1240932 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種適合採用在成爲電氣製品、電子製 品、半導體製品、汽車等之所使用之各種基板或零件之導 電性薄片。 【先前技術】 向來，使用在電氣製品、電子製品、半導體製品等之 導電性薄片係使得以銅作爲中心之各種金屬之壓延箔或電 解箔，成爲導電層，透過接著劑而將這個貼合在絕緣性薄 膜上，來進行使用。此外，不透過此種接著劑，在對於前 述箔之表面來進行粗化處理或者是進行稱爲黑處理之藉由 Ni、Ti、Cr等之金屬所造成之前處理後，在這些導電層 上，直接地塗敷絕緣性之樹脂或進行加熱融合，來進行使 用。另一方面，也知道作爲導電層係使用濺鍍法或蒸鍍法 等之真空技術而將銅等之金屬來層積在絕緣性薄膜上或者 是在該導電層之層積後、還藉由電鍍法而附加其厚度之導 電性薄片。但是，不論是在任何一種導電性薄片，該導電 層和絕緣性薄膜間之密合力變弱，無法滿足其密合強度（ 剝離強度）。此外，爲了提高其密合力，因此，嘗試不對 於導電層而是藉由對於絕緣性薄膜方面之表面，進行粗化 處理，或者是藉由利用在導電層和絕緣性薄膜間，插入 Cr、Ni、Ti等之金屬層而防止構成導電層之銅等之金屬 發生氧化，以便於提高其密合力，但是，藉由這些方法而 -4- (2) 1240932 達到某種程度之密合力之提升，不論是在任何一種嘗試， 也在形成微細化之電路圖案上，會有所謂造成困難或其他 問題產生。 此外，也提議嘗試藉由融合前述兩種技術而達到密合 力之提升。也就是說，在日本特開平2001— 277424號公 報，提議：對於聚醯亞胺薄膜之表面，進行粗化處理，在 該粗化處理之表面，形成由鉬或矽等之所構成之中間層， 在其上面，形成金屬層。但是，即使是在該嘗試中，成爲 絕緣性薄膜之聚醯亞胺薄膜之表面係進行粗化處理，以致 於起因於該表面凹凸而不容易形成微細化之電路圖案。此 外，連動於該表面粗化之表面之表面粗糙度Ra而決定前 述中間層之厚度，因此，也假設中間層之厚度變得過薄而 無法發揮作爲中間層之效果之狀態。 另一方面，在日本特開2002 — 192646號公報，記載 有關在基材上具有氧化砍膜之氣體障蔽薄膜，但是，並無 顯示關於導電層之密合力提升，也並無顯示關於微細化之 電路圖案之形成。 此外，在日本特開平10— 192773號公報、日本特開 平11— 29645號公報、日本特開平η— 4055號公報、日 本特公平5— 88851號公報、日本特開2002-317046號公 報及日本特開2002 — 2 73 830號公報，記載有關於聚醯亞 胺薄膜等之基體薄片’但是，即使是在這些公報，也並無 顯示關於導電層之密合力提升，並且，也並無顯示關於微 細化之電路圖案之形成。 -5- 1240932 (3) 【發明內容】 Φ發明係有鑒於前述現狀而構成的；其目的係提供一 種能夠形成微細化之電路圖案並且提高成爲絕緣性薄膜之 $體薄片和導電層間之密合力而且改善基體薄片之吸濕性 而確保高度之尺寸穩定性同時也具有良好之高頻特性的導 電性薄片。 本發明人係在爲了解決前述課題而全心重複地進行硏 究時’得到在減少基體薄片之水分量時而提高和導電層間 之密合性之看法，此外，也得到如果藉由某種層而被覆基 體薄片的話、則能夠防止經時地吸濕之看法，在根據這些 看法而還重複地進行硏究時，終於以致於完成本發明。 也就是說，本發明之導電性薄片，其特徵爲：具有不 進行表面粗化處理之表面，並且，使得包含水分之揮發性 成分之含有率成爲1質量％以下之絕緣性薄膜，成爲基體 薄片，在該基體薄片表背至少某一邊之表面，形成含矽層 ，在該含矽層上，形成導電層。 可以藉由成爲此種構造而提高基體薄片和導電層間之 密合力，並且，絕緣性薄膜之表面係不進行粗化處理，因 此，不造成困難，能夠形成微細化之圖案。像這樣，在基 體薄片和導電層間而得到高度之密合力係認爲由於以下之 理由所造成的。也就是說，認爲在習知之導電性薄片而密 合力呈降低者係主要起因於包含在基體薄片之水分等之揮 發性成分之影響，認爲像這樣’於存在水分等之揮發性成 -6 - (4) 1240932 分時，助長構成導電層之金屬氧化而顯著地降低對於基體 薄片之密合力係成爲其原因。相對於此，本發明之前述構 造係更加強調這些要因；藉由選擇包含水分之揮發性成分 之含有率成爲1質量％以下之絕緣性薄膜，成爲基體薄片 ，並且，在基體薄片上，層積含矽層，而防止基體薄片經 時地吸濕。 此外，本發明之導電性薄片，其特徵爲：具有不進行 表面粗化處理之表面，並且，使得包含水分之揮發性成分 之含有率成爲1質量％以下之絕緣性薄膜，成爲基體薄片 ，在該基體薄片表背兩邊之表面，形成含矽層，在該某一 邊之含矽層上，形成導電層。 可以藉由成爲此種構造而更加防止基體薄片吸濕，同 時，能夠成爲導電性薄片整體而確保高度之尺寸穩定性， 並且，提高高頻特性。 此外，在本發明中，可以使得導電層，成爲在第1導 電層上形成第2導電層之層積構造，同時，也可以在含矽 層和導電層間，還形成中間金屬層。此外，本發明之導電 性薄片係也可以進行空孔、通孔或對準孔之其中某1個以 上之孔加工。 此外，在本發明中，所謂水分等之揮發性成分之含有 率成爲1質量％以下係根據在105 °c來對於基體薄片或導 電性薄片進行3 0分鐘加熱及乾燥之狀態下之其前後之質 量變化。 (5) 1240932 【實施方式】 <導電性薄片> 本發明之導電性薄片係正如前面敘述，具 薄膜作爲基體薄片而在該基體薄片上層積複數層 以下’就各個構造而進行說明。 <基體薄片> 本發明之基體薄片係藉由具有不進行表面粗 表面並且使得水分含有率成爲1質量％以下之絕 而構成。由於不進行表面粗化處理，因此，能夠 化之電路圖案，並且，藉由使得包含水分之揮發 含有率成爲1質量％以下而不論是否進行表面粗 來高度地提高絕緣性薄膜和導電層間之密合力。 此提到之所謂揮發性成分、其主要是水分，但是 個以外之成分係包含存在於絕緣性薄膜中之殘留 作爲此種絕緣性薄膜係可以列舉例如合成樹 熱塑性彈性體薄膜、橡膠薄膜等。作爲合成樹脂 以列舉例如由PET、PEN、丙烯、耐綸、聚乙烯 、氯乙烯、聚醯亞胺、液晶聚合物、環氧等之合 構成之薄膜。作爲熱塑性彈性體薄膜係可以列舉 乙烯系、氯乙烯系、烯烴系、胺基甲酸乙酯系、 胺系等之熱塑性彈性體所構成之薄膜。此外，作 膜係例如天然橡膠以外，還可以列舉丁二烯橡膠 烯橡膠、氯丁二烯橡膠、苯乙烯-丁二烯橡膠、 以絕緣性 之構造。 化處理之 緣性薄膜 形成微細 性成分之 化處理， 此外，在 ，作爲這 單體等。 脂薄膜、 薄膜係可 、聚丙烯 成樹脂所 例如由苯 酯系、醯 爲橡膠薄 、異戊二 腈橡膠、 -8 - 1240932 (6) 丁基橡膠、乙烯一丙烯橡膠、丙烯橡膠、胺基甲酸乙酯橡 膠、氟橡膠、矽酮等之合成橡膠所構成之薄膜。在此所列 舉之合成樹脂、熱塑性彈性體或橡膠之種類係究竟是例舉 而並非限定於此。在本發明中，可以配合其用途而選擇前 述合成樹脂、熱塑性彈性體或橡膠之種類。例如在要求耐 熱性之用途，作爲合成樹脂係最好是選擇聚醯亞胺或液晶 聚合物，在不要求耐熱性之狀態，適合考慮成本等而選擇 P ET等，此外，在要求彈性之用途，適合選擇熱塑性彈性 體或橡膠。此外，作爲目的係在此種絕緣性薄膜，提高強 度或賦予難燃效果等，例如可以添加玻璃纖維等之各種塡 充劑類。 另一方面’此種絕緣性薄膜係適合厚度成爲4〜200 //m、最好是10〜100//m。在厚度未滿4//m之狀態下， 作爲支持後面敘述之導電層之基體係不容易充分地發揮功 能，另一方面，在超過2 00 μ m之狀態下，僅在經濟上， 變成高價而成爲不利，或者是缺乏可彎曲性，不容易加工 成爲滾筒狀.之形狀。此外，該絕緣性薄膜之形狀係並無任 何限定，例如列舉連續狀者（滾筒狀者）或片狀用者（薄 片狀者）。此外，該絕緣性薄膜之表面粗糙度係適合採用 成爲Ra値之O.lnm〜5//m、最好是llnm〜2//m者。在 考慮對於電路圖案之微細化之對應時，如果Ra値變小的 話，則的確變得理想，但是，也有絕緣性薄膜本身之製造 成本變高之狀態發生，因此，必須考慮該方面而選擇Ra 値。另一方面，在Ra値變大時，由於該表面凹凸之關係 -9 - (7) 1240932 而不容易進行電路圖案之微細化，因此， 以下、最好是2 v m以下之R a値。但是 這樣所謂可以採用寬廣範圍之Ra値係本 ，起因於所謂根據藉由採用本發明之構造 降低而造成之尺寸穩定性之確保之方面。 此外，此種絕緣性薄膜係正如前面敘 含水分之揮發性成分之含有率成爲1質量 好是〇 . 5質量％以下、更加理想是〇. 1質 ，本發明所使用之絕緣性薄膜係最好是在 各層前，進行乾燥處理。作爲此種乾燥處 舉例如在加熱至 40〜200 °C、最好是 60 -真空狀態（1 X 1 0 ·3〜1 · 5 X 1 0 ·1 P a )而進行 理之方法。 <含矽層> 本發明之含矽層係層積及形成在前述 至少某一邊之表面或者是其兩面。此種含 薄片，具有有效地防止基體薄片吸濕之作 有賦予高頻特性之作用。此外，該含矽層 敘述之導電層藉由酸或鹼來進行蝕刻處理 時，也不會由於此種蝕刻所除去，殘留在 此，前述作用係並不會由於鈾刻處理而減 係最好是形成在基體薄片之表背兩面上。 面敘述之導電層等係不一定必須形成在該 適合採用5 β m ’不論怎樣，像 發明之1個特徵 所達成之吸濕性 述，必須使得包 %以下，適合最 量％以下。因此 形成後面敘述之 理方法係可以列 -180°C之溫度之 真空加熱乾燥處 基體薄片之表背 矽層係被覆基體 用，同時，也具 係即使是在後面 而形成電路圖案 基體薄片上，因 少。此種含矽層 在該狀態下，後 兩邊之面上，可 -10- (8) 1240932 以形成在其中某一邊之含矽層上。 此種含矽層係藉由非結晶質s i、結晶質S : 砂（SiO)或二氧化砂（si〇2)之其中某 1種或 而形成。作爲其形成方法係最好是藉由濺鍍法所 該狀態下，非結晶質S i係適合在—2 0 °C〜1 8 0 °C 進行’結晶質S i係適合在丨8 (TC以上之溫度而 一方面’含矽層之厚度係適合爲80A〜3#m 5 00A〜5 000 A。在該厚度未滿80A之狀態下， 前述蝕刻處理所除去或者是無法充分地發揮基體 濕防止效果之狀態產生，此外，在形成超過3 μ 彎曲導電性薄片之狀態下，產生裂縫，因此，皆 相 〇 <導電層> 本發明之導電層係層積及形成在前述含矽層 ，主要是藉由銅等之導電性金屬所構成，具有賦 至導電性薄片之作用。在本發明中，也可以成爲 之導電層，但是，最好是正如下面敘述，可以成 導電層上形成第2導電層之層積構造。 <第1導電層> 本發明之第1導電層係在形成前述含矽層之 面敘述之中間金屬層之狀態下，藉由在其表面上 金屬而形成。該第1導電層係具有導電特性’同 i、一氧化 2種以上 形成，在 之溫度而 進行。另 、最好是 會有由於 薄片之吸 m時，於 變得不理 上。通常 予導電性 單獨一層 爲在第1 表面或後 層積第1 時，具有 -11 - 1240932 (9) 作爲將後面敘述之第2導電層強力地保持在基體薄片上之 密合性輔助層之作用。作爲此種第1導電層之形成方法係 適合採用濺鍍法或蒸鍍法。接著，做爲該濺鍍之條件係適 合採用真空度1x10 4〜1.5xl0」Pa、最好是ΙχΙΟ-4〜1 χ l(T2Pa、電流 0.000 1 〜15A/ cm2、最好是 0.01 〜0.5A/ cm 、Ar氣體50〜400cc /分鐘、最好是 180〜250cc /分 鐘之條件。此外，做爲該蒸鍍之條件係適合採用真空度！ X 10·5 〜1.5xl(T2Pa、最好是 1 χ1〇·4 〜lx l(T3Pa、電流 0·0001〜15A/cm2、最好是0.001〜l〇A/cm2之條件。作 爲構成此種第1導電層之第1金屬係可以列舉銅、鎳、鋅 、金、銀、錫、鋁、鈦、鈷、鉻及包含這些金屬之至少1 種之合金。接著，特別最好是採用銅（Cu )。此外，作爲 第1導電層之厚度係適合爲500A〜2/im、最好是1000〜 3 000 A。由於在未滿5 00A之狀態下，並無充分地顯示作 爲前述密合性輔助層之作用，另一方面，即使是超過2 //m，也在前述作用效果，不產生大差異，相反地，在經 濟上，變得不利之緣故。 此外，在後面敘述之第2導電層之形成前，最好是在 第1導電層上，藉由利用〇 . 5〜5 0 %、最好是1〜1 0 %.濃 度之硫酸而進行0.1〜3分鐘、最好是〇·5〜1.5分鐘之酸 活化處理，以便於進行活化。可以藉由進行此種酸活化處 理而即使是在構成第1導電層之第1金屬來進行例如氧化 之狀態下（也就是說、即使是在第1金屬成爲Cu之狀態 本身進行氧化而變成氧化銅），也有效地還原或溶解除去 -12- 1240932 do) 這個，使得第2金屬呈高度密合性地形成在第 <第2導電層> 本發明之第2導電層係藉由第2金屬而形 1導電層上。該第1導電層係主要顯示作爲第 之密合性輔助層之作用，相對地，該第2導電 到賦予導電性之作用。因此，由保證導電性之 話，該第2導電層係必須形成更加厚於前述第 也就是說，此種第2導電層係適合藉由0.5〜 好是1〜35//m之厚度所形成。在厚度未滿0 態下，並無顯示充分之導電性，另一方面，即 過5 0 M m，也在導電性，並無大差異，相反地 ，變得不利。此外，此種第2導電層係適合藉 形成。作爲此種電鍍法係可以是無電解電鍍法 電氣電鍍法，也能夠皆採用；可以由於成爲目 選擇任意之方法。在此，作爲構成此種第2導 金屬係可以列舉銅、銀、金、鎳、鉻、鋅、鐵 包含這些金屬1種以上所構成之合金等。接著 是採用銅（Cu )。由於顯示極爲良好之導電性 外，，還由於在藉由銅（Cu )而形成第1導電層 在和這個之間，特別得到強力之密合性之緣故 電層藉由在第1導電層上使用此種銅（Cu)來 鍍而形成之狀態下，作爲電鍍浴係並無特別限 1導電層上 成在前述第 2導電層用 層係主要達 觀點來看的 1導電層。 50 // m、最 .5 // m 之狀 使是形成超 ，在經濟上 由電鍍法而 ，也可以是 的之厚度而 電層之第2 、鈀、錫或 ，特別最好 之緣故，此 之狀態下’ 。在第2導 進行電氣電 定，但是’ -13- 1240932 (11) 特別最好是使用硫酸銅電鍍浴。由於能夠 之應力之緣故。 <中間金屬層〉 本發明之中間金屬層係依照要求而形 上。此種中間金屬層係具有作爲在形成前 種電極之作用，特別是前述導電層係藉由 所構成，有用在僅藉由電鍍法而形成之狀 中間金屬層係也具有作爲防止形成於更加 之前述第1導電層或第2導電層發生氧化 作用。也就是說，前述含矽層係主要發揮 吸濕之作用，相對地，該中間金屬層係擔 導電層或第2導電層發生吸濕及氧化之功 包含在由絕緣性薄膜開始擴散至導電層方 係有效地被進行捕捉或遮蔽。具有此種氧 間金屬層係特別有效在導電層藉由容易氧 銅（C U )所構成之狀態下，在藉由這個以 之狀態下，根本不需要形成。 此種中間金屬層係正如前面敘述，形 面和（第1)導電層之間，厚度成爲20〜 50〜100A，並且，由鎳（Ni)、鈷（Co 鈦（Ti )、鉻（Cr )、這些金屬之氧化物 這些金屬至少1種之合金所構成之群組而 成，藉由潑鍍法或蒸鍍法之其中一種方法 容易調整電鑛膜 成在前述含矽層 述導電層時之1 第2導電層單獨 態下。此外，該 高於該層之上層 之氧化防止層之 防止絕緣性薄膜 任防止前述第1 能。藉此而使得 向之水分等之氧 化防止效果之中 化之鐵（Fe )或 外之金屬所構成 成在含矽層之表 1 0 0 0 A、最好是 )、鋅（Zn )、 、氮化物及包含 選出之1種來形 而形成1層或2 -14- (12) 1240932 層以上。在厚度未滿2 0 A之狀態下，無法顯示前 ，此外，在超過1 000A之狀態下，電路圖案之微 變得困難。此外，構成成分限定在前述金屬類係由 金屬顯示良好之導電性或氧化防止效果之緣故，並 於適合於藉由濺鍍法或蒸鍍法所形成之緣故。 例如在此種中間金屬層藉由濺鍍法所形成之狀 作爲其條件係適合採用真空度1 X 1 0·4〜1 . 5 X 1 (Γ 1 好是 lxl〇·4 〜1.5xl(T2Pa、電流 0.0001 〜15A/c 好是0.01〜0.5A/cm2、Ar氣體100〜400cc/分鐘 是100〜25 Occ/分鐘之條件。此外，在藉由蒸鍍 成之狀態下，作爲其條件係適合採用真空度1x10 lCT2Pa、最好是 lxl(T4〜lxlCT3Pa、電流 0.0001 〜 cm2、最好是0.001〜l〇A/cm2之條件。 此外，在此種中間金屬層上形成前述（第1 ) 之前，最好是對於該中間金屬層上，藉由利用〇·5 、最好是1〜10%濃度之硫酸而進行0.1〜3分鐘、 〇 · 5〜1 · 5分鐘之酸活化處理，以便於進行活化。可 進行此種酸活化處理而即使是在構成中間金屬層之 進行例如氧化之狀態下，也有效地還原或溶解除去 使得（第1 )導電層呈高度密合性地形成在中間金 <孔加工> 本發明之導電性薄片係可以進行空孔、通孔或 述作用 細化係 於這些 且，由 態下， P a、最 m2、最 、最好 法而形 •5 〜1 X Μ 5 A/ 導電層 〜50% 最好是 以藉由 金屬來 這個， 屬層上 對準孔 -15- 1240932 (13) 之其中某1個以上之孔加工。這些孔加工係可以藉由沖壓 、穿孔、C02雷射、釔鋁石榴石（YAG )雷射、準分子雷 射等而進行。通常作爲空孔係可以成爲直徑1 0〜3 0 0 β m 、最好是20〜1 50 " m。由於不容易形成未滿10 // m之空 孔，並且，在超過300//m時，不容易施加埋孔加工之緣 故。此外，作爲通孔係可以成爲1 0 0 // m〜3 m m、最好是 20〜800/im。由於在未滿 100/im，充分地作用在空孔， 並且，在超過3 mm時，佔有於導電性薄片整體之比例變 得過大之緣故。此外，作爲對準孔係可以成爲直徑5 0 # m 〜3mm、最好是 200//m〜1mm。由於在未滿 50//m，不 容易檢測對準孔，並且，在超過3 mm時，使得對準孔之 精度變差之緣故。 以下，列舉實施例而更加詳細地說明本發明，但是， 本發明係並非限定於這些。 <實施例1〉 本實施例係關於一種導電性薄片1 〇 0，正如第1圖所 示，形成在基體薄片101之某一邊表面形成含矽層102並 且在其上面層積第1導電層103a和第2導電層l〇3b所構 成之導電層1 〇3。 作爲構成基體薄片1 〇 1之絕緣性薄膜係在對於不進行 表面粗化處理之厚度之聚醯亞胺薄膜（商品名稱 :Apicar、鍾淵化學工業公司製；表面粗糙度Ra : 12nm )縫隙化成爲幅寬2 5 0 n m、長度3 0 n m後，捲繞在不銹鋼 -16- 1240932 (14) 製芯部上’裝設在濺鍍裝置之處理室內之送出軸，同時， 將其前端部’安裝在捲繞軸上。接著，在同樣濺鍍裝置之 第1標靶，安裝Si，在第2、第3、第4之各個標靶，安 裝Cu。然後，在藉由真空幫浦而使得室內成爲lxl(r2Pa 之真空狀態後，藉由加熱器而設定溫度在1 5 (TC，藉由分 別旋轉冷卻裝置所附帶之驅動轉筒、送出軸及捲繞軸，分 別往復地進行1次之正轉和逆轉而以0.3 m /分鐘之速度 ’來捲繞前述聚醯亞胺薄膜，以便於進行真空加熱乾燥， 來使得聚醯亞胺薄膜之包含水分之揮發性成分之含有率， 成爲1質量％以下。 接著，在停止藉由加熱器所造成之加熱後，僅啓動真 空幫浦而使得室內之真空度，更加提高至lx 1 0_3Pa爲止 。然後，在前述第1〜第4之各個標靶，分別以21 Occ/ 分鐘，來注入Ar氣體，在經過3分鐘後，分別旋轉冷卻 裝置所附帶之驅動轉筒、送出軸及捲繞軸而以l .〇m/分 鐘之速度，來進行捲繞，藉由分別在第1標靶，流動 0.02A/cm2之電流，在第2〜第4標靶，流動0.018A/ cm2之電流，而在基體薄片101上，形成由非結晶質Si所 構成之含矽層102，同時，分別在其上面’形成由Cu所 構成之第1導電層103a。採樣該基體薄片之一部分，在 藉由FIB裝置而對於其厚度來進行剖面測定時，含矽層 102之厚度係900A，第1導電層l〇3a之厚度係2100A。 然後，像這樣，由濺鍍裝置而取出形成含矽層102和 第1導電層l〇3a之基體薄片101，接著’安裝在連續電 -17- (15) 1240932 鍍裝置上。藉由在塡充3 %硫酸之3 0 °C之酸活化槽，以 1 .〇m/分鐘之移動速度，使得前述基體薄片連續地浸漬 3 〇秒鐘，而對於前述第1導電層1 〇 3 a，進行酸活化處理 。接著，在重複地進行3次之藉由純水所造成之水洗後， 藉由在前述裝置之電鍍浴，塡充電鍍液（由硫酸銅110g /1、硫酸 150 g/1、氯 55ppm 及 Toprutina 380H (商品 名稱、奧野製藥工業（股）公司製）lOcc/1所構成）， 以1.0m /分鐘之移動速度而連續地浸漬前述基體薄片， 在液溫29°C、電流密度4A/ dm2之條件下，進行1 1分鐘 之電氣電鍍，以便在前述第1導電層10 3a上，形成由Cu 所構成之第2導電層103b。接著，重複地進行5次之藉 由純水所造成之水洗，在進行藉由空氣所造成之除水後， 藉由在70 °C，進行2分鐘之熱風乾燥而得到第1圖所示 之本發明之導電性薄片1 〇〇。採樣該導電性薄片之一部分 ，在藉由FIB裝置而對於其厚度來進行剖面測定時，第2 導電層103b之厚度係10.3//m。 在使用剝離試驗機而測定像這樣所得到之導電性薄片 之層間密合力時，其剝離強度係1 . 4 5 k g / c m2。此外，在 同樣測定於相對溼度80% 、60 °C而保管1〇天後之層間密 合力時，其剝離強度係1.43kg/ cm2，在和前述數値間， 並無明確之差異產生，幾乎成爲包含在測定誤差範圍內之 程度。