TWI697573B - 附有載體之銅箔、銅層積板及印刷配線板 - Google Patents

附有載體之銅箔、銅層積板及印刷配線板 Download PDF

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TWI697573B
TWI697573B TW108102636A TW108102636A TWI697573B TW I697573 B TWI697573 B TW I697573B TW 108102636 A TW108102636 A TW 108102636A TW 108102636 A TW108102636 A TW 108102636A TW I697573 B TWI697573 B TW I697573B
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Taiwan
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carrier
copper foil
layer
ultra
printed wiring
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TW108102636A
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TW201940709A (zh
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細川眞
髙梨哲聡
西田𤥨磨
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日商三井金屬鑛業股份有限公司
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    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
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  • Quality & Reliability (AREA)
  • Laminated Bodies (AREA)
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  • Manufacturing Of Printed Wiring (AREA)

Abstract

本發明提供可顯著抑制伴隨對樹脂基材之熱壓積層之膨脹發生的附有載體之銅箔。 本發明之附有載體之銅箔係依序具有載體、剝離層及極薄銅箔之附有載體之銅箔，剝離層包含含羧基之化合物及其衍生物，附有載體之銅箔之每單位面積之H2 O分子的個數為3.44×1016 個/cm2 以下，且附有載體之銅箔之每單位面積之CO2 分子的個數為1.39×1016 個/cm2 以下。

Description

附有載體之銅箔、銅層積板及印刷配線板
本發明有關附有載體之銅箔、銅層積板及印刷配線板。
作為用以製造印刷配線板之材料已廣泛使用附有載體之銅箔。附有載體之銅箔係將玻璃-環氧基材、酚基材、聚醯亞胺等之絕緣樹脂基材藉由熱加壓而貼合作成銅層積板，使用於製造印刷配線板。
