TW200908847A - Conductive paste composition for via hole filling, printed board using the same, and method for manufacturing the printed board - Google Patents

Conductive paste composition for via hole filling, printed board using the same, and method for manufacturing the printed board Download PDF

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Publication number
TW200908847A
TW200908847A TW97114465A TW97114465A TW200908847A TW 200908847 A TW200908847 A TW 200908847A TW 97114465 A TW97114465 A TW 97114465A TW 97114465 A TW97114465 A TW 97114465A TW 200908847 A TW200908847 A TW 200908847A
Authority
TW
Taiwan
Prior art keywords
epoxy
hole
resin
group
conductive
Prior art date
Application number
TW97114465A
Other languages
Chinese (zh)
Other versions
TWI405519B (en
Inventor
Masaaki Katsumata
Katsunori Hashiguchi
Original Assignee
Matsushita Electric Ind Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Ind Co Ltd filed Critical Matsushita Electric Ind Co Ltd
Publication of TW200908847A publication Critical patent/TW200908847A/en
Application granted granted Critical
Publication of TWI405519B publication Critical patent/TWI405519B/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
    • H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
    • H05K3/4069—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques for via connections in organic insulating substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10227—Other objects, e.g. metallic pieces
    • H05K2201/10378—Interposers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/14—Related to the order of processing steps
    • H05K2203/1461—Applying or finishing the circuit pattern after another process, e.g. after filling of vias with conductive paste, after making printed resistors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4614—Manufacturing multilayer circuits by laminating two or more circuit boards the electrical connections between the circuit boards being made during lamination
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)
  • Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

Disclosed is a conductive paste composition for via hole filling, which contains 30-70% by volume of a conductive particle having an average particle diameter of 0.5-20 [mu]m and a specific surface area of 0.05-1.5 m<2>/g, and 70-30% by volume of a resin which contains not less than 10% by weight of an epoxy compound having one or more epoxy groups in a molecule, wherein the total amount of hydroxy groups, amino groups and carboxyl groups is not more than 5% by mole of the epoxy groups and the epoxy equivalent is 100-350 g/eq. This conductive paste composition for via hole filling contains chlorine in an amount of 20-2000 ppm.