此外，在1 〇5 °C，對於該導電性薄片，進行30分 鐘之加熱乾燥，在藉由比較該乾燥前後之質量而測定絕緣 性薄膜之包含水分之揮發性成分之含有率時，其含有率係 -18- (16) 1240932 0.1質量％以下，在其乾燥前後之質量變化，並無明確之 差異產生，幾乎成爲包含在測定誤差範圍內之程度。 此種導電性薄片係能夠形成微細化之電路圖案，也具 有良好之尺寸穩定性，同時，具有良好之高頻特性。因此 ，可以依照要求，藉由施加形成空孔、通孔或對準孔之孔 加工而適合採用在成爲電氣製品、電子製品、半導體製品 、汽車等之所使用之各種基板或零件上。此外，前述孔加 工係可以對於層積各層前之基體薄片而進行，此外，也可 以對於層積各層後之導電性薄片而進行。 <實施例2 > 本實施例係關於一種導電性薄片200，正如第2圖所 示，形成在基體薄片201之表背兩面形成含矽層202並且 在其某一邊之含矽層202上層積第1導電層203a和第2 導電層203b所構成之導電層203。 作爲構成基體薄片20 1之絕緣性薄膜係在對於不進行 表面粗化處理之厚度5 0 // m之聚醯亞胺薄膜（商品名稱 :Apicar、鍾淵化學工業公司製；表面粗糙度Ra : 12nm )縫隙化成爲幅寬25 0nm、長度30nm後，捲繞在不銹鋼 製芯部上，裝設在濺鍍裝置之處理室內之送出軸，同時， 將其前端部，安裝在捲繞軸上。接著，在同樣濺鍍裝置之 第1標靶，安裝Si，在第2、第3、第4之各個標靶，安 裝Cii。然後，在藉由真空幫浦而使得室內成爲lxl.(T2Pa 之真空狀態後，藉由加熱器而設定溫度在150°C，藉由分 -19- (17) 1240932 別旋轉冷卻裝置所附帶之驅動轉筒、送出軸及捲繞軸’分 別往復地進行1次之正轉和逆轉而以〇 · 3 m /分鐘之速度 ，來捲繞前述聚醯亞胺薄膜，以便於進行真空加熱乾燥’ 來使得聚醯亞胺薄膜之包含水分之揮發性成分之含有率’ 成爲1質量％以下。 接著，在停止藉由加熱器所造成之加熱後，僅啓動真 空幫浦而使得室內之真空度，更加提高至lx 1 (T3Pa爲止 。然後，在前述第1〜第4之各個標靶，分別以210c c/ 分鐘，來注入Ar氣體，在經過3分鐘後，分別旋轉冷卻 裝置所附帶之驅動轉筒、送出軸及捲繞軸而以l.〇m/分 鐘之速度，來進行捲繞，藉由分別在第1標靶，流動 0.02A/cm2之電流，在第2〜第4標靶，流動0.018A/ cm2之電流，而在基體薄片201上，形成由非結晶質Si所 構成之含矽層202，同時，分別在其上面，形成由Cii所 構成之第1導電層2 03 a。採樣該基體薄片之一部分，在 藉由FIB裝置而對於其厚度來進行剖面測定時，含矽層 202之厚度係905A，第1導電層203a之厚度係2110A。 接著，重新安裝在同一濺鍍裝置上，以便於能夠處理 正如前面敘述所處理之基體薄片201之另外一邊之面。然 後’在第1標靶，安裝Si，在藉由真空幫浦而使得室內 成爲1 X l(T2Pa之真空狀態後，藉由加熱器而設定溫度在 1 5 0 °C，藉由分別旋轉冷卻裝置所附帶之驅動轉筒、送出 軸及捲繞軸，分別往復地進行1次之正轉和逆轉而以 0.3m/分鐘之速度，來捲繞前述基體薄片201，以便對於 -20- (18) 1240932 基體薄片20 1，來進行真空加熱乾燥。 接著，在停止藉由加熱器所造成之加熱後，僅啓動真 空幫浦而使得室內之真空度，更加提高至1x1 (T3pa爲止 。然後，在前述第1標靶，以210CC/分鐘，來注入 Ar 氣體，在經過3分鐘後，分別旋轉冷卻裝置所附帶之驅動 轉筒、送出軸及捲繞軸而以1·〇ηι /分鐘之速度，來進行 捲繞，藉由在第1標靶，流動〇.〇2 A / cm2之電流，而在 基體薄片201之另外一邊之表面上，形成由非結晶質Si 所構成之含矽層202。採樣該基體薄片之一部分，在藉由 FIB裝置而對於其厚度來進行剖面測定時，含矽層202之 厚度係910A。 然後，像這樣，由濺鍍裝置而取出形成各層之基體薄 片201，接著，安裝在連續電鍍裝置上。藉由在塡充3% 硫酸之3(TC之酸活化槽，以1.0m/分鐘之移動速度，使 得前述基體薄片連續地浸漬30秒鐘，而對於前述第1導 電層203 a，進行酸活化處理。接著，在重複地進行3次 之藉由純水所造成之水洗後，藉由在前述裝置之電鍍浴’ 塡充電鍍液（由硫酸銅ll〇g/l、硫酸150 g〆1、氯 55ppm及Toprutina 380H (商品名稱、奧野製藥工業（股 )公司製）lOcc/1所構成），以l.〇m/分鐘之移動速度 而連續地浸漬前述基體薄片，在液溫29 °C、電流密度4A / dm2之條件下，進行1 1分鐘之電氣電鍍’以便在前述 第1導電層203 a上，形成由Cii所構成之第2導電層 2 0 3 b。接著，重複地進行5次之藉由純水所造成之水洗’ -21 - (19) 1240932 在進行藉由空氣所造成之除水後，藉由在7 0 °C ，進行2 分鐘之熱風乾燥而得到第2圖所示之本發明之導電性薄片 2 〇 〇。採樣該導電性薄片之一部分，在藉由F I B裝置而對 於其厚度來進行剖面測定時，第2導電層2 0 3 b之厚度係 1 0 · 5 // m。 在使用剝離試驗機而測定像這樣所得到之導電性薄片 之層間密合力時，其剝離強度係1.46kg/ cm2。此外，在 同樣測定於相對溼度80% 、6〇t而保管10天後之層間密 合力時，其剝離強度係1.45kg/ cm2，在和前述數値間， 並無明確之差異產生，幾乎成爲包含在測定誤差範圍內之 程度。此外，在l〇5°C，對於該導電性薄片，進行30分 鐘之加熱乾燥，在藉由比較該乾燥前後之質量而測定絕緣 性薄膜之包含水分之揮發性成分之含有率時，其含有率係 〇 · 1質量％以下，在其乾燥前後之質量變化，並無明確之 差異產生，幾乎成爲包含在測定誤差範圍內之程度。 此種導電性薄片係能夠形成微細化之電路圖案，也具 有良好之尺寸穩定性，同時，具有良好之高頻特性。因此 ，可以依照要求，藉由施加形成空孔、通孔或對準孔之孔 加工而適合採用在成爲電氣製品、電子製品、半導體製品 、汽車等之所使用之各種基板或零件上。此外，前述孔加 工係可以對於層積各層前之基體薄片而進行’此外，也可 以對於層積各層後之導電性薄片而進行° <實施例3 > -22- (20) 1240932 本實施例係關於一種導電性薄片3 0 0，正如第3圖所 示’形成在基體薄片301之表背兩面形成含矽層302並且 在各個含矽層上層積第1導電層303a和第2導電層303b 所構成之導電層3 0 3。 作爲構成基體薄片3 0 1之絕緣性薄膜係在對於不進行 表面粗化處理之厚度25//m之聚醯亞胺薄膜（商品名稱 :Capton (聚醯亞胺）、東麗杜邦公司製；表面粗糙度 Ra: 1.9nm)縫隙化成爲幅寬2 5 0nm、長度30nm後，捲 繞在不銹鋼製芯部上，裝設在濺鍍裝置之處理室內之送出 軸，同時，將其前端部，安裝在捲繞軸上。接著，在同樣 濺鍍裝置之第1標靶，安裝Si，在第2、第3、第4之各 個標靶，安裝Cu。然後，在藉由真空幫浦而使得室內成 爲lxl(T2Pa之真空狀態後，藉由加熱器而設定溫度在 1 5 0 °C，藉由分別旋轉冷卻裝置所附帶之驅動轉筒、送出 軸及捲繞軸，分別往復地進行1次之正轉和逆轉而以 0.3m /分鐘之速度，來捲繞前述基體薄片301，以便於進 行真空加熱乾燥，來使得聚醯亞胺薄膜之包含水分之揮發 性成分之含有率，成爲1質量％以下。 接著，在停止藉由加熱器所造成之加熱後，僅啓動真 空幫浦而使得室內之真空度，更加提高至lxl (Γ3 Pa爲止 。然後，在前述第1〜第4之各個標靶，分別以21 Occ/ 分鐘，來注入Ar氣體，在經過3分鐘後，分別旋轉冷卻 裝置所附帶之驅動轉筒、送出軸及捲繞軸而以l.〇m /分 鐘之速度，來進行捲繞，藉由分別在第1標靶，流動 -23- (21) 1240932 0.0 1 5 A / c m 2之電流，在第2〜第4標靶，流動0.0 I 5 A / cm2之電流，而在基體薄片301上，形成由非結晶質Si所 構成之含矽層3 02，同時，分別在其上面，形成由CU所 構成之第1導電層3 0 3 a。採樣該基體薄片之一部分，在 藉由FIB裝置而對於其厚度來進行剖面測定時，含矽層 302之厚度係700A，第1導電層303a之厚度係1810A。 接著，重新安裝在同一濺鍍裝置上，以便於能夠處理 正如前面敘述所處理之基體薄片301之另外一邊之面。然 後，在第1標靶安裝Si而在第2、第3、第4之各個標靶 安裝Cu後，在藉由真空幫浦而使得室內成爲1x10 _2 Pa 之真空狀態後，藉由加熱器而設定溫度在1 5 0 °C，藉由分 別旋轉冷卻裝置所附帶之驅動轉筒、送出軸及捲繞軸，分 別往復地進行1次之正轉和逆轉而以1 ·〇ηι/分鐘之速度 ，來捲繞前述基體薄片3 01，以便對於基體薄片，來進行 真空加熱乾燥。 接著，在停止藉由加熱器所造成之加熱後，僅啓動真 空幫浦而使得室內之真空度，更加提高至1 X 1 〇·3 Pa爲止 。然後，在前述第1標靶，以210cc/分鐘，來注入 Ar 氣體，在經過3分鐘後，.分別旋轉冷卻裝置所附帶之.驅動 轉筒、送出軸及捲繞軸而以l.〇m /分鐘之速度，來進行 捲繞，藉由分別在第1標靶，流動0 · 0 1 5 A / c m2之電流， 在第2〜第4標IE，流動0.015A/cm2之電流，而分別在 基體薄片301之另外一邊之表面上，形成由非結晶質Si 所構成之含矽層3 0 2，同時，在其上面，形成由C u所構 -24- (22) 1240932 成之第1導電層3 03 a。採樣該基體薄片之一部分， 由FIB裝置而對於其厚度來進行剖面測定時，含矽層 之厚度係705A，第1導電層303a之厚度係1800A。 然後，像這樣，由濺鍍裝置而取出形成各層之基 片301，接著，安裝在連續電鍍裝置上。藉由在塡充 硫酸之30°C之酸活化槽，以1.0m/分鐘之移動速度 得前述基體薄片連續地浸漬3 0秒鐘，而對於前述兩 之第1導電層3 03 a，進行酸活化處理。接著，在重 進行3次之藉由純水所造成之水洗後，藉由在前述裝 電鍍浴，塡充電鍍液（由硫酸銅1 l〇g / 1、硫酸150 、氯55ppm及Toprutina 380H (商品名稱、奧野製藥 (股）公司製）10cc/l所構成），以1.0m/分鐘之 速度而連續地浸漬前述基體薄片，在液溫29t、電 度4A/ dm2之條件下，進行1 1分鐘之電氣電鍍，以 前述兩側面之第1導電層3 0 3 a上，分別形成由C u所 之第2導電層303b。接著，重複地進行5次之藉由 所造成之水洗，在進行藉由空氣所造成之除水後，藉 70 °C，進行2分鐘之熱風乾燥而得到第3圖所示之本 之導電性薄片3 00。採樣該導電性薄片之一部分，在 FIB裝置而對於其厚度來進行剖面測定時，兩側面之 導電層303b之厚度係分別成爲10.3/zm和10.4//m。 在使用剝離試驗機而測定像這樣所得到之導電性 之層間密合力時，就兩側面之各個而言，其剝離強度 別成爲1.35 kg / cm2和1.41kg / cm2。此外，在同樣 在藉 302 體薄 3°/〇 ，使 側面 複地 置之 g/ 1 工業 移動 流密 便在 構成 純水 由在 發明 藉由 第2 薄片 係分 測定 -25- 1240932 (23) 於相對溼度80% 、6 0°C而保管1〇天後之層間密合力時， 其剝離強度係分別成爲1.35 kg/cm2和l.34kg/cm2。此 外，在1 〇 5 °C，對於該導電性薄片’進行3 0分鐘之加熱 乾燥，在藉由比較該乾燥前後之質量而測定絕緣性薄膜之 包含水分之揮發性成分之含有率時，其含有率係〇. 1質量 %以下，在其乾燥前後之質量變化，並無明確之差異產生 ，幾乎成爲包含在測定誤差範圍內之程度。 此種導電性薄片係能夠形成微細化之電路圖案，也具 有良好之尺寸穩定性，同時，具有良好之高頻特性。因此 ，可以依照要求，藉由施加形成空孔、通孔或對準孔之孔 加工而適合採用在成爲電氣製品、電子製品、半導體製品 、汽車等之所使用之各種基板或零件上。此外，前述孔加 工係可以對於層積各層前之基體薄片而進行，此外，也可 以對於層積各層後之導電性薄片而進行。 <實施例4 > 本實施例係關於一種導電性薄片400，正如第4圖所 示，在基體薄片401之表背兩面，形成含矽層402，在其 某一邊之含矽層上，形成中間金屬層404，在該中間金屬 層上，形成導電層403。 作爲構成基體薄片40 1之絕緣性薄膜係在對於不進行 表面粗化處理之厚度25//m之聚醯亞胺薄膜（商品名稱 :Capton (聚醯亞胺）、東麗杜邦公司製；表面粗糙度 Ra: 1.9nm)縫隙化成爲幅寬250nm、長度30nm後，捲 -26- 1240932 (24) 繞在不銹鋼製芯部上，裝設在濺鍍裝置之處理室 軸’同時，將其前端部，安裝在捲繞軸上。接著 濺鍍裝置之第1標靶，安裝Si，在第2、第3、 個標靶，安裝Cu。然後，在藉由真空幫浦而使 爲1 X 1 (T2Pa之真空狀態後，藉由加熱器而設 1 5 0 °C，藉由分別旋轉冷卻裝置所附帶之驅動轉 軸及捲繞軸，分別往復地進行1次之正轉和 0.3m /分鐘之速度，來捲繞前述聚醒亞胺薄膜， 行真空加熱乾燥，來使得聚醯亞胺薄膜之包含水 性成分之含有率，成爲1質量％以下。1240932 (1) Description of the invention [Technical field to which the invention belongs] The present invention relates to a conductive sheet suitable for various substrates or parts used in electrical products, electronic products, semiconductor products, automobiles, and the like. [Prior art] Conventionally, conductive sheets used in electrical products, electronic products, semiconductor products, etc. are used to make rolled or electrolytic foils of various metals centered on copper as conductive layers, which are bonded to each other through an adhesive. It is used on an insulating film. In addition, the surface of the aforementioned foil is subjected to roughening treatment or a black treatment by a metal such as Ni, Ti, Cr, etc. without passing through the adhesive, and then on these conductive layers, It can be used by directly applying insulating resin or heat-fusion. On the other hand, it is also known that as a conductive layer, a metal such as copper is laminated on an insulating film using a vacuum technique such as sputtering or vapor deposition, or after the conductive layer is laminated, The electroplating method adds a conductive sheet having a thickness. However, in any of the conductive sheets, the adhesive force between the conductive layer and the insulating film is weak, and the adhesive strength (peel strength) cannot be satisfied. In addition, in order to improve the adhesion, it is attempted to roughen the surface of the insulating film instead of the conductive layer, or to insert Cr, Ni between the conductive layer and the insulating film by using it. And Ti metal layers to prevent oxidation of copper and other metals constituting the conductive layer in order to improve its adhesion, but by these methods -4- (2) 1240932 achieves a certain degree of adhesion improvement, No matter what kind of attempt is being made, the so-called cause of difficulty or other problems will also arise in forming a miniaturized circuit pattern. In addition, it is also proposed to improve the cohesion by combining the two technologies mentioned above. That is, in Japanese Unexamined Patent Publication No. 2001-277424, it is proposed that the surface of the polyimide film be roughened, and an intermediate layer composed of molybdenum or silicon be formed on the roughened surface. On it, a metal layer is formed. However, even in this attempt, the surface of the polyimide film used as the insulating film was roughened so that it was difficult to form a fine circuit pattern due to the unevenness of the surface. In addition, the thickness of the aforementioned intermediate layer is determined in conjunction with the surface roughness Ra of the roughened surface. Therefore, it is also assumed that the thickness of the intermediate layer becomes too thin to exert its effect as an intermediate layer. On the other hand, Japanese Patent Application Laid-Open No. 2002-192646 describes a gas barrier film having an oxide film on a substrate. However, it does not show improvement in adhesion of the conductive layer, nor does it show improvement in miniaturization. Formation of circuit patterns. In addition, in Japanese Patent Laid-Open No. 10-192773, Japanese Patent Laid-Open No. 11-29645, Japanese Patent Laid-Open No. η-4055, Japanese Patent Laid-Open No. 5-88851, Japanese Patent Laid-Open No. 2002-317046, and Japanese Patent No. Publication No. 2002-2 73 830 describes substrate sheets such as polyimide films. However, even in these publications, the adhesion strength of the conductive layer is not shown, and the fineness is not shown. Formation of a transformed circuit pattern. -5- 1240932 (3) [Summary