附有載體之銅箔已提案有典型上具有依序具備載體、剝離層及極薄銅箔之構成，使用含有機化合物之有機剝離層作為該剝離層。例如專利文獻1(日本特開2003-328178號公報)中，揭示附有載體之銅箔之製造方法，其包含使用含有50ppm～2000ppm有機劑之酸洗溶液，將載體表面酸洗溶解，同時藉由吸附有機劑而形成酸洗吸附有機被膜作為有機剝離層，亦揭示使用羧基苯并三唑(CBTA)作為該有機劑。且，專利文獻2(日本專利第5842077號公報)中，亦揭示使用羧基苯并三唑(CBTA)作為有機剝離層之附有載體之銅箔。
然而，將附有載體之銅箔藉熱加壓貼合於樹脂基材時，於極薄銅箔與載體之間會發生凹坑(blister)(氣泡)。由於凹坑對電路形成造成不良影響，故導致製品良率降低。為了對該問題採取對策，提案有減低剝離層中水分量之技術。例如於專利文獻3(日本特開2015-199355號公報)中，揭示以30℃/分鐘加熱至500℃時所發生之水分量為160ppm/g以下之附有載體之銅箔，藉由設為水分發生受抑制之附有載體之銅箔，而可良好地抑制凹坑之發生。 [先前技術文獻] [專利文獻]
[專利文獻1] 日本特開2003-328178號公報 [專利文獻2] 日本專利第5842077號公報 [專利文獻3] 日本特開2015-199355號公報
然而，如專利文獻3所揭示之先前技術，關於因凹坑發生所致之良率降低問題尚未滿足地解決，而期望進一步改善。
本發明人等如今得到如下見解：於具備含羧基之化合物及其衍生物之剝離層之附有載體之銅箔中，藉由將H2 O分子及CO2 分子之個數密度減低為特定值以下，可顯著抑制隨著對樹脂基材之熱加壓積層而發生之凹坑。
因此，本發明之目的在於提供可顯著抑制隨著對樹脂基材之熱加壓積層而發生之凹坑的附有載體之銅箔。
依據本發明之一態樣，提供一種附有載體之銅箔，其係依序具有載體、剝離層及極薄銅箔之附有載體之銅箔， 前述剝離層包含含羧基之化合物及其衍生物， 前述附有載體之銅箔之每單位面積之H2 O分子的個數為3.44×1016 個/cm2 以下，且前述附有載體之銅箔之每單位面積之CO2 分子的個數為1.39×1016 個/cm2 以下。
依據本發明其他一態樣，提供一種具備前述附有載體之銅箔的銅層積板。
依據本發明其他一態樣，提供一種具備前述附有載體之銅箔的印刷配線板。
依據本發明其他一態樣，提供一種印刷配線板之製造方法，其特徵係使用上述附有載體之銅箔，製造印刷配線板。
附有載體之銅箔 本發明之附有載體之銅箔係依序具有載體、剝離層及極薄銅箔者。剝離層包含含羧基之化合物(典型上為具有羧基之有機化合物)及其衍生物。附有載體之銅箔之每單位面積之H2 O分子的個數為3.44×1016 個/cm2 以下。且附有載體之銅箔之每單位面積之CO2 分子的個數為1.39×1016 個/cm2 以下。如此，於具備包含含羧基之化合物及其衍生物之剝離層的附有載體之銅箔中，藉由將H2 O分子及CO2 分子之個數密度減低至特定值以下，可顯著抑制伴隨對樹脂基材之熱加壓積層而發生之凹坑。由於凹坑對電路形成造成不良影響，故藉由減低凹坑可實現製品良率之提高。
發生凹坑之機制雖尚未明確，但可認為係如下。圖2顯示含羧基之化合物的一種即亞油酸之升溫脫離輪廓之圖。圖2所示之升溫脫離輪廓係顯示將試料(亞油酸)以特定速度升溫時於各溫度下自試料表面脫離之H2 O分子及CO2 分子之個數。如圖2所示，與水的脫離有關之主要波峰存在三點，該等自低溫起依序為i)起因於吸附於試料表面之水的脫離(吸附水之脫離)之波峰，ii)起因於與羧基共振之水的脫離(共振水之脫離)之波峰，及iii)起因於水伴隨相鄰亞油酸彼此之脫水縮合反應(酯化反應)而脫離之波峰。另一方面，與二氧化碳之脫離有關之主要波峰於180℃附近存在1點，其係起因於二氧化碳自亞油酸之羧基脫離之脫碳酸反應的波峰。引起該脫碳酸反應之溫度雖隨有機化合物之種類而異，但一般為150℃以上。