TW200905397A - Method for film formation, resin composition for use in the method, structure having insulating film, process for producing the structure, and electronic component - Google Patents

Method for film formation, resin composition for use in the method, structure having insulating film, process for producing the structure, and electronic component Download PDF

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Publication number
TW200905397A
TW200905397A TW097111057A TW97111057A TW200905397A TW 200905397 A TW200905397 A TW 200905397A TW 097111057 A TW097111057 A TW 097111057A TW 97111057 A TW97111057 A TW 97111057A TW 200905397 A TW200905397 A TW 200905397A
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Taiwan
Prior art keywords
film
resin composition
substrate
solvent
mass
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TW097111057A
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Chinese (zh)
Inventor
Ryuichi Okuda
Takayoshi Tanabe
Hirofumi Goto
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Jsr Corp
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Priority claimed from JP2007307985A external-priority patent/JP2009133924A/en
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW200905397A publication Critical patent/TW200905397A/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H01L21/3083—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
    • H01L21/76831—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
    • H—ELECTRICITY
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    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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    • H01L2224/05001—Internal layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/02—Bonding areas; Manufacturing methods related thereto
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    • H01L2224/05005—Structure
    • H01L2224/05009—Bonding area integrally formed with a via connection of the semiconductor or solid-state body
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
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    • H01L2224/0502—Disposition
    • H01L2224/05025—Disposition the internal layer being disposed on a via connection of the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/0554—External layer
    • H01L2224/0556—Disposition
    • H01L2224/05568—Disposition the whole external layer protruding from the surface
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/0556—Disposition
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    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
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    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • H01L2924/151—Die mounting substrate
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    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA

Abstract

This invention provides a method for film formation, which can easily form, with high accuracy, an even film on an inner wall face or a bottom face in a fine pore or groove part having a bottom provided on, for example, on a stepped silicon substrate, and a resin composition for use in the method, a structure having an insulating film, a process for producing the structure, and an electronic component. The method for film formation comprises [1] a solvent coating step of coating a solvent (13) on a stepped substrate (1) having at least one of (a) a pore part (11) having an opening part area of 25 to 10000 μm<2> and a depth of 10 to 200 μm and (b) a groove part (12) having an opening part line width of 5 to 200 μm and a depth of 10 to 200 μm, [2] a resin composition coating step of coating a positive-working photosensitive resin composition onto the stepped substrate (1) so as to come into contact with the solvent (13) within the pore part (11) and the groove part (12), and [3] a drying step of drying the coating film (14). Further, a film (16) containing a resin component is formed on the inner wall face and bottom face in the pore part (11) and the groove part (12).

