &lt;磺醯亞胺化合物&gt; 就磺醯亞胺化合物而言,可以列舉例如Ν-(三氟甲基磺 醯氧基)琥珀醯亞胺、Ν-(樟腦磺醯氧基)琥珀醯亞胺、Ν-(4-甲基苯基磺醯氧基)琥珀醯亞胺、Ν-(2-三氟甲基苯基磺醯 氧基)琥珀醯亞胺、Ν-(4-氟苯基磺醯氧基)琥珀醯亞胺、 Ν-(三氟甲基磺醯氧基)鄰苯二甲醯亞胺、Ν-(樟腦磺醯氧基) 鄰苯二甲醯亞胺、Ν-(2-三氟甲基苯基磺醯氧基)鄰苯二甲 醯亞胺、Ν-(2-氟苯基磺醯氧基)鄰苯二甲醯亞胺、Ν-(三氟 甲基磺醯氧基)二苯基馬來醯亞胺、Ν-(樟腦磺醯氧基)二苯 -34- 201142515 基馬來醯亞胺、N-(4 -甲基苯基磺醯氧基)二苯基馬來醯亞 胺、N-(2-三氟甲基苯基磺醯氧基)二苯基馬來醯亞胺、N-(4-氟苯基磺醯氧基)二苯基馬來醯亞胺、N-(4_氟苯基磺醯氧 基)二苯基馬來醯亞胺、N-(苯基磺醯氧基)雙環[2·2·1]庚- 5-烯-2,3-二甲醯亞胺、N-(4_甲基苯基磺醯氧基)雙環[2.2.1] 庚-5-烯-2,3 -二甲醯亞胺、N-(三氟甲磺醯氧基)雙環[2.2.1] 庚-5-烯-2,3 -二甲醯亞胺、N-(九氟丁磺醯氧基)雙環[2.2.1] 庚-5-烯-2,3 -二甲醯亞胺、N-(樟腦磺醯氧基)雙環[2.2.1]庚 -5 -烯-2,3 -二甲醯亞胺、Ν·(樟腦磺醯氧基)-7_氧雜雙環 [2.2.1]庚-5-烯-2,3 -二甲醯亞胺、N-(三氟甲基磺醯氧基)_7_ 氧雜雙環[2.2.1]庚-5-烯-2,3 -二甲醯亞胺、N-(4 -甲基苯基磺 醯氧基)雙環[2·2·1]庚-5-烯_2,3_二甲醯亞胺、N-(4-甲基苯 基磺醯氧基氧雜雙環I:2.2·1]庚-5-烯·2,3_二甲醯亞胺、 &gt;1_(2-三氟甲基苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二甲 醯亞胺、N-(2 -三氟甲基苯基磺醯氧基)-7 -氧雜雙環[2.2.1] 庚-5-烯-2,3 -二甲醯亞胺、N-(4 -氟苯基磺醯氧基)雙環[2.2.1] 庚-5-烯-2,3 -二甲醯亞胺、Ν-(4·氟苯基磺醯氧基)-7 -氧雜雙 環[2.2.1]庚-5-烯-2,3 -二甲醯亞胺、N-(三氟甲基磺醯氧基) 雙環‘[2.2.1]庚烷-5,6 -氧基-2,3 -二甲醯亞胺、N-(樟腦磺醯氧 基)雙環[2.2.1]庚烷-5,6 -氧基-2,3 -二甲醯亞胺、N-(4 -甲基 苯基磺醯氧基)雙環[2.2.丨]庚烷-5,6_氧基-2,3_二甲醯亞 胺、N-(2-三氟甲基苯基磺醯氧基)雙環[2.2.1]庚烷-5,6_氧 基-2,3 -二甲醯亞胺、N-(4·氟苯基磺醯氧基)雙環[2.2.1]庚 -35- 201142515 烷-5,6 -氧基-2,3 -二甲醯亞胺、N-(三氟甲基磺醯氧基)萘基 二甲醯亞胺、(樟腦磺醯氧基)萘基二甲醯亞胺、Ν·(4·甲 基苯基磺醯氧基)萘基二甲醯亞胺、N-(苯基磺醯氧基)萘基 二甲醯亞胺、N_( 2-三氟甲基苯基磺醯氧基)萘基二甲醯亞 胺、N-(4-氟苯基磺醯氧基)萘基二甲醯亞胺、N-(五氟乙基 磺醯氧基)萘基二甲醯亞胺、N-(七氟丙基磺醯氧基)萘基二 甲醯亞胺、N·(九氟丁基磺醯氧基)萘基二甲醯亞胺、N_(乙 基磺醯氧基)萘基二甲醯亞胺、N-(丙基磺醯氧基)萘基二甲 醯亞胺、N-(丁基磺醯氧基)萘基二甲醯亞胺、N-(戊基磺醯 氧基)萘基二甲醯亞胺、N-(己基磺醯氧基)萘基二甲醯亞 胺、N-(庚基磺醯氧基)萘基二甲醯亞胺、N-(辛基磺醯氧基) 萘基二甲醯亞胺、N-(壬基磺醯氧基)萘基二甲醯亞胺等。 (含鹵化合物) 就含鹵化合物而言,可以列舉例如含鹵烷基的烴化合 物、含鹵烷基的雜環化合物等。 (重氮甲烷化合物) 就重氮甲烷化合物而言,可以列舉例如雙(三氟甲基磺 醯)重氮甲烷、雙(環己基磺醯)重氮甲烷、雙(苯基磺醯)重 氮甲烷、雙(對三磺醯)重氮甲烷、雙(2,4-二甲苯基磺醯)重 氮甲烷、雙(對氯苯基磺醯)重氮甲烷、甲基磺醯-對甲苯磺 醯重氮甲烷、環己基磺醯(1,1-二甲基乙基磺醯)重氮甲烷、 雙(1,1-二甲基乙基磺醯)重氮甲烷、苯基磺醯(苯甲醯)重氮 甲烷等。 -36- 201142515 (颯化合物) 就颯化合物而言,可以列舉例如β-酮颯化合物、β-擴 醯颯化合物、二芳基二颯化合物等。 (磺酸酯化合物) 就磺酸酯化合物而言,可以列舉例如烷基磺酸酯、_ 烷磺酸酯、芳基磺酸酯、亞胺基磺酸酯等。 (羧酸酯化合物) 就羧酸酯化合物而言,可以列舉例如羧酸鄰硝基苄基 酯。 在這些[Β]光酸產生劑中,從放射線靈敏度、溶解性的 角度來看,較佳係肟磺酸酯化合物,更佳係含上式(2)表示 的肟磺酸酯基的化合物,進一步更佳係上式(3)表示的肟擴 酸酯化合物,其中特佳係市售商品可購買的[(5-丙基磺醯氧 亞胺基- 5Η-噻吩-2-亞基)-(2-甲基苯)乙腈]、[(5Η-辛基磺醯 氧亞胺基- 5H -噻吩-2_亞基)-(2 -甲基苯)乙腈]、[(5 -對甲苯 磺醯氧亞胺基- 5H-噻吩-2-亞基)-(2-甲基苯)乙腈]、[(樟腦 磺醯氧亞胺基-5H-噻吩-2-亞基)-(2-甲基苯)乙腈]、[(5-辛 基磺醯氧亞胺基-(4-甲氧基苯)乙腈]。另外,亦較佳係鑰 鹽,更佳係四氫噻吩鑰鹽和苄基鏑鹽,4,7-二-正丁氧基-1-萘四氫噻吩鑰鹽三氟甲烷磺酸鹽和苄基-4-羥基苯基甲基 锍六氟磷酸鹽。 [B]光酸產生劑可以單獨使用一種,也可以兩種以上混 合使用。該組成物中的[B]光酸產生劑的含量,相對於1〇〇 -37- 201142515 質量份[A]聚合物,較佳爲0.1質量份〜10質量份,更 1質量份~5質量份。若[B]光酸產生劑的含量在上述範 則可使該組成物的放射線靈敏度最佳化,可以維持透 的同時,形成層間絕緣膜等。 &lt; [C]化合物&gt; 在該正型感放射線性組成物中,爲了防止自由基 氧化物導致化合物的鍵的分解,而含有[C]化合物。就 化合物而言,可以例舉具有受阻酚結構的化合物以及 受阻胺結構的化合物等的自由基捕獲劑,以及具有亞 烷酯結構的化合物以及具有硫醚結構的化合物等的過 物分解劑等。 藉由含有上述[C]化合物,曝光時或加熱時發生的 基的捕獲,或者因氧化生成的過氧化物的分解變得可 因此可防止該自由基或過氧化物導致的聚合物分子的 分解。其結果,由該組成物得到的層間絕緣膜等能夠 優異的耐光性和耐熱性。另外,該組成物中,由於採 有上述特定結構的自由基捕獲劑或過氧化物分解劑作 化合物,所以即使添加它們,也在能夠保持該組成物 放射線度在高水準的同時,防止由該組成物得到的層 緣膜等的透光率以及電壓保持率的降低。 就具有上述受阻酚結構的化合物而言,可以列舉 新戊四醇肆[3-(3, 5-二第三丁基-4-羥基苯基)丙酸酯]、 伸乙基雙[3-(3,5_二第三丁基-4-羥基苯基)丙酸酯]、十 佳爲 圍, 明性 或過 這種 具有 磷酸 氧化 自由 能, 鍵的 發揮 用具 爲[C] 的感 間絕 例如 硫二 八烷 -38- 201142515 基- 3-(3,5-二第三丁基_4_羥基苯基)丙酸酯、參- (3, 5-二第三 丁基·4_羥基苄基)異氰酸酯、1,3,5-三甲基-2,4,6-參(3,5-二 第三丁基-4-羥基苄基)苯、N,N'-己-1,6-二基雙[3-(3,5-二第 三丁基-4-羥基苯基丙醯胺)]、3,3',3',5’,5|,5'-六第三丁基 ^,&amp;',&amp;|-(均三甲苯-2,4,6-三基)三對甲酚、4,6-雙(辛硫基甲 基)-鄰甲酚、4,6-雙(十二烷硫基甲基)-鄰甲酚、亞乙基雙(氧 亞乙基)雙[3-(5-第三丁基-4-羥基-間甲苯基)丙酸酯]、六亞 甲基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、1,3,5-參 [(4-第三丁基-3-羥基-2,6-二甲苯基)甲基]-I,3,5·三阱 -2,4,6-(111,3^1,51^-三酮、2,6-二第三丁基-4-(4,6-雙(辛硫 基)-1,3,5-三阱-2-基胺)苯酚。 作爲上述受阻酚結構的化合物,其市售商品可以列舉 例如(股)ADEKA生產的 Adekastab AO-20、Adekastab AO-30、 Adekastab AO-40 ' Adekastab AO-50 ' Adekastab AO-60 ' Adekastab AO-70 ' Adekastab AO-80 ' Adekastab AO-3 3 0 ' 住友化學(股)生產 sumilizerGM、sumilizerGS、sumilizer MDP-S、 sumilizer BBM-S、 sumilizer WX-R、 sumilizer GA-80 ; Ciba Japan(股)生產的 IRGANOX 1010、IRGANOX 1 03 5 ' IRGANOX 1 076、IRGANOX 1 098、IRGANOX 1135、 IRGANOX 1 3 3 0、IRGANOX 1 726、IRGANOX 1 42 5WL、 IRGANOX 1 520L 'IRGANOX 245 'IRGANOX 259 'IRGANOX 3114、IRGANOX 565、IRGAMOD 295 ;(股)API Corporation 生產的 Yoshinox BHT、Yoshinox BB、Yoshinox 2246G、 -39- 201142515O These may be used singly or in combination of two or more kinds, or may be used in combination with other photoacid generators as a component. The above compound (3_i) [(5_g oxime oxyimino-5H-thiophene-2.subunit)-(2-methylphenyl)acetonitrile], 2 (3-ii)[(5H-octylsulfonate) Oxyiminyl·5η_thiophene. 2_ fenyl)-(2-methyl-acetonitrile), compound (3 - iii) [( camphor sulfonate, oxy-oxygen, hydrazine, 5-H-thiophen-2-yl)-( 2-methylbenzene)acetonitrile], compound (3_iv) p-toluenesulfonyloxy 3 -31- 201142515 yl-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile] and compound (3-v [(5_octylsulfonyloxyimino-(4-methoxyphenyl)acetonitrile] can be obtained by a commercially available product. &lt;Key Salt&gt; As the onium salt, diphenyl can be exemplified a iodine salt, a triphenyl sulfonium salt, a sulfonium salt, a benzothiazolium salt, a tetrahydrothiophene key salt. Examples of the diphenyl iodine salt include diphenyl iodine tetrafluoroborate, and Phenyl iodine hexafluorophosphate, diphenyl iodine hexafluoroarsenate, diphenyl iodine triflate, diphenyl iodine trifluoroacetate, diphenyl iodonium - p-toluene Sulfonate, diphenyl iodide butyl succinate (2,6-difluorophenyl) borate, 4-methoxyphenyl-phenyl iodide tetrafluoroborate Bis(4-tert-butylphenyl) iodine tetrafluoroborate, bis(4-tert-butylphenyl) iodine hexafluoroarsenate, bis(4_t-butylphenyl) iodine gun Triflate, bis(4-t-butylphenyl) iodine trifluoroacetate, bis(4-t-butylphenyl) iodine-p-toluenesulfonate, double (4- Tributylphenyl) iodonium sulfonate, etc. Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, and triphenylsulfonium. Tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylphosphonium butyl (2,6-difluorophenyl) borate, etc. For example, an alkyl sulfonium salt, a benzyl sulfonium salt, a dibenzyl sulfonium salt, a substituted benzyl sulfonium salt, etc. may be mentioned. 'In terms of an alkyl sulfonium salt, for example, 4-ethenyloxyphenyl group Dimethyl sulfonium hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, -32- 201142515 dimethyl-4-(benzyloxycarbonyloxy)phenyl sulfonium hexafluoride Citrate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, two Methyl 4-(benzylideneoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenylphosphonium hexafluoroantimonate, etc. Examples of the salt include benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl shovel hexafluorophosphate, and 4-ethenoxyphenylbenzyl chloride. Methyl hydrazine hexafluoroantimonate, benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate , benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, etc.; For example, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethyloxyphenyldibenzylphosphonium can be cited. Fluoride, dibenzyl-4-methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl_3_A 4--4-hydroxy-5-t-butylphenylphosphonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, etc.; substituted benzyl For salt, For example, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyl Phenylmethyl hydrazine hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenyl Based on hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroantimonate. -33- 201142515 For the benzothiazole salt, for example, 3-benzylbenzothiazole hexafluoroantimonate, 3-benzylbenzothiazole hexafluorophosphate, 3-benzylbenzothiazole Key tetrafluoroborate, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazole hexafluoroantimonate, 3-benzyl - 5-Chlorobenzothiazole key hexafluoroantimonate. The tetrahydrothiophene sulfonium salt may, for example, be 4,7-di-n-butoxy-naphthalene tetrahydrothiophene trifluoromethanesulfonate or 1-(4-n-butoxynaphthalen-1-yl)tetra Hydrothiophene. Key triflate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene hexafluoro-n-butyl sulfonate, 1-(4-n-butoxynaphthalene-1 -yl)tetrahydrothiophene-1,1,2,2-tetrafluoro-2-(nordecen-2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl) Tetrahydrothiophene gun 2-(5-t-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4 -n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(6-t-butoxycarbonyloxybicyclo[2.2.1]hept-2-yl)-1,1,2,2- Tetrafluoroethanesulfonate. &lt;sulfonimide compound&gt; Examples of the sulfonimide compound include fluorene-(trifluoromethylsulfonyloxy) succinimide, hydrazine-(camphorsulfonyloxy) amber Amine, Ν-(4-methylphenylsulfonyloxy) succinimide, Ν-(2-trifluoromethylphenylsulfonyloxy) succinimide, Ν-(4-fluorophenyl Sulfomethoxy) succinimide, Ν-(trifluoromethylsulfonyloxy) phthalimide, Ν-(camphorsulfonyloxy) phthalimide, Ν-( 2-trifluoromethylphenylsulfonyloxy) phthalimide, fluorene-(2-fluorophenylsulfonyloxy) phthalimide, hydrazine-(trifluoromethylsulfonate醯oxy)diphenylmaleimide, Ν-(camphorsulfonyloxy)diphenyl-34- 201142515 carbamazepine, N-(4-methylphenylsulfonyloxy) Phenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenyl醯iimine, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2·2·1]hept-5-ene -2,3-dimethylimine, N-(4_ Phenyl sulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]g-5 -ene-2,3-dimethylimine, N-(nonafluorobutsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-( camphor Sulfomethoxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν·(camphorsulfonyloxy)-7_oxabicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4-methylphenylsulfonyloxy)bicyclo[2·2·1]hept-5-ene_2,3-dimethylimine, N-(4-methylphenylsulfonyloxy) Alkylheterobicyclic ring I: 2.2·1]hept-5-ene·2,3-dimethylimine, &gt; 1_(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]g -5-ene-2,3-dimethylimine, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν-(4·fluorobenzene Sulfosulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(trifluoromethylsulfonate) Bi) 'bicyclo'[2.2.1]heptane-5,6-oxy-2,3-dimethylimine, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6 -oxy-2,3-dimethylimine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.