TW540281B - Manufacturing method of conductive paste material and manufacturing method of printing wiring base board - Google Patents

Manufacturing method of conductive paste material and manufacturing method of printing wiring base board Download PDF

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Publication number
TW540281B
TW540281B TW091117754A TW91117754A TW540281B TW 540281 B TW540281 B TW 540281B TW 091117754 A TW091117754 A TW 091117754A TW 91117754 A TW91117754 A TW 91117754A TW 540281 B TW540281 B TW 540281B
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Taiwan
Prior art keywords
manufacturing
conductive particles
conductive paste
conductive
particles
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TW091117754A
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English (en)
Inventor
Takeshi Suzuki
Satoru Tomekawa
Yosihiro Tomita
Yuichiro Sugita
Shigeru Yamane
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Matsushita Electric Ind Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B22F9/007—Transformation of amorphous into microcrystalline state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B22F9/008—Rapid solidification processing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C22C1/0441—Alloys based on intermetallic compounds of the type rare earth - Co, Ni
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K1/02—Details
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    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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Description

A7 540281 五、發明說明（/ ) [技術領域] 本發明係關於導電性糊料以及印刷配線基板之製造方 法。此導電性糊料在多層配線基板中可適用做爲將各層間 之配線圖案加以連接之通孔(via hole)塡充用糊料。 [背景技術] 伴隨電子儀器急速的小型化、高密度化，在搭載電子 零件之印刷配線基板方面也朝向高密度印刷配線基板之開 發邁進。 在印刷配線基板方面，已提出將成爲配線高密度化之 因素的鍍敷貫通孔(through hole)取代爲使用導電性糊料之 內通孔連接(例如日本專利特開平6-268345號公報）。依據 此連接方式，可高效率地提供高密度印刷配線基板。 此高密度印刷配線基板係以下述方式所製作。首先， 在兩面有具脫模性之脫模性薄膜（高分子薄膜）貼附著之被 壓縮性之多孔質預浸片（絕緣基板）設置貫通孔。其次，於 貫通孔塡充導電性糊料，將薄膜剝離。接著，於預浸片之 兩面貼附金屬箔進行加熱與加壓，讓絕緣基板兩面之金屬 箔以通孔導體（已硬化之導電性糊料)做電連接。進而，爲 了形成電路，乃對金屬箔進行選擇性蝕刻。 以下參照圖式對該製造方法做具體的說明。 首先，如圖6A所示般，準備兩面貼合有脫模性薄膜 11之多孔質預浸片12。多孔質預浸片12可爲例如在芳香 族聚醯胺纖維之不織布中含浸環氧樹脂所得之複合材。 其次，如圖6B所示般，於預浸片12之既定位置照射 ________ 3 ________ 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閲讀背面之注意事項再填寫本頁) — --------訂---------線丨▲ -ϋ n n I ! «I n n n n n ·1 n ! n n n ϋ fl— ϋ ϋ ▲ 540281 A7 - ~—__Β7_ ___ — 五、發明說明（2 ) 雷射光等之能束來形成貫通孔13。接著，如圖6C所示般 ，在印刷機(省略圖示)之工作台上，將導電性糊料14自脫 模性薄膜11上方塗佈於預浸片12，塡充到貫通孔13之內 部。此時，脫模性薄膜11係做爲預浸片12之防止污染膜 而作用。 進而，如圖6D所示般，將脫模性薄膜11剝離，如圖 6E所示般，在預浸片12之兩面貼附例如銅箔等之金屬箔 15。在此狀態下，一邊對預浸片12加熱一邊自兩側進行加 壓來壓縮。於是，如圖6F所示，預浸片12與金屬箔15得 以接著，同時間預浸片12受到壓縮，兩面之金屬箔乃可透 過貫通孔13所塡充之導電性糊料14做電連接(通孔連接) 。與此同時，於預浸片12所含之環氧樹脂以及導電性糊料 14會硬化。 之後，如圖6G所示般，對兩面之金屬箔15進行選擇 性蝕刻來形成配線圖案16。如此，得以製作出印刷配線基 板。 但是，上述製造方法存在著以下課題。 如圖7A所示，預浸片12多採用以層合製法而含浸於 熱硬化性樹脂之不織布17,在加熱前處於半硬化狀態（例 如特開平7-106760號公報）。通常，於預浸片12之表面會 存在著因露出於表面之不織布或於表面附近所存在之不織 布17所造成之凹部18。此凹部18會以脫模性薄膜11與 預浸片12間之空隙的形式殘存。 若於此狀態下將導電性糊料14塡充於貫通孔13並對 j；_ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） (請先閱讀背面之注意事項再填寫本頁) .丨_-----------訂·！ ！線， 540281 A7 ___B7 ___ 五、發明說明（5 ) 預浸片12進行壓縮，則如圖7B所示般，導電性糊料14 會進入凹部18，或在鄰接之通孔間出現短路部份20，或造 成配線間之絕緣可靠性降低。 特別是，對於高密度印刷配線基板而言，由於通孔亦 以高密度方式形成，所以容易發生通孔間之短路。 高密度印刷配線基板爲了取得配線層間之良好的電導 通，如圖7A所示，係使用內部分散著空隙19之被壓縮性 預浸片12。但是，由於導電性糊料14有時也會流入該空 隙19，所以空隙19與凹部18同樣會伴隨配線圖案之高密 度化而成爲短路發生的原因。 爲了解決此問題，想到將預浸片12之表面平滑化來抑 制凹部18之做法。又，也想到減少預浸片12中之空隙19 的做法。但是，此種預浸片欠缺被壓縮性，所以塡充於貫 通孔內之導電性糊料無法被充分壓縮。因而，要確保配線 層間之良好的電導通乃困難。 [發明之揭示] 本發明有鑒於上述問題，乃提供一種導電性糊料之製 造方法，其包含··以對導電體粒子施加應力使其變形度成 爲1.01〜1.5的方式來讓導電體粒子變形之製程；以及，將 變形後之導電體粒子與以熱固性樹脂爲主成分之黏結劑 (binder)加以混合之製程。 此處所說的變形度係針對以雷射繞射法所測定之平均 粒徑，將變形後之導電體粒子之平均粒徑R2除以變形前之 導電體粒子之平均粒徑心所得之値(R2/Ri)。 ___ 5 _ — 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ;0 -線 540281 A7 ________________B7 五、發明說明（f ) 若使用本發明之導電性糊料，將可輕易地確保良好之 層間連接。是以，即使適用於欠缺被壓縮性之預浸片，仍 可輕易地得到低基板電阻値。 本發明亦提供印刷配線基板之製造方法。此製造方法 包含：製造本發明之導電性糊料之製程；於至少〜側面貼 合有脫模性薄膜之預浸片形成貫通孔之製程：於該曾通孔 塡充該導電性糊料之製程；使得預浸片隨同脫楔性薄膜與 導電性糊料進行壓縮之製程；以及，在此壓縮製程之後， 將脫模性薄膜自預浸片加以剝離之製程。 做爲前述預浸片以含有補強纖維與樹脂，且存在著表 面無補強纖維存在之樹脂層，又於壓縮製程之前樹脂層之 厚度爲Ιμιη〜30μιη之預浸片爲適宜。 [圖式之簡單說明] 圖1所示係以掃描型電子顯微鏡(SEM)來觀察導電體 粒子變形後之狀態之一例之圖。 圖2所示係以SEM來觀察導電體粒子變形後之狀態之 另一例之圖。 圖3所示係以SEM來觀察導電體粒子變形後之狀態之 再一例之圖。 圖4所示係以SEM來觀察導電體粒子變形前之狀態之 一例之圖。 圖5Α〜圖5F分別表示本發明之印刷配線基板之製造 方法之一例的截面圖。 圖6Α〜圖6G分別表示習知之印刷配線基板之製造方 _______ 6 _—_ 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線， A7 540281 _____B7__ 五、發明說明（t ) 法之截面圖。 (請先閱讀背面之注意事項再填寫本頁) 圖7A、圖7B係顯示習知方法之印刷配線基板中短路 之圖，圖7A係顯示印刷配線基板中短路與空隙之圖，圖 7B係顯示凹部所導致之短路之圖。 [發明之實施形態] 使用雷射光之雷射繞射法，係以粒子投影狀態下測定 粒徑。因此，若粒子扁平化，則即使體積相同所測定之粒 徑也會增加。在本發明中，在變形之尺度方面使用上述變 形度’以使得該値成爲1.01〜1·5(更佳爲1.02〜1.30)的方式 對導電體粒子施加應力，來讓粒子扁平化。藉由扁平化， 導電體粒子彼此之接觸面積可增加，其結果基板電阻値乃 下降。 線 導電體粒子之比表面積藉由上述變形以成爲 0.05m2/g〜1.5m2/g爲佳。隨著比表面積之增加，導電性糊 料之黏度會上升。導電性糊料之黏度若過高，將難以塡充 到貫通孔，有時會發生於脫模性薄膜剝離時貫通孔兩端之 糊料隨同薄膜一起被剝落之現象(即所謂的「糊料被帶走」 )。從此觀點來看，比表面積以1.0m2/g以下爲佳。 導電體粒子變形後由雷射繞射法所測定之平均粒徑以 0·2μιη〜20μιη爲佳。若平均粒徑未滿〇·2μιη，要使得比表 面積維持1.5m2/g以下有其困難。因此，糊料黏度會變得 過高，進而欲使得導電體粒子以高濃度分散會變得困難。 另一方面，當平均粒徑超過20μιη，於一個通孔內所能塡充 之導電體粒子數量會減少。導電體粒子之數量若少，則導 ___7_____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 540281 B7 五、發明說明（6 ) 電體粒子之接觸面積會減少’無法得到充分之低基板電阻 値。 又，比表面積低於〇.〇5m2/g之導電體粒子，由於平均 粒徑大，基於與上述相同理由’將難以實現低基板電阻。 在導電性糊料中，除了導電體粒子以外，尙含有以熱 固性樹脂爲主成分之黏結劑。導電性糊料中以導電體粒子 30〜70體積％、黏結劑70〜30體積％的方式來混合即可。採 用此混合比的情況下，導電性糊料之較佳黏度爲l〇〇〇Pa· S以下。 導電體粒子以含有擇自金、鉑、銀、鈀、銅、鎳、錫 、鉛、麵、鉢以及絡之至少1種爲佳，尤其是含有擇自金 、鉑、銀、、銅、鎳、錫、鉛以及銦之至少1種爲特佳 。導電體粒子可爲例如下述（I)〜(IV)之任一種。 (I)金、鉑、銀、鈀、銅、鎳、錫、鉛或銦； (Π)擇自金、鈾、銀、鈀、銅、鎳、錫、鉛、銦、鋅 以及絡之任意的組合之合金粒子； (皿）以導電性或非導電體粒子爲核，以擇自金、鉑、 銀、紀、銅、鎳、錫、鉛以及銦之至少丨種金屬所被覆之 粒子； (IV)以導電性或非導電體粒子爲核，以擇自金、鉑、 銀、祀、銅、鎳、錫、鉛、銦、鋅以及鉻之任意的組合之 合金所被覆之粒子。 