Description

200905397 九、發明說明 【發明所屬之技術領域】 本發明，係關於一種被膜形成方法及其所 組成物、具有絕緣膜之構造物及其製造方法與 進一步詳細而固’本發明’係關於一種被膜形 於設置於段差基板細微之有底之孔部或溝部之 面’可高精度且容易地形成均勻之被膜；及其 脂組成物，具有絕緣膜之構造物及其製造方法 【先前技術】 過去以來，在電子機器之半導體元件之製 在基板上形成抗蝕劑圖案而使用感光性樹脂組 感光性樹脂組成物而言，將鹼可溶性樹脂及二 物等之感光劑溶解於有機溶劑而成之正型感光 物係廣泛地被採用著。關於此正型感光性樹脂 了改良感度、解像性、被膜形成性等之各種抗 對於樹脂骨格之構造或分子量、感光劑之構造 劑或溶劑之種類等多方面檢討正進行著。 具體的感光性樹脂組成物而言，可列舉蘇 徵爲含鹼可溶性樹脂、感光劑、無機粒子（鋁 ，不透明之正型感光性樹脂，可抑制浮渣之發 像時間者（參照專利文獻1 )或、（2 )特徵在 性樹脂、二重氮醌化合物、無機微粒子（膠態 使用之樹脂 電子零件。 成方法，對 內壁面或底 所使用之樹 與電子零件 造中，爲了 成物。就此 重氮醌化合 性樹脂組成 組成物，爲 蝕劑特性， 、各種添加 !)如（1 )特 粒子）而成 生、短縮顯 於含鹼可溶 二氧化矽） -5- 200905397 、胺化合物而成、解像性等優異，且可抑制顯像後之表面 粗糙者（參照專利文獻2 )、（ 3 )含鹼可溶性樹脂、感光 劑、與2種之搖變劑（二氧化矽微粉末），特徵在於爲了 抑制解像性之降低將前述2種之搖變劑定爲相對於組成物 之固形量合計6〜2 0質量％ (特別是6〜1 2質量％ )，可 使用於印刷配線板之回路形成者（參照專利文獻3 )，及 (4 )特徵在於由於若流體特性顯現搖變性則變爲無法得 到均勻膜厚之被膜，故爲塑性流體或擬塑性流體，且具有 特定之視黏度，添加經疏水化處理之微粉體、可藉由浸漬 法形成均勻膜厚之被膜者（專利文獻4參照）等。 另一方面，過去以來，揭示有藉由將在通孔用之孔、 通路之內壁面及基板兩面形成有金屬導體層之絕緣基板， 浸漬於黏度爲20〜200mPa· s、表面張力爲30mN/m以下 '且搖變性値爲1.0〜3.0之感光性抗蝕劑液中，然後提起 ，會至少在通孔之內壁面形成絕緣性被膜之方法（專利文 獻5參照）。藉由在此通孔充塡金屬銅等，可形成貫通電 極。 此外，於非專利文獻1中，揭示有上下貫通之矽晶片 、與在貫通孔充塡金屬銅之貫通電極。其製造方法，係具 備藉由乾式蝕刻在矽晶圓形成深孔之步驟、藉由CVD法 在孔之內壁形成Si02膜之步驟、藉由電鍍銅將孔內塡滿 金屬銅之步驟、由晶圓之裏側硏磨之步驟等。 專利文獻1 :特開2006- 1 263 54號公報 專利文獻2 :國際公開W02004/1 1 4020號公報 200905397 專利文獻3 :特開平6- 1 80499號公報 專利文獻4 :特開平4-2 1 8049號公報 專利文獻5 :特開2005 - 1 5 8907號公報 非專利文獻 1 :富坂學等「DENSO TECHNICAL REVIEW」Vol.6 No.2 ( 200 1 ) ρ.78 〜84 【發明內容】 [發明所欲解決之課題] 在三維封裝爲必要之電子元件（例如CMOS影像感測 器、快閃記憶體或CPU等），形成貫通電極者多被採用 。形成此貫通電極之方法而言，可列舉藉由在Si基板形 成細微孔或細微溝，於所形成之細微孔或細微溝之含內壁 面及底面之表面，使用感光性樹脂組成物形成被膜，對此 被膜進行曝光及顯像而圖案化，將其作爲光罩使用而對細 微孔等之內部作蝕刻處理，形成貫通電極用之孔部，於此 貫通電極用之孔部充塡導電性材料之方法等。 於是，在半導體回路之高集積化進展之今日，爲了提 升集積率，孔部或溝部之細微化被要求著。 然而，即使使用上述之以往之感光性樹脂組成物，從 對形成細微之孔部或溝部之段差基板之被膜形成性或金屬 雜質之濃度之觀點看來，仍然無法說爲充分，現狀爲要求 著一種可高精度且容易地形成較爲均勻之被膜之感光性樹 脂組成物。 此外，根據專利文獻5所揭示之感光性抗蝕劑液，在 200905397 通孔用之內壁面，可形成被膜，然而若欲在並非貫通孔、 開口部之面積小之細微孔（以下，稱爲「孔部」。）之內 壁面形成被膜，則會有組成物之沈降發生、孔部因組成物 而造成被充塡之問題。 本發明’係鑑於前述實情而完成者，目的爲提供一種 被膜形成方法，對於設置於矽基板等之有底之孔部或溝部 之內壁面或底面’可高精度且容易地形成均勻並且金屬雜 質含量低之被膜；及其所使用之樹脂組成物、具有絕緣膜 之構造物及其製造方法與電子零件。 [解決課題所用之方法] 本發明，係如同以下之敘述。 1. 一種被膜形成方法，其係用於藉由在形成於基板之 孔部或溝部充塡導電性材料，將經層合之基板之層間、或 基板之表面和裏面作電氣性連接之方法，並具備：[1 ]在具 有（Ο開口部之面積爲 25〜10000 μιη2且深度爲10〜 2 00 μιη之孔部及（b)開口部之線寬爲5〜200 μιη且深度爲 10〜200 μηι之溝部之中之至少一者之段差基板，塗佈溶劑 之溶劑塗佈步驟、[2]將正型感光性樹脂組成物，以與該孔 部及溝部內之溶劑接觸之方式，塗佈於該段差基板之樹脂 組成物塗佈步驟、與[3 ]使塗膜乾燥之乾燥步驟，且在該孔 部與溝部之內壁面及底面形成含該樹脂成分之被膜之被膜 形成方法，其特徵爲： 該正型感光性樹脂組成物，係含有（A )鹼可溶性樹 -8- 200905397 脂、（B)具有二重氮醌基之化合物、（C )經疏水化處理 且平均粒徑爲1〜1 〇〇nm之二氧化矽、與（d )溶劑，該 正型感光性樹脂組成物，係具有搖變性，同時，在該正型 感光性樹脂組成物中之鈉含量爲1 ppm以下，且該（C ) 二氧化矽之含有比例，在將該正型感光性樹脂組成物之固 體成分定爲1 〇 〇質量％之情況下，係超過2 0質量％、6 0質 量％以下。 2. 如前述1.所記載之被膜形成方法，其中，該（A) 鹼可溶性樹脂，係含有重量平均分子量爲4000〜50000之 具有酚性羥基之鹼可溶性樹脂。 3. 如前述2.所記載之被膜形成方法，其中，該（a) 鹼可溶性樹脂，進一步含有重量平均分子量未滿2000之 鹼可溶性樹脂。 4. 如前述1.至3.中任一項所記載之被膜形成方法，其 中，進一步含有低分子酚性化合物。 5. 如前述1.至4.中任一項所記載之被膜形成方法，其 中，進一步含有密著助劑。 6. 如前述1.至5.中任一項所記載之被膜形成方法，其 中，該（C )二氧化矽之疏水化率爲20〜80%。 7 .—種正型感光性樹脂組成物，其係具備[1 ]用於藉由 在形成於基板之孔部或溝部充塡導電性材料，將經層合之 基板之層間、或基板之表面和裏面作電氣性連接之方法， 在具有（a)開口部之面積爲25〜1 0000 μιη2且深度爲10〜 200μη!之孔部及（b )開口部之線寬爲5〜200μηι且深度爲 200905397 10〜200μιη之溝部之中至少，者之段差基板，塗佈溶劑之 溶劑塗佈步驟、[2]將正型感光性樹脂組成物，以與該孔部 及溝部內之溶劑接觸之方式’塗佈於該段差基板之樹脂組 成物塗佈步驟、[3]將乾燥塗膜之乾燥步驟，且係用於在該 孔部與溝部之內壁面及底面形成含該樹脂成分之被膜之被 膜形成方法之該正型感光性樹脂組成物，其特徵爲：含有 (A )鹼可溶性樹脂、（B )具有二重氮醌基之化合物、（ C )經疏水化處理且平均粒徑爲1〜1 0 〇nm之二氧化矽、 與（D )溶劑，本組成物，係具有搖變性，同時，該正型 感光性樹脂組成物中之鈉含量爲lppm以下，且該（C)二 氧化矽之含有比例，係在將本組成物之固體成分定爲1 〇〇 質量％之情況下，係超過20質量％、在60質量％以下。 8 . —種被膜形成方法，其係用於藉由在形成於基板之 孔部充塡導電性材料，將經層合之基板之層間、或基板之 表面和裏面作電氣性連接之方法，並具備Π]在具有開口部 之面積爲25〜ΙΟΟΟΟμιη2且深度爲10〜200μΐΏ之孔部之砂 基板，塗佈溶劑之溶劑塗佈步驟、[2]將剪切速度在6rpm 時之黏度Vi (mPa. s)、與剪切速度60rPm時之黏度v2 (mPa . s )之比（Vi/Vz )爲1 · 1以上之樹脂組成物，以 該樹脂組成物與該孔部內之該溶劑接觸之方式’塗佈於該 基板之樹脂組成物塗佈步驟'[3 ]將塗膜乾燥之乾燥步驟’ 且在孔部之內壁面及底面之內之至少該內壁面形成含該樹 脂成分之被膜之被膜形成方法，其特徵爲’· 該樹脂組成物，係含有鹼可溶性樹脂、二氧化矽、溶 -10- 200905397 劑，該樹脂組成物，係具有搖變性、且該二氧化矽之含有 比例，在將該樹脂組成物之固體成分定爲1 00質量％之情 況下，超過20質量％、在60質量％以下。 9. 如前述8.所記載之被膜形成方法，其中，該樹脂組 成物，係進一步含有具有二重氮醌基之化合物。 10. 如前述8.或9.所記載之被膜形成方法，其中，該 被膜，係形成於該孔部之內壁面及底面之兩者。 1 1.如前述8.至10.中任一項所記載之被膜形成方法， 其中，該樹脂組成物，係進一步含有交聯劑。 12. 如前述8.至1 1.中任一項所記載之被膜形成方法， 其中，該樹脂組成物，係進一步含有交聯聚合物所構成之 粒子。 13. 如前述8.至12.中任一項所記載之被膜形成方法， 其中’該樹脂組成物之固體成分濃度，係在5〜80質量％ 之範圍。 14. 如前述8.至13.中任一項所記載之被膜形成方法， 其中’該黏度V,，係在1〇〜i〇〇〇〇mpa· s之範圍。 1 5 .如前述8 .至1 4 .中任一項所記載之被膜形成方法， 其中’於該樹脂組成物中，剪切速度在1.5rpm時之黏度 V3(mPa.s)、與剪切速度在600rpm時之黏度V4(mPa • s )之比（V3/V4 )爲2.0以上。 16. —種具有絕緣膜之構造物之製造方法，其特徵爲 :具備：將藉由前述8 .至1 5 .中任一項所記載之方法所得 到之形成於該基板之表面之被膜及形成於該基板之該孔部 -11 - 200905397 之底面之被膜除去，留下形成於該孔部之內壁面之被膜之 表底面側被膜除去步驟、與將留在該孔部之內壁面之被膜 加熱之加熱硬化步驟。 1 7 . —種具有絕緣膜之構造物之製造方法，其特徵爲 :具備：將藉由前述8 .至1 5 .中任一項所記載之方法所得 到之形成於包含該孔部之內壁面及底面之該基板之全表面 之被膜加熱，製成含該樹脂成分之硬化物之絕緣膜之加熱 硬化步驟、將形成於該基板之表面之絕緣膜及形成於該基 板之該孔部之底面之絕緣膜除去，留下形成於該孔部之內 壁面之絕緣膜之表底面側絕緣膜除去步驟。 18. 如前述16.或17.所記載之具有絕緣膜之構造物之 製造方法，其中，進一步具備由在具有該絕緣膜之構造物 之不具有該孔部之面將基板硏磨，將該孔部製爲貫通孔之 硏磨步驟。 19. 一種具有絕緣膜之構造物，其特徵爲：藉由前述 16.至18.中任一項所記載之方法而得到。 20. —種電子零件，其特徵爲：具備含藉由前述16.至 1 8.中任一項所記載之方法所得到之具有絕緣膜之構造物 、與在該構造物之至少貫通孔內充塡導電材料而成之電極 部之構件。 2 1 . —種樹脂組成物，其係用於藉由在形成於基板之 孔部或溝部充塡導電性材料’將經層合之基板之層間、或 基板之表面和裏面作電氣性連接之方法，具備：Π]在具有 開口部之面積爲25〜ΙΟΟΟΟμηι2且深度爲]〇〜200μπι之孔 -12- 200905397 部之矽基板，塗佈溶劑之溶劑塗佈步驟、[2]剪切速度在 6rpm時之黏度V, (mPa. s)與剪切速度在60rpm時之黏 度V2 ( mPa · s )之比（Vi/V〗）爲1.1以上之樹脂組成物 ，以該樹脂組成物與該孔部內之該溶劑接觸之方式，塗佈 於該基板之樹脂組成物塗佈步驟、[3]將塗膜乾燥之乾燥步 驟，且在孔部之內壁面及底面之內之至少該內壁面形成含 該樹脂成分之被膜之被膜形成方法所使用之樹脂組成物， 其特徵爲： 含有鹼可溶性樹脂、具有二重氮醌基之化合物、二氧 化矽、溶劑、與交聯劑，本組成物，係具有搖變性，且該 二氧化矽之含有比例，係在將本組成物之固體成分定爲 1 0 0質量％之情況下，爲超過2 0質量％、在6 0質量％以下 〇 22.如前述21.所記載之樹脂組成物，其中，進一步含 有交聯聚合物所構成之粒子。 發明之效果 根據本發明之被膜形成方法，在設置於段差矽基板有 底之細微孔部或細微溝部之內壁面及底面可容易地形成均 勻之被膜。因此，對於形成前述被膜之基板，藉由曝光、 顯像，可在細微之孔部內或溝部內、及基板表面形成任意 之圖案。於是，在圖案形成後，由於可使用作爲蝕刻阻劑 ，故可將所形成之樹脂被膜作爲光罩，對Si、Si02等之蒸 鍍氧化膜或金屬氧化膜等進行蝕刻處理，在蝕刻處理後， -13- 200905397 可容易地將樹脂被膜剝離，故可適合利用於對細微之孔部 或溝部之內部之細微加工。 特別是’可容易地形成貫通電極等。因此，在CMOS 影像感測器、快閃記憶體、CPU等之三維封裝爲必要之電 子元件製作領域非常有用。 此外’根據本發明之正型感光性樹脂組成物，可在設 置於段差矽基板細微之有底之孔部或溝部之內壁面及底面 以高精度形成均勻之被膜。進一步而言，由於此樹脂組成 物，係藉由汎用且簡便之旋轉塗佈法，可塗佈於基板表面 ，故可容易地形成前述被膜。 根據本發明之其他被膜形成方法，藉使用具有特定之 搖變性之樹脂組成物，可在基板之孔部之內壁面形成均勻 之被膜。此外，亦可在孔部之底面形成均勻之被膜。 根據本發明之具有絕緣膜之構造物之製造方法，可在 貫通孔之內壁效率良好地形成均勻之絕緣膜。因此，所得 到之構造物，係藉由使金屬銅等充塡於將絕緣膜作爲內壁 之貫通孔內，可容易地形成貫通電極。此外，亦適合於多 孔質膜之改質等。 根據本發明之電子零件，即適合於CPU、記憶體、影 像感測器等之半導體元件之封裝。 【實施方式】 以下，詳細地說明本發明。另外，在本說明書中之「 (甲基）丙烯酸」，係意指丙烯酸及甲基丙烯酸，「（甲 -14 - 200905397 基）丙烯酸酯」，係意指丙烯酸酯及甲基丙烯酸酯。 1.被膜形成方法（I ) 本發明之被膜形成方法（I)，特徵爲：用於藉由在 形成於基板之孔部或溝部充塡導電性材料，將經靥合之基 板之層間、或基板之表面和裏面電氣性連接之方法，並具 備：[1]在具有（a)開口部之面積爲25〜ΙΟΟΟΟμιη2且深度 爲10〜200μιη之孔部（以下，單稱爲「孔部」，亦或稱爲 「細微孔部」。）及（b )開口部之線寬爲5〜2〇〇μιη且深 度爲10〜200μπι之溝部（以下，單稱爲「溝部」，亦或稱 爲「細微溝部」。）之中至少一者之段差基板，塗佈溶劑 之溶劑塗佈步驟、[2]將正型感光性樹脂組成物，以與前述 孔部及溝部內之溶劑接觸之方式，塗佈於前述段差基板之 樹脂組成物塗佈步驟、[3]將塗膜乾燥之乾燥步驟、且在前 述孔部與溝部之內壁面及底面形成含前述樹脂成分之被膜 〈溶劑塗佈步驟〉 在前述溶劑塗佈步驟中，溶劑係塗佈於段差基板。 前述段差基板而言，可使用矽、各種金屬、氧化鋁、 環氧玻璃、酚醛紙、玻璃等之構成材料所構成者、或於該 等形成各種金屬薄膜或金屬氧化物薄膜者。特別是以段差 s i (矽）基板爲適合使用。另外，基板之厚度係通常100 〜1 0 0 0 μηι ° -15- 200905397 前述段差基板’係如圖1之剖面圖所示般，在段差基 板1之至少其中一面上具有由表面往內部以縱方向之方式 形成，（Ο開口部之面積爲25〜1 ΟΟΟΟμηι2，良好爲1 00 〜ΙΟΟΟΟμηι2 ’較佳爲25 0〜7000μηι2，且深度爲10〜 200μιη’良好爲30〜200μηι，較佳爲50〜150μηι之孔部11 及（b)開口部之線寬爲5〜200μηι，良好爲5〜150μηι， 較佳爲10〜ΙΟΟμηι且深度爲10〜200μιη，良好爲30〜 200μιη’較佳爲50〜150μηι之溝部12之內之至少一者。 前述孔部及溝部（以下，以包含兩者之意思，亦稱爲 「孔部等」。）之形狀或數目，係並非特別受到限定者， 可依照必要適當調整。對前述孔部等之基板面之垂直方向 之斷面形狀（縱斷面形狀），係可定爲柱狀[圖](a)參 照〕、順錐形狀〔圖1 ( b )參照〕、逆錐形狀〔圖1 ( c )參照〕等。另外，對孔部之基板面之平行方向之横斷面 形狀，係可定爲圓形、橢圓形、多角形等。此外，溝部係 以直線狀般形成亦可，以曲線狀般形成亦可。再者，孔部 等爲多數個之情況，各孔部等之大小及深度，係亦可各自 相異，相鄰孔部等彼此之間隔（長度）亦並未特別受到限 定。 此外，前述孔部之良好形狀而言，横斷面形狀爲圓形 且縱斷面形狀爲順錐形狀。 前述孔部，橫斷面形狀爲圓形之情況而言，孔部表面 之開口徑與孔部深度之比（孔部深度/開口徑，良好爲1〜 ]〇，較佳爲1〜5，更佳爲1〜4。 -16- 200905397 此外，前述溝部之良好形狀而言，溝部以直線形狀般 形成，且縱斷面形狀爲柱狀或順錐形狀者。 前述溝部之縱斷面形狀爲柱狀之情況而言，縱斷面之 四角形之縱橫比（孔部之深度/孔部上面之1邊之長度） ，良好爲1〜10，較佳爲1〜5，更佳爲1〜4。 此外，前述溶劑而言，可列舉乙二醇單甲基醚醋酸酯 、乙二醇單乙基醚醋酸酯等之乙二醇單烷醚醋酸酯類·，丙 二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二 醇單丁基醚等之丙二醇單烷醚類；丙二醇二甲基醚、丙二 醇二乙基醚、丙二醇二丙基醚、丙二醇二丁醚等之丙二醇 二烷醚類；丙二醇單甲基醚醋酸酯、丙二醇單乙基醚醋酸 酯、丙二醇單丙基醚醋酸酯、丙二醇單丁基醚醋酸酯等之 丙二醇單烷醚醋酸酯類；乙基溶纖劑、丁基溶纖劑等之溶 纖劑類；丁基卡必醇等之卡必醇類；乳酸甲酯、乳酸乙酯 、乳酸正丙酯 '乳酸異丙酯等之乳酸酯類；醋酸乙酯、醋 酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、醋酸 正戊酯、醋酸異戊酯、丙酸異丙酯、丙酸正丁酯、丙酸異 丁酯等之脂肪族羧酸酯類；3 -甲氧丙酸甲酯、3 -甲氧丙酸 乙酯、3-乙氧丙酸甲酯、3-乙氧丙酸乙酯、丙酮酸甲酯、 丙酮酸乙酯等之其他酯類；甲苯、二甲苯等之芳香族烴類 ;2 -庚酮、3 -庚酮、4 -庚酿、環己酮等之酮類；N -二甲基 甲醯胺、N·甲基乙醯胺、N，N -二甲基乙醯胺、N -甲基吡咯 烷酮等之醯胺類；γ-丁內酯等之內酯類。該等，係以]種 單獨使用亦可，組合2種以上使用亦可。 -17- 200905397 在前述溶劑塗佈步驟之中，將前述溶劑 板之方法而言’並未特別受到限定，而可列 、旋轉塗佈法等之塗佈法、浸潰法等。另外 劑’在前述孔部內充塡溶劑之情況下溶劑之 未特別受到限定。 〈樹脂組成物塗佈步驟〉 在前述樹脂組成物塗佈步驟，係以與在 之孔部等內之溶劑接觸之方式，塗佈正型感 物。另外’關於此正型感光性樹脂組成物， 明。 在前述樹脂組成物塗佈步驟中，將感光 塗佈於前述段差基板之方法，只要是此感光 與前述孔部等內之溶劑接觸之方式塗佈加工 特別受到限定，而可列舉例如旋轉塗佈法、 塗佈法等。該等之中，尤其以使用旋轉塗佈 另外，在此樹脂組成物塗佈步驟中，考 組成物之固體成分濃度、黏度等，以藉由稍 步驟’使形成於前述段差基板之表面之被 0·1〜ΙΟμηι範圍之方式形成塗膜者爲佳。 〈乾燥步驟〉 在前述乾燥步驟中，藉由前述樹脂組成 形成之塗膜係被乾燥。亦即，僅被含於塗膜 塗佈於段差基 舉例如噴塗法 ，藉由塗佈溶 充塡率，係並 前述段差基板 光性樹脂組成 在後段詳細說 性樹脂組成物 性樹脂組成物 之方法則並未 噴塗法、棒式 法爲佳。 慮感光性樹脂 後進行之乾燥 膜厚度爲進入 物塗佈步驟所 之溶劑被除去 -18- 200905397 ，在含孔部等內表面之段差基板表面形成被膜。 此步驟中之乾燥溫度，係考慮在前述溶劑塗佈步驟中 所充塡溶劑之沸點，或由在前述溶劑塗佈步驟中所充塡之 溶劑與感光性樹脂組成物所構成之混合物所含混合溶劑之 沸點而適宜地選擇。 此外，乾燥條件係並未特別受到限定，以一定溫度進 行亦可，一邊昇溫或降溫一邊進行亦可，將該等組合亦可 。此外，關於壓力，亦係在大氣壓下進行亦可，在真空下 進行亦可。另外，環境氣氛氣體等亦並未特別受到限定。 此處，對於本發明之被膜形成方法（I)作具體地說 明（參照圖2 )。 首先，藉由溶劑塗佈步驟，將溶劑塗佈於段差基板1 。此時，溶劑1 3，係通常如圖2 ( b )之方式，充塡在設 置於段差基板1之孔部1 1 (溝部12 )內，此外，將段差 基板1之表面均勻地潤濕亦可。 接著，在樹脂組成物塗佈步驟中，若塗佈感光性樹脂 組成物，則於段差基板1之表面，形成均勻之塗膜14，成 爲在孔部Π內收容有由前述溶劑塗佈步驟中所充塡之溶 劑、與感光性樹脂組成物所構成之混合物1 5〔參照圖2 ( c)〕° 其後，藉由乾燥步驟除去溶劑，在含孔部之內壁面及 底面之段差基板表面，形成感光性樹脂組成物之固體成分 所構成之均勻之被膜1 6 (在孔部以外之段差基板1之全表 面形成之被膜16a、在孔部之內壁面形成之被膜16b、在 -19- 200905397 孔部之底面形成之被膜16c)〔參照圖2(d)〕。另外， 被膜16a、16b及16c之厚度，係相同亦可，而相異亦可 〇 根據本發明之被膜形成方法（I)，由於可在設置於 段差砍基板有底之孔部或溝部之內壁面及底面形成均句之 被膜’藉著將所形成之被膜利用作爲光罩，可對Si、si〇2 等之蒸鍍氧化膜或金屬氧化膜等進行蝕刻處理。進一步而 言’於蝕刻處理後，由於可容易地將樹脂被膜剝離，故可 適合利用於對細微之孔部或溝部之內部之細微加工。例如 ，在基板之單面形成細微孔部或細微溝部且相對於對應至 其細微孔部或細微溝部之位置之反對面具備電極部之段差 基板中’藉由在此孔部或溝部之底面形成圖案，對底部施 以蝕刻處理，可容易地形成貫通電極。 此處、對於前述貫通電極之形成方法作具體地說明（ 參照圖3 )。 首先’於在單面形成有細微孔部11 (或細微溝部i 2 )且在其反對面具備電極部2之段差基板1〔參照圖3(a )〕表面，藉由使用感光性樹脂組成物之本發明之被膜形 成方法（I )形成被膜1 6〔參照圖3 ( b )〕。 其後，由上方對孔部照射紫外線、可見光、遠紫外線 、X射線、電子射線等，將形成於前述孔部1 1之底面之 被膜〗6c之既定區域曝光〔參照圖3(c)〕。另外，曝光 量’係依照使用之光源、被膜之厚度等適宜地選擇，而例 如對於厚度爲5〜5 0 μ m程度之被膜，由高壓水銀燈照射紫 -20- 200905397 外線之情況下，良好曝光量爲1 000〜2000(U/m2程度。 於是，圖3(c)所示之被膜曝光部161，係成爲鹼可 溶性’故使用鹼性溶液處理，在孔部底面形成圖案3〔參 照圖3(d)〕。另外’前述鹼性溶液而言，可使用氫氧化 鈉、氫氧化鉀、氨、氫氧化四甲基銨、膽鹼等之水溶液、 或於此水溶液、適量添加甲醇、乙醇等之水溶性之有機溶 劑、界面活性劑等之溶液等。 接著，將留下之被膜16作爲光罩，對在孔部之基板 17施以蝕刻處理〔參照圖3(e)〕。此外，蝕刻方法而 言，可使用乾式蝕刻、使用氫氟酸等之濕式蝕刻等之公知 之方法。 其後’將殘存之被膜1 6，使用既定之剝離液（例如， N -甲基吡咯烷酮、二甲基亞颯等之溶劑、或在該等溶劑適 量添加鹼、界面活性劑等之溶液等）作剝離，形成貫通電 極用孔部4〔參照圖3 ( f)〕。 接著’在貫通電極孔部4，可藉由充塡導電材料形成 貫通電極。另外，導電材料而言，可列舉銅、銀、鎢、鉅 、鈦、釘、金、錫、鋁、及含該等之合金等。 2·正型感光性樹脂組成物 本發明之被膜形成方法（I)之中所使用之正型感光 性樹脂組成物（以下，亦單稱爲「感光性樹脂組成物」。 )’係含有（A)鹼可溶性樹脂、（B)具有二重氮醌基之 化合物' (C )經疏水化處理且平均粒徑爲1〜100nm之 -21 - 200905397 二氧化矽、與（D )溶劑，且具有搖變性者。 〈（A )鹼可溶性樹脂〉 前述驗可溶性樹脂〔以下，亦稱爲「鹼可溶性樹脂（ A )」〕而言，可列舉例如，（1 )具有酚性羥基之樹脂（ 以下’亦稱爲「樹脂（A1 )」）、（2 )使用具有酚性羥 基之單體與含（甲基）丙烯酸酯之單體所得到之共聚物（ 以下’亦稱爲「樹脂（A2)」）、（3)具有羧基之樹脂 (以下，亦稱爲「樹脂（A3)」）等》 前述樹脂（A1)而言’可使用例如藉由將酚類與醛類 在觸媒之存在下’使其縮合所得到之酚醛樹脂。 前述酚類而言’可列舉例如酚、鄰甲苯酚、間甲苯酚 '對甲苯酚、鄰乙苯酚、間乙苯酚、對乙苯酚、鄰丁苯酚 、間丁苯酚、對丁苯酚、2,3-茬酚、2,4-茬酚、2,5-茬酚、 2,6·茬酚、3,4_茬酚、3,5·茬酚、2,3,5-三甲苯酚、3,4,5-三 甲苯酚、兒茶酚、間苯二酚、苯三酚、〇:·萘酚、沒·萘酚 等。 前述醛類而言，可列舉例如甲醛、三聚甲醛、乙醛、 苯甲醛等。 前述酚醛樹脂而言，可列舉例如酚/甲醛縮合酚醛樹 脂、甲苯酚/甲醛縮合酚醛樹脂、酚-萘酚/甲醛縮合酚醛樹 脂等。該等，係以1種單獨使用亦可、組合2種以上使用 亦可。 另外’前述酚醛樹脂以外之樹脂（a 1 )而言’可列舉 -22- 200905397 聚羥苯乙烯、羥苯乙烯與其他單體〔除了（甲基）丙烯酸 及（甲基）丙烯酸酯〕之共聚物、聚異丙烯酚、異丙烯酚 與其他單體〔除了（甲基）丙烯酸及（甲基）丙烯酸酯〕 之共聚物、酚/伸茬二醇縮合樹脂、甲苯酚/伸茬二醇縮合 樹脂、酚/二環戊二烯縮合樹脂等。該等，係以1種單獨 使用亦可，組合2種以上使用亦可。 前述樹脂（A2 )，係使用具有酚性羥基之單體、與含 (甲基）丙烯酸酯且不含（甲基）丙烯酸等之具有羧基之 化合物之單體所得到之共聚物。 前述具有酚性羥基之單體而言，可列舉例如對羥苯乙 烯、間羥苯乙烯、鄰羥苯乙烯、對異丙烯酚、間異丙烯酚 、鄰異丙烯酚等。 前述（甲基）丙烯酸酯而言，可列舉（甲基）丙烯酸 甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸異丙酯、（ 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、（甲基）丙烯酸環己酯、（甲基）丙 烯酸2-甲基環己酯、（甲基）丙烯酸苯酯、（甲基）丙烯 酸苄酯等之（甲基）丙烯酸烷酯等。另外，該等之（甲基 )丙烯酸烷酯中之烷基之氫原子，係亦可被羥基所取代。 此外，前述樹脂（A2 )之形成時’具有酣性羥基之單 體及（甲基）丙烯酸酯以外，將具有聚合性不飽和鍵之化 合物作爲其他單體使用亦可。 前述其他單體而言，可列舉例如苯乙烯' 甲基苯 乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯 '甲 -23- 200905397 基苯乙烯、乙烯二甲苯、鄰甲氧苯乙烯、間甲氧苯乙烯、 對甲氧本乙細等之芳香族乙烯化合物；無水馬來酸、無水 檸康酸等之不飽和酸無水物；前述不飽和羧酸之酯；（甲 基）丙烯腈、馬來腈、富馬腈、中康腈、檸康腈、伊康腈 等之不飽和腈；（甲基）丙烯醯胺、巴豆醯胺、馬來醯胺 、富馬醯胺、中康醯胺、檸康醯胺、伊康醯胺等之不飽和 醯胺；馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯 亞胺等之不飽和醯亞胺；（甲基）丙烯醇等之不飽和醇； N-乙烯苯胺、乙烯吡啶、N-乙烯-ε -己內醯胺、N_乙烯吡 咯烷酮、N -乙烯咪唑、N -乙烯咔唑等。該等，係以1種單 獨使用亦可，組合2種以上使用亦可。 前述樹脂（A3)，係同元聚合物亦可，共聚物亦可。 通常，此樹脂（A3 )，係使用含具有羧基之化合物（以下 ’稱爲「單體（m )」）之單體所得到之聚合物。 前述單體（m )而言，可列舉例如（甲基）丙烯酸、 馬來酸、富馬酸、巴豆酸、中康酸、檸康酸、伊康酸、4-乙烯安息香酸等之不飽和羧酸或不飽和二羧酸；不飽和二 羧酸之單酯等。該等，係以1種單獨使用亦可，組合2種 以上使用亦可。 前述樹脂（A3 )而言，可例示以下之共聚物。 [1] 使用單體（m )、與具有酚性羥基之單體所得到之 共聚物 [2] 使用單體（m)、具有酚性羥基之單體、與（甲基 )丙烯酸酯所得到之共聚物 -24 - 200905397 [3] 使用單體（m)、具有酚性羥基之單體、芳香族乙 烯化合物、與（甲基）丙烯酸酯所得到之共聚物 [4] 使用單體（m)、芳香族乙烯化合物、與（甲基） 丙烯酸酯所得到之共聚物 [5] 使用單體（m)、芳香族乙烯化合物、與共軛二烯 烴所得到之共聚物 [6] 使用單體（m)、（甲基）丙烯酸酯、與共軛二烯 烴所得到之共聚物 [7] 使用單體（m)、（甲基）丙烯酸酯、與脂肪酸乙 烯化合物所得到之共聚物 另外，在前述態樣中，關於具有酚性羥基之單體、（ 甲基）丙烯酸酯及芳香族乙烯化合物，可直接適用前述之 說明。 另外，前述共軛二烯烴而言，可列舉例如1，3-丁二烯 、異戊二烯、1,4-二甲基丁二烯等。 此外，前述脂肪酸乙烯化合物而言，可列舉例如醋酸 乙烯、巴豆酸乙烯等。 在本發明中之感光性樹脂組成物，係僅含有1種前述 鹼可溶性樹脂（A )亦可，含有2種以上亦可。 此外，在本發明中之感光性樹脂組成物作爲前述鹼可 溶性樹脂（A )，以含有重量平均分子量（Mw )爲4000 〜5 0000 (較佳爲4000〜30000 )之樹脂爲佳。特別是，作 爲前述鹼可溶性樹脂，係以（i )僅含有Mw爲4000〜 50000之樹脂，或（ii)含有Mw爲4000〜5 0000之樹脂 -25- 200905397 、與Mw爲2000未滿（較佳爲500〜1900)之樹脂者爲佳 。該等之情況而言，可控制鹼可溶性。另外’樹脂之重量 平均分子量，係可藉由將單分散聚苯乙烯定爲標準之凝膠 滲透層析法（GPC )測定。 前述Mw爲4000〜50000之鹼可溶性樹脂而言，具有 酚性羥基之樹脂爲佳，特別是使用羥苯乙烯所得到之共聚 物、及酚醛樹脂爲佳。 前述Mw爲未滿2000之鹼可溶性樹脂而言，以使用 酚-伸茬二醇縮合樹脂、甲苯酚/伸茬二醇縮合樹脂、酚/二 環戊二烯縮合樹脂、羥苯乙烯所得到之共聚物、及酚醛樹 脂爲佳。 作爲前述鹼可溶性樹脂（A )，就含Mw爲4000〜 50000之鹼可溶性樹脂、與Mw爲未滿2000之鹼可溶性樹 脂之情況而言，Mw爲4000〜5 0000之鹼可溶性樹脂之含 有比例，在將鹼可溶性樹脂（A )全體定爲1 〇 〇質量％之 情況下，以30〜100質量％者爲佳，較佳爲40〜1〇〇質量 %，更佳爲5 0〜1 0 0質量％。 此外，在前述感光性樹脂組成物中之前述鹼可溶性樹 脂（A )之含有比例，係將感光性樹脂組成物所含固體成 分全體定爲100質量％之情況下，以30〜60質量％者爲佳 ，較佳爲3 0〜5 0質量％，更佳爲3 5〜5 0質量％。此含有 比例爲30〜60質量％之情況而言，係鹼溶解性優異。 〈（B )具有二重氮醌基之化合物〉 -26- 200905397200905397 IX. Description of the Invention The present invention relates to a film forming method and a composition thereof, a structure having an insulating film, a manufacturing method thereof, and a further detail of the present invention relating to a film. a film formed on a surface of a hole or a groove having a fine bottom portion of a stepped substrate, which can form a uniform film with high precision and easily; and a fat composition thereof, a structure having an insulating film, and a method for producing the same [Prior Art] In the case of forming a semiconductor device of an electronic device, a resist pattern is formed on a substrate, and a photosensitive resin composition photosensitive resin composition is used, and a photosensitive agent such as an alkali-soluble resin or a second substance is dissolved in an organic solvent. Positive photoreceptors are widely used. Various positive resistances such as improved sensitivity, resolution, and film formation properties of the positive photosensitive resin are being reviewed for various aspects such as the structure or molecular weight of the resin skeleton, the type of the sensitizer, or the type of the solvent. Specific examples of the photosensitive resin composition include an alkali-soluble resin, a sensitizer, and an inorganic particle (aluminum, an opaque positive-type photosensitive resin, which can suppress the scum generation time (refer to Patent Document 1) ) or (2) a characteristic resin, a diazide compound, or an inorganic fine particle (a resin electronic component used in a colloidal state, a method for forming a tree or an electronic component for an inner wall surface or a bottom, for the purpose of forming a product. In this case, the composition of the diazonium hydrazine compound resin is an etchant characteristic, and various additions are made as follows: (1) special particles are formed and shortened to the alkali-soluble soluble cerium oxide. -5-200905397, amine compound Excellent in resolution, resolution, etc., and can suppress surface roughness after development (refer to Patent Document 2), (3) alkali-soluble resin, sensitizer, and two kinds of shaker (cerium oxide fine powder) In order to suppress the decrease in the resolution, the above two types of the shake agent are set to be 6 to 20% by mass (particularly 6 to 12% by mass) based on the total solid content of the composition, and can be used for printing. Circuit board circuit The product (see Patent Document 3) and (4) are characterized in that if the fluid property is shaken, the film having a uniform film thickness cannot be obtained, so that it is a plastic fluid or a pseudoplastic fluid, and has a specific apparent viscosity. The hydrophobized fine powder can be formed into a film having a uniform film thickness by a dipping method (refer to Patent Document 4). On the other hand, in the past, an insulating substrate in which a metal conductor layer is formed on a hole for a through hole, an inner wall surface of a via, and both surfaces of a substrate is immersed in a viscosity of 20 to 200 mPa·s and a surface tension of 30 mN/ Below m' and the shaken 値 is 1. 0~3. In the photosensitive resist liquid of 0, it is lifted, and at least an insulating film is formed on the inner wall surface of the through hole (refer to Patent Document 5). The through electrode can be formed by filling the through hole with metal copper or the like. Further, Non-Patent Document 1 discloses a tantalum wafer that penetrates vertically, and a through electrode that is filled with metal copper in the through hole. The manufacturing method includes the steps of forming a deep hole in the germanium wafer by dry etching, forming a SiO 2 film on the inner wall of the hole by a CVD method, and filling the hole with metal copper by electroplating copper. The step of honing the inside of the wafer, etc. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 5: JP-A-2005-1558907 Non-Patent Document 1: "DENSO TECHNICAL REVIEW" Vol. 6 No. 2 ( 200 1 ) ρ. 78 to 84 [Disclosure of the Invention] [Problems to be Solved by the Invention] In an electronic component (for example, a CMOS image sensor, a flash memory, a CPU, or the like) necessary for three-dimensional packaging, a through electrode is often used. The method of forming the through electrode is formed by forming a fine pore or a fine groove on the Si substrate, and forming a surface of the inner wall surface and the bottom surface of the fine pore or fine groove formed by using a photosensitive resin composition. The film is patterned by exposure and development of the film, and is used as a mask to etch the inside of the fine pores or the like to form a hole for the through electrode, and the hole for the through electrode is filled. A method of a conductive material or the like. Therefore, in order to increase the accumulation rate, the hole portion or the groove portion is required to be fined in order to increase the accumulation rate of the semiconductor circuit. However, even if the above-mentioned conventional photosensitive resin composition is used, it is not sufficient from the viewpoint of the film formation property of the stepped substrate or the concentration of the metal impurities in the formation of the fine hole portion or the groove portion. A photosensitive resin composition capable of forming a relatively uniform film with high precision and easily. Further, according to the photosensitive resist liquid disclosed in Patent Document 5, a film can be formed on the inner wall surface of the through hole of 200905397. However, if it is intended to be a fine hole having a small area which is not a through hole or an opening portion (hereinafter referred to as When a film is formed on the inner wall surface of the "hole portion", there is a problem that sedimentation of the composition occurs and the hole portion is filled due to the composition. The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a method for forming a film which can form a uniform and metal impurity with high precision and easily for an inner wall surface or a bottom surface of a bottomed hole portion or a groove portion provided on a ruthenium substrate or the like. a film having a low content; a resin composition used therefor, a structure having an insulating film, a method for producing the same, and an electronic component. [Method for Solving the Problem] The present invention is as follows. 1.  A film forming method for electrically connecting a layer of a laminated substrate or a surface of a substrate and a surface thereof by filling a conductive material in a hole portion or a groove portion formed in a substrate, and : [1] has a hole width of 5 to 200 μm and a depth of 10 to 200 μηη, which has an opening area of 25 to 10000 μm 2 and a depth of 10 to 200 μm, and (b) an opening. a retardation substrate of at least one of the groove portions, a solvent application step of applying a solvent, and [2] applying a positive photosensitive resin composition to the solvent in the hole portion and the groove portion. a resin composition coating step of the step substrate, a drying step of drying the coating film by [3], and a film forming method for forming a film containing the resin component on the inner wall surface and the bottom surface of the hole portion and the groove portion, wherein: The positive photosensitive resin composition contains (A) an alkali-soluble tree-8-200905397 fat, (B) a compound having a diazide group, and (C) a hydrophobized treatment and an average particle diameter of 1 to 1 〇〇nm of cerium oxide, and (d) solvent, The photosensitive resin composition has a shake property, and the sodium content in the positive photosensitive resin composition is 1 ppm or less, and the content ratio of the (C) cerium oxide is in the positive photosensitive When the solid content of the resin composition is set to 1% by mass, it is more than 20% by mass and 60% by mass or less.  As mentioned above 1. In the method for forming a film according to the above aspect, the (A) alkali-soluble resin contains an alkali-soluble resin having a phenolic hydroxyl group having a weight average molecular weight of 4,000 to 50,000. 3.  As mentioned above 2. In the method for forming a film according to the above aspect, the (a) alkali-soluble resin further contains an alkali-soluble resin having a weight average molecular weight of less than 2,000. 4.  As mentioned above 1. To 3. The method for forming a film according to any one of the preceding claims, further comprising a low molecular phenolic compound. 5.  As mentioned above 1. To 4. The method for forming a film according to any one of the preceding claims, further comprising an adhesion promoter. 6.  As mentioned above 1. To 5. The method for forming a film according to any one of the present invention, wherein the (C) ceria has a hydrophobization ratio of 20 to 80%. 7 . a positive photosensitive resin composition comprising [1] for charging a conductive material in a hole or a groove formed in a substrate, and laminating a layer of the substrate, or a surface and a substrate of the substrate The method of electrically connecting is a hole having a (a) opening area of 25 to 1 0000 μm 2 and a depth of 10 to 200 μm! and (b) an opening having a line width of 5 to 200 μm and a depth of 200905397 10 . At least one of the groove portions of the layer of 200 μm η, the solvent coating step of the coating solvent, and [2] the positive photosensitive resin composition is coated with the solvent in the hole portion and the groove portion. a resin composition application step of the step substrate, [3] a drying step of drying the coating film, and a method for forming a film containing the resin component on the inner wall surface and the bottom surface of the hole portion and the groove portion. The positive photosensitive resin composition characterized by comprising (A) an alkali-soluble resin, (B) a compound having a diazide group, (C) being hydrophobized and having an average particle diameter of 1 to 10 〇 Nm of cerium oxide, and (D) solvent, the composition And having a shake content, and the sodium content of the positive photosensitive resin composition is 1 ppm or less, and the content ratio of the (C) cerium oxide is set to 1 〇〇 of the solid content of the composition. In the case of % by mass, it is more than 20% by mass and not more than 60% by mass. 8 .  A method for forming a film for electrically connecting a layer of a laminated substrate or a surface of a substrate and a surface thereof by filling a conductive material in a hole formed in the substrate, and is provided with a method a sand substrate having a hole portion having an opening area of 25 to ΙΟΟΟΟμηη2 and a depth of 10 to 200 μΐΏ, a solvent coating step of applying a solvent, and [2] a viscosity Vi (mPa.) at a shear rate of 6 rpm.  s), viscosity v2 at a shear rate of 60 rPm (mPa.  a resin composition having a ratio (Vi/Vz) of s or more of 1 or more, and a resin composition coating step applied to the substrate in a manner of contacting the resin composition with the solvent in the hole portion [3 a method for forming a film containing the resin component in at least the inner wall surface of the inner wall surface and the bottom surface of the hole portion, wherein the resin composition contains a base. Soluble resin, cerium oxide, and lysole-10-200905397, the resin composition has a shake ratio and a content ratio of the cerium oxide, and the solid content of the resin composition is set to 100% by mass. The amount is more than 20% by mass and not more than 60% by mass. 9.  As mentioned above 8. The method for forming a film according to the above aspect, wherein the resin composition further contains a compound having a diazide group. 10.  As mentioned above 8. Or 9. In the method of forming a film according to the above aspect, the film is formed on both the inner wall surface and the bottom surface of the hole portion. 1 1. As mentioned above 8. To 10. The method for forming a film according to any one of the preceding claims, wherein the resin composition further contains a crosslinking agent. 12.  As mentioned above 8. To 1 1. The method for forming a film according to any one of the preceding claims, wherein the resin composition further comprises particles composed of a crosslinked polymer. 13.  As mentioned above 8. To 12. In the method for forming a film according to any one of the preceding claims, the solid content concentration of the resin composition is in the range of 5 to 80% by mass. 14.  As mentioned above 8. To 13. The method for forming a film according to any one of the preceding claims, wherein the viscosity V is in the range of 1 〇 to i 〇〇〇〇 mpa·s. 1 5 . As mentioned above 8 . To 1 4 . The method for forming a film according to any one of the preceding claims, wherein, in the resin composition, the shear rate is 1. Viscosity at 5 rpm V3 (mPa. s), the ratio of the viscosity V4 (mPa • s ) at a shear rate of 600 rpm (V3/V4 ) is 2. 0 or more. 16.  A method of manufacturing a structure having an insulating film, characterized in that it comprises: To 1 5 . The film formed on the surface of the substrate obtained by the method described in any one of the methods, and the film formed on the bottom surface of the hole portion -11 - 200905397 of the substrate are removed, leaving a film formed on the inner wall surface of the hole portion. The surface side surface film removing step and the heat hardening step of heating the film remaining on the inner wall surface of the hole portion. 1 7 .  A method of manufacturing a structure having an insulating film, characterized in that it comprises: To 1 5 . The film formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole portion obtained by the method described in the above, is heated to form a heat-hardening step of the insulating film containing the cured product of the resin component, and The insulating film formed on the surface of the substrate and the insulating film formed on the bottom surface of the hole portion of the substrate are removed, and the insulating film of the insulating film formed on the inner wall surface of the hole portion is left. 18.  As mentioned above 16. Or 17. In the method for producing a structure having an insulating film, the method further includes honing a substrate on a surface of the structure having the insulating film without the hole, and forming the hole as a through hole. step. 19.  A structure having an insulating film characterized by: To 18. Obtained by the method described in any one of them. 20.  An electronic component characterized by having the aforementioned 16. To 1 8. A structure having an insulating film obtained by the method described in any one of the above, and a member having an electrode portion in which at least a through hole of the structure is filled with a conductive material. twenty one .  a resin composition for electrically connecting a layer of a laminated substrate or a surface of a substrate and a surface thereof by filling a conductive material in a hole portion or a groove portion formed in a substrate :Π] in the substrate with the opening area of 25~ΙΟΟΟΟμηι2 and the depth of the hole -12~200μπι -12-200905397, the solvent coating step of the coating solvent, [2] the shear rate at 6 rpm Viscosity V, (mPa.  s) The ratio of the viscosity V2 (mPa · s ) at a shear rate of 60 rpm (Vi/V) is 1. a resin composition of 1 or more, which is applied to the resin composition coating step of the substrate, and a drying step of drying the coating film, in the hole, in a manner in which the resin composition is in contact with the solvent in the hole portion, and in the hole a resin composition for forming a film forming method of a film containing the resin component in at least the inner wall surface of the inner wall surface and the bottom surface, characterized by comprising an alkali-soluble resin, a compound having a diazide group, and two The composition of the cerium oxide, the solvent, and the crosslinking agent is shaken, and the content of the cerium oxide is such that when the solid content of the composition is set to 100% by mass, 20% by mass, below 60% by mass 〇 22. As mentioned above 21. The resin composition described further contains particles composed of a crosslinked polymer. According to the method for forming a film of the present invention, a uniform film can be easily formed on the inner wall surface and the bottom surface of the fine hole portion or the fine groove portion provided on the stepped substrate. Therefore, in the substrate on which the film is formed, an arbitrary pattern can be formed in the fine hole portion, the groove portion, and the substrate surface by exposure and development. Therefore, since the resin film can be used as a mask after the pattern formation, the vapor deposited oxide film such as Si or SiO 2 or a metal oxide film can be etched, and after the etching process. -13-200905397 The resin film can be easily peeled off, so that it can be suitably used for fine processing of the inside of a fine hole or a groove. In particular, a through electrode or the like can be easily formed. Therefore, it is very useful in the field of electronic component fabrication in which a three-dimensional package of a CMOS image sensor, a flash memory, a CPU, or the like is necessary. Further, according to the positive photosensitive resin composition of the present invention, a uniform film can be formed with high precision on the inner wall surface and the bottom surface of the hole portion or the groove portion which is provided with a fine bottom portion of the step substrate. Further, since the resin composition can be applied to the surface of the substrate by a general-purpose and simple spin coating method, the film can be easily formed. According to another method of forming a film of the present invention, by using a resin composition having a specific shake property, a uniform film can be formed on the inner wall surface of the hole portion of the substrate. Further, a uniform film may be formed on the bottom surface of the hole portion. According to the method for producing a structure having an insulating film of the present invention, a uniform insulating film can be efficiently formed on the inner wall of the through hole. Therefore, the obtained structure can be easily formed by filling metal with copper or the like in the through hole of the inner wall. In addition, it is also suitable for the modification of porous membranes. The electronic component according to the present invention is a package suitable for a semiconductor component such as a CPU, a memory, an image sensor or the like. [Embodiment] Hereinafter, the present invention will be described in detail. In addition, in the present specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid, and "(A-14-200905397) acrylate" means acrylate and methacrylate. 1. Film Forming Method (I) The film forming method (I) of the present invention is characterized in that, for filling a conductive material in a hole portion or a groove portion formed in a substrate, a layer of the bonded substrate or a substrate is used The method of electrically connecting the surface and the inside is: [1] a hole having a (a) opening area of 25 to ΙΟΟΟΟμηη2 and a depth of 10 to 200 μm (hereinafter, simply referred to as "hole portion", or It is called "fine pores".) and (b) the line width of the opening is 5 to 2 〇〇μηη and the depth is 10 to 200 μπι (hereinafter, simply referred to as "groove", or "subtle" At least one of the groove portions "), a solvent coating step of applying a solvent, and [2] applying a positive photosensitive resin composition to the solvent in the hole portion and the groove portion. a resin composition coating step of the step substrate, [3] a drying step of drying the coating film, and forming a film containing the resin component on the inner wall surface and the bottom surface of the hole portion and the groove portion. <Solvent coating step> Solvent coating step in solvent coating step On the step substrate. The step substrate may be formed of a constituent material such as tantalum, various metals, alumina, epoxy glass, phenolic paper, or glass, or a metal thin film or a metal oxide thin film. In particular, the step s i (矽) substrate is suitable for use. In addition, the thickness of the substrate is usually 100 to 1 0 0 0 μηι ° -15-200905397. The step substrate ' is as shown in the cross-sectional view of FIG. 1 , and has at least one of the surfaces of the step substrate 1 from the surface to the inside. The direction is formed by (the area of the opening portion is 25 to 1 ΟΟΟΟμηι2, preferably 100 ΙΟΟΟΟ ΙΟΟΟΟ η ηι 2 ' is preferably 25 0 to 7000 μηι 2, and the depth is 10 to 200 μηη' is preferably 30 to 200 μηι, preferably 50 to 50 The line width of the hole portion 11 of the 150 μηι and the opening of the (b) opening portion is 5 to 200 μm, preferably 5 to 150 μm, preferably 10 to ΙΟΟμηι, and the depth is 10 to 200 μm, and preferably 30 to 200 μm, preferably 50 to 150 μm. At least one of the inside of the groove portion 12. The shape and the number of the hole portion and the groove portion (hereinafter referred to as "hole portion" or the like) are not particularly limited, and may be necessary The cross-sectional shape (longitudinal section shape) in the vertical direction of the substrate surface of the hole portion or the like can be determined as a column shape [Fig.] (a) Reference] and a tapered shape (refer to Fig. 1 (b) 〕, inverse cone shape 1 (c), etc., and the cross-sectional shape of the parallel direction of the substrate surface of the hole portion may be circular, elliptical, polygonal, etc. Further, the groove portion may be formed in a straight line shape. Further, in the case of a plurality of holes, etc., the size and depth of each hole portion may be different, and the interval (length) between adjacent holes and the like may be Further, the good shape of the hole portion has a circular cross-sectional shape and a vertical cross-sectional shape. The hole portion has a circular cross-sectional shape and is a hole. The ratio of the opening diameter of the surface of the portion to the depth of the hole portion (the depth of the hole portion/the diameter of the opening is preferably 1 to 〇, preferably 1 to 5, more preferably 1 to 4.) -16 - 200905397 In addition, the groove portion is good. In the shape, the groove portion is formed in a linear shape, and the vertical cross-sectional shape is a columnar shape or a tapered shape. When the longitudinal section shape of the groove portion is a columnar shape, the aspect ratio of the square shape of the longitudinal section (hole) The depth of the portion/the length of one side of the hole portion), preferably 1 to 10, preferably 1 to 5, more preferably 1 to 4. Further, the solvent may, for example, be ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate. · propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether Propylene glycol dialkyl ether such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate Acetate; cellosolve such as ethyl cellosolve or butyl cellosolve; carbitol such as butyl carbitol; methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, etc. Lactic acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate , aliphatic carboxylic acid esters such as isobutyl propionate; methyl 3-methoxypropionate, 3-methyl Other esters such as ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; a ketone of 2-heptanone, 3-heptanone, 4-glycol, cyclohexanone or the like; N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide And lactones such as N-methylpyrrolidone; and lactones such as γ-butyrolactone. These may be used singly or in combination of two or more. -17-200905397 In the solvent coating step, the method of the solvent plate is not particularly limited, and a coating method such as a spin coating method or the like, a dipping method, or the like can be used. Further, the solvent is not particularly limited in the case where the solvent is filled in the pore portion. <Resin composition coating step> In the resin composition application step, a positive type feeling is applied in contact with a solvent in a hole or the like. In addition, regarding this positive photosensitive resin composition, it is clear. In the resin composition application step, the method of applying the photosensitive layer to the stepped substrate is particularly limited as long as the light is in contact with the solvent in the hole or the like, and for example, spin coating is exemplified. Method, coating method, etc. In the above, in particular, by using spin coating, in the resin composition coating step, the solid content concentration, viscosity, and the like of the composition are measured by a slight step of 'forming the surface formed on the surface of the step substrate. It is preferable to form a coating film in the form of 0·1 to ΙΟμηι. <Drying Step> In the above drying step, the coating film formed by the aforementioned resin composition is dried. That is, the method of coating the coating film only by the coating method, for example, by spraying, by coating the enthalpy of filling, and forming the substrate with the retardation substrate, and the composition of the resin composition in the latter stage. There is no spray method or stick method. The photosensitive resin is dried and then dried. The film thickness is removed by the solvent in the entry coating step -18-200905397, and a film is formed on the surface of the stepped substrate on the inner surface including the hole portion. The drying temperature in this step is considered to be the boiling point of the solvent charged in the solvent coating step, or the mixture of the solvent filled in the solvent coating step and the photosensitive resin composition. The boiling point of the solvent is suitably selected. Further, the drying conditions are not particularly limited, and may be carried out at a constant temperature, and may be carried out while raising or lowering the temperature, and the combination may be carried out. Further, the pressure may be carried out under atmospheric pressure, and may be carried out under vacuum. Further, the ambient atmosphere gas and the like are not particularly limited. Here, the film formation method (I) of the present invention will be specifically described (see Fig. 2). First, a solvent is applied to the step substrate 1 by a solvent coating step. At this time, the solvent 13 is normally filled in the hole portion 1 1 (groove portion 12) provided in the step substrate 1 as shown in FIG. 2(b), and the surface of the step substrate 1 is uniformly wetted. can. Then, in the resin composition application step, when the photosensitive resin composition is applied, a uniform coating film 14 is formed on the surface of the step substrate 1, and the solvent coating step is accommodated in the hole portion. a mixture of the charged solvent and the photosensitive resin composition 15 (refer to Fig. 2 (c)). Thereafter, the solvent is removed by a drying step to form a surface of the substrate on the inner wall surface and the bottom surface of the hole-containing portion. A uniform film 16 formed of a solid component of the photosensitive resin composition is formed (the film 16a formed on the entire surface of the stepped substrate 1 other than the hole portion, and the film 16b formed on the inner wall surface of the hole portion, at -19- 200905397 The film 16c) formed on the bottom surface of the hole portion (see Fig. 2(d)). In addition, the thicknesses of the films 16a, 16b, and 16c may be the same, and the film forming method (I) according to the present invention may be different, since it may be disposed in a hole or a groove having a bottom portion of the substrate. The film forming the uniform film on the wall surface and the bottom surface can be etched by vapor-depositing an oxide film such as Si or Si 2 or a metal oxide film by using the formed film as a mask. Further, since the resin film can be easily peeled off after the etching treatment, it can be suitably used for fine processing of the inside of the fine hole portion or the groove portion. For example, a microporous portion or a fine groove portion is formed on one surface of the substrate and is provided in the stepped substrate in which the electrode portion is opposed to the opposite surface corresponding to the position of the fine hole portion or the fine groove portion. The bottom surface is patterned, and the bottom portion is etched to form a through electrode. Here, a method of forming the through electrode described above will be specifically described (see FIG. 3). First, the surface of the stepped substrate 1 (see FIG. 3(a)) having the fine hole portion 11 (or the fine groove portion i 2 ) formed on one surface thereof and having the electrode portion 2 on the opposite surface thereof is formed by using a photosensitive resin. The film forming method (I) of the present invention forms the film 16 (see Fig. 3 (b)). Thereafter, the hole portion is irradiated with ultraviolet rays, visible light, far ultraviolet rays, X-rays, electron beams, or the like from above, and a predetermined region of the film 6c formed on the bottom surface of the hole portion 1 1 is exposed (see Fig. 3(c)). In addition, the exposure amount is appropriately selected depending on the light source to be used, the thickness of the film, and the like, and for example, for a film having a thickness of about 5 to 50 μm, a high-pressure mercury lamp is used to illuminate the purple-20-200905397 outer line, and good exposure is performed. The amount is from 1 000 to 2,000 (U/m2). Then, the film exposure portion 161 shown in Fig. 3(c) is alkali-soluble, so that it is treated with an alkaline solution, and a pattern 3 is formed on the bottom surface of the hole portion (see Fig. 3). (d)]. In addition, 'the alkaline solution may be an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide or choline, or an aqueous solution or an appropriate amount of methanol, ethanol or the like. A solution of a water-soluble organic solvent, a surfactant, etc. Next, the remaining film 16 is used as a mask, and the substrate 17 in the hole portion is subjected to an etching treatment (see FIG. 3(e)). As the method, a known method such as dry etching or wet etching using hydrofluoric acid or the like can be used. Thereafter, the remaining film 16 is used, and a predetermined stripping liquid (for example, N-methylpyrrolidone, dimethyl) is used. a solvent such as Kea, or These solvents are appropriately added with a solution such as a base or a surfactant, and the like, and are peeled off to form a through electrode hole portion 4 (see FIG. 3( f)). Next, the through electrode hole portion 4 can be filled with a conductive material. The conductive material may, for example, be copper, silver, tungsten, giant, titanium, nail, gold, tin, aluminum, or the like, etc. 2. Positive photosensitive resin composition of the present invention The positive photosensitive resin composition (hereinafter, simply referred to as "photosensitive resin composition") used in the method for forming a film (I) contains (A) an alkali-soluble resin, and (B) has two The diazonium group-based compound '(C) is hydrophobized and has an average particle diameter of 1 to 100 nm - 21 - 200905397 cerium oxide, and (D) solvent, and has a shaker. <(A) alkali soluble resin The above-mentioned soluble resin (hereinafter also referred to as "alkali-soluble resin (A)"), for example, (1) a resin having a phenolic hydroxyl group (hereinafter referred to as "resin (A1)"), (2) using a monomer having a phenolic hydroxyl group and containing (meth) propylene a copolymer obtained from an ester monomer (hereinafter referred to as "resin (A2)"), (3) a resin having a carboxyl group (hereinafter also referred to as "resin (A3)"), etc." The above resin (A1) The phenolic resin obtained by condensing, for example, a phenol and an aldehyde in the presence of a catalyst can be used. The phenols are exemplified by, for example, phenol, o-cresol, and m-cresol. Cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butyrrol, 2,3-indophenol, 2,4-nonanol, 2,5-nonylphenol, 2, 6·nonanol, 3,4-quinol, 3,5·nonanol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, benzenetriol, 〇: naphthol, no naphthol, etc. Examples of the aldehydes include formaldehyde, trioxane, acetaldehyde, benzaldehyde, and the like. The phenol resin may, for example, be a phenol/formaldehyde condensed phenol resin, a cresol/formaldehyde condensed phenol resin, a phenol-naphthol/formaldehyde condensed phenol resin or the like. These may be used alone or in combination of two or more. Further, 'the resin (a 1 ) other than the aforementioned phenol resin' may be exemplified by the copolymerization of polyhydroxystyrene, hydroxystyrene and other monomers [except (meth)acrylic acid and (meth) acrylate]. , polyisopropenol, isopropenol and other monomers [except for (meth)acrylic acid and (meth) acrylate] copolymer, phenol / hydrazine condensate resin, cresol / hydrazine condensate Resin, phenol/dicyclopentadiene condensation resin, and the like. These may be used alone or in combination of two or more. The resin (A2) is a copolymer obtained by using a monomer having a phenolic hydroxyl group and a monomer containing a (meth) acrylate and not containing a compound having a carboxyl group such as (meth)acrylic acid. The monomer having a phenolic hydroxyl group may, for example, be p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenol, meta-isopropenol or o-isopropenol. Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (methyl). Second butyl acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, phenyl (meth) acrylate, (methyl) An alkyl (meth)acrylate such as benzyl acrylate. Further, the hydrogen atom of the alkyl group in the alkyl (meth)acrylate may be substituted with a hydroxyl group. Further, in addition to the monomer having a hydrophobic hydroxyl group and the (meth) acrylate in the formation of the resin (A2), a compound having a polymerizable unsaturated bond may be used as another monomer. Examples of the other monomer include styrene's methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene 'methyl-23-200905397 styrene, ethylene xylene, and o. An aromatic vinyl compound such as methoxystyrene, m-methoxystyrene or p-methoxybenzidine; an unsaturated acid anhydride of anhydrous maleic acid, anhydrous citraconic acid or the like; an ester of the aforementioned unsaturated carboxylic acid; Unsaturated nitrile of methyl)acrylonitrile, maleonitrile, fumaronitrile, mesocarbonitrile, citracarbonitrile, and econazole; (meth) acrylamide, crotonamide, maleamide, fuma Insoluble decylamines such as decylamine, mesaconamine, cimolamide, and econylamine; maleic imine, N-phenyl maleimide, N-cyclohexylmaleimide, etc. Unsaturated quinone imine; unsaturated alcohol such as (meth) propylene alcohol; N-vinyl aniline, vinyl pyridine, N-ethylene-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N- Vinyl carbazole and the like. These may be used singly or in combination of two or more. The resin (A3) may be a homopolymer or a copolymer. Usually, the resin (A3) is a polymer obtained by using a monomer having a carboxyl group-containing compound (hereinafter referred to as "monomer (m)"). The monomer (m) may, for example, be unsaturated with (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, 4-vinylbenzoic acid or the like. a carboxylic acid or an unsaturated dicarboxylic acid; a monoester of an unsaturated dicarboxylic acid; and the like. These may be used alone or in combination of two or more. The resin (A3) is exemplified by the following copolymers. [1] A copolymer obtained by using a monomer (m) and a monomer having a phenolic hydroxyl group [2] using a monomer (m), a monomer having a phenolic hydroxyl group, and a (meth) acrylate Copolymer-24 - 200905397 [3] A monomer (m), a monomer having a phenolic hydroxyl group, an aromatic vinyl compound, and a copolymer obtained with (meth) acrylate [4] using a monomer (m) , an aromatic vinyl compound, and a copolymer obtained with (meth) acrylate [5] using a monomer (m), an aromatic vinyl compound, and a copolymer obtained with a conjugated diene [6] using a monomer (m), (meth) acrylate, copolymer obtained with a conjugated diene [7] using a monomer (m), a (meth) acrylate, and a copolymer obtained with a fatty acid ethylene compound In the above aspect, the above description can be directly applied to the monomer having a phenolic hydroxyl group, the (meth) acrylate, and the aromatic vinyl compound. Further, examples of the conjugated diene include 1,3-butadiene, isoprene, and 1,4-dimethylbutadiene. Further, examples of the fatty acid ethylene compound include vinyl acetate and ethyl crotonate. The photosensitive resin composition of the present invention may contain only one type of the above-mentioned alkali-soluble resin (A), and may contain two or more types. Further, the photosensitive resin composition of the present invention is preferably a resin containing a weight average molecular weight (Mw) of from 4,000 to 50,000 (preferably from 4,000 to 30,000) as the alkali-soluble resin (A). In particular, the alkali-soluble resin is (i) a resin containing only Mw of 4000 to 50000, or (ii) a resin having a Mw of 4000 to 50,000 -25 to 200905397, and a Mw of less than 2000 (more) It is better for the resin of 500 to 1900). In such cases, alkali solubility can be controlled. Further, the weight average molecular weight of the resin can be determined by gel permeation chromatography (GPC) which defines monodisperse polystyrene as a standard. The alkali-soluble resin having a Mw of from 4,000 to 50,000 is preferable as the resin having a phenolic hydroxyl group, and particularly preferably a copolymer obtained by using hydroxystyrene or a phenol resin. The above Mw is an alkali-soluble resin of less than 2,000, which is obtained by using a phenol-derived diol condensation resin, a cresol/ethylene glycol condensation resin, a phenol/dicyclopentadiene condensation resin, and hydroxystyrene. Copolymers and phenolic resins are preferred. The alkali-soluble resin (A) contains an alkali-soluble resin having a Mw of 4,000 to 50,000, and an alkali-soluble resin having a Mw of less than 2,000, and an alkali-soluble resin having a Mw of 4,000 to 50,000. When the total amount of the alkali-soluble resin (A) is set to 1% by mass, it is preferably 30 to 100% by mass, preferably 40 to 1% by mass, more preferably 5 to 10%. quality%. In addition, when the total content of the solid content of the photosensitive resin composition is 100% by mass, the content of the alkali-soluble resin (A) in the photosensitive resin composition is 30 to 60% by mass. Preferably, it is preferably from 30 to 50% by mass, more preferably from 3 to 50% by mass. When the content is in the range of 30 to 60% by mass, the alkali solubility is excellent. <(B) Compounds with a diazide group> -26- 200905397