丨]heptane-5,6-oxy-2,3-di Yttrium, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dimethylimine, N-(4 ·Fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-35- 201142515 alk-5,6-oxy-2,3-dimethylimine, N-(trifluoromethylsulfonyloxy) )naphthyldimethylimine, (camphorsulfonyloxy)naphthyldimethylimine, Ν·(4·methylphenylsulfonyloxy)naphthyldimethylimine, N-(benzene Sulfosulfonyloxy)naphthyldimethylimine, N_(2-trifluoromethylphenylsulfonyloxy)naphthyldimethylimine, N-(4-fluorophenylsulfonyloxy) Naphthyldimethylimine, N-(pentafluoroethylsulfonyloxy)naphthyldimethylimine, N-(heptafluoropropylsulfonyloxy)naphthyldimethylimine, N· (nonafluorobutylsulfonyloxy)naphthyldimethylimine, N_(ethylsulfonyloxy)naphthyldimethylimine, N-(propylsulfonyloxy)naphthalene Dimethylimine, N-(butylsulfonyloxy)naphthyldimethylimine, N-(pentylsulfonyloxy)naphthyldimethylimine, N-(hexylsulfonyloxy) Naphthyldimethylimine, N-(heptylsulfonyloxy)naphthyldimethylimine, N-(octylsulfonyloxy)naphthyldimethylimine, N-(fluorenyl) Sulfomethoxy) naphthyldimethylimine or the like. (Homohalogen-containing compound) The halogen-containing compound may, for example, be a halogenated alkyl group-containing hydrocarbon compound or a haloalkyl group-containing heterocyclic compound. (Diazomethane compound) Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonium)diazomethane, and bis(phenylsulfonyl)diazo Methane, bis(p-sulfonate) diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonium-p-toluene醯Diazomethane, cyclohexylsulfonium (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonate (benzene) Hyperthyroidism, etc. -36- 201142515 (Indole compound) Examples of the ruthenium compound include a β-ketoxime compound, a β-amplifier compound, and a diaryldiamine compound. (Sulphonate Compound) Examples of the sulfonate compound include an alkylsulfonate, an alkylsulfonate, an arylsulfonate, and an imidosulfonate. (Carboxylate Compound) The carboxylate compound may, for example, be an o-nitrobenzyl carboxylate. Among these [Β] photoacid generators, from the viewpoint of radiation sensitivity and solubility, a sulfonate compound is preferable, and a compound containing an oxime sulfonate group represented by the above formula (2) is more preferable. Further preferably, the oxime ester compound represented by the formula (3) is commercially available as [(5-propylsulfonyloxyimino-5-thiophen-2-indenyl)]. (2-methylbenzene)acetonitrile], [(5Η-octylsulfonyloxyimino-5H-thiophene-2-yl)-(2-methylphenyl)acetonitrile], [(5-p-toluene)醯Ominoimido-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], [(camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-A Benzobenzene) acetonitrile], [(5-octylsulfonyloxyimido-(4-methoxyphenyl)acetonitrile]. Further, a key salt is preferred, and a tetrahydrothiophene key salt and a benzyl group are more preferred. Onium salt, 4,7-di-n-butoxy-1-naphthalene tetrahydrothiophene key salt trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate. [B] Photoacid The generating agent may be used singly or in combination of two or more. The content of the [B] photoacid generator in the composition is relative to 1 〇〇. -37- 201142515 parts by mass of [A] polymer, preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass. If the content of the [B] photoacid generator is in the above-mentioned range, the composition can be made. The radiation sensitivity of the object is optimized, and an interlayer insulating film or the like is formed while maintaining the permeability. [C] Compound&gt; In the positive-type radiation-sensitive linear composition, in order to prevent radical oxides, the bond of the compound is caused. Decomposition, and the compound [C] is contained. As the compound, a radical scavenger such as a compound having a hindered phenol structure and a compound having a hindered amine structure, a compound having an alkylene ester structure, and a thioether structure can be exemplified. a compound decomposing agent such as a compound, etc. By containing the above-mentioned [C] compound, the capture of a group which occurs during exposure or heating, or the decomposition of a peroxide generated by oxidation can be prevented, thereby preventing the radical or The decomposition of the polymer molecules by the oxide, and as a result, the interlayer insulating film obtained from the composition can have excellent light resistance and heat resistance. Since a radical scavenger or a peroxide decomposing agent having a fixed structure is used as a compound, even if they are added, it is possible to prevent the transparency of the layer film and the like obtained from the composition while maintaining the radioactivity of the composition at a high level. The rate and the reduction of the voltage holding ratio. For the compound having the above hindered phenol structure, neopentyl quinone [3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionate] , Ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Ten Best, Peripheral or Excessive Free Energy of Phosphoric Oxidation The appliance is [C] sensitive, such as thio-d-octane-38- 201142515-based 3-(3,5-di-t-butyl-4-yl-hydroxyphenyl)propionate, ginseng-(3, 5- Di-tert-butyl-4-hydroxybenzyl)isocyanate, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxybenzyl)benzene, N,N'-hex-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], 3,3',3',5', 5|,5'-hexa-tert-butyl^,&amp;',&amp;|-(mesitylene-2,4,6-triyl)tris-cresol, 4,6-bis(octyl sulphur Methyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4) -hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-para [ (4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-I,3,5·Tri-trap-2,4,6-(111,3^1,51^-three Ketone, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-tri-tac-2-ylamine)phenol. As a compound of the above-mentioned hindered phenol structure, commercially available products include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40 'Adekastab AO-50 ' Adekastab AO-60 ' Adekastab AO-70, produced by ADEKA. ' Adekastab AO-80 ' Adekastab AO-3 3 0 ' Sumitomo Chemical Co., Ltd. produces sumilizerGM, sumilizerGS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80; produced by Ciba Japan IRGANOX 1010, IRGANOX 1 03 5 'IRGANOX 1 076, IRGANOX 1 098, IRGANOX 1135, IRGANOX 1 3 3 0, IRGANOX 1 726, IRGANOX 1 42 5WL, IRGANOX 1 520L 'IRGANOX 245 'IRGANOX 259 'IRGANOX 3114, IRGANOX 565, IRGAMOD 295 ; (share) API Corporation produced by Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, -39- 201142515

Yoshinox 425、Yoshinox 250、Yoshinox 93 0、Yoshinox SS、 Yoshinox TT、Yoshinox 917、Yoshinox 314 等。 就具有上述受阻胺結構的化合物而言,可以列舉例如 雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(2,2,6,6-四甲基 -4-哌啶基)琥珀酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二 酸酯、雙(N-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、 雙(N-苄氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(N-環 己氧基- 2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4 -哌啶基)2-(3,5 -二第三丁基_4_羥基苄基)_2_ 丁基 丙二酸酯、雙(1-丙烯醯基-2,2,6,6-四甲基-4-哌啶基)2,2-雙(3,5 -一第二丁基-4 -經基节基)_2_ 丁基丙二酸醋、雙 (1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、2,2,6,6_四甲基·4_ 哌啶基甲基丙烯酸酯、4-[3-(3,5 -二第三丁基-4-經基苯基) 丙醯氧基]-l-[2-(3-(3,5 -二第三丁基_4_羥基苯基)丙醯氧基] 乙基]-2,2,6,6-四甲基哌啶、2-甲基_2-(2,2,6,6-四甲基-4-哌 陡基)胺基-N-(2,2,6,6-四甲基_4_哌啶基)丙醯胺、肆 (2,2,6,6-四甲基-4-哌啶基)12,3,4- 丁烷四羧酸酯、肆 (1,2,2,6,6-五甲基·4-哌啶基Η』」〆 —丁烷四羧酸酯等化合 物; N,N’,N’’,N’’’-肆-[4,6-雙-〔丁基 _(N-甲基 _2,2,6,6_ 四甲 基哌啶基-4-基)胺基〕-三阱_2·基]_4,7_二吖癸烷丨,&quot;·二 胺、一丁基胺與1,3,5-三阱與1^,;^1_雙(2,2,6,6-四甲基_4_ 哌啶基)-1,6-己二胺與Ν-(2,2,6,6·四甲基-4-哌啶基)丁基胺 -40- 201142515 的聚縮合物、一丁基θ女與1,3,5·二哄與ν,Ν1-雙(2,2,6 6 -四 甲基哌啶基)丁基胺的聚縮合物、聚〔((m3 -四甲基 丁基)胺基-1,3,5-三阱-2,4-二基}{(2,2,6,6-四甲基-4-哌啶 基)亞胺基}六亞甲基{(2,2,6,6-四甲基-4 -岐u定基)亞胺 基}〕、1,6 -己二胺- Ν,Ν'-雙(2,2,6,6 -四甲基-4-哌啶基)與味 啉-2,4,6-三氯-1,3,5-三畊的聚縮合物、聚[(6_味啉基-均三 畊- 2,4-二基)〔(2,2,6,6-四甲基-4-哌啶基)亞胺基〕-六亞甲 基〔(2,2,6,6-四甲基-4-哌啶基)亞胺基〕]等的哌啶環藉由 三哄骨架進行多個鍵結的高分子量HALS;琥珀酸二甲醋與 4-羥基-2,2,6,6-四甲基-1-哌啶乙醇的共聚物、12,3,4-丁烷 四羧酸與1,2,2,6,6-五甲基-4-哌啶醇與3,9-雙(2-羥基-1,1- 一甲基乙基)-2,4,8,10 -四氧雜螺[5,5]~(--院的混合醋化物 等的哌啶環藉由酯鍵而鍵結的化合物等的聚合物類型。 作爲具有上述受阻胺結構的化合物,就市售者而言例 如(股)ADEKA 製造的 Adekastab LA-52、Adekastab LA57、 Adekastab LA-62、Adekastab LA-67、Adekastab LA-63 P ' Adekastab LA-68LD 'Adekastab LA-77 'Adekastab LA-82、 Adekastab LA-87、住友化學(股.)製造的 sumilizer9A、Ciba Japan( 股) 製造的 CΗ IM A S S ORB 1 1 9FL 、 CHIMASSORB2020FDL 、 C Η IM A S S O R B 9 4 4 F D L 、 TINUVIN622LD 、 TINUVIN144 、 TIMUVIN7 65 、 TINUVIN770DF 等。 -41 - 201142515 就具有亞磷酸烷基酯結構的化合物而言,可以例舉有 亞磷酸參(壬基苯基)酯、亞磷酸參(對第三辛基苯基)酯、亞 磷酸參〔2,4,6-參(α-苯基乙基)〕酯、亞磷酸參(對2-丁烯 基苯基)酯、亞磷酸雙(對壬基苯基)環己酯、亞磷酸參(2,4_ 二第三丁基苯基)酯、二(2,4_二第三丁基苯基)新戊四醇二 亞磷酸酯、2,2'-亞甲基雙(4,6-二第三丁基-卜苯基氧基)(2-乙基己基氧基)磷、二硬脂基新戊四醇二亞磷酸酯、4,4'-異亞丙基-二酚烷基亞磷酸酯、四(十三烷基)-4,4’-亞丁基-雙(3-甲基-6-第三丁基酚)二亞磷酸酯、肆(2,4-二第三丁基 苯基)-4,4’-伸聯苯基亞磷酸酯、2,6-二第三丁基_4_甲基苯 基.苯基·新戊四醇二亞磷酸酯、2,6-二第三戊基-4-甲基 苯基•苯基.新戊四醇二亞磷酸酯、2,6-二第三丁基-4-乙 基苯基•硬脂基•新戊四醇二亞磷酸酯、(2,6-二第三丁基 -4-甲基苯基)新戊四醇二亞磷酸酯、2,6-二第三戊基-4-甲基 苯基•苯基•新戊四醇二亞磷酸酯等。 就具有亞磷酸烷基酯結構的化合物而言,市售者有例 如(股)ADEKA 製造的 Adekastab PEP-4C 'Adekastab PEP-8 ' Adekastab PEP-8W 'Adekastab PEP-24G 'Adekastab PEP-36 ' Adekastab HP-10 ' Adekastab 2 112、 Adekastab 2 6 0、 Adekastab 5 2 2 A、 Adekastab 117 8、 Adekastab 1 5 0 0、 Adekastab C、Adekastab 135A ' Adekastab 3010、Adekastab TPP、Ciba Japan(股)製造的 IRGAFOS168 等。 -42 - 201142515 就具有硫醚結構的化合物而言,可以例舉例如有二月 桂基硫二丙酸酯、二(十三烷基)硫二丙酸酯、二(十四烷基) 硫二丙酸酯、二硬脂基硫二丙酸酯、新戊四醇肆(3-月桂基 硫丙酸酯)、新戊四醇肆(3-十八烷基硫丙酸酯)、新戊四醇 肆(3-十四烷基硫丙酸酯)、新戊四醇肆(3-硬脂基硫丙酸酯) 等。 就硫醚結構的化合物而言,市售者可以例舉例如 (股)ADEKA 製造的 Adekastab AO-412S、Adekastab AO-503、 住友化學(股)製造的 sumilizerTPL-R、sumilizerTPM ' sumilizerTPS、sumilizerTP-D、sumilizerMB、Ciba Japan(股) 製造的 IRGANOXPS800FD、IRG ANOXP S 8 02FD ' (股)API Corporation 製造的 DLTP、DSTP、DMTP、DTTP 等。 這些化合物中,可以單獨或混合兩種以上使用。 本發明的感放射線性組成物中,[C ]化合物的含量,相 對於1〇〇質量份[A]聚合物,較佳爲0.1質量份以上、10質 量份以下,更佳爲〇 · 5質量份以上、5質量份以下,特佳爲 1.5質量份以上、3質量份以下。相對於1〇〇質量份[A]聚 合物的[C]化合物的含量處於上述範圍內,由此可以保持該 組成物的感放射線度的同時,進一步提高由組成物得到的 層間絕緣膜等的透光率、電壓保持率、耐光性以及耐熱性。 &lt;其他任意成分&gt; 該組成物中’在上述的[A]~[C]成分的基礎上,在不影 響所期望的效果的範圍內,根據需要可以含有界面活性 -43- 201142515 劑、密合助劑、鹼性化合物、醌二疊氮化合物、可塑劑等 其他任意成分。以下的任意成分可以單獨或混合兩種以上 使用。 &lt;界面活性劑&gt; 爲了使該正型感放射線性組成物的塗膜形成性進一步 提高’較佳係添加界面活性劑。就這類界面活性劑而言可 以列舉例如氟系界面活性劑、聚矽氧系界面活性劑和其他 界面活性劑。 就氟系界面活性劑而言,較佳係末端、主鏈和側鏈中 至少一個部位具有氟烷基和/或氟伸烷基的化合物。就氟系 界面活性劑的例子而言,可以列舉例如1,1,2,2-四氟正辛基 (1,1,2,2-四氟正丙基)醚、ι,ι,2,2-四氟正辛基(正己基)醚、 六乙二醇二(1,1,2,2,3,3-六氟正戊基)醚、八乙二醇二 (1,1,2,2-四氟正丁基)醚、六丙二醇二(^,2,2,3,3-六氟正戊 基)醚、八丙二醇二(1,1,2,2-四氟正丁基)醚、全氟正十二烷 磺酸鈉、1,1,2,2,3,3-六氟正癸烷、1,1,2,2,3,3,9,9,10,10-十氟正十二烷、氟烷基苯磺酸鈉、氟烷基磷酸鈉、氟烷基 羧酸鈉、二甘油肆(氟烷基聚氧乙烯醚)、氟烷基碘銨、氟 烷基甜菜鹼、其他的氟烷基聚氧乙烯醚、全氟烷基聚氧乙 醇、全氟烷基烷氧化物、羧酸氟烷基酯等。 