如此，即使於比發生吸附水自含羧基之有機化合物脫離之溫度(例如90℃左右)更高之溫度(例如110～200℃)，亦大量發生水及二氧化碳。因此，具備包含含羧基化合物之剝離層的附有載體之銅箔藉熱加壓貼合於樹脂基材時，經加熱之剝離層中引起上述反應，大量發生水及二氧化碳。其結果，認為於極薄銅箔與載體之間發生起因於水及二氧化碳氣體之凹坑。此點，依據本發明，藉由事先將附有載體之銅箔中之H2 O分子及CO2 分子之個數密度減低至特定值以下，認為可有效防止對樹脂基材之熱加壓積層時自剝離層大量產生水及二氧化碳，而可顯著抑制凹坑發生者。
因此，附有載體之銅箔中每單位面積之H2 O分子的個數較好為3.44×1016 個/cm2 以下，更好為3.38×1016 個/cm2 以下，又更好為3.30×1016 個/cm2 以下。每單位面積之H2 O分子的個數之下限值並未特別限定，但典型上為1.00×1015 個/cm2 以上，更典型為1.50×1015 個/cm2 以上，再更典型為1.04×1016 個/cm2 以上。又，附有載體之銅箔中每單位面積之CO2 分子的個數為1.39×1016 個/cm2 以下，較好為1.34×1016 個/cm2 以下，又更好為1.32×1016 個/cm2 以下。每單位面積之CO2 分子的個數之下限值並未特別限定，但典型上為1.00×1015 個/cm2 以上，更典型為1.50×1015 個/cm2 以上，再更典型為9.17×1015 個/cm2 以上。附有載體之銅箔中H2 O分子及CO2 分子的個數，如後述實施例所言，可藉由升溫脫離法(TDS：Thermal Desorption Spectrometry)較好地測定。
剝離層係具有使載體與極薄銅箔間之剝離強度較弱，擔保該強度安定性，進而抑制熱加壓成形時於載體與銅箔間引起之相互擴散的功能。剝離層一般係形成於載體之一面，但亦可形成於兩面。剝離層包含含羧基化合物及其衍生物。因此，剝離層典型上為有機剝離層，但亦可為有機剝離層與無機剝離層之複合剝離層，或包含有機剝離劑及無機剝離劑之混合剝離層。此處，所謂含羧基化合物之衍生物包含含羧基化合物之分子內的一部分藉由脫離反應或取代反應等而變化之化合物，或藉由加成反應等而於含羧基化合物之分子內之一部分加成原子團之化合物等。作為此等衍生物之例，舉例為含羧基化合物藉由脫水縮合反應而成為酸酐(典型上為二聚物)之化合物、藉由脫碳酸反應而自羧基脫離CO2 分子之化合物、對含羧基化合物附加甲基等之取代基之化合物等。因此，剝離層只要為自層形成之初包含含羧基化合物及其衍生物即可，但較好為因後述之加熱處理而於事後不可避免地使含羧基化合物之一部分變化為衍生物。亦即，亦可係剝離層最初包含含羧基化合物而不伴隨其衍生物，之後，施以後述之加熱處理而使一部分之含羧基化合物反應(例如脫水縮合反應或脫碳酸反應)，而成為包含含羧基化合物及其衍生物之剝離層。
含羧基化合物較好為羧基苯并三唑(CBTA)。或者，含羧基化合物亦可為單羧酸及/或二羧酸。作為單羧酸之較佳例舉例為亞油酸、油酸、亞麻酸、硫代乙醇酸、3-巰基-2-吡啶羧酸等。作為二羧酸之較佳例舉例為硫代蘋果酸、偶氮二羧酸異丙酯、偶氮二羧酸二乙酯等。藉由剝離層包含上述含羧基化合物，即使於施加熱加壓成形(例如250℃以上)或長時間之烘烤處理(例如於200℃8小時)等之情況下，亦可更進一步維持容易使載體剝離去除之狀態。
載體係用以支持極薄銅箔提高其處理性之支持體，典型之載體包含金屬層。作為此等載體之例，舉例為鋁箔、銅箔、不鏽鋼(SUS)箔、表面以銅等金屬塗佈之樹脂膜或玻璃等，較好為銅箔。銅箔可為壓延銅箔及電解銅箔之任一者。載體厚度典型上為250μm以下，較好為9～200μm。