，2-萘醌-2-重 氮_5_磺酸酯或I，2 -萘醌-2-重氮-4-磺酸醋。 前述酣類化合物’只要是具有至少1個酹性經基之化 合物’並未特別受到限定，而以例如以下述—般式（i ) 〜（5 )所表示之化合物等爲佳。 [化1]2-naphthoquinone-2-diazo_5_sulfonate or I,2-naphthoquinone-2-diazo-4-sulfonic acid vinegar. The above-mentioned anthracene compound 'is not particularly limited as long as it is a compound having at least one anthracene group, and is preferably a compound represented by the following formulas (i) to (5), for example. [Chemical 1]

〔式中’ X1〜XIQ，各自相同或相異皆可，係氫原子 、碳數1〜4之院基、碳數1〜4之院氧基或經基。另外， χ1〜X5之內之至少1個爲羥基。此外，Α爲單鍵、0、S ' ch2、c(CH3) 2 ' c ( cf3 ) 2、c = 0、或 s〇2。〕[In the formula, X1 to XIQ are each the same or different, and are a hydrogen atom, a hospital group having a carbon number of 1 to 4, or a oxy group or a mercapto group having a carbon number of 1 to 4. Further, at least one of χ1 to X5 is a hydroxyl group. Further, Α is a single bond, 0, S ' ch2, c(CH3) 2 ' c ( cf3 ) 2, c = 0, or s 〇 2 . 〕

〔式中，X11〜X2 4，各自相同或相異皆可，係氫原子 、碳數1〜4之烷基、碳數1〜4之烷氧基或羥基。另外’ x 1 1〜X 15之內之至少1個爲羥基。此外，R1〜R4 ’各自相 同或相異皆可，係氫原子或碳數1〜4之烷基。〕 -27- 200905397 [化3][In the formula, X11 to X2 4 may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. Further, at least one of 'x 1 1 to X 15 is a hydroxyl group. Further, each of R1 to R4' may be the same or different, and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 〕 -27- 200905397 [化3]

〔式中，χ25〜χ39,各自相同或相異皆可， 係_ te 、碳數1〜4之院基、碳數1〜4之院氧基或淫趣 壞子 X25〜X29之內之至少1個及X3。〜x34之內之运 努外， 羥基。此外，R5 ,係氫原子或碳數丨〜4 1個埼 [化4] 〔沅基。〕 X43 X44 X45 X46[wherein, χ25~χ39, each of the same or different, may be at least _ te, a carbon number of 1 to 4, a carbon number of 1 to 4, or a sinister child X25 to X29. 1 and X3. Within the x34, the nucleus. Further, R5 is a hydrogen atom or a carbon number of 4~4 1 埼 [Chemical 4] [沅. 〕 X43 X44 X45 X46

X 〔式中，X1〜X5 ，各自相同或相異皆可， 碳數1〜4之院基、碳數1〜4之院氧基或 4 0 X44之內之至少 個X [wherein, X1 to X5 are each the same or different, and the number of carbon atoms of 1 to 4, the number of carbons of 1 to 4, or at least of 40 X44

X χ49之內之至少 係氮 羥基》Θ 男外， 個及 χ χ之內之至少1個爲羥基。此外，r6〜r8，各自相 同或相異皆可’係氫原子或碳數1〜4之院基。〕 -28- 1 200905397 [化5]At least one of the nitrogen and the hydroxyl groups in the X χ 49 is at least one of the hydroxyl groups. Further, r6 to r8 may each be the same or different, and may be a hydrogen atom or a hospital having a carbon number of 1 to 4. 〕 -28- 1 200905397 [Chemical 5]

〔式中，x59〜x72 ,各自相同或相異皆可，係 、碳數1〜4之烷基、碳數1〜4之烷氧基或羥基。 X59〜X62之內之至少1個及X63〜X67之內之至少 羥基。〕 在前述一般式（1)〜（5)中，碳數1〜4之 而言’可列舉例如甲氧基、乙氧基、丙氧基、異丙 丁氧基、異丁氧基、第二丁氧基、第三丁氧基等之 或分枝狀之烷氧基。 此外，前述一般式（1)〜（5)中，碳數1〜 基而g，可列舉例如甲基、乙基、丙基、異丙基、 異丁基、第二丁基、第三丁基等之直鏈狀或分枝狀 〇 前述酚類化合物之具體例而言，可列舉例如4， 基二苯甲烷、4,4··二羥基二苯醚、2,3,4·三羥基二 、2,3,4,4·-四羥基二苯甲酮、2,3,4,2’，4’ -五羥基二 、參（4_羥苯基）甲烷、參（4_羥苯基）乙烷、1 4-羥苯基）-卜苯乙烷、1,3-雙[】-(4-羥苯基）-1- 氫原子 另外， 1個爲 烷氧基 氧基、 直鏈狀 4之烷 丁基、 之院基 4，-二羥 苯甲酮 苯甲酮 ,]-雙（ 甲基乙 -29- 200905397 基]苯、1，4-雙[1-(4-羥苯基）-；1-甲基乙基]苯、4,6-雙[卜 (4-羥苯基）-1-甲基乙基]-1，3-二羥基苯、1，1-雙（4-羥苯 基）羥苯基）-1-甲基乙基]苯基]乙烷等。該 等之酚類化合物，係以1種單獨使用亦可，組合2種以上 使用亦可。 因此，前述二重氮醌化合物（B)而言，係可將使選 自上述之酚類化合物之中至少1種、與1，2-重氮萘醌-4-磺 酸或1,2-重氮萘醌-5-磺酸反應所得到之酯化物等，以1種 單獨使用，組合2種以上使用亦可。 前述感光性樹脂組成物中之前述二重氮醌化合物（B )之含有比例，在將感光性樹脂組成物所含之固體成分全 體定爲100質量％之情況下，以1〜40質量％者爲佳，較 佳爲5〜3 0質量％，更佳爲5〜2 0質量％。此含有比例爲1 〜40質量％之情況而言，可使所得到之被膜之曝光部與未 曝光部之溶解度之差變大，並可使顯像性更加提升故爲佳 〈（C )二氧化矽〉 於本發明中之感光性樹脂組成物，爲了表現出搖變性 且作控制，因此配合了至少一部爲經疏水化處理之二氧化 石夕〔以下，亦稱爲「二氧化砂（C)」〕。 經疏水化處理之二氧化矽之種類係並未特別受到限定 ’而可列舉例如，膠態二氧化矽、氣相二氧化矽、玻璃等 。另外，該等之粒子形狀，係並未特別受到限定，可定爲 -30- 200905397 球狀、橢圓形狀、扁平狀、棒狀、纖維狀等。 前述二氧化矽（C )之疏水化率，係20〜80%者爲佳 ，較佳爲30〜70%，更佳爲40〜70%。此疏水化率爲20〜 8 0%之情況而言，二氧化矽於溶劑之分散性及與前述樹脂 之相溶性成爲良好，進一步而言可表現出前述感光性樹脂 組成物之搖變性，故爲佳。 另外，前述感光性樹脂組成物中之二氧化矽（C )之 疏水化率，係對疏水化前及疏水化後之二氧化矽表面之矽 醇基數藉由以0. 1 N氫氧化鈉水溶液所進行之中和滴定法 作測定，由下式所求得之値。 疏水化率（％ )=(疏水化後之矽醇基數/疏水化前之 矽醇基數）χίοο 此外’前述二氧化矽（C)之平均粒徑係1〜lOOnm， 良好爲 5〜80nm ’較佳爲 1 〇〜50nm。此平均粒徑爲 1〜 1 OOnm之情況而言’可得到對於曝光光線充分之透明性、 及充分之鹼溶解性等。另一方面，超過l〇〇nm之情況而言 ’無法得到對於曝光光線充分之透明性，解像性有惡化之 傾向。 另外’此平均粒徑，係使用光散射流動分布測定裝置 (大塚電子公司製’型號「LPA-3000」），將二氧化矽粒 子之分散液依照常法稀釋而作測定之値。 此外’此平均粒徑，係可藉由二氧化矽粒子之分散條 件作控制。 此外’前述二氧化矽（C )中之鈉含量，係以1 ppm -31 - 200905397 以下者爲佳，較佳爲0.5ppm以下，更佳爲0.1 ppm以下。 此鈉含量爲1 PPm以下之情況而言，可將所得到之感光性 樹脂組成物中之鈉含量定爲1 ppm以下。 另外，二氧化矽（C)中之鈉含量，係可藉由原子吸 收光譜計（珀金埃爾默製、型號「Z5 1 00」）等作測定》 前述感光性樹脂組成物中之前述二氧化矽（C )之含 有比例，在將感光性樹脂組成物中之固體成分全體定爲 100質量％之情況下，爲超過20質量％而在60質量％以下 ，良好爲3 0質量％以上、6 0質量％以下’更佳爲3 0質量 %以上、5 0質量％以下。此含有比例爲超過2 0質量％、6 0 質量％以下之情況而言，可得到充分之搖變性，可在段差 基板等之細微孔或細微溝之內壁面及底面形成均勻之被膜 。此外，此含有比例爲20質量％以下之情況’則有無法得 到充分之搖變性、無法在段差基板等之細微孔或細微溝之 內壁面及底面形成均勻之被膜之虞。另—方面’超過7〇 質量％之情況，則有無法控制曝光部與未曝光部之溶解度 之差、無法得到充分之顯像性之虞。 另外，在本發明中之感光性樹脂組成物，係僅含有1 種前述二氧化矽（C)亦可，含有2種以上亦可，而二氧 化矽粒子之良好之分散性之觀點看來’以僅含有1種者爲 佳。 〈（D )溶劑〉 爲了使感光性樹脂組成物之使用性提升、調節黏度或 -32- 200905397 保存安定性而含有前述溶劑〔以下，亦稱爲「溶劑（D ) J ] ° 就目u述彳谷劑（D )而g ’可列舉例如乙二醇單甲基醚 醋酸酯、乙一醇單乙基醚醋酸酯等之乙二醇單烷醚醋酸酯 類；丙一醇單甲基醚 '丙二醇單乙基醚、丙二醇單丙基醚 、丙一_單丁基醚等之丙一醇單烷醚類；丙二醇二甲基醚 、丙二醇二乙基醚、丙二醇二丙基醚 '丙二醇二丁基醚等 之丙二醇二烷醚類；丙二醇單甲基醚醋酸酯、丙二醇單乙 基醚醋酸酯、丙二醇單丙基醚醋酸酯、丙二醇單丁基醚醋 酸酯等之丙二醇單烷醚醋酸酯類；乙基溶纖劑、丁基溶纖 劑等之溶纖劑類、丁基卡必醇等之卡必醇類；乳酸甲酯、 乳酸乙酯、乳酸正丙酯、乳酸異丙酯等之乳酸酯類；醋酸 乙酯、醋酸正丙酯、醋酸異丙酯 '醋酸正丁酯、醋酸異丁 酯、醋酸正戊酯、醋酸異戊酯、丙酸異丙酯、丙酸正丁酯 、丙酸異丁酯等之脂肪族羧酸酯類；3 -甲氧丙酸甲酯、3-甲氧丙酸乙酯、3-乙氧丙酸甲酯、3-乙氧丙酸乙酯、丙酮 酸甲酯、丙酮酸乙酯等之其他酯類；甲苯、二甲苯等之芳 香族烴類；2-庚酮、3-庚酮、4-庚酮、環己酮等之酮類； N-二甲基甲醯胺、N-甲基乙醯胺、N，N-二甲基乙醯胺、N-甲基吡咯烷酮等之醯胺類；γ-丁內酯等之內酯類。該等之 溶劑（D )，係以1種單獨使用亦可，組合2種以上使用 亦可。 〈低分子酚性化合物〉 -33- 200905397 於本發明中之感光性樹脂組成物，爲了使鹼可溶性提 升，亦可含有分子量爲未滿500之低分子酚性化合物作爲 添加劑。 前述低分子酚性化合物而言，可列舉例如4,4·-二羥二 苯甲烷、4,4’-二羥二苯醚、參（4-羥苯基）甲烷、1，1-雙 (4-羥苯基）-1-苯乙烷、參（4-羥苯基）乙烷、1,3-雙[1-(4-羥苯基）-1-甲基乙基]苯、1，4-雙[1-(4-羥苯基）-1-甲基乙基]苯、4,6-雙[1-(4-羥苯基）-1-甲基乙基]-1，3-二 羥苯、1，1-雙（4-羥苯基）-1-[4-[1·(4-羥苯基）-1·甲基 乙基]苯基]乙烷、1,1，2,2-四（4-羥苯基）乙烷等。該等， 係以1種單獨使用亦可，組合2種以上使用亦可。 此外，前述低分子酚性化合物之含量，係相對於前述 鹼可溶性樹脂（A ) 1 0 0質量份，以1〜3 0質量份者爲佳 ，較佳爲3〜25質量份，更佳爲5〜20質量份。 〈密著助劑〉 於本發明中之感光性樹脂組成物，爲了提升與基板之 密著性，含有密著助劑作爲添加劑亦可。 前述密著助劑而言，可列舉例如具有羧基、甲基丙烯 醯基、異氰酸基、環氧基等之反應性取代基之官能性矽烷 偶合劑等。具體而言，可列舉例如安息香酸三甲氧基矽基 酯、r-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、r-異氰酸丙基三乙 氧基矽烷、r-甲基丙烯醯氧丙基三甲氧基矽烷、θ-( -34- 200905397 3,4-環氧環己基）甲基三甲氧基矽烷、1,3,5-N-參（三甲 氧基矽基丙基）三聚異氰酸酯等。該等之密著助劑，係以 1種單獨使用亦可，組合2種以上使用亦可。 此外，前述密著助劑之含量，係將前述鹼可溶性樹脂 (A )與低分子酚性化合物之合計定爲1 00質量份之情況 下，0.5〜10質量份者爲佳，更佳爲0.5〜8質量份。此含 量爲0.5〜1 0質量份之情況而言，由於表現出與基板之良 好密著性故爲佳。 〈界面活性劑〉 於本發明中之感光性樹脂組成物，爲了提升樹脂組成 物之塗佈性，亦可含有界面活性劑（調平劑）作爲添加劑 〇[wherein, x59 to x72 may be the same or different, and are an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. At least one of X59 to X62 and at least one of X63 to X67. In the above general formulas (1) to (5), the carbon number is 1 to 4, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, an isobutoxy group, and a second. a butoxy group, a third butoxy group or the like or a branched alkoxy group. Further, in the above general formulae (1) to (5), the carbon number is 1 to the group and g, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a second butyl group, and a third butyl group. Specific examples of the linear or branched phenolic compound such as a group include, for example, 4, phenyldiphenylmethane, 4,4·dihydroxydiphenyl ether, and 2,3,4·trihydroxyl group. 2,3,4,4·-tetrahydroxybenzophenone, 2,3,4,2',4'-pentahydroxydiene, ginseng (4-hydroxyphenyl)methane, ginseng (4-hydroxybenzene) Ethyl, 1 4-hydroxyphenyl)-phenylethylethane, 1,3-bis[]-(4-hydroxyphenyl)-1-hydrogen atom, additionally, one is alkoxyoxy, straight Chain 4 alkyl butyl, the hospital base 4,-dihydroxybenzophenone benzophenone,]-bis (methylethyl-29- 200905397 base) benzene, 1,4-bis[1-(4-hydroxyl Phenyl)-; 1-methylethyl]benzene, 4,6-bis[(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-double (4-Hydroxyphenyl)hydroxyphenyl)-1-methylethyl]phenyl]ethane and the like. These phenolic compounds may be used singly or in combination of two or more. Therefore, the above didiazonium compound (B) may be at least one selected from the above phenolic compounds, and 1,2-diazonaphthoquinone-4-sulfonic acid or 1,2- The esterified product obtained by the reaction of the diazonaphthoquinone-5-sulfonic acid may be used singly or in combination of two or more kinds. In the case where the total content of the solid component contained in the photosensitive resin composition is 100% by mass, the content of the above-mentioned diazide compound (B) in the photosensitive resin composition is 1 to 40% by mass. Preferably, it is preferably 5 to 30% by mass, more preferably 5 to 20% by mass. In the case where the content ratio is from 1 to 40% by mass, the difference in solubility between the exposed portion and the unexposed portion of the obtained film can be increased, and the developability can be further improved, so that it is preferable ((C) 2矽 矽 矽 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光C)"]. The type of the hydrophobized cerium oxide is not particularly limited, and examples thereof include colloidal cerium oxide, gas phase cerium oxide, glass, and the like. Further, the shape of the particles is not particularly limited, and may be -30-200905397 spherical, elliptical, flat, rod-shaped, fibrous, and the like. The hydrophobization rate of the cerium oxide (C) is preferably from 20 to 80%, preferably from 30 to 70%, more preferably from 40 to 70%. When the hydrophobization ratio is from 20 to 80%, the dispersibility of the cerium oxide in the solvent and the compatibility with the resin are good, and further, the sensitization of the photosensitive resin composition can be exhibited. It is better. The hydration of the cerium oxide (C) in the photosensitive resin composition is the sterol group of the surface of the cerium oxide before and after the hydrophobization. The middle and the titration method were used for the measurement, and the enthalpy was obtained by the following formula. Hydrophobicity ratio (%) = (number of sterol groups after hydrophobization / number of sterol groups before hydrophobization) χίοο Further, the average particle diameter of the above-mentioned cerium oxide (C) is 1 to 100 nm, preferably 5 to 80 nm. Good for 1 〇 ~ 50nm. In the case where the average particle diameter is from 1 to 100 nm, sufficient transparency to the exposure light, and sufficient alkali solubility can be obtained. On the other hand, in the case of more than 10 nm, the transparency to the exposure light is not obtained, and the resolution tends to be deteriorated. In addition, the average particle diameter was measured by using a light scattering flow distribution measuring apparatus (Model "LPA-3000" manufactured by Otsuka Electronics Co., Ltd.), and the dispersion of the cerium oxide particles was measured by a conventional method. Further, the average particle diameter can be controlled by the dispersion condition of the cerium oxide particles. Further, the sodium content in the above-mentioned ceria (C) is preferably 1 ppm -31 to 200905397 or less, preferably 0.5 ppm or less, more preferably 0.1 ppm or less. In the case where the sodium content is 1 ppm or less, the sodium content in the obtained photosensitive resin composition can be made 1 ppm or less. Further, the sodium content in the cerium oxide (C) can be measured by an atomic absorption spectrometer (manufactured by PerkinElmer, model "Z5 00") or the like. When the total content of the solid content in the photosensitive resin composition is 100% by mass, the content of the cerium oxide (C) is more than 20% by mass and is preferably 60% by mass or less, and preferably 30% by mass or more. 60% by mass or less is more preferably 30% by mass or more and 50% by mass or less. When the content ratio is more than 20% by mass and 60% by mass or less, sufficient shakeability can be obtained, and a uniform film can be formed on the inner wall surface and the bottom surface of the fine pores or fine grooves of the step substrate or the like. In addition, when the content ratio is 20% by mass or less, sufficient shakeability cannot be obtained, and a uniform film cannot be formed on the inner wall surface and the bottom surface of the fine pores or fine grooves of the step substrate. On the other hand, when the amount exceeds 7 〇 mass%, the difference in solubility between the exposed portion and the unexposed portion cannot be controlled, and sufficient development performance cannot be obtained. In addition, the photosensitive resin composition of the present invention may contain only one type of the above-mentioned ceria (C), and may contain two or more kinds of them, and the viewpoint of good dispersibility of the ceria particles is ' It is preferable to contain only one type. <(D) Solvent> The solvent is contained in order to improve the usability of the photosensitive resin composition, adjust the viscosity, or to preserve the stability of the -32-200905397 (hereinafter, also referred to as "solvent (D) J ] °) The glutinous agent (D) and g' may, for example, be ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate or ethyl alcohol monoethyl ether acetate; propylene monomethyl ether' Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propanol monoethyl ether, etc.; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether 'propylene glycol dibutyl Propylene glycol monoalkyl ethers such as propylene glycol monoalkyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. ; a cellosolve such as ethyl cellosolve or butyl cellosolve; a carbitol such as butyl carbitol; a lactate such as methyl lactate, ethyl lactate, n-propyl lactate or isopropyl lactate; Class; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, vinegar Aliphatic esters of isobutyl ester, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate, etc.; methyl 3-methoxypropionate, 3 - other esters such as ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene a ketone of 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc.; N-dimethylformamide, N-methylacetamide, N,N-dimethyl B The lactones such as decylamine and N-methylpyrrolidone; and the lactones such as γ-butyrolactone. The solvent (D) may be used singly or in combination of two or more. <Low-Molecular Phenolic Compound> -33- 200905397 The photosensitive resin composition of the present invention may contain a low molecular phenolic compound having a molecular weight of less than 500 as an additive in order to improve alkali solubility. The compound may, for example, be 4,4·-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, quinone (4-hydroxyphenyl)methane or 1,1-bis(4-hydroxyphenyl). )-1-phenylethane, ginseng (4-hydroxyl) Ethyl, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methyl Ethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)- 1-[4-[1·(4-hydroxyphenyl)-1·methylethyl]phenyl]ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, etc. The amount of the low molecular weight phenolic compound may be 1 to 3 parts by mass per 100 parts by mass of the alkali-soluble resin (A), and may be used alone or in combination of two or more. It is preferably 0 parts by mass, preferably 3 to 25 parts by mass, more preferably 5 to 20 parts by mass. <Adhesive Aid> The photosensitive resin composition of the present invention may contain an adhesion promoter as an additive in order to improve the adhesion to the substrate. The above-mentioned adhesion aid may, for example, be a functional decane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group. Specific examples thereof include trimethoxydecyl benzoate, r-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, and r-iso Cyanate propyl triethoxy decane, r-methyl propylene oxypropyl trimethoxy decane, θ-( -34- 200905397 3,4-epoxycyclohexyl)methyltrimethoxy decane, 1,3 , 5-N-gin (trimethoxydecylpropyl) trimeric isocyanate, and the like. These adhesion aids may be used singly or in combination of two or more. In addition, when the total amount of the above-mentioned alkali-soluble resin (A) and the low-molecular phenolic compound is 100 parts by mass, it is preferably 0.5 to 10 parts by mass, more preferably 0.5. ~ 8 parts by mass. In the case where the content is from 0.5 to 10 parts by mass, it is preferred because it exhibits good adhesion to the substrate. <Surfactant> The photosensitive resin composition of the present invention may contain a surfactant (leveling agent) as an additive in order to improve the coating property of the resin composition.