Description

200908847 九、發明說明： 【明所屬領】 技術領域 本發明係有關於通孔充填用導電體糊組成物、使用其 5之雙面印刷基板與多層印刷基板、及該等基板之製造方法 【先前技術;j 背景技術 近年來，隨著電子機器之高性能化、小型化，正尋长 電路基板之高多層、高密度化。於IC間或零件間藉由^ 10孔連接作為可以最短距離連結之基板之層間連接方式，以 謀求高密度化是已知的。於一般之玻璃環氧多層基板中使 用之穿通孔連接，因於穿通孔電鍍以進行連接，故不易僅 於所需之層間進行連接，且因係於基板最上層具有電極之 平台的構造，故未能於基板最上層構成表面封裝零件之電 15極平台（dectrode land)，因該等之限制而不易提升封裝密 度。雖可進行於基板之一半開孔來取代穿通孔以減少穿通 孔之方法、及於穿通孔充填導電體糊並以電鍍程序塞住基 板最上層之孔以提升封裝密度之方法等，作為解決該等問 題之方法，但製造程序複雜。 2〇 相對於此，内通孔連接因可僅於所需之各層間進行連 接，且於基板最上層亦無穿通孔，而具有優異之封裝性。 將及連接方式應用於樹脂基板(例如，玻璃環氧基板)之例包 括’於雙面基板上使用印刷法將低黏度之溶劑型銀糊嵌入 穿通孔中，並使其乾燥硬化以得到導通之基板。然而，其 200908847 接觸電阻率高達ΙΟηιΩ ·cm左右，且缺乏對熱循環等耐熱衝 擊之可靠性。又，可進行使用較少之導電體粒子量、添加 低沸點之溶劑或活性稀釋劑等方法，作為導電體糊之低黏 度化方法，以提高導電體糊對穿通孔之嵌入性。 5 然而，若減少導電體粒子之添加量，則填料間之接觸 點會變少、通孔接觸電阻率變大，且於產生熱循環等熱應 力之試驗中未能確保可靠性。又，於添加低沸點之溶劑或 活性稀釋劑之方法中，因於熱壓之硬化中該等成分之揮發 產生的重量減少量增加，且因該揮發成分而於基材產生膨 10 脹、或降低與配線銅箔之接著力。因此，藉由含有高濃度 之導電體粒子並以亞麻油酸雙聚體縮水甘油酯環氧樹脂作 為主成分，可實現無溶劑且具低黏度、高導電性、耐熱衝 擊導電連接可靠性之導電體糊。 另外，與前述申請之發明相關之先前技術文獻資訊， 15 例如專利文獻1是已知的。 然而，前述習知例以亞麻油酸雙聚體縮水甘油S旨環氧 樹脂作為主成分，雖因樹脂之交聯密度降低而具低黏度且 熱衝擊強，但因吸水率高而於高溼度試驗中之導電連接可 靠性不足。又，因亞麻油酸雙聚體縮水甘油酯環氧樹脂係 20 屬環氧樹脂中接著強度較低者，故於通孔中使用以其為主 成分之導電體糊時，其與配線銅箔之接著力不足。 一般而言，為降低環氧樹脂之吸水率並提高接著強 度，混合可更提高交聯密度且環氧當量低之，例如雙酚型 環氧樹脂等之方法是已知的。然而，降低吸水率並提高接 200908847 低錢當量之樹脂，具錢亞麻油酸雙聚體 =:::氧樹一。因此，成為無法充填通 率大又係只要内通孔内具有導電性之導電體粒子之存在比 多之導電=導Γ電：：，使導電性糊盡量含有較 之導電性好m卩可增料電性H因混合有固體 η 液狀之黏合劑，故可糊化之混合比有限， / 10 15 二度過高，會損害對通孔之充填性。特別是，内通孔 l越小’越容易受導電性粒子密度之影響。故，内通 孔之導通性受到嚴重影響。 ;1-方面’為降低通孔内之導通電阻，可藉於導電體 糊中3有氯，以還原含於導電體糊中之導電性粒子之表 面，但若氯之含有量過多，則印刷基板之絕緣性降低。特 別是，若導電體糊中氣之含有率較預浸體中氣之含有率 尚，則含於通孔内之導電體糊之氯會侵入預浸體内，故印 刷基板之絕緣性將更容易降低。 【專利文獻1】特開平7-176846號公報 【發明内容】 發明揭示 本發明係製作一種可藉小孔徑之内通孔連接，得到電 極層間之電連接、高耐熱衝擊性、高耐濕性、及高連接強 度之導電體糊組成物。又，本發明係由含有使用該糊之内 通孔連接之雙面印刷基板製作多層印刷基板。 又，本發明之導電體糊組成物係充填於通孔之導電體 7 200908847 糊組成物，並包含有：（a)3G〜7()體積％之導電體粒子，係平 均粒徑為0.5〜2〇/zm，S其比表面積為〇 〇5〜i 5m2/g者； (b)70〜30體積％之樹月旨，係含有1G重量％以上之環氧化合物 者’該環氧化合物於-分子中具有_以上之環氧基，且經 5基、胺基及缓基之合計量為環氧基之5莫耳％以下，環氧當 量為 100〜350g/eq ;及氣20〜20〇〇ppm。 依據使用本發明之通孔充填用導電體糊之雙面印刷基 板、其形成方法及使用其之多層基板，可實現不需使用穿 通孔電鑛技術、即可簡便地具有高可靠性之小孔徑内通孔 10 的雙面印刷基板，亦可輕易地實現其多層化。 圖式簡單說明 第1圖係顯示本發明之一實施形態之雙面印刷基板之 構造截面圖。 第2A圖係相同實施形態之雙面印刷基板之形成方法之 15 工程圖。 第2B圖係相同實施形態之雙面印刷基板之形成方法之 工程圖。 第2C圖係相同實施形態之雙面印刷基板之形成方法之 工程圖。 20 第2D圖係相同實施形態之雙面印刷基板之形成方法之 工程圖。 第3A圖係相同實施形態之多層印刷基板之形成方法之 工程圖。 第3B圖係相同實施形態之多層印刷基板之形成方法之 200908847 工程圖。 第4 A圖係相同實施形態之多層印刷基板之其他形成方 法之工程圖。 第4B圖係相同實施形態之多層印刷基板之其他形成方 5 法之工程圖。 第5圖係相同實施形態之印刷基板中使用之導電性粒 子之構造圖。 【實施方式3 實施發明之最佳形態 10 (實施形態1) 以下，依據圖式詳細說明使用本發明之通孔充填用導 電體糊之雙面印刷基板、其形成方法、及使用其之多層印 刷基板。 第1圖係本發明之雙面印刷基板之一實施形態之構造 15截面圖。於第1圖中，雙面印刷基板104係由積層基材10卜 銅箔102(配線圖形之銅箔）、及導電體通孔1〇3構成，且該導 電體通孔103係硬化充填有導電體糊之孔徑為15〇Am以下 之小孔徑。本發明之重點係導電體糊組成物為低黏度故充 填谷易’且為充滿有高含有量之導電體粒子之連接。也就 20是說，本發明係低電阻率、低熱膨脹率，且導電體糊組成 物中之樹脂係低吸水率、高接著強度、無溶劑具低揮發性， 故於所有之環境試驗中，仍可製作出具有高連接可靠性之 小孔徑之内通孔基板。另外，内通孔連接，係於任意位置 連接雙面、及多層印刷基板之各層間之方法。 200908847 /成導电體通孔103之導電體糊組成物中之導電體粒 2，需於導電體組成物中含有高濃度。其原因係如前述， 4由麵1鬲導電體粒子間之接觸機率使連接通孔低電阻率 化、及於因熱或機械應力使基板歪斜增加時，亦需維持連 接可靠性。為使導電體粒子高濃度地分散，導電體粒子之 平均粒杈係於0 2〜2〇 &quot; m之範圍内，且其比表面積越小越 又，其值宜為〇.〇5〜1.5m2/g。若平均粒徑小於〇 2&quot; m， 比表面積會大於15m2/g，而未能高濃度地分散，若大於加 時，充填於1個通孔之導電體糊中之導電體粒子個數會 過少，而降低連接可靠性。又，因不易於比表面積小於 〇’〇5m /g中使平均粒徑為2〇#m以下，且若大於i.5m2/g時導 電體粒子未能高濃度地分散故不佳。此外，為提高該導電 體糊組成物對通孔之充填性，其黏度與TI值越低越好，且 TI值宜為ΐ·〇以下。另外，耵值係表示於黏度具有剪切速度 15相依性之糊中，不同之剪切速度下各黏度之相對比。於本 發明中，τι值係於溫度25tT1[1/sec]之黏度(A)、及於溫度 25 C下2[l/sec]之黏度(B)之比（A/B)。又，黏度測定係使用 東機產業（股）製，E型黏度計（DVU_E型），於25 π下 R=14mm，3°圓錐’〇.5rpm(相當於剪切速度1(1/s))之條件下 20 測定。 為確保絕緣性，本發明中氯之含有率需較預浸體中氯 之含有率低，宜為20〜20〇〇ppm。若大於2〇〇〇ppm，印刷基 板之絕緣性會降低。又，若小於2〇ppm，因通孔之接觸電阻 值會變大，故不佳。 200908847 更詳細說明大於2000ppm時之情形。此時，因充填於 通孔内之導電體糊中氯之含有率較預浸體中氣之含有率 高’而有侵入預浸體並提高預浸體中之氣濃度之疑慮，藉 此’基板之絕緣性會降低，而容易產生位移。又，於通孔 正上方之平台上封裝半導體裝置時，通孔内之氣容易移動 至半導體裝置’使對半導體裝置之絕緣性降低。 又一電體粒子之種類大致可使用金、銘、銀、I巴等 貝金屬或銅、錄、錫、錯、銦等卑金屬，亦可併用該等2 種以上。 1〇 ' 只训^ 也·&lt;- *T 丞极丫 1尤用之導 電性粒子之構造圖。於第5圖中，核501為球狀，導電性材 料502具有作為覆蓋核5Q1表面之導電性填料之作用。如 亦可使用以導電性之材料覆蓋不僅為單—之金屬，亦 15 I為合金、金屬或絕緣性之核者。又，導電體粒子之形狀 、要係具有前述平均粒徑 ^比表面積者的話，並未特別限 ‘== 抑制、經濟上之供應及價格之穩定 〜般係容易氧化銅私末作為導電體粒子。然而’因鋼粉末 易乳化，故於作為通孔 2〇 之氧化會阻礙導電性。l %使料’鋼粉末 %以下。 因此，銅粉末之氣濃度宜為1.0重量 一况㈣成導電體通孔ι〇3之 月旨。為形錢接可靠性t 冑體卿3中之樹 罪性问之内通孔用導書 上樹脂係、需要無溶敎低Μ 組成物’基本 ,+ 且低黏度、低吸水率、&gt; &amp; μ &amp; 句脂。為得到該物理性新 咼接者強度之 貝樹脂之組成係使用含有1〇重量％ 200908847 10 15 20 以上之環氧化合物之樹脂，該環氧化合物於一分子中含有1 個以上之環氧基，且羥基、胺基及羧基為環氧基之5莫耳％ 以下’環氧當量為100〜350g/eq。以環氧化合物作為必要成 分之原因係為得到高接著強度。於該環氧化合物中，羥基、 胺基及羧基需為環氧基之5莫耳％以下之低濃度的原因 係，因該等具有氫鍵結力高之官能基，故即使樹脂黏度低， 導電體糊之黏度仍為高。相反地，只要該等氫鍵結力高之 官能基為環氧基之5莫耳以下之低濃度的話，即使樹脂黏度 高仍可得低黏度之導電體糊。另外，羥基、胺基及羧基與 環氧基之比可以化學定量分析確認，亦可簡單地以紅外分 光分析中3500cm-1附近之吸光度（因羥基、胺基及羧基所產 生者）、及910cm-1附近之吸光度（因環氧基所產者)之比來確 認。於該環氧化合物中’以⑽〜35Gg/eq為環氧當量之原因 係，當為350g/eq以上時交聯密度會過低則吸水率增高而成 為低接著強度，當小於⑽g/eq時㈣密度會過冑則硬化收 縮歪斜增大導致接著強度低下。若於樹脂中含有1〇重量％ 以上之環氧化合物’可得低吸水率、高接著強度之導電體 糊組成物。環氧化合物以外之樹脂成分，只要為無溶劑的 活’並未特別限制。又，亦可視需要混合用以使環氧化合 物反應硬化之環氧硬化劑。另外，導電體糊之點度宜為 2000Pa s以下、TI值為（以下當黏度為2麵μ以上、耵 值大於1時’將產生未能進行通孔充填作業之不良情況。 又、於本《明中使樹腊為無溶劑之原因係，若含有溶劑時’ 於、孔中充填°轉電體組成物後加熱壓縮時，其中之揮發 12 200908847The present invention relates to a conductive paste composition for through-hole filling, a double-sided printed substrate using the same, a multilayer printed substrate, and a method of manufacturing the same. BACKGROUND ART In recent years, with the increase in performance and miniaturization of electronic devices, high-rise and high-density circuit boards have been being sought. It is known to increase the density by connecting the interlayers of the substrates which can be connected at the shortest distance between the ICs or between the parts. The through-hole connection used in a general glass epoxy multilayer substrate is difficult to connect only between the required layers because of the connection through the through-hole plating, and the structure having the platform of the electrode on the uppermost layer of the substrate is The electric 15 pole platform that fails to form the surface package part on the uppermost layer of the substrate is not easy to increase the package density due to such restrictions. Although it is possible to perform a method in which one of the substrate is half-opened to replace the through-hole to reduce the through-hole, and the through-hole is filled with the conductive paste and the uppermost layer of the substrate is plugged by a plating process to increase the package density, etc. The method of the problem, but the manufacturing process is complicated. In contrast, the inner via connection can be connected only between the required layers, and there is no through hole in the uppermost layer of the substrate, and the package is excellent. Examples of applying and connecting a method to a resin substrate (for example, a glass epoxy substrate) include embedding a low-viscosity solvent-type silver paste into a through-hole through a printing method on a double-sided substrate, and drying and hardening it to obtain a conduction. Substrate. However, its 200908847 contact resistivity is as high as ΙΟηιΩ · cm and lacks the reliability of heat shock resistance such as thermal cycling. Further, a method of using a small amount of the conductor particles, adding a solvent having a low boiling point, or a reactive diluent can be used as a method for lowering the viscosity of the conductor paste to improve the embedding property of the conductor paste to the through-hole. 5 However, if the amount of addition of the conductor particles is reduced, the contact point between the fillers is reduced, the contact resistance of the via hole is increased, and reliability is not ensured in the test for generating a thermal stress such as thermal cycle. Further, in the method of adding a solvent having a low boiling point or a reactive diluent, the amount of weight loss due to volatilization of the components during hardening is increased, and swelling of the substrate occurs due to the volatile component, or Reduce the adhesion to the wiring copper foil. Therefore, by containing a high concentration of conductive particles and using linoleic acid dimer glycidyl epoxy resin as a main component, it is possible to realize a solvent-free and low-viscosity, high-conductivity, heat-resistant and impact-resistant conductive connection. Body paste. Further, prior art document information related to the invention of the aforementioned application, 15 is known, for example, from Patent Document 1. However, the above-mentioned conventional example uses a linoleic acid dimer glycidol S-based epoxy resin as a main component, and has a low viscosity and a strong thermal shock due to a decrease in the crosslinking density of the resin, but a high water absorption rate due to a high water absorption rate. The reliability of the conductive connection in the test was insufficient. In addition, since the strength of the linoleic acid dimer glycidyl ester epoxy resin is 20, the epoxy resin has a lower adhesive strength. Therefore, when a conductive paste containing the main component is used for the through hole, the wiring copper foil is used. The force is not enough. In general, in order to lower the water absorption rate of the epoxy resin and increase the strength of the subsequent bonding, the mixing can further increase the crosslinking density and the epoxy equivalent is low, and a method such as a bisphenol type epoxy resin is known. However, lowering the water absorption rate and increasing the resin with a low equivalent weight of 200908847, the money linoleic acid dimer =::: oxygen tree one. Therefore, it is impossible to fill the flux rate as long as the conductivity of the conductive particles in the inner via hole is more than the conductivity = conductive::, the conductive paste is contained as much as possible, which is better than the conductivity. Since the material H is mixed with the solid η liquid binder, the mixing ratio of the gelatinization is limited, and the / 10 15 is too high, which may impair the filling of the through holes. In particular, the smaller the inner through hole l is, the more susceptible it is to the density of the conductive particles. Therefore, the continuity of the inner through hole is seriously affected. In the 1-first aspect, in order to reduce the on-resistance in the via hole, chlorine may be present in the conductor paste to reduce the surface of the conductive particles contained in the conductor paste, but if the chlorine content is excessive, printing is performed. The insulation of the substrate is lowered. In particular, if the gas content of the conductive paste is higher than the gas content of the prepreg, the chlorine of the conductive paste contained in the through holes will intrude into the prepreg, so the insulation of the printed substrate will be more Easy to lower. [Patent Document 1] JP-A-7-176846 DISCLOSURE OF THE INVENTION [Invention] The present invention is capable of making an electrical connection between electrode layers, high thermal shock resistance, high moisture resistance, and the like. And a conductive paste composition having a high connection strength. Further, in the present invention, a multilayer printed board is produced from a double-sided printed board having a through-hole connected therein. Further, the conductor paste composition of the present invention is filled with the conductor 7 200908847 paste composition of the through hole, and comprises: (a) 3G to 7 (% by volume) of the conductor particles, the average particle diameter of 0.5~ 2〇/zm, S has a specific surface area of 〇〇5~i 5m2/g; (b) 70~30% by volume of the tree is intended to contain 1G by weight or more of the epoxy compound of the epoxy compound - having an epoxy group of _ or more in the molecule, and having a total of 5 groups, an amine group and a slow group being 5 mol% or less of the epoxy group, and having an epoxy equivalent of 100 to 350 g/eq; and gas 20 to 20 〇〇ppm. According to the double-sided printed circuit board using the conductive paste for via filling of the present invention, the method for forming the same, and the multilayer substrate using the same, it is possible to realize a small aperture which can be easily and highly reliable without using the through-hole electrowinning technique. The double-sided printed substrate of the inner through hole 10 can also be easily multi-layered. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the structure of a double-sided printed circuit board according to an embodiment of the present invention. Fig. 2A is a plan view showing a method of forming a double-sided printed circuit board of the same embodiment. Fig. 2B is a view showing a method of forming a double-sided printed circuit board of the same embodiment. Fig. 2C is a view showing a method of forming a double-sided printed circuit board of the same embodiment. 20D is a drawing of a method of forming a double-sided printed circuit board of the same embodiment. Fig. 3A is a plan view showing a method of forming a multilayer printed substrate of the same embodiment. Fig. 3B is a 200908847 drawing of a method of forming a multilayer printed substrate of the same embodiment. Fig. 4A is a plan view showing another method of forming a multilayer printed board of the same embodiment. Fig. 4B is a plan view showing another method of forming a multilayer printed circuit board of the same embodiment. Fig. 5 is a structural view showing conductive particles used in a printed circuit board of the same embodiment. [Embodiment 3] BEST MODE FOR CARRYING OUT THE INVENTION (Embodiment 1) Hereinafter, a double-sided printed circuit board using a conductive paste for via filling according to the present invention, a method for forming the same, and multilayer printing using the same will be described in detail with reference to the drawings. Substrate. Fig. 1 is a cross-sectional view showing the structure of an embodiment of a double-sided printed circuit board of the present invention. In the first embodiment, the double-sided printed circuit board 104 is composed of a laminated base material 10, a copper foil 102 (a copper foil of a wiring pattern), and a conductor through hole 1〇3, and the conductive through hole 103 is hardened and filled. The pore size of the conductor paste is a small pore size of 15 〇 Am or less. The main point of the present invention is that the conductor paste composition has a low viscosity and is filled with a valley and is filled with a high content of conductive particles. In other words, the present invention is low resistivity, low coefficient of thermal expansion, and the resin in the electrical conductor paste composition has low water absorption, high adhesion strength, and low solvent-free volatility, so in all environmental tests, It is still possible to produce a via substrate having a small aperture with high connection reliability. Further, the inner via connection is a method of connecting the double-sided and the layers of the multilayer printed substrate at any position. 200908847 / The conductor particles 2 in the conductor paste composition of the conductor via 103 are required to have a high concentration in the conductor composition. The reason is as described above. 4 The contact probability between the surface and the conductor particles makes the connection vias low in resistivity, and when the substrate skew increases due to thermal or mechanical stress, the connection reliability needs to be maintained. In order to disperse the conductor particles at a high concentration, the average particle size of the conductor particles is in the range of 0 2 to 2 〇 &quot; m, and the smaller the specific surface area, the more the value is preferably 〇.〇5~1.5 M2/g. If the average particle size is less than 〇2&quot; m, the specific surface area will be greater than 15 m2/g, but it will not be dispersed at a high concentration. If it is larger than the time, the number of conductive particles filled in the conductive paste of one via hole will be too small. , while reducing the reliability of the connection. Further, since the specific surface area is less than 〇' 〇 5 m / g, the average particle diameter is 2 Å or less, and if it is more than 1. 5 m 2 /g, the conductive particles are not dispersed at a high concentration, which is not preferable. Further, in order to improve the filling property of the conductive paste composition to the via hole, the viscosity and the TI value are preferably as low as possible, and the TI value is preferably ΐ·〇 or less. In addition, the enthalpy value is expressed as the relative ratio of the viscosities at different shear velocities in the paste having a viscosity of 15 dependence. In the present invention, the value of τι is the ratio (A/B) of the viscosity (A) at a temperature of 25tT1 [1/sec] and the viscosity (B) at a temperature of 25 C at 2 [l/sec]. In addition, the viscosity measurement system was made by Toki Shoji Co., Ltd., E-type viscometer (DVU_E type), R=14 mm at 25 π, 3° cone '〇.5 rpm (corresponding to shear rate 1 (1/s) Under the conditions of 20 determination. In order to ensure insulation, the chlorine content in the present invention is required to be lower than the chlorine content in the prepreg, and is preferably 20 to 20 ppm. If it is more than 2 〇〇〇 ppm, the insulation of the printed substrate will be lowered. Further, if it is less than 2 〇 ppm, the contact resistance value of the via hole becomes large, which is not preferable. 200908847 describes in more detail the situation greater than 2000ppm. At this time, since the content of chlorine in the conductive paste filled in the through-hole is higher than the content of the gas in the prepreg, there is a concern that the prepreg is invaded and the concentration of gas in the prepreg is increased, thereby The insulation of the substrate is lowered and displacement is likely to occur. Further, when the semiconductor device is packaged on the stage directly above the via hole, the gas in the via hole is easily moved to the semiconductor device' to lower the insulation property of the semiconductor device. Further, as the type of the electric particles, a base metal such as gold, melamine, silver or I bar, or a base metal such as copper, tin, tin, or indium may be used, or two or more of them may be used in combination. 1〇 'Only training ^ Also · &lt;- *T 丞 丫 1 The structural diagram of conductive particles used in particular. In Fig. 5, the core 501 is spherical, and the conductive material 502 has a function as a conductive filler covering the surface of the core 5Q1. For example, it is also possible to use a conductive material to cover not only a single metal, but also 15 I as an alloy, metal or insulating core. Further, the shape of the conductor particles and the average particle diameter of the specific surface area are not particularly limited to '== suppression, economical supply, and stable price. . However, since the steel powder is easily emulsified, the oxidation as the through hole 2 阻碍 hinders the conductivity. l % of the material 'steel powder below %. Therefore, the gas concentration of the copper powder is preferably 1.0%. (4) The purpose of forming the electric conductor through hole ι〇3. Reliability for the shape of money t 胄 卿 卿 3 3 3 3 3 3 3 3 用 用 用 用 用 用 用 用 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂&amp; μ &amp; A resin containing an epoxy compound containing 1% by weight of 200908847 10 15 20 or more, which contains one or more epoxy groups in one molecule, in order to obtain the composition of the shell resin of the physical strength of the new joint. And the hydroxyl group, the amine group and the carboxyl group are 5 mol% of the epoxy group, and the 'epoxy equivalent' is 100 to 350 g/eq. The reason why an epoxy compound is an essential component is to obtain a high adhesion strength. In the epoxy compound, the hydroxyl group, the amine group and the carboxyl group are required to have a low concentration of 5 mol% or less of the epoxy group, and since these have a functional group having a high hydrogen bonding force, even if the resin has a low viscosity, The viscosity of the conductor paste is still high. On the contrary, as long as the functional group having a high hydrogen bonding strength is a low concentration of 5 m or less of the epoxy group, a low-viscosity conductor paste can be obtained even if the resin has a high viscosity. In addition, the ratio of a hydroxyl group, an amine group, and a carboxyl group to an epoxy group can be confirmed by chemical quantitative analysis, and the absorbance near 3500 cm-1 (produced by a hydroxyl group, an amine group, and a carboxyl group), and 910 cm can be simply analyzed by infrared spectroscopic analysis. The ratio of the absorbance near -1 (produced by the epoxy group) was confirmed. In the epoxy compound, the reason why the epoxy equivalent is (10) to 35 Gg/eq is that when the crosslinking density is 350 g/eq or more, the water absorption rate is increased to become low adhesion strength, and when it is less than (10) g/eq. (4) If the density is too high, the hardening shrinkage will increase and the strength will be low. When the epoxy compound is contained in an amount of 1% by weight or more in the resin, a conductive paste composition having a low water absorption rate and a high adhesion strength can be obtained. The resin component other than the epoxy compound is not particularly limited as long as it is solvent-free. Further, an epoxy hardener for reacting and curing the epoxide may be mixed as needed. In addition, the dot thickness of the conductor paste is preferably 2,000 Pa s or less, and the TI value (hereinafter, when the viscosity is 2 μm or more and the 耵 value is greater than 1), there is a problem that the through hole filling operation cannot be performed. "The reason why the tree wax is solvent-free in the Ming Dynasty is that if the solvent is contained, the hole is filled with the composition of the electroconducting body and then heated and compressed, and the volatilization thereof 12 200908847