of the invention] Φ The invention is constructed in view of the foregoing situation; its purpose is to provide a circuit pattern that can be miniaturized and improve the adhesion between the body sheet and the conductive layer that becomes an insulating film. Furthermore, it is a conductive sheet that improves the moisture absorption of the base sheet and ensures a high degree of dimensional stability while also having good high-frequency characteristics. In order to solve the aforementioned problems, the present inventors made an intensive and repetitive investigation to obtain the idea of improving the adhesion with the conductive layer when reducing the water content of the base sheet, and also obtained that if a certain layer is used, On the other hand, if the substrate sheet is coated, it is possible to prevent the moisture absorption over time, and when the research is repeated based on these opinions, the present invention has finally been completed. That is, the conductive sheet of the present invention is characterized in that it has a surface that is not subjected to surface roughening treatment, and an insulating film that has a content of volatile components containing moisture to 1% by mass or less, and is a base sheet. A silicon-containing layer is formed on the surface of at least one side of the front and back of the base sheet, and a conductive layer is formed on the silicon-containing layer. By adopting such a structure, the adhesion between the base sheet and the conductive layer can be improved, and the surface of the insulating film is not roughened. Therefore, it is possible to form a finer pattern without causing difficulties. As described above, it is considered that the high adhesion force between the base sheet and the conductive layer is caused by the following reasons. That is, it is thought that the decrease in the adhesion force in the conventional conductive sheet is mainly due to the influence of volatile components such as moisture contained in the base sheet, and it is considered that 'the presence of volatile components such as moisture in this way- 6-(4) 1240932 minutes, which promotes the oxidation of the metal constituting the conductive layer and significantly reduces the adhesion force to the base sheet is the reason. On the other hand, the aforementioned structure of the present invention emphasizes these factors more. By selecting an insulating film having a volatile component content of 1% by mass or less to form a base sheet, the base sheet is laminated on the base sheet. Contains a silicon layer to prevent the substrate sheet from absorbing moisture over time. In addition, the conductive sheet of the present invention is characterized in that it has a surface that is not subjected to surface roughening treatment, and an insulating film that has a content of volatile components containing moisture to be 1% by mass or less, and becomes a base sheet. A silicon-containing layer is formed on the surface of the substrate sheet on the front and back sides, and a conductive layer is formed on the silicon-containing layer on one side. With such a structure, it is possible to further prevent moisture absorption of the base sheet, and at the same time, it is possible to form the entire conductive sheet to ensure high dimensional stability and improve high-frequency characteristics. In addition, in the present invention, the conductive layer may have a laminated structure in which a second conductive layer is formed on the first conductive layer, and an intermediate metal layer may be formed between the silicon-containing layer and the conductive layer. In addition, the conductive sheet of the present invention may be processed with one or more holes, such as holes, through holes, or alignment holes. In addition, in the present invention, the content rate of volatile components such as moisture is 1% by mass or less is based on the state before and after heating and drying the base sheet or the conductive sheet for 30 minutes at 105 ° C. Quality change. (5) 1240932 [Embodiment] < Conductive sheet > As described above, the conductive sheet of the present invention has a film as a base sheet, and a plurality of layers are laminated on the base sheet. The following description is made of each structure. < Substrate sheet > The substrate sheet of the present invention is formed by having a rough surface without making the water content ratio 1% by mass or less. Since the surface roughening treatment is not performed, a circuit pattern can be formed, and the density between the insulating film and the conductive layer can be highly improved by making the volatile content rate containing water less than or equal to 1% by mass, regardless of whether or not the surface is roughened. Heli. The so-called volatile components mentioned here are mainly moisture, but other components include residues present in the insulating film. Examples of such insulating film systems include synthetic tree thermoplastic elastomer films and rubber films. Examples of the synthetic resin include films made of a combination of PET, PEN, acrylic, nylon, polyethylene, vinyl chloride, polyimide, liquid crystal polymer, and epoxy. Examples of the thermoplastic elastomer film system include films made of a thermoplastic elastomer such as ethylene-based, vinyl chloride-based, olefin-based, urethane-based, or amine-based. Examples of the film system include natural rubber, butadiene rubber, chloroprene rubber, styrene-butadiene rubber, and an insulating structure. The marginal film of chemical treatment forms chemical treatment of fine components, and it is also used as a monomer. Lipid film, film system, polypropylene resin, such as phenyl ester system, rubber is thin, isoprene nitrile rubber, -8-1240932 (6) butyl rubber, ethylene-propylene rubber, acrylic rubber, amine-based Film made of synthetic rubber such as ethyl formate rubber, fluorine rubber, and silicone. The types of synthetic resins, thermoplastic elastomers, or rubbers listed here are examples and are not limited thereto. In the present invention, the types of the aforementioned synthetic resin, thermoplastic elastomer, or rubber can be selected according to the application. For example, in applications where heat resistance is required, polyimide or liquid crystal polymer is the best choice for synthetic resin systems. In a state where heat resistance is not required, P ET and the like are suitable in consideration of cost, etc., and in applications where elasticity is required. Suitable for choosing thermoplastic elastomer or rubber. In addition, the purpose is to increase the strength of the insulating film and provide a flame retardant effect. For example, various fillers such as glass fiber can be added. On the other hand, such an insulating film is suitable for a thickness of 4 to 200 // m, preferably 10 to 100 // m. In a state where the thickness is less than 4 // m, it is not easy to fully function as a base system for supporting a conductive layer described later. On the other hand, in a state exceeding 200 μm, it becomes economically expensive. It is disadvantageous, or lacks flexibility, and is not easy to be processed into a roll-like shape. In addition, the shape of the insulating film is not limited in any way, and examples thereof include a continuous one (roller-shaped) or a sheet-shaped user (thin-shaped). The surface roughness of the insulating film is preferably 0.1 to 5 // m, preferably 11 to 2 // m. When considering the correspondence to the miniaturization of circuit patterns, it is indeed ideal if Ra 値 becomes smaller. However, there are also cases where the manufacturing cost of the insulating film itself becomes high. Therefore, Ra must be selected in consideration of this aspect value. On the other hand, when Ra 値 becomes large, it is not easy to miniaturize the circuit pattern due to the relationship between the surface irregularities. Therefore, it is preferable that R a 値 below is 2 v m or less. However, it can be said that a wide range of Ra series can be used, which is due to the aspect of ensuring the dimensional stability based on the reduction in the structure of the present invention. In addition, such an insulating thin film is as described above. The content of the volatile component of the water content is 1 mass, preferably 0.5 mass% or less, and more preferably 0.1 mass. The insulating thin film used in the present invention is the most Fortunately, before each layer, a drying process is performed. Such a dry place is, for example, a method of heating to 40 to 200 ° C, preferably 60-vacuum state (1 X 1 0 · 3 to 1 · 5 X 1 0 · 1 P a). < Silicon-containing layer > The silicon-containing layer of the present invention is laminated and formed on at least one of the aforementioned surfaces or both surfaces. Such a sheet-containing sheet has the effect of effectively preventing the base sheet from absorbing moisture and imparting high-frequency characteristics. In addition, when the conductive layer described by the silicon-containing layer is etched by acid or alkali, it will not be removed due to such etching, and it