以下就導電體粒子之變形處理做說明。導電體粒子之 變形只要施加機械應力即可，所使用之裝置並無特別限定 -------- 8 本紙張尺度適用中國國家標準(CNS)A4規格（21〇>< 297公爱） (請先閱讀背面之注意事項再填寫本頁) .0 一-OJ· n n I ai_i «ϋ ϋ in I n ϋ n n n n -ϋ n A7 540281 _____B7 ___ 五、發明說明（7 ) ，可使用球磨機、噴磨機等之磨機。使用磨機的情況下， 變形度可利用陶瓷球之直徑與裝入量、球磨機之旋轉速度 、處理時間等之各條件來控制。 導電體粒子之變形處理以將粒子隔離於氧與水分之外 來進行爲佳。此乃由於，於導電體粒子之表面所存在之氧 或水分係造成導電性糊料之黏度上升的因素。一般認爲氧 與水分之所以會造成黏度上升，是因爲黏結劑樹脂對粒子 表面之吸附量的增加或是水分子促使黏結劑樹脂進行交聯 反應之故。 是以，導電體粒子例如在非水系溶劑、具體而言在有 機溶劑中變形即可。做爲有機溶劑可使用例如乙醇等之醇 類。有機溶劑中可依必要性灌入氮等之非氧化性氣體來降 低溶氧。有機溶劑中之溶氧以lmg/L爲佳。又，與溶劑接 觸之磨機內之環境氣氛以保持在非氧化環境氣氛中爲佳。 在非氧化環境氣氛方面，除了減壓環境氣氛以外，尙可舉 出氮環境氣氛、惰性氣體環境氣氛等之非氧化性氣體環境 氣氛。爲了抑制氧與水之吸附，導電體粒子之變形儘可能 在短時間內結束乃爲所希望者。 經本發明者檢討發現，爲了減低糊料黏度，導電體粒 子之表面的吸附水以l〇〇〇ppm以下爲適宜。又，導電體粒 子之表面的氧濃度以1.0重量％以下爲佳。 爲了降低導電體粒子之.表面氧濃度與吸附水濃度，只 要追加導電體粒子之乾燥處理即可。乾燥處理只要使用前 面所舉出之非氧化環境氣氛即可。乾燥處理之較佳環境氣 __ 9___ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） <請先閱讀背面之注意事項再填寫本頁) ϋ IW ί ί ί n n^eJt n n n MmMmm i I n I 1« n n «I n ϋ n n ϋ ·ϋ i n n ϋ ϋ ϋ I n ϋ n · A7 540281 五、發明說明（） (請先閱讀背面之注意事項再填寫本頁) 氛溫度爲50°C〜200°C。乾燥處理只需在變形處理之前或之 後進行，若有必要亦可在變形處理之前後皆進行。 變形處理前之導電體粒子並無特別限定，爲近球形者 即可。此處所說的近球形嚴格地來說係粒子之最長徑相對 於最短徑之比例爲1〜2.0、更佳爲1〜1.5之粒子，係包含理 想球形之槪念。 當變形後之導電體粒子之比表面積會過高的情況，可 在變形之前使得導電體粒子之表面平滑化。即使是前述之 變形處理，導電體粒子彼此也會接觸，所以其表面可達某 種程度之平滑化。惟，當此平滑化並不充分的情況下，只 要使用例如捏合機或行星式攪拌機等之粉體分散機事先進 行導電體粒子之平滑化處理即可。關於平滑化處理，以在 非水系溶劑中、非氧化性氣體環境氣氛中等之非氧化環境 氣氛中進行爲佳。 -線· 如上所說明般，只要對導電體粒子在變形處理之前後 適宜地實施乾燥處理、平滑化處理等即可。又，亦可在變 形處理之後，進行讓凝集之粒子分離之破碎處理。導電體 粒子係經由例如乾燥、變形、（再）乾燥、破碎之各處理而 製造。在此一連串之處理之間，與導電體粒子接觸之氣相 以保持在非氧化環境氣氛(例如氮環境氣氛)爲佳。 只要使用本發明之導電性糊料，即使爲了避免配線間 之短路而對預浸片之被壓縮性做了限制，仍可得到配線層 間之電阻相當小之印刷配線基板。此乃由於導電體粒子之 扁平化使得粒子彼此之接觸面積增加之故。以往已知之導 一 —___ίο____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 540281 ___B7 ____ 五、發明說明（？） 電體粒子’係藉由電解法所製作之所謂鱗片狀導電體粒子 ，惟此導電體粒子會因其製作方式而具有松林石（dendrite) 狀之形狀’所以比表面積會過大。因此’導電性糊料之黏 度變得過高，會導致對貫通孔塡充導電性糊料之際之塡充 不良、脫模性薄膜剝離之際導電性糊料被薄膜帶走之缺點 等。 