前述界面活性劑而言，可列舉例如聚氧乙烯月桂醚、 聚氧乙烯硬脂醚、聚氧乙烯鯨蠟醚、聚氧乙烯油酸醚等之 聚氧乙烯烷醚類、聚氧乙烯辛基酚醚、聚氧乙烯壬基酌醚 等之聚氧乙烯烷丙烯醚類、聚氧乙烯聚氧丙烯塊狀共聚物 類、去水山梨醇單月桂酸酯、去水山梨醇單棕櫚酸醋、去 水山梨醇單硬脂酸酯等之去水山梨醇脂肪酸酯類、聚氧乙 稀去水山梨醇單月桂酸醋、聚氧乙稀去水山梨醇單棕櫚酸 酯、聚氧乙烯去水山梨醇單硬脂酸酯、聚氧乙稀去水山梨 醇三油酸酯、聚氧乙烯去水山梨醇三硬脂酸酯等之聚氧乙 烯去水山梨醇脂肪酸酯之非離子性界面活性劑、EFTOP EF301、EF3 03、EF3 52 (東北化學成品）、MEGAFACE -35- 200905397 F171、F172、F173 (大日本墨水化學工業）、Fluorad FC43 0、FC431 (住友 3M ) 、AsahiGuard A G 7 1 0、S u rf 1 ο η S-381、S-382、SC101、SC 102 &gt; SC103、SC104、SC105、 SC 1 06 ' Surfynol E 1 004 ' KH-10、KH-20、KH-30、KH-40 (旭硝子）、FTERGENT 25 0、251、222F、FTX-218 ( NEOS )等之氟系界面活性劑、有機矽氧烷聚合物 KP341 、X-70-092、X-70-093 (信越化學工業）、SH8400 (東麗 •道康寧）、丙烯酸系或甲基丙烯酸系 Poly-Flow No.75 、Νο·77、No.90、No.95 (共榮社油脂化學工業）。該等 之界面活性劑，係以1種單獨使用亦可，組合2種以上使 用亦可。 此外，前述界面活性劑之含量，係將前述鹼可溶性樹 脂（A )與低分子酚性化合物之合計定爲1 〇〇質量份之情 況下，以〇.〇1〜1質量份者爲佳，較佳爲0.01〜0.5質量 份。此含量爲0.01〜1質量份之情況而言，可在段差基板 等之細微孔或細微溝之內壁面及底面形成平地性優異之被 膜。 〈其他添加劑〉 在本發明中之感光性樹脂組成物而言，可依照必要在 不損及本發明之特性之程度含有其他添加劑。就如此之其 他添加劑而言，可列舉增感劑、調平劑等。 〈鈉含量〉 -36- 200905397 係 〇 中 光 變 段 差 適 係 25 質 製 之 成 切 在 則述感光性樹脂組成物之固體成分中之鈉含量， lppm以下’較佳爲〇.8ppm以下，更佳爲〇.5ρρηι以下 此鈉含量爲lppm以下之情況而言，由於使用在本發明 之感光性樹脂組成物所製作之電子元件中之金屬雜質少 可製作電氣信頼性優異之電子元件故爲佳。 另外’樹脂組成物中之鈉含量，係可藉由原子吸收 譜計（珀金埃爾默製，型號「Z5 1 〇〇」）等測定。 此外’在本發明中之感光性樹脂組成物，係具有搖 性者’由於在形成有細微孔部及細微溝部之至少一者之 差基板形成被膜故可適合地使用。具體而言，由於在段 基板之孔部或溝部之內壁面及底面形成均勻之被膜故可 合地使用。 在本發明中之感光性樹脂組成物之固體成分濃度， 以5〜8 0質量％者爲佳，較佳爲1 〇〜6 0質量％，更佳爲 〜6 0質量％。 再者，感光性樹脂組成物之固體成分濃度爲5〜80 量％時之黏度，係1 0〜1 OOOOmPa . s者爲佳，較佳爲20 7000mPa· s，更佳爲30〜5000mPa· s。此黏度若爲10 1 OOOOmPa · s，對細微之孔部或溝部之內壁面及底面之 膜性優異，可得到較爲均勻之被膜。另外，樹脂組成物 黏度，係在溫度2 5 °C，以回轉速度2 0 rpm所測定之値。 此外，在本發明中之感光性樹脂組成物，係樹脂組 物之固體成分濃度爲在5〜80質量％之範圍之情況，剪 速度在6rpm時之黏度 Vi ( mPa . s )、與剪切速度 -37- 200905397 60rpm時之黏度v2(mPa. s)之比（VWV；!)係以 上者爲佳，較佳爲 1.1〜10.0’更佳爲 1.2〜8.0’ 1 .3〜6.0。此比（W/V2 )爲1 _ 1以上之情況而言’ 之孔部或溝部之內壁面及底面之製膜性優異’可得 之被膜。 再者，樹脂組成物之固體成分濃度爲在1 2〜80 之範圍之情況’剪切速度在Urpm時之黏度V3( )、與剪切速度在600rpm時之黏度V4(mPa· s) V3/V4 )係以2.0以上者爲佳、較佳爲2.0〜80， 2.0〜70，特佳爲3.0〜60。此比（V3/V4)爲2.0以 況而言，可得到較爲均勻之被膜。 3 .感光性樹脂組成物之調製方法 在本發明中之感光性樹脂組成物之調製方法係 別受到限定，可藉由公知之方法調製。此外，前述 性樹脂（A )、前述二重氮醌化合物（B )、前述二 (C )、前述溶劑（D )，進一步依照必要亦可藉由 加入有前述之各添加劑且完全栓緊之樣本瓶，在波 轉器等之上作攪拌而調製。 1.1以 特佳爲 對細微 到均勻 質量％ mPa * s 之比（ 更佳爲 上之情 並未特 鹼可溶 氧化石夕 將當中 浪式旋 形成於 板之層 具備： -38- 1 .被膜形成方法（11 ) 2 本發明之被膜形成方法（II )，係用於藉由在 基板之孔部或溝部充塡導電性材料，將經層合之基 間' 或基板之表面和裏面作電氣性連接之方法，並 200905397 [1]在具有開口部之面積爲25〜ΙΟΟΟΟμηι2且深度爲10〜 2 00 μηι之孔部之矽基板，塗佈溶劑之溶劑塗佈步驟、[2]將 剪切速度在 6rpm時之黏度 V] (mPa· s)與剪切速度在 60rpm時之黏度V2(mPa. s)之比（V^VJ爲1.1以上 之樹脂組成物，以該樹脂組成物與前述孔部內之前述溶劑 接觸之方式，塗佈於前述基板之樹脂組成物塗佈步驟、[3] 將塗膜乾燥之乾燥步驟，且在孔部之內壁面及底面之內之 至少該內壁面形成含前述樹脂成分之被膜。 本發明之被膜形成方法（Π)中所使用基板之構成材 料而言，可列舉矽、各種金屬、各種金屬濺鑛膜、氧化鋁 、環氧玻璃、酚醛紙、玻璃等。此基板之厚度通常爲1〇〇 〜1,0 0 0 μηι 〇 前述基板5 1，係如圖7之剖面圖所示般，在基板5 1 之至少其中一面上，具有由表面往內部以縱方向般形成之 ，開口部之面積爲25〜ΙΟΟΟΟμιη2，良好爲1〇〇〜ΙΟΟΟΟμιη2 ，較佳爲25 0〜7,000μιη2且深度爲10〜200μιη，良好爲30 〜120 μιη，較佳爲50〜100 μιη之孔部511。 此孔部之形狀及數，係並未特別受到限定。此外，前 述孔部之形狀，係可定爲柱狀（參照圖7 ( a ))、順錐形 狀（參照圖7(b))、逆錐形狀（參照圖7 ( c ))等， 其横斷面形狀，亦可定爲圓形、橢圓形、多角形等。另外 ，孔部爲多數個之情況，各孔部之大小及深度爲相異亦可 ’相鄰孔部彼此之間隔（長度）亦並未特別受到限定。 作爲前述孔部形狀，良好爲横斷面形狀爲四角形（正 -39- 200905397 方形或長方形）之柱狀或順錐形狀者。 前述孔部’在横斷面形狀爲四角形之柱狀之情況，縱 斷面之四角形之縱橫比（孔部之深度與孔部底面之1邊之 長度之比），良好爲1〜10，較佳爲1〜5，更佳爲1〜4。 將本發明之被膜形成方法（11 )使用圖8作說明，首 先，藉由溶劑塗佈步驟，將溶劑塗佈於基板5 1。此時，溶 劑513，係通常以如圖8(b)之方式，充塡在設置於基板 51之孔部5 1 1內，此外，將基板51之表面均勻地潤濕亦 可。其後，藉由樹脂組成物塗佈步驟，將樹脂組成物塗佈 於基板5 1形成塗膜5 1 5 (圖8 ( c ))。此時，在孔部5 1 1 內，由前述溶劑塗佈步驟而來之溶劑、與由樹脂組成物塗 佈步驟而來之樹脂組成物會被混合。接著，藉由乾燥步驟 ，除去孔部5 1 1內所含之由前述溶劑塗佈步驟而來之溶劑 及前述樹脂組成物中之溶劑，可得到具有在含孔部5 1 1之 內表面之基板51之全表面形成之被膜519’附有被膜之基 板5。 以下，對於各步驟作說明。 前述溶劑塗佈步驟’係在前述基板塗佈溶劑之步驟。 就所使用之溶劑而言’可列舉乙二醇單甲基醚醋酸酯、乙 二醇單乙基醚醋酸酯等之乙二醇單烷醚醋酸酯頰；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 丁基醚等之丙二醇單烷醚類；丙二醇二甲基醚 '丙二醇二 乙基醚、丙二醇二丙基醚 '丙二醇二丁基醚等之丙二醇二 烷醚類；丙二醇單甲基醚醋酸酯 '丙二醇單乙基醚醋酸醋 -40- 200905397 、丙二醇單丙基醚醋酸酯、丙二醇單丁基醚醋酸酯等之丙 二醇單烷醚醋酸酯類；乙基溶纖劑、丁基溶纖劑等之溶纖 劑類；丁基卡必醇等之卡必醇類；乳酸甲酯、乳酸乙酯、 乳酸正丙酯、乳酸異丙酯等之乳酸酯類；醋酸乙酯、醋酸 正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、醋酸正 戊酯 '醋酸異戊酯 '丙酸異丙酯、丙酸正丁酯 '丙酸異丁 酯等之脂肪族羧酸酯類；3 -甲氧丙酸甲酯、3 -甲氧丙酸乙 酯、3-乙氧丙酸甲酯、3-乙氧丙酸乙酯、丙酮酸甲酯、丙 酮酸乙酯等之其他酯類；甲苯、二甲苯等之芳香族烴類； 2-庚酮、3-庚酮、4-庚酮、環己酮等之酮類；N-二甲基甲 醯胺、N -甲基乙醯胺、Ν,Ν -二甲基乙醯胺、N -甲基吡咯烷 酮等之醯胺類；γ-丁內酯等之內酯類。該等’係可單獨1 種或組合2種以上使用。 在前述溶劑塗佈步驟中，將前述溶劑塗佈於基板之方 法而言，並未特別受到限定，而可列舉噴塗法、旋轉塗佈 法等之塗佈法、浸漬法等。另外，藉由塗佈溶劑，在前述 孔部內溶劑充塡之情況下溶劑充塡率，係並未特別受到限 定。 前述樹脂組成物塗佈步驟，係將含有樹脂成分、二氧 化矽及溶劑、具有特定之搖變性之樹脂組成物，以該樹脂 組成物與前述孔部內之前述溶劑接觸之方式，塗佈於前述 基板之步驟。 前述樹脂組成物，剪切速度在6rpm時之黏度 V】（ mPa.s)、與剪切速度在60rpm時之黏度V2(mPa.s) -41 - 200905397 之比（V&quot;v2 )，係1.1以上，良好爲1 .1〜10.0，較佳爲 1.2〜8.0、更佳爲在1.3〜5.0之範圍。前述比（VWV2)若 在前述範圍，則對孔部之內壁面及底面之至少內壁面之製 膜性優異，可得到均勻之被膜。 前述樹脂組成物之固體成分濃度，良好爲5〜80質量 %、較佳爲2 0〜6 0質量％。Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleate, and polyoxyethylene octyl groups. a polyoxyethylene alkane propylene ether such as a phenol ether or a polyoxyethylene decyl ether, a polyoxyethylene polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, Desorbed sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene dehydrated Nonionic interface of polyoxyethylene sorbitan fatty acid esters such as sorbitol monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Active agent, EFTOP EF301, EF3 03, EF3 52 (Northeast Chemical Finished Product), MEGAFACE -35- 200905397 F171, F172, F173 (Greater Japan Ink Chemical Industry), Fluorad FC43 0, FC431 (Sumitomo 3M), AsahiGuard AG 7 1 0 , S u rf 1 ο η S-381, S-382, SC101, SC 102 &gt; SC103, SC104 SC105, SC 1 06 ' Surfynol E 1 004 'KH-10, KH-20, KH-30, KH-40 (Asahi Glass), FTERGENT 25 0, 251, 222F, FTX-218 (NEOS), etc. Agent, organic siloxane polymer KP341, X-70-092, X-70-093 (Shin-Etsu Chemical Industry), SH8400 (Toray Dow Corning), acrylic or methacrylic Poly-Flow No.75, Νο · 77, No. 90, No. 95 (Kyoeisha Oil Chemical Industry). These surfactants may be used singly or in combination of two or more. In addition, when the total amount of the above-mentioned alkali-soluble resin (A) and the low-molecular phenolic compound is 1 part by mass, the content of the surfactant is preferably 1 to 1 part by mass. It is preferably 0.01 to 0.5 parts by mass. When the content is 0.01 to 1 part by mass, a film having excellent flatness can be formed on the inner wall surface and the bottom surface of the fine pores or fine grooves of the step substrate. <Other Additives> The photosensitive resin composition of the present invention may contain other additives to the extent necessary to impair the characteristics of the present invention as necessary. As such other additives, sensitizers, leveling agents and the like can be mentioned. <Sodium content> -36- 200905397 In the 〇 光 光 光 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体In the case where the sodium content is less than or equal to 1 ppm, it is preferable to use an electronic component having excellent electrical conductivity without using a small amount of metal impurities in the electronic component produced by the photosensitive resin composition of the present invention. . Further, the sodium content in the resin composition can be measured by an atomic absorption spectrometer (manufactured by Perkin Elmer, model "Z5 1 〇〇"). In addition, the photosensitive resin composition of the present invention is suitably used because it forms a film on the difference substrate in which at least one of the fine pore portion and the fine groove portion is formed. Specifically, since a uniform film is formed on the inner wall surface and the bottom surface of the hole portion or the groove portion of the segment substrate, it can be used in combination. The solid content concentration of the photosensitive resin composition in the present invention is preferably from 5 to 80% by mass, more preferably from 1 to 60% by mass, even more preferably from 260% by mass. Further, the viscosity of the photosensitive resin composition at a solid concentration of 5 to 80% by weight is preferably 10 to 1 OOOOmPa.s, preferably 20 7000 mPa·s, more preferably 30 to 5000 mPa·s. . When the viscosity is 10 1 OOOOmPa · s, the film properties of the inner wall surface and the bottom surface of the fine hole portion or the groove portion are excellent, and a relatively uniform film can be obtained. Further, the viscosity of the resin composition was measured at a temperature of 25 ° C and measured at a rotational speed of 20 rpm. Further, in the photosensitive resin composition of the present invention, when the solid content concentration of the resin group is in the range of 5 to 80% by mass, the viscosity Vi (mPa.s) at a shear rate of 6 rpm, and shearing Speed -37- 200905397 The ratio of viscosity v2 (mPa.s) at 60 rpm (VWV;!) is preferably the above, preferably 1.1 to 10.0', more preferably 1.2 to 8.0'1.3 to 6.0. When the ratio (W/V2) is 1 _ 1 or more, the film formation property of the inner wall surface and the bottom surface of the hole portion or the groove portion is excellent. Further, the solid content concentration of the resin composition is in the range of from 1 to 80%, the viscosity V3 of the shear rate at Urpm, and the viscosity V4 (mPa·s) at a shear rate of 600 rpm. V4) is preferably 2.0 or more, preferably 2.0 to 80, 2.0 to 70, and particularly preferably 3.0 to 60. When the ratio (V3/V4) is 2.0, a relatively uniform film can be obtained. 3. Method of Preparing Photosensitive Resin Composition The method of preparing the photosensitive resin composition in the present invention is not limited, and can be prepared by a known method. Further, the above-mentioned resin (A), the above-mentioned diedragon compound (B), the above-mentioned two (C), and the above solvent (D) may further be added to the sample which is completely tethered by adding the aforementioned respective additives as necessary. The bottle is prepared by stirring on a rotator or the like. 1.1 is particularly good for the ratio of fine to uniform mass % mPa * s (better than the above, there is no special alkali soluble oxidized oxide. The middle wave is formed on the layer of the plate: -38- 1 . Forming method (11) 2 The film forming method (II) of the present invention is for electrically coating the surface of the laminated substrate or the surface of the substrate by filling the conductive material with the hole or the groove portion of the substrate. Method of sexual connection, and 200905397 [1] in a substrate having an opening portion having an area of 25 to ΙΟΟΟΟμηι2 and a depth of 10 to 200 μηι, a solvent coating step of applying a solvent, [2] cutting The ratio of the viscosity V] (mPa·s) at a speed of 6 rpm to the viscosity V2 (mPa·s) at a shear rate of 60 rpm (V^VJ is a resin composition of 1.1 or more, and the resin composition and the aforementioned pores a method of coating the resin composition in the portion, a coating step of applying the resin composition on the substrate, [3] a drying step of drying the coating film, and forming at least the inner wall surface in the inner wall surface and the bottom surface of the hole portion The film of the resin component. The film forming method (Π) of the present invention Examples of the constituent material of the substrate include ruthenium, various metals, various metal splash films, alumina, epoxy glass, phenolic paper, glass, etc. The thickness of the substrate is usually 1 〇〇 1 , 0 0 0 μηι. As shown in the cross-sectional view of FIG. 7, the substrate 51 is formed on at least one surface of the substrate 5 1 in the longitudinal direction from the surface to the inside, and the area of the opening is 25 to ΙΟΟΟΟμιη2, which is good. 1〇〇~ΙΟΟΟΟμιη2, preferably 25 0 to 7,000 μm 2 and a depth of 10 to 200 μm, preferably 30 to 120 μm, preferably 50 to 100 μm, of the hole portion 511. The shape and number of the hole portion are The shape of the hole portion may be a columnar shape (see FIG. 7( a )), a tapered shape (see FIG. 7( b )), and a reverse tapered shape (refer to FIG. 7 ( c ). ), etc., the cross-sectional shape may be defined as a circle, an ellipse, a polygon, etc. In addition, when there are a plurality of holes, the size and depth of each hole portion may be different or adjacent holes. The interval (length) between them is also not particularly limited. The shape of the portion is preferably a columnar shape or a tapered shape in which the cross-sectional shape is a quadrangular shape (positive-39-200905397 square or rectangular). The hole portion 'in the case where the cross-sectional shape is a quadrangular columnar shape, the longitudinal section The aspect ratio of the square shape (the ratio of the depth of the hole portion to the length of one side of the bottom surface of the hole portion) is preferably from 1 to 10, preferably from 1 to 5, more preferably from 1 to 4. The film formation method of the present invention (11) As described with reference to Fig. 8, first, a solvent is applied to the substrate 51 by a solvent coating step. At this time, the solvent 513 is usually filled in the hole portion 51 1 provided in the substrate 51 as shown in Fig. 8 (b), and the surface of the substrate 51 may be uniformly wetted. Thereafter, the resin composition is applied onto the substrate 51 by the resin composition coating step to form a coating film 5 15 (Fig. 8 (c)). At this time, in the hole portion 51 1 , the solvent from the solvent application step and the resin composition from the resin composition coating step are mixed. Then, the solvent in the solvent coating step and the solvent in the resin composition contained in the pore portion 51 are removed by a drying step, and the inner surface of the pore-containing portion 51 is obtained. A substrate 5 on which the film is formed is attached to the film 519' formed on the entire surface of the substrate 51. Hereinafter, each step will be described. The solvent coating step described above is a step of coating a solvent on the substrate. Examples of the solvent to be used include ethylene glycol monoalkyl ether acetate chelate such as ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether and propylene glycol monoethyl bromide Propylene glycol monoalkyl ethers such as propyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dialkyl ether such as propylene glycol dimethyl ether 'propylene glycol diethyl ether, propylene glycol dipropyl ether' propylene glycol dibutyl ether Ethers; propylene glycol monomethyl ether acetate 'propylene glycol monoethyl ether acetate vinegar-40- 200905397, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. propylene glycol monoalkyl ether acetate; ethyl a cellosolve such as a cellosolve or a butyl cellosolve; a carbitol such as butyl carbitol; a lactate such as methyl lactate, ethyl lactate, n-propyl lactate or isopropyl lactate; Ethyl ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate 'isoamyl acetate' isopropyl propionate, n-butyl propionate 'isobutyl propionate Or aliphatic carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate , other esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2-heptanone, Ketones such as 3-heptanone, 4-heptanone, cyclohexanone, etc.; N-dimethylformamide, N-methylacetamide, hydrazine, hydrazine-dimethylacetamide, N-methyl a lactone such as pyrrolidone or a lactone such as γ-butyrolactone. These may be used alone or in combination of two or more. In the solvent application step, the method of applying the solvent to the substrate is not particularly limited, and examples thereof include a coating method such as a spray coating method and a spin coating method, a dipping method, and the like. Further, the solvent charging ratio in the case where the solvent is filled in the pore portion by the application of the solvent is not particularly limited. In the resin composition coating step, a resin composition containing a resin component, cerium oxide, a solvent, and a specific thixotropy is applied to the solvent in a manner that the resin composition is in contact with the solvent in the pore portion. The steps of the substrate. The resin composition, the viscosity V § ( mPa.s) at a shear rate of 6 rpm, and the viscosity V2 (mPa.s) -41 - 200905397 (V&quot;v2 ) at a shear rate of 60 rpm, is 1.1. The above is preferably from 1.1 to 10.0, preferably from 1.2 to 8.0, more preferably from 1.3 to 5.0. When the ratio (VWV2) is in the above range, the film forming property of at least the inner wall surface of the inner wall surface and the bottom surface of the hole portion is excellent, and a uniform film can be obtained. The solid content concentration of the resin composition is preferably from 5 to 80% by mass, preferably from 20 to 60% by mass.

另外，前述樹脂組成物之固體成分濃度在5〜8 0質量 %之範圍時之黏度Vi，良好爲10〜1 0,000mPa . S，較佳爲 20〜7,000mPa. s，更佳爲50〜5,000mPa. s。若在則述車E 圍，可得到對於孔部之內壁面及底面之至少內壁面製膜性 優異、較爲均勻之被膜。 前述樹脂組成物，係如前述般，剪切速度在6rpm時 之黏度VjmPa.s)，與剪切速度在6 0rpm時之黏度V2 (mPa . s )之比（V&quot;V2 )爲1 .1以上。另外，爲了得到 較爲均勻之被膜，前述樹脂組成物，剪切速度在 Urpm 時之黏度V3(mPa. s)、與剪切速度在600rpm時之黏度 V4 ( mPa · s )之比（V3/V4 )，係以2.0以上者爲佳。較 佳比（V3/V 4)爲2.0〜80，更佳爲2.0〜50，特佳爲3·〇〜 5 0之範圍。 前述黏度，係在溫度2 5 °C ，將剪切速度，由例如 lrpm上升至l，000rpm爲止同時作測定之値。 作爲構成前述樹脂組成物之溶劑，係並未特別受到限 定，可使用例示作爲在前述溶劑塗佈步驟中所使用之溶劑 者。前述樹脂組成物所含有之溶劑，係可與在前述溶劑塗 -42- 200905397 佈步驟中所使用之溶劑相同，相異亦可。 此外，作爲構成前述樹脂組成物之樹脂成分’係並未 特別受到限定，熱硬化性樹脂、熱可塑性樹脂及該等以外 之樹脂之任一者皆可，而以含熱硬化性樹脂者爲佳。 構成前述樹脂組成物之樹脂成分含熱硬化性樹脂之情 況下，此樹脂組成物，係感光性及非感光性之任一者皆可 〇 前述樹脂組成物爲感光性樹脂組成物之情況下’正型 感光性樹脂組成物及負型感光性樹脂組成物之任一者皆可 ，而以正型感光性樹脂組成物者爲佳。 前述正型感光性樹脂組成物而言，可列舉例如含有選 自具有酚性羥基之樹脂（以下，亦稱爲「樹脂（A1 )」。 );使用含具有酚性羥基之單體、與（甲基）丙烯酸酯之 單體所得到之共聚物（以下，亦稱爲「樹脂（A2 )」）； 具有羧基之樹脂（以下，亦稱爲「樹脂（A3)」）等之鹼 可溶性樹脂[A]、與具有二重氮醌基之化合物[B]之組成物 等。 前述樹脂（A 1 )而言，可使用例如藉由使酚類與醛類 在觸媒存在下縮合所得到之酚醛樹脂。 酚類而言’可列舉酚、鄰甲苯酚、間甲苯酚、對甲苯 酚、鄰乙苯酚、間乙苯酚、對乙苯酚、鄰丁苯酚、間丁苯 酚、對丁苯酚、2,3-茬酚、2,4-茬酚、2,5-茬酹' 2,6-茬酚 、3,4-茬酚、3,5-茬酚、2,3,5-三甲苯酚、3,4,5-三甲苯酚 、兒茶酚、間苯二酚、苯三酚、α-萘酚' 萘酚等。 -43- 200905397 醛類而言，可列舉甲醛、三聚甲醛、乙 〇 前述酚醛樹脂而言，可列舉酚/甲醛縮 甲苯酚/甲醛縮合酚醛樹脂、酚-萘酚/甲醛縮 。該等’係可單獨1種或組合2種以上使用 前述酚醛樹脂以外之樹脂（A1)而言， 乙烯、羥苯乙烯與其他單體（（甲基）丙烯 丙嫌酸醋除外）之共聚物、聚異丙稀酹、異 單體（（甲基）丙烯酸及（甲基）丙烯酸酯 物、酚/伸茬二醇縮合樹脂、甲苯酚/伸茬二 酣/ 一環戊一稀縮合樹脂等。該等，係可單獨 種以上使用。 前述樹脂（A2 )，係使用具有酚性羥基 (甲基）丙烯酸酯，且不含如（甲基）丙烯 基之化合物之單體所得到之共聚物。 具有酚性羥基之單體而言，可列舉對羥 苯乙烯、鄰羥苯乙烯、對異丙烯酚、間異丙 烯酚等。 此外，（甲基）丙烯酸酯而言，可列舉 酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙 (甲基）丙烯酸正丁酯、（甲基）丙烯酸第 基）丙烯酸第三丁酯、（甲基）丙烯酸環己 丙烯酸2-甲基環己酯、（甲基）丙烯酸苯酯 烯酸苄酯等之（甲基）丙烯酸烷酯等。另外 醛、苯甲醛等 合酚醛樹脂、 合酚醛樹脂等 〇 可列舉聚羥苯 酸及（甲基） 丙烯酚與其他 除外）之共聚 醇縮合樹脂、 1種或組合2 之單體，與含 酸等之具有羧 苯乙稀、間經 烯酚、鄰異丙 (甲基）丙烯 烯酸異丙酯、 二丁酯、（甲 酯、（甲基） 、（甲基）丙 ，該等之（甲 -44 - 200905397 基）丙烯酸烷酯中之烷基之氫原子，係以羥基取代亦可。 前述樹脂（A2 )之形成時，具有酚性羥基之單體及（ 甲基）丙烯酸酯以外，使用具有聚合性不飽和鍵之化合物 作爲其他單體亦可。 其他單體而言，可列舉苯乙烯、α -甲基苯乙烯、鄰 甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯 '乙基苯乙烯 、乙烯二甲苯、鄰甲氧苯乙烯、間甲氧苯乙烯、對甲氧苯 乙烯等之芳香族乙烯化合物；馬來酸酐、檸康酸酐等之不 飽和酸酐；前述不飽和羧酸之酯；（甲基）丙烯腈、馬來 腈、富馬腈、中康腈、檸康腈 '伊康腈等之不飽和腈；（ 甲基）丙烯醯胺、巴豆醯胺、馬來醯胺、富馬醯胺、中康 醯胺、檸康醯胺、伊康醯胺等之不飽和醯胺；馬來醯亞胺 、：Ν-苯馬來醯亞胺、Ν-環己基馬來醯亞胺等之不飽和醯亞 胺；（甲基）丙烯醇等之不飽和醇；Ν-乙烯苯胺、乙烯吡 啶、Ν -乙烯-e -己內醯胺、Ν -乙烯吡略烷酮、Ν -乙烯咪唑 、N -乙烯咔唑等。該等，係可單獨1種或組合2種以上使 用。 前述樹脂（A3 )，係單獨聚合物亦或共聚物皆可，通 常爲使用含具有羧基之化合物（以下，稱爲「單體（m) 」）之單體所得到之聚合物。 前述單體（m)而言，可列舉（甲基）丙烯酸、馬來 酸、富馬酸、巴豆酸、中康酸、檸康酸、伊康酸、4 -乙烯 安息香酸等之不飽和羧酸或不飽和二羧酸；不飽和二殘酸 之單酯等。該等，係可單獨〗種或組合2種以上使用。 -45- 200905397 就前述樹脂（A3 )而言，例示於以下。 [1 ]使用單體（m )、與具有酚性羥基之單體所得到之 共聚物 [2] 使用單體（m) '具有酚性羥基之單體、與（甲基 )丙烯酸酯所得到之共聚物 [3] 使用單體（m )、具有酚性羥基之單體、芳香族乙 烯化合物、與（甲基）丙烯酸酯所得到之共聚物 [4] 使用單體（m)、芳香族乙烯化合物、與（甲基） 丙烯酸酯所得到之共聚物 [5] 使用單體（m)、芳香族乙烯化合物、與共軛二燦 烴所得到之共聚合物 [6] 使用單體（m)、（甲基）丙烯酸酯、與共軛二嫌 烴所得到之共聚物 [7] 使用單體（m)、（甲基）丙烯酸酯、與脂肪酸乙 烯化合物所得到之共聚物 另外，在前述態樣中，具有酚性羥基之單體、（甲基 )丙烯酸酯及芳香族乙烯化合物，係可使用前述例示者° 此外，共軛二烯烴而言，可列舉1，3-丁二烯、異戊二 烯、1，4-二甲基丁二烯等。 脂肪酸乙烯化合物而言，可列舉醋酸乙烯、巴豆酸乙 烯等。Further, the viscosity Vi of the solid content concentration of the resin composition in the range of 5 to 80% by mass is preferably 10 to 10,000 mPa·s, preferably 20 to 7,000 mPa·s, more preferably 50 to 5,000. mPa. s. When the vehicle E is surrounded, it is possible to obtain a film which is excellent in film formation property on at least the inner wall surface of the inner wall surface and the bottom surface of the hole portion. The resin composition has a viscosity (VjmPa.s) at a shear rate of 6 rpm and a viscosity V2 (mPa.s) at a shear rate of 60 rpm (V&quot;V2) of 1.1 as described above. the above. Further, in order to obtain a relatively uniform film, the resin composition has a viscosity V3 (mPa.s) at a Urpm and a viscosity V4 (mPa·s) at a shear rate of 600 rpm (V3/). V4), preferably 2.0 or more. The ratio (V3/V 4) is 2.0 to 80, more preferably 2.0 to 50, and particularly preferably 3 to 〇 to 50. The viscosity is measured at a temperature of 25 ° C and the shear rate is increased from, for example, 1 rpm to 1,000 rpm. The solvent constituting the resin composition is not particularly limited, and those used as the solvent used in the solvent coating step can be used as exemplified. The solvent contained in the resin composition may be the same as the solvent used in the solvent coating step-42-200905397, and may be different. In addition, the resin component constituting the resin composition is not particularly limited, and any of a thermosetting resin, a thermoplastic resin, and the like may be used, and a thermosetting resin is preferred. . When the resin component constituting the resin composition contains a thermosetting resin, the resin composition may be any one of photosensitive property and non-photosensitivity when the resin composition is a photosensitive resin composition. Any of the positive photosensitive resin composition and the negative photosensitive resin composition may be used, and a positive photosensitive resin composition is preferred. The positive-type photosensitive resin composition contains, for example, a resin selected from the group consisting of a phenolic hydroxyl group (hereinafter also referred to as "resin (A1)"); and a monomer having a phenolic hydroxyl group; a copolymer obtained by a monomer of a methyl acrylate (hereinafter also referred to as "resin (A2)"); an alkali-soluble resin such as a resin having a carboxyl group (hereinafter also referred to as "resin (A3)") [ A], a composition of the compound [B] having a diazide group, and the like. As the resin (A 1 ), for example, a phenol resin obtained by condensing a phenol with an aldehyde in the presence of a catalyst can be used. Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butyrrol, 2,3-fluorene. Phenol, 2,4-nonanol, 2,5-茬酹' 2,6-nonanol, 3,4-nonanol, 3,5-nonanol, 2,3,5-trimethylphenol, 3,4, 5-trimethylphenol, catechol, resorcinol, benzenetriol, α-naphthol, naphthol, and the like. -43- 200905397 Examples of the aldehydes include formaldehyde, trioxane, and ethylene. The phenol resin may be phenol/formaldehyde cresol/formaldehyde condensed phenol resin or phenol-naphthol/formaldehyde. The copolymers of ethylene, hydroxystyrene and other monomers (except (meth)acrylic acid vinegar) may be used alone or in combination of two or more kinds of resins (A1) other than the above phenol resin. , polyisopropyl hydride, isomeric ((meth)acrylic acid and (meth) acrylate, phenol / hydrazine condensed resin, cresol / hydrazine dioxime / a cyclopentane condensed resin. These resins (A2) are those obtained by using a monomer having a phenolic hydroxyl (meth) acrylate and not containing a compound such as a (meth) propylene group. Examples of the monomer having a phenolic hydroxyl group include p-hydroxystyrene, o-hydroxystyrene, p-isopropenol, meta-isopropenol, etc. Further, examples of the (meth)acrylate include methyl ester, Ethyl (meth) acrylate, n-butyl (meth) propyl (meth) acrylate, tert-butyl acrylate (meth) acrylate, 2-methylcyclohexane (meth) acrylate Ester, benzyl (meth) acrylate, etc. (methyl) Acid alkyl esters and the like. Further, a phenol resin such as an aldehyde or benzaldehyde or a phenol resin such as a phenol resin may, for example, be a copolyol condensation resin of polyhydroxybenzoic acid or (meth) propylene phenol and others, or a monomer of one type or combination 2, and an acid group. Etc. with carboxystyrene, m-phenylene, isopropyl isopropyl (meth) acrylate, dibutyl ester, (methyl ester, (methyl), (methyl) propyl, etc. In the alkyl group of the alkyl acrylate, the hydrogen atom of the alkyl group may be substituted with a hydroxyl group. When the resin (A2) is formed, a monomer having a phenolic hydroxyl group and (meth) acrylate may be used. A compound having a polymerizable unsaturated bond may be used as the other monomer. Examples of other monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylbenzene. An aromatic vinyl compound such as ethylene 'ethyl styrene, ethylene xylene, o-methoxy styrene, m-methoxy styrene or p-methoxy styrene; an unsaturated acid anhydride such as maleic anhydride or citraconic anhydride; Saturated carboxylic acid ester; (meth)acrylonitrile, Malay An unsaturated nitrile such as nitrile, fumaronitrile, mesocarbonitrile, citracarbonitrile, oricononitrile; (methyl) acrylamide, crotonamide, maleamide, fumarine, mesaconamine, An unsaturated decylamine such as citraconazole or econylamine; an unsaturated quinone imine such as maleic imine, bismuth-phenylmaleimide or fluorene-cyclohexylmaleimide; An unsaturated alcohol such as methyl)propenol; anthracene-vinylaniline, vinylpyridine, hydrazine-ethylene-e-caprolactam, anthracene-vinylpyrrolidone, anthracene-vinylimidazole, N-vinylcarbazole, and the like. These may be used alone or in combination of two or more. The above-mentioned resin (A3) may be a single polymer or a copolymer, and a compound having a carboxyl group (hereinafter, referred to as "monomer (m) is usually used. The polymer obtained by the monomer of ")). The monomer (m) may, for example, be (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, orkang. An unsaturated carboxylic acid or an unsaturated dicarboxylic acid such as an acid or 4-vinylbenzoic acid; a monoester of an unsaturated diacid; etc. These may be used alone or in combination of two or more. -45- 200905397 The above-mentioned resin (A3) is exemplified below. [1] A copolymer obtained by using a monomer (m) and a monomer having a phenolic hydroxyl group [2] Using a monomer (m) 'A monomer having a phenolic hydroxyl group and a copolymer obtained with a (meth) acrylate [3] using a monomer (m), a monomer having a phenolic hydroxyl group, an aromatic vinyl compound, and (meth) Copolymer obtained from acrylate [4] A monomer (m), an aromatic vinyl compound, and a copolymer obtained with (meth) acrylate [5] using a monomer (m), an aromatic vinyl compound, and a copolymer obtained by conjugated dicanthene [6] using a monomer (m), a (meth) acrylate, a copolymer obtained with a conjugated suspicion hydrocarbon [7] using a monomer (m), ( Methyl) acrylate and a copolymer obtained from a fatty acid ethylene compound. In the above aspect, a monomer having a phenolic hydroxyl group, a (meth) acrylate, and an aromatic vinyl compound may be used as described above. Further, examples of the conjugated diene include 1,3-butadiene, isoprene, and 1,4- Dimethyl butadiene and the like. Examples of the fatty acid ethylene compound include vinyl acetate and ethyl crotonate.