成分會揮發散出，於通孔充填組成物中產生空隙、或產生 預浸體之剝離等，造成連接不穩定。 適合使用之環氧化合物，可舉例如：縮水甘油醚型環 氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、 5 及脂環式環氧樹脂等。其中，藉由使用雙酚縮水甘油醚型 環氧樹脂，例如：雙酚A型環氧樹脂(化1)、雙酚F型環氧樹 月旨（化2)、雙酚AD型（化3)、氫化雙酚型環氧樹脂（化4)、環 氧烷改質雙酚型環氧樹脂(化5)、烷氧基改質雙酚型環氧樹 脂（化6)等，可以低黏度得到低吸水率與高接著強度。該等 10 雙酚縮水甘油醚型環氧樹脂可單獨亦可以任意之組合使 用。 【化1】The components are volatilized, voids are formed in the through-hole filling composition, or peeling of the prepreg or the like occurs, resulting in unstable connection. The epoxy compound to be used may, for example, be a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, or a alicyclic epoxy resin. Among them, by using a bisphenol glycidyl ether type epoxy resin, for example, a bisphenol A type epoxy resin (Chemical 1), a bisphenol F type epoxy resin (Chemical 2), and a bisphenol AD type (3) ), hydrogenated bisphenol epoxy resin (chemical 4), alkylene oxide modified bisphenol epoxy resin (chemical 5), alkoxy modified bisphenol epoxy resin (chemical 6), etc., can be low viscosity A low water absorption rate and a high adhesion strength are obtained. These 10 bisphenol glycidyl ether type epoxy resins may be used singly or in any combination. 【化1】