remains here. It is best that the aforementioned action system is not reduced by uranium etching. It is formed on the front and back surfaces of the base sheet. The conductive layer and the like described above do not necessarily have to be formed in such a manner that 5 β m ′ is suitable. In any case, the hygroscopic property achieved by one feature of the invention must be less than or equal to the package%, and the optimum amount or less. Therefore, the method described below can be used to coat the substrate on the front and back silicon layers of the substrate sheet under vacuum heating and drying at a temperature of -180 ° C. At the same time, it can also be used to form circuit pattern substrate sheets on the back. Because less. In this state, such a silicon-containing layer may be formed on the silicon-containing layer on one of the sides -10- (8) 1240932. Such a silicon-containing layer is formed by one of an amorphous si, a crystalline S: sand (SiO) or a sand dioxide (si02). As the formation method, it is preferable that the amorphous Si is suitable for the state of -20 ° C ~ 180 ° C under the condition of sputtering. Above the temperature, on the one hand, the thickness of the silicon-containing layer is suitable to be 80A to 3 # m 5 00A to 5,000 A. In the state where the thickness is less than 80A, the substrate is removed by the aforementioned etching process or the substrate is not fully wet. The effect is prevented, and cracks are generated in the state where the conductive thin sheet is bent more than 3 μ, so they are all similar. < Conductive layer > The conductive layer of the present invention is laminated and formed on the aforementioned silicon-containing layer, and is mainly composed of a conductive metal such as copper, and has a function of imparting a conductive sheet. In the present invention, it may be a conductive layer. However, as described below, it is preferable to have a laminated structure in which a second conductive layer is formed on the conductive layer. < First conductive layer > The first conductive layer of the present invention is formed by forming a metal on the surface in a state where the intermediate metal layer described in the aforementioned silicon-containing layer is formed. The first conductive layer is formed of two or more kinds of oxides having the same conductive characteristics as i, and is formed at a temperature of. In addition, it is best to ignore the sheet due to the suction of the sheet. Usually, a single layer of pre-conductivity is -11-1240932 (9) when the first layer is laminated on the first surface or back. (9) It is an adhesive auxiliary layer that strongly holds the second conductive layer described later on the substrate sheet. effect. A method for forming such a first conductive layer is preferably a sputtering method or a vapor deposition method. Next, as the conditions for the sputtering, a vacuum degree of 1x10 4 to 1.5xl0 "Pa, preferably ΙχΙΟ-4 to 1 χ l (T2Pa, current 0.000 1 to 15A / cm2, and preferably 0.01 to 0.5A) is suitable. / cm, Ar gas 50 ~ 400cc / minute, preferably 180 ~ 250cc / minute. In addition, the vacuum conditions are suitable for the vacuum! X 10 · 5 ~ 1.5xl (T2Pa, preferably 1 χ10.4 · l ~ lxl (T3Pa, current 0 · 0001 ~ 15A / cm2, preferably 0.001 ~ 10A / cm2. Conditions for the first metal system constituting the first conductive layer include copper, Nickel, zinc, gold, silver, tin, aluminum, titanium, cobalt, chromium, and alloys containing at least one of these metals. Next, copper (Cu) is particularly preferred. In addition, the thickness of the first conductive layer is based on It is suitable for 500 A to 2 / im, and preferably 1000 to 3 000 A. Since the effect as the aforementioned adhesion auxiliary layer is not sufficiently displayed in a state of less than 500 A, on the other hand, even if it exceeds 2 // m, also in the aforementioned effect, does not produce a large difference, on the contrary, it becomes economically disadvantageous. In addition, it will be described later 2 Before the formation of the conductive layer, it is preferable to perform the method on the first conductive layer by using sulfuric acid at a concentration of 0.5 to 50%, preferably 1 to 10%, for 0.1 to 3 minutes, preferably 0.5 to 1.5 minutes of acid activation treatment to facilitate activation. This acid activation treatment can be performed even when the first metal constituting the first conductive layer is oxidized (that is, Even when the first metal becomes Cu in the state where it is oxidized to become copper oxide), it is effectively reduced or dissolved to remove -12-1240932 do) This makes the second metal form a highly adhesive < Second conductive layer > The second conductive layer of the present invention is formed on the first conductive layer by the second metal. The first conductive layer mainly functions as a first adhesion auxiliary layer, and relatively, the second conductive layer functions to impart conductivity. Therefore, in order to ensure the conductivity, the second conductive layer must be formed thicker than the first. In other words, this second conductive layer is suitable for a thickness of 0.5 to preferably 1 to 35 // m. form. In the state where the thickness is less than 0, it does not show sufficient conductivity. On the other hand, even if it is over 50 M m, there is no large difference in conductivity. On the contrary, it becomes unfavorable. The second conductive layer is suitable for formation. As such a plating method, electroless plating or electric plating can be used; any method can be selected as the purpose. Here, examples of such a second conductive metal system include copper, silver, gold, nickel, chromium, zinc, iron, and alloys including one or more of these metals. This is followed by copper (Cu). In addition to showing extremely good conductivity, the first conductive layer is formed by copper (Cu), and a strong adhesion is obtained between the first conductive layer and this, so that the electric layer is formed on the first conductive layer. In the state formed by plating using such copper (Cu), the electroplating bath system is not particularly limited to the one conductive layer formed on the second conductive layer layer, which is mainly a conductive layer from a viewpoint. 50 // m, the most .5 // m is the formation of super, economically by electroplating, but also the thickness of the second layer, palladium, tin or, especially for the sake of the electric layer, In this state '. Electricity is performed in the second lead, but it is particularly preferable to use a copper sulfate plating bath. Due to the stress of being able. < Intermediate metal layer > The intermediate metal layer of the present invention is shaped as required. Such an intermediate metal layer has the function of forming an electrode of the former type. In particular, the aforementioned conductive layer is composed, and it is useful to form the intermediate metal layer only by a plating method. The first conductive layer or the second conductive layer is oxidized. In other words, the aforementioned silicon-containing layer mainly functions to absorb moisture. On the other hand, the intermediate metal layer is responsible for the moisture absorption and oxidation of the conductive layer or the second conductive layer, and the diffusion from the insulating film to the conductive layer is included. The squares are effectively captured or hidden. Having such an inter-oxygen metal layer is particularly effective in a state where the conductive layer is made of easily oxidized copper (CU), and in this state, there is no need to form it at all. As described above, this intermediate metal layer has a thickness between 20 to 50 to 100 A between the surface and the (first) conductive layer, and is made of nickel (Ni), cobalt (Co, titanium (Ti), chromium (Cr)). The oxides of these metals are formed by a group consisting of alloys of at least one of these metals. It is easy to adjust the electric ore film to the conductive layer of the aforementioned silicon-containing layer by one of the sputtering method and the evaporation method. 1 The second conductive layer is in a single state. In addition, the oxidation-preventive insulating film that is higher than the oxidation-preventive layer above the layer can prevent the aforementioned first function. This can neutralize the oxidation prevention effect of moisture and the like. Iron (Fe) or other metals are formed on the silicon-containing layer in the table 1 0 0 0 A, preferably), zinc (Zn), nitride, and a selected one to form a layer or 2 -14- (12) 1240932 and above. In the state where the thickness is less than 20 A, the front cannot be displayed. In addition, in the state where the thickness exceeds 1 000 A, it becomes difficult to make the circuit pattern small. In addition, the constituent components are limited to those in which the aforementioned metals are excellent in electrical conductivity or oxidation prevention effect, and are suitable for formation by a sputtering method or a vapor deposition method. For example, it is suitable to use a vacuum degree of 1 X 1 0 · 4 ~ 1. 