就氟系界面活性劑的市售商品而言,可以列舉例如 BM-1000、BM-1100(以上,BMCHEMIE 公司製造)、 MEGAFAC F142D、 MEGAFAC F172、 MEGAFAC F173 ' -44 - 201142515 MEGAFAC F183、MEGAFAC F178、MEGAFAC F19 1、 MEGA FA C F471' MEGA FAC F476(以上,大曰本印墨化學 工業公司製造)、FLUORADFC-170C、FLUORADFC-171、 FLUORADFC-430、FLUORADFC-431(以上,住友 3M(股)製 造)、SurflonS-1 12 、 SurflonS-1 1 3 、 SurflonS-13 1 、Yoshinox 425, Yoshinox 250, Yoshinox 93 0, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314, etc. As the compound having the above hindered amine structure, for example, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetra) Methyl-4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octyloxy-2, 2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacic acid Ester, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl- 4-(piperidinyl)2-(3,5-di-t-butyl-4-ylhydroxybenzyl)_2-butylmalonate, bis(1-propenylfluorenyl-2,2,6,6-tetra Methyl-4-piperidinyl) 2,2-bis(3,5-a-second-butyl-4-butanosyl)_2_butylmalonate, bis(1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethyl·4_piperidinyl methacrylate, 4-[3-(3,5-di Tributyl-4-phenylphenyl)propanyloxy]-l-[2-(3-(3,5-di-t-butyl-4-ylhydroxy)propenyloxy]ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperazino)amino-N-(2,2 6, 6-tetramethyl-4(piperidinyl)propanamide, hydrazine (2,2,6,6-tetramethyl-4-piperidinyl) 12,3,4-butane tetracarboxylate, hydrazine (1,2,2,6,6-pentamethyl- 4-piperidinyl oxime", a compound such as 〆-butane tetracarboxylate; N, N', N'', N'''-肆- [4,6-bis-[butyl-(N-methyl-2,2,6,6-tetramethylpiperidinyl-4-yl)amino]-tripper-2·yl]_4,7_ Dioxane oxime, &quot;diamine, monobutylamine and 1,3,5-tri-trap with 1^,;^1_bis(2,2,6,6-tetramethyl_4_piperidine Poly) condensate of 1,6-hexanediamine and ruthenium-(2,2,6,6-tetramethyl-4-piperidyl)butylamine-40- 201142515 Polycondensate of 1,3,5·diindole and ν,Ν1-bis(2,2,6 6 -tetramethylpiperidyl)butylamine, poly[((m3 -tetramethylbutyl)amine) Base-1,3,5-tritrap-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2, 2,6,6-tetramethyl-4-indolyl)imine}], 1,6-hexanediamine-oxime, Ν'-bis(2,2,6,6-tetramethyl-4 -piperidinyl) and polyglycosate of porphyrin-2,4,6-trichloro-1,3,5-three tillage, poly[(6_morpholinyl-average tillage-2,4-diyl) )[(2,2 ,6,6-tetramethyl-4-piperidinyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imido]] a multi-bonded high molecular weight HALS of a piperidine ring by a triterpene skeleton; a copolymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 12,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-methylidene Base)-2,4,8,10-tetraoxaspiro[5,5]~ (----------------------------------------------------------------------------------------------------- As a compound having the above-mentioned hindered amine structure, for example, Adekastab LA-52, Adekastab LA57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63 P 'Adekastab LA-68LD manufactured by ADEKA, for example, are commercially available. 'Adekastab LA-77 'Adekastab LA-82, Adekastab LA-87, sumilizer9A manufactured by Sumitomo Chemical Co., Ltd., CΗ IM ASS ORB 1 1 9FL, CHIMASSORB2020FDL, C Η IM ASSORB 9 4 4 manufactured by Ciba Japan FDL, TINUVIN622LD, TINUVIN144, TIMUVIN7 65, TINUVIN770DF, etc. -41 - 201142515 In the case of a compound having an alkyl phosphite structure, ginylphosphoric acid phosphite, phosphite (p-octylphenyl) ester, and phosphorous acid ginate may be exemplified. 2,4,6-e (α-phenylethyl)]ester, phosphite (p-butenylphenyl) ester, bis(p-nonylphenyl)cyclohexyl phosphite, phosphite (2,4_ di-t-butylphenyl) ester, bis(2,4-di-t-butylphenyl)neopentitol diphosphite, 2,2'-methylene double (4,6 -di-t-butyl-b-phenyloxy)(2-ethylhexyloxy)phosphorus, distearyl neopentyl alcohol diphosphite, 4,4'-isopropylidene-diphenol Phosphite, tetrakis(tridecyl)-4,4'-butylene-bis(3-methyl-6-tert-butylphenol) diphosphite, bismuth (2,4-second third Butylphenyl)-4,4'-extended biphenyl phosphite, 2,6-di-t-butyl-4-methylphenyl.phenyl-neopentitol diphosphite, 2, 6-di-t-pentyl-4-methylphenyl•phenyl.neopentitol diphosphite, 2,6-di-t-butyl-4-ethylphenyl•stearyl • neopenta Tetrahydrin diphosphite (2,6-di-t-butyl-4-methylphenyl)neopentitol diphosphite, 2,6-di-t-pentyl-4-methylphenyl-phenyl-pivala Alcohol diphosphite and the like. For compounds having an alkyl phosphite structure, commercially available, for example, Adekastab PEP-4C 'Adekastab PEP-8 ' Adekastab PEP-8W 'Adekastab PEP-24G 'Adekastab PEP-36 ' Adekastab manufactured by ADEKA HP-10 'Adekastab 2 112, Adekastab 2 6 0, Adekastab 5 2 2 A, Adekastab 117 8, Adekastab 1 5 0 0, Adekastab C, Adekastab 135A 'Adekastab 3010, Adekastab TPP, IGAGAOS168 manufactured by Ciba Japan . -42 - 201142515 For the compound having a thioether structure, for example, dilaurylthiodipropionate, ditridecylthiodipropionate, di(tetradecyl)sulfide may be exemplified. Propionate, distearyl thiodipropionate, neopentyl quinone oxime (3-lauryl thiopropionate), neopentyl quinone oxime (3-octadecyl thiopropionate), neopentyl Tetrapropanol (3-tetradecylthiopropionate), neopentyl pentoxide (3-stearyl thiopropionate), and the like. As the compound of the thioether structure, for example, Adekastab AO-412S manufactured by ADEKA, Adekastab AO-503, sumilizer TPL-R manufactured by Sumitomo Chemical Co., Ltd., sumilizer TPM 'sumilizer TPS, sumilizer TP-D can be exemplified. SUMTP, DSTP, DMTP, DTTP, etc. manufactured by IRGANOXPS800FD, IRG ANOXP S 8 02FD ' (share) API Corporation manufactured by sumilizer MB and Ciba Japan. These compounds may be used alone or in combination of two or more. In the radiation sensitive composition of the present invention, the content of the [C] compound is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 〇·5 by mass based on 1 part by mass of the [A] polymer. More than 5 parts by weight, more preferably 1.5 parts by mass or more and 3 parts by mass or less. When the content of the [C] compound of the [A] polymer is in the above range, the sensitivities of the composition can be maintained, and the interlayer insulating film obtained from the composition can be further improved. Light transmittance, voltage holding ratio, light resistance, and heat resistance. &lt;Other optional components&gt; The composition may contain an interfacial activity -43-201142515 as needed, in addition to the above-mentioned [A] to [C] components, within a range that does not affect the desired effect. Other optional components such as an adhesion aid, a basic compound, a quinonediazide compound, a plasticizer, and the like. The following optional components may be used singly or in combination of two or more. &lt;Interacting Agent&gt; In order to further improve the coating film formability of the positive-type radiation-sensitive composition, it is preferable to add a surfactant. As such a surfactant, for example, a fluorine-based surfactant, a polysiloxane surfactant, and other surfactants may be mentioned. In the case of the fluorine-based surfactant, a compound having a fluoroalkyl group and/or a fluorine-extended alkyl group in at least one of a terminal, a main chain and a side chain is preferred. Examples of the fluorine-based surfactant include, for example, 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, ι, ι, 2, 2-tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene glycol bis(1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octaethylene glycol di(1,1,2 ,2-tetrafluoro-n-butyl)ether, hexapropanediol bis(^,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl Ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10 - decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin (fluoroalkyl polyoxyethylene ether), fluoroalkyl iodide, halothane Betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxide, fluoroalkyl carboxylate, and the like. The commercially available product of the fluorine-based surfactant may, for example, be BM-1000, BM-1100 (above, manufactured by BMCHEMIE), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173 '-44 - 201142515 MEGAFAC F183, MEGAFAC F178, MEGAFAC F19 1, MEGA FA C F471' MEGA FAC F476 (above, manufactured by Otsuka Ink Chemical Industry Co., Ltd.), FLUORADFC-170C, FLUORADFC-171, FLUORADFC-430, FLUORADFC-431 (above, Sumitomo 3M (share) manufacturing ), SurflonS-1 12, SurflonS-1 1 3, SurflonS-13 1 ,

SurflonS-141 'SurflonS -1 45 ' S u r f 1 ο n S - 3 8 2 ' S u r f 1 ο n S C -1 0 1 ' SurflonS C-1 02 、 S u r f 1 ο n S C -1 0 3 、 SurflonSC-1 04 、SurflonS-141 'SurflonS -1 45 ' S urf 1 ο n S - 3 8 2 ' S urf 1 ο n SC -1 0 1 ' SurflonS C-1 02 , S urf 1 ο n SC -1 0 3 , SurflonSC- 1 04 ,

SurflonSC-105、SurflonSC-106(以上,旭硝子(股)製造)、 EFTOP EF301' EFTOP EF303、EFTOP EF352(以上,新秋 田化成(股)製造)、FTERGENT FT-100、FTERGENT FT-110、 FTERGENT FT-140A、 FTERGENT FT-1 50、 FTERGENT FT-250 'FTERGENT FT-251 'FTERGENT FT-3 00 'FTERGENT FT-310、 FTERGENT FT-400S 、 FTERGENT FTX-218 、 FTERGENT FT-251(以上,NEOS(股)製造)等。 就聚矽氧系界面活性劑,可以列舉例如 TORAY SILICONE DC3PA、TORAY SILICONE DC7PA、TORAY SILICONE SH11PA、TORAY SILICONE SH21PA、TORAY SILICONE SH28PA、TORAY SILICONE SH29PA、TORAY SILICONE SH30PA、TORAY SILICONE SH-190、TORAY SILICONE SH-193、TORAY SILICONE SZ- 6 03 2、TORAY SILICONE SF-8428、TORAY SILICONE DC-57、TORAY SILICONE DC-190、S H 8 4 0 0 F L UID (以上,TORAY · DOW CORNING · SILICONE(股)製造)、TSF-4440、TSF-43 00、 -45- 201142515 T S F-4445 、 TSF-4446 、 TSF-4460 、 TSF-4452(以上, GETOSHIB A S ILI C Ο N E (股)製造)、Organo Siloxane P〇lymerKP341(信越化學工業(股)製造)等。 這些界面活性劑可以單獨或混合兩種以上使用。界面 活性劑的使用量相對於100質量份[A]成分較佳爲0.01質 量份〜2質量份,更佳爲0.05質量份〜1質量份。藉由界面 活性劑的使用量在0.01質量份〜2質量份時,可以減少塗膜 不句 。 &lt;密合助劑&gt; 在該正型感放射線性組成物中,可以使用用於提高作 爲基板的無機物和絕緣膜的粘結性的密合助劑,所述作爲 基板的無機物例如矽、氧化矽、氮化矽等矽化合物、矽酸 鹽 '石英等的玻璃、以及金、銅、鋁等金屬。就這種密合 助劑而言較佳係使用官能性矽烷偶合劑。就官能性矽烷偶 合劑的例子而言,可以列舉出具有羧基、甲基丙烯醯基、 異氰酸基、環氧基(較佳係環氧乙烷基)、硫醇基等反應性 取代基的矽烷偶合劑等。 就官能性矽烷偶合劑的具體例子而言,可以列舉出三 甲氧基矽烷基苯甲酸、γ -甲基丙烯醯氧基丙基三甲氧基矽 烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異 氰酸酯基丙基三乙氧基矽烷、γ -縮水甘油氧基丙基三甲氧 基矽烷、γ-縮水甘油氧基丙基烷基二烷氧基矽烷、γ-氯丙 基三烷氧基矽烷、γ-锍基丙基三烷氧基矽烷、β-(3,4-環氧 -46- 201142515 環己基)乙基三甲氧基矽烷等。它們之中,較佳係γ-縮水甘 油氧基丙基烷基二烷氧基矽烷、β-(3,4-環氧環己基)乙基三 甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷。 在該正型感放射線性組成物中,相對於1 00質量份[Α] 聚合物,這種密合助劑較佳係以0.5質量份〜20質量份,更 佳係以1質量份〜1 0質量份的量而使用。藉由使密合助劑 的量爲上述範圍,可以改善形成的層間絕緣膜和基板的密 合性。 &lt;鹼性化合物&gt; 就鹼性化合物而言,可以從化學增幅光阻劑中使用的 鹼性化合物中任意選擇使用。就鹼性化合物而言可以列舉 出例如脂肪族胺、芳香族胺、雜環胺、四級銨氫氧化物、 羧酸四級銨鹽等。藉由在該正型感放射線性組成物中含有 鹼性化合物,可以適當控制曝光而由光酸產生劑產生的酸 的擴散長度,可以形成良好的圖案顯影性。 就脂肪族胺而言,可以列舉出例如三甲基胺、二乙基 胺、三乙基胺、二正丙基胺、三正丙基胺、二正戊基胺、 三正戊基胺、二乙醇胺、三乙醇胺、二環己基胺、二環己 基甲基胺等。 就芳香族胺而言’可以列舉出例如苯胺、苄基胺、Ν,Ν - 二甲基苯胺、二苯基胺等。 就雜環胺而言’可以列舉出例如啦陡、2 _甲基吡啶' 4 -甲基卩比u定、2 -乙基卩比Π定' 4 -乙基妣淀、2 -苯基啦D定、4 - -47 - 201142515 苯基吡啶、N -甲基-4 -苯基吡啶、4 -二甲基胺基吡啶、咪唑、 苯并咪唑、4 -甲基咪唑、2-苯基苯并咪唑、2,4,5-三苯基咪 唑、菸鹼、菸鹼酸、菸鹼酸醯胺、喹啉、8 -氧基唾啉、吡 哄、吡唑、嗒哄、嘌呤、吡咯啶、哌啶、哌阱、味啉、4 -甲基味啉、1,5-二吖雙環[4,3,0]-5-壬烯、1,8-二吖雙環 [5,3,0]-7-十一烯等。 就四級銨氫氧化物而言,可以列舉出例如氫氧化四甲 基銨、氫氧化四乙基銨、氫氧化四正丁基銨、氫氧化四正 己基銨等。 就羧酸四級銨鹽而言,可以列舉出例如乙酸四甲基 銨、苯甲酸四甲基銨、乙酸四正丁基銨、苯甲酸四正丁基 銨等。 該正型感放射線性組成物中的鹼性化合物的含量相對 於100質量份[A]聚合物,較佳爲1質量份以下,更佳爲0.2 質量份以下。藉由使鹼性化合物的含量爲上述範圍,圖案 顯影性良好。 &lt;醌二疊氮化合物〉 醌二疊氮化合物是藉由照射放射線產生羧酸的化合 物。可以使用酚性或醇性化合物(以下,稱作「母核」)和 1,2-萘醌二疊氮磺醯鹵化物的縮合物作爲醌二疊氮化合物。 就上述母核而言,可以列舉出例如三羥基二苯基酮、 四羥基二苯基酮、五羥基二苯基酮、六羥基二苯基酮、(多 羥基苯基)烷、其他母核。 -48- 201142515 就這些母核而言可以列舉出: 三羥基二苯基酮是例如2,3,4-三羥基二苯基酮、2,4,6-三羥基二苯基酮等; 四羥基二苯基酮是例如2,2’,4,4'-四羥基二苯基酮、 2,3,4,3'-四羥基二苯基酮、2,3,4,4'-四羥基二苯基酮、 2,3,4,2'-四羥基- 4'-甲基二苯基酮、2,3,4,4'-四羥基- 3’-甲氧 基二苯基酮等; 五羥基二苯基酮是例如 2,3,4,2’,6’-五羥基二苯基酮 等; '六羥基二苯基酮是例如 2,4,6,3’,4',5’-六羥基二苯基 酮、3,4,5,3、4|,5'-六羥基二苯基酮等; (多羥基苯基)烷是例如雙(2,4-二羥基苯基)甲烷、雙(對 羥基苯基)甲烷、參(對羥基苯基)甲烷、1,1,1-參(對羥基苯 基)乙烷、雙(2,3,4-三羥基苯基)甲烷、2,2·雙(2,3,4-三羥基 苯基)丙烷、1,1,3·參(2,5_二甲基-4-羥基苯基)-3-苯基丙 烷、4,4’-[1-[4-[1-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基] 雙酚、雙(2,5-二甲基-4-羥基苯基)-2-羥基苯基甲烷、 3,3,3’,3'-四甲基-1,1'-螺雙茚-5,6,7,5’,6’,7'-己醇、2,2,4-三 甲基-7,2’,4、三羥基黃烷等; 就其他母核而言是例如 2-甲基-2-(2,4-二羥基苯 基)-4-(4-羥基苯基)-7-暁皖、卜[1-(3-{1-(4-羥基苯基)-1-甲 基乙基卜4,6-二羥基苯基)-1-甲基乙基]-3-(1-(3-{1-(4-羥基 苯基)-1-甲基乙基}-4,6-二羥基苯基)-1-甲基乙基)苯、4,6-雙U-(4-羥基苯基)-1-甲基乙基}-1,3-二羥基苯。 -49- 201142515 在這些母核中,較佳係 2,3,4,4’ -四羥基二苯基酮、 三(對羥基苯基)乙烷、4,4'-[1-[4-Π-[4-羥基苯基]-1-甲基乙基]苯基]亞乙基]雙酚。 另外,就1,2 -萘醌二疊氮磺醯鹵化物而言,較佳係1,2 -萘醌二疊氮磺醯氯。就1,2·萘醌二疊氮磺醯氯的具體例子 而言,可以列舉出1,2-萘醌二疊.氮-4-磺醯氯和l,2-萘醌二 疊氮-5-磺醯氯。其中’特佳係使用1,2 -萘醌二疊氮-5-磺醯 氯。 就酚性化合物或醇性化合物和1,2 -萘醌二疊氮磺醯鹵 的縮合物的合適的例子而言,可以列舉出1,1,1_三(對經基 苯基)乙烷和1,2 -萘醌二疊氮-5 -磺醯氯的縮合物、 4,4'-[1-[4-[1-[4_羥基苯基]-1·甲基乙基]苯基]亞乙基]雙酚 和1,2-萘醌二疊氮-5-擴醯氯的縮合物。 在酚性化合物或醇性化合物(母核)和1,2 -萘醌二疊氮 磺酸醯鹵化物的縮合反應中,相對於酚性化合物或醇性化 合物中的ΟΗ基數量’可使用相當於較佳爲30〜85 m〇l%, 更佳爲50〜70mol%的1,2-萘醌二疊氮磺醯鹵。縮合反應藉 由公知的方法進行。 另外’就醌二疊氮化合物而言還適合使用將上述例示 的母核的酯鍵改變爲醯胺鍵的1,2 -萘醌二疊氮磺醯胺類, 例如2,3,4 -三胺基二苯基酮-1,2 -萘醌二疊氮-4-磺醯胺等。 這些[B]成分可以單獨使用或組合兩種以上使用。 -50- 201142515 &lt;可塑劑〉 就可塑劑而言可以例舉鄰苯二甲酸二丁酯、鄰苯二甲 酸二辛酯、鄰苯二甲酸二月桂酯、聚乙二醇、丙三醇、鄰 苯二甲酸二甲基丙三醇酯、酒石酸二丁酯、己二酸二辛酯、 三乙醯丙三醇等。 &lt;溶劑&gt; . 就可以在該正型感放射線性組成物的製備中使用的溶 劑而言,適合使用將各成分均勻地溶解或者分散,並且不 和各成分反應的溶劑。就這種溶劑而言,可以列舉出例如 醇類、醚類、二乙二醇烷基醚類、乙二醇烷基醚乙酸酯類、 丙二醇單烷基醚類、丙二醇單烷基醚乙酸酯類、丙二醇單 烷基醚丙酸酯類、芳香族烴類、酮類、酯類等。 就這些溶劑而言分別可以列舉出: 醇類是例如苄醇、二丙酮醇等; 醚類是例如四氫呋喃以及二異丙基醚、二正丁基醚、 二正戊基醚、二異戊基醚、二正己基醚等二烷基醚等; 二乙二醇烷基醚類是例如二乙二醇單甲基醚、二乙二 醇單乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二 乙二醇乙基甲基醚等; 乙二醇烷基醚乙酸酯類是例如甲基溶纖素乙酸酯、乙 基溶纖素乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙基 醚乙酸酯等; 丙二醇單烷基醚類是例如丙二醇單甲基醚、丙二醇單 乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等; -51- 201142515 丙二醇單烷基醚乙酸酯類是例如 酯、丙二醇單乙基醚乙酸酯、丙二醇 二醇單丁基醚乙酸酯等; 丙二醇單烷基醚丙酸酯類是例如 酯、丙二醇單乙基醚丙酸酯、丙二醇 二醇單丁基醚丙酸酯等; 芳香族烴類是例如甲苯、二甲苯 酮類是例如甲基乙基酮、甲基異 庚酮' 4-羥基-4-甲基-2-戊酮等; 酯類是例如乙酸甲酯、乙酸乙酯 丙酯、乙酸丁酯、2-羥基丙酸乙酯、 酯、2-羥基-2-甲基丙酸乙酯、羥基乙 酯、羥基乙酸丁酯、乳酸甲酯、乳酸 酸丁酯、3-羥基丙酸甲酯、3-羥基丙g 酯、3-羥基丙酸丁酯、2-羥基-3-甲基 酸甲酯 '甲氧基乙酸乙酯、甲氧基乙 丁酯、乙氧基乙酸甲酯、乙氧基乙酸 酯、乙氧基乙酸丁酯、丙氧基乙酸甲酉 丙氧基乙酸丙酯、丙氧基乙酸丁酯、 氧基乙酸乙酯、丁氧基乙酸丙酯、丁 氧基丙酸甲酯、2 -甲氧基丙酸乙酯、 2-甲氧基丙酸丁酯、2-乙氧基丙酸甲g 等。 丙二醇單甲基醚乙酸 單丙基醚乙酸酯、丙 丙二醇單甲基醚丙酸 單丙基醚丙酸酯、丙 等; 丁基酮、環己酮、2- 、乙酸丙酯、乙酸異 2-羥基-2-甲基丙酸甲 酸甲酯、羥基乙酸乙 乙酯、乳酸丙酯、乳 ?乙酯、3-羥基丙酸丙 丁酸甲酯、甲氧基乙 酸丙酯、甲氧基乙酸 乙酯、乙氧基乙酸丙 旨、丙氧基乙酸乙酯、 丁氧基乙酸甲酯、丁 氧基乙酸丁酯、2-甲 2-甲氧基丙酸丙酯、 旨、2-乙氧基丙酸乙酯 -52- 201142515 這些溶劑中,從溶解性或分散性優異性、與各成分的 非反應性以及形成塗膜的容易性的觀點來看,較佳係二烷 基醚等醚類,二乙二醇烷基醚類、乙二醇烷基醚乙酸酯類、 丙二醇單烷基醚類、丙二醇單烷基醚乙酸酯類、酮類和酯 類,特佳係二乙二醇二乙基醚、二乙二醇乙基甲基醚、甲 基溶纖素乙酸酯、乙基溶纖素乙酸酯、丙二醇單甲基醚、 丙二醇單乙基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基 醚乙酸酯、環己酮、乙酸丙酯、乙酸異丙酯、乙酸丁酯、 2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基 丙酸乙酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、 2 -甲氧基丙酸甲酯、2 -甲氧基丙酸乙酯。這些溶劑可以單 獨或混合使用。 另外,這些溶劑中,較佳係二異丙基醚、二正丁基醚、 二正戊基醚、二異戊基醚、二正己基醚等二烷基醚等醚類’ 最較佳係二異戊基醚。藉由使用這種溶劑’藉由狹縫塗布 法在大型玻璃基板上塗布感放射線性組成物時’可以縮短 乾燥步驟時間,同時可以更進一步提高塗布性(抑制塗布不 勻)。 除了上述溶劑以外’根據需要’還可以和苄基乙基醚、 二己基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙 二醇單丁基醚、丙酮基丙酮、異佛爾酮、己酸、癸酸、1-辛醇、1·壬醇、苄醇、乙酸苄酯、苯甲酸乙酯、草酸二乙 酯 '馬來酸二乙酯、γ -丁內酯、碳酸伸乙酯、碳酸伸丙酯、 苯基溶纖素乙酸酯、卡畢醇乙酸酯等高沸點溶劑一起使用。 -53- 201142515 &lt;正型感放射線性組成物的製備&gt; 本發明的正型感放射線性組成物以上述[A ]聚合物、[b ] 光酸產生劑、[C]化合物以及根據需要混合任意成分而製 備。通常,正型感放射線性組成物較佳係在溶解或分散適 當的溶劑的狀態被製備並使用。例如,在溶劑中,藉由以 規定的比例混合[A]、[B]、[C]成分以及任意成分,能夠製 備正型感放射線性組成物。 正型感放射線性組成物的固體成分濃度(聚合物溶液 中所含聚合物的質量占聚合物溶液的總重量的比例)可以 根據使用目的或所希望的膜厚等任意設定,較佳爲5〜50質 量%、更佳爲10〜40質量%、進一步較佳爲】5〜35質量%。 &lt;層間絕緣膜等的硬化膜的形成方法&gt; 接著’對使用上述的正型感放射線性組成物,在基板 上形成層間絕緣膜等的硬化膜的方法進行說明。該方法包 含以下順序記載的以下步驟。 (1 )在基板上形成該正型感放射線性組成物的塗膜的 步驟, (2) 對步驟(1 )中形成的塗膜的至少一部分照射放射線 的步驟, (3) 將步驟(2)中照射了放射線的塗膜顯影的步驟,以及 (4) 對步驟(3)中顯影的塗膜加熱的步驟。 &lt;(1)在基柩上形成該正型感放射線性組成物的塗膜的步驟&gt; 在上述(1)的步驟中,將該正型感放射線性組成物的溶 -54- 201142515 液或分散液塗敷到基板上後,較佳係藉由加熱(預烘烤)塗 敷面除去溶劑,形成塗膜。就可以使用的基棋的例子而言, 可以列舉出玻璃、石英、矽、樹脂等。就樹脂的具體例子 而言,可以列舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丁 二酯、聚醚颯、聚碳酸酯、聚醯亞胺'環狀烯烴的開環聚 合物及其氫化物等。 就組成物溶液或分散液的塗布方法而言沒有特別的限 定’可以採用例如噴霧法、輥塗法、旋轉塗布法(旋塗法)、 縫模塗布法、棒塗布法等適當的方法。這些塗布方法中, 較佳係旋塗法或縫模塗布法,特佳係縫模塗布法。預烘烤 的條件根據各成分的種類、混合比例等而異,較佳係在 70〜12(TC下進行1〜10分鐘左右。 &lt;(2)對塗膜的至少一部分照射放射線的步驟&gt; 在上述(2)的步驟中,將形成的塗膜的至少一部分曝 光。在這種情況下,對塗膜的一部分曝光時,通常藉由具 有規定圖案的光罩曝光。就曝光時使用的放射線而言,合 適的是對光酸產生劑使用的放射線。這些放射線中,較佳 係波長在190〜450nm的範圍的放射線,特佳係含有3 65nm 的紫外線的放射線。 該步驟中的曝光量是藉由照度計(OAImodel356,OAI Optical Associates Inc.製造)測定放射線的波長365nm下 的強度得到的値,較佳爲 500J/m2〜6,000J/m2,更佳爲 l,500J/m2〜1,800J/m2 ° -55- 201142515 &lt;(3)顯影步驟&gt; 上述(3)的步驟中,藉由將曝光後的塗膜顯影,除去不 需要的部分(放射線的照射部分),形成規定的圖案。就顯 影步驟中使用的顯影液而言,較佳係鹼性的水溶液。就鹼 的例子而言,可以列.舉出氫氧化鈉、氫氧化鉀、碳酸鈉、 矽酸鈉、偏矽酸鈉、氨等無機鹼,氫氧化四甲銨、氫氧化 四乙銨等四級銨鹽等。 另外,在這種鹼水溶液中,還可以適量添加甲醇、乙 醇等水溶性有機溶劑或界面活性劑。從得到適當的顯影性 的觀點來看,鹼水溶液中的鹼的濃度較佳爲0.1質量%〜5 質量%。就顯影方法例如可以利用覆液法、浸漬法、震動 浸漬法、淋浴法等適當的方法。顯影時間根據正型感放射 線性組成物的組成而異,較佳爲1 〇〜1 8 0秒左右。在這種顯 影處理之後,例如進行3〇〜90秒鐘流水洗滌後,例如藉由 壓縮空氣或壓縮氮氣風乾,可以形成所希望的圖案。 &lt;(4)加熱步驟&gt; 在上述(4)的步驟中,使用加熱板、烘箱等加熱裝置, 對形成圖案的薄膜加熱,可促進上述[A]成分和[C]成分的 硬化反應,而得到硬化物。本步驟中的加熱溫度例如是 1 2 0〜2 5 0 °C。加熱時間根據加熱設備的種類而異,例如在加 熱板上進行加熱步驟時,進行5〜30分鐘;在烘箱中進行加 熱步驟時’是30〜90分鐘。還可以使用進行兩次以上的加 熱步驟的階段性烘烤法等。這樣,可以在基板表面形成對 應於所需要的層間絕緣膜的圖案狀薄膜。 -56- 201142515 另外,上述硬化膜不被限定爲層間絕緣膜’可以作爲 隔板或保護膜而利用。 &lt;層間絕緣膜&gt; 這樣形成的層間絕緣膜的膜厚較佳爲0.1〜8’更佳 爲0.1〜6μιη,進一步較佳爲0.1~4μιηβ 由本發明的正型感放射線性組成物形成的層間絕緣膜 還如下述實施例表明的那樣,能均衡性良好地滿足耐熱性 和透明性以及電壓保持率這樣一般要求的性質,同時具有 無塗布不勻的高度平整性。因此,該層間絕緣膜適合作爲 顯示元件的用途使用。 [實施例] 以下,表示合成例、實施例,對本發明進行更具體地 說明,但是本發明並不受到以下實施例的限定。 在下文中,聚合物的質量平均分子量(Mw)和數量平均 分子量(Μη)藉由下述條件進行的凝膠滲透色譜法(Gpc)測 定。 裝置:GPC-101(昭和電工(股)製造) 管柱:組合 GPC-KF-801、gpc-KF-802、GPC-KF-803 和 GPC-KF-804 移動相:四氫呋喃Surflon SC-105, Surflon SC-106 (above, manufactured by Asahi Glass Co., Ltd.), EFTOP EF301' EFTOP EF303, EFTOP EF352 (above, manufactured by New Akita Chemicals Co., Ltd.), FTERGENT FT-100, FTERGENT FT-110, FTERGENT FT- 140A, FTERGENT FT-1 50, FTERGENT FT-250 'FTERGENT FT-251 'FTERGENT FT-3 00 'FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FT-251 (above, NEOS) Manufacturing) and so on. Examples of the polyoxo-based surfactant include TORAY SILICONE DC3PA, TORAY SILICONE DC7PA, TORAY SILICONE SH11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH-190, TORAY SILICONE SH- 193, TORAY SILICONE SZ- 6 03 2. TORAY SILICONE SF-8428, TORAY SILICONE DC-57, TORAY SILICONE DC-190, SH 8 4 0 0 FL UID (above, TORAY · DOW CORNING · SILICONE) TSF-4440, TSF-43 00, -45- 201142515 TS F-4445, TSF-4446, TSF-4460, TSF-4452 (above, manufactured by GETOSHIB AS ILI C Ο NE (share)), Organo Siloxane P〇lymerKP341 ( Shin-Etsu Chemical Co., Ltd. manufactures) and so on. These surfactants may be used singly or in combination of two or more. The amount of the surfactant to be used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.05 parts by mass to 1 part by mass, per 100 parts by mass of the component [A]. When the amount of the surfactant used is 0.01 parts by mass to 2 parts by mass, the coating film can be reduced. &lt;Adhesion aid&gt; In the positive-acting radiation-linear composition, an adhesion aid for improving the adhesion of the inorganic material and the insulating film as a substrate, for example, ruthenium, A ruthenium compound such as ruthenium oxide or ruthenium nitride, a glass such as citrate 'quartz, and a metal such as gold, copper or aluminum. It is preferred to use a functional decane coupling agent for such an adhesion aid. Examples of the functional decane coupling agent include reactive substituents such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group (preferably an oxiran group), and a thiol group. Decane coupling agent, etc. Specific examples of the functional decane coupling agent include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethylene decyl decane, and vinyl trimethyl. Oxydecane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl alkyl dialkoxy decane, γ-chloropropyl Trialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxy-46-201142515 cyclohexyl)ethyltrimethoxydecane, and the like. Among them, preferred are γ-glycidoxypropylalkyl dialkoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and γ-methacryloxyloxy group. Propyltrimethoxydecane. In the positive-type radiation-sensitive linear composition, the adhesion aid is preferably 0.5 parts by mass to 20 parts by mass, more preferably 1 part by mass to 1 part by mass per 100 parts by mass of the [Α] polymer. It is used in an amount of 0 parts by mass. By setting the amount of the adhesion aid to the above range, the adhesion between the formed interlayer insulating film and the substrate can be improved. &lt;Basic compound&gt; As the basic compound, it can be arbitrarily selected from the basic compound used in the chemically amplified photoresist. The basic compound may, for example, be an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide or a quaternary ammonium carboxylic acid salt. By including a basic compound in the positive-type radiation-sensitive composition, the diffusion length of the acid generated by the photo-acid generator during exposure can be appropriately controlled, and good pattern developability can be formed. Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentylamine. Diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like. The aromatic amine may, for example, be aniline, benzylamine, hydrazine, hydrazine-dimethylaniline or diphenylamine. In the case of a heterocyclic amine, it can be exemplified by, for example, a sharp, 2 -methylpyridine ' 4 -methyl oxime ratio, 2 -ethyl oxime Π ' ' 4 -ethyl yttrium, 2 - phenyl D, 4 - -47 - 201142515 Phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzene Imidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid decylamine, quinoline, 8-oxo porphyrin, pyridinium, pyrazole, hydrazine, hydrazine, pyrrolidine , piperidine, pipe trap, porphyrin, 4-methyl morpholine, 1,5-dioxinbicyclo[4,3,0]-5-nonene, 1,8-diguanidine [5,3,0 ]-7-undecene and the like. The quaternary ammonium hydroxide may, for example, be tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide or tetra-n-hexylammonium hydroxide. The carboxylic acid quaternary ammonium salt may, for example, be tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate or tetra-n-butylammonium benzoate. The content of the basic compound in the positive-type radiation-sensitive composition is preferably 1 part by mass or less, more preferably 0.2 part by mass or less based on 100 parts by mass of the [A] polymer. By setting the content of the basic compound to the above range, the pattern developability is good. &lt;Hydrazine diazide compound> The quinonediazide compound is a compound which generates a carboxylic acid by irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic or alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinonediazidesulfonium halide can be used. Examples of the above-mentioned mother nucleus include, for example, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, pentahydroxydiphenyl ketone, hexahydroxydiphenyl ketone, (polyhydroxyphenyl) alkane, and other mother nucleus. . -48- 201142515 For these mother cores, there may be mentioned: trihydroxydiphenyl ketone is, for example, 2,3,4-trihydroxydiphenyl ketone, 2,4,6-trihydroxydiphenyl ketone, etc.; Hydroxydiphenyl ketone is, for example, 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3,4,3'-tetrahydroxydiphenyl ketone, 2,3,4,4'-tetra Hydroxydiphenyl ketone, 2,3,4,2'-tetrahydroxy-4'-methyldiphenyl ketone, 2,3,4,4'-tetrahydroxy-3'-methoxydiphenyl ketone Et.; pentahydroxydiphenyl