極薄銅箔可為附有載體之極薄銅箔中採用之習知構成而未特別限定。例如極薄銅箔可為利用無電解銅鍍敷法及電解銅鍍敷法等之濕式成膜法、濺鍍及化學蒸鍍等之乾式成膜法、或該等之組合而形成者。極薄銅箔之較佳厚度為0.1～7.0μm，更好為0.5～5.0μm，又更好為1.0～3.0μm。
極薄銅箔之最外面(亦即遠離剝離層之側的面)較好為粗化面。亦即，較好於極薄銅箔之一面進行粗化處理。如此，可提高銅層積板或印刷配線板製造時之與樹脂層的密著性。該粗化處理較好依據經過包含如下步驟之至少2種步驟的習知鍍敷方法進行：於極薄銅箔上析出附著微細銅粒並燒結鍍敷之步驟，及用以防止該微細銅粒脫落之外覆鍍敷步驟。
於剝離層與載體及/或極薄銅箔之間亦可設置其他功能層。作為此等其他功能層之例舉例為輔助金屬層。輔助金屬層較好由鎳及/或鈷所成。藉由於載體表面側及/或極薄銅箔表面側形成此輔助金屬層，可進一步抑制高溫或長時間熱加壓成形時於載體及極薄銅箔之間引起之相互擴散，可擔保載體之剝離強度之安定性。輔助金屬層厚度較好為0.001～3μm。
依據期望，亦可對極薄銅箔實施防鏽處理。防鏽處理較好包含使用鋅之鍍敷處理。使用鋅之鍍敷處理可為鋅鍍敷處理及鋅合金鍍敷處理之任一者，鋅合金鍍敷處理特佳為鋅-鎳合金處理。鋅-鎳合金處理若為包含Ni及Zn之鍍敷處理即可，亦可進而包含Sn、Cr、Co等之其他元素。鋅-鎳合金鍍敷中Ni/Zn附著比例，以質量比計，較好為1.2～10，更好為2～7，又更好為2.7～4。又，防鏽處理較好進而包含鉻酸鹽處理。此鉻酸鹽處理更好係於使用鋅之鍍敷處理後，對包含鋅之鍍敷表面進行。若如此則可進而提高防鏽性。特佳之防鏽處理係鋅-鎳合金鍍敷處理與其後之鉻酸鹽處理之組合。
依據期望，亦可於極薄銅箔表面實施矽烷偶合劑處理，形成矽烷偶合劑層。藉此可提高耐濕性、耐藥品性及與接著劑等之密著性等。矽烷偶合劑層可藉由適當稀釋矽烷偶合劑並塗佈、乾燥而形成。作為矽烷偶合劑之例舉例為4-縮水甘油基丁基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷等之環氧官能性矽烷偶合劑，或3-胺基丙基三甲氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷等之胺基官能性矽烷偶合劑，或3-巰基丙基三甲氧基矽烷等之巰基官能性矽烷偶合劑，或乙烯基三甲氧基矽烷、乙烯基苯基三甲氧基矽烷等之烯烴官能性矽烷偶合劑，或3-甲基丙烯醯氧基丙基三甲氧基矽烷等之丙烯酸官能性矽烷偶合劑，或咪唑基矽烷等之咪唑官能性矽烷偶合劑，或三嗪矽烷等之三嗪官能性矽烷偶合劑等。
附有載體之銅箔之製造方法 本發明之附有載體之銅箔可依據習知方法藉由於載體上依序形成剝離層、極薄銅箔等之各層製作附有載體之銅箔後，實施以下所述之2階段加熱處理步驟，促進自剝離層之水及二氧化碳產生及排出而較好地製造。
第1階段之加熱處理步驟係藉由高溫處理上述發生水及二氧化碳之反應而進行之步驟。較佳之加熱處理條件係隨附有載體之銅箔的尺寸或形狀、所用之烘烤爐種類等而變動。因此，只要對應於該等變動要素，適當設定充分發生水及二氧化碳之加熱處理條件即可，亦即適當設定不僅使吸附水脫離，而且使共振水自剝離層所含之含羧基化合物脫離以及伴隨脫水縮合反應及脫碳酸反應而產生水及二氧化碳之脫離的加熱處理條件即可。典型上，第1階段之加熱處理溫度為超過180℃之溫度，較好為200～280℃，更好為220～250℃。又，第1階段之加熱處理時間典型上為0.5～40小時，較好為1～30小時，更好為2～24小時。若如此，可邊有效地防止銅箔之劣化或根據期望設定之矽烷偶合劑層的剝落等，邊可較好地自附有載體之銅箔(典型上為剝離層)發生水及二氧化碳。尤其，於接近用以貼合於樹脂基材之熱加壓的溫度進行第1階段之加熱處理，有助於有效抑制伴隨熱加壓積層之凹坑發生。又，典型上，藉由第1階段之高溫加熱處理，可將剝離層中所含之含羧基化合物之一部分變化為其衍生物(例如二聚物或CO2 分子經脫離之化合物)。