前述鹼可溶性樹脂[A]，係含單獨1種聚合物者亦可 ，含2種以上之組合者亦可。在本發明中，係以含具有酸 性羥基之樹脂者爲佳，特別是以使用酚醛樹脂、及羥苯Z -46 - 200905397 烯所得到之共聚物爲佳。 前述鹼可溶性樹脂[A]之重量平均分子量，係可藉由 GPC (凝膠滲透層析法）測定，良好爲2000以上，較佳 爲2000〜5 0000程度。若在此範圍，則所得到之硬化膜之 機械的物性、耐熱性及電氣絕緣性優異。 構成前述正型感光性樹脂組成物之前述鹼可溶性樹脂 [A]之含有比例，在將前述正型感光性樹脂組成物所含固 體成分定爲100質量％之情況下，良好爲20〜90質量％， 較佳爲20〜80質量％，更佳爲30〜70質量％。若在此範 圍，則鹼溶解性優異，同時，所得到之硬化膜之機械的物 性、耐熱性及電氣絕緣性優異。 其次，前述二重氮醌化合物[B]，係酚類化合物之、 1，2 -萘醌-2-重氮-5-磺酸酯或1，2 -萘醌-2-重氮-4-磺酸酯。 前述酚類化合物’係只要爲具有至少1個酚性羥基之 化合物’並未特別受到限定，而以前述之通式（1 )〜（5 )所表示之化合物爲佳。 前述酚類化合物而言，可列舉4，V_二羥基二苯甲烷、 4,4'- 一經基—苯酸、2,3,4-三經基二苯甲酮、2,3,4，4’ -四經 基二苯甲酮、2,3,4,2',4'-五羥基二苯甲酮、參（4-羥苯基 )甲烷、參（4·羥苯基）乙烷、1，1-雙（4_羥苯基）-1-苯 乙烷、1,3-雙[1-(4-羥苯基）-I-甲基乙基]苯、1;4_雙[卜 (4 -羥苯基）-1-甲基乙基]苯、4,6 -雙[Ι·(4 -羥苯基）-I-甲基乙基]-〗，3 -一經基苯、1，1_雙（4·經苯基）-ΐ-[4-〔 1-(4·羥苯基）-1-甲基乙基]苯基]乙烷等。該等，係可單獨 -47- 200905397 1種或組合2種以上使用。 因此，前述二重氮醌化合物[B]而言，可將使 等之酚類化合物之中至少1種、與1,2-重氮萘醌-4-1，2-重氮萘醌-5-磺酸反應所得到之酯化物等，以單； 或組合2種以上來使用。 構成前述正型感光性樹脂組成物之前述二重氮 物[B]之含有比例，在將前述鹼可溶性樹脂[A]定爲 量份時，良好爲10〜100質量份，較佳爲1〇〜50 ，更佳爲1 5〜5 0質量份。若在此範圍，則曝光部 光部之溶解度差異大、鹼溶解性優異。 此外，前述二氧化矽而言，由搖變性之控制之 看來，以一部份經疏水化處理之二氧化矽爲佳。 前述二氧化矽之種類係並未特別受到限定，而 例如膠態二氧化矽、氣相二氧化矽、玻璃等。另外 之粒子形狀，係並未特別受到限定，可定爲球狀、 狀、扁平狀、棒狀、纖維狀等。 前述二氧化矽之疏水化率係以20〜80%者爲佳 爲 30-70%，更佳爲40〜70 %。此疏水化率爲 20〜 情況而言，二氧化矽之往溶劑之分散性及與前述樹 性成爲良好，進一步而言可使前述樹脂組成物之搖 現出來故爲佳。 另外，前述樹脂組成物中之二氧化矽之疏水化 藉由以0 · 1 N氫氧化鈉水溶液所進行之中和滴定法 水化前及疏水化後之二氧化矽表面之矽醇基數’再 選自該 磺酸或 濁1種 醌化合 1 00質 質量份 與未曝 容易度 可列舉 ，該等 橢圓形 ，較佳 8 0 %之 脂相溶 變性表 率，係 測定疏 藉由下 -48- 200905397 式所求得之値。 疏水化率（％)：(疏水化後之砂醇基數/疏水化前之 矽醇基數）χ 1 〇 〇 此外，前述二氧化矽之平均粒徑爲1〜l〇〇nm，良好 爲5〜80nm，較佳爲1 0〜5 0 n m。此平均粒徑爲1〜1 0〇nm 之情況而言，可得到對曝光光線充分之透明性、及充分之 鹼溶解性等。 另外，此平均粒徑，係使用光散射流動分布測定裝置 (大塚電子公司製，型號「LPA-3000」），將二氧化矽粒 子之分散液依照常法稀釋而作測定之値。此外，此平均粒 徑，係可藉由二氧化矽粒子之分散條件控制。 此外，在前述二氧化矽中之鈉含量，係以1 ppm以下 者爲佳，較佳爲0.5ppm以下，更佳爲0.1 ppm以下。此鈉 含量爲1 ppm以下之情況而言，可將所得到之樹脂組成物 中之鈉含量定爲1 ppm以下。另外，二氧化矽中之鈉含量 ，係可藉由原子吸收光譜計（珀金埃爾默製 '型號「 Z5 100」）等測定。 在前述樹脂組成物中之二氧化矽之含有比例’在將樹 脂組成物中之固體成分全體定爲1 〇〇質量％之情況下’爲 超過20質量％而在60質量％以下’良好爲30質量°/。以上 、60質量％以下，更佳爲30質量％以上、50質量％以下。 此含有比例爲超過20質量％而在60質量％以下之情況而 言，可得到充分之搖變性，可在有底孔部之內壁面形成均 勻之被膜。 -49 - 200905397 另外，在本發明中之樹脂組成物 二氧化矽亦可，含有2種以上亦可， 良好之分散性之觀點看來，以僅含有 前述正型感光性樹脂組成物，進 屬氧化物粒子；交聯聚合物所構成之 交聯聚合物粒子」）；可定爲含有低 〇 前述交聯劑而言，可列舉在分子 之經過烷醚化之胺基之化合物；環氧 醛基之酚類化合物；具有羥甲基之酚 環化合物；含有乙氧甲基酸基之化合 化合物（含經塊狀化者）等。 在前述分子中具有至少2個以上 之化合物而言，可使用（聚）羥甲基 甲基甘脲、（聚）羥甲基苯胍胺、（ 化合物中之活性羥甲基（CH2OH基） 2個）爲經過烷醚化之化合物。此處 言’可列舉甲基、乙基、丁基等，多 相同亦可，相異亦可。此外，並未經 係在分子內自縮合亦可，在二分子間 聚物成分亦可。具體例而言，可列舉 '六丁氧甲基三聚氰胺、四甲氧甲基 脲等。另外’該等，係可單獨1種或 前述環氧基含有化合物而言，可 ’係僅含有1種前述 而由一氧化砂粒子之 1種者爲佳。 一步係由交聯劑；金 粒子（以下，稱爲「 分子酚性化合物等者 中具有至少2個以上 基含有化合物；具有 類化合物；含有噻喃 物；含有異氰酸基之 之經過烷醚化之胺基 三聚氰胺、（聚）羥 聚）羥甲基脲等之氮 之全部或一部（至少 ，構成烷醚之烷基而 數個之烷基，係彼此 過烷醚化之羥甲基， 縮合，其結果形成寡 六甲氧甲基三聚氰胺 甘脲、四丁氧甲基甘 組合2種以上使用。 列舉苯酚酚醛型環氧 -50- 200905397 樹脂、甲苯酚酚醛型環氧樹脂、雙酚型環氧樹脂、三酚型 環氧樹脂、四酸型環氧樹脂、酚-二甲苯型環氧樹脂、萘 酚-二甲苯型環氧樹脂、酚-萘酚型環氧樹脂、酚-二環戊二 燒型環氧樹脂、脂環式環氧樹脂'芳香族環氧樹脂、脂肪 族環氧樹脂、環氧環己烷樹脂等。該等，係可單獨1種或 組合2種以上使用。 前述之環氧基含有化合物之內，以苯酚酚醛型環氧樹 脂、雙酚A型環氧樹脂、間苯二酚二環氧丙基醚、季戊四 醇環氧丙基醚、三羥甲基丙烷聚環氧丙基醚、甘油聚環氧 丙基醚、苯環氧丙基醚、新戊二醇二環氧丙基醚、乙烯/ 聚乙二醇二環氧丙基醚、丙烯/聚丙二醇二環氧丙基醚、 1，6_己二醇二環氧丙基醚、山梨醇聚環氧丙基醚、丙二醇 二環氧丙基醚、三羥甲基丙烷三環氧丙基醚等爲佳。 前述具有醛基之酚類化合物而言，可列舉鄰羥苯甲醛 等。 此外，具有羥甲基之酚類化合物而言，可列舉2,6-雙 (羥甲基）-對甲苯酚等。 前述正型感光性樹脂組成物，在含有前述交聯劑之情 況下，其含有比例，係將前述鹼可溶性樹脂[A]定爲1 00 質量份時，良好爲1〜100質量份，較佳爲〜75質量份 ，更佳爲1 0〜5 0質量份。若在此範圍，則鹼溶解性優異 ，同時，所得到之硬化膜之機械的物性、耐熱性及電氣絕 緣性優異。 前述金屬氧化物粒子而言，可列舉氧化鋁、氧化鈦、 -51 - 200905397 氧化銷、氧化鈽、氧化鋅、氧化銅、氧化鉛、氧化釔、氧 化錫、氧化銦、氧化鎂等。 前述金屬氧化物粒子之表面，爲了提高與前述鹼可溶 性樹脂[A]之親和性或相溶性等，藉由官能基等作修飾亦 可 ° 此外，前述金屬氧化物粒子之形狀，係並未特別受到 限定，可定爲球狀、橢圓形狀、扁平狀 '棒狀、纖維狀等 〇 前述金屬氧化物粒子之平均粒徑，係1〜5 00nm、良 好爲 5〜200nm、較佳爲1 0〜1 OOnm。前述金屬氧化物粒 子之平均粒徑若在前述範圍，則對放射線之透明性、鹼溶 解性等優異。 前述金屬氧化物粒子，係可單獨1種或組合2種以上 使用。 前述金屬氧化物粒子而言，以搖變性之控制容易者爲 佳。 前述正型感光性樹脂組成物，而含有前述金屬氧化物 粒子之情況，其含有比例，係將前述鹼可溶性樹脂[A]定 爲100質量份時，良好爲10〜200質量份、較佳爲50〜 200質量份，更佳爲70〜150質量份。前述金屬氧化物粒 子之含有比例若在前述範圍，則具有適合之搖變性 '可在 有底孔部之內壁面形成均勻之被膜。 另外，前述正型感光性樹脂組成物，含有碳酸鈣、碳 酸鎂等之碳酸鹽；硫酸鋇、硫酸鈣等之硫酸鹽：磷酸鈣、 -52- 200905397 磷酸鎂等之磷酸鹽；碳化物；氮化物等所構成之其他無機 粒子亦可。 前述交聯聚合物粒子而言，可使用含具有2個以上聚 合性不飽和鍵之交聯性化合物（以下，稱爲「交聯性單體 」）之單體之單獨聚合物或共聚物。 前述交聯性單體而言，可列舉二乙烯苯、苯二甲酸二 烯丙酯、乙二醇二（甲基）丙烯酸酯、丙二醇二（甲基） 丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇 三（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、聚 丙二醇二（甲基）丙烯酸酯等。該等，係可單獨1種或組 合2種以上使用。此外，前述之內，以二乙烯苯爲佳。 在前述交聯聚合物粒子爲共聚物之情況下，與前述交 聯性單體聚合之其他單體而言，並未特別受到限定，而可 使用具有羥基、羧基、腈基、醯胺基、胺基、環氧基等之 1種以上之官能基之不飽和化合物；（甲基）丙烯酸脲烷 酯；芳香族乙烯化合物；（甲基）丙烯酸酯；二烯化合物 等。該等，係可單獨1種或組合2種以上使用。 前述交聯聚合物粒子而言’以由前述交聯性單體 '與 具有羥基之不飽和化合物及/或具有羧基之不飽和化合物 所構成之共聚物（d 1 )，並且還有以前述交聯性單體、與 具有羥基之不飽和化合物及/或具有羧基之不飽和化合物 、與其他單體所構成之共聚物（d 2 )爲佳，特別是以共聚 物（d2 )爲佳。 具有羥基之不飽和化合物而言’可列舉（甲基）丙烯 -53- 200905397 酸羥甲酯、（甲基）丙烯酸羥丙酯、（甲基）丙烯酸羥丁 酯等。 具有羧基之不飽和化合物而言，可列舉（甲基）丙烯 酸、伊康酸' 琥珀酸-β-(甲基）丙烯醯氧基乙酯、馬來 酸-甲基）丙烯醯氧基乙酯、苯二甲酸-石-(甲基） 丙烯醯氧基乙酯、六氫苯二甲酸-石-(甲基）丙烯醯氧基 乙酯等。 前述共聚物（d2 )之形成所使用之其他單體之中，具 有腈基之不飽和化合物而言’可列舉（甲基）丙烯腈、 α-氯丙烯腈、α-氯甲基丙稀腈、α -甲氧丙燒腈、α -乙 氧丙烯腈、巴豆酸腈、桂皮酸腈、伊康酸二腈、馬來酸二 腈、富馬酸二腈等。 具有醯胺基之不飽和化合物而言，可列舉（甲基）丙 烯醯胺、二甲基（甲基）丙烯醯胺、ν，ν〜亞甲基雙（甲 基）丙烯醯胺、Ν,Ν’-伸乙基雙（甲基）丙烯醯胺、Ν，Ν'-六亞甲基雙（甲基）丙烯醯胺、Ν-羥甲基（甲基）丙烯醯 胺、Ν- ( 2-羥乙基）（甲基）丙烯醯胺、Ν,Ν-雙（2-羥乙 基）（甲基）丙烯醯胺、巴豆酸醯胺、桂皮酸醯胺等。 具有胺基之不飽和化合物而言，可列舉二甲基胺基（ 甲基）丙烯酸酯、二乙基胺基（甲基）丙烯酸酯等。 具有環氧基之不飽和化合物而言，可列舉藉由（甲基 )丙烯酸縮水甘油酯、（甲基）丙烯環氧丙基醚、雙酚A 之二環氧丙基醚、乙二醇之二環氧丙基醚等與（甲基）丙 烯酸、（甲基）丙烯酸羥烷酯等之反應所得到之（甲基） -54- 200905397 丙烯酸環氧酯等。 (甲基）丙烯酸脲院醋而言’可列舉藉由（甲基）丙 烯酸羥烷酯與聚異氰酸酯之反應所得到之化合物等。 芳香族乙烯化合物而言，可列舉苯乙烯、α-甲基苯 乙烯、鄰甲氧苯乙烯、對羥苯乙烯 '對異丙烯酚等。 (甲基）丙烯酸酯而言，可列舉（甲基）丙烯酸甲酯 、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基） 丙烯酸丁酯、（甲基）丙烯酸己酯、（甲基）丙烯酸月桂 酯、聚乙二醇（甲基）丙烯酸酯、聚丙二醇（甲基）丙烯 酸酯等。 此外，二烯化合物而言，可列舉丁二烯、異戊二烯、 二甲基丁二烯、氯丁二烯、1,3-戊二烯等。 前述交聯聚合物粒子由共聚物（d2)所構成之情況下 ，交聯性單體所構成之單位量（d21)、具有羥基之不飽 和化合物所構成之單位及/或具有羧基之不飽和化合物所 構成之單位之合計量（d22)，並且，其他單體所構成之 單位量（d23 )，係構成共聚物（d2 )之單位量之合計， 亦即，在（d21 ) 、（ d22 )及（d23 )之和定爲1 OOmol% 之情況下，分別以 0.1〜1 0 m ο 1 %、5〜5 0 m ο 1 %及 4 0〜 94_9mol°/。爲良好，較佳爲 〇_5 〜7mol%、6〜45mol% 及 48 〜93.5mol%，更佳爲 1 〜5mol%、7 〜40mol% 及 55 〜 92mol%。各單位量之比例在前述範圍之情況下，可製成形 狀安定性、及與鹼可溶性樹脂之相溶性優異之交聯聚合物 粒子。 -55- 200905397 此外’前述交聯聚合物粒子，係橡膠亦或樹脂皆可、 其玻璃轉移溫度（Tg )，係並未特別受到限定。良好Tg 爲2 0 c以下，較佳爲1 0。(：以下，更佳爲〇 °C以下。另外’ 下限係通常爲-7 0 t以上。 前述交聯聚合物粒子係粒子狀，其平均粒徑’良好爲 30〜100nm，較佳爲40〜90nm，更佳爲 50〜80nm。前述 交聯聚合物粒子之平均粒徑若在前述範圍，則與鹼可溶性 樹脂之相溶性、鹼溶解性等優異。另外，前述平均粒徑， 係指使用光散射流動分布測定裝置「LPA-3 000」（大塚電 子公司製）’將交聯聚合物粒子之分散液依照常法稀釋作 測定之値。 前述正型感光性樹脂組成物，在含有前述交聯聚合物 粒子之情況下’其含有比例’在將前述鹼可溶性樹脂[A] 定爲100質量份時，良好爲1〜100質量份，較佳爲5〜80 質量份，更佳爲5〜50質量份。前述交聯聚合物粒子之含 有比例若在前述範圍’所得到之硬化膜之耐熱衝撃性等優 異〇 此外，前述低分子酚性化合物而言，可列舉4,4'-二羥 基二苯甲烷、4,4'-二羥基二苯醚、參（4-羥苯基）甲烷、 1，1-雙（4-羥苯基）-1-苯乙烷、參（4-羥苯基）乙烷、 1，3-雙[1-(4-羥苯基）-1-甲基乙基]苯、1,4-雙[1-(4-羥 苯基）-1-甲基乙基]苯、4,6 -雙[1-(4 -羥苯基）-1-甲基乙 基]-1,3-二羥基苯、1，1_雙（4-羥苯基）-卜[4·〔 1- ( 4-羥 苯基）-卜甲基乙基〕苯基]乙烷、1，1，2,2·四（4-羥苯基） -56- 200905397 乙烷等。該等，係可單獨1種或組合2種以上使用。 前述正型感光性樹脂組成物’在含有前述低分子酚性 化合物之情況下，其含有比例’係將前述鹼可溶性樹脂 [A]定爲100質量份時，良好爲1〜20質量份，較佳爲2〜 1 5質量份，更佳爲3〜1 0質量份。前述低分子酚性化合物 之含有比例若在前述範圍’則不會損及所得到之硬化物之 耐熱性，可使鹼性提升。 此外，在本發明中，前述正型感光性樹脂組成物，係 可定爲含有前述鹼可溶性樹脂、前述二氧化矽、與前述溶 劑者。此外，可定爲進一步含有前述具有二重氮醌基之化 合物者。進一步，可定爲進一步含有後段之交聯劑者。此 外，可定爲含有前述交聯聚合物所構成之粒子者。 前述樹脂組成物塗佈步驟所使用之樹脂組成物爲前述 正型感光性樹脂組成物之情況，其固體成分濃度，良好爲 ，5〜80質量％，較佳爲10〜60質量％，更佳爲25〜60質 量％。 前述樹脂組成物爲非感光性樹脂組成物之情況，以含 有鹼可溶性樹脂及交聯劑之硬化性樹脂組成物爲佳。 前述鹼可溶性樹脂而言，以使用具有酚性羥基之樹脂 、具有羧基之樹脂、具有酚性羥基及醇性羥基之樹脂，及 具有羧基及醇性羥基之樹脂者爲佳。該等，係單獨使用亦 可，組合使用亦可。另外，亦可直接使用作爲前述正型感 光性樹脂組成物之構成成分所例示之樹脂。 此外，前述交聯劑而言，以使用在分子中具有至少2 -57- 200905397 個以上烷醚化之胺基之化合物，並且，以含有環氧基之化 合物者爲佳。該等’係單獨使用亦可，組合使用亦可。另 外，亦可直接使用作爲前述正型感光性樹脂組成物之構成 成分所例示之交聯劑。 作爲前述交聯劑，使用在分子中具有至少2個以上之 經過烷醚化之胺基之化合物之情況下，非感光性樹脂組成 物中之含有比例，在將前述鹼可溶性樹脂定爲1 00質量份 時，良好爲1〜質量份，較佳爲5〜50質量份。前述 化合物之含有比例若在前述範圍，則所得到之硬化膜之機 械的物性、耐熱性及電氣絕緣性優異。 此外，使用環氧基含有化合物作爲前述交聯劑之情況 ，非感光性樹脂組成物中之含有比例，係將前述鹼可溶性 樹脂定爲100質量份時，良好爲1〜70質量份，較佳爲3 〜30質量份。前述環氧基含有化合物之含有比例若在前述 範圍，則所得到之硬化膜之機械的物性、耐熱性及電氣絕 緣性優異。 前述非感光性樹脂組成物，係可進一步定爲含有金屬 氧化物粒子、交聯聚合物粒子、低分子酚性化合物等者， 該等，係可直接使用作爲前述正型感光性樹脂組成物之構 成成分所例示者。 前述樹脂組成物塗佈步驟所使用之樹脂組成物，係前 述非感光性樹脂組成物之情況’其固體成分濃度，良好爲 5〜8 〇質量％，較佳爲1 0〜6 0質量％。 在前述樹脂組成物塗佈步驟中，將具有特定之物性之 -58- 200905397 樹脂組成物，塗佈於前述基板之方法，只要是以該樹脂組 成物與前述孔部內之溶劑接觸之方式塗佈加工之方法，並 未特別受到限定，可列舉旋轉塗佈法、噴塗法、棒式塗佈 法等。該等之內，以旋轉塗佈法爲佳。 另外，在前述樹脂組成物塗佈步驟中，考慮樹脂組成 物之固體成分濃度、黏度等，以藉由稍後進行之乾燥步驟 ’使形成於前述基板表面之被膜厚度爲進入0.1〜ΙΟμιη之 範圍之方式形成塗膜者爲佳。 在前述樹脂組成物塗佈步驟中，若塗佈樹脂組成物， 則在基板5 1之表面，會形成均勻之塗膜5 1 5，在孔部內， 成爲收容有由前述溶劑塗佈步驟中所充塡之溶劑、與樹脂 組成物所構成之混合物5 1 6 (參照圖8 ( c ))。 其次，前述乾燥步驟，係將藉由前述樹脂組成物塗佈 步驟所形成之塗膜乾燥之步驟，亦即，僅除去塗膜所含之 溶劑之步驟。 乾燥溫度，係考慮在前述溶劑塗佈步驟所充塡之溶劑 沸點、或由在前述溶劑塗佈步驟所充塡之溶劑、與樹脂組 成物所構成之混合物5 1 6所含之混合溶劑之沸點來作選擇 〇 此外，乾燥條件，係並未特別受到限定，而可在一定 溫度進行，一邊昇溫或降溫一邊進行亦可，將該等組合亦 可。此外，關於壓力，在大氣壓下進行亦可，在真空下進 行亦可。再者’環境氣氛氣體等亦並未特別受到限定。 根據前述乾燥步驟，溶劑會被除去，在至少含孔部之 -59- 200905397 內壁面之基板表面，形成樹脂組成物之固體成分所構成之 均勻被膜（參照圖8(d))。 圖8 ( d )所示之附有被膜之基板5，係具備：形成於 具有孔部之基板51與孔部以外之基板5 1之全表面之被膜 519、形成於孔部之內壁面之被膜517、與形成於孔部之底 面之被膜518。該等之被膜，係通常形成連續相，然而有 僅被膜5 1 7及5 1 8形成連續相之情況。此外，關於各被膜 之厚度，被膜519之厚度、孔部之內壁面之被膜517之厚 度、與孔部之底面之被膜518之厚度，係通常爲相異，而 依照樹脂組成物之種類、固體成分濃度、黏度等，孔部之 內壁面之被膜517之厚度，及孔部之底面之被膜518之厚 度，有成爲相同或幾乎相同之情形。 5.具有絕緣膜之構造物及其製造方法 本發明之具有絕緣膜之構造物之製造方法（以下，稱 爲「構造物之製造方法（I)」。），係於圖8(d)及圖 9(a)表示’其特徵爲：具備：使用藉由前述本發明之被 膜形成方法（II )所得到之附有被膜之基板5，將形成於 前述基板51之表面之被膜519及形成於前述基板51之前 述孔部之底面之被膜518除去，留下形成於前述孔部之內 壁面之被膜517之表底面側被膜除去步驟、與將被留在前 述孔部之內壁面之被膜5 1 7加熱之加熱硬化步驟。 在本發明之構造物之製造方法（I)中，前述被膜517 〜5 1 9 ’係以由正型感光性樹脂組成物所構成者爲佳，關 -60- 200905397 於此情況’使用圖9作說明。前述表底面側被膜除去步驟 ’係將形成於前述基板之表面之被膜519及形成於前述基 板之前述孔部之底面之被膜518除去，留下形成於前述孔 部之內壁面之被膜517之步驟。 首先’對於圖9(a)所示之附有被膜之基板5，由上 方照射紫外線、可見光、遠紫外線、X射線、電子射線等 ，使形成於前述基板51之表面之被膜519及形成於前述 基板51之孔部之底面之被膜518曝光。此時，對於形成 於前述孔部之內壁面之被膜517而言係使其成爲不曝光。 曝光量，係依照所使用之光源、被膜之厚度等適宜地 選擇’而例如，對於厚度爲5〜50μπι程度之被膜，由高壓 水銀燈照射紫外線之情況，良好曝光量爲1,000〜 20,000J/m2 程度。 圖9 ( b )所示之被膜曝光部52 8及529，由於成爲鹼 可溶性，故藉由使用鹼性溶液處理，可留下形成於前述孔 部之內壁面之被膜517。 前述鹼性溶液而言，氫氧化鈉、氫氧化鉀、氨、氫氧 四化甲基銨、膽鹼等之水溶液、或可使用在此水溶液適量 添加甲醇、乙醇等之水溶性之有機溶劑、界面活性劑等之 溶液等。 以鹼性溶液處理之後，藉由水洗及乾燥，可得到僅於 孔部之內壁面具有被膜517之基板（參照圖9(c))。 加熱硬化步驟，係將殘存於前述孔部之內壁面之被膜 5 1 7加熱之步驟，藉由此步驟，將被膜5 1 7製成硬化膜 -61 - 200905397 6 1 7 ’可得到具有絕緣膜之構造物6 (參照圖9 ( d ))。 加熱方法，係並未特別受到限定，而通常定爲在1 〇〇 〜25 0°c之範圍之溫度，30分〜10小時程度者爲佳。以一 定條件加熱或以多階段加熱皆可。加熱裝置而言，可使用 烘箱、紅外線爐等。 圖9(d)所示之具有絕緣膜之構造物6,係具備具有 孔部之基板5 1、與形成於此基板之孔部之內壁面之硬化膜 6 17° 另外’在本發明之構造物之製造方法（I)中，可進 一步具備前述加熱硬化步驟之後，由前述基板51中之不 具有孔部之面作硏磨，使孔部爲貫通孔62之硏磨步驟（ 參照圖9 ( e ))。 硏磨方法，係並未特別受到限定，而可適用化學機械 硏磨法等。 圖9(e)所示之具有絕緣膜之構造物6'，係具備具有 貫通孔62之基板51、與形成於此貫通孔62之內壁面之硬 化膜6 1 7。 其他本發明之具有絕緣膜之構造物之製造方法（以下 ，稱爲「構造物之製造方法（Π)」），係如圖8(d)及 圖10(a)所示，其特徵爲：具備：使用藉由前述本發明 之被膜形成方法（Π )所得到之附有被膜之基板5，將形 成於前述含孔部之內壁面及底面之前述基板之全表面之被 膜517、518及519加熱，製成含前述樹脂成分之硬化物 之絕緣膜之加熱硬化步驟、與將形成於前述基板之表面之 -62 - 200905397 絕緣膜及形成於前述基板之前述孔部之底面之絕緣膜除去 ，留下形成於前述孔部之內壁面之絕緣膜之表底面側絕緣 膜除去步驟。 在本發明之構造物之製造方法（II)中，前述被膜， 係以由非感光性樹脂組成物所構成者爲佳，對於此情況使 用圖1 0作說明。 前述加熱硬化步驟，係將形成於含前述孔部之內壁面 及底面之前述基板之全表面之被膜517、518及519加熱 ，製成含前述樹脂成分之硬化物之絕緣膜之步驟（參照圖 10(b) ) ° 加熱方法，係並未特別受到限定，而可與本發明之構 造物之製造方法（I )中之加熱硬化步驟相同。 藉由前述加熱硬化步驟，可得到圖1 0 ( b )所示之構 造物，此構造物，係具備：具有孔部之基板5 1、形成於前 述基板之表面之絕緣膜619、形成於前述孔部之內壁面之 絕緣膜617、與形成於前述孔部之底面之絕緣膜618。 其次，前述表底面側絕緣膜除去步驟，係將形成於前 述基板之表面之絕緣膜619及形成於前述基板之前述孔部 之底面之絕緣膜618除去，留下形成於前述孔部之內壁面 之絕緣膜6 1 7之步驟。將前述絕緣膜6 1 8及6 1 9選擇性地 除去之方法而言，可列舉異方性鈾刻（乾式蝕刻）等。 藉由前述表底面側絕緣膜除去步驟，可得到如圖1〇( C)所示之具有絕緣膜之構造物6，此構造物6，係具備： 具有孔部之基板5 1、形成於此基板之孔部之內壁面之硬化 -63- 200905397 膜 617。 另外，在本發明之構造物之製造方法（11)中’前述 表底面側絕緣膜除去步驟之後’與前述本發明之構造物之 製造方法（I)同樣地，可進一步具備由在前述基板51之 不具有孔部之面作硏磨，將孔部製成貫通孔62之硏磨步 驟（參照圖10(d))。圖1 〇 ( d )所示之具有絕緣膜之 構造物6’，係具備具有貫通孔62之基板5 1、與形成於此 貫通孔62之內壁面之硬化膜617。 6.電子零件 本發明之電子零件，其特徵爲：具備含藉由前述本發 明之構造物之製造方法所得到之具有絕緣膜之構造物（具 有於內壁形成絕緣膜之貫通孔之構造物）、與在此構造物 之至少貫通孔內充塡導電材料而成之電極部（導電材料充 塡部）之構件。 本發明之電子零件而言，可爲例如具備含圖9(e)及 圖10(d)所示之構造物6’、與此構造物6’之至少貫通孔 內之電極部（導電材料充塡部）7 1 1之構件7 (參照圖1 1 (g ))者。 對於前述構件7作說明。構成前述構件7之前述電極 部71 1之形成材料（導電材料）而言，可使用選自銅、銀 、鎢、鉬、鈦、釘、金、錫、鋁，及含該等之合金者等。 前述電極部711，係如圖u(g)之方式，其表面部 爲較基板51之平滑表面突出之凸狀亦可，成爲與基板51 -64 - 200905397 同平面亦可。此外’前述電極部711之表面，係平滑面或 粗面皆可。 將圖Π (g)所示構件7製造方法之—例，使用圖n 作說明。首先’準備圖9(d)及圖10(c)所示之具有絕 緣膜之構造物6 (參照圖1 1 ( a ))。對於此構造物6之 具有孔部一側之表面，進行Cu濺鍍等，在含孔部之內表 面全部之構造物6表面，形成厚度10〜2〇〇nm之銅膜（晶 種層）63a及63b(參照圖11 (b))。其後，在孔部之內 表面以外之銅膜6 3 a表面’藉由印刷等，形成絕緣性抗蝕 劑被膜64 (參照圖1 1 ( c ))。接著，使用硫酸銅水溶液 等，進行往孔內之C u充塡鍍敷（參照圖1 1 ( d ))。其 後，使用既定之剝離液等，將絕緣性抗蝕劑被膜64剝離 (參照圖11(e))。接著，藉由使用稀硫酸、稀鹽酸等 之蝕刻，將形成於基板5 1之表面之銅膜6 3 a除去（參照 圖11(f))。然後，由基板51之裏面，至充塡於孔部之 金屬銅露出爲止作硏磨，得到圖11(g)所示，具備金屬 銅充塡部711所構成之貫通電極之構件7。 前述具備貫通電極之構件，爲圖〗2所示之構件7’亦 可。此構件7，係具備：表裏貫通，且在絕緣膜6 1 7形成 於內壁面而成之貫通孔，具有充塡有導電材料之導電材料 充塡部7 1 1之基板5 1 ;與至少被覆此導電材料充塡部7 1 1 之下側露出面（圖面之下方側露出面）之電極極板713。 圖1 2之構件7 ’，係可藉由具備在圖1 1 ( g )所示之構 件7之導電材料充塡部7 1 ]之下方側露出面（圖1 1 ( g ) -65- 200905397 之下側）’形成電極極板之電極極板形成步驟之方法製造 。此電極極板形成步驟之具體的方法而言，可列舉鍍敷、 導電膏之塗佈等。關於其他製造方法，於之後敘述。 此外，圖1 3所示之構件7 &quot;，係使用圖1 1 ( g )所示 之構件7 '或圖1 2所示之構件7而成之例。 此構件7係複合構件，係使用在金屬銅充塡部（貫 通電極）711a及711b之下側露出面（圖面之下方側露出 面）分別配設電極極板7 1 3 a及7 1 3 b之上側構件7 1，和在 金屬銅充塡部（貫通電極）721a及7hb之下側露出面（ 圖面之下方側露出面）分別配設電極極板723a及723 b之 下側構件72’將上側構件71之電極極板713a之表面與下 側構件72之金屬銅充塡部（貫通電極）72 la之表面接合 ，且將上側構件71之電極極板713b之表面與下側構件72 之金屬銅充塡部（貫通電極）721b之表面接合而成。在上 側構件7 1及下側構件7 2之界面配置有絕緣層7 4 (參照圖 13)。電極極板713a及金屬銅充塡部（貫通電極）721a 等之接合方法，係並未特別受到限定，而可列舉例如熱壓 著（加熱同時加壓）等之方法。 本發明之電子零件，可爲配設有圖11(g)所示之構 件7 '圖12所示之構件7 ·、圖13所示之構件7，，等者。例 如’圖1 4之電子零件8，係圖1 3所示之構件7&quot;之電極極 板723a及723b與中介層81隔著配設於此中介層81之表 面之2個凸塊82作導通連接而成，進一步，爲在中介層 8 1之下方側配設有用於與其他構件等導通連接之凸塊8 3 -66- 200905397 而成者。 本發明之電子零件，係含前述構件7、7’及7”等之複 合體，可爲例如具備其他基板、層間絕緣膜、其他電極等 他之構件之複合體（回路基板、半導體元件、感測器等） 〇 另外，圖1 2所示之構件7 ’，係可藉由具備以下步驟 之方法製造：預先形成有導電材層713，使用孔部之底面 爲導電材層713之複合基板，對在藉由圖9(a)〜（c) 之步驟，或圖10(a)〜（c)之步驟所得到之構件6’（圖 9 ( d )或圖1 0 ( d ))之貫通孔之開口部下側（圖9 ( e ) 之下側或圖1 0 ( d )之下側）具有導電材層7 1 3之孔部， 藉由圖11(b)〜（f)之步驟充塡導電材料之步驟。 再者，使用具有圖15(a)所示之凹部之層合基板9 ，適用本發明之被膜形成方法（Π)、及具有絕緣膜之構 造物之製造方法而製造亦可。 圖15(a)所示之層合基板9，係具備：由砂、各種 金屬、各種金屬濺鍍膜、氧化鋁、環氧玻璃、酚醛紙、玻 璃等所構成，以由其中一面往另外一面之方式，具有柱狀 (參照圖7 ( a ))、順錐形狀（參照圖7 ( b ))、逆錐 形狀（參照圖7 ( c ))等貫通孔之基板91、與以塞住前 述貫通孔之方式配設於基板91其中一面上之導電材層93 。此層合基板9,係藉由導電材層93，貫通孔之其中一方 被塞住而具有凹部。另外，此層合基板9，爲由不具有貫 通孔之平板狀基板與導電材層所構成之層合體之該平板狀 -67- 200905397 基板之表面，不使導電材層貫通之方式作切削加工所得到 者亦可。 因此，前述基板91之厚度，良好爲1〇〜200μιη，較 佳爲30〜120μιη’更佳爲50〜ΙΟΟμηι，藉由將凹部之開口 部之面積、横斷面形狀等定爲前述本發明之被膜形成方法 (Π)中之說明相同，適用前述本發明之被膜形成方法（ II)、及具有絕緣膜之構造物之製造方法，可製造圖15 ( e )所示之構件7'，亦即圖1 2所示之構件7'。 將圖1 5 ( e )所示之構件7 ’之製造方法作簡單地說明 。首先，藉由在構成層合基板9之基板91之表面塗佈溶 劑（溶劑塗佈步驟），其後，如前述般塗佈具有特定之搖 變性之樹脂組成物（樹脂組成物塗佈步驟），形成塗膜。 接著，將在基板91之表面之樹脂組成物所構成之塗膜、 及凹部內之混合物乾燥，除去溶劑，在基板9 1之表面、 凹部之內壁面、及導電材層93之凹部側表面形成被膜（ 分別爲92 1,922及923 )，得到附有被膜之基板100 (參 照圖 1 5 ( b ))。 其後，依照樹脂組成物之種類，適用前述本發明之具 有絕緣膜之構造物之製造方法，得到在凹部之內壁面具有 絕緣膜925之層合構造物200(參照圖15(c))。 接著’以不使凹部貫通之方式，藉由將導電材層93 之一部份蝕刻等除去而形成電極極板9 3 5 (參照圖1 5 ( d ))，在凹部充塡選自銅、銀、鎢、鉬、鈦、釘、金、錫 、鋁、及含該等之合金中之導電材料，可得到構件7，，其 -68- 200905397 係具備：圖15(e)所示，具有在表裏貫通、且於內壁面 形成絕緣膜925而成之貫通孔充塡導電材料之導電材料充 塡部96之基板91、與至少被覆此導電材料充塡部96之下 方側露出面（圖1 5 ( e)之下側）之電極極板93 5。 因此，將使用圖1 5 ( a )所示之層合基板9所得到之 構件7_用來構成本發明之電子零件亦可。 實施例 以下，列舉實施例將本發明作進一步具體地說明。但 是，本發明係毫無受到該等之實施例制約。 [1 ]正型感光性樹脂組成物之調製 (實施例1 ) 如同表1所示，藉由將（A)鹼可溶性樹脂（A-1) 100質量份、（B )二重氮醌化合物（B-1 ) 25質量份、（ C )二氧化矽（C-1 ) 100質量份及（F )界面活性劑（F-1 )0.1質量份，以固體成分濃度成爲47質量％之方式，溶 解於（D)溶劑（D- 1 ) 25 5質量份而調製感光性樹脂組成物 (實施例2〜8及比較例1〜5 ) 與實施例1同樣之方式，如同表1所示，藉由將（A )鹼可溶性樹脂、（a )低分子酚性化合物、（B )二重氮 醌化合物、（C )二氧化矽、（E )密著助劑及（F )界面 -69- 200905397 活性劑，以固體成分濃度成爲4 7質量％之方式，溶解於（ D )溶劑而調製各感光性樹脂組成物。 g 起戔 d o o o o o r-H O o o o 〇 〇 r—* 〇 jg® w \ \ \ \ \ \ \ \ \ \ \ \ \ i. tL tL \L· 1 IL, 1 tl· i 1 lin cl 1 IL· 丄 1 IL g II I I in \ I 1 1 I 1 1 1 1 1 1 ΤΊ~ i1mi1 ώ ΙΛ ΙΛ LO CO O ΙΛ CO in CN3 lO CSl to Cn3 o § in Cvi o LC CN： Si \ \ \ \ \ \ \ \ \ \ \ \ 班_ Q T a a 1 a 1 Q 1 Q a 1 Q a Q 1 〇 a 1 a 〇 in O i〇 LO ΙΛ m m 卜 l〇 卜 in \ •w 要画·Μ ri 00 C&lt;1 卜· ID 1 CO 卜· CO 祕 II i 腿 wns tlmll s ο LO to s LQ to Ln LO in l〇 in CSI ΰ LO \ l U \ 1 U \ 1 〇 \ 1 u \ »—&lt; 1 〇 \ 1 U \ 1 U \ »«4 1 U \ 1 U 1 \ CS3 ! U \ 1 U 翻圣 §1| s in CN3 in Cn3 LT5 (NJ ID CS) C^3 m oa in CN3 in ΙΛ l〇 CS3 L〇 CN1 in 03 3 \ \ \ \ \ \ \ \ \ \ \ \ \ m CQ CQ ώ CQ CQ ώ CD CQ ώ 1 CQ 1 CQ it m s 3 翁ί-ϊ o I 1 1 \ \ 1 1 1 1 1 1 ^&lt;ini i. 丄 m ® m 1 o o o O o § 〇 o l〇 CN3 o o 00 CSJ o O o o 〇 \ \ \ \ \ \ \\ \\ \ \ \ \ \ f^ggS ·—H CNJ 1 7 ? »—1 1 1 繼癍P &lt; &lt; &lt; &lt; &lt; &lt; &lt; &lt; &lt; &lt; &lt; &lt; C &lt; &lt; CN) Γ0 l〇 ID 卜 00 03 CO in -70- 200905397 另外，表1所記載之組成，係如同以下之敘述。 〈（A)鹼可溶性樹脂〉 A-Ι:間甲苯酚/對甲苯酚= 60/40 (莫耳比）所構成之甲 苯酚酚醛樹脂、聚苯乙烯換算重量平均分子量（Mw) = 65 00 A-2:聚羥苯乙烯（九善石油化學製、商品名「 MARUKA LYNCUR S-2P」）、Mw = 5 000 A-3 :酚-伸茬二醇縮合樹脂（三井化學製、商品名「 Mirex XLC-3L」、Mw=1500 〈（a )低分子酚性化合物〉 a_l: II-雙（4-羥苯基）·1-[4-(1-(4-羥苯基） 甲基乙基）苯基]乙烷 〈（Β )二重氮醌化合物〉 Β_1: 1，1_ 雙（4 -羥苯基）·1-[4-(1-(4 -羧苯基）_1· 甲基乙基）苯]乙烷、與1，2-重氮萘醌-5-磺酸之2·0胃$ 縮合物 &lt; (C)二氧化矽〉 y A 工業 C-l ：商品名「QUARTRON PL-2L」（扶桑化手 製、疏水化處理物（疏水化率：50% ) '平均粒徑：2〇nm 鈉含量：〇.〇2ppm) -71 - 200905397 C-2:商品名「PMA-ST」（日產化學工業製' 疏水化 處理物（疏水化率：60% )、平均粒徑：20nm、鈉含量： 600ppm ) C-3:商品名「QUARTRON PL-30」（扶桑化學工業製 、疏水化處理物（疏水化率：40% )、平均粒徑：300nm、 鈉含量：〇.〇2ppm) 〈（D)溶劑〉 D-1 :丙二醇單甲基醚醋酸酯 〈（E )密著助劑〉 E-1 : γ -甲基丙烯醯氧丙基三甲氧基矽烷（日本 UNICAR製、商品名「Α-187」） 〈（F )界面活性劑（調平劑）〉 F-1:商品名「FTX-218」 （NEOS 製） 另外，前述（C )二氧化矽中各疏水化率，係如下述 之方式作測定之値。 〈疏水化率〉 首先，於二氧化矽之10%水分散液150mL使氯化鈉 3〇g溶解，用1N鹽酸調整以成爲pH4。接著’滴入0.1N 氫氧化鈉水溶液至成爲PH9爲止。然後，藉由下式求得二 氧化矽表面之矽醇基數目。 -72- 200905397 A= ( ax〇. 1 χΝ ) / ( WxS ) [但是，A係矽醇基數目（個/m2 ) 、a係0_1N氫氧 鈉水溶液之滴下量（L ) 、N係亞佛加厥數（個/ m ο 1 )、 係二氧化矽重量（g) 'S係二氧化矽之BET面積（nm: )° 如此之方式，分別求得疏水化前及疏水化後之二氧 矽之矽醇基數目，藉由下式計算二氧化矽之疏水化率。 疏水化率（％ )=(疏水化後之矽醇基數目/疏水化 之矽醇基數目）X100 [2]正型感光性樹脂組成物之評估 對前述實施例1〜8及比較例1〜5之各感光性樹脂 成物，依照下述之方法作評估。將其結果示於表2。 (1)被膜形成性 於在表面具有開口部形狀爲正方形（80μπι&gt;&lt;80μιη) 深度爲ΙΟΟμπι、及底面形狀爲正方形（60μηιχ60μιη )之 錐形狀之孔部〔參照圖1(b)〕、直徑1 5 0mm及厚 5 〇〇 μπι之段差Si基板上，將丙二醇單甲基醋酸酯作爲 劑作旋轉塗佈（1 OOOrpm、3秒鐘），將此溶劑充塡於 部〔參照圖2 ( b )〕。 其後，將感光性樹脂組成物作旋轉塗佈（第1階段 300rpm、10秒鐘、第2階段；600rpm、20秒鐘），在 孔部內之溶劑表面之段差S i基板之表面形成塗膜。 化 W !/g 化 刖 組 順 度 溶 孔 » 含 -73- 200905397 接著’將附有塗膜之S i基板，在溫度〗i 〇 °c之熱板上 靜置5分鐘’使溶劑揮發，於Si基板之表面與孔部之內 壁面及底面使被膜形成’得到附有被膜之S i基板〔參照 圖 2 ( d )〕。 然後’藉由電子顯微鏡觀察孔部之斷面形狀，藉著以 下之基準評估被膜形成性。 〇；表面開口部之肩部完全地受到被膜所被覆，孔部 之內壁面及底面之被膜膜厚成爲大致一定之情況（參照圖 4) △;表面開口部之肩部完全地受到被膜所被覆，而孔 部之內壁面及底面之膜厚並未成爲大致一定之情況（參照 圖5 ) X ;表面開口部之肩部並未完全地受到被膜被覆之情 況、或將孔部完全地埋住之情況（參照圖6 ) (2 )鈉含量 將感光性樹脂組成物藉由丙二醇單甲基醚醋酸酯稀釋 ，使用原子吸收光譜計（珀金埃爾默製、型號^ Z5 1 00」 )測定鈉含量。 (3 )解像性 於6英吋之矽晶圓將感光性樹脂組成物旋轉塗佈，使 用熱板在1 10°C加熱5分鐘’製作ΙΟμίΏ厚之均勻之樹脂 塗膜。其後，使用對準器（Suss Microtec公司製、型號「 -74 - 200905397 MA-150」），隔著圖案光罩由高壓水銀燈之紫外線在波 長3 50nm，以曝光量成爲6000J/m2之方式曝光。接著，使 用2.38質量％氫氧化四甲基銨水溶液，在23 °C作3分鐘 浸漬顯像。然後，將所得到之圖案之最小尺寸定爲解像度 (4 )蝕刻性 於6英吋之矽晶圓將感光性樹脂組成物作旋轉塗佈， 使用熱板在1 l〇°C加熱5分鐘，製作ΙΟμηι厚之均勻樹脂 塗膜。其後，使用乾式蝕刻裝置（神港精機公司製、型號 「E1113-C23」，CF4氣體環境氣氛中，以4500Wxl20秒 鐘之條件進行乾式蝕刻處理。然後，測定在此時因乾式蝕 刻而消失之膜厚，藉著以下之基準對鈾刻性作評估。 〇：因蝕刻處理而消失之膜厚爲1 .5 μιη以下之情況 X :因蝕刻處理而消失之膜厚爲超過1 . 5 μπι之情況 (5 )感光性樹脂組成物之物性（黏度測定） 關於各樹脂組成物，使用流變儀（型名「AR2000」、 ΤΑ儀器公司製），在溫度25 °C、將剪切速度由1 rpm上 升至l,000rpm爲止’測定在1_5、5、6、50、60及在 600rpm時之黏度，算出剪切速度在6rpm時之黏度V,與 剪切速度在60rpm時之黏度v2(mPa. s)之比（νι/ν2) 、剪切速度在l.Srpm時之黏度V3(mPa· s)與剪切速度 在600rpm時之黏度V4(mPa.s)之比（V3/V4) ’及剪 -75- 200905397 切速度在5rpm時之黏度 V5 ( mPa · s )與剪切速度在 5 0rpm 時之黏度 V6 ( mPa . s)之比（V5/V6)。 此外，將各樹脂組成物之黏度V1 ( mPa · s )之値倂 記於表2。 -76- 200905397 (sd)〇 I OS (s3〇 (S3〇 (ss〇 (s)〇uso 0-1)〇 ae〇 (s.o)〇 (se〇 (s3〇(sso(s)〇 【sy.)li:iBiK裝】65 ΓΟ (uldd) 1.0 οζι Ι·οThe alkali-soluble resin [A] may be a single polymer, and may be a combination of two or more. In the present invention, a resin containing an acid hydroxyl group is preferred, and a copolymer obtained by using a phenol resin and a hydroxybenzene Z-46 - 200905397 olefin is preferred. The weight average molecular weight of the alkali-soluble resin [A] can be measured by GPC (gel permeation chromatography), and is preferably 2,000 or more, preferably about 2,000 to 50,000. When it is in this range, the obtained cured film is excellent in mechanical properties, heat resistance, and electrical insulating properties. The content ratio of the alkali-soluble resin [A] constituting the positive-type photosensitive resin composition is preferably 20 to 90% when the solid content of the positive-type photosensitive resin composition is 100% by mass. %, preferably 20 to 80% by mass, more preferably 30 to 70% by mass. In this range, the alkali solubility is excellent, and the obtained cured film is excellent in mechanical properties, heat resistance, and electrical insulation properties. Next, the above didiazonium compound [B] is a phenolic compound, 1,2-naphthoquinone-2-diazo-5-sulfonate or 1,2-naphthoquinone-2-diazo-4- Sulfonate. The phenolic compound ' is not particularly limited as long as it is a compound having at least one phenolic hydroxyl group, and the compound represented by the above formulas (1) to (5) is preferred. Examples of the phenolic compound include 4,V-dihydroxydiphenylmethane, 4,4'-mono-based benzoic acid, 2,3,4-trisylbenzophenone, 2,3,4, 4'-tetracarboxylic benzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, ginseng (4-hydroxyphenyl)methane, ginseng (4 hydroxyphenyl)ethane 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-I-methylethyl]benzene, 1;4_double [Bu (4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[Ι·(4-hydroxyphenyl)-I-methylethyl]-, 3-amino-benzene 1,1_bis(4·phenyl)-fluorene-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane, and the like. These may be used alone or in combination of two or more types from -47 to 200905397. Therefore, in the above didiazonium compound [B], at least one of the phenolic compounds and the 1,2-diazonaphthoquinone-4-1,2-diazonaphthoquinone-5 can be used. The esterified product obtained by the sulfonic acid reaction or the like may be used singly or in combination of two or more. The content ratio of the above-mentioned diazo compound [B] constituting the positive-type photosensitive resin composition is preferably from 10 to 100 parts by mass, preferably 1%, when the alkali-soluble resin [A] is used in an amount. ~50, more preferably 1 5~5 0 parts by mass. When it is in this range, the difference in solubility of the light portion of the exposed portion is large and the alkali solubility is excellent. Further, in the case of the above-mentioned cerium oxide, it is preferable to control a portion of the hydrophobized cerium oxide by the control of the thixotropy. The type of the above-mentioned cerium oxide is not particularly limited, and examples thereof include colloidal cerium oxide, gas phase cerium oxide, glass, and the like. Further, the shape of the particles is not particularly limited, and may be a spherical shape, a flat shape, a rod shape, a fibrous shape or the like. The hydrophobization rate of the above-mentioned cerium oxide is preferably from 30 to 80%, more preferably from 40 to 70%, in terms of 20 to 80%. In the case where the hydrophobization ratio is 20 to 20, the dispersibility of the cerium oxide to the solvent and the above-described denaturation property are good, and further, it is preferable that the resin composition is shaken. Further, the hydrophobization of the cerium oxide in the above resin composition is reselected by the number of sterol groups on the surface of the cerium oxide before and after hydrophobization by neutralization titration with a 0.1 N aqueous sodium hydroxide solution. From the sulfonic acid or turbidity, a hydrazine compound of 100 parts by mass and the ease of exposure can be enumerated, and the elliptical shape, preferably 80% of the fat phase-dependent denaturation rate, is determined by the following -48-200905397 The formula is obtained. Hydrophobicization rate (%): (number of sorbitol groups after hydrophobization / number of sterol groups before hydrophobization) χ 1 〇〇 In addition, the average particle diameter of the cerium oxide is 1 to l 〇〇 nm, preferably 5 〜 80 nm, preferably 10 0 to 50 nm. In the case where the average particle diameter is from 1 to 10 nm, sufficient transparency to the exposure light, and sufficient alkali solubility can be obtained. In addition, the average particle diameter was measured by diluting the dispersion of cerium oxide particles by a conventional method using a light scattering flow distribution measuring apparatus (manufactured by Otsuka Electronics Co., Ltd., model "LPA-3000"). Further, the average particle size can be controlled by the dispersion conditions of the ceria particles. Further, the sodium content in the cerium oxide is preferably 1 ppm or less, preferably 0. 5 ppm or less, more preferably 0. 1 ppm or less. In the case where the sodium content is 1 ppm or less, the sodium content in the obtained resin composition can be made 1 ppm or less. Further, the sodium content in the cerium oxide can be measured by an atomic absorption spectrometer (Model "Z5 100" manufactured by PerkinElmer). In the case where the total content of the cerium oxide in the resin composition is set to 1% by mass based on the total solid content in the resin composition, it is more than 20% by mass and is 60% by mass or less. Quality ° /. The above is 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less. When the content ratio is more than 20% by mass and 60% by mass or less, sufficient shakeability can be obtained, and a uniform film can be formed on the inner wall surface of the bottomed hole portion. -49 - 200905397 In addition, the resin composition of the present invention may contain two or more kinds of cerium oxide, and it may contain only the above-mentioned positive photosensitive resin composition from the viewpoint of good dispersibility. Oxide particles; crosslinked polymer particles composed of a crosslinked polymer"); a compound containing an amine group which is alkyl etherified in a molecule, which is a low ruthenium crosslinking agent; a phenolic compound; a phenol ring compound having a methylol group; a compound containing an ethoxymethyl acid group (including a block), and the like. In the case of having at least two or more compounds in the above molecule, (poly)methylolmethylglycolide, (poly)hydroxymethylbenzamide, (active hydroxymethyl group (CH2OH group) 2 in the compound) can be used. (a) is a compound that has been etherified. Here, the methyl group, the ethyl group, the butyl group and the like may be mentioned, and the same may be used. Further, it may not be self-condensed in the molecule, and may be a di-molecular-weight component. Specific examples include 'hexabutoxymethyl melamine, tetramethoxymethyl urea, and the like. In addition, it is preferable that one type of the epoxy group-containing compound or one type of the above-mentioned epoxy group-containing compound may be used alone or one type of the oxidized sand particles. One step is a cross-linking agent; gold particles (hereinafter, referred to as "a molecular phenolic compound or the like, having at least two or more base-containing compounds; having a compound-like compound; containing a thiopyran; and an alkyl ether having an isocyanate group; All or part of the nitrogen of the amine melamine, (poly)hydroxyl) hydroxymethyl urea, etc. (at least, the alkyl group constituting the alkyl ether and several alkyl groups, which are methylol groups which are ether-etherified with each other) , condensation, the result is oligohexamethoxymethyl melamine glycoluril, tetrabutoxymethyl ganide combination of two or more. Listed phenol novolac type epoxy-50- 200905397 resin, cresol novolac type epoxy resin, bisphenol type Epoxy resin, trisphenol epoxy resin, tetraacid epoxy resin, phenol-xylene epoxy resin, naphthol-xylene epoxy resin, phenol-naphthol epoxy resin, phenol-bicyclic ring Ethylene oxide type epoxy resin, alicyclic epoxy resin 'aromatic epoxy resin, aliphatic epoxy resin, epoxy cyclohexane resin, etc. These may be used alone or in combination of two or more. The above epoxy group contains a compound, and the phenol novolac Epoxy resin, bisphenol A epoxy resin, resorcinol diepoxypropyl ether, pentaerythritol epoxy propyl ether, trimethylolpropane polyepoxypropyl ether, glycerol polyepoxypropyl ether , phenylepoxypropyl ether, neopentyl glycol diepoxypropyl ether, ethylene/polyethylene glycol diepoxypropyl ether, propylene/polypropylene glycol diepoxypropyl ether, 1,6-hexanediol Di-epoxypropyl ether, sorbitol polyepoxypropyl ether, propylene glycol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, etc., in view of the aforementioned phenolic compound having an aldehyde group, The phenolic compound having a methylol group may, for example, be 2,6-bis(hydroxymethyl)-p-cresol or the like. The positive photosensitive resin composition is contained. In the case of the above-mentioned crosslinking agent, the content of the alkali-soluble resin [A] is preferably from 1 to 100 parts by mass, preferably from 75 to 75 parts by mass, more preferably from 1 to 10 parts by mass. ～50 parts by mass. If it is in this range, the alkali solubility is excellent, and at the same time, the mechanical properties, heat resistance and electrical insulation of the obtained cured film are obtained. Examples of the metal oxide particles include alumina, titanium oxide, -51 - 200905397 oxidation pin, cerium oxide, zinc oxide, copper oxide, lead oxide, cerium oxide, tin oxide, indium oxide, magnesium oxide, and the like. The surface of the metal oxide particles may be modified by a functional group or the like in order to improve the affinity or compatibility with the alkali-soluble resin [A]. Further, the shape of the metal oxide particles is not particularly The average particle diameter of the metal oxide particles may be defined as a spherical shape, an elliptical shape, a flat shape, a rod shape, or a fibrous shape, and is preferably 1 to 500 nm, preferably 5 to 200 nm, preferably 10 0. When the average particle diameter of the metal oxide particles is within the above range, it is excellent in transparency to radiation, alkali solubility, and the like. The metal oxide particles may be used alone or in combination of two or more. It is preferable that the metal oxide particles are easily controlled by shaking. In the case where the above-mentioned alkali-soluble resin [A] is used in an amount of 100 parts by mass, the positive-type photosensitive resin composition is preferably 10 to 200 parts by mass, preferably 10 parts by mass or more. 50 to 200 parts by mass, more preferably 70 to 150 parts by mass. When the content ratio of the metal oxide particles is within the above range, it has a suitable shakeability, and a uniform film can be formed on the inner wall surface of the bottomed hole portion. Further, the positive photosensitive resin composition contains a carbonate such as calcium carbonate or magnesium carbonate; a sulfate such as barium sulfate or calcium sulfate: calcium phosphate, phosphate such as -52-200905397 magnesium phosphate; carbide; nitrogen Other inorganic particles composed of a compound or the like may be used. As the crosslinked polymer particles, a single polymer or copolymer containing a monomer having a crosslinkable compound having two or more polymerizable unsaturated bonds (hereinafter referred to as "crosslinkable monomer") can be used. Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and trimethylolpropane tri ( Methyl) acrylate, pentaerythritol tri(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, and the like. These may be used alone or in combination of two or more. Further, in the above, divinylbenzene is preferred. In the case where the crosslinked polymer particles are copolymers, the other monomers polymerized with the crosslinkable monomer are not particularly limited, and a hydroxyl group, a carboxyl group, a nitrile group, a guanamine group, or the like may be used. An unsaturated compound of one or more functional groups such as an amine group or an epoxy group; a urethane (meth) acrylate; an aromatic vinyl compound; a (meth) acrylate; a diene compound. These may be used alone or in combination of two or more. In the above crosslinked polymer particles, a copolymer (d 1 ) composed of the above-mentioned crosslinkable monomer and an unsaturated compound having a hydroxyl group and/or an unsaturated compound having a carboxyl group, and also having the aforementioned A copolymer (d 2 ) which is a coupling monomer, an unsaturated compound having a hydroxyl group and/or an unsaturated compound having a carboxyl group, and another monomer is preferred, and a copolymer (d2) is particularly preferred. Examples of the unsaturated compound having a hydroxyl group include (meth)acryl-53-200905397 hydroxymethyl methacrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. Examples of the unsaturated compound having a carboxyl group include (meth)acrylic acid, itaconic acid-succinic acid-β-(meth)acryloxyethyl ester, and maleic acid-methyl)acryloxyethyl ester. And phthalic acid-stone-(meth) propylene methoxyethyl ester, hexahydrophthalic acid-stone-(meth) propylene methoxyethyl ester, and the like. Among the other monomers used for the formation of the copolymer (d2), the unsaturated compound having a nitrile group is exemplified by (meth)acrylonitrile, α-chloroacrylonitrile, and α-chloromethylacrylonitrile. , α-methoxypropenyl nitrile, α-ethoxy acrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile, and the like. Examples of the unsaturated compound having a guanamine group include (meth) acrylamide, dimethyl (meth) acrylamide, ν, ν 〜 methylene bis (meth) acrylamide, hydrazine, Ν'-Extended ethyl bis(methyl) acrylamide, hydrazine, Ν'-hexamethylene bis(methyl) acrylamide, hydrazine-hydroxymethyl (meth) acrylamide, hydrazine - ( 2 -Hydroxyethyl)(meth)acrylamide, hydrazine, hydrazine-bis(2-hydroxyethyl)(meth)acrylamide, crotonamide, cinnamate, and the like. Examples of the unsaturated compound having an amino group include dimethylamino (meth) acrylate, diethylamino (meth) acrylate, and the like. Examples of the epoxy group-containing unsaturated compound include glycidyl (meth)acrylate, (meth)acryloxypropyl ether, diglycidyl ether of bisphenol A, and ethylene glycol. (Methyl)-54-200905397 Acrylate epoxy ester obtained by reaction of di-epoxypropyl ether or the like with (meth)acrylic acid, hydroxyalkyl (meth)acrylate or the like. The (meth)acrylic acid urea vinegar is a compound obtained by a reaction of a hydroxyalkyl (meth) acrylate with a polyisocyanate. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methoxystyrene, and p-hydroxystyrene 'p-isopropenol. Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate. And lauryl (meth)acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and the like. Further, examples of the diene compound include butadiene, isoprene, dimethylbutadiene, chloroprene, and 1,3-pentadiene. When the crosslinked polymer particles are composed of the copolymer (d2), the unit amount (d21) composed of the crosslinkable monomer, the unit composed of the unsaturated compound having a hydroxyl group, and/or the unsaturated group having a carboxyl group. The total amount of the units constituted by the compound (d22), and the unit amount (d23) of the other monomers is the total of the unit amounts constituting the copolymer (d2), that is, at (d21), (d22) And when the sum of (d23) is set to 1 00 mol%, respectively, 0. 1 to 1 0 m ο 1 %, 5 to 5 0 m ο 1 % and 4 0 to 94_9 mol ° /. Preferably, it is preferably 〇5~7mol%, 6~45mol% and 48~93. 5 mol%, more preferably 1 to 5 mol%, 7 to 40 mol% and 55 to 92 mol%. When the ratio of each unit amount is within the above range, crosslinked polymer particles excellent in shape stability and compatibility with an alkali-soluble resin can be obtained. Further, the above-mentioned crosslinked polymer particles are either rubber or resin, and the glass transition temperature (Tg) thereof is not particularly limited. The good Tg is 2 0 c or less, preferably 10 0. (The following is more preferably 〇 ° C or less. Further, the lower limit is usually -7 0 t or more. The crosslinked polymer particles are in the form of particles, and the average particle diameter is preferably from 30 to 100 nm, preferably 40 to 40. 