5 X 1 (Γ 1 is preferably 1 × 10 · 4 to 1.5 × 1 (T2Pa) as a condition for forming the intermediate metal layer by a sputtering method. The current is 0.0001 to 15 A / c, preferably 0.01 to 0.5 A / cm2, and the Ar gas 100 to 400 cc / minute is 100 to 25 Occ / minute. In addition, the conditions are suitable in the state formed by evaporation. The vacuum conditions are 1x10 lCT2Pa, preferably lxl (T4 ~ lxlCT3Pa, current 0.0001 ~ cm2, preferably 0.001 ~ 10A / cm2. In addition, before forming the aforementioned (first) on the intermediate metal layer, It is preferable to perform acid activation treatment on the intermediate metal layer for 0.1 to 3 minutes and 0.5 to 1.5 minutes by using sulfuric acid with a concentration of 0.5, preferably 1 to 10%. Activation. This type of acid activation treatment can be performed to effectively reduce or dissolve and remove (1) the conductive layer into the intermediate gold with high adhesion even in the state where the intermediate metal layer is subjected to, for example, oxidation. < Hole processing > The conductive sheet system of the present invention can be made into holes, through holes, or the above-mentioned thinning effect. In the state, P a, the most m2, the most, and the best method are shaped. 5 ~ 1 X Μ 5 A / conducting layer ~ 50% It is best to process this with a metal, one or more of the aligning holes -15-1240932 (13) on the metal layer. These hole processing can be performed by punching, perforating, C02 laser, yttrium aluminum garnet (YAG) laser, excimer laser, and the like. Generally, the hole system can have a diameter of 10 to 3 0 β m, preferably 20 to 1 50 " m. It is not easy to form voids less than 10 // m, and when it exceeds 300 // m, it is not easy to apply buried holes. In addition, the through-hole system may be 1 0 0 // m to 3 m m, preferably 20 to 800 / im. It is because the voids are fully acted below 100 / im, and when it exceeds 3 mm, the proportion of the entire conductive sheet becomes too large. In addition, as the alignment hole system, the diameter can be 50 # m to 3 mm, preferably 200 // m to 1 mm. It is difficult to detect the alignment hole when it is less than 50 // m, and when it exceeds 3 mm, the accuracy of the alignment hole is deteriorated. Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these. < Example 1> This example relates to a conductive sheet 100. As shown in FIG. 1, a silicon-containing layer 102 is formed on a surface of one side of the base sheet 101, and a first conductive layer is laminated thereon. A conductive layer 103 composed of 103a and a second conductive layer 103b. The insulating film constituting the base sheet 100 is formed by slitting a polyimide film (trade name: Apicar, manufactured by Zhongyuan Chemical Industry Co., Ltd .; surface roughness Ra: 12 nm) with a thickness not subjected to surface roughening treatment. After it has a width of 250 nm and a length of 30 nm, it is wound around a stainless steel -16-1240932 (14) core to be a 'sending shaft installed in the processing chamber of a sputtering device, and its front end' Installed on the winding shaft. Next, Si was mounted on the first target of the same sputtering apparatus, and Cu was mounted on each of the second, third, and fourth targets. Then, after making the room into a vacuum state of lxl (r2Pa by vacuum pump), set the temperature at 15 (TC) by the heater, and rotate the drive drum, the delivery shaft, and the coil attached to the cooling device. Around the shaft, the forward and reverse rotations are performed once and back, respectively, and the aforementioned polyimide film is wound at a speed of 0.3 m / min, so as to facilitate vacuum heating and drying, so that the polyimide film contains moisture. The content of volatile components is 1% by mass or less. Then, after heating by the heater is stopped, only the vacuum pump is started to increase the degree of vacuum in the room to lx 1 0_3Pa. Then, For each of the first to fourth targets, the Ar gas was injected at 21 Occ / minute, and after 3 minutes, the driving drum, the sending shaft, and the winding shaft attached to the cooling device were rotated to l 〇m / minute speed to wind, by flowing a current of 0.02A / cm2 on the first target, a current of 0.018A / cm2 on the second to fourth targets, and On the sheet 101, amorphous Si is formed. The silicon-containing layer 102 is formed, and at the same time, first conductive layers 103a made of Cu are formed thereon. When a part of the base sheet is sampled and the thickness is measured by a FIB device, the silicon-containing layer 102 is formed. The thickness of the layer 102 is 900A, and the thickness of the first conductive layer 103a is 2100A. Then, the substrate sheet 101 containing the silicon-containing layer 102 and the first conductive layer 103a is taken out by a sputtering device like this, and then ' Installed on a continuous electric -17- (15) 1240932 plating device. By activating the acid activation tank filled with 3% sulfuric acid at 30 ° C, the aforementioned substrate sheet is continuously moved at a speed of 1.0 m / min. After immersion for 30 seconds, the first conductive layer 103a was subjected to an acid activation treatment. Then, three times of water washing with pure water were repeatedly performed, and then the plating bath in the aforementioned device was used.塡 Rechargeable plating solution (consisting of 110g / 1 of copper sulfate, 150g / 1 of sulfuric acid, 55ppm of chlorine, and Toprutina 380H (trade name, manufactured by Okuno Pharmaceutical Industry Co., Ltd.) lOcc / 1), 1.0m / min. The substrate sheet was continuously immersed at a moving speed at a liquid temperature of 29 C. Under the condition of a current density of 4A / dm2, electroplating is performed for 11 minutes to form a second conductive layer 103b made of Cu on the first conductive layer 103a. Then, it is repeated 5 times. The conductive sheet 1 of the present invention shown in FIG. 1 was obtained by washing with pure water and drying with hot air at 70 ° C for 2 minutes after dewatering with air. 〇. When a part of the conductive sheet was sampled and the thickness was measured by a FIB device, the thickness of the second conductive layer 103b was 10.3 // m. When the interlayer adhesion force of the conductive sheet obtained in this manner was measured using a peel tester, the peel strength was 1. 4 5 g / cm2. In addition, when the interlayer adhesion force was measured at 80% relative humidity and 60 ° C for 10 days, the peel strength was 1.43 kg / cm2, and there was no clear difference between the above-mentioned values. It is included in the measurement error range. In addition, the conductive sheet was heated and dried at 105 ° C for 30 minutes. When the content of the volatile component containing moisture of the insulating film was measured by comparing the mass before and after the drying, its content The rate is -18- (16) 1240932 0.1 mass% or less. There is no clear difference in the mass change before and after drying, and it is almost included in the measurement error range. This conductive sheet is capable of forming fine circuit patterns, has good dimensional stability, and has good high-frequency characteristics. Therefore, it can be applied to various substrates or parts used as electrical products, electronic products, semiconductor products, automobiles, etc. by applying hole processing to form voids, through holes or alignment holes according to requirements. In addition, the aforementioned hole processing may be performed on the base sheet before the layers are laminated, or may be performed on the conductive sheet after the layers are laminated. < Embodiment 2 > This embodiment relates to a conductive sheet 200. As shown in FIG. 2, a silicon-containing layer 202 is formed on both front and back surfaces of a base sheet 201, and a silicon-containing layer 202 is formed on one side of the substrate. A conductive layer 203 including a first conductive layer 203a and a second conductive layer 203b. The insulating film constituting the base sheet 20 1 is a polyimide film having a thickness of 5 0 // m without surface roughening treatment (trade name: Apicar, manufactured by Zhongyuan Chemical Industry Co., Ltd .; surface roughness Ra: 12nm) after slitting to a width of 250nm and a length of 30nm, it is wound on a stainless steel core and installed in a sending shaft of a processing chamber of a sputtering device. At the same time, its front end is mounted on a winding shaft. Next, Si was mounted on the first target of the same sputtering device, and Cii was mounted on each of the second, third, and fourth targets. Then, after making the room 1xl. (T2Pa vacuum state by vacuum pump), set the temperature to 150 ° C by the heater, and divide it with -19- (17) 1240932. Drive the drum, the delivery shaft and the winding shaft 'reciprocally forward and reverse once, respectively, and wind the aforementioned polyimide film at a speed of 0.3 m / min to facilitate vacuum heating and drying' In order to make the content of the volatile component containing water of the polyimide film 'below 1% by mass. Next, after stopping the heating