ch3 I CH2-CH-CH2-〇-\/ 0 &lt;^)-C-&lt;Q)-0-CH2-CH-CH2-0-(Q)-C-^)-0-CH2-CH-CH2 -CH3 OH Jn CH3 \(/ 15 o 2 但是，ng〇。 2'nv I© I oCh3 I CH2-CH-CH2-〇-\/ 0 &lt;^)-C-&lt;Q)-0-CH2-CH-CH2-0-(Q)-C-^)-0-CH2-CH- CH2 -CH3 OH Jn CH3 \(/ 15 o 2 However, ng〇. 2'nv I© I o

HICIH ◎ n2 c H-H CIO I„2 c -0- ◎ nHICIH ◎ n2 c H-H CIO I„2 c -0- ◎ n

HIC1H H -c ό d -CH-CHs \/ 0 但是，ng〇 【化3】HIC1H H -c ό d -CH-CHs \/ 0 However, ng〇 [化3]

H IH I

H CH2-CH-CH2-0-\/ 0 &lt;^)-c-^)-o-ch2-ch-ch2-o-^&gt;-c-&lt;^)-o-ch2-ch-ch2 CH3 OH Jn CH3 、〇/ 13 200908847 n&gt;0 但是 【化4】 ch3 ch3 CH2-CH-CH2-O-\/ 但是 (^|&lt;^-o-ch2-ch-ch2-〇-(h).c-(h).〇.CH2.CHch2 、CH3 OH Jn CH3 \〇/ 0 0 【化5】 CH3H CH2-CH-CH2-0-\/ 0 &lt;^)-c-^)-o-ch2-ch-ch2-o-^&gt;-c-&lt;^)-o-ch2-ch-ch2 CH3 OH Jn CH3 , 〇 / 13 200908847 n&gt;0 But [化4] ch3 ch3 CH2-CH-CH2-O-\/ But (^|&lt;^-o-ch2-ch-ch2-〇-(h) .c-(h).〇.CH2.CHch2, CH3 OH Jn CH3 \〇/ 0 0 【化5】CH3

CH2-CH-CH2-(0-CH-CH2)m-0-^)-C-{g)-0-(CH2-CH-0)n-CH2.CH-CH 'O’ R CH3 R \〇/2 但是，R=CpH2p+l(pg 1)，且m+n^2。 【化6】 CH3 CH, CH-CH2-0-CH2-CH-CH2-0-^-C-&lt;g).〇.CH2.CH.CH2_〇_cH 0 15 ch2 1 CH3 CH2 0 1 1 0 R l R 但是，kCpmp+KpM)。 CH-CH2 \/ 20 環氧化合物係由90〜20重量%之雙盼縮 %乳樹脂(A群)、及1〇，重量%之選自 7 肪族醇縮水甘_型環氧樹脂 之=鏈脂 :=氧樹…少-種環_:::::: 此處，含通孔之連接可靠性。 树月“列，可使用：雙酚A型環氧樹脂 14 200908847 5 二 (化1)雙紛卩型％氧樹脂(化2)、雙紛型（化、氫化雙酚 里％乳樹Μ化4)、環氧燒改質雙粉型環氧樹脂(化5)、炫氧 基改質雙_環氧樹脂(化6)等。χ，含於轉之樹脂例， 可使用：亞麻油酸雙聚體縮水甘油型魏樹脂(化7)、異戊 二烯己酸二聚物縮水甘油酯型環氧樹脂(化8)、烷烴羧酸 (versatic acid)縮水甘油酯型環氧樹脂(化9)、月桂基縮水甘 油醚型環氧樹脂(化1G)等。該等群之樹脂可單獨亦可 以任意之組合使用。 【化7】 10 (CH2)7-C〇OCH2CH-CH2 I \/ CH Ο CH CH-(CH2)7COOCH2CH-CH2 CH CH-CH2-CH=CH(CH2)4CH3 、CH I (CH2)5-CH3 15 【化8】 CJH3CH2-CH-CH2-(0-CH-CH2)m-0-^)-C-{g)-0-(CH2-CH-0)n-CH2.CH-CH 'O' R CH3 R \〇 /2 However, R = CpH2p + l (pg 1), and m + n ^ 2. [Chemical 6] CH3 CH, CH-CH2-0-CH2-CH-CH2-0-^-C-&lt;g).〇.CH2.CH.CH2_〇_cH 0 15 ch2 1 CH3 CH2 0 1 1 0 R l R However, kCpmp+KpM). The CH-CH2 \/ 20 epoxy compound is composed of 90 to 20% by weight of a double-preferable % latex resin (Group A), and 1% by weight, and the weight % is selected from the group consisting of 7 aliphatic alcohol glycosyl-type epoxy resins. Chain fat: = oxygen tree... less - kind of ring _:::::: Here, the connection reliability of the through hole is included. Tree month "column, can be used: bisphenol A type epoxy resin 14 200908847 5 two (chemical 1) double sputum type oxygen resin (chemical 2), double type (chemical, hydrogenated bisphenol% eucalyptus 4), epoxy-fired modified double-powder epoxy resin (chemical 5), oxyoxy modified double _ epoxy resin (chemical 6), etc. χ, contained in the resin case, can be used: linoleic acid Dimer glycidyl type Wei resin (Chemical 7), isoprene hexanoic acid dimer glycidyl ester type epoxy resin (Chemical 8), alkane carboxylic acid (versatic acid) glycidyl ester type epoxy resin 9), lauryl glycidyl ether type epoxy resin (chemical 1G), etc. The resins of the groups may be used singly or in any combination. [Chemical 7] 10 (CH2)7-C〇OCH2CH-CH2 I \/ CH Ο CH CH-(CH2)7COOCH2CH-CH2 CH CH-CH2-CH=CH(CH2)4CH3, CH I (CH2)5-CH3 15 [Chemical 8] CJH3

CH2-CH-CH2-〇p-(CH2)6-C=CH-(CH2)2-CH=C-(CH2}6-CO-CH2_CH-CHo 丄 〇 V o 2CH2-CH-CH2-〇p-(CH2)6-C=CH-(CH2)2-CH=C-(CH2}6-CO-CH2_CH-CHo 丄 〇 V o 2