90 nm, and more preferably 50 to 80 nm. When the average particle diameter of the crosslinked polymer particles is within the above range, it is excellent in compatibility with an alkali-soluble resin, alkali solubility, etc. Further, the average particle diameter means light use. The scattering flow distribution measuring device "LPA-3 000" (manufactured by Otsuka Electronics Co., Ltd.) "measures the dispersion of the crosslinked polymer particles in accordance with a conventional method. The positive photosensitive resin composition contains the aforementioned crosslinking. In the case of the polymer particles, the content of the alkali-soluble resin [A] is preferably from 1 to 100 parts by mass, preferably from 5 to 80 parts by mass, more preferably from 5 to 50, per 100 parts by mass of the alkali-soluble resin [A]. The content of the crosslinked polymer particles is excellent in heat resistance and the like of the cured film obtained in the above range ', and the low molecular weight phenolic compound is 4, 4'-dihydroxy Benzene, 4,4'-dihydroxy Diphenyl ether, ginseng (4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, ginseng (4-hydroxyphenyl)ethane, 1,3-double [ 1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-double [ 1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-bu [4·[ 1-( 4-hydroxyl) Phenyl)-p-methylethyl]phenyl]ethane, 1,1,2,2·tetrakis(4-hydroxyphenyl)-56- 200905397 Ethane, etc. These may be used alone or in combination When the above-mentioned alkali-soluble resin composition [A] is contained in an amount of 100 parts by mass, the positive-type photosensitive resin composition is in the range of 1 to 20 by mass. The portion is preferably 2 to 15 parts by mass, more preferably 3 to 10 parts by mass. If the content ratio of the low molecular phenolic compound is in the above range, the heat resistance of the obtained cured product is not impaired. Further, in the present invention, the positive photosensitive resin composition may be selected to contain the alkali-soluble resin, and the second Further, it may be determined to further contain the compound having a diazide group. Further, it may be determined to further contain a cross-linking agent in the subsequent stage. Further, it may be determined to contain the aforementioned cross-linking polymerization. In the case where the resin composition used in the coating step of the resin composition is the positive photosensitive resin composition, the solid content concentration is preferably 5 to 80% by mass, preferably 10 The amount of the resin composition is preferably from 25 to 60% by mass. The resin composition is a non-photosensitive resin composition, and a curable resin composition containing an alkali-soluble resin and a crosslinking agent is preferred. The alkali-soluble resin is preferably a resin having a phenolic hydroxyl group, a resin having a carboxyl group, a resin having a phenolic hydroxyl group and an alcoholic hydroxyl group, and a resin having a carboxyl group and an alcoholic hydroxyl group. These may be used singly or in combination. Further, a resin exemplified as a constituent component of the positive photosensitive resin composition may be used as it is. Further, in the above crosslinking agent, a compound having at least 2 - 57 to 200905397 or more alkyl etherified amine groups in the molecule is used, and a compound containing an epoxy group is preferred. These may be used singly or in combination. Further, a crosslinking agent exemplified as a constituent component of the positive photosensitive resin composition can be used as it is. In the case where a compound having at least two or more alkylated amine groups in the molecule is used as the crosslinking agent, the content of the non-photosensitive resin composition is set to 100% in the alkali-soluble resin. In the case of parts by mass, it is preferably from 1 to part by mass, preferably from 5 to 50 parts by mass. When the content ratio of the above compound is within the above range, the obtained cured film is excellent in mechanical properties, heat resistance and electrical insulating properties. In addition, when the epoxy group-containing compound is used as the crosslinking agent, the content of the non-photosensitive resin composition is preferably from 1 to 70 parts by mass, preferably from 1 to 70 parts by mass, based on 100 parts by mass of the alkali-soluble resin. It is 3 to 30 parts by mass. When the content ratio of the epoxy group-containing compound is within the above range, the obtained cured film is excellent in mechanical properties, heat resistance, and electrical insulation. The non-photosensitive resin composition may further contain metal oxide particles, crosslinked polymer particles, low molecular phenolic compounds, etc., and these may be used as the positive photosensitive resin composition as described above. The constituents are exemplified. In the case of the above-mentioned non-photosensitive resin composition, the resin composition used in the resin composition coating step has a solid content concentration of preferably 5 to 8 % by mass, preferably 10 to 60% by mass. In the resin composition coating step, a method of applying a resin composition having a specific physical property of -58 to 200905397 to the substrate is carried out in such a manner that the resin composition is in contact with the solvent in the pore portion. The method of processing is not particularly limited, and examples thereof include a spin coating method, a spray coating method, and a bar coating method. Within these, spin coating is preferred. Further, in the coating step of the resin composition, the solid content concentration, viscosity, and the like of the resin composition are considered to cause the film thickness formed on the surface of the substrate to enter 0 by a drying step which is performed later. It is preferable to form a coating film in a range of 1 to ΙΟμιη. In the resin composition application step, when the resin composition is applied, a uniform coating film 515 is formed on the surface of the substrate 51, and in the hole portion, the solvent coating step is accommodated. A mixture of a solvent and a resin composition 5 1 6 (see Fig. 8 (c)). Next, the drying step is a step of drying the coating film formed by the coating step of the resin composition, that is, a step of removing only the solvent contained in the coating film. The drying temperature is determined by the boiling point of the solvent charged in the solvent coating step, or the boiling point of the mixed solvent contained in the mixture of the solvent and the resin composition in the solvent coating step. Further, the drying conditions are not particularly limited, but may be carried out at a constant temperature, and may be carried out while raising or lowering the temperature. Further, the pressure may be carried out under atmospheric pressure, and may be carried out under vacuum. Further, 'the ambient atmosphere gas and the like are not particularly limited. According to the drying step, the solvent is removed, and a uniform film composed of a solid component of the resin composition is formed on the surface of the substrate having at least the inner wall surface of -59 - 200905397 (see Fig. 8 (d)). The substrate 5 with the film shown in Fig. 8 (d) includes a film 519 formed on the entire surface of the substrate 51 having the hole portion and the substrate 51, and a film formed on the inner wall surface of the hole portion. 517, and a film 518 formed on the bottom surface of the hole portion. These films generally form a continuous phase, but there are cases where only the film 5 17 and 5 18 form a continuous phase. Further, the thickness of each film, the thickness of the film 519, the thickness of the film 517 on the inner wall surface of the hole portion, and the thickness of the film 518 on the bottom surface of the hole portion are generally different, and depending on the kind of the resin composition, solid The thickness of the component, the viscosity, and the like, the thickness of the film 517 on the inner wall surface of the hole portion, and the thickness of the film 518 on the bottom surface of the hole portion may be the same or almost the same. 5. Structure having an insulating film and method for producing the same The method for producing a structure having an insulating film of the present invention (hereinafter referred to as "the method for manufacturing a structure (I)") is shown in Fig. 8(d) and Fig. 9 (a) is characterized in that: the substrate 519 having the film obtained by the film forming method (II) of the present invention is used, and the film 519 formed on the surface of the substrate 51 is formed on the substrate. The film 518 on the bottom surface of the hole portion of 51 is removed, and the film bottom surface side film removal step formed on the inner wall surface of the hole portion is left, and the film 5 17 which is left on the inner wall surface of the hole portion is heated. The heat hardening step. In the method (I) for producing a structure of the present invention, the film 517 to 5 1 9 ' is preferably composed of a positive photosensitive resin composition, and is used in the case of -60-200905397. Give instructions. The film bottom surface side film removing step ' is a step of removing the film 519 formed on the surface of the substrate and the film 518 formed on the bottom surface of the hole portion of the substrate, leaving the film 517 formed on the inner wall surface of the hole portion. . First, the substrate 5 with the film shown in Fig. 9(a) is irradiated with ultraviolet rays, visible light, far ultraviolet rays, X-rays, electron beams, or the like, and the film 519 formed on the surface of the substrate 51 is formed on the surface. The film 518 on the bottom surface of the hole portion of the substrate 51 is exposed. At this time, the film 517 formed on the inner wall surface of the hole portion is made to be unexposed. The exposure amount is appropriately selected according to the light source to be used, the thickness of the film, and the like. For example, for a film having a thickness of about 5 to 50 μm, a high-pressure mercury lamp is used to irradiate ultraviolet rays, and a good exposure amount is 1,000 to 20,000 J/m 2 . . Since the film exposure portions 528 and 529 shown in Fig. 9(b) are alkali-soluble, the film 517 formed on the inner wall surface of the hole portion can be left by treatment with an alkaline solution. The alkaline solution may be an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia, hydroxyammonium methylammonium or choline, or a water-soluble organic solvent such as methanol or ethanol may be added thereto in an appropriate amount. A solution such as a surfactant or the like. After the treatment with an alkaline solution, the substrate having the film 517 only on the inner wall surface of the hole portion can be obtained by washing with water and drying (see Fig. 9(c)). The heat-hardening step is a step of heating the film 51 which remains on the inner wall surface of the hole portion, and by this step, the film 5 17 is made into a cured film -61 - 200905397 6 1 7 ' to obtain an insulating film. Structure 6 (refer to Fig. 9 (d)). The heating method is not particularly limited, and is usually set to a temperature in the range of 1 〇〇 to 25 ° ° C, preferably 30 minutes to 10 hours. Heating under certain conditions or heating in multiple stages is acceptable. For the heating device, an oven, an infrared furnace or the like can be used. The structure 6 having an insulating film shown in Fig. 9(d) is provided with a substrate 51 having a hole portion and a cured film 6 at an inner wall surface of a hole portion formed in the substrate. In the method (I) for producing a material, the honing step of honing the surface of the substrate 51 having no hole portion and forming the hole portion as the through hole 62 may be further provided after the heat curing step (refer to FIG. 9 (refer to FIG. 9 ( e)). The honing method is not particularly limited, and a chemical mechanical honing method or the like can be applied. The structure 6' having an insulating film shown in Fig. 9(e) includes a substrate 51 having a through hole 62 and a hardened film 161 formed on the inner wall surface of the through hole 62. Another method for producing a structure having an insulating film according to the present invention (hereinafter referred to as "manufacturing method of structure") is as shown in Fig. 8 (d) and Fig. 10 (a), and is characterized by: The substrate 517, 518, and 519 having the entire surface of the substrate formed on the inner wall surface and the bottom surface of the hole-containing portion by using the substrate 5 with the film obtained by the film forming method (Π) of the present invention. Heating to form a heat-hardening step of an insulating film containing a cured product of the resin component, and removing an insulating film of -62 - 200905397 formed on the surface of the substrate and an insulating film formed on a bottom surface of the hole portion of the substrate, The surface-side insulating film removing step of the insulating film formed on the inner wall surface of the hole portion is left. In the method (II) for producing a structure of the present invention, the film is preferably composed of a non-photosensitive resin composition, and this case will be described with reference to Fig. 10 . The heat-hardening step is a step of heating the film 517, 518, and 519 formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole portion to form an insulating film containing the cured product of the resin component (refer to the drawing). 10(b)) ° The heating method is not particularly limited, and may be the same as the heat-hardening step in the production method (I) of the structure of the present invention. According to the heat-hardening step, the structure shown in FIG. 10(b) is obtained, and the structure includes a substrate 51 having a hole portion, and an insulating film 619 formed on the surface of the substrate, which is formed in the foregoing An insulating film 617 on the inner wall surface of the hole portion and an insulating film 618 formed on the bottom surface of the hole portion. Then, the insulating film 619 formed on the surface of the substrate and the insulating film 618 formed on the bottom surface of the hole portion of the substrate are removed, and the inner surface of the hole portion is formed on the inner surface of the hole portion. The step of insulating film 6 1 7 . Examples of the method of selectively removing the insulating films 618 and 619 include anisotropic uranium engraving (dry etching). According to the above-described surface-side insulating film removing step, a structure 6 having an insulating film as shown in FIG. 1A(C) is provided, and the structure 6 includes a substrate 5 1 having a hole portion formed therein. Hardening of the inner wall surface of the hole portion of the substrate - 63 - 200905397 Film 617. In the manufacturing method (11) of the structure of the present invention, the "subsurface side insulating film removing step" is similar to the manufacturing method (I) of the structure of the present invention, and may be further provided on the substrate 51. The honing step in which the surface of the hole portion is not honed and the hole portion is formed as the through hole 62 (see FIG. 10(d)). The structure 6' having an insulating film shown in Fig. 1 (d) is provided with a substrate 5 1 having a through hole 62 and a cured film 617 formed on the inner wall surface of the through hole 62. 6. The electronic component according to the present invention is characterized in that it has a structure including an insulating film obtained by the method for producing a structure of the present invention (a structure having a through hole in which an insulating film is formed on an inner wall), A member of an electrode portion (a conductive material filling portion) in which at least a through hole of the structure is filled with a conductive material. The electronic component of the present invention may include, for example, a structure including at least the through-holes of the structure 6' shown in FIGS. 9(e) and 10(d) and the structure 6'.塡部) 7 1 1 member 7 (refer to Figure 1 1 (g)). The foregoing member 7 will be described. The material (conductive material) constituting the electrode portion 71 1 of the member 7 may be selected from the group consisting of copper, silver, tungsten, molybdenum, titanium, nail, gold, tin, aluminum, and the like. . The electrode portion 711 may have a convex shape protruding from the smooth surface of the substrate 51 as shown in Fig. u(g), and may be flush with the substrate 51 - 64 - 200905397. Further, the surface of the electrode portion 711 may be a smooth surface or a rough surface. The example of the manufacturing method of the member 7 shown in Fig. (g) will be described using Fig. n. First, the structure 6 having the insulating film shown in Fig. 9 (d) and Fig. 10 (c) is prepared (see Fig. 1 1 (a)). The surface of the structure 6 having the hole portion is subjected to Cu sputtering or the like, and a copper film (seed layer) having a thickness of 10 to 2 nm is formed on the surface of all the structures 6 on the inner surface of the hole-containing portion. 63a and 63b (refer to Fig. 11 (b)). Thereafter, the insulating resist film 64 is formed by printing or the like on the surface of the copper film 613a other than the inner surface of the hole portion (see Fig. 1 1 (c)). Next, Cu plating is performed in the pores using a copper sulfate aqueous solution or the like (see Fig. 11 (d)). Thereafter, the insulating resist film 64 is peeled off using a predetermined peeling liquid or the like (see Fig. 11(e)). Next, the copper film 633 formed on the surface of the substrate 51 is removed by etching using dilute sulfuric acid or dilute hydrochloric acid (see Fig. 11(f)). Then, the inside of the substrate 51 is honed until the metal copper filled in the hole portion is exposed, and the member 7 having the through electrode formed of the metal copper filling portion 711 is obtained as shown in Fig. 11(g). The member having the through electrode may be the member 7' shown in Fig. 2 . The member 7 is provided with a through-hole formed in the surface of the insulating film 6 17 and formed on the inner wall surface, and has a substrate 5 1 filled with a conductive material filling portion 7 1 1 of a conductive material; and at least covered The electrode pad 713 of the exposed surface of the conductive material filling portion 7 1 1 on the lower side of the exposed surface (the exposed surface on the lower side of the drawing surface). The member 7' of Fig. 12 can be exposed by the lower side of the conductive material filling portion 7 1 1 having the member 7 shown in Fig. 11 (g) (Fig. 1 1 (g) -65 - 200905397 The lower side) is manufactured by the method of forming the electrode pad forming step of the electrode pad. Specific examples of the electrode electrode forming step include plating, application of a conductive paste, and the like. Other manufacturing methods will be described later. Further, the member 7 &quot; shown in Fig. 13 is an example in which the member 7' shown in Fig. 1 1 (g) or the member 7 shown in Fig. 12 is used. The member 7 is a composite member, and the electrode plates 7 1 3 a and 7 1 3 are respectively disposed on the lower exposed side of the metal copper filling portions (through electrodes) 711a and 711b (the lower side exposed surface of the drawing). The b-side member 161 and the lower side member 72 of the electrode copper plates 723a and 723b are respectively disposed on the lower surface of the metal copper filling portions (through electrodes) 721a and 7hb (the lower surface of the drawing surface). The surface of the electrode pad 713a of the upper member 71 is joined to the surface of the metal copper filling portion (through electrode) 72 la of the lower member 72, and the surface of the electrode pad 713b of the upper member 71 and the lower member 72 are joined. The surface of the metal copper filling portion (through electrode) 721b is joined. An insulating layer 7 4 is disposed at the interface between the upper member 7 1 and the lower member 7 2 (see Fig. 13). The bonding method of the electrode pad 713a and the metal copper filling portion (through electrode) 721a is not particularly limited, and examples thereof include a method of hot pressing (heating at the same time). The electronic component of the present invention may be provided with the member 7 shown in Fig. 11 (g), the member 7 shown in Fig. 12, the member 7 shown in Fig. 13, and the like. For example, the electronic component 8 of FIG. 14 is connected to the interposer 81 via the two bumps 82 disposed on the surface of the interposer 81, and the electrode pads 723a and 723b of the member 7&quot; shown in FIG. Further, a bump 83-160-200905397 for electrically connecting to another member or the like is disposed on the lower side of the interposer 81. The electronic component of the present invention is a composite body including the above-described members 7, 7' and 7", and may be, for example, a composite body including other substrates, interlayer insulating films, and other electrodes (circuit substrate, semiconductor element, and sense). Further, the member 7' shown in Fig. 12 can be manufactured by a method in which a conductive material layer 713 is formed in advance, and a bottom surface of the hole portion is a composite substrate of the conductive material layer 713. Through the member 6' (Fig. 9 (d) or Fig. 10 (d)) obtained by the steps of Figs. 9(a) to (c) or the steps of Figs. 10(a) to (c) The lower side of the opening of the hole (the lower side of FIG. 9(e) or the lower side of FIG. 10(d)) has a hole portion of the conductive material layer 713, which is filled by the steps of FIGS. 11(b) to (f). The step of forming the conductive material by using the laminated substrate 9 having the concave portion shown in Fig. 15 (a), the method for forming the film of the present invention, and the method for producing the structure having the insulating film The laminated substrate 9 shown in Fig. 15(a) is provided with sand, various metals, various metal sputtering films, alumina, epoxy glass, and phenol. An aldehyde paper, glass, or the like is formed in a columnar shape (see Fig. 7 (a)), a tapered shape (see Fig. 7 (b)), and a reverse tapered shape (see Fig. 7 (see Fig. 7 (b)) c)) a substrate 91 such as a through hole, and a conductive material layer 93 disposed on one surface of the substrate 91 so as to close the through hole. The laminated substrate 9 is formed by a conductive material layer 93, a through hole One of the laminated substrates 9 is a flat plate-67-200905397 substrate which is a laminate of a flat substrate and a conductive material layer having no through holes, and is not recessed. The conductive material layer may be formed by cutting. The thickness of the substrate 91 is preferably from 1 to 200 μm, preferably from 30 to 120 μm, more preferably from 50 to ΙΟΟμηι, by opening the recess. The area of the portion, the cross-sectional shape, and the like are the same as those described in the film forming method (Π) of the present invention, and the method for forming a film (II) of the present invention and the method for producing a structure having the insulating film are applicable. Manufacturing the member 7' shown in Figure 15 (e) That is, the member 7' shown in Fig. 12 is a simple description of the manufacturing method of the member 7' shown in Fig. 15(e). First, by coating the surface of the substrate 91 constituting the laminated substrate 9. After the solvent (solvent coating step), a resin composition having a specific shake resistance (resin composition coating step) is applied as described above to form a coating film. Next, the resin composition on the surface of the substrate 91 is formed. The coating film and the mixture in the concave portion are dried, and the solvent is removed, and a film (92, 922, and 923, respectively) is formed on the surface of the substrate 9 1 , the inner wall surface of the concave portion, and the concave side surface of the conductive material layer 93 to obtain a coating. The substrate 100 having a film (see Fig. 15 (b)). Then, the method for producing a structure having an insulating film according to the present invention is applied in accordance with the type of the resin composition, and a laminated structure 200 having an insulating film 925 on the inner wall surface of the concave portion is obtained (see Fig. 15 (c)). Then, the electrode pad 9 3 5 (see FIG. 15 (d)) is formed by removing a portion of the conductive material layer 93 without etching the recess, and the recess is filled with copper, Silver, tungsten, molybdenum, titanium, nail, gold, tin, aluminum, and a conductive material in the alloy, the member 7 can be obtained, and the -68-200905397 system is provided as shown in Fig. 15(e), A substrate 91 which is formed in the surface of the conductive material 925 and has a conductive film 925 formed on the inner wall surface, and a substrate 91 having a conductive material filling portion 96 and a lower surface of the conductive material filling portion 96 (FIG. 1) 5 (e) lower side of the electrode plate 93 5 . Therefore, the member 7_ obtained by using the laminated substrate 9 shown in Fig. 15 (a) may be used to constitute the electronic component of the present invention. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited by the embodiments. [1] Preparation of Positive Photosensitive Resin Composition (Example 1) As shown in Table 1, (A) alkali-soluble resin (A-1) 100 parts by mass, (B) diazonium compound ( B-1) 25 parts by mass, (C) cerium oxide (C-1) 100 parts by mass and (F) surfactant (F-1) 0. 1 part by mass, dissolved in (D) solvent (D-1) 25 5 parts by mass to prepare a photosensitive resin composition (Examples 2 to 8 and Comparative Examples 1 to 5) In the same manner as in Example 1, as shown in Table 1, (A) an alkali-soluble resin, (a) a low molecular phenolic compound, (B) a diazide compound, (C) cerium oxide, ( E) adhesion promoter and (F) interface-69-200905397 The active agent is dissolved in (D) solvent so that the solid content concentration is 47% by mass, and each photosensitive resin composition is prepared. g 戋 d o o o o o r-H O o o o 〇 〇 r—* 〇 jg® w \ \ \ \ \ \ \ \ \ \ \ \ \ i.  tL tL \L· 1 IL, 1 tl· i 1 lin cl 1 IL· 丄1 IL g II II in \ I 1 1 I 1 1 1 1 1 1 ΤΊ~ i1mi1 ώ ΙΛ ΙΛ LO CO O ΙΛ CO in CN3 lO CSl to Cn3 o § in Cvi o LC CN: Si \ \ \ \ \ \ \ \ \ \ \ \ Class _ QT aa 1 a 1 Q 1 Q a 1 Q a Q 1 〇a 1 a 〇in O i〇LO ΙΛ mm 卜 l〇卜 in \ •w to draw·Μ ri 00 C &lt;1 Bu· ID 1 CO Bu· CO Secret II i Leg wns tlmll s ο LO to s LQ to Ln LO in l〇 in CSI ΰ LO \ l U \ 1 U \ 1 〇 \ 1 u \ »- &lt; 1 〇\ 1 U \ 1 U \ »«4 1 U \ 1 U 1 \ CS3 ! U \ 1 U 翻 §1| s in CN3 in Cn3 LT5 (NJ ID CS) C^3 m oa in CN3 In ΙΛ l〇CS3 L〇CN1 in 03 3 \ \ \ \ \ \ \ \ \ \ \ \ \ m CQ CQ ώ CQ CQ ώ CD CQ ώ 1 CQ 1 CQ it ms 3 翁ί-ϊ o I 1 1 \ \ 1 1 1 1 1 1 ^ &lt;ini i. 丄m ® m 1 ooo O o § 〇ol〇CN3 oo 00 CSJ o O oo 〇\ \ \ \ \ \ \\ \\ \ \ \ \ \ f^ggS ·-H CNJ 1 7 ? »—1 1 1 Successive P &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; C &lt;&lt;CN) Γ0 l〇 ID 00 00 03 CO in -70- 200905397 The composition described in Table 1 is as follows. <(A) Alkali-soluble resin> A-Ι: cresol phenolic resin composed of m-cresol/p-cresol = 60/40 (mole ratio), polystyrene-equivalent weight average molecular weight (Mw) = 65 00 A -2: Polyhydroxystyrene (made by Jiushan Petrochemical Co., Ltd., trade name "MARUKA LYNCUR S-2P"), Mw = 5 000 A-3: Phenol-retinodiol condensation resin (manufactured by Mitsui Chemicals, trade name "Mirex" XLC-3L", Mw=1500 <(a) low molecular phenolic compound> a_l: II-bis(4-hydroxyphenyl)·1-[4-(1-(4-hydroxyphenyl)methylethyl Phenyl]ethane <(Β)diadiazepine compound Β_1: 1,1_bis(4-hydroxyphenyl)·1-[4-(1-(4-carboxyphenyl)_1·methyl b Benzene] ethane, dimethyl condensate with 1,2-diazonaphthoquinone-5-sulfonic acid &lt; (C) cerium oxide > y A Industrial Cl: trade name "QUARTRON PL-2L" (Fusang hand-made, hydrophobized (hydrophobicization rate: 50%) 'Average particle size: 2 〇 nm Sodium content: 〇.〇2ppm) -71 - 200905397 C-2: Trade name "PMA-ST" (manufactured by Nissan Chemical Industry) Hydrophobic treatment (hydrophobicization rate: 60%), average particle size: 20 nm, sodium content: 600 ppm) C-3: The product name "QUARTRON PL-30" (made by Fuso Chemical Industry, hydrophobized (hydrophobicization rate: 40%), average particle diameter: 300 nm, sodium content: 〇.〇2 ppm) <(D) solvent 〉 D-1 : propylene glycol monomethyl ether acetate < (E ) adhesion aid > E-1 : γ - methacryl oxiranyl trimethoxy decane (made by Japan UNICAR, trade name "Α-187" <(F) Surfactant (Leveling Agent)> F-1: Trade name "FTX-218" (manufactured by NEOS) In addition, the hydrophobization ratio of the above (C) cerium oxide is as follows After the measurement. <Hydrophilization rate> First, 3 mL of sodium chloride was dissolved in 150 mL of a 10% aqueous dispersion of cerium oxide, and adjusted to pH 4 with 1N hydrochloric acid. Then, a 0.1 N aqueous sodium hydroxide solution was added dropwise until pH 9 was reached. Then, the number of sterol groups on the surface of the cerium oxide was determined by the following formula. -72- 200905397 A= ( ax〇. 1 χΝ ) / ( WxS ) [However, the number of sterol groups in A system (units/m2), the amount of a system of 0_1N sodium hydroxide solution (L), N-type Yafo The number of twists (pieces / m ο 1 ), the weight of bismuth dioxide (g) The BET area of the S-type cerium oxide (nm: ) ° In this way, the dioxins before and after hydrophobization were determined. The number of sterol groups in hydrazine was calculated by the following formula to calculate the hydrophobization rate of cerium oxide. Hydrophobization rate (%) = (number of sterol groups after hydrophobization / number of hydrophobized sterol groups) X100 [2] Evaluation of positive type photosensitive resin composition For the above Examples 1 to 8 and Comparative Example 1 Each of the photosensitive resin compositions of 5 was evaluated in accordance with the method described below. The results are shown in Table 2. (1) Film formability The shape of the opening portion on the surface is square (80 μm). &lt;80μιη) a propylene glycol single on a Si substrate having a depth of ΙΟΟμπι and a conical shape having a square shape of a square shape (60μηιχ60μηη) (see Fig. 1(b)), a diameter of 150 mm, and a thickness of 5 〇〇μπι Methyl acetate was spin-coated (1 OOO rpm, 3 seconds) as a solvent, and the solvent was filled in a portion (see Fig. 2 (b)). Thereafter, the photosensitive resin composition was spin-coated (first stage 300 rpm, 10 seconds, second stage; 600 rpm, 20 seconds), and a coating film was formed on the surface of the solvent surface in the hole portion. . WW !/g 刖 刖 顺 » » » » » » » » » » » » » » » » » » » » » » » » 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 73 The film is formed on the inner surface of the Si substrate and the inner wall surface and the bottom surface of the hole portion to obtain a substrate having a film (see FIG. 2(d)). Then, the cross-sectional shape of the hole portion was observed by an electron microscope, and the film formation property was evaluated on the basis of the following.肩; the shoulder portion of the surface opening portion is completely covered by the film, and the film thickness of the inner wall surface and the bottom surface of the hole portion is substantially constant (see FIG. 4) Δ; the shoulder portion of the surface opening portion is completely covered by the film The film thickness of the inner wall surface and the bottom surface of the hole portion is not substantially constant (see FIG. 5) X; the shoulder portion of the surface opening portion is not completely covered by the film, or the hole portion is completely buried. (Refer to Fig. 6) (2) Sodium content The photosensitive resin composition was diluted with propylene glycol monomethyl ether acetate and determined by atomic absorption spectrometry (manufactured by PerkinElmer, model: ^5 5 00) Sodium content. (3) Resolving property The photosensitive resin composition was spin-coated on a 6-inch wafer, and heated at 10 ° C for 5 minutes using a hot plate to prepare a uniform resin coating film. Thereafter, an aligner (Suss Microtec, model "-74 - 200905397 MA-150") was used, and the ultraviolet light of the high-pressure mercury lamp was exposed through the pattern mask to a wavelength of 3 50 nm, and the exposure amount was 6000 J/m 2 . . Subsequently, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used, and immersion imaging was carried out at 23 ° C for 3 minutes. Then, the minimum size of the obtained pattern is set to resolution (4) etching is performed on a 6-inch ruthenium wafer, and the photosensitive resin composition is spin-coated, and heated at 1 l ° C for 5 minutes using a hot plate. A uniform resin coating film of ΙΟμηι thick was produced. Thereafter, a dry etching process was performed using a dry etching apparatus (manufactured by Shinko Seiki Co., Ltd., model "E1113-C23", in a CF4 gas atmosphere at a temperature of 4500 Wxl for 20 seconds. Then, the measurement was disappeared by dry etching at this time. The thickness of the film is evaluated by the following criteria: 〇: The film thickness disappeared by the etching treatment is 1.5 μm or less X: The film thickness disappeared by the etching treatment is more than 1. 5 μπι (5) Physical properties of the photosensitive resin composition (viscosity measurement) For each resin composition, a rheometer (type name "AR2000", manufactured by Konica Minolta Co., Ltd.) was used, and the shear rate was 1 at a temperature of 25 °C. The rpm was raised to 1,000 rpm. The viscosity at 1 to 5, 5, 6, 50, 60 and at 600 rpm was measured, and the viscosity V at a shear rate of 6 rpm was calculated, and the viscosity at a shear rate of 60 rpm was v2 (mPa. s) ratio (νι/ν2), viscosity V3 (mPa·s) at a shear rate of l.Srpm, and viscosity V4 (mPa.s) at a shear rate of 600 rpm (V3/V4)' and Shear-75- 200905397 Viscosity V5 (mPa · s ) at 5 rpm and shear speed at 50 rpm The ratio of V6 (mPa.s) is V5/V6. In addition, the viscosity V1 (mPa · s ) of each resin composition is shown in Table 2. -76- 200905397 (sd) 〇I OS (s3 〇(S3〇(ss〇(s)〇uso 0-1)〇ae〇(so)〇(se〇(s3〇(sso(s)〇[sy.)li:iBiK装)65 ΓΟ (uldd) 1.0 Ζζι Ι·ο