第2階段之加熱處理步驟係將因第1階段之加熱處理步驟所產生之水及二氧化碳藉由比較低溫且長時間之加熱處理而自附有載體之銅箔排出之步驟。亦即，由於藉由第1階段之加熱處理而自附有載體之銅箔發生之水及二氧化碳典型上係源自包含含羧基化合物之剝離層者，故該水及二氧化碳駐留於附有載體之銅箔中(例如載體與極薄銅箔之間)，而成為凹坑之要因。因此，期望藉由第2階段之加熱處理，將駐留於附有載體之銅箔中之水及二氧化碳迫出系外。其結果，可將附有載體之銅箔(尤其是剝離層)改質至每單位面積之H2 O分子的個數為3.44×1016 個/cm2 以下，且每單位面積之CO2 分子的個數為1.39×1016 個/cm2 以下者。此時，基於進而防止自剝離層發生水及二氧化碳之觀點，第2階段之加熱處理溫度較好低於第1階段之加熱處理溫度。典型上，第2階段之加熱處理溫度為180℃以下，較好為90～180℃，更好為100～180℃。且第2階段之加熱處理時間典型上為3～40小時，較好為5～35小時，更好為5～30小時。若如此，則可將於第1階段之加熱處理所發生之水及二氧化碳有效地自附有載體之銅箔排出。又，與第1階段之加熱處理條件同樣，第2階段之較佳加熱處理條件亦根據附有載體之銅箔的尺寸或形狀、所用之烘烤爐種類等而變動。
銅層積板 本發明之附有載體之銅箔較好使用於製作印刷配線板之銅層積板。亦即依據本發明之較佳態樣，提供具備上述附載體之銅箔的銅層積板。該銅層積板具備本發明之附有載體之銅箔與密著於該附有載體之銅箔而設置之樹脂層。附有載體之銅箔可設於樹脂層之單面，亦可設於兩面。樹脂層包含樹脂較好包含絕緣性樹脂而成。樹脂層較好為預浸片及/或樹脂薄片。所謂預浸片係於合成樹脂板、玻璃板、玻璃織布、玻璃不織布、紙等之基材中含浸合成樹脂之複合材料的總稱。作為絕緣性樹脂之較佳例舉例為環氧樹脂、氰酸酯樹脂、雙馬來醯亞胺三嗪樹脂(BT樹脂)、聚苯醚樹脂、酚樹脂等。且，作為構成樹脂薄片之絕緣性樹脂舉例為環氧樹脂、聚醯亞胺樹脂、聚酯樹脂等之絕緣樹脂。又，基於對樹脂層提高絕緣性等之觀點，亦可含有由氧化矽、氧化鋁等之各種無機粒子而成之填料粒子等。樹脂層的厚度並未特別限定，但較好為1～1000μm，更好為2～400μm，再更好為3～200μm。樹脂層亦可以複數層構成。預浸片及/或樹脂薄片等之樹脂層亦可經由預先塗佈於極薄銅箔表面之底塗樹脂層而設於附有載體之銅箔上。
印刷配線板 本發明之附有載體之銅箔較好使用於製作印刷配線板。亦即依據本發明之較佳態樣，提供具備上述附有載體之銅箔之印刷配線板或其製造方法。本態樣之印刷配線板包含樹脂層與銅層依此順序積層而成之層構成。又，針對樹脂層係如關於銅層積板有關之上述。總之，印刷配線板可採用習知之層構成。關於印刷配線板之具體例，舉例為於預浸片之單面或雙面接著本發明之極薄銅箔並硬化作成積層體之後，形成電路之單面或雙面印刷配線板或使該等多層化之多層印刷配線板等。又，作為其他具體例亦舉例有於樹脂膜上形成本發明之極薄銅箔並形成電路之可撓性印刷配線板、COF、TAB帶等。作為進而其他具體例舉例為形成於本發明之極薄銅箔上塗佈有上述樹脂層之附樹脂銅箔(RCC)，將該樹脂層作為絕緣接著材層積層於上述印刷配線板後，將極薄銅箔作為配線層之全部或一部分而藉改良・半加成(MSAP)法、減去法等之方法形成電路之增層配線板、或去除極薄銅箔並藉半加成法(SAP)形成電路之增層配線板、重複對半導體積體電路上積層附樹脂銅箔與電路形成之晶圓上直接增層(Direct Buildup On Wafer)等。本發明之附有載體之銅箔亦可較好地使用於利用未使用所謂之芯基板，而使絕緣樹脂層與導體層交替積層之無芯增層法之製造方法。 [實施例]
