TW523532B - Epoxy/clay nanocomposite for copper clad laminate applications - Google Patents

Epoxy/clay nanocomposite for copper clad laminate applications Download PDF

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TW523532B
TW523532B TW090119526A TW90119526A TW523532B TW 523532 B TW523532 B TW 523532B TW 090119526 A TW090119526 A TW 090119526A TW 90119526 A TW90119526 A TW 90119526A TW 523532 B TW523532 B TW 523532B
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Taiwan
Prior art keywords
clay
item
scope
patent application
prepreg
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TW090119526A
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English (en)
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Tsung-Yen Tsai
Sung-Jeng Jong
An-Chi Yeh
Joshua Chiang
Bor-Ren Fang
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Ind Tech Res Inst
Nanya Plastics Corp
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Priority to TW090119526A priority Critical patent/TW523532B/zh
Priority to US09/987,165 priority patent/US6548159B2/en
Priority to DE10157937A priority patent/DE10157937C2/de
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Publication of TW523532B publication Critical patent/TW523532B/zh

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    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • 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
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
    • 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
    • H05K2201/07—Electric details
    • H05K2201/0753—Insulation
    • H05K2201/0769—Anti metal-migration, e.g. avoiding tin whisker growth
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/251—Mica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • Y10T442/2049—Each major face of the fabric has at least one coating or impregnation