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X ο -77- 200905397 〔3〕實施例9 (1 )樹脂.組成物之調製及黏度測定 使酚樹脂（商品名「SUMILITERESINS-2」、住友電 木公司製）]00質量份、三聚氰胺交聯劑（商品名「 CYMEL300」、三井CYTEC公司製）30質量份、及平均 粒徑1 〇〜2〇nm之經疏水化處理之二氧化矽粒子（商品名 「MEK-ST」、新中村化學公司製、鈉含量：800ppm) 100 質量份，在乳酸乙酯及甲基乙基酮之混合溶劑（混合比 60/40 )中分散，得到固體成分濃度47質量％之樹脂組成 物。 關於此樹脂組成物，使用流變儀（型號「AR2000」、 TA儀器公司製），在溫度25°C，將剪切速度由Irpm上 升至 1，000邛1«爲止，測定在1.5、5、6、50、60及在 600rpm時之黏度，算出剪切速度在6rpm時之黏度V!( = 900mPa · s)與剪切速度在 6 0 r p m時之黏度V 2 ( m P a · s )之比（V&quot;V2)、剪切速度在1.5rpm時之黏度V3(mPa • s)與剪切速度在600rpm時之黏度 V4(mPa. s)之比 (V3/V4 )、及剪切速度在5rpm時之黏度V5(mPa.s) 與剪切速度在50rpm時之黏度V6 ( mPa · S )之比（V5/V6 )(參照表3)。 (2 )被膜形成 於表面具有開口部形狀爲正方形（)、深 度爲]ΟΟμηι、及底面形狀爲正方形（6〇μηΐχ60μηι )之順錐 -78- 200905397 形狀之孔部、直徑1 50mm及厚度50 Ομηι之矽基板（參照 圖16)上，將丙二醇單甲基醋酸酯作爲溶劑旋轉塗佈（ l，00 0rpm、3秒鐘），於孔部充塡此溶劑（參照圖7 ( Μ )° 其後，將在前述所得到之樹脂組成物，作2階段旋轉 塗佈（第1階段；3 00rpm、10秒鐘、第2階段；600rpm 、2 0秒鐘），在含孔部內之溶劑表面之矽基板之表面形成 塗膜。 其次，將附有塗膜之矽基板，於溫度1 1 〇 °c之熱板上 靜置3分鐘，使溶劑揮發，在矽基板之表面與孔部之內壁 面及底面使被膜形成，得到附有被膜之矽基板（參照圖8 (d))。於圖17表示由電子顯微鏡而得來之斷面照片。 測定被膜之厚度，在內壁面爲9.0μπα、在底面則爲5.8μπι (參照表3 )。目視觀察此孔部內表面之被膜形成性，則 爲均勻。 [4]比較例6 將二氧化矽粒子之配合量定爲0質量份以外，係與實 施例9同樣之方式調製樹脂組成物（固體成分濃度47質 量。/❶）’測定黏度（V^TSOmPa . s )。其後，使被膜形成 (圖1 8參照）。由圖1 8，可知樹脂組成物之固形物將孔 部塡滿（參照表3 )。 -79- 200905397 [表3]X ο -77- 200905397 [3] Example 9 (1) Resin. Composition and viscosity measurement of phenol resin (trade name "SUMILITERESINS-2", manufactured by Sumitomo Bakelite Co., Ltd.)] 00 parts by mass, melamine cross-linking 30 parts by mass of the agent (trade name "CYMEL300", manufactured by Mitsui CYTEC Co., Ltd.) and hydrophobized cerium oxide particles having an average particle diameter of 1 〇 to 2 〇 nm (trade name "MEK-ST", Shin-Nakamura Chemical Co., Ltd. Preparation, sodium content: 800 ppm) 100 parts by mass, and dispersed in a mixed solvent of ethyl lactate and methyl ethyl ketone (mixing ratio 60/40) to obtain a resin composition having a solid concentration of 47% by mass. About the resin composition, using a rheometer (model "AR2000", manufactured by TA Instruments Co., Ltd.), the shear rate was raised from 1 rpm to 1,000 邛 1 « at a temperature of 25 ° C, and the measurement was performed at 1.5, 5, 6, 50, 60 and the viscosity at 600 rpm, calculate the viscosity V! (= 900 mPa · s) at a shear rate of 6 rpm and the viscosity V 2 ( m P a · s) at a shear rate of 60 rpm. Ratio (V&quot;V2), viscosity V3 (mPa • s) at a shear rate of 1.5 rpm and viscosity V4 (mPa.s) at a shear rate of 600 rpm (V3/V4), and shear rate at The viscosity V5 (mPa.s) at 5 rpm and the viscosity V6 (mPa · S) at a shear rate of 50 rpm (V5/V6) (refer to Table 3). (2) The film is formed on the surface of a hole having a shape of a square having an opening shape of a square (), a depth of ΟΟμηι, and a shape of a bottom surface of a square (6〇μηΐχ60μηι)-78-200905397, a diameter of 50 mm, and a thickness of 50 Ομηι On the substrate (see Fig. 16), propylene glycol monomethyl acetate was spin-coated as a solvent (100,000 rpm, 3 seconds), and the solvent was filled in the pores (see Fig. 7 ( Μ ) ° thereafter The resin composition obtained as described above was subjected to two-stage spin coating (first stage; 300 rpm, 10 seconds, second stage; 600 rpm, 20 seconds), and the surface of the solvent in the pore-containing portion A coating film is formed on the surface of the substrate. Next, the substrate with the coating film is allowed to stand on a hot plate at a temperature of 1 〇 ° C for 3 minutes to volatilize the solvent, and the surface of the substrate and the inner wall surface of the hole portion are The film was formed on the bottom surface to obtain a ruthenium substrate with a film (see Fig. 8 (d)). Fig. 17 shows a cross-sectional photograph obtained by an electron microscope. The thickness of the film was measured, and the inner wall surface was 9.0 μπα on the bottom surface. Then it is 5.8μπι (refer to Table 3). Visually observe this hole The film formation property of the inner surface was uniform. [4] Comparative Example 6 The resin composition (solid content concentration 47 mass) was prepared in the same manner as in Example 9 except that the amount of the cerium oxide particles was 0 parts by mass. ./❶)'The viscosity is measured (V^TSOmPa.s). Thereafter, the film is formed (refer to Fig. 18). From Fig. 18, it can be seen that the solid content of the resin composition fills the hole (refer to Table 3) -79- 200905397 [Table 3]