參照圖5A〜圖5F來說明印刷配線基板之製造方法之 較佳一例。 以圖5A所示之預浸片2來說，例如芳族聚醯胺纖維 之補強纖維7係集中配置在預浸片之內部。於預浸片之兩 面係形成實質上僅由樹脂成分所構成之樹脂層8。在此樹 脂層中由於沒有纖維，所以在此預浸片2之表面不易發生 會引發短路之凹部。樹脂層之厚度較佳爲1〜3〇μιη，特佳爲 5〜15μπι。此預浸片2之表面粗度Ra較佳爲ΙΟμιη以下。 又，預浸片2之整體厚度並無特別限定，較佳爲 50〜150μιη 〇 此預浸片2中，可隨同表面之凹部來減少內部之空隙 ，或是全部沒有空隙。一旦限制被壓縮性，則使用以往之 球形之導電體粒子無法確保充分之電氣導通。但是本發明 之導電體粒子，即使預浸片之壓縮率低仍可實現低基板電 阻値。 圖5Β〜圖5F所示之製程基本上與圖6C〜圖6G所示之 製程相同。預浸片2係以兩面貼附著脫模性薄膜1之狀態 來形成貫通孔3(圖5Β)。在貫通孔3中塡充導電性糊料4( _______jj____ . 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 0________訂_________線—黪_______________! — — A7 540281 五、發明說明（，。） 圖5C)。脫模性薄膜1被剝離（圖5D)，預浸片2係以兩面 配置有金屬箔5之狀態下被壓縮（圖5E)，金屬箔5經圖案 化形成配線圖案6(圖5F)。 對使用變形處理所得之銅粒子以掃描型電子顯微鏡 (SEM)觀察，其狀態示於圖1〜圖3。該等粒子係使其變形 度分別成爲1.20、1.02、1.11的方式來得到近球狀之銅粒 子（圖4)。圖4之銅粒子係將利用濕式反應所析出之銅加以 平滑化處理之後進行篩選來調整粒度而得者。 該等銅粒子皆呈現日本古代金幣狀(俯視爲橢圓狀之金 幣)乃至柿子之種子狀的形狀。 該等之銅粒子係使得近球狀之銅粒子與乙醇一同加入 球磨機中，以陶瓷球做適度的變形所得者。變形度係藉由 適宜變更磨機之旋轉速度與旋轉時間來調整。又，在變形 處理中球磨機內之環境氣氛係以氮氣置換。 變形度係使得變形後之銅粒子的一部分分散於水中， 使用日機裝公司製造之「麥可羅崔克(microtrack)hra ，模式9320-100」（雷射波長780nm，雷射輸出3mW)藉由 雷射繞射法來測定。在導電性糊料之調製方面係使用已變 形之銅粒子之殘餘部分。 對所得之銅粒子添加黏結劑以3輥機混練來得到導電 性糊料。具體而言，相對於銅粒子65體積％，在由雙酚F 型環氧樹脂（日本環氧樹脂公司製造「愛皮克特807」）10 體積％、二聚酸二縮水甘油酯型環氧樹脂（日本環氧樹脂公 司製造愛皮克特871)20體積％所構成之環氧主劑添加胺加 _____ 12 —_____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) n ϋ n n n n n · n ϋ n n ϋ emmmt I n . -ϋ ϋ n 1· n «I ϋ n ! i— I I n n n n «I ϋ ϋ I I - A7 540281 ____ B7___ 五、發明說明（丨1 ) 合物型硬化劑(味之素製造阿米邱亞MY-24)5體積％。 又，在黏結劑所使用之熱固性樹脂，並不侷限於雙酚 F型環氧樹脂等，亦可爲雙酚A型環氧樹脂、雙酚Ad型 環氧樹脂等之縮水甘油醚型環氧樹脂，脂環式環氧樹脂、 縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂等之含有 兩個以上環氧基之環氧樹脂等。 亦可使得含有一個環氧基之環氧化合物當作反應稀釋 劑加入前述環氧樹脂主劑中。再者，除了上述環氧樹脂以 外，將聚醯亞胺樹脂、氰酸酯樹脂、可溶酚醛樹脂等當作 黏結劑之主劑使用來形成導電性糊料亦無妨。 上述所說明之導電性糊料被稱爲無溶劑型，但爲了調 整印刷特性，亦可依必要性進一步添加丁基溶纖劑、乙基 溶纖劑、丁基卡必醇、乙基卡必醇、丁基卡必醇乙酸酯、 乙基卡必醇乙酸酯、α—蔥品醇等之溶劑，或是分散劑等 之添加劑。 預浸片係與上述導電性糊料一同準備。此預浸片係如 圖5Α所示般，使得補強纖維(芳族聚醯胺纖維)集中於預浸 片內部，於片體兩側之表面分別形成由厚度約5μιη之環氧 樹脂所構成之樹脂層。 