ketone is, for example, 2,3,4,2',6'-pentahydroxydiphenyl ketone or the like; 'hexahydroxydiphenyl ketone is, for example, 2, 4, 6, 3', 4' , 5'-hexahydroxydiphenyl ketone, 3,4,5,3,4|,5'-hexahydroxydiphenyl ketone, etc.; (polyhydroxyphenyl) alkane is, for example, bis(2,4-dihydroxyl) Phenyl)methane, bis(p-hydroxyphenyl)methane, cis (p-hydroxyphenyl)methane, 1,1,1-paraxyl (p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxybenzene) Methane, 2,2·bis(2,3,4-trihydroxyphenyl)propane, 1,1,3·g (2,5-dimethyl-4-hydroxyphenyl)-3-phenyl Propane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5- Methyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiguanidine-5,6,7,5',6 ',7'-hexanol, 2,2,4-trimethyl-7,2',4,trihydroxyflavan, etc.; for other parent cores, for example 2-methyl-2-(2,4 -dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-indole, [1-(3-{1-(4-hydroxyphenyl)-1-methylethyl b 4,6 -dihydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl -1-methylethyl)benzene, 4,6-bis U-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene. -49- 201142515 Among these mother cores, 2,3,4,4'-tetrahydroxydiphenyl ketone, tris(p-hydroxyphenyl)ethane, 4,4'-[1-[4- Π-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol. Further, in the case of the 1,2-naphthoquinonediazidesulfonium halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. Specific examples of 1,2,naphthoquinonediazide sulfonium chloride include 1,2-naphthoquinone quinone, nitrogen-4-sulfonium chloride, and 1,2-naphthoquinonediazide-5. - sulfonium chloride. Among them, '1,2-naphthoquinonediazide-5-sulfonyl chloride is used. As a suitable example of the condensate of the phenolic compound or the alcohol compound and the 1,2-naphthoquinonediazidesulfonium halide, 1,1,1-tris(p-phenylphenyl)ethane can be exemplified. And condensate of 1,2-naphthoquinonediazide-5-sulfonyl chloride, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1.methylethyl]benzene A condensate of bis]ethylene]bisphenol and 1,2-naphthoquinonediazide-5-open chlorobenzene. In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) and a 1,2-naphthoquinonediazidesulfonium sulfonium halide, the amount of the thiol group in the phenolic compound or the alcoholic compound can be used as Preferably, it is 30 to 85 m〇l%, more preferably 50 to 70 mol% of 1,2-naphthoquinonediazidesulfonium halide. The condensation reaction is carried out by a known method. Further, as the quinonediazide compound, it is also suitable to use 1,2-naphthoquinonediazidesulfonamide which changes the ester bond of the above-exemplified parent core to a guanamine bond, for example, 2, 3, 4 - 3 Aminodiphenyl ketone-1,2-naphthoquinonediazide-4-sulfonamide and the like. These [B] components may be used singly or in combination of two or more. -50- 201142515 &lt;Plasticizer&gt; In the case of a plasticizer, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, polyethylene glycol, glycerin, Dimethyl glycerol phthalate, dibutyl tartrate, dioctyl adipate, triethylene glycerol, and the like. &lt;Solvent&gt;. A solvent which can be used for the preparation of the positive-type radiation-sensitive composition is preferably a solvent which uniformly dissolves or disperses each component and does not react with each component. Examples of such a solvent include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. Classes, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, esters, and the like. Examples of the solvent include alcohols such as benzyl alcohol and diacetone alcohol; and ethers such as tetrahydrofuran and diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, and diisoamyl. a dialkyl ether such as ether or di-n-hexyl ether; and a diethylene glycol alkyl ether such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; ethylene glycol alkyl ether acetates such as methyl fibrin acetate, ethyl fibrin acetate, B Glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; propylene glycol monoalkyl ethers are, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol single Butyl ether and the like; -51- 201142515 Propylene glycol monoalkyl ether acetates are, for example, esters, propylene glycol monoethyl ether acetate, propylene glycol diol monobutyl ether acetate, etc.; propylene glycol monoalkyl ether propionate The class is, for example, an ester, a propylene glycol monoethyl ether propionate, a propylene glycol diol monobutyl ether propionate or the like; an aromatic hydrocarbon is, for example, The benzene or xylone is, for example, methyl ethyl ketone, methyl isoheptanone 4-hydroxy-4-methyl-2-pentanone or the like; the ester is, for example, methyl acetate, ethyl acetate propyl acetate, acetic acid Butyl ester, ethyl 2-hydroxypropionate, ester, ethyl 2-hydroxy-2-methylpropionate, hydroxyethyl ester, butyl glycolate, methyl lactate, butyl lactate, 3-hydroxypropionic acid Ester, 3-hydroxypropyl g-ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylate 'methoxyacetate, methoxyethyl butyrate, methyl ethoxyacetate, Ethoxyacetate, butyl ethoxyacetate, propyl propyl propyl acetate, butyl propyl acetate, ethyl oxyacetate, propyl butoxyacetate, butoxy Methyl propionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, and the like. Propylene glycol monomethyl ether acetate monopropyl ether acetate, propylene glycol monomethyl ether propionic acid monopropyl ether propionate, propane, etc.; butyl ketone, cyclohexanone, 2-, propyl acetate, acetic acid Methyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, propyl lactate, ethyl lactate, methyl 3-propylpropionate, propyl methoxyacetate, methoxyacetic acid Ethyl ester, ethoxyacetic acid, ethyl propoxyacetate, methyl butoxyacetate, butyl butoxyacetate, propyl 2-methyl 2-methoxypropionate, 2-ethoxy Ethyl propyl propionate-52-201142515 Among these solvents, ethers such as dialkyl ethers are preferred from the viewpoints of excellent solubility or dispersibility, non-reactivity with each component, and easiness of formation of a coating film. Classes, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters, especially good diethylene glycol Diethyl ether, diethylene glycol ethyl methyl ether, methyl fibrin acetate, ethyl fibrin acetate, propylene glycol monomethyl ether, propylene glycol monoethyl , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy-2- Methyl methacrylate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate, 2-methoxy Ethyl propyl propionate. These solvents may be used singly or in combination. Further, among these solvents, ethers such as dialkyl ethers such as diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisoamyl ether and di-n-hexyl ether are preferred. Diisoamyl ether. By using such a solvent 'when the radiation sensitive composition is coated on a large glass substrate by a slit coating method', the drying step time can be shortened, and the coatability can be further improved (the coating unevenness is suppressed). In addition to the above solvents, 'as needed' can also be combined with benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone Acetone, isophorone, hexanoic acid, citric acid, 1-octanol, 1-decyl alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyl A high boiling point solvent such as lactone, ethyl carbonate, propyl propyl carbonate, phenyl cellosolve acetate, or carboxol acetate is used together. -53- 201142515 &lt;Preparation of positive-type radiation-sensitive composition&gt; The positive-type radiation-sensitive composition of the present invention comprises the above-mentioned [A] polymer, [b] photo-acid generator, [C] compound, and as needed Prepared by mixing arbitrary ingredients. In general, the positive-acting radiation linear composition is preferably prepared and used in a state in which a suitable solvent is dissolved or dispersed. For example, a positive-type radiation-sensitive composition can be prepared by mixing the components [A], [B], and [C] and arbitrary components in a predetermined ratio in a solvent. The solid content concentration of the positive-type radiation-sensitive composition (the ratio of the mass of the polymer contained in the polymer solution to the total weight of the polymer solution) can be arbitrarily set depending on the purpose of use, the desired film thickness, and the like, and is preferably 5 It is 50% by mass, more preferably 10 to 40% by mass, still more preferably 5 to 35% by mass. &lt;Method of Forming Cured Film of Interlayer Insulating Film, etc.&gt; Next, a method of forming a cured film such as an interlayer insulating film on a substrate using the above-described positive-type radiation-sensitive composition will be described. This method includes the following steps described in the following order. (1) a step of forming a coating film of the positive-type radiation-sensitive composition on a substrate, (2) a step of irradiating at least a part of the coating film formed in the step (1), and (3) a step (2) The step of developing the coating film irradiated with radiation, and (4) the step of heating the coating film developed in the step (3). &lt;(1) Step of forming a coating film of the positive-type radiation-sensitive composition on the substrate&gt; In the step (1) above, the solution of the positive-type radiation-sensitive composition is -54-201142515 After the dispersion is applied onto the substrate, it is preferred to remove the solvent by heating (pre-baking) the coated surface to form a coating film. Examples of the base chess that can be used include glass, quartz, enamel, resin, and the like. Specific examples of the resin include a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and polyamidene 'cyclic olefin. And its hydride and the like. The coating method of the composition solution or the dispersion is not particularly limited. For example, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is preferred, and a slit die coating method is particularly preferred. The pre-baking conditions vary depending on the type of each component, the mixing ratio, etc., and are preferably 70 to 12 (about 1 to 10 minutes under TC.) (2) Step of irradiating at least a part of the coating film with radiation> In the step (2) above, at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed by a mask having a predetermined pattern. Radiation is preferably used for the photoacid generator. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet rays of 3 to 65 nm is particularly preferable. The amount of exposure in this step. The enthalpy obtained by measuring the intensity at a wavelength of 365 nm of the radiation by an illuminometer (OAI Model 356, manufactured by OAI Optical Associates Inc.) is preferably 500 J/m 2 to 6,000 J/m 2 , more preferably 1,500 J/m 2 〜1. 