本發明藉由以下之例進一步具體說明。
例1、2及4～8 如以下般來進行附有載體之銅箔之製作及評價。
(1)載體之準備 準備以IPC規格分類為等級3之厚度18μm之電解銅箔作為載體。作為該載體之電解銅箔係經電解製箔之狀態的銅箔(所謂生箔)，未施以防鏽處理、粗化處理等之表面處理者。進行酸洗處理以將附著於載體表面之油脂成分或表面氧化被膜去除。
(2)剝離層之形成 經酸洗處理之載體的電極面側於CBTA(羧基苯并三唑)濃度1g/L、硫酸濃度150g/L及銅濃度10g/L之CBTA水溶液中於液溫30℃浸漬30秒，將CBTA成分吸附於載體之電極面。如此，於載體之電極面表面形成CBTA層作為剝離層。
(3)輔助金屬層之形成 形成有剝離層之載體浸漬於使用硫酸鎳製作之鎳濃度20g/L之溶液中，於液溫45℃、pH3、電流密度5A/dm2 之條件，於剝離層上附著相當於厚度0.001μm之附著量的鎳。如此，於剝離層上形成鎳層作為輔助金屬層。
(4)極薄銅箔之形成 將形成輔助金屬層之載體浸漬於銅濃度60g/L及硫酸濃度200g/L的硫酸銅溶液中，以液溫50℃、電流密度5～30A/dm2 電解，於輔助金屬層上形成厚度1.5μm之極薄銅箔。
(5)粗化處理 對極薄銅箔表面進行粗化處理。該粗化處理藉由以下2階段鍍敷進行。第1階段鍍敷步驟係使用包含銅10g/L及硫酸120g/L之酸性硫酸銅溶液，於液溫40℃、電流密度30A/dm2 之鍍敷條件進行電鍍。第2階段鍍敷步驟係使用包含銅70g/L及硫酸120g/L之酸性硫酸銅溶液，於液溫40℃、電流密度30A/dm2 之鍍敷條件進行電鍍。
(6)防鏽處理 對粗化處理後之附有載體之銅箔兩面進行由無機防鏽處理及鉻酸鹽處理而成之防鏽處理。作為無機防鏽處理，係使用焦磷酸浴，以焦磷酸鉀濃度80g/L、鋅濃度0.2g/L、鎳濃度2g/L、液溫40℃、電流密度0.5A/dm2 進行鋅-鎳合金防鏽處理。其次，作為鉻酸鹽處理，係於鋅-鎳合金防鏽處理之後，進而形成鉻酸鹽層。該鉻酸鹽處理係以鉻酸濃度1g/L、pH11、液溫25℃、電流密度1A/dm2 進行。
(7)矽烷偶合劑處理 將施以上述防鏽處理之銅箔進行水洗，隨後立即進行矽烷偶合劑處理，於粗化處理面之防鏽處理層上吸附矽烷偶合劑。該矽烷偶合劑處理係藉由使用以純水作為溶劑，3-胺基丙基三甲氧基矽烷濃度為3g/L之溶液，利用淋洗環將該溶液吹附至粗化處理面進行吸附處理而進行。矽烷偶合劑吸附後，最終藉由電熱器使水分蒸散，獲得具備厚度1.5μm之粗化處理銅箔之附有載體之銅箔。
(8)加熱處理 對於如此所得之附有載體之銅箔，於大氣氛圍中，以烘箱於表1所示之條件下進行1階段或2階段之加熱處理。此時，將例1、2及4～8之各例中之加熱條件如表1所示般適當變化，而製作剝離層中之水分含量及二氧化碳含量不同之各種樣品。又，加熱處理條件係根據樣品之尺寸或烘烤爐種類等而異，當然本發明絕不因該等條件而受到限制。
(9)附有載體之銅箔評價 針對所得附有載體之銅箔進行以下評價。