by the heater, only start the vacuum pump to make the vacuum in the room, It is further increased to lx 1 (T3Pa.) Then, each of the first to fourth targets is injected with Ar gas at 210c c / min, and after 3 minutes, the drive rotation of the cooling device attached to the target is rotated. The tube, the delivery shaft, and the winding shaft are wound at a speed of 1.0 m / min. By flowing a current of 0.02 A / cm2 on the first target, and on the second to fourth targets, A current of 0.018 A / cm2 flows, and on the substrate sheet 201, the shape A silicon-containing layer 202 made of amorphous Si was formed, and at the same time, a first conductive layer 2 03 a made of Cii was formed on each of them. A part of the base sheet was sampled, and a FIB device was applied to the When measuring the thickness, the thickness of the silicon-containing layer 202 is 905A, and the thickness of the first conductive layer 203a is 2110A. Then, it is remounted on the same sputtering device so that the substrate sheet 201 processed as described above can be processed. The other side. Then, 'Si is installed on the first target, and the room is set to a vacuum state of 1 X l (T2Pa by vacuum pumping), and the temperature is set to 150 ° C by a heater. The above-mentioned substrate sheet 201 is wound at a speed of 0.3 m / min by rotating the driving drum, the sending shaft and the winding shaft attached to the cooling device, respectively, to perform a forward rotation and a reverse rotation at a speed of 0.3 m / min. For -20- (18) 1240932 substrate sheet 20 1, vacuum heating and drying are performed. Then, after stopping the heating by the heater, only the vacuum pump is started to increase the vacuum in the room to 1x1 ( Up to T3pa Then, the Ar target gas was injected at 210 CC / minute into the first target, and after 3 minutes, the driving drum, the delivery shaft, and the winding shaft attached to the cooling device were rotated to 1 · 〇ηι / Winding is performed at a speed of one minute, and a current of 0.02 A / cm2 flows through the first target, and on the other surface of the substrate sheet 201, a layer of amorphous Si is formed. Silicon layer 202. The thickness of the silicon-containing layer 202 is 910A when a part of the base sheet is sampled and the thickness is measured by a FIB device. Then, the base sheet 201 forming each layer is taken out by a sputtering apparatus, and is then mounted on a continuous plating apparatus. A 3% TC acid activation tank filled with 3% sulfuric acid was used to continuously immerse the substrate sheet for 30 seconds at a moving speed of 1.0m / minute, and the first conductive layer 203a was subjected to acid activation. Then, after three times of washing with pure water, the plating solution was charged in a plating bath of the aforementioned apparatus (from copper sulfate 110 g / l, sulfuric acid 150 g, 1, 55ppm of chlorine and Toprutina 380H (commercial name, manufactured by Okuno Pharmaceutical Co., Ltd.) 10cc / 1), the substrate sheet was continuously immersed at a moving speed of 1.0m / min, and the liquid temperature was 29 ° C, Under the condition of a current density of 4A / dm2, electrical plating was performed for 11 minutes to form a second conductive layer 2 0 3 b made of Cii on the first conductive layer 203 a. Then, it was repeated 5 times. Water washing by pure water '-21-(19) 1240932 After dewatering by air, dry by hot air at 70 ° C for 2 minutes to obtain the figure 2 The conductive sheet of the present invention is 200. A part of the conductive sheet is sampled, When the thickness of the IB device is used for cross-section measurement, the thickness of the second conductive layer 2 0 3 b is 1 0 · 5 // m. The interlayer adhesion force of the conductive sheet thus obtained is measured using a peel tester. At this time, the peel strength was 1.46 kg / cm2. In addition, when the interlayer adhesion force was similarly measured after storage at 80% relative humidity and 60 t for 10 days, the peel strength was 1.45 kg / cm2. There was no clear difference between them, and it was almost included in the measurement error range. In addition, the conductive sheet was heated and dried at 105 ° C for 30 minutes. When measuring the content of volatile components containing moisture in insulating films based on quality, the content rate is less than or equal to 0.1% by mass. There is no clear difference in the quality change before and after drying, and it is almost included in the measurement error. The range is within the range. This kind of conductive sheet can form a fine circuit pattern, has good dimensional stability, and has good high frequency characteristics. Therefore, according to requirements, It is suitable to be applied to various substrates or parts used for electrical products, electronic products, semiconductor products, automobiles, etc. by applying hole processing for forming holes, through holes or alignment holes. In addition, the aforementioned hole processing can be applied to layers. The lamination of the base sheet before each layer is performed. In addition, the lamination can also be performed for the conductive sheet after each layer. < Embodiment 3 > -22- (20) 1240932 This embodiment relates to a conductive sheet 3 0 0. As shown in FIG. 3, 'a silicon-containing layer 302 is formed on both the front and back surfaces of the base sheet 301, and A conductive layer 303 composed of a first conductive layer 303a and a second conductive layer 303b is laminated on each silicon-containing layer. The insulating film constituting the base sheet 3 01 is a polyimide film (trade name: Capton (polyimide), manufactured by Toray DuPont) with a thickness of 25 // m without surface roughening treatment; Surface roughness Ra: 1.9nm) After slitting to a width of 250nm and a length of 30nm, it is wound around a stainless steel core and installed in the feed shaft of the processing chamber of a sputtering device. Installed on the winding shaft. Next, Si was mounted on the first target of the same sputtering apparatus, and Cu was mounted on each of the second, third, and fourth targets. Then, after the room was brought into a vacuum state of lxl (T2Pa by vacuum pumping), the temperature was set to 150 ° C by a heater, and the driving drum, the sending shaft and the The winding shaft is reciprocated forward and backward once, and the substrate sheet 301 is wound at a speed of 0.3m / min, so as to facilitate vacuum heating and drying, so that the polyimide film contains moisture. The content of volatile components is 1% by mass or less. Then, after heating by the heater is stopped, only the vacuum pump is started to increase the degree of vacuum in the room to lxl (Γ3 Pa. Then, For each of the first to fourth targets, the Ar gas was injected at 21 Occ / minute, and after 3 minutes, the driving drum, the sending shaft, and the winding shaft attached to the cooling device were rotated to l At a speed of .0 m / min, winding is performed, and a current of -23- (21) 1240932 0.0 1 5 A / cm 2 flows through the first target, and flows through the second through fourth targets, respectively. 0.0 I 5 A / cm2 while the substrate sheet 301 A silicon-containing layer 302 made of amorphous Si was formed, and at the same time, a first conductive layer 3 0 3 a made of CU was formed on each of them. A part of the substrate sheet was sampled, and the FIB device was used. When measuring the thickness, the thickness of the silicon-containing layer 302 is 700A, and the thickness of the first conductive layer 303a is 1810A. Then, reinstall it on the same sputtering device so that it can be processed as described above. The other side of the substrate sheet 301. Then, Si is installed on the first target, and Cu is installed on each of the second, third, and fourth targets, and the room is set to 1x10 _2 Pa by vacuum pumping. After the vacuum state, the temperature is set to 150 ° C by the heater, and the driving drum, the sending shaft and the winding shaft attached to the cooling device are rotated respectively, and the forward rotation and the reverse rotation are performed back and forth once. The substrate sheet 3 01 was wound at a speed of 1 · ηι / minute, so that the substrate sheet was vacuum-heated and dried. Then, after the heating by the heater was stopped, only the vacuum pump was started and Make indoor The airspace is further increased to 1 X 1 0.3 Pa. Then, the Ar target gas is injected at 210 cc / min on the first target, and after 3 minutes, the drive provided with the rotary cooling device is driven separately. The drum, the delivery shaft, and the winding shaft are wound at a speed of 1.0 m / min, and a current of 0 · 0 1 5 A / c m2 flows through the first target, respectively, at the second target. ~ No. 4 IE, a current of 0.015 A / cm2 flows, and a silicon-containing layer 3 2 of amorphous silicon is formed on the other surface of the substrate sheet 301, and at the same time, on the surface, The first conductive layer 3 03 a made of -24-24 (22) 1240932 made of Cu. When a part of the base sheet was sampled and the thickness was measured by a FIB device, the thickness of the silicon-containing