800J/m2 ° -55 - 201142515 &lt;(3) Developing step&gt; In the step (3), the exposed coating film is developed to remove unnecessary portions (irradiated portions of radiation) to form a predetermined Pattern The developing solution used in the step is preferably an alkaline aqueous solution. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia. An inorganic base, a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, etc. Further, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution in an appropriate amount. The concentration of the alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass in view of appropriate developability. For the development method, for example, a suitable method such as a liquid coating method, a dipping method, a vibration dipping method, or a shower method can be used. The development time varies depending on the composition of the positive-type radiation-radiating composition, and is preferably about 1 1 to about 180 seconds. After the development treatment, for example, after 3 to 90 seconds of running water washing, for example, by The compressed air or compressed nitrogen is air-dried to form a desired pattern. &lt;(4) Heating step&gt; In the step (4), heating of the patterned film using a heating means such as a hot plate or an oven can promote Above [A] The hardening reaction of the component [C] is carried out to obtain a cured product. The heating temperature in this step is, for example, 1 2 0 to 250 ° C. The heating time varies depending on the type of the heating device, for example, heating on a hot plate. In the step, it is carried out for 5 to 30 minutes; when the heating step is carried out in an oven, it is '30 to 90 minutes. It is also possible to use a stepwise baking method in which two or more heating steps are performed. Thus, it is possible to form a corresponding surface on the substrate surface. A pattern-like film of the interlayer insulating film is required. -56- 201142515 Further, the above-mentioned cured film is not limited to the interlayer insulating film 'which can be used as a separator or a protective film. &lt;Interlayer insulating film&gt; The film thickness of the interlayer insulating film thus formed is preferably 0.1 to 8', more preferably 0.1 to 6 μm, still more preferably 0.1 to 4 μm, and an interlayer formed by the positive-type radiation-sensitive composition of the present invention. Further, as shown in the following examples, the insulating film can satisfactorily satisfy the generally required properties such as heat resistance, transparency, and voltage holding ratio, and has high flatness without uneven coating. Therefore, the interlayer insulating film is suitable for use as a display element. [Examples] Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples, but the present invention is not limited by the following examples. Hereinafter, the mass average molecular weight (Mw) and the number average molecular weight (?n) of the polymer were measured by gel permeation chromatography (Gpc) under the following conditions. Device: GPC-101 (manufactured by Showa Denko Co., Ltd.) Column: Combination GPC-KF-801, gpc-KF-802, GPC-KF-803 and GPC-KF-804 Mobile phase: Tetrahydrofuran

管柱溫度:40°C 流速:l.OmL /分鐘 試樣濃度:1 .0質量% -57- 201142515 i式樣注入量:1 0 0 μ L 檢測器:差示折射率計 標準物質:單分散聚苯乙烯 &lt;(A)聚合物的合成&gt; [合成例I] 在具有冷凝管和攪拌器的燒瓶中,加入7質量份2,2,-偶氮雙(2,4-二甲基戊腈)、200質量份二乙二醇乙基甲基 醒。接著,加入5質量份甲基丙烯酸' 40質量份甲基丙烯 酸1-乙氧基乙基酯、5質量份苯乙烯、40質量份甲基丙烯 酸縮水甘油基酯、10質量份甲基丙烯酸2 -羥基乙基酯和3 質量份α_甲基苯乙烯二聚物,氮氣置換後,開始緩慢攪拌。 將溶液的溫度上升到7 0。(:,保持該溫度5小時,得到含有 共聚物(A-1)的聚合物溶液。共聚物(A—〗)的聚苯乙烯換算的 質量平均分子量(Mw)是9,000。另外,這裏得到的聚合物 溶液的固體成分濃度是3 2 . 1質量%。 [合成例2] 在具有冷凝管和攪拌器的燒瓶中,加入7質量份2,2,_ 偶氮雙(2,4 -二甲基戊腈)、200質量份二乙二醇乙基甲基 醚。接著’加入5質量份甲基丙烯酸、40質量份甲基丙嫌 酸四氫-2H-哌喃_2_基酯、5質量份苯乙烯、40質量份甲基 丙烯酸縮水甘油基酯、10質量份甲基丙烯酸2-羥基乙基醋 和3質量份α-甲基苯乙烯二聚物,氮氣置換後,開始緩慢 攪拌。將溶液的溫度上升到7 0 °C,保持該溫度5小時,得 •58- 201142515 到含有共聚物(A-〗)的聚合物溶液。共聚物(Α·2)的聚苯乙烯 換算的質量平均分子量(Mw)是9, 〇〇〇。另外,這裏得到的 聚合物溶液的固體成分濃度是31.3質量%。 [合成例3 ] 在具有冷凝管和攪拌器的燒瓶中’加入7質量份2,2'-偶氮雙(2 -甲基丙酸甲酯)、200質量份丙二醇單甲基醚乙酸 酯。接著,加入67質量份甲基丙烯酸1-正丁氧基乙基酯、 23質量份甲基丙烯酸苄基酯、10質量份甲基丙烯酸’氮氣 置換後,開始緩慢攪拌。將溶液的溫度上升到8 0 °C,將該 溫度保持6小時,得到含有共聚物(a- 1 )的聚合物溶液。共 聚物(a-Ι)的聚苯乙烯換算的質量平均分子量(Mw)是 9,000。另外,這裏得到的聚合物溶液的固體成分濃度是 3 0.3質量%。 [合成例4] 在具有冷凝管和攪拌器的燒瓶中,加入7質量份2,2’-偶氮雙(2-甲基丙酸甲酯)、200質量份丙二醇單甲基醚乙酸 酯。接著,加入90質量份甲基丙烯酸1-苄氧基乙基酯、6 質量份甲基丙烯酸2-羥基乙基酯、4質量份甲基丙烯酸, 氮氣置換後,開始緩慢攪拌將溶液的溫度上升到8 0 °C,將 該溫度保持6小時,得到含有共聚物(a_ 2)的聚合物溶液。 共聚物(a-2)的聚苯乙烯換算的質量平均分子量(Mw)是 9,〇〇〇。另外’這裏得到的聚合物溶液的固體成分濃度是 3 1.2質量%。 -59- 201142515 [合成例5] 在具有冷凝管和攪拌器的燒瓶中,加入7質量份2,2’-偶氮雙(2-甲基丙酸甲酯)、200質量份丙二醇單甲基醚乙酸 酯。接著,加入85質量份甲基丙烯酸四氫-2H-哌喃-2-基 酯、7質量份甲基丙烯酸2_羥基乙基酯、8質量份甲基丙烯 酸,氮氣置換後,開始緩慢攪拌。將溶液的溫度上升到8 0 °C,將該溫度保持6小時,得到含有共聚物(a-3)的聚合物 溶液。共聚物(a-3)的聚苯乙烯換算的質量平均分子量(Mw) 是1 0,000。另外,這裏得到的聚合物溶液的固體成分濃度 是2 9.2質量%。 [合成例6] 在具有冷凝管和攪拌器的燒瓶中,加入7質量份2,2,_ 偶氮雙(2,4-二甲基戊腈)、200質量份二乙二醇乙基甲基 醚。接著,加入52質量份甲基丙烯酸縮水甘油基酯、48 質量份甲基丙嫌酸苄基酯,氮氣置換後,開始緩慢攪拌。 將溶液的溫度上升到8 0 °C,將該溫度保持6小時,得到含 有共聚物(aa-Ι)的聚合物溶液。共聚物(aa—丨)的聚苯乙稀換 算的質量平均分子量(Mw)是10,000。另外,這裏得到的聚 合物溶液的固體成分濃度是32.3質量%。 [合成例7] 在具有冷凝管和攪拌器的燒瓶中,加入7質量份2,2,_ 偶氮雙(2,4- —甲基戊腈)、200質量份二乙二醇乙基甲基 醚。接著’加入45質量份甲基丙烯酸3,4_環氧環己基甲基 -60- 201142515 酯、45質量份甲基丙烯酸苄基酯、ι〇質量份甲基丙烯酸, 氮氣置換後’開始緩慢攪拌。將溶液的溫度上升到8 01:, 將該溫度保持6小時,得到含有共聚物(aa_2)的聚合物溶 液。共聚物(aa-2)的聚苯乙烯換算的質量平均分子量(Mw) 是1 0,000。另外’這裏得到的聚合物溶液的固體成分濃度 是3 3.2質量%。 [合成例8] 在具有冷凝管和攪拌器的燒瓶中,加入7質量份2,2·-偶氮雙(2,4_二甲基戊腈)、200質量份二乙二醇乙基甲基 醚。接著’加入35質量份甲基丙烯酸丨_正丁氧基乙基酯、 35質量份甲基丙烯酸苄基酯、30質量份甲基丙烯酸縮水甘 油酯,氮氣置換後’開始緩慢攬拌。將溶液的溫度上升到 8〇°C ’將該溫度保持6小時,得到含有共聚物(aa_3)的聚合 物溶液。共聚物(aa-3)的聚苯乙烯換算的質量平均分子量 (Mw)是1 0,000。另外’這裏得到的聚合物溶液的固體成分 濃度是3 2.3質量%。 &lt;感放射線性組成物的製備&gt; [實施例1 ] 在含有合成例1得到的聚合物(A-1)的溶液[相當於1〇〇 質量份(固體含量)聚合物(A-1)的量]中混合:作爲[B]成分 的4質量份[(樟腦磺醯氧亞胺基_5H_噻吩-2-亞基)_(2_甲基 本)乙腈](Ciba · Specialty . Chemicals 公司製造的 「CGI 1 3 8 0」)、作爲[C]成分的1質量份參-(3,5-二第三丁 -61- 201142515 基-4-羥基苄基)-異氰酸酯(ADEKA公司製造的「Adekastab AO-20」)、作爲[D]成分的0.20質量份有機矽樹脂類界面 活性劑((股)TORAY · DOW CORNING 製造的 「SH8400FLUID」)、作爲[E]成分的3.0質量份γ-縮水甘油 丙基三甲氧基矽烷,以孔徑0.2 μηι的薄膜濾器過濾,由此 製備感放射線性組成物(S -1 )。 〈實施例2〜10、比較例1~4&gt; 除了各成分的種類以及量如表1記載以外,與實施例 1相同製備正型感放射線性組成物。另外,在各實施例以 及比較例採用的成分如下。 〈光酸產生劑[Β] &gt; (Β-1): 4,7-二正丁氧基-1-萘基四氫噻吩鑰三氟甲磺酸 鹽 (Β-2):苄基-4-羥基苯基甲基鏑六氟磷酸鹽 (Β-3): [(5-丙基磺醯氧亞胺基- 5Η_噻吩-2-亞基)-(2-甲 基苯)乙腈](Ciba . Specialty · Chemicals 公司製造的 「IRGACUREPAG 1 03」) (B-4): [(5-辛基磺醯氧亞胺基- 5H-噻吩-2-亞基)-(2-甲 基苯)乙腈](Ciba . Specialty · Chemicals 公司製造的 「IRGACUREPAG108」) (B-5): [(5-對甲苯磺醯氧亞胺基- 5H-噻吩-2-亞基)-(2-甲基苯)乙腈](Ciba. Specialty. Chemicals公司製造的 「IRGACUREPAG 1 2 1」) -62- 201142515 (Β·6):[(樟腦磺醯氧亞胺基- 5H-噻吩-2-亞基)-(2-甲基 苯)乙腈](Ciba . Specialty . Chemicals 公司製造的 「CGI 1 3 80」) (B-7): [(5 -辛基磺醯氧亞胺基-(4-甲氧基苯)乙 腈](Ciba· Specialty · C h em i c a 1 s 社製 Φ「C G17 2 5」) 〈化合物[C ] &gt; (C-l):參- (3,5-二-第三丁基-4·羥基苄基)-異氰酸酯 (ADEKA 公司製造的「AdekastabAO-20」) (C-2): 1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基 苄基)苯(ADEKA公司生產「AdekastabAO-330」) (C-3) : 2,2·-亞甲基二(4,6·二-第三丁基-1-苯基氧 基)(2-乙基己基氧基)磷(ADEKA公司生產的「Adekastab HP-1 0」) (C-4):二硬脂醯新戊四醇二亞磷酸酯(ADEKA公司生 產的「AdekastabPEP-8」) (C-5):新戊四醇肆(3_月桂基硫丙酸酯)(ADEKA公司 生產的「AdekastabAO-412S」) 〈界面活性劑[D ] &gt; (D-1):聚矽氧系界面活性劑(TORAY . DOW CORNING 公司生產的「SH8400FLUID」)Column temperature: 40 ° C Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass -57- 201142515 i Sample injection amount: 1 0 0 μ L Detector: Differential refractometer standard material: monodisperse Synthesis of Polystyrene &lt;(A) Polymer&gt; [Synthesis Example I] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2,-azobis(2,4-dimethyl group) was added. Valeronitrile), 200 parts by mass of diethylene glycol ethyl methyl group. Next, 5 parts by mass of methacrylic acid '40 parts by mass of 1-ethoxyethyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, and 10 parts by mass of methacrylic acid 2 - were added. The hydroxyethyl ester and 3 parts by mass of the α-methylstyrene dimer were slowly stirred after being replaced by nitrogen. The temperature of the solution was raised to 70. (: While maintaining the temperature for 5 hours, a polymer solution containing the copolymer (A-1) was obtained. The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (A-) was 9,000. The solid content concentration of the polymer solution was 32.1% by mass. [Synthesis Example 2] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2,_ azobis (2,4-dimethicone) was added. Base valeronitrile), 200 parts by mass of diethylene glycol ethyl methyl ether, followed by 'addition of 5 parts by mass of methacrylic acid, 40 parts by mass of methyl propyl succinic acid tetrahydro-2H-piperidin-2-yl ester, 5 A part by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate and 3 parts by mass of α-methylstyrene dimer, after nitrogen substitution, started to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-) from 58-201142515. The polystyrene-converted mass of the copolymer (Α·2) The average molecular weight (Mw) is 9, 〇〇〇. In addition, the solid content concentration of the polymer solution obtained here is 31.3. [Synthesis Example 3] In a flask having a condenser and a stirrer, '7 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether were added. Acetate. Then, 67 parts by mass of 1-n-butoxyethyl methacrylate, 23 parts by mass of benzyl methacrylate, and 10 parts by mass of methacrylic acid 'nitrogen substitution were added, and stirring was started slowly. The temperature was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (a-1). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (a-fluorene) was Further, the solid content concentration of the polymer solution obtained here was 3 0.3% by mass. [Synthesis Example 4] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2) was added. -methyl methacrylate), 200 parts by mass of propylene glycol monomethyl ether acetate. Next, 90 parts by mass of 1-benzyloxyethyl methacrylate and 6 parts by mass of 2-hydroxyethyl methacrylate were added. Ester, 4 parts by mass of methacrylic acid, after nitrogen replacement, start slowly stirring to raise the temperature of the solution The temperature was maintained at 80 ° C for 6 hours to obtain a polymer solution containing the copolymer (a-2). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (a-2) was 9, 〇〇〇 Further, the solid content concentration of the polymer solution obtained here was 3 1.2% by mass. -59- 201142515 [Synthesis Example 5] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2'-azo was added. Bis(methyl 2-methylpropionate), 200 parts by mass of propylene glycol monomethyl ether acetate, and then, 85 parts by mass of tetrahydro-2H-pentan-2-yl methacrylate, 7 parts by mass After 2-hydroxyethyl acrylate and 8 parts by mass of methacrylic acid were replaced by nitrogen, stirring was started slowly. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (a-3). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (a-3) was 1,0,000. Further, the solid content concentration of the polymer solution obtained here was 29.2% by mass. [Synthesis Example 6] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2,-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl group were added. Ether. Next, 52 parts by mass of glycidyl methacrylate and 48 parts by mass of benzyl propyl methacrylate were added, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing a copolymer (aa-Ι). The mass average molecular weight (Mw) of the polystyrene of the copolymer (aa-丨) was 10,000. Further, the solid content concentration of the polymer solution obtained here was 32.3% by mass. [Synthesis Example 7] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2,-azobis(2,4-methylpentanenitrile) and 200 parts by mass of diethylene glycol ethyl group were added. Ether. Then, '45 parts by mass of 3,4_epoxycyclohexylmethyl-60-201142515 methacrylate, 45 parts by mass of benzyl methacrylate, and 1 part by mass of methacrylic acid were added, and the mixture was slowly stirred. . The temperature of the solution was raised to 801:, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (aa_2). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (aa-2) was 1,0,000. Further, the solid content concentration of the polymer solution obtained here was 33.3% by mass. [Synthesis Example 8] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2·-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl group were added. Ether. Then, 35 parts by mass of cesium-n-butoxyethyl methacrylate, 35 parts by mass of benzyl methacrylate, and 30 parts by mass of glycidyl methacrylate were added, and after the replacement with nitrogen, the mixture was slowly stirred. The temperature of the solution was raised to 8 ° C to maintain the temperature for 6 hours to obtain a polymer solution containing the copolymer (aa - 3). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (aa-3) was 1,0,000. Further, the solid content concentration of the polymer solution obtained here was 3 2.3% by mass. &lt;Preparation of Radiation-sensitive Composition&gt; [Example 1] A solution containing the polymer (A-1) obtained in Synthesis Example 1 [corresponding to 1 part by mass (solid content) polymer (A-1) Mixture: 4 parts by mass of [B] component [(camphorsulfonyloxyimido]5H_thiophene-2-ylidene)-(2-methylbenzidine)acetonitrile] (Ciba · Specialty . Chemicals "CGI 1 3 80" manufactured by the company, 1 part by mass of ginseng-(3,5-di-tert-butyl-61-201142515-based 4-hydroxybenzyl)-isocyanate (made by ADEKA) as component [C] "Adekastab AO-20"), 0.20 parts by mass of the organic resin resin surfactant ("SH8400FLUID" manufactured by TORAY DOW CORNING), and 3.0 parts by mass of γ as the component [E] as the component [D] - Glycidylpropyltrimethoxydecane, which was filtered through a membrane filter having a pore size of 0.2 μm, thereby preparing a radiation sensitive composition (S-1). <Examples 2 to 10, Comparative Examples 1 to 4> A positive-type radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of the respective components were as described in Table 1. Further, the components used in the respective examples and comparative examples were as follows. <Photoacid generator [Β] &gt; (Β-1): 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate (Β-2): benzyl-4 -hydroxyphenylmethylphosphonium hexafluorophosphate (Β-3): [(5-propylsulfonyloxyimido-5 Ηthiophen-2-yl)-(2-methylphenyl)acetonitrile] ( "IRGACUREPAG 1 03" (B-4) manufactured by Ciba Specialty Chemicals, Inc. (B-4): [(5-octylsulfonyloxyimido-5H-thiophene-2-ylidene)-(2-methylbenzene) Acetonitrile] ("IRGACUREPAG108", manufactured by Ciba. Specialty Chemicals, Inc.) (B-5): [(5-p-toluenesulfonyloxyimido-5H-thiophene-2-ylidene)-(2-methylbenzene) ) acetonitrile] ("IRGACUREPAG 1 2 1", manufactured by Ciba. Specialty. Chemicals) - 62- 201142515 (Β·6): [( camphorsulfonyloxyimino- 5H-thiophene-2-ylidene)-( 2-methylbenzene)acetonitrile] ("CGI 1 3 80" manufactured by Ciba. Specialty.) (B-7): [(5-octylsulfonyloxyimino-(4-methoxybenzene) ) acetonitrile] (Φ "C G17 2 5" manufactured by Ciba· Specialty · C h em ica 1 s) <Compound [C ] &gt; (Cl): gin-(3,5-di-t-butyl-4 ·Hydroxybenzyl)-isocyanate (ADEKA "AdekastabAO-20" (C-2) manufactured by the company: 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) Benzene ("Adekastab AO-330" produced by ADEKA) (C-3) : 2,2·-methylenebis(4,6·di-t-butyl-1-phenyloxy)(2-ethyl Hexyloxy)phosphorus ("Adekastab HP-1 0" by ADEKA) (C-4): Distearyl neopentyl glycol diphosphite ("AdekastabPEP-8" by ADEKA) (C- 5): Neopentyl alcohol oxime (3_lauryl thiopropionate) ("Adekastab AO-412S" manufactured by ADEKA Corporation) <Interfacial agent [D ] &gt; (D-1): Polyoxonium interface activity Agent ("SH8400FLUID" by DOW CORNING)

(D-2):氟系界面活性劑(NE〇S公司生產的「FTERGENT FTX-2 1 8」) -63- 201142515 〈密合助劑[E] &gt; (E-l) : γ-縮水甘油氧基丙基三甲氧基矽烷 (Ε-2): β-(3,4-環氧環己基)乙基三甲氧基矽烷 (Ε-3): γ-甲基丙烯醯氧基丙基三甲氧基矽烷 &lt;鹼性化合物[F]〉 (F-1) : 4-二甲基胺基吡啶 (F-2) : 1,5-二吖雙環[4,3,0]-5-壬烯 &lt;物性評價&gt; 使用如上製備的各種正型感放射線性組成物,如下評 價該組成物及其作爲塗膜或層間絕緣膜等的各種性質。評 價結果在下述表1中表示。 (1)感放射線度的評價 在550x650mm的鉻成膜的玻璃上,塗布六甲基二矽氮 烷(HMDS),在60 °C加熱1分鐘(以下,也稱爲「HMDS處 理」)。在該HMDS處理後的鉻成膜的玻璃上將如上述製備 的感放射線性組成物以縫模塗布機「TR63 2 1 0 5 -CL」進行 塗布,將極限壓力設置爲1 OOPa,在真空下除去溶劑。其 後,進一步在90°C環境下,進行2分鐘預烘烤,由此形成 膜厚 3·0μιη的塗膜。接著,採用 CANON(股)製造的 MPA-600FA光刻機,以具有60μιη的線與間隙比(10比1) 的圖案的光罩對塗膜以曝光量作爲變數而照射放射線,然 後以表1所記載的濃度的氫氧化四甲銨水溶液,在2 5 t的 環境下以覆液法進行顯影。在此,顯影時間如下,在採用 -64 - 201142515 氫氧化四甲銨水溶液濃度在〇.4〇質量%的顯影液的情況τ 爲8 0秒,在採用2 · 3 8質量%的顯影液的情況下爲5 〇秒。 接著,採用超純水進行1分鐘的流水清洗,其後,藉由乾 燥’在HMDS處理後的鉻成膜的玻璃基板上形成圖案。此 時,爲了使6 μ m的間隙圖案完全溶解,調整必要的曝光量, 進行評價。該値在5 0 0J / m 2以下的情況可稱之爲敏感度良 (2 )耐光性的評價 在矽基板上採用旋塗器塗覆組成物,然後,在90°C環 境下,在加熱板上進行2分鐘預烘烤,由此形成膜厚3.Ομηι 的塗膜。將該有機矽基板在無塵烘箱內以220°C加熱1小 時,得到硬化膜。在該硬化膜上,以UV照射裝置(US ΗIO 公司生產的「UVX-02516S1JS01」)在 13 0mW的照度下照 射8 00,0 00 J/m2。與照射前的膜厚比較,如果照射後的膜厚 的減少量在2%以下,則可稱之爲膜耐光性良好。 另外,耐光性的評價中,形成的膜的形成圖案是不需 要的,因此省略了顯影步驟,僅進行了塗膜形成步驟、.耐 光性實驗以及加熱步驟,進行評價。 (3)耐熱性的評價 與上述耐光性的評價相同,在矽基板上形成塗膜。將 該矽基板在無塵烘箱內以2 2 0 t加熱1小時,得到硬化 膜。測定所得硬化膜的膜厚(T2)。接著’將形成有該硬化 膜的矽基板在乾淨烘箱內以240°C追加烘烤1小時’然後 -65- 201142515 測定該硬化膜的膜厚(t2) ’算出基於追加烘烤的膜厚變化 率{丨t2-T2| /T2}xl〇〇〔%〕。耐熱性的評價結果在表1中 表示。該値在3%以下的情況下,可稱之爲耐熱性良好。 (4) 透光率的評價 與上述耐光性的評價相同,在矽基板上形成塗膜。將 該矽基板在乾淨烘箱內以220°C加熱1小時,得到硬化膜。 將在波長400nm下的透光率以分光光度計(日立製作所製 造的「150-20型DoubleBeam」)進行測定,進行評價。此 時,不足90%的情況下,稱之爲透明性不合格。 (5) 耐熱透明性的評價 對於以上述(4)透光率的評價測定的基板,進一步在無 塵烘箱內以250°C加熱1小時,將加熱前後的光線透光率 以上述(4)「透光率的評價」所記載的方法測定之後’按照 下述式算出耐熱透明性。該値在4%以下時,判斷爲耐熱透 明性良好。 耐熱透明性(%)=「(4)透光率的評價」所測定的透光 率(%)-加熱後的透光率(%) (6) 電壓保持率的評價 在製備的液狀組成物的表面,形成防止鈉離子析出的 Si 02膜、進一步將ITO(銦-氧化錫合金)電極在以規定形狀 蒸鑛後的鈉鈣玻璃基板上進行旋塗,然後在9〇°C的無塵烘 箱內以10分鐘進行預烘烤,形成膜厚2.0 μπι的塗膜。 -66- 201142515 接著’不藉由光罩而對塗膜以5 00 J/m2的曝光量進行 曝光。其後’在2 3 0 °C進行3 0分鐘的後烘烤,使塗膜硬化, 形成永久硬化膜。 接著,將形成了該畫素的基板和僅將ITO電極以規定 形狀蒸鍍後的基板採用密封劑進行貼合,該密封劑混合了 0.8mm的玻璃珠,然後,注入 Merck公司生產的液晶 MLC660 8 (商品名),製作液晶胞。 接著,將液晶胞放入60°C的恆溫層,將液晶胞的電壓 保持率以液晶電壓保持率測定系統(TOYO Technica公司生 產的「VHR-1A型」)進行測定。此時的外加電壓爲5.5V的 方形波、測定頻率爲60Hz。在此,所謂電壓保持率爲(16.7 毫秒後的液晶胞的電位差/0毫秒施加的電壓)的値。液晶胞 的電壓保持率在9 0 %以下的情況下’表示液晶胞在1 6 · 7毫 秒的時間,無法將施加電壓保持在規定水準,不能充分的 將液晶進行取向,引起殘影等的燒屏的危險性高。 -67- 201142515 i 丨比關4 1 寸 1 i/i 〇*» 〇 〇 ι^&gt; ο» 丨比纖3 CO 1 Μ 〇 cr\ o 8 1〇 U-) l£&gt; 丨比較例2 (Μ 1 ω § ίΛ 〇 rr, o ΓΛ ΓΛ Ό Ο» 卜 s 1比關1 r*H 1 w O *r 〇 m o 8 U-) ΓΛ kD 〇\ 卜 a; I實施例10 ο »-Η 1 00 00 1〇 cn fvj — 一 〇 rn O o 8 — (Ν ι〇 Ο 丨實施例9 σ) 1 ΙΟ LO on csj - 一 〇 m o o 8 ι〇 &lt;^\ &lt;SJ 施例8 /—V CO 1 00 VwZ LO CsJ —1 - 〇 o o 另 - ΟΟ m 3; 實施例7 卜 1 t/i Sw&lt;· S — — Ο o ο — CN3 § &lt;S) 實施例6 CO 1 CO Sw^ — — 〇 CT) o 8 *— Γ&lt;1 CNJ 丨實施例5 in I lO V__' 另 — 〇 ΓΛ o 03 沒 ci 寶施例4 寸 1 CO Nw^ 〇 rr, 一 Ο ΓΤ» &lt;^3 寸 CVJ &lt;*&lt;*ί &lt;D\ C^J 實施例3 /»—N CO 1 in v_/ 8 — 〇 ο 〇 «Ν (Μ s m 1實施例2 r—N cs] 1 w 8 一 Ο cn o o § 05 ΓΛ S; rr\ 1實施例1 «•&quot;S r-H 1 w 8 — 〇 ίΛ o § ΓΛ y〇 Oi m s •-H 1 &lt; 03 1 &lt;: J—S 1 03 1 03 C0 1 C3 1 C0 03 1 03 03 y&lt;~&gt;\ 00 1 OT /^~v 1 PQ (M 1 DP 1 (B-3) , 1 m 1 m Ξ 1 CQ 1 DQ 1 o 1 〇 1 〇 ✓ 1 〇 &gt;w· 1 〇 1 Q 03 1 Q 1 ω Nw^ CM 1 ω CO 1 ω 1 {X4 s 1 tL, 顯影液濃度(質簠%)1 放射線感度U/m2) 耐光性(%) 1 耐熱性(%) 1 透醉(%) 1 耐熱透明性(%) 1 電壓保持率(½) 1 〔A ]結構 單元: (質量份) S ^ 米E $ 〇□ S 〔c〕防氧 化劑 (質量份) 51 Q靼 S—J 〔E〕密合 助劑 (質量份) 1〔F〕鹼性 化合物 :放射線感度 組成物 評價 -89- s 201142515 從表1的結果可以明白如下,含[A]、[B]以及[C]成分 的實施例1〜1 0的正型感放射線性組成物與不含[C]成分的 比較例1 ~4正型感放射線性組成物相比,具有高耐光性、 高耐熱性,而且可以形成下述層間絕緣膜,即能夠充分滿 足感放射線度、透明性、耐熱透明性以及耐溶劑性這些一 般的要求特性。 [產業上的利用可能性] 本發明的正型感放射線性組成物如上所述,在高水準 的保持感放射線性組成物的感放射線度的同時’抑制自由 基或過氧化物的發生,由此可形成具有優異的耐光性以及 耐熱性,而且抑制透光率、耐熱透明性以及電壓保持率的 降低的層間絕緣膜的正型感放射線性組成物而適宜使用。 【圖式簡單說明】 無。 【主要元件符號說明】 無0 -69-(D-2): Fluorine-based surfactant ("FTERGENT FTX-2 1 8" by NE〇S) -63- 201142515 <Adhesion aid [E] &gt; (El) : γ-glycidyloxy Propyltrimethoxydecane (Ε-2): β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (Ε-3): γ-methylpropenyloxypropyltrimethoxy Decane &lt;Basic Compound [F]> (F-1) : 4-Dimethylaminopyridine (F-2) : 1,5-Dioxabicyclo[4,3,0]-5-decene &lt;lt Physical Property Evaluation&gt; Using the various positive-type radiation-sensitive compositions prepared as above, the composition and various properties thereof as a coating film or an interlayer insulating film were evaluated as follows. The evaluation results are shown in Table 1 below. (1) Evaluation of sensitivities hexamethyldioxane (HMDS) was applied to 550 x 650 mm chromium-formed glass and heated at 60 ° C for 1 minute (hereinafter also referred to as "HMDS treatment"). On the HMDS-treated chromium-formed glass, the radiation-sensitive composition prepared as described above was applied by a slit die coater "TR63 2 1 0 5 -CL", and the ultimate pressure was set to 100 Pa under vacuum. Remove the solvent. Thereafter, prebaking was further carried out for 2 minutes in an environment of 90 ° C to form a coating film having a film thickness of 3.0 μm. Next, using a MPA-600FA lithography machine manufactured by CANON, a reticle having a pattern of a line-to-gap ratio (10:1) of 60 μm was used to irradiate the radiation on the coating film with the exposure amount as a variable, and then to Table 1 The tetramethylammonium hydroxide aqueous solution having the stated concentration was developed by a liquid coating method in an environment of 25 t. Here, the development time is as follows, in the case where the concentration of the aqueous solution of tetramethylammonium hydroxide in -64 - 201142515 is 0.4% by mass in the case of τ is 80 seconds, and in the case of using 23.8% by mass of the developer In the case of 5 sec. Next, water washing was performed for 1 minute using ultrapure water, and thereafter, a pattern was formed by drying on a glass substrate formed by chrome plating after HMDS treatment. At this time, in order to completely dissolve the 6 μm gap pattern, the necessary exposure amount was adjusted and evaluated. The case where the 値 is below 500 J / m 2 may be referred to as good sensitivity. (2) Evaluation of light resistance The composition is coated on a ruthenium substrate by a spin coater, and then heated at 90 ° C. The plate was prebaked for 2 minutes to form a coating film having a film thickness of 3.