＜評價1：水分及二氧化碳之測定＞ 藉由升溫脫離法(TDS：Thermal Desorption Spectrometry)如以下般進行所得附有載體之銅箔(尤其剝離層)中所含之水分及二氧化碳之測定。首先，為了去除上述(8)中施以加熱處理之附有載體之銅箔表面吸附之水分，而以真空定溫乾燥器，於50℃、對於大氣壓為-0.1 MPa之條件進行7天真空乾燥。其次，將已進行真空乾燥之附有載體之銅箔以衝壓機衝打成直徑1cm的大小，作成試驗片，快速測定該試驗片之重量。將試驗片以載體與極薄銅箔分離之狀態(亦即剝離層露出之狀態)設定於升溫脫離分析裝置(電子科學股份有限公司製，TDS1200II)之腔室中，流通氮氣3分鐘後，進行5分鐘抽真空。隨後，對試驗片照射燈光，利用光吸收以30℃/分鐘之升溫速度使試驗片升溫至400℃，針對其間自試驗片產生之氣體，藉由質量分析計進行定性及定量。此時，將m/z=18作為H2 O氣體，將m/z=44作為CO2 氣體進行解析，分別獲得附有載體之銅箔中直徑1cm的圓內所佔之H2 O分子及CO2 分子之各個數。藉由將如此獲得之值除以直徑1cm的圓面積(0.785cm2 )，算出每單位面積之H2 O分子及CO2 分子之各個數。結果彙總示於表1及圖1。又，表1中，為了參考，亦一併示出藉由將H2 O及CO2 之各重量(自分子個數換算者)除以試驗片重量而算出之附有載體的銅箔之H2 O及CO2 之各重量比例(ppm)。
＜評價2：凹坑之測定＞ 準備厚度100μm之預浸片(三菱瓦斯化學股份有限公司製，GHPL-830NSF)作為樹脂基材。對該樹脂基材將上述(8)中施以加熱處理之附有載體之銅箔以其極薄銅箔側與樹脂基材抵接之方式進行積層，以壓力2.4MPa及溫度250℃進行90分鐘熱加壓成形後，進一步以烘烤爐於溫度200℃進行8小時烘烤處理，獲得銅層積板樣品。自該銅層積板樣品剝離載體後，使用光學顯微鏡(KYENCE股份有限公司製，VHX-5000)，以倍率20倍及測定視野18mm×13.5mm之條件，計算於極薄銅箔表面形成之凹陷數，將不同3視野之平均值作為凹坑數。亦即由於於載體剝離後之銅層積板樣品表面(亦即極薄銅箔表面)形成凹陷作為起因於載體與極薄銅箔之間發生之凹坑的痕跡，故該凹陷數視為所發生之凹坑數。結果彙總示於表1。
例3(比較) 除了不對附有載體之銅箔施以加熱處理水以外，與例1同樣進行附有載體之銅箔的製作及評價。結果彙總示於表1及圖1。
例9(比較) 除了於剝離層之形成步驟中，替代CBTA水溶液，而使用亞油酸濃度1000重量ppm之亞油酸水溶液以外，與例2同樣進行附有載體之銅箔的製作及評價。結果彙總示於表1及圖1。
Figure 02_image001
圖1係對例1～9之附有載體之銅箔之每單位面積之H2 O分子及CO2 分子的各個數作圖之圖。 圖2係顯示亞油酸之升溫脫離輪廓之圖。

Claims (8)

  1. 一種附有載體之銅箔，其係依序具有載體、剝離層及極薄銅箔之附有載體之銅箔，前述剝離層包含含羧基之化合物及其衍生物，前述附有載體之銅箔之每單位面積之H2O分子的個數為3.44×1016個/cm2以下，且前述附有載體之銅箔之每單位面積之CO2分子的個數為1.39×1016個/cm2以下。
  2. 如請求項1之附有載體之銅箔，其中前述含羧基之化合物係羧基苯并三唑(CBTA)。
  3. 如請求項1之附有載體之銅箔，其中前述含羧基之化合物係單羧酸及/或二羧酸。
  4. 如請求項1至3中任一項之附有載體之銅箔，其中前述載體包含金屬層。
  5. 如請求項1至3中任一項之附有載體之銅箔，其中於前述剝離層與前述載體及/或前述極薄銅箔之間進而具備輔助金屬層。
  6. 一種銅層積板，其具備如請求項1至5中任一項之附有載體之銅箔。
  7. 一種印刷配線板，其具備如請求項1至5中任一項之附有載體之銅箔。
  8. 一種印刷配線板之製造方法，其特徵係使用如請求項1至5中任一項之附有載體之銅箔，製造印刷配線板。
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