___樹脂組成物之物性 被膜厚度（μη〇 被膜 形成性 Vi/V2 v3/v4 v5/v6 Vi (mPa • s) 內壁面 底面 實施例9 2.4 16.2 2.5 900 9.0 5.8 ◎ 比較例6 1.0 1.0 1.0 760 - - X___The physical film thickness of the resin composition (μη〇 film formation property Vi/V2 v3/v4 v5/v6 Vi (mPa • s) inner wall surface bottom surface Example 9 2.4 16.2 2.5 900 9.0 5.8 ◎ Comparative Example 6 1.0 1.0 1.0 760 - - X

[5 ]實施例1 〇〜1 8及比較例7〜1 1 (1 )樹脂組成物之調製（實施例1 〇 ) 如同表4所示，藉由將（A )鹼可溶性樹脂（A-1 ) 100質量份、（B)二重氮醌化合物（B-l)25質量份、（ C )二氧化矽（C-1 ) 100質量份、（E )密著助劑（Ε·1 ) 2.5質量份、（F )界面活性劑（F -1 ) 〇 . 1質量份、（G ) 交聯劑（G-1) 20質量份與（G-2) 10質量份、及（Η)交 聯聚合物（Η-1) 10質量份，以固體成分濃度成爲47質 量％之方式，溶解於（D )溶劑（D-1 ) 3 00質量份，調製 了樹脂組成物。 (2 )樹脂組成物之調製（實施例1 1〜1 8及比較例7 〜1 1 ) 與實施例10同樣地，如同表4及表5所示，藉由將 (A )鹼可溶性樹脂、（a )低分子酚性化合物、（B )二 重氮醌化合物、（C )二氧化矽、（E )密著助劑、（F ) 界面活性劑、（G )交聯劑、及（Η )交聯聚合物，以固 體成分濃度成爲4 7質量％之方式，溶解於（D )溶劑而調 製各樹脂組成物。 -80- 200905397 X 交聯 聚合物 (種類/份） H-1/10 H-1/10 H-1/10 H-1/10 H-1/10 H-1/10 1 H-1/10 H-1/10 0 交聯劑 mmm G-1/20 G-2/10 G-1/20 G-2/10 G-1/20 G-2/10 G-1/20 G-2/10 G-1/20 ! G-2/10 G-1/20 G-2/10 ! G-1/20 G-2/10 G-1/20 G-2/10 g 界面 活性劑 (種類/份) F-1/0.1 F-1/0.1 F-1/0.1 F-1/0.1 F-1/0.1 F-1/0.1 1 F-1/0.1 F-1/0.1 F-1/0.1 g 密著助劑 (種類/份） E-1/2.5 E-1/2.5 E-1/2.5 E-1/2.5 E-1/2.5 E-1/2.5 丨 E-1/2.5 E-1/2.5 E-1/2.5 溶劑 (種類/份） D-1/300 D-1/275 D-1/245 D-l/245 D-1/275 D-1/275 ' D-1/260 D-l/265 D-l/250 二氧化矽 相對於 全固體 成分之 比例(％) $ o ΓΟ C^i LO CO Oi ύ 05 C&gt;3 CO Μ CO CO (種類/份） C-1/100 C-1/75 C-l/50 C-1/75 丨 C-1/75 C-1/75 C-1/75 C-1/75 C-1/75 s 二重氮醌 化合物 (種類/份） B-1/25 B-1/25 B-1/25 1 B-1/25 B-1/25 B-1/25 B-1/25 B-1/25 3 低分子 酚性 化合物 (種類/份) 1 1 1 I 1 o 1 1 1 鹼可溶性 樹脂 (種類/份) A-1/100 A-1/100 A-1/100 A-1/100 1 A-2/I00 A-1/90 A-1/100 A-1/100 A-1/100 〇 CO LO 卜 2 -81 - 200905397 5 交聯 聚合物 (種類/份） H-1/10 H-1/10 H-1/10 H-1/10 H-1/10 0 交聯劑 (種類/份） Ο 〇 ώ ο G-l/20 G-2/10 o o CO CS3 o o G-l/20 G-2/10 0 o CO 1 1 〇 〇 S j i 界面 活性劑 (種類/份） F-1/0.1 F-1/0.1 F-l/0.1 F-l/0.1 F-l/0.1 w 密著助劑 (種類/份） E-l/2.5 E-l/2.5 E-l/2.5 E-l/2.5 E-l/2.5 1 溶劑 (種類/份） _i D-1/220 D-l/190 D-l/275 1 D-l/220 D-l/275 二氧化矽 葙画Φ荽 Ο CO 1 03 o CO cn (種類/份) _1 C-l/25 1 C-2/75 C-2/25 ! I- C-3/75 g 二重氮醌 化合物 (種類/份） _1 B-l/25 B-l/25 B-l/25 ... B-l/25 1 B-l/25 -111 /&lt;—s Μ A-l/100 i ! A-l/100 . ...1 A-l/100 A-l/100 A-l/100 卜 00 o * -82- 200905397 另外，表4及表5所記載之組成[(G)及（F)成分] ’係如同以下之敘述。此外，關於（A )〜（F )成分，係 使用與在前述之實施例1〜8及比較例1〜5所使用者爲相 同者。 &lt; (G)交聯劑〉 G-1:六甲氧甲基三聚氰胺（商品名；CYMEL300、三 井CYTEC公司製） G-2:苯酚酚醛型環氧樹脂（商品名；EP-152、日本環 氧樹脂公司製） 〈（H)交聯聚合物所構成之粒子〉 H-1: 丁二烯/甲基丙烯酸羥丁酯/甲基丙烯酸/二乙烯苯 = 60/32/6/2 (質量 ％)(平均粒徑：70nm) [6]樹脂組成物之評估 在前述實施例1 〇〜1 8及比較例7〜1 1之各樹脂組成 物中，關於（1 )被膜形成性、（2 )樹脂組成物之物性（ 黏度測定）、（3 )鈉含量、（4 )解像性、（5 )電氣絕 緣性作評估。將其結果示於表6。 另外，關於前述（1 )被膜形成性、（2 )樹脂組成物 之物性（黏度測定）、（3 )鈉含量、及（4 )解像性，分 別藉由與在前述之[2]之（1) 、 （5) 、 （2)及（3)同樣 之方法進行評估。此外，僅供參考用，於圖19表示在實 -83- 200905397 施例Π所得到之附有被膜之矽基板之由電子顯微鏡而得 來之斷面照片。此外，於圖2 0表示在比較例8所得到之 附有被膜之矽基板之由電子顯微鏡而得來之斷面照片。 (5 )電氣絕緣性（體積電阻率） 將樹脂組成物藉由旋轉塗佈機（型號「1H-3 60S」、 MIKASA公司製）塗佈於SUS基板。其後，使用熱板在 1 1(TC加熱3分鐘，形成膜厚ΙΟμπι之均勻薄膜。接著，使 用對流式烘箱在1 70 °C加熱2小時，得到試驗片（絕緣層 )。將此所得到之試驗片使用加壓蒸煮測試裝置（田葉井 ESPEC公司製），在溫度：121 °C、濕度：1 〇〇%、壓力： 2.1氣壓之條件下處理1 6 8小時。測定處理前後之層間之 體積電阻率（Ω · cm )，定爲電氣絕緣性之指標。 -84- 200905397 9« 體積電阻率(Ω · cm) 測試後 IX ΙΟ14 4Χ1014 4Χ1014 8X1013 4X1014 4X1014 6X 1013 「1X10 丨4 IX 1014 5 Χίο14 7Χ1014 4Χ1010 4X1011 4X1014 測試前 1 2Χ1015 _1 5X10IS _1 5 ΧΙΟ15 1X1015 5X101S 5X1015 8X1014 3XI0IS 3Χ1015 5Χ1015 6Χ ΙΟ15 5Χ1013 8X1013 5X1015 J 解像性 (βτή) ΙΟ ΙΛ m l〇 ΙΛ in ΙΛ LO ΙΛ LO LO ΙΛ LO S 鈉含量 (ppm) CS) ο c^a ο 03 ο o oa o DO o 〇 〇 CS1 Ο CS] c&gt; CSI ο S ι Ή § oa d 樹脂組成物之物性 vt (mPa.s) ο 卜 s (£&gt; 710 卜 690 690 o 卜 700 I ο ΙΛ 沄 ΙΛ 卜 Ο 0¾ in o 00 ΙΏ vs/v6 σ\ LTD CO 卜 to in LO tO 卜 r*™4 Ο UD oo 卜 v3/v4 Oi to* 寸 c6 CO ui 5 tD ①· ΙΛ CX5 ΙΟ ο u5 t£) # 4 tn (£J V,/V2 〇0 ΙΌ· CO 卜 tD L〇 卜 ρ· Η ο LO w 1 1 卜 被膜形成性 〇 〇 〇 〇 〇 〇 〇 〇 X X 〇 X 〇 ο (&gt;3 CO 寸 LO VD 卜 00 卜 C0 σ&gt; o -85- 200905397 【圖式簡單說明】 圖1 ·表示形成於段差基板之孔部（溝部）之斷面之模 式圖。 圖2.表示本發明之被膜形成方法（I )之模式圖。 圖3·表示貫通電極之製作方法之模式圖。 圖4.表示形成被膜之孔部斷面之圖像。 圖5.表示形成被膜之孔部斷面之圖像。 圖6.表示形成被膜之孔部斷面之圖像。 圖7 .表示設置於基板之孔部之槪略剖面圖。 圖8.說明本發明之被膜形成方法（π )之槪略剖面圖 〇 圖9.說明本發明之具有絕緣膜之構造物之製造方法之 一例之槪略剖面圖。 圖10.說明本發明之具有絕緣膜之構造物之製造方法 之其他例之槪略剖面圖。 圖11·說明本發明之電子零件之構成要素（構件8) 之製造方法之槪略剖面圖。 圖1 2 ·說明構成本發明之電子零件之構件8 ’之槪略剖 面圖。 圖1 3 .說明本發明之電子零件之構成要素（構件8 &quot;) 之槪略剖面圖。 圖1 4 ·說明本發明之電子零件之例之槪略剖面圖。 圖1 5 .說明圖1 2之構件3 '之其他製造方法之槪略剖面 圖。 -86- 200905397 圖16.表示實施例之中所使用之被膜形成前之矽基板 之孔部破斷面之斜視圖像。 圖1 7.表示在實施例9所得到之附有被膜之矽基板之 孔部破斷面之斜視圖像。 圖1 8.表示在比較例6所得到之附有被膜之矽基板之 孔部破斷面之斜視圖像。 圖1 9 .表示在實施例1 1所得到之附有被膜之矽基板之 孔部破斷面之斜視圖像。 圖20.表示在比較例8所得到之附有被膜之矽基板之 孔部破斷面之斜視圖像。 明 說 WBIU 符 件 元 要 主 板 基 差 段 物 合 混 之 劑 溶 及 物 成 組 脂 部部 樹 孔溝 性 微微劑膜光 細細溶塗感 膜 被 部 光 曝 膜 被 板 基 極案通 電圖貫 部 部 孔 用 極 電 -87- 200905397 5 :附有被膜之基板 5 1 :基板 5 1 1 :孔部 5 1 3 :溶劑 5 1 5 :塗膜 5 1 6 :樹脂組成物及溶劑之混合物 5 1 7 :孔部內壁面之被膜 5 1 8 :孔部底面之被膜 519:基板表面之被膜 5 2 8 :孔部底面之被膜曝光部 529:基板表面之被膜曝光部 6、 6' ··具有絕緣膜之構造物 6 1 7 :孔部內壁面之絕緣膜（硬化膜） 6 1 8 :孔部底面之絕緣膜（硬化膜） 6 1 9 :基板表面之絕緣膜（硬化膜） 6 2 :貫通孔 63a、63b:銅膜（晶種層） 64 :絕緣性抗蝕劑被膜 66:金屬銅充塡部 7、 71、7&quot;:構件 71 :上側構件 7 1 1 :電極部（導電材料充塡部） 711a、711b:貫通電極（導電材料充塡部） 713、 713a、 713b:電極極板 -88- 200905397 72 :下側構件 721a、721b:貫通電極（導電材料充塡部） 723a、723b:電極極板 74 :絕緣層 8 :電子零件 8 1 :中介層 82 :凸塊 83 :凸塊 9 :層合基板 9 1 :基板 921、 922 ' 923 ：被膜 92 5 :絕緣膜 93 :導電材層 9 3 5 :電極極板 96 :導電材料充塡部 1〇〇 :附有被膜之基板 200:層合構造物 -89-[5] Example 1 〇~1 8 and Comparative Example 7 to 1 1 (1) Preparation of Resin Composition (Example 1 〇) As shown in Table 4, by (A) alkali-soluble resin (A-1) 100 parts by mass, (B) 25 parts by mass of the diazide compound (Bl), (C) 100 parts by mass of ceria (C-1), and (E) adhesion promoter (Ε·1) 2.5 parts by mass (F) surfactant (F -1 ) 〇. 1 part by mass, (G) crosslinking agent (G-1) 20 parts by mass and (G-2) 10 parts by mass, and (Η) crosslinked polymer (Η-1) 10 parts by mass, dissolved in (D) solvent (D-1) 300 parts by mass, so as to have a solid content concentration of 47% by mass, to prepare a resin composition. (2) Preparation of Resin Composition (Examples 1 to 18 and Comparative Examples 7 to 1 1) As in Example 10, as shown in Tables 4 and 5, (A) an alkali-soluble resin, (a) a low molecular phenolic compound, (B) a diazide compound, (C) cerium oxide, (E) an adhesion aid, (F) a surfactant, (G) a crosslinking agent, and (Η) The crosslinked polymer was dissolved in (D) solvent so that the solid content concentration became 47% by mass to prepare each resin composition. -80- 200905397 X Crosslinked polymer (type / part) H-1/10 H-1/10 H-1/10 H-1/10 H-1/10 H-1/10 1 H-1/10 H-1/10 0 Crosslinker mmm G-1/20 G-2/10 G-1/20 G-2/10 G-1/20 G-2/10 G-1/20 G-2/10 G-1/20 ! G-2/10 G-1/20 G-2/10 ! G-1/20 G-2/10 G-1/20 G-2/10 g Surfactant (type/part F-1/0.1 F-1/0.1 F-1/0.1 F-1/0.1 F-1/0.1 F-1/0.1 1 F-1/0.1 F-1/0.1 F-1/0.1 g Additives (types/parts) E-1/2.5 E-1/2.5 E-1/2.5 E-1/2.5 E-1/2.5 E-1/2.5 丨E-1/2.5 E-1/2.5 E- 1/2.5 Solvent (type/part) D-1/300 D-1/275 D-1/245 Dl/245 D-1/275 D-1/275 'D-1/260 Dl/265 Dl/250 II Ratio of cerium oxide to total solids (%) $ o ΓΟ C^i LO CO Oi ύ 05 C&gt;3 CO Μ CO CO (type/part) C-1/100 C-1/75 Cl/50 C- 1/75 丨C-1/75 C-1/75 C-1/75 C-1/75 C-1/75 s Didiazepine compound (type/part) B-1/25 B-1/25 B-1/25 1 B-1/25 B-1/25 B-1/25 B-1/25 B-1/25 3 Low-molecular phenolic compound (type/part) 1 1 1 I 1 o 1 1 1 Alkali-soluble resin (type/part) A-1/100 A-1/100 A-1/100 A-1/100 1 A-2/I00 A-1/90 A-1/100 A-1/10 0 A-1/100 〇CO LO 卜 2 -81 - 200905397 5 Crosslinked polymer (type/part) H-1/10 H-1/10 H-1/10 H-1/10 H-1/10 0 Crosslinker (type/part) Ο 〇ώ ο Gl/20 G-2/10 oo CO CS3 oo Gl/20 G-2/10 0 o CO 1 1 〇〇S ji Surfactant (type/part) F-1/0.1 F-1/0.1 Fl/0.1 Fl/0.1 Fl/0.1 w Adhesive aid (type/part) El/2.5 El/2.5 El/2.5 El/2.5 El/2.5 1 Solvent (type/part ) _i D-1/220 Dl/190 Dl/275 1 Dl/220 Dl/275 二 矽葙 荽Ο CO 1 03 o CO cn (type / part) _1 Cl/25 1 C-2/75 C -2/25 ! I- C-3/75 g Bistamine Compound (Type / Part) _1 Bl/25 Bl/25 Bl/25 ... Bl/25 1 Bl/25 -111 /&lt;-s Μ Al/100 i ! Al/100 . ...1 Al/100 Al/100 Al/100 00 o * -82- 200905397 In addition, the composition described in Tables 4 and 5 [(G) and (F) Ingredients] ' is as described below. Further, the components (A) to (F) were the same as those of the above-described Examples 1 to 8 and Comparative Examples 1 to 5. &lt; (G) Crosslinking agent > G-1: hexamethoxymethyl melamine (trade name; CYMEL300, manufactured by Mitsui CYTEC Co., Ltd.) G-2: phenol novolac type epoxy resin (trade name; EP-152, Japan epoxy) Manufactured by Resin Co., Ltd. <(H) Particles composed of crosslinked polymer> H-1: Butadiene/Hydroxybutyl methacrylate/methacrylic acid/divinylbenzene = 60/32/6/2 (% by mass) (Average particle diameter: 70 nm) [6] Evaluation of resin composition In each of the resin compositions of the above Examples 1 to 18 and Comparative Examples 7 to 1 1, (1) film formability, (2) The physical properties (viscosity measurement), (3) sodium content, (4) resolution, and (5) electrical insulation of the resin composition were evaluated. The results are shown in Table 6. Further, regarding the above (1) film formability, (2) physical properties (viscosity measurement), (3) sodium content, and (4) resolution of the resin composition, respectively, by the above [2] ( 1), (5), (2) and (3) are evaluated in the same way. Further, for reference only, a cross-sectional photograph of an electron microscope obtained from a substrate having a film obtained in the example of the present invention is shown in Fig. 19. Further, Fig. 20 shows a photograph of a cross section obtained by an electron microscope of the substrate with the film obtained in Comparative Example 8. (5) Electrical Insulation (Volume Resistivity) The resin composition was applied to a SUS substrate by a spin coater (model "1H-3 60S", manufactured by MIKASA Co., Ltd.). Thereafter, a hot plate was used for heating at 1 1 (TC for 3 minutes to form a uniform film having a film thickness of ΙΟμπι. Then, it was heated at 1, 70 ° C for 2 hours using a convection oven to obtain a test piece (insulating layer). The test piece was treated with a pressure cooker tester (manufactured by Tanabe ESPEC Co., Ltd.) at a temperature of 121 ° C, a humidity of 1 〇〇%, and a pressure of 2.1 at a pressure of 2.1 ° C. The layers before and after the treatment were measured. The volume resistivity (Ω · cm ) is an indicator of electrical insulation. -84- 200905397 9« Volume resistivity (Ω · cm) After test IX ΙΟ14 4Χ1014 4Χ1014 8X1013 4X1014 4X1014 6X 1013 "1X10 丨4 IX 1014 5 Χίο14 7Χ1014 4Χ1010 4X1011 4X1014 Before test 1 2Χ1015 _1 5X10IS _1 5 ΧΙΟ15 1X1015 5X101S 5X1015 8X1014 3XI0IS 3Χ1015 5Χ1015 6Χ ΙΟ15 5Χ1013 8X1013 5X1015 J Resolution (βτή) ΙΟ ΙΛ ml〇ΙΛ in ΙΛ LO ΙΛ LO LO ΙΛ LO S Sodium content ( Ppm) CS) ο c^a ο 03 ο o oa o DO o 〇〇CS1 Ο CS] c&gt; CSI ο S ι Ή § oa d Physical properties of the resin composition vt (mPa.s) ο s (£&gt; 710 卜 690 69 0 o 卜700 I ο ΙΛ 沄ΙΛ Ο Ο 03⁄4 in o 00 ΙΏ vs/v6 σ\ LTD CO 卜 to in LO tO 卜r*TM4 Ο UD oo 卜 v3/v4 Oi to* inch c6 CO ui 5 tD 1 · ΙΛ CX5 ΙΟ ο u5 t£) # 4 tn (£JV, /V2 〇0 ΙΌ· CO 卜tD L〇卜ρ· Η ο LO w 1 1 卜膜形成性〇〇〇〇〇〇〇〇XX 〇 X 〇ο (&gt;3 CO inch LO VD 00 00 C0 σ&gt; o -85- 200905397 [Simplified illustration of the drawings] Fig. 1 is a schematic view showing a cross section of a hole portion (groove portion) formed in a step substrate. 2. A schematic view showing a method (I) for forming a film of the present invention. Fig. 3 is a schematic view showing a method of producing a through electrode. Fig. 4 is a view showing an image of a cross section of a hole forming a film. Fig. 5 is a view showing an image of a cross section of a hole forming a film. Fig. 6 is a view showing an image of a cross section of a hole forming a film. Fig. 7 is a schematic cross-sectional view showing a hole portion provided in a substrate. Fig. 8 is a schematic cross-sectional view showing a method of forming a film (π) of the present invention. Fig. 9. is a schematic cross-sectional view showing an example of a method for producing a structure having an insulating film of the present invention. Fig. 10 is a schematic cross-sectional view showing another example of the method for producing a structure having an insulating film of the present invention. Fig. 11 is a schematic cross-sectional view showing a method of manufacturing the constituent elements (member 8) of the electronic component of the present invention. Fig. 1 2 is a schematic cross-sectional view showing a member 8' constituting an electronic component of the present invention. Fig. 13 is a schematic cross-sectional view showing the constituent elements (member 8 &quot;) of the electronic component of the present invention. Figure 14 is a schematic cross-sectional view showing an example of an electronic component of the present invention. Fig. 15. A schematic cross-sectional view showing another manufacturing method of the member 3' of Fig. 12. -86-200905397 Fig. 16. A squint image showing a broken portion of a hole portion of a ruthenium substrate before film formation used in the embodiment. Fig. 1 is a squint image showing a broken portion of a hole portion of a substrate with a film obtained in Example 9. Fig. 1 is a squint image showing a broken portion of a hole portion of a substrate with a film obtained in Comparative Example 6. Fig. 19. shows a squint image of a broken portion of the hole portion of the substrate with the film obtained in Example 11. Fig. 20 is a squint image showing a broken portion of a hole portion of a substrate with a film obtained in Comparative Example 8. It is said that the WBIU symbol is required to be mixed with the main body of the substrate, and the composition of the component is formed into a group of fats. The tree hole and the micro-agent film are finely coated and coated. The film is exposed to the light. Electrode for part hole -87- 200905397 5 : Substrate with film 5 1 : Substrate 5 1 1 : Hole 5 1 3 : Solvent 5 1 5 : Coating film 5 1 6 : Mixture of resin composition and solvent 5 1 7 : film 5 1 8 of the inner wall surface of the hole portion: film 519 on the bottom surface of the hole portion: film 5 2 8 on the substrate surface: film exposure portion 529 on the bottom surface of the hole portion: film exposure portion 6 and 6' on the surface of the substrate · Insulation Membrane structure 6 1 7 : Insulating film on the inner wall surface of the hole (cured film) 6 1 8 : Insulating film on the bottom surface of the hole (cured film) 6 1 9 : Insulating film on the surface of the substrate (cured film) 6 2 : Through hole 63a, 63b: copper film (seed layer) 64: insulating resist film 66: metal copper filling portion 7, 71, 7 &quot; member 71: upper member 7 1 1 : electrode portion (conductive material filling portion) 711a, 711b: through electrode (conductive material filling portion) 713, 713a, 713b: electrode plate -88- 200905397 72 :下下Side members 721a, 721b: through electrodes (conductive material filling portions) 723a, 723b: electrode plates 74: insulating layer 8: electronic parts 8 1 : interposer 82: bumps 83: bumps 9: laminated substrates 9 1 : Substrate 921, 922 ' 923 : film 92 5 : insulating film 93 : conductive material layer 9 3 5 : electrode pad 96 : conductive material filling portion 1 : substrate 200 with film: laminated structure - 89 -

Claims (1)

200905397 十、申請專利範圍 1 · 一種被膜形成方法，其係用於藉由在形成 之孔部或溝部充塡導電性材料，將經層合之基板之 或基板之表面和裏面作電氣性連接之方法，並具備 具有（a )開口部之面積爲25〜ΙΟΟΟΟμιη2且深度J 2 00 μηι之孔部及（b)開口部之線寬爲5〜200μιη且 10〜200μιη之溝部之中之至少一者之段差基板，塗 之溶劑塗佈步驟、[2]將正型感光性樹脂組成物，以 部及溝部內之溶劑接觸之方式，塗佈於該段差基板 組成物塗佈步驟、與[3]使塗膜乾燥之乾燥步驟，且 部與溝部之內壁面及底面形成含該樹脂成分之被膜 形成方法，其特徵爲： 該正型感光性樹脂組成物，係含有（A )鹼可 脂、（B)具有二重氮醌基之化合物、（C )經疏水 且平均粒徑爲1〜〗00nm之二氧化矽、與（D)溶 正型感光性樹脂組成物，係具有搖變性，同時，在 感光性樹脂組成物中之鈉含量爲1 ppm以下，且言 二氧化矽之含有比例，在將該正型感光性樹脂組成 體成分定爲1 〇〇質量％之情況下，係超過20質量％ 質量％以下。 2 ·如申請專利範圍第1項之被膜形成方法， 該（A)鹼可溶性樹脂，係含有具有重量平均分 4000〜50000之酚性羥基之鹼可溶性樹脂。 3-如申請專利範圍第2項之被膜形成方法， 於基板 層間、 :[1]在 i ίο〜 深度爲 佈溶劑 與該孔 之樹脂 在該孔 之被膜 溶性樹 化處理 劑，該 該正型 〔（c) 物之固 、在60 其中， 子量爲 其中， • 90 - 200905397 該（A)鹼可溶性樹脂，進一步含有重量平均分子量未滿 2000之鹼可溶性樹脂。 4 ·如申請專利範圍第I至3項中任一項之被膜形成 方法，其中’進一步含有低分子酚性化合物。 5 ·如申請專利範圍第1至4項中任一項之被膜形成 方法，其中，進一步含有密著助劑。 6-如申請專利範圍第1至5項中任一項之被膜形成 方法，其中，該（C)二氧化矽之疏水化率爲2〇〜80 %。 7 · —種正型感光性樹脂組成物，其係具備[1 ]用於藉 由在形成於基板之孔部或溝部充塡導電性材料，將經層合 之基板之層間、或基板之表面和裏面作電氣性連接之方法 ，在具有（a)開口部之面積爲25〜ΙΟΟΟΟμιη2且深度爲1〇 〜200μιη之孔部及（b )開口部之線寬爲5〜200μιη且深度 爲10〜200μηι之溝部之中之至少一者之段差基板，塗佈溶 劑之溶劑塗佈步驟、[2]將正型感光性樹脂組成物，以與該 孔部及溝部內之溶劑接觸之方式，塗佈於該段差基板之樹 脂組成物塗佈步驟、[3]將塗膜乾燥之乾燥步驟，且係用於 在該孔部與溝部之內壁面及底面形成含該樹脂成分之被膜 之被膜形成方法之該正型感光性樹脂組成物，其特徵爲： 含有（Α)鹼可溶性樹脂、（Β)具有二重氮醌基之化合物 、（C )經疏水化處理且平均粒徑爲1〜1 〇〇nm之二氧化 矽、（D )溶劑，本組成物，係具有搖變性，同時，在該 正型感光性樹脂組成物中之鈉含量爲1 PPm以下，且該（ C )二氧化矽之含有比例’在將本組成物之固體成分定爲 -91 - 200905397 1 00質量％之情況下，係超過20質量％、在60質量％以下 〇 8. 一種被膜形成方法’其係用於藉由在形成於基板 之孔部充塡導電性材料’將經層合之基板之層間 '或基板 之表面和裏面作電氣性連接之方法’並具備：Π]在具有開 口部之面積爲25〜10000 μιη2且深度爲10〜200 μιη之孔部 之矽基板，塗佈溶劑之溶劑塗佈步驟、[2]將剪切速度在 6rpm時之黏度Vi (mPa· s)、與剪切速度在60rpm時之 黏度V2 ( mPa · s)之比（V!/V2)爲1.1以上之樹脂組成 物，以該樹脂組成物與該孔部內之該溶劑接觸之方式，塗 佈於該基板之樹脂組成物塗佈步驟、[3]將塗膜乾燥之乾燥 步驟，且在孔部之內壁面及底面之中之至少該內壁面形成 含該樹脂成分之被膜之被膜形成方法，其特徵爲： 該樹脂組成物，係含有鹼可溶性樹脂、二氧化矽、與 溶劑，該樹脂組成物，係具有搖變性，且該二氧化矽之含 有比例，在將該樹脂組成物之固體成分定爲1 00質量％之 情況下，超過20質量％、在60質量％以下。 9. 如申請專利範圍第8項之被膜形成方法，其中， 該樹脂組成物，係進一步含有具有二重氮醌基之化合物。 10. 如申請專利範圍第8或9項之被膜形成方法，其 中’該被膜’係形成於該孔部之內壁面及底面之兩者。 1 1 ·如申請專利範圍第8至丨〇項中任一項之被膜形 成方法’其中，該樹脂組成物，係進一步含有交聯劑。 12.如申請專利範圍第8至Π項中任一項之被膜形 -92 - 200905397 成方法’其中’該樹脂組成物，係進一步含有由交聯聚合 物所構成之粒子。 1 3 ·如申請專利範圍第8至1 2項中任一項之被膜形 成方法’其中’該樹脂組成物之固體成分濃度，係在5〜 8 0質量％之範圍。 1 4 .如申請專利範圍第8至1 3項中任一項之被膜形 成方法’其中，該黏度V,，係在10〜lOOOOmPa. s之範 圍。 1 5 ·如申請專利範圍第8至1 4項中任一項之被膜形 成方法’其中，於該樹脂組成物中，剪切速度在1.5rpm 時之黏度V3(mpa.s)、與剪切速度在6〇〇rpm時之黏度 V4(mPa. s)之比（v3/V4)爲 2.0 以上。 16_ —種具有絕緣膜之構造物之製造方法，其特徵爲 :具備：將藉由申請專利範圍第8至15項中任一項之方 法所得到之形成於該基板之表面之被膜及形成於該基板之 該孔部之底面之被膜除去，留下形成於該孔部之內壁面之 被膜之表底面側被膜除去步驟、與將被留在該孔部之內壁 面之被膜加熱之加熱硬化步驟。 17. —種具有絕緣膜之構造物之製造方法，其特徵爲 :具備：將藉由申請專利範圍第8至1 5項中任一項之方 法所得到之形成於包含該孔部之內壁面及底面之該基板之 全表面之被膜加熱，製成含該樹脂成分之硬化物之絕緣膜 之加熱硬化步驟、將形成於該基板之表面之絕緣膜及形成 於該基板之該孔部之底面之絕緣膜除去，留下形成於該孔 -93- 200905397 部之內壁面之絕緣膜之表底面側絕緣膜除去步驟。 1 8 .如申請專利範圍第1 6或1 7項之具有絕緣膜之構 造物之製造方法，其中，進一步具備由在具有該絕緣膜之 構造物之不具有該孔部之面將基板硏磨，將該孔部製爲貫 通孔之硏磨步驟。 1 9 . 一種具有絕緣膜之構造物，其特徵爲：藉由申請 專利範圍第〗6至1 8項中任一項之方法而得到。 20. —種電子零件，其特徵爲：具備含藉由申請專利 範圍第1 6至1 8項中任一項之方法所得到之具有絕緣膜之 構造物、與在該構造物之至少貫通孔內充塡導電材料而成 之電極部之構件。 21. 一種樹脂組成物，其係用於藉由在形成於基板之 孔部或溝部充塡導電性材料，將經層合之基板之層間、或 基板之表面和裏面作電氣性連接之方法，具備：Π]在具有 開口部之面積爲25〜ΙΟΟΟΟμηα2且深度爲10〜200μιη之孔 部之矽基板，塗佈溶劑之溶劑塗佈步驟、[2]將剪切速度在 6rpm時之黏度V! (mPa· s)、與剪切速度在60rpm時之 黏度V2(mPa.s)之比（VUD爲1.1以上之樹脂組成 物，以該樹脂組成物與該孔部內之該溶劑接觸之方式’塗 佈於該基板之樹脂組成物塗佈步驟、[3]將塗膜乾燥之乾燥 步驟，且在孔部之內壁面及底面之中之至少該內壁面形成 含該樹脂成分之被膜之被膜形成方法所使用之樹脂組成物 ，其特徵爲： 含有鹼可溶性樹脂、具有二重氮醌基之化合物、二氧 -94- 200905397 化矽、溶劑、與交聯劑’本組成物’係具有搖變性’且該 二氧化矽之含有比例，在將本組成物之固體成分定爲100 質量％之情況下，超過2 0質量％、在6 0質量％以下。 22.如申請專利範圍第21項之樹脂組成物，其中， 進一步含有由交聯聚合物所構成之粒子。 -95-200905397 X. Patent Application No. 1 · A method for forming a film for electrically connecting a surface of a laminated substrate or a substrate to a surface thereof by filling a conductive material in a formed hole portion or groove portion The method further comprises at least one of (a) an opening portion having an area of 25 to ΙΟΟΟΟμηη2 and a depth of J 2 00 μηι and (b) an opening having a line width of 5 to 200 μm and a thickness of 10 to 200 μm. The step of coating the substrate, the solvent coating step of coating, and [2] applying the positive photosensitive resin composition to the step of coating the step substrate composition, and [3] A method of forming a film containing the resin component in a drying step of drying a coating film, and forming a film containing the resin component on the inner wall surface and the bottom surface of the groove portion, wherein the positive photosensitive resin composition contains (A) alkali fat, ( B) a compound having a diazide group, (C) a cerium dioxide having a hydrophobic average particle diameter of from 1 to 00 nm, and (D) a positive photosensitive resin composition having a thixotropy, and Photosensitive resin composition In the case where the content of the positive-type photosensitive resin component is set to 1% by mass, the content of the sodium is more than 20% by mass or less. (2) The method for forming a film according to the first aspect of the invention, wherein the (A) alkali-soluble resin contains an alkali-soluble resin having a phenolic hydroxyl group having a weight average of 4,000 to 50,000. 3- The method for forming a film according to item 2 of the patent application, between the substrate layers, :[1] at a depth of i ίο~, a solvent of the solvent and a resin of the pore in the pore-coated dendritic treatment agent, the positive type [(c) Solids of matter, in 60 of which are sub-quantities, • 90 - 200905397 The (A) alkali-soluble resin further contains an alkali-soluble resin having a weight average molecular weight of less than 2,000. The method of forming a film according to any one of claims 1 to 3, wherein the further comprises a low molecular phenolic compound. The method of forming a film according to any one of claims 1 to 4, further comprising an adhesion aid. The method of forming a film according to any one of claims 1 to 5, wherein the (C) cerium oxide has a hydrophobization ratio of from 2 Å to 80%. 7 - a positive photosensitive resin composition comprising [1] for filling a conductive material with a hole or a groove formed in a substrate, and laminating a layer of the substrate or a surface of the substrate The method of electrically connecting to the inside is as follows: (a) an opening having an area of 25 to ΙΟΟΟΟμηη2 and a depth of 1 〇 to 200 μm, and (b) an opening having a line width of 5 to 200 μm and a depth of 10 〜 a retardation substrate of at least one of 200 μηι grooves, a solvent coating step of a coating solvent, and [2] a positive photosensitive resin composition is applied in contact with the solvent in the holes and the grooves. a resin composition application step of the step substrate, [3] a drying step of drying the coating film, and a method for forming a film containing the resin component on the inner wall surface and the bottom surface of the hole portion and the groove portion. The positive photosensitive resin composition characterized by comprising (a) alkali-soluble resin, a compound having a diazide group, (C) being hydrophobized and having an average particle diameter of 1 to 1 〇〇 NrO2, (D) solvent, this group The product has a shaken property, and the sodium content in the positive photosensitive resin composition is 1 PPm or less, and the content ratio of the (C) cerium oxide is set to "the solid content of the composition" -91 - 200905397 In the case of 1 00% by mass, it is more than 20% by mass and is 60% by mass or less. 8. A film forming method 'which is used to fill a conductive material in a hole formed in a substrate' A method of electrically connecting the interlayer of the laminated substrate or the surface of the substrate and the inside thereof is: Π] after the hole having an opening area of 25 to 10000 μm 2 and a depth of 10 to 200 μm The substrate, the solvent coating step of the coating solvent, [2] the viscosity Vi (mPa·s) at a shear rate of 6 rpm, and the viscosity V2 (mPa · s) at a shear rate of 60 rpm (V! /V2) is a resin composition of 1.1 or more, a resin composition applied to the substrate in a coating step in which the resin composition is in contact with the solvent in the hole portion, and [3] a drying step of drying the coating film And at least the inner wall surface of the inner wall surface and the bottom surface of the hole portion A method for forming a film comprising a film of the resin component, characterized in that the resin composition contains an alkali-soluble resin, cerium oxide, and a solvent, and the resin composition has a shake property and the cerium oxide is contained. When the solid content of the resin composition is set to 100% by mass, the ratio is more than 20% by mass and not more than 60% by mass. 9. The method of forming a film according to the eighth aspect of the invention, wherein the resin composition further contains a compound having a diazide group. 10. The method of forming a film according to claim 8 or 9, wherein the film is formed on both the inner wall surface and the bottom surface of the hole portion. The method of forming a film according to any one of claims 8 to 10 wherein the resin composition further contains a crosslinking agent. The method of forming a film of any one of the above-mentioned claims, wherein the resin composition further comprises particles composed of a crosslinked polymer. The method of forming a film according to any one of claims 8 to 12, wherein the solid content concentration of the resin composition is in the range of 5 to 80% by mass. The method of forming a film according to any one of claims 8 to 13 wherein the viscosity V is in the range of 10 to 100 mPa·s. The method of forming a film according to any one of claims 8 to 14, wherein in the resin composition, the viscosity V3 (mpa.s) at a shear rate of 1.5 rpm, and shearing The ratio of the viscosity V4 (mPa.s) at a speed of 6 rpm (v3/V4) is 2.0 or more. And a method for producing a structure having an insulating film, comprising: forming a film formed on a surface of the substrate obtained by the method of any one of claims 8 to 15 The film on the bottom surface of the hole portion of the substrate is removed, and the step of removing the film on the bottom surface side of the film formed on the inner wall surface of the hole portion and the step of heating and hardening the film to be left on the inner wall surface of the hole portion are left. . A method of producing a structure having an insulating film, comprising: forming the inner wall surface including the hole portion by the method of any one of claims 8 to 15 And a heat-hardening step of forming an insulating film containing the cured material of the resin component on the bottom surface of the substrate, an insulating film formed on the surface of the substrate, and a bottom surface of the hole formed on the substrate The insulating film is removed, leaving a surface-side insulating film removing step of the insulating film formed on the inner wall surface of the hole-93-200905397 portion. The method for producing a structure having an insulating film according to the invention of claim 16 or claim 17, further comprising: honing the substrate by a surface having the structure of the insulating film without the hole portion The hole portion is made into a through hole honing step. A structure having an insulating film, which is obtained by the method of any one of claims 6 to 18. 20. An electronic component, comprising: a structure having an insulating film obtained by the method of any one of claims 16 to 18, and at least a through hole in the structure The member of the electrode portion which is filled with a conductive material. A resin composition for electrically connecting a layer of a laminated substrate or a surface of a substrate and a surface thereof by filling a conductive material in a hole portion or a groove portion formed in the substrate,具备] A substrate having a hole portion having an opening area of 25 to ΙΟΟΟΟμηα2 and a depth of 10 to 200 μm, a solvent coating step of applying a solvent, and [2] a viscosity V at a shear rate of 6 rpm! (mPa·s), the ratio of the viscosity V2 (mPa.s) at a shear rate of 60 rpm (a resin composition having a VUD of 1.1 or more, in which the resin composition is in contact with the solvent in the hole portion) a resin composition coating step on the substrate, [3] a drying step of drying the coating film, and a method of forming a film containing the resin component on at least the inner wall surface of the inner wall surface and the bottom surface of the hole portion The resin composition used is characterized by: an alkali-soluble resin, a compound having a diazide group, a dioxin-94-200905397 bismuth, a solvent, and a crosslinking agent 'this composition' has a shake- And the content of the cerium oxide In the case where the solid content of the composition is 100% by mass, it is more than 20% by mass and 60% by mass or less. 22. The resin composition of claim 21, further comprising Particles composed of crosslinked polymers. -95-
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