    • Y10T442/209—At least one coating or impregnation contains particulate material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Description

五 發明說明（1) 【發明領域 t發明係有M t、h 21種環旨料及其應用’且特別 之應用。 卡複合材料及其在電路基板 【發明背景】 從尼龍β / . 無機礦物材料以層品料實例中得知，當 複合材料的機械強⑨、孰二U::基質中時’對此種 :等物性具有加成改善的功效：：於匕阻氣性與阻水 產業已非常之普遍 及=脂應用於電子 限制,成在銅箱基板上之應定性的 :此’卢發明利用具有層狀結構的枯 勾刀月欠，形成有機/無機奈米混成材芦、衣氧树月曰均 一片片诂總士 1 ^ 人々 便专層化的粘土如 ，可有效的臺刮2分散在環氧樹脂中，利用奈米微分散時 ^ 、牵制二度空間的尺寸安定性，預期將可楹曰 用上的瓶頸 寸女疋性，龜吸水性’解決其應 【發明概述】 、本發明的目的之一就是提供一種環氧樹脂/黏土奈米 複合材料，以降低電路基板的吸水性，並提高尺寸安、定、 與耐熱性。 1 本發明的目的之二就是提供一種含有上述複合材料之 電路基板用預浸體（prepreg)。 本發明的目的之三就是提供一種使用上述預浸體之印
523532
刷電路基板。 為達上述目的，本發明使用（1)氯化节烷銨 Cbenzalkonium chloride)以及^ a, ^ ^ ^ 一鼠胺(dicyandi amide 土 Λ Λ ethylenepentamine)混合插層黏 1備成改質型黏土 * ’再與環氧樹脂募聚物進行交聯 使無機層狀材料均句分散於環氧樹脂基材巾，以製 !二：級均句分散層狀矽酸鹽類黏土的環氧樹脂複合 枓，以達成其降低吸水性與增加尺寸安定性的目的。直 中，層狀矽酸鹽類枯土經由硬化劑與疏水性官能基改質後 ，，再加入與欲合成之環氧樹脂募聚物進行均勻分散處理， 形成具有活化基且層間距離已略微撐開的層狀粘土，可以 有效改善钻土在高分子複合材料分散的特性。 【本發明詳細說明】 本發明之環氧樹脂/黏土奈米複合材料，包括：一包 含環氧樹脂之高分子基質；以及一層狀黏土材料，均勻分 f於上述高分子基質中，且該層狀黏土材料經過（1)氣化 节烧銨’以及（2)二氰胺或四伸乙基戊胺插層處理。 本發明所使用之層狀黏土材料可為陽離子交換當量 50〜200 meq/lOOg之層狀矽酸鹽。適用於本發明之層狀黏 土材料例如有：硅礬石類黏土（smectite cUy)，蛭石 (vermiculite)，管狀高嶺土（hall〇ysite)，絹雲母 (sericite)、雲母（mica)等。硅礬石類黏土（sm = tite clay)包括··蒙脫土（montmori11〇nite)，皂土（sap〇nite) ，富鋁蒙脫土（beidellite)，矽鐵石（nontronite)，
523532 五、發明說明（3) hectorite ， stevensite 等。 许® ί發明之層狀黏土材料係以兩種不同的改質劑進；T义 狀：土、，可進一步改善枯土在高分子複合材料 方法，可將無機層狀黏土沈浸在含# ^ :雛，拌持續一段時間後，以水洗去除多餘以j 成，子父換程序。本發明所使用之第一種改質二 烷銨（benzalkonium chloride)，氣化节燒# A 、下 2樹脂中容易達成高分散的狀態。本發明所使 種改質劑為擇自二氰胺（dicyandiamide)與四伸乙第一 (tetraethylenepentaraine)其中一種硬化 =…產生一反應性官能基，以增高黏土與 互作用☆’進一步改善環氧樹脂的耐熱性與J = 亡述經過改質的層狀黏土材料，#與環氧樹脂寡 進订父聯反應，以形成無機層狀材料均與 於：J層距撐開至少18Α，以形成高度分散的狀態。適曰用 樹月匕人^氧樹脂包括··雙^系環氧樹脂，演化環氧 壞氧樹脂，脂肪系環氧樹脂，以及前述之混合 ：基 子包括有·雙紛A環氧樹脂、目漠雙盼A環氧樹脂、四填雙 0424-6591TWF;02900021;e smond.p t d 第7頁 523532 五、發明說明（4) 酚A聚苯酚環氧樹脂、鄰-甲酚novo lac環氧樹脂、N，N，N，， ^-肆-（2,3-環氧丙烷基）4，？，—亞甲基苯胺^—雙 (2,3 - %氧丙烷基4_胺基-苯基環氧丙醚、4-環氧丙羥美 -N，N-雙環氧丙烷基苯胺等。 工土 ^本發明的環氧樹脂/黏土複合材料中可包括一環氧樹 脂，用的硬化劑，例如包括二氰胺（dicyandiamide)、酚 醛樹脂（phenol nov〇iak)、苯偏三酸酐（TMA ; anhydride)#。