H2 \CH ΛΧ c t,2 c - 0 1 one 9]R1l-c--R3 化½ [ R 但是，R1、R2、R3均為炫基，且其碳數之合計為8 15 200908847 【化10】 c12H25-〇-CH2-CH-CH2 ο 又’其他適用之環氧化合物可舉平均分子量600〜10000 5之％氧寡聚物為例。環氧寡聚物之羥基、胺基、及羧基量 相對於環氧基量非常地少，且於作為導電體糊時，隨著樹 脂分子量的增加黏度之剪切速度相依性(ΤΙ值）會變小，故具 有可得低黏度導電體糊之效果。此外，環氧寡聚物亦有提 升剝離接著強度之效果。 10 又’當環氧化合物係由90〜19重量％之雙酚縮水甘油趟 型環氧樹脂(A群）、9〜80重量％之〇8以上之長鏈脂肪族醇縮 水甘油醚型環氧樹脂與C8以上之長鏈脂肪酸縮水甘油酯型 環氧樹脂(B群）、及1〜30重量％之平均分子量600〜1 〇〇〇〇之環 氧募聚物(C群)所構成之樹脂時，可特別地以低黏度得到低 15吸水率與高接著強度’且其對應力之緩和效果強，故可提 高通孔之連接可靠性。 此處，含於A群之樹脂例，可使用：雙酚A型環氧樹脂 (化1)、雙酚F型環氧樹脂（化2)、雙酚AD型（化3)、氫化雙盼 型環氧樹脂(化4)、環氧烷改質雙酚型環氧樹脂(化5)、烧氧 20基改質雙酚型環氧樹脂（化6)等。又，含於B群之樹脂例， 可使用：亞麻油酸雙聚體縮水甘油型環氧樹脂（化7)、異戊 二烯己酸二聚物縮水甘油酯型環氧樹脂（化8)、烷烴綾酸 (versatic acid)縮水甘油酯型環氧樹脂（化9)、月桂基縮水甘 油醚型環氧樹脂（化10)等。此外’含於c群之樹脂例，可使 16 200908847 用：環氧化不飽和脂肪酸改質物(化11)、環氧化聚丁二烯(化 12)、環氧化聚苯乙稀丁二烯共聚物(化π)等。該等A群B群 C群之樹脂可單獨亦可以任意之組合使用。 【化11】 0 〇 5 II /\ R1 -C-0-R2-(CH-CH-R3)n-R4 但是，Rl、R4均為碳數1〜18之烷基，R2、R3均為碳數 0〜8之亞烧基，且ngl。 【化12】 1〇 R-(CH2-CH-CH-CH2)q-{CH2-CH=CH-CH2)r(CH2-CH)s-(CH2-CH)rR，H2 \CH ΛΧ ct,2 c - 0 1 one 9]R1l-c--R3 1⁄2 [R However, R1, R2, R3 are all sleek, and the total carbon number is 8 15 200908847 [10] c12H25-〇-CH2-CH-CH2 ο Further, other suitable epoxy compounds are exemplified by oxygen oligomers having an average molecular weight of 600 to 10000%. The amount of the hydroxyl group, the amine group, and the carboxyl group of the epoxy oligomer is extremely small relative to the amount of the epoxy group, and when it is used as the conductor paste, the shear rate dependence (ΤΙ value) of the viscosity increases as the molecular weight of the resin increases. It becomes smaller, so it has the effect of obtaining a low-viscosity conductor paste. In addition, the epoxy oligomer also has the effect of improving the peeling strength. 10 'When the epoxy compound is 90 to 19% by weight of bisphenol glycidol oxime type epoxy resin (Group A), 9 to 80% by weight of 长8 or more of long-chain aliphatic alcohol glycidyl ether type epoxy A resin composed of a resin and a long-chain fatty acid glycidyl ester epoxy resin (Group B) of C8 or higher and 1 to 30% by weight of an epoxy polymer (Group C) having an average molecular weight of 600 to 1 Å In particular, a low 15 water absorption rate and a high adhesion strength can be obtained with a low viscosity, and the stress relaxation effect is strong, so that the connection reliability of the through holes can be improved. Here, examples of the resin contained in Group A can be used: bisphenol A type epoxy resin (chemical 1), bisphenol F type epoxy resin (chemical 2), bisphenol AD type (chemical 3), hydrogenation double expectation Type epoxy resin (chemical 4), alkylene oxide modified bisphenol type epoxy resin (chemical 5), burned oxygen 20-based modified bisphenol type epoxy resin (chemical 6), and the like. Further, examples of the resin contained in the group B can be used: linoleic acid dimer glycidyl type epoxy resin (chemical 7), isoprene hexanoic acid dimer glycidyl ester type epoxy resin (chemical 8) An alkane citric acid glycidyl ester type epoxy resin (chemical 9), a lauryl glycidyl ether type epoxy resin (10). In addition, the resin contained in group c can be used for 16 200908847: epoxidized unsaturated fatty acid modification (11), epoxidized polybutadiene (12), epoxidized polystyrene butadiene copolymer (chemical π) and so on. The resins of the Group A Group B Group C may be used singly or in any combination. 0 〇5 II /\ R1 -C-0-R2-(CH-CH-R3)n-R4 However, Rl and R4 are all alkyl groups having 1 to 18 carbon atoms, and R2 and R3 are all carbon. A number of 0 to 8 sub-alkyl groups, and ngl. [Chemical 12] 1〇 R-(CH2-CH-CH-CH2)q-{CH2-CH=CH-CH2)r(CH2-CH)s-(CH2-CH)rR,

0 CH CH0 CH CH

ϋ\ I I ch2 ch2 但是，R、R’均為碳數0〜8之烷基，且qg 1，rg 1，sg 1，1 ° 15【化13】ϋ\ I I ch2 ch2 However, R and R' are all alkyl groups having a carbon number of 0 to 8, and qg 1, rg 1, sg 1, 1 ° 15 [Chemical 13]

R-(CH2-CH)v-(CH2-CH-CH-CH2)w-(CH2-CH=CH-CH2)x-(CH2-CH)y-(CH2-CH)z-RR-(CH2-CH)v-(CH2-CH-CH-CH2)w-(CH2-CH=CH-CH2)x-(CH2-CH)y-(CH2-CH)z-R