又’對預浸片做補強之纖維並不限定於芳族聚醯胺纖 維，亦可使用ΡΒΟ(聚對苯撐苯并二噁唑）纖維、ΡΒΙ(聚苯 并咪唑）纖維、PTFE(聚四氟乙烯）纖維、ΡΒΖΤ(聚對苯撐苯 并二噻唑)纖維、全芳香族聚酯纖維等之有機纖維 '或是玻 璃纖維等之無機纖維。又，在樹脂方面，亦可取代環氧樹 ___ _13 ___ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) it --線· A7 540281 五、發明說明（U ) 脂，改用聚醯亞胺樹脂、酚醛樹脂、氟樹脂、不飽和聚酯 樹脂、PPE(聚二苯醚)樹脂、氰酸酯樹脂等之熱固性樹脂或 熱塑性樹脂。 接下來，依照圖5B〜圖5F所示之順序，製作印刷配線 基板。脫模性薄膜1係於厚度約20μιη之PET(聚對苯二甲 酸乙二醇酯)高分子薄膜的單面形成矽酮系脫模層之積層體 。金屬箔5係使用銅箔。壓縮條件係定在加壓溫度200°C 、壓力50kg/cm2、壓縮時間60分鐘。 除了圖1〜圖3所示之導電體粒子，尙使用變形度經過 適宜調整之導電體粒子來製作印刷配線基板，測定基板電 阻値(樣品1〜8)。再者，直接使用未進行變形處理之球形導 電體粒子(樣品9、10)。樣品9係使用未經過平滑化處理之 球狀導電體粒子，樣品10係使用經過平滑化處理之球狀導 電體粒子。 針對所得之各導電體粒子以及印刷配線基板測定導電 體粒子之變形度、比表面積、平均粒徑、以及印刷配線基 板之糊料黏度與基板電阻値。 變形度與平均粒徑均是以上述雷射繞射法來測定。又 ，比表面積係以BET-1點法利用比表面積測定計來測定。 此時之吸拊質係使用氮。糊料之黏度係使用E型黏度計在 常溫、0.5rpm之條件下測定。 基板電阻値係孔徑ΙΟΟμιη之通孔導體500個之串聯電 阻値，爲含有配線電阻〇·7之値。 又，測定樣品1〜7之吸附水濃度發現，所有的導電體 _ __14____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)
·1111111 — — — — — — — —— I I I I I 540281 A7 B7 五、發明說明（G ) 粒子之吸附水濃度均爲lOOOppm以下。吸附水濃度係使用 卡爾一費歇(Kad Fischer’s)水分計測定加熱到4〇(rc時之水 分量。樣品8之處理時間長，可料想爲吸附水濃度上升之 結果。 又’測定樣品1〜8之氧濃度發現，所有的導電體粒子 之氧濃度均爲1·〇重量％以下。氧濃度係對在坩堝內受熱所 產生之二氧化碳以紅外線吸收法定量來決定(依據日本工業 規格(JIS)Z 2613)。 測定結果係示於表1。 (表1) 樣品 變形度 糊料濃度 比表面積 平均粒徑 基板電阻値 (Pa . s) (m2/g) (μιη) (Ω) 1 1.01 21 0.17 5.98 2.78 2 1.02 22 0.20 6.04 2.55 3 1.05 23 0.24 6.22 2.50 4 1.10 30 0.23 6.50 2.49 5 1.20 35 0.26 7.11 2.48 6 1.40 400 0.30 8.29 2.42 7 1.50 1000 0.50 8.88 2.43 8 1.60 1500 0.62 9.48 4.88 9 1.00 90 0.19 5.92 3.25 10 1.00 15 0.16 5.94 3.75 如表1所示般，若使用變形度爲1.50以下之扁平狀的 導電體粒子，則基板電阻値會變得相當低（3Ω以下；樣品 1〜7爲2.42〜2.78)。以往之近球狀之導電體粒子基本上係以 15______ 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） (請先閱讀背面之注意事項再填寫本頁) « -------"-訂---------線 — 一· 540281 A7 —______B7 ___ 五、發明說明（咚） 點接觸來確保電氣導通，相對於此，本發明之導電體粒子 其粒子彼此間之面接觸有利於電阻値之降低。 經變形處理之導電體粒子，其受到外部應力之作用而 產生塑性變形，一般認爲在晶格中殘存有應力。積存在結 晶內部之內部應力使得加熱與加壓之際之原子的再排列變 得容易。