硬化劑的添加量通常為環氧 2V氧美上量，如果硬化劑的添加量小於〇·7或大於1· 2衣乳基的虽$可能會造成環氧樹脂硬化不完全。此 化促進劑加速環氧樹脂的硬化。“之硬化 促進劑包括咪唑類（imidazole)化合物 唾、1甲基-2-甲…；或三級胺類化合物甲=， ^更化促進劑可單獨或合併使用 ^ : 準，可添加0.卜1重量份的硬化促進劑。 曰為基 本發明之環氧樹脂組成物可以習知 (Prepreg)的製作。更詳細的說，本之^ ^用在預次材 物可以-適當的有機溶劑加以稀釋以 脂組成 (varnish)，再將一玻纖布塗佈或沉浸此凡立水 後便可得到所需的預浸體。上述用 水’經加熱 有：二甲基甲醯胺、丙酮、显 、機溶液例如 述所得的預浸材便可依照習知方 ；甲乙_等。上 方式進-步製成積層板、多
523532 發明說明（5) 層積層板、印刷電路板，但由於這 點’在此不予贅述。根據本發明所得心路其f發明之f 孓軸的熱膨脹係數小於60_/1 ( 二’在Tg刚 二r。。錫爐所能忍受的爆板時間可γ3=Γ/， 且在120 C二小時下的吸水率小於〇 42wU)。無論在尺寸安定性、· : 可小於〇. 有改善。 〖 以及吸水性方面都 為讓本發明之上述和其他 顯易懂，下文特舉出較佳實施 細說明如下： 【圖式之簡單說明】 目的、特徵、和優點能更明 例，並配合所附圖式，作詳
第1圖為（a)裱氧樹脂/黏土、（b)環氧樹脂/8題/黏土
、（c) %氧樹脂/DICY /黏土、（d)環氧樹脂/TEp /黏土之X 光繞射圖。 第2圖為（a)DICY/BEN /黏土與（b)環氧樹脂/DICY/BEN/ 黏土（5wt%黏土）之X光繞射圖。 第3圖為（a)TEP/BEN /黏土與（b)環氧樹脂/TEP/BEN /黏 土（5wt%黏土）之X光繞射圖。 【比較例1 ··未添加黏土】
環氧樹酯玻纖板的製備是以2.6g二氰胺（DICY; dicyandiamide)硬化劑、105.6g EB453 環氧樹脂（南亞） 與少量的2-曱基咪唾（2-MI ; 2- methylimidazole)溶於58. lg丙酮與28.6g二甲基甲醯胺（DMf)中，將此溶液攪拌均 勻。然後含浸於玻纖布上，於1 7 0 °C烘乾製成預浸體
0424-6591TWF;02900021;esmond.ptd 第9頁 — 523532 五、發明說明（6) (prepreg)，然後將此8片烘乾之預浸體疊合，上下外加兩 層銅箔經1 7 0 °C高溫硬化壓合1小時製成銅箔基板。外層銅 箔再以蝕刻的方法除去。所得樣品測量其吸水率、熱膨漲 係數（CTE , coefficient of thermal expansion)與耐熱 性，結果列於表2。 【比較例2 :添加未改質黏土】 傳統的環氧樹脂/黏土組成物以台灣百康（Pai Kong Co·)生產的高純度蒙脫土pK —8〇2製備。將2· 6g DICY、 105.6g EB453環氧樹脂與少量的2一甲基口米唾溶於gg.ig 丙酮與28· 6g二甲基甲醯胺，將此溶液攪拌均勻，並加入2 w t %的黏土’另授拌1 6小時。然後含浸於玻纖布上，於1 7 〇 °C烘乾製成預浸體，然後將此8片烘乾之預浸體疊合，上 下外加兩層銅箔經丨70它高溫硬化壓合1小時製成銅箔基板 。外層銅猪再以蝕刻的方法除去。此組成物以χ—光繞射光 譜儀（XRD)檢測其層間距，其XRI)圖形顯示於圖丨，層間 距的數據則顯示於表1。原始粘土的層間距為1 2 · 4埃，此 組成物的钻土層間距為1 5 · 7埃，此顯示未經改質的粘土層 間只有插層少量的環氧樹酯，粘土的分散性低。 【比較例3 ··添加單一改質劑改質過之黏土】 枯土使用前先以不同改質劑改質。先將5 〇 g粘土均勻 分散於4 5 0 0 m 1的水中膨潤4小時以上，然後於劇烈攪拌下 分別緩缓加入不同種類的改質劑：DICY水溶液（4. 73 g DICY + 56ml 1M HC1)、四伸乙基戊胺（TEP)水溶液 (10·65 g TEP + ^1 1M HC1)或氣化苄烷銨（BEN)水