0 /CH CH 〇、ck ch2 但是，R、R’均為碳數〇〜8之燒基，且丨，1 ’ x 20 $ 1，yg 1，zg 1。 又，導電體糊中亦可視需要添加環氧化合物以外之樹 脂。適用之樹脂可使用例如：以提升耐熱性為目的之醯亞 胺樹脂、酚醛樹脂等；以提升與銅箔之剝離接著強度為目 的之聚烯烴等乙烯聚合物、丙烯酸樹脂、聚醚、聚酯、聚 17 200908847 醯胺、聚胺酯等。該等樹脂可單獨亦可以任意之組合使用。 另外，導電體糊中亦可視需要混合環氧硬化劑。環氧 硬化劑可使用一般作為單成分組成物使用之硬化劑。可使 用例如：二氰二胺、羧基醯肼等胺系硬化劑、十七基咪唑 5 等咪唑系硬化劑、3-(3,4-三氯苯基)-1、1-二甲基尿素等尿 素系硬化劑、甲基六酞酸酐、内亞甲四氫酞酐等酸酐系硬 化劑、三苯膦等膦系硬化劑、及六氟銻鹽等路易斯酸(Lewis Acid)等。於該等中，特別地由組成物之穩定性及作業性之 觀點來看，以潛在性硬化劑為佳。此處，潛在性硬化劑係， 10 具有於室溫下反應呈停止狀態時，長期特性無改變並可保 存，且當加熱於預定溫度以上時，粒子會熔融、分解或溶 解，顯現出被封存之活性基，一起使反應開始並快速硬化 之機能者。 又，亦可視需要於導電體糊中混合分散劑。分散劑可 15 使用一般所使用之分散劑，可使用具代表性之第一種，高 級脂肪酸之環氧乙烷、環氧丙烷添加酯化物、山梨醇酐與 脂肪酸之酯化合物、山梨醇酐等多元醇之環氧乙烷、環氧 丙烧添加醚化合物、烧基苯之環氧乙烧、環氧丙烧添加物 等非離子性分散劑；第二種，烷基苯磺酸鹼金屬鹽、高級 20 醇硫酸酯鹼金屬鹽、磷酸酯化合物、高級脂肪酸、高級脂 肪酸之環氧乙烷、環氧丙烷添加物之硫酸鹼金屬鹽等陰離 子系分散劑；第三種，4級銨鹽型之陽離子分散劑。此處所 指之分散劑藉於糊中增加與作為與金屬粒子表面之黏合劑 所混合之有機樹脂的親和性，具有促進糊之低黏度化及低 18 200908847 τι值化的效果。 5 10 15 20 積層基材101只要為擠壓時其厚度較預浸體於硬化後 薄者即可’並無限制，可使用目前所知之所有積層基材。 可使用例如.玻璃織布、玻璃不織布、酿胺織布、醯胺不 織布之任一者與環氧樹脂等熱硬化性樹脂之複合材料、或 玻璃織布、玻璃不織布、醯胺織布、醯胺不織布之任一者 與玻璃轉移溫度18(rC以上之熱可塑性樹脂(例如：全芳香 族礅S曰树脂、聚醚砜、聚醚酮、聚醚醚酮等）之複合材料、 或者薄膜材料，以形成絕緣材料。 2A圖〜第2D圖係本發明雙面基板之形成方法之工程 圖於第2A圖中，積層基材2〇1係預浸體，且該預浸體開有 孔=150#m以下之穿通孔，一般而言常使用鑽孔，但依據 料之不同亦可使用雷射束等其他之加工法。並且，於穿 通孔内充填有導電體糊加。第2B圖係顯示以銅㈣2夾著 第圖之狀態。第2CW係顯示對第糊施加加熱加壓後之 狀’。又’第2C圖係顯示開於預浸體之穿通孔於加熱加壓 後金屬充填#增加之狀態，預浸體受到壓縮厚度變薄，且， 硬化’導電體糊加係呈壓縮狀態，且該呈壓縮狀態之 導電體糊係導電體通孔1G3。導電體通孔1()3具有電連接上 ，兩面之作用。第2D圖係顯不加工表面銅㈣顺刻等)且 :成有配線圖形後之狀態。加工後之銅㈣2會成為電路導 電體。可供實用之印刷基板於之後有塗布阻烊（s〇Mer =吟印刷文字或記號、開設摘入零件用之孔等步驟，此 处因非本發明之本質故省略。 19 200908847 第3A、B圖係顯示重複使用前述雙面基板之形成方法 以製作多層印刷基板之步驟。第3A圖係顯示於芯層雙面印 刷基板104之兩側（上下面）配置於第2A圖之穿通孔充填有 導電體糊者’並設有銅箔202之狀態。於此狀態下，由上下 5面加熱加壓的話，可製作第3B圖之多層印刷基板，且已做 成内通孔連接。此外，若將上下面之銅箔202加工成圖形狀 即可完成4層之多層印刷基板。之後，重複該步驟，可做出 層數更多之多層印刷基板。 於第3A、B圖之多層印刷基板之形成方法中，芯層之 10雙面印刷基板雖使用本發明之雙面基板，但非為必要，可 使用習知穿通孔雙面印刷基板。因此，不需重新準備可做 成雙面基板之設備，可減少成本。此時，宜預先設有穿通 孑匕（貝通孔）。此處之穿通孔基板係指樹脂基板。另外，穿通 孔基板除了樹脂基板之外亦可使用陶瓷基板等。 15 第4A、B圖係顯示多層印刷基板之其他形成方法。於 第4A圖中，以2片雙面印刷基板1〇4夾著充填有導電體糊2〇3 之加熱加壓前之積層基材201。於該狀態下加熱加壓，可得 到第4B圖之4層多層印刷基板。除了4層之外，若準備複數 片之雙面印刷基板，並於各雙面基板間夹著充填有前述導 20電體粒子之加熱加壓前之積層基材進行加熱加壓的話，可 製作更多層之多層印刷基板。 於第4A、B圖之多層印刷基板之形成方法中之雙面基 板雖使用本發明之雙面基板，但並非為必要，可使用習知 穿通孔雙面印刷基板。又，穿通孔基板除了樹脂基板之外 20 200908847 亦可使用陶瓷基板等。 接著，使用圖表說明相對於本發明導電體糊組成物之 氯含有量之印刷配線板的特性。 ' 第1表係顯示相對於含於糊中之可水解氯量與通孔直 - 5 徑之通孔接觸電阻值與絕緣電阻值。 【第1表】 可水解氣量 (PPM) 通孔直徑 (// m) 接觸電阻值 (ηιΩ /通孔） 絕緣電阻值 (kV/mm) 10 200 8.9 18 10 150 15.5 20 10 100 21.7 20 10 75 25.4 21 15 75 11.8 19 20 200 5.8 18 20 150 5.5 20 20 100 4.2 20 20 75 6.1 19 100 75 3.9 20 500 75 2.7 18 1000 75 3.1 17 2000 200 1.8 9 2000 150 2.1 14 2000 100 2.5 15 2000 75 2.3 18 3000 200 2.0 6 如第1表所示，只要本發明之填充於印刷配線板之通孔 之導電體糊組成物之可水解氯量為20ppm以上的話，即使通 孔直徑為150//m以下，接觸電阻值仍為ΙΟιηΩ/通孔以下， 21 200908847 得到電導通性良好之結果。 _又，當導電體糊組成物之可水解氯量較預浸體中氣之 含有率低時，即為2_ppm的話，亦可於絕緣電阻值中得到 良好之結果。 5 且’可使用玻璃織布、玻璃不織布、酿胺織布、醯胺 不織布之任一者與環氧樹脂等熱硬化性樹脂之複合材料、 或玻璃織布、玻璃不織布、醢胺織布、醯胺不織布之任一 者與玻璃轉移溫度18(TC以上之熱可塑性樹脂（例如：全芳 香族聚酯樹脂、聚醚颯、聚醚酮、聚醚醚酮等）之複合材料、 10或者薄膜材料，以形成絕緣材料。 如以上所述，依據本實施形態卜本發明之導電體糊組 成物至少包含有：（a)30〜70體積％之導電體粒子，係平均粒 徑為0.5〜20㈣，且其比表面積為m.5m2/g者、（b)7〇〜3〇 體積％之樹脂，係含有1〇重量％以上之環氧化合物者，該環 15氧化合物於一分子中具有1個以上之環氧基，且羥基、胺基 及羧基之合計量為環氧基之5莫耳％以下，環氧當量為 100〜350g/eq、及氣20〜2000ppm，因此，藉由將該導電體糊 組成物充填於孔徑150 &quot;m以下之通孔，可實現具高可靠性 内通孔之雙面或多層印刷基板。 20 另外，本發明之實施形態1中，通孔之孔徑雖為15〇u m以下，但亦可為較150/zm大之孔徑。 產業上利用之可能性 本發明之導電體糊組成物可作為高密度配線基板，並 具有於可尚速傳輸之南頻電路用途、半導體封裝等細微之 22 200908847 配線圖形用途、及需小型、輕量化之可攜式電子機器用途 等中所需之高連接可靠性，且有助於低廉印刷配線基板之 形成。 【圖式簡單說明】 5 第1圖係顯示本發明之一實施形態之雙面印刷基板之 構造截面圖。 第2 A圖係相同實施形態之雙面印刷基板之形成方法之 工程圖。 第2B圖係相同實施形態之雙面印刷基板之形成方法之 10 工程圖。 第2C圖係相同實施形態之雙面印刷基板之形成方法之 工程圖。 第2D圖係相同實施形態之雙面印刷基板之形成方法之 工程圖。 15 第3A圖係相同實施形態之多層印刷基板之形成方法之 工程圖。 第3B圖係相同實施形態之多層印刷基板之形成方法之 工程圖。 第4A圖係相同實施形態之多層印刷基板之其他形成方 20 法之工程圖。 第4B圖係相同實施形態之多層印刷基板之其他形成方 法之工程圖。 第5圖係相同實施形態之印刷基板中使用之導電性粒 子之構造圖。 23 200908847 【主要元件符號說明】 101,201…積層紐 102.202.. .銅箔 103.. .導電體通孔 104.. .雙面印刷基板 203…導電體糊 501…核 502…導電性材料 240 /CH CH 〇, ck ch2 However, R and R' are each a carbon number of 〇8, and 丨, 1' x 20 $ 1, yg 1, zg 1. Further, a resin other than the epoxy compound may be added to the conductor paste as needed. For the resin to be used, for example, an yttrium imide resin or a phenol resin for the purpose of improving heat resistance, and an ethylene polymer, an acrylic resin, a polyether, and a polyester such as polyolefin for the purpose of improving the peeling strength of the copper foil. , poly 17 200908847 guanamine, polyurethane and so on. These resins may be used singly or in any combination. Further, an epoxy hardener may be mixed in the conductor paste as needed. As the epoxy hardener, a hardener which is generally used as a one-component composition can be used. For example, an amine hardener such as dicyandiamide or carboxyhydrazine, an imidazole hardener such as heptadecyl imidazole 5, or 3-(3,4-trichlorophenyl)-1,1-dimethylurea can be used. An acid-based curing agent such as a urea-based curing agent, methyl hexaic anhydride or nematic tetrahydrophthalic anhydride, a phosphine-based curing agent such as triphenylphosphine, or a Lewis acid such as hexafluoroantimony salt. Among these, a latent curing agent is preferred from the viewpoint of stability of the composition and workability. Here, the latent curing agent system 10 has a long-term characteristic that does not change and can be stored when the reaction is stopped at room temperature, and when heated above a predetermined temperature, the particles melt, decompose or dissolve, and appear to be sealed. The active group, together with the function of the start of the reaction and rapid hardening. Further, the dispersant may be mixed in the conductor paste as needed. The dispersing agent can be used as a dispersing agent which is generally used, and can be used as a representative first one, an ethylene oxide of a higher fatty acid, an esterified product of propylene oxide, an ester compound of sorbitan with a fatty acid, sorbitan, etc. a nonionic dispersing agent such as an ethylene oxide of a polyhydric alcohol, an epoxy ether-added ether compound, an alkylene oxide ethidium bromide or a propylene-acrylic acid additive; and a second, an alkylbenzenesulfonic acid alkali metal salt , an advanced 20 alcohol sulfate alkali metal salt, a phosphate compound, a higher fatty acid, an ethylene oxide of a higher fatty acid, an alkali metal salt of a propylene oxide additive, an anionic dispersant; a third, a grade 4 ammonium salt type a cationic dispersant. The dispersant referred to herein has an effect of promoting the low viscosity of the paste and the low value of the organic resin mixed with the binder on the surface of the metal particles. 5 10 15 20 The laminated substrate 101 is not limited as long as it is thinner than the prepreg after curing, and any laminated substrate known to date can be used. For example, a composite material of a glass woven fabric, a glass nonwoven fabric, a woven amine woven fabric, or a guanamine non-woven fabric, and a thermosetting resin such as an epoxy resin, or a glass woven fabric, a glass nonwoven fabric, a amide woven fabric, or a enamel can be used. Any of the amine non-woven fabrics and a composite material having a glass transition temperature of 18 (rC or higher thermoplastic resin (for example, wholly aromatic 礅S曰 resin, polyether sulfone, polyether ketone, polyether ether ketone, etc.) or a film material 2A to 2D are drawings of a method for forming a double-sided substrate of the present invention. In FIG. 2A, a laminated substrate 2〇1 is a prepreg, and the prepreg is opened with a hole= For the through hole of 150#m or less, drilling is generally used, but other processing methods such as laser beam can be used depending on the material. Moreover, the through hole is filled with a conductive paste. Fig. 2B The state in which the copper (four) 2 is sandwiched between the figures is shown. The second CW shows the state after the heating and pressurization of the second paste. The second 2C shows the metal filling of the through-holes of the prepreg after heating and pressurization. In the state of increase, the prepreg is thinned by compression and hard 'The conductor paste is in a compressed state, and the conductor paste-based conductor through hole 1G3 is in a compressed state. The conductor through hole 1 () 3 has an electrical connection and functions on both sides. The 2D figure is not processed. Surface copper (four), etc.): The state after the wiring pattern is formed. The processed copper (4) 2 will become the circuit conductor. The printed circuit board that can be used is subsequently coated with a barrier (s〇Mer = 吟 printed characters or symbols, and a hole for opening the parts), which is omitted here because it is not the essence of the present invention. 19 200908847 3A, B The figure shows a step of repeatedly forming the double-sided substrate to form a multilayer printed substrate. Fig. 3A shows the through-holes of the double-sided printed substrate 104 on both sides (upper and lower sides) arranged in the second A-picture. In the state in which the conductive paste paste is provided with the copper foil 202. In this state, when the upper and lower surfaces are heated and pressurized, the multilayer printed circuit board of Fig. 3B can be produced and connected as an inner via hole. The upper and lower copper foils 202 are processed into a patterned shape to complete a four-layer multilayer printed substrate. Thereafter, this step is repeated to make a multilayer printed circuit board having a larger number of layers. The multilayer printed substrate of FIGS. 3A and B In the forming method, although the double-sided substrate of the present invention is used for the double-sided printed circuit board of the present invention, it is not necessary, and the substrate can be printed on both sides by a conventional through-hole. Therefore, it is not necessary to prepare for a double-sided substrate. Equipment, can be reduced In this case, it is preferable to provide a through-hole (beacon hole) in advance. The through-hole substrate here means a resin substrate, and the through-hole substrate may be a ceramic substrate or the like in addition to the resin substrate. Fig. B shows another method of forming a multilayer printed substrate. In Fig. 4A, a laminated substrate 201 before heating and pressing filled with a conductor paste 2〇3 is sandwiched between two double-sided printed boards 1〇4. In this state, heating and pressurization are performed to obtain a four-layer multilayer printed circuit board as shown in Fig. 4B. In addition to the four layers, a plurality of double-sided printed boards are prepared, and the above-mentioned conductive wires are filled between the double-sided substrates. When the laminated substrate before heating and pressing of the bulk particles is heated and pressurized, a multilayer printed circuit board of a plurality of layers can be produced. The double-sided substrate in the method for forming a multilayer printed substrate according to FIGS. 4A and 4B uses the present invention. A double-sided substrate is not necessarily required, and a conventional through-hole double-sided printed substrate can be used. Further, a through-hole substrate can be used in addition to a resin substrate. 20 200908847 A ceramic substrate or the like can also be used. Next, a graph will be used to explain the conductor with respect to the present invention. The characteristics of the printed wiring board of the chlorine content of the composition. 'The first table shows the contact resistance value and the insulation resistance value of the through hole with respect to the amount of hydrolyzable chlorine contained in the paste and the through-hole diameter of the through hole. 1 Table] Hydrolyzable gas volume (PPM) Through hole diameter (// m) Contact resistance value (ηιΩ / through hole) Insulation resistance value (kV/mm) 10 200 8.9 18 10 150 15.5 20 10 100 21.7 20 10 75 25.4 21 15 75 11.8 19 20 200 5.8 18 20 150 5.5 20 20 100 4.2 20 20 75 6.1 19 100 75 3.9 20 500 75 2.7 18 1000 75 3.1 17 2000 200 1.8 9 2000 150 2.1 14 2000 100 2.5 15 2000 75 2.3 18 3000 200 2.0 6 As shown in the first table, as long as the amount of hydrolyzable chlorine of the conductor paste composition filled in the through hole of the printed wiring board of the present invention is 20 ppm or more, the contact resistance is 150/m or less. The value is still below ΙΟιηΩ/through hole, 21 200908847 The result of good electrical conductivity is obtained. Further, when the amount of hydrolyzable chlorine of the conductor paste composition is lower than the gas content of the prepreg, that is, 2 ppm, good results can be obtained from the insulation resistance value. 5 and 'a composite material of a glass woven fabric, a glass non-woven fabric, a woven amine woven fabric, a guanamine non-woven fabric, and a thermosetting resin such as an epoxy resin, or a glass woven fabric, a glass non-woven fabric, or a amide woven fabric, Any of the guanamine non-woven fabrics and a composite material of 10 or more thermoplastic resins (for example, wholly aromatic polyester resin, polyether oxime, polyether ketone, polyether ether ketone, etc.) having a glass transition temperature of 18 or more The material is formed to form an insulating material. As described above, the conductive paste composition of the present invention comprises at least (a) 30 to 70% by volume of conductive particles having an average particle diameter of 0.5 to 20 (4). And a resin having a specific surface area of m. 5 m 2 /g or (b) 7 〇 to 3 vol%, which is an epoxy compound containing 1% by weight or more, and the ring 15 oxygen compound has 1 in one molecule. More than one epoxy group, and the total amount of the hydroxyl group, the amine group and the carboxyl group is 5 mol% or less of the epoxy group, the epoxy equivalent is 100 to 350 g/eq, and the gas is 20 to 2000 ppm. The conductive paste composition is filled in a through hole having a diameter of 150 &quot;m or less In addition, in the first embodiment of the present invention, the aperture of the through hole is 15 um or less, but may be larger than 150/zm. (Aperture) Industrial Applicability The conductive paste composition of the present invention can be used as a high-density wiring substrate, and has a subtle 22 such as a south-frequency circuit that can be transmitted at a constant speed, and a semiconductor package. The high connection reliability required for lightweight portable electronic equipment applications and the like, and contributes to the formation of a low-cost printed wiring board. [Fig. 1] FIG. 1 shows an embodiment of the present invention. Fig. 2A is a plan view showing a method of forming a double-sided printed circuit board of the same embodiment. Fig. 2B is a plan view showing a method of forming a double-sided printed circuit board of the same embodiment. 2C is a drawing of a method of forming a double-sided printed board of the same embodiment. Fig. 2D is a drawing of a method of forming a double-sided printed board of the same embodiment. 15 Fig. 3A Fig. 3B is a plan view showing a method of forming a multilayer printed circuit board of the same embodiment. Fig. 4A is a view showing another method of forming a multilayer printed circuit board of the same embodiment. Fig. 4B is a plan view showing another method of forming a multilayer printed circuit board of the same embodiment. Fig. 5 is a structural view showing conductive particles used in a printed circuit board of the same embodiment. 23 200908847 [Description of main component symbols] 101,201...layered layer 102.202.. copper foil 103.. conductor through hole 104.. double-sided printed substrate 203...conductor paste 501...core 502...conductive material 24