在上述的例子中，積存在導電體粒子中之內部應 力被認爲是粒子彼此間之凝集更爲容易且更爲強固之因素 Ο 依據本發明，可提供例如含有平均粒徑爲0.2〜20μιη( 更佳爲〇·5μιη以上，例如6〜20μηι)、比表面積爲 0.05〜1.5m2/g(更佳爲0.2 m2/g以上，尤佳爲l.〇m2/g以下) 之扁平狀導電體粒子以及以熱固性樹脂爲主成分之黏結劑 ，其中黏結劑含有率爲70〜30體積％、且黏度爲lOOOPa · s 以下之導電性糊料。 又，本發明從另一個角度來看，爲一種導電性糊料之 製造方法，其含有一使得導電體粒子以比表面積成爲 0.05〜1.5m2/g(更佳爲0.2 m2/g〜1.0m2/g)的方式變形之製程 〇 如以上所說明般，依據本發明，可提供易於確保電氣 導通之導電性糊料。若使用此導電性糊料，則即使使用欠 缺被壓縮性之預浸片仍可保持低的配線層間電阻。 L____ 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ϋ ϋ n ·ϋ —a* I ϋ· 一5eJ· n n n l tmmt i temmr I ϋ 一 540281 五、發明說明（1/ ) [符號說明] A7 1，11 脫模性薄膜 2,12 預浸片 3，13 貫通孔 4，14 導電性糊料 5,15 金屬箔 6,16 配線圖案 7 補強樹脂 8 樹脂層 17 不織布 18 凹部 19 空隙 20 短路部分 (請先閱讀背面之注意事項再填寫本頁) ^1 ϋ -ϋ n ϋ ϋ I^OJt n I ϋ n 1 ϋ n 1 n ϋ ϋ n n n n ϋ n ϋ i>— ϋ n 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

Claims (1)

  1. 540281 - C8 D8 六、申請專利範圍 (請先閲讀背面之注意事項再塡寫本頁) 1·一種導電性糊料之製造方法，其包含··以對導電體 粒子施加應力使其變形度成爲1·01〜1.5的方式來讓導電體 粒子變形之製程；以及，將變形後之導電體粒子與以熱固 性樹脂爲主成分之黏結劑加以混合之製程； 此處所說的變形度係針對以雷射繞射法所測定之平均 粒徑，將變形後之導電體粒子之平均粒徑除以變形前之導 電體粒子之平均粒徑所得之値。 2. 如申請專利範圍第1項之導電性糊料之製造方法， 其中，導電體粒子變形後之比表面積爲0.05m2/g〜1.5m2/g * 〇 3. 如申請專利範圍第1項之導電性糊料之製造方法， 其中，導電體粒子變形後由雷射繞射法所測定之平均粒徑 爲 0·2μιη〜20μπι 0 4. 如申請專利範圍第1項之導電性糊料之製造方法， 係以導電體粒子30〜70體積％、以熱固性樹脂爲主成分之 黏結劑70〜30體積％的方式來混合導電體粒子與黏結劑。 5. 如申請專利範圍第1項之導電性糊料之製造方法， 其中，導電體粒子係含有擇自金、鉑、銀、鈀、銅、鎳、 錫、鉛、銦、鋅以及鉻之至少1種。 6. 如申請專利範圍第1項之導電性糊料之製造方法， 其中，係在有機溶劑中對導電體粒子施加應力。 7. 如申請專利範圍第1項之導電性糊料之製造方法， 係進一步包含在非氧化環境氣氛中使得導電體粒子乾燥之 製程。 _______Λ----- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公f) 540281 A8 Cl D8 六、申請專利範圍 8. —種印刷配線基板之製造方法，其包含： 以申請專利範圍第1項之方法來製造導電性糊料之製 壬口 · 不壬， 對至少一側面貼合有脫模性薄膜之預浸片形成貫通孔 之製程； 於該貫通孔塡充該導電性糊料之製程； 使得該預浸片隨同該脫模性薄膜與該導電性糊料一起 壓縮之製程；以及 在該壓縮製程之後，將該脫模性薄膜自該預浸片剝離 之製程。 9. 如申請專利範圍第8項之印刷配線基板之製造方法 ，其中，預浸片係含有補強纖維與樹脂，該預浸片之表面 存在著樹脂層（不具補強纖維），於壓縮製程之前，該樹脂 層之厚度爲Ιμιη〜30μιη。 (請先閲讀背面之注意事項再塡寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐)
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