layer was 705A, and the thickness of the first conductive layer 303a was 1800A. Then, the substrate 301 for forming each layer is taken out by the sputtering apparatus, and then mounted on the continuous plating apparatus. By immersing in an acid-activated tank at 30 ° C filled with sulfuric acid, the aforementioned substrate sheet was continuously immersed for 30 seconds at a moving speed of 1.0 m / minute, and the first conductive layer 3 03 a of the two was subjected to acidification. Activation treatment. Next, after three times of washing with pure water, the plating bath was charged with a plating bath (from copper sulfate 10 g / 1, sulfuric acid 150, chlorine 55 ppm, and Toprutina 380H ( Product name, made by Okuno Pharmaceutical Co., Ltd.) (consisting of 10cc / l), continuously immersing the aforementioned base sheet at a speed of 1.0m / min, and performing 1 1 under the conditions of a liquid temperature of 29t and a power of 4A / dm2 In the electroless plating of the minute, a second conductive layer 303b made of Cu is formed on the first conductive layer 3 0 3 a on both sides. Next, the washing with water was repeated 5 times. After removing the water with air, it was dried at 70 ° C for 2 minutes with hot air to obtain the conductivity shown in Figure 3. Sheet 3 00. When a part of the conductive sheet was sampled and the thickness was measured in a FIB apparatus, the thickness of the conductive layer 303b on both sides was 10.3 / zm and 10.4 // m, respectively. When the interlayer adhesion force of the electrical conductivity thus obtained was measured using a peel tester, the peel strength of each of the two sides was 1.35 kg / cm2 and 1.41 kg / cm2. In addition, in the same way, by borrowing 302 body thin 3 ° / 〇, the g / 1 industrial mobile fluid density placed on the side is composed of pure water. In the invention, it is determined by the second sheet system. -25-1240932 (23) When the interlayer adhesion force was kept at 80% relative humidity and 60 ° C for 10 days, the peel strengths were 1.35 kg / cm2 and 1.34 kg / cm2, respectively. In addition, the conductive sheet was heated and dried at 105 ° C for 30 minutes. When the content of the volatile component containing moisture of the insulating film was measured by comparing the mass before and after the drying, the The content rate is 0.1% by mass or less. There is no clear difference between the mass change before and after drying, and it is almost included in the measurement error range. This conductive sheet is capable of forming fine circuit patterns, has good dimensional stability, and has good high-frequency characteristics. Therefore, it can be applied to various substrates or parts used as electrical products, electronic products, semiconductor products, automobiles, etc. by applying hole processing to form voids, through holes or alignment holes according to requirements. In addition, the aforementioned hole processing may be performed on the base sheet before the layers are laminated, or may be performed on the conductive sheet after the layers are laminated. < Embodiment 4 > This embodiment relates to a conductive sheet 400. As shown in FIG. 4, a silicon-containing layer 402 is formed on the front and back surfaces of a base sheet 401, and a silicon-containing layer is formed on one side of the substrate. An intermediate metal layer 404 is formed, and a conductive layer 403 is formed on the intermediate metal layer. The insulating film constituting the base sheet 40 1 is a polyimide film (trade name: Capton (Polyimide), manufactured by Toray DuPont) having a thickness of 25 // m without surface roughening treatment; the surface Roughness Ra: 1.9nm) After slitting to a width of 250nm and a length of 30nm, Vol.-26-1240932 (24) is wound around a stainless steel core and mounted on the processing chamber shaft of a sputtering device. Part, mounted on the winding shaft. Next, Si is mounted on the first target of the sputtering device, and Cu is mounted on the second, third, and third targets. Then, after the vacuum state is set to 1 X 1 (T2Pa), the heater is set to 150 ° C, and the drive shaft and the winding shaft attached to the cooling device are rotated respectively. The forward rotation and the speed of 0.3 m / min were performed back and forth to wind the polyimide film, and vacuum heating and drying were performed so that the content of the polyimide film containing the aqueous component became 1% by mass. the following.
接著，在停止藉由加熱器所造成之加熱後， 空幫浦而使得室內之真空度，更加提高至1x10· 。然後，在前述第1〜第4之各個標靶，分別以 分鐘，來注入Ar氣體，在經過3分鐘後，分別 裝置所附帶之驅動轉筒、送出軸及捲繞軸而以 鐘之速度，來進行捲繞，藉由分別在第1標4 0.0 1 5A / cm2之電流，在第2〜第4標靶，流動 cm2之電流，而在基體薄片401上，形成由非結| 構成之含矽層402，同時，分別在其上面，形成 構成之金屬中間層404。採樣該基體薄片之一部 由FIB裝置而對於其厚度來進行剖面測定時，含 之厚度係695A，金屬中間層404之厚度係1 490A 接著，重新安裝在同一濺鍍裝置上，以便於 正如前面敘述所處理之基體薄片401之另外一邊 內之送出 ，在同樣 第4之各 得室內成 定溫度在 筒、送出 逆轉而以 以便於進 分之揮發 僅啓動真 3Pa爲止 2 1 Occ/ 旋轉冷卻 1 · 0 m / 分 ®，流動 0.01 5 A/ I質s i所 由 Ni所 分，在藉 5夕層402 〇 能夠處理 之面。然 -27- (25) 1240932 後，在第1標靶，安裝Si，在藉由真空幫浦而使得室內 成爲1 X 1 (Γ2 Pa之真空狀態後，藉由加熱器而設定溫度在 1 5 0 °C，藉由分別旋轉冷卻裝置所附帶之驅動轉筒、送出 軸及捲繞軸，分別往復地進行1次之正轉和逆轉而以 1.0m/分鐘之速度，來捲繞前述基體薄片401，以便對於 基體薄片，來進行真空加熱乾燥。 接著，在停止藉由加熱器所造成之加熱後，僅啓動真 空幫浦而使得室內之真空度，更加提高至lx 1 (Γ3 Pa爲止 。然後，在前述第1標靶，以21 Occ/分鐘，來注入Ar 氣體，在經過3分鐘後，分別旋轉冷卻裝置所附帶之驅動 轉筒、送出軸及捲繞軸而以l.〇m/分鐘之速度，來進行 捲繞，藉由在第1標靶，流動〇.〇 15 A / cm2之電流，而在 基體薄片401之另外一邊之表面上，形成由非結晶質Si 所構成之含矽層402。採樣該基體薄片之一部分，在藉由 FIB裝置而測定其厚度時，含矽層402之厚度係700A。 然後，像這樣，由濺鍍裝置而取出形成各層之基體薄 片401，接著，安裝在連續電鍍裝置上。藉由在塡充10% 硫酸之30°C之酸活化槽，以1 .〇m/分鐘之移動速度，使 得前述基體薄片連續地浸漬3 0秒鐘，而對於前述金屬中 間層404，進行酸活化處理。接著’在重複地進行3次之 藉由純水所造成之水洗後，藉由在前述裝置之電鍍浴，塡 充電鍍液（由硫酸銅i〇〇g/l、硫酸145 g〆1、氯6〇PPm 及Toprutina 380H (商品名稱、奧野製藥工業（股）公司 製）llcc/Ι所構成），以1.0m /分鐘之移動速度而連續 -28- 1240932 (26) 地浸漬前述基體薄片，在液溫28 °C、電流密度4.0 A/ dm2 之條件下，進行1 〇分鐘之電氣電鍍，以便在前述金屬中 間層404上，形成由Cii所構成之導電層403。接著，重 複地進行5次之藉由純水所造成之水洗，在進行藉由空氣 所造成之除水後，藉由在7〇 °C，進行2分鐘之熱風乾燥 而得到第4圖所示之本發明之導電性薄片4 0 0。採樣該導 電性薄片之一部分，在藉由FIB裝置而對於其厚度來進行 剖面測定時，導電層4 0 3之厚度係9.5 // m。 在使用剝離試驗機而測定像這樣所得到之導電性薄片 之層間密合力時，其剝離強度係成爲1.51kg/ cm2。此外 ，在同樣測定於相對溼度80% 、60°C而保管10天後之層 間密合力時，其剝離強度係成爲1.51kg/ cm2。此外，在 1 05 °C，對於該導電性薄片，進行30分鐘之加熱乾燥，在 藉由比較該乾燥前後之質量而測定絕緣性薄膜之包含水分 之揮發性成分之含有率時，其含有率係〇. 1質量％以下， 在其乾燥前後之質量變化，並無明確之差異產生，幾乎成 爲包含在測定誤差範圍內之程度。 此種導電性薄片係能夠形成微細化之電路圖案，也具 有良好之尺寸穩定性，同時，具有良好之高頻特性。因此 ，可以依照要求，藉由施加形成空孔、通孔或對準孔之孔 加工而適合採用在成爲電氣製品、電子製品、半導體製品 、汽車等之所使用之各種基板或零件上。此外，前述孔加 工係可以對於層積各層前之基體薄片而進行，此外，也可 以對於層積各層後之導電性薄片而進行。 -29- 1240932 (27) <比較例1 > 除了在實施例1’將安裝在同一濺鍍裝置內之第1標 革巴之S i來取代成爲N i以外’其他係全部相同於實施例1 ，得到導電性薄片。在使用剝離試驗機而測定所得到之導 電性薄片之層間密合力時’其剝離強度係成爲1 · 2 1 k g / cm2。此外，在同樣測定於相對溼度80% 、60 °C而保管1 〇 天後之層間密合力時’其剝離強度係成爲0 · 9 2 k g / c m 2。 此外，在1 〇 5 °C ’對於該導電性薄片’進行3 0分鐘之加 熱乾燥，在藉由比較該乾燥前後之質量而測定絕緣性薄膜 之包含水分之揮發性成分之含有率時，其含有率係1.5質 量％ ，非常進行吸濕。 〈比較例2 > 除了在實施例1，不進行對於同一濺鍍裝置之絕緣性 薄膜之1 X 1 (T2Pa、150°C之真空加熱乾燥處理以外，其他 係全部相同於實施例1，得到導電性薄片。在使用剝離試 驗機而測定所得到之導電性薄片之層間密合力時，其剝離 強度係成爲1.19kg/ cm2。此外，在同樣測定於相對溼度 8 0% 、6(TC而保管10天後之層間密合力時，其剝離強度 係成爲〇.89kg/ cm2。此外，在1 〇5 °C，對於該導電性薄 片，進行3 0分鐘之加熱乾燥，在藉由比較該乾燥前後之 質量而測定絕緣性薄膜之包含水分之揮發性成分之含有率 時，其含有率係1 .4質量％ ，非常進行吸濕。 -30- (28) 1240932 在整理以上之各個實施例及各個比較例之結果時，則 正如以下之表1所示。此外，就尺寸穩定性及高頻特性而 言，評價成爲良好者「A」、中庸程度者「B」及變差者 「C」。 <表1 >Then, after stopping the heating caused by the heater, the vacuum was increased to 1x10 · by the air pump. Then, inject the Ar gas in minutes for each of the first to fourth targets, and after 3 minutes, the drive drum, the delivery shaft, and the winding shaft attached to the device are clocked at a clock speed. The winding is performed, and a current of cm2 flows on the second target to the fourth target by a current of 4 0.0 1 5A / cm2 on the first target, and a non-junction | At the same time, the silicon layers 402 form metal intermediate layers 404 formed thereon. When one part of the base sheet was sampled and measured by the FIB device for its thickness, the thickness included was 695A, and the thickness of the metal intermediate layer 404 was 1 490A. Then, it was reinstalled on the same sputtering device to make it as before. Describe the delivery on the other side of the processed substrate sheet 401. In the same fourth chamber, the temperature is set at a fixed temperature. The delivery is reversed to facilitate the evaporation of the content. Only the true 3Pa is activated. · 0 m / min®, flowing 0.01 5 A / I mass si is divided by Ni, which can be processed by borrowing layer 402 〇. After -27- (25) 1240932, install Si on the first target, and set the temperature to 1 5 by the heater after the vacuum is applied to make the room 1 X 1 (Γ2 Pa). At 0 ° C, the above-mentioned substrate sheet is wound at a speed of 1.0 m / min by rotating the driving drum, the sending shaft, and the winding shaft attached to the cooling device, respectively, to perform forward and reverse rotations once and for all at a speed of 1.0 m / min. 401, so that the substrate sheet can be vacuum-heated and dried. Then, after stopping the heating by the heater, only the vacuum pump is started to increase the vacuum in the room to lx 1 (Γ3 Pa. Then Inject the Ar gas at 21 Occ / minute on the first target, and after 3 minutes, rotate the drive drum, the delivery shaft, and the winding shaft attached to the cooling device to 1.0 m / minute. Winding is performed at a speed of 1.05 A / cm2 through the first target, and silicon-containing silicon composed of