Claims (1)

200908847 十、申請專利範圍： 1. 一種通孔充填用導電體糊組成物，係氯之含有量為 20〜2000ppm者，包含有： 30〜70體積％之導電體粒子，係平均粒徑為0.5〜20 5 //m，且其比表面積為0.05〜1.5m2/g者；及 70〜30體積％之樹脂，係含有10重量％以上之環氧化 合物者，該環氧化合物於一分子中具有1個以上之環氧 基，且羥基、胺基及羧基之合計量為環氧基之5莫耳％ 以下，環氧當量為100〜350g/eq。 10 2.如申請專利範圍第1項之通孔充填用導電體糊組成物， 其中前述導電體粒子係選自於以下（1)至（4)之至少一種 粒子： (1)選自於金、銘、銀、纪、銅、鎳、錫、錯、銦之至 少一種粒子； 15 (2)選自於金、翻、銀、把、銅、鎳、錫、錯、銦、鋅、 絡之任意組合之合金粒子； (3)以導電性或非導電性粒子作為核，並以選自於金、 銘、銀、把、銅、鎳、錫、錯、銦之至少一種金屬披覆 之粒子；及 20 (4)以導電性或非導電性粒子作為核，並以選自於金、 鉑 '銀 '鈀 '銅 '鎳 '錫 '鉛 '銦 '鋅' 鉻之任意組合 之合金彼覆之粒子。 3.如申請專利範圍第1項之通孔充填用導電體糊組成物， 其中前述導電體粒子含有表面氧濃度為1.0重量％以下 25 之句。 4·如申請專利範圍第1項之通孔充填用道 …述環氧化合物係選自於二導電體糊組成物， 5腸、縮水甘_型錢_ ^相型環氧樹 脂環式環氣榭, 甘油胺型環氧樹脂及 5·如申过:糾曰之至少一種環氧樹骑。 甲叫專利範圍第丨項之通孔充 其中前述iff!/μ yw 、導電體糊組成物， 6.如由 乳化合物係雙_水甘油_型環氧樹月匕 10 、中别杨氧化合物係含有 賴 之環氧寡聚物。 重®刀子置600〜10000 7·如申請專利範圍第i項之通孔充填 其中前述環氧化合物係由9〇〜2 =成物， :型環氧樹脂、及!。〜8。重量%之選;=水甘油 月旨肪族醇墻欢^ ； 上之長鏈 15 叫細水甘油鍵型環氧樹 酸縮水甘油酷型環氣 、8以上之長鏈脂肪 之樹脂。 θ V —種環氧樹脂所構成 8.如申請專利範圍第丨項 # φ ^ .s . 、之通孔充填用導電體糊組成物， 其令則述環氧化合物係由9〇〜 峻型環氧樹脂、9〜8〇h 置/。之雙_水甘油 20 重里％之選自於碳數（C)8以上之| 鏈脂肪族醇縮水甘 之長 長鮮靜^ '喊型環氧樹脂與碳數(c)8以上之 长鍵知肪酸水甘、、丄k , / 環氧樹脂之至少一種樹 1〜30重量％之重哥伞认 U钿及 所構成之樹脂。句分子量6〇〇〜1〇_之環氧寡聚物 如項之通孔充填用導電體糊組成物， 26 200908847 其中關於糊組成物之黏度特性，係於溫度25 下， 1 [ 1 /sec]之黏度(A)與2[ 1 /sec]之黏度⑻之比（A/B)為i以 下。 10. —種印刷基板，係於絕緣基材内所開設之通孔中，充填 5 有導電性樹脂組成物，且電連接前述絕緣基材表面之上 下電極層者，前述導電性樹脂組成物，包含有： 30〜70體積％之導電體粒子，係平均粒徑為〇 5〜2〇#爪， 且其比表面積為0_05〜1.5m2/g者； 70〜30體積％之樹脂，係含有1〇重量％以上之環氧化合 10 物者，該環氧化合物於一分子中具有1個以上之環氧 基，且羥基、胺基及羧基之合計量為環氧基之5莫耳％ 以下，環氧當量為100〜350g/eq ;及 20 〜2000ppm之氣， 且前述導電性樹脂組成物於前述通孔中硬化。 15丨1·如申請專利範圍第10項之印刷基板，其中前述通孔之孔 徑係150/z m以下。 12. —種印刷基板之製造方法，包含有以下步驟： 於用以製造印刷基板之預浸體預先形成通孔； 於前述通孔中充填導電體糊組成物，且前述導電體糊組 20 成物包含有： 3〇〜70體積％之導電體粒子，係平均粒徑為〇 5〜2〇 私m，且其比表面積為〇 〇5〜丨5m2/g者； 70〜30體積％之樹脂’係含有1〇重量。/。以上之環氧化 合物，該環氧化合物於一分子中具有丨個以上之環氧 27 200908847 基，且羥基、胺基及羧基之合計量為環氧基之5莫耳％ 以下，環氧當量為100〜350g/eq ;及 20 〜2000ppm之氯； 於前述預浸體之上下層隔著銅箔進行加熱加壓；及 5 藉Ί虫刻前述銅箔形成電路。 13.如申請專利範圍第12項之印刷基板之製造方法，其更具 有一將前述通孔之孔徑形成為150//m以下之步驟。 28200908847 X. Patent application scope: 1. A conductive paste composition for through-hole filling, which has a chlorine content of 20 to 2000 ppm, and contains: 30 to 70% by volume of electrical conductor particles having an average particle diameter of 0.5. ~20 5 / / m, and its specific surface area is 0.05 ~ 1.5m2 / g; and 70 ~ 30% by volume of the resin, containing 10% by weight or more of the epoxy compound, the epoxy compound has one molecule One or more epoxy groups, and the total amount of the hydroxyl group, the amine group and the carboxyl group is 5 mol% or less of the epoxy group, and the epoxy equivalent is 100 to 350 g/eq. The conductive paste composition for through-hole filling according to the first aspect of the invention, wherein the conductive particles are selected from at least one of the following (1) to (4): (1) selected from gold , at least one particle of Ming, silver, Ji, copper, nickel, tin, wrong, indium; 15 (2) selected from gold, turn, silver, handle, copper, nickel, tin, wrong, indium, zinc, Any combination of alloy particles; (3) particles coated with conductive or non-conductive particles as a core and coated with at least one metal selected from the group consisting of gold, magnesium, silver, copper, nickel, tin, aluminum, and tin And 20 (4) using conductive or non-conductive particles as a core, and alloyed with any alloy selected from the group consisting of gold, platinum 'silver' palladium 'copper 'nickel' tin 'lead' indium 'zinc' chromium Particles. 3. The conductor paste composition for via filling according to the first aspect of the invention, wherein the conductor particles have a surface oxygen concentration of 1.0% by weight or less. 4. The through-hole filling method of the first application of the patent scope is described above. The epoxy compound is selected from the group consisting of a two-conductor paste composition, and the intestine is reduced in the form of an epoxy resin ring.榭, glycerol amine type epoxy resin and 5· as claimed: at least one epoxy tree ride. The through hole of the third paragraph of the patent scope is filled with the above iff!/μ yw, the conductor paste composition, 6. If the milk compound is bis-glycidyl _ type epoxy tree 匕 10, the middle arsenic compound It contains an epoxy oligomer of Lai. The weight of the knife is set to 600~10000. 7. The through-hole filling of the i-th item of the patent application range is as follows: The above epoxy compound is composed of 9〇~2 = compound, epoxy resin, and !. ~8. The choice of % by weight; = water glycerin. The long-chain of 15 is called glycerin bond type epoxy tree, acid glycidol cool type ring, 8 or more long chain fat resin. θ V is an epoxy resin composition. 8. The application of the conductive paste composition for through-hole filling according to the scope of the patent application # # # 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧Epoxy resin, 9~8〇h. The double _ glycerol 20% of the weight is selected from the carbon number (C) 8 or more | The chain aliphatic alcohol shrinks the long and quiet ^ ^ The screaming epoxy resin and the carbon number (c) 8 or more long bonds At least one kind of tree of 1 to 30% by weight of the tree of fatty acid, 丄k, / epoxy resin, and the resin. An epoxy oligomer having a molecular weight of 6〇〇~1〇_, such as a conductive paste composition for through-hole filling, 26 200908847 wherein the viscosity characteristic of the paste composition is at a temperature of 25, 1 [1 /sec The ratio (A/B) of the viscosity (A) to the viscosity (8) of 2 [1/sec] is i or less. 10. A printed circuit board, which is filled in a through hole formed in an insulating substrate, filled with a conductive resin composition, and electrically connected to a lower electrode layer on the surface of the insulating substrate, the conductive resin composition, The method comprises: 30 to 70% by volume of the conductive particles, wherein the average particle diameter is 〇5~2〇# claw, and the specific surface area is 0_05~1.5m2/g; 70~30% by volume of the resin contains 1 In the case of epoxidized 10% by weight or more, the epoxy compound has one or more epoxy groups in one molecule, and the total amount of the hydroxyl group, the amine group and the carboxyl group is 5 mol% or less of the epoxy group. The epoxy equivalent is 100 to 350 g/eq; and 20 to 2000 ppm of gas, and the conductive resin composition is hardened in the through hole. The printed circuit board of claim 10, wherein the through hole has a hole diameter of 150/z m or less. 12. A method of manufacturing a printed circuit board comprising the steps of: forming a via hole in advance in a prepreg for manufacturing a printed substrate; filling a conductive paste composition in the through hole; and forming the conductive paste group 20 The material comprises: 3〇~70% by volume of the conductive particles, the average particle diameter is 〇5~2〇m, and the specific surface area is 〇〇5~丨5m2/g; 70~30% by volume of the resin 'The system contains 1 〇 weight. /. In the above epoxy compound, the epoxy compound has more than one epoxy group 27 200908847 in one molecule, and the total amount of the hydroxyl group, the amine group and the carboxyl group is 5 mol% or less of the epoxy group, and the epoxy equivalent is 100 to 350 g/eq; and 20 to 2000 ppm of chlorine; the lower layer of the prepreg is heated and pressurized via a copper foil; and 5 the copper foil is formed by an aphid to form an electric circuit. 13. The method of manufacturing a printed circuit board according to claim 12, further comprising the step of forming the aperture of the through hole to be 150//m or less. 28
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TWI620253B (en) * 2016-04-26 2018-04-01 Method for building conductive substrate

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