Οηη. The organic tantalum substrate was heated at 220 ° C for 1 hour in a dust-free oven to obtain a cured film. On the cured film, a UV irradiation device ("UVX-02516S1JS01" manufactured by US IO Corporation) was irradiated at 800 00 J/m 2 at an illuminance of 130 mW. When the amount of reduction in film thickness after irradiation is 2% or less as compared with the film thickness before irradiation, it can be said that the film has good light resistance. Further, in the evaluation of the light resistance, the formation pattern of the formed film was not required, so that the development step was omitted, and only the coating film forming step, the light resistance test, and the heating step were carried out, and evaluation was performed. (3) Evaluation of heat resistance A coating film was formed on the ruthenium substrate in the same manner as the above evaluation of light resistance. The tantalum substrate was heated in a dust-free oven at 2 200 t for 1 hour to obtain a cured film. The film thickness (T2) of the obtained cured film was measured. Then, the base material on which the cured film was formed was additionally baked at 240 ° C for 1 hour in a clean oven. Then, the film thickness (t2) of the cured film was measured at -65 to 201142515. Rate {丨t2-T2| /T2}xl〇〇[%]. The evaluation results of heat resistance are shown in Table 1. When the enthalpy is 3% or less, it can be said that the heat resistance is good. (4) Evaluation of light transmittance A coating film was formed on the ruthenium substrate in the same manner as the above evaluation of light resistance. The crucible substrate was heated at 220 ° C for 1 hour in a clean oven to obtain a cured film. The light transmittance at a wavelength of 400 nm was measured by a spectrophotometer ("150-20 type DoubleBeam" manufactured by Hitachi, Ltd.) and evaluated. At this time, less than 90% of the cases are called unacceptable transparency. (5) Evaluation of heat-resistant transparency The substrate measured by the above (4) evaluation of light transmittance was further heated at 250 ° C for 1 hour in a dust-free oven, and the light transmittance before and after heating was as described above (4) After the measurement of the method described in "Evaluation of Light Transmittance", the heat-resistant transparency was calculated according to the following formula. When the enthalpy is 4% or less, it is judged that the heat resistance and transparency are good. Heat-resistant transparency (%) = "(4) Light transmittance (%) - Light transmittance after heating (%) (6) Evaluation of voltage retention rate In preparation of liquid composition On the surface of the object, a Si 02 film for preventing precipitation of sodium ions is formed, and an ITO (indium-tin oxide alloy) electrode is further spin-coated on a soda lime glass substrate having a predetermined shape and then subjected to spin coating at 9 ° C. The film was prebaked in a dust oven for 10 minutes to form a coating film having a film thickness of 2.0 μm. -66- 201142515 Next, the coating film was exposed to an exposure amount of 500 J/m 2 without using a photomask. Thereafter, post-baking was performed at 30 ° C for 30 minutes to cure the coating film to form a permanent cured film. Next, the substrate on which the pixel was formed and the substrate on which only the ITO electrode was vapor-deposited in a predetermined shape were bonded together with a sealant. The sealant was mixed with a glass bead of 0.8 mm, and then injected into a liquid crystal MLC660 manufactured by Merck. 8 (trade name), making liquid crystal cells. Then, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measuring system ("VHR-1A type" manufactured by TOYO Technica Co., Ltd.). At this time, the applied voltage was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is 値 (the potential difference of the liquid crystal cell after 16.7 milliseconds / the voltage applied by 0 milliseconds). When the voltage holding ratio of the liquid crystal cell is less than 90%, 'the liquid crystal cell is in the time of 16.7 milliseconds, and the applied voltage cannot be maintained at a predetermined level, and the liquid crystal cannot be sufficiently oriented to cause burnt of the residual image or the like. The danger of the screen is high. -67- 201142515 i 丨比关4 1 inch 1 i/i 〇*» 〇〇ι^&gt; ο» 丨比纤3 CO 1 Μ 〇cr\ o 8 1〇U-) l£&gt; 丨Comparative example 2 (Μ 1 ω § ίΛ 〇rr, o ΓΛ ΓΛ Ό Ο » 卜 s 1 to 1 1 r*H 1 w O *r 〇mo 8 U-) ΓΛ kD 〇\ 卜 a; I Example 10 ο »- Η 1 00 00 1〇cn fvj — 一〇rn O o 8 — (Ν ι〇Ο 丨Example 9 σ) 1 ΙΟ LO on csj - One moo 8 ι〇&lt;^\ &lt;SJ Example 8 / —V CO 1 00 VwZ LO CsJ —1 — 〇oo - ΟΟ m 3; Example 7 卜 1 t/i Sw&lt;· S — — Ο o ο — CN3 § &lt;S) Example 6 CO 1 CO Sw ^ — — 〇CT) o 8 *— Γ&lt;1 CNJ 丨Example 5 in I lO V__' Another — 〇ΓΛ o 03 No ci Bao Example 4 Inch 1 CO Nw^ 〇rr, 一Ο ΓΤ» &lt;^ 3 inch CVJ &lt;*&lt;*ί &lt;D\ C^J Example 3 /»—N CO 1 in v_/ 8 — 〇ο 〇«Ν (Μ sm 1 Example 2 r—N cs] 1 w 8 一Ο cn oo § 05 ΓΛ S; rr\ 1 Example 1 « •&quot;S rH 1 w 8 — 〇ίΛ o § ΓΛ y〇Oi ms •-H 1 &lt; 03 1 &lt;: J—S 1 03 1 03 C0 1 C3 1 C0 03 1 03 03 y&lt;~&gt; \ 00 1 OT /^~v 1 PQ (M 1 DP 1 (B-3) , 1 m 1 m Ξ 1 CQ 1 DQ 1 o 1 〇1 〇✓ 1 〇&gt;w· 1 〇1 Q 03 1 Q 1 ω Nw^ CM 1 ω CO 1 ω 1 {X4 s 1 tL, developer concentration (mass 簠%) 1 radiation sensitivity U/m2) light resistance (%) 1 heat resistance (%) 1 drunk (%) 1 Heat resistance and transparency (%) 1 Voltage holding ratio (1⁄2) 1 [A ] Structural unit: (mass) S ^ m E $ 〇 □ S [c] Antioxidant (parts by mass) 51 Q靼S—J [E] Adhesive auxiliary (parts by mass) 1 [F] Basic compound: Evaluation of radiation sensitivity composition -89- s 201142515 From the results of Table 1, it can be understood that the implementation of [A], [B], and [C] components is included. The positive-type radiation linear composition of Examples 1 to 10 is not contained in [C] Comparative Example 1 to 4 The positive-type radiation-sensitive linear composition has high light resistance and high heat resistance, and the following interlayer insulating film can be formed, that is, the radiation sensitivity, transparency, heat-resistant transparency, and resistance can be sufficiently satisfied. These general required characteristics of solvent properties. [Industrial Applicability] As described above, the positive-type radiation-sensitive composition of the present invention suppresses the generation of radicals or peroxides while maintaining the radiation sensitivity of the radiation-sensitive linear composition at a high level. This can be suitably used by forming a positive-type radiation-sensitive composition of an interlayer insulating film which has excellent light resistance and heat resistance and which suppresses reduction in light transmittance, heat-resistant transparency, and voltage holding ratio. [Simple description of the diagram] None. [Main component symbol description] No 0 -69-

Claims (1)

201142515 七、申請專利範圍: 1 · 一種正型感放射線性組成物,其包括:[A]在相同或不同 聚合物分子中具有包含下述式(1)所示的基的結構單元和 含環氧基的結構單元的聚合物; [B]光酸產生劑;以及 [C ]從含受阻酚結構的化合物、含受阻胺結構的化合 物、含亞磷酸烷基酯結構的化合物以及含硫醚結構的化 合物構成的群組中選出的一種或兩種以上化合物, R1 —〇—C—OR3 (1) I Rz 式(1)中,R1和R2各自獨立地是氫原子、烷基、環烷 基或芳基,這些烷基、環烷基或芳基的氫原子的一部分 或全部可以被取代基取代,其中,不包括R1和R2都是氫 原子的情形,R3是烷基、環烷基、芳烷基、芳基或-M(R3m) 3 所示的基’ Μ是Si、Ge或Sn,R3m是烷基,這些的氫原 子的一部分或全部可以被取代基取代,R1和R3可以連接 形成環狀醚。 2 .如申請專利範圍第1項的正型感放射線性組成物,其中 [B]光酸產生劑含有下述式(2)所表示的肟磺酸酯基, -70- 201142515 ο 、C=N—〇 —s — Rb, (2) / II ο 式(2)中,RB1表示烷基、環烷基或芳基,這些基的氫 原子的一部分或全部可以被取代基取代。 3 .如申請專利範圍第1或2項的正型感放射線性組成物, 其中相對於1〇〇質量份[A]聚合物,[C]化合物的含量在 〇 · 1質量份以上、1 〇質量份以下。 4 .如申請專利範圍第1或2項的正型感放射線性組成物’ 其係用於形成顯示元件用的層間絕緣膜。 5. —種顯示元件用層間絕緣膜的形成方法,其係具有下述 步驟: (1 )將如申請專利範圍第4項的正型感放射線性組成 物的塗膜形成於基板上的步驟; (2) 對在步驟(1 )形成的塗膜的至少一部分照射放射 線的步驟; (3) 對在步驟(2)中經照射放射線的塗膜進行顯影的 步驟;以及 (4) 對在步驟(3)經顯影的塗膜進行加熱的步驟。 6. —種顯示元件用的層間絕緣膜,其係由如申請專利範圍 第4項的正型感放射線性組成物形成。 -71 - 201142515 四、指定代表圖: (一) 本案指定代表圖為:無。 (二) 本代表圖之元件符號簡單說明: Μ 〇 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式:201142515 VII. Patent Application Range: 1 · A positive-type radiation-linear composition comprising: [A] a structural unit having a group represented by the following formula (1) and a ring-containing ring in the same or different polymer molecules a polymer of a structural unit of an oxy group; [B] a photoacid generator; and [C] a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and a thioether-containing structure One or two or more compounds selected from the group consisting of compounds, R1 - 〇 - C - OR3 (1) I Rz In the formula (1), R1 and R2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group Or an aryl group, a part or all of the hydrogen atom of the alkyl group, the cycloalkyl group or the aryl group may be substituted by a substituent, wherein R1 and R2 are both a hydrogen atom, and R3 is an alkyl group or a cycloalkyl group. The arylalkyl group, the aryl group or the group represented by -M(R3m) 3 is Si, Ge or Sn, and R3m is an alkyl group. Some or all of these hydrogen atoms may be substituted by a substituent, and R1 and R3 may be bonded. A cyclic ether is formed. 2. The positive-type radiation-sensitive linear composition according to claim 1, wherein the [B] photo-acid generator contains an oxime sulfonate group represented by the following formula (2), -70-201142515 ο, C= N—〇—s — Rb, (2) / II In the formula (2), RB1 represents an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent. 3. The positive-type radiation-sensitive linear composition according to claim 1 or 2, wherein the content of the [C] compound is 〇·1 part by mass or more and 1 相对 with respect to 1 part by mass of the [A] polymer. Below the mass. 4. A positive-type radiation-sensitive composition as claimed in claim 1 or 2 which is used for forming an interlayer insulating film for a display element. 5. A method of forming an interlayer insulating film for a display element, comprising the steps of: (1) forming a coating film of a positive-type radiation-sensitive composition according to claim 4 of the patent application form on a substrate; (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation; (3) a step of developing the coating film irradiated with radiation in the step (2); and (4) a step in the step ( 3) A step of heating the developed coating film. An interlayer insulating film for a display element which is formed of a positive type radiation-sensitive composition as in the fourth aspect of the patent application. -71 - 201142515 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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