amorphous Si is formed on the other surface of the substrate sheet 401. Layer 402. Sample a portion of the substrate sheet and load it with FIB When the thickness is measured, the thickness of the silicon-containing layer 402 is 700 A. Then, the base sheet 401 forming each layer is taken out by a sputtering device like this, and then mounted on a continuous electroplating device. By charging 10% The acid activation tank at 30 ° C in sulfuric acid was continuously immersed for 30 seconds at a moving speed of 1.0 m / min, and the metal intermediate layer 404 was subjected to the acid activation treatment. Then, 'repeated After three times of water washing with pure water, the plating bath (from copper sulfate iOOg / l, 145 g sulfuric acid, chlorine 60 ppm and Toprutina 380H (commercial name, made by Okuno Pharmaceutical Co., Ltd.) llcc / I), continuously dipping the aforementioned substrate sheet at a moving speed of 1.0m / min from -28-1240932 (26), at a liquid temperature of 28 ° C. Under the condition of a current density of 4.0 A / dm2, electroplating is performed for 10 minutes so as to form a conductive layer 403 made of Cii on the aforementioned metal intermediate layer 404. Then, 5 times by pure Washing by water is carried out by air After the water is removed, the conductive sheet of the present invention shown in Fig. 4 is obtained by drying with hot air at 70 ° C for 2 minutes to obtain a portion of the conductive sheet of the present invention. When the FIB device is used to measure the thickness, the thickness of the conductive layer 403 is 9.5 // m. When the interlayer adhesion force of the conductive sheet thus obtained is measured using a peel tester, the peel strength is determined. It was 1.51 kg / cm2. In addition, when the interlayer adhesion was measured at 80% relative humidity and 60 ° C for 10 days, the peel strength was 1.51 kg / cm2. In addition, the conductive sheet was heated and dried at 1 05 ° C for 30 minutes, and the content rate of the volatile component containing moisture of the insulating film was measured by comparing the mass before and after the drying, and the content rate It is 0.1% by mass or less. There is no clear difference in the mass change before and after drying, and it is almost included in the measurement error range. This conductive sheet is capable of forming fine circuit patterns, has good dimensional stability, and has good high-frequency characteristics. Therefore, it can be applied to various substrates or parts used as electrical products, electronic products, semiconductor products, automobiles, etc. by applying hole processing to form voids, through holes or alignment holes according to requirements. In addition, the aforementioned hole processing may be performed on the base sheet before the layers are laminated, or may be performed on the conductive sheet after the layers are laminated. -29- 1240932 (27) < Comparative Example 1 > Except for the replacement of Si of the first standard Gaba installed in the same sputtering device as Ni in Example 1 ', all other systems are the same as the implementation. Example 1 to obtain a conductive sheet. When the interlayer adhesion force of the obtained conductive sheet was measured using a peel tester, its peel strength was 1.2 kg / cm2. In addition, when the interlayer adhesion force was measured at 80% relative humidity and 60 ° C and stored for 10 days, its peel strength was 0 · 92 kg / cm2. In addition, the conductive sheet was heated and dried for 30 minutes at 105 ° C. When the content of the volatile component containing moisture of the insulating film was measured by comparing the mass before and after the drying, the The content rate is 1.5% by mass, and it is extremely hygroscopic. <Comparative Example 2> Except that in Example 1, the 1 X 1 (T2Pa, 150 ° C vacuum heating and drying treatment) was not performed on the insulating film of the same sputtering device, and the other systems were the same as in Example 1 to obtain Conductive sheet. When the interlayer adhesion force of the obtained conductive sheet was measured using a peel tester, the peel strength was 1.19 kg / cm2. In addition, the relative humidity was measured at 80% and 6 (TC and stored). When the interlayer adhesion force was 10 days later, the peel strength was 0.89 kg / cm2. In addition, the conductive sheet was heat-dried at 105 ° C for 30 minutes, and compared before and after the drying. When measuring the content rate of the volatile component containing moisture of the insulating film, the content rate is 1.4% by mass, and it is very hygroscopic. -30- (28) 1240932 In finishing each of the above examples and each The results of the comparative examples are shown in Table 1 below. In terms of dimensional stability and high-frequency characteristics, the evaluation was "A" for the good, "B" for the moderate, and "C" for the worse. < Table 1 >
絕緣性薄膜之包 含水分之揮發性 成分之含有率 [質量％] 在製造後之馬上 之層間密合力 [kg/cm2] 相對濕度80%、 60°C、1〇日後之 層間密合力 [kg/cm2] 尺寸穩定性 高頻特性 實施例I 0.1以下 1.45 1.43 A A 實施例2 0.1以下 1.46 1.45 A A 實施例3 0.1以下 1.35/1.41 1.35/1.34 A A 實施例4 -_t· _ 0.1以下 1.51 1.51 A A 比較例1 1.5 1.21 0.92 C C 比較例2 1.4 1.19 0.89 B A 正如由表1而明白地顯示，得知：在對比各個實施例 及各個比較例時，藉由使用包含水分之揮發性成分之含有 率成爲1質量％以下之絕緣性薄膜，並且，形成含矽層’ 而提高層間密合力、也就是基體薄片和導電層間之密合性 ，同時，具有良好之尺寸穩定性及高頻特性。 〔產業上之可利用性〕 -31 · (29) 1240932 本發明之導電性薄片係能夠形成微細化之電路®案， 並且，提高成爲絕緣性薄膜之基體薄片和導電層間之密合 力，而且，改善基體薄片之吸濕性，確保高度之尺寸穩定 性’同時，也具有良好之高頻特性。 因此，本發明之導電性薄片係可以適合採用在成爲電 氣製品、電子製品、半導體製品、汽車等之所使用之各種 基板或零件。 【圖式簡單說明】 第1圖係形成在基體薄片之某一邊表面形成含矽層而 在其上面層積第1導電層和第2導電層所構成之導電層之 導電性薄片之槪略剖面圖。 第2圖係形成在基體薄片之表背兩面形成含矽層而在 其某一邊之含矽層上層積第1導電層和第2導電層所構成 之導電層之導電性薄片之槪略剖面圖。 第3圖係形成在基體薄片之表背兩面形成含矽層而在 各個含矽層上層積第1.導電層和第2導電層所構成之導電 層之導電性薄片之槪略剖面圖。 第4圖係在基體薄片之表背兩面形成含矽層而在其某 一邊之含矽層上形成中間金屬層並且在該中間金屬層上形 成導電層之導電性薄片之槪略剖面圖。 〔圖號說明〕 100 :導電性薄片 -32- (30) (30)1240932 101 :基體薄片 1 0 2 :含矽層 1 03 :導電層 l〇3a：第1導電層 1 03b :第2導電層 2 0 0 :導電性薄片 201 :基體薄片 2 0 2 :含砂層 203 :導電層 203 a :第1導電層 203 b :第2導電層 400 :導電性薄片 4 0 2 :含砂層 403 :導電層 4 0 4 :中間金屬層The content of the volatile component of the insulating film containing moisture [% by mass] The interlayer adhesion force [kg / cm2] immediately after manufacture [Relative humidity 80%, 60 ° C, 10 days later [kg / cm] cm2] Dimensional stability, high frequency characteristics Example I 0.1 or less 1.45 1.43 AA Example 2 0.1 or less 1.46 1.45 AA Example 3 0.1 or less 1.35 / 1.41 1.35 / 1.34 AA Example 4 -_t · _ 0.1 or less 1.51 1.51 AA Comparative Example 1 1.5 1.21 0.92 CC Comparative Example 2 1.4 1.19 0.89 BA As clearly shown in Table 1, it is understood that when comparing each example and each comparative example, the content rate of volatile components containing water becomes 1 mass. It has an insulating film of less than%, and forms a silicon-containing layer to increase the interlayer adhesion, that is, the adhesion between the base sheet and the conductive layer, and has good dimensional stability and high-frequency characteristics. [Industrial Applicability] -31 · (29) 1240932 The conductive sheet of the present invention can form a miniaturized circuit, and improve the adhesion between the base sheet and the conductive layer, which becomes an insulating film. Improve the hygroscopicity of the base sheet and ensure a high degree of dimensional stability. At the same time, it also has good high frequency characteristics. Therefore, the conductive sheet of the present invention can be suitably used for various substrates or parts used in electrical products, electronic products, semiconductor products, automobiles, and the like. [Brief description of the figure] FIG. 1 is a schematic cross-section of a conductive sheet in which a silicon-containing layer is formed on one side surface of a base sheet, and a conductive layer composed of a first conductive layer and a second conductive layer is laminated thereon. Illustration. FIG. 2 is a schematic cross-sectional view of a conductive sheet formed with a silicon-containing layer formed on the front and back surfaces of a base sheet and a conductive layer composed of a first conductive layer and a second conductive layer laminated on the silicon-containing layer on one side. . Fig. 3 is a schematic cross-sectional view of a conductive sheet in which a silicon-containing layer is formed on both the front and back surfaces of a base sheet and a conductive layer composed of a first conductive layer and a second conductive layer is laminated on each silicon-containing layer. FIG. 4 is a schematic cross-sectional view of a conductive sheet in which a silicon-containing layer is formed on both the front and back surfaces of a base sheet, an intermediate metal layer is formed on the silicon-containing layer on one side, and a conductive layer is formed on the intermediate metal layer. [Illustration of drawing number] 100: conductive sheet-32- (30) (30) 1240932 101: base sheet 1 02: silicon-containing layer 1 03: conductive layer 103a: first conductive layer 103b: second conductive Layer 200: conductive sheet 201: base sheet 2 02: sand-containing layer 203: conductive layer 203a: first conductive layer 203b: second conductive layer 400: conductive sheet 402: sand-containing layer 403: conductive Layer 4 0 4: Intermediate metal layer