0424-6591TWF;02900021;esmond,ptd 第10頁 523532 五、發明說明（7) ' — -----— 夜(172 ml，10 wt%)。此步驟完成後再持續在室溫下攪 、/、日守。將完成交換的粘土懸浮液過濾，所得的濾餅以 一乂去離子水清洗，反覆三次。洗淨的濾餅經乾燥、粉 碎。所得樣品分別以DICY/黏土、TEp/黏土、βΕΝ/黏土表 不。環氧樹脂/黏土玻纖基板的製備是以2,6g DICY的硬 化劑、105.6 g EB453環氧樹脂與少量的2_甲基咪唑溶於 58· lg丙嗣與28· 6g二甲基曱醯胺，將此溶液攪拌均勻， 並分別加入2 wt%的DICY/黏土、TEP/黏土與BEN/黏土， 另攪拌16小時。然後含浸於玻纖布上，於17〇 t烘乾製成 預浸體，然後將此8片烘乾之預浸體疊合，上下外加兩層 銅箔經17(TC高溫硬化壓合1小時製成銅猪基板。外層銅箔 再以蝕刻的方法除去。各樣品的XRD圖形顯示於圖1，層間 距的數據則顯示於表1。以DICY/黏土、TEP/黏土所製備的 壤氧樹脂/黏土複合材，其粘土層間距分別為丨9 · 2、丨4埃 (改質枯土的原始層間距分別為15、13· 5埃），粘土的分散 性不高。但經親油化改質的βΕΝ /黏土樣品，其所製備的複 合材’其XRD圖譜於2-1〇。幾乎未發現任何繞射峰證明大 部分枯土的層間距撐開至44埃以上而形成高度分散的狀 態。 【實施例··添加本發明以兩種改質劑改質過之黏土】 枯土使用前先以DICY與BEN(或ΤΕΡ與BEN)混合改質。 先將50 g粘土均勻分散於45〇〇 ^1的水中膨潤4小時以上， 然後於劇烈攪拌下分別緩緩加入適量的改質液：（a).】. 25 g DICY、30 mi 1M HC1 與 172 ml 10 wt% BEN 水溶液或
523532 五、發明說明（8) 一 (b). 2.85 g TEP 、20 ml 1M HC1 或（c)172 ml 1〇 ㈣ ben的水溶液。此步驟完成後再持續在室溫下攪拌6小時。 將完成交換的枯土懸浮液過據’所得的濾餅以二次去 離子水清洗，反覆三次。洗淨的濾餅於經乾燥、粉碎。所 得樣品分別以DICY/BEN/黏土與TEP/BEN/黏土表示。環氧 樹脂/黏土玻纖基板的製備是以2. 6g DI(：Y、1Q5 6 g EB453環氧樹脂與少量的2_甲基咪唑溶於58. ig丙酮盥28 k DMF中，將此溶液攪拌均勻，並分別加入3與5的 DICY/BM/黏土或TEP/BEN/黏土，另攪拌16小時。缺後含 浸於玻纖布上，於17(TC烘乾製成預浸體，然後將此8片烘 乾之預浸體疊合，上下外加兩層銅箔經丨7〇高溫硬化壓 合1小時製成銅箔基板。外層銅箔再以蝕刻的方法除去。 樣品的XRD圖譜顯示於圖2，層間距的數㈣顯示於表i。
Epoxy/DICY/BEN/黏土樣品的XRD圖譜顯示於圖2。於 2〜10。幾乎未發現任何繞射峰證明大部分粘土的層間距撐 開至44埃以上’證明枯土與環氧樹脂已形成奈米複合材 /BEN/黏土樣品的xRD圖譜則顯示於圖3。圖上ΐ68埃的微 ^繞射峰顯*此樣品只#才亟少部分枯土未達冑分散的狀 以上兩種樣品的吸水率、熱膨漲係數（CTE)盘耐埶性 列於表2。原始基板Tg前的z—gTE ( 約為59 7、 C，Tg後的Z-軸CTE ( 0：2)約為313 ppm/ t。隨著粘土含 量的增加至5 wt%時，αι逐漸減低至41 ppm/t左右，而
523532 五、發明說明（9)
七逐漸減低至260 ppm/艺左右（環氧樹脂/DICY/BEN/黏土 )°雖然奈米環氧樹脂/黏土玻纖基板的T g並沒有明顯的改 變’但基板的耐熱性穫得很大的改善。在經pCT CPFessure Cooker Test) 2小時後，試片置入288 °C錫爐 所能忍受的爆板時間從原來的8 6秒提高至3分鐘以上（表2) ’改善很明顯，且粘土添加量只需3 wt%。另外，粘土的 添加也使奈米環氧樹脂/黏土基板的吸水率大為降低（表2) 。例如，粘土添加量為5 wt%的環氧樹脂/DICY/BEN/黏土 试片的吸水率（PCT ’2小時）由原來的〇·50 wt%降低至0.41 w t %，降低幅度為1 8 %，改善幅度明顯。 表ΐ·改質粘土的特性分祈數攄 黏土 d-spacing (A) 黏土 環氧樹脂/黏土(2 wt %) 比較例2 :黏土 12.4 15.7 比較例3: BEN/黏土 18.9 >44 比較例3:DICY/黏土 15.0 19.2 比較例3:TEP/黏土 13.5 14 霣施例：DICY/BEN/黏土 19.2 >44 賓施例：TEP/BEN/黏土 19.9 16.8 (weak intensity)
0424-6591TWF;02900021;e smond.p t d 第13頁 523532 五、發明說明（ίο) 表2· 奈米環氧樹脂/黏土坡_基板的特性分祈數攄 環氧樹脂/黏土複合材料 mdm (¥t. %) CTE (ppm/°C) JiMm) A me 2h 耐 Tg fC) m 生 (sec) 0 1.62 59.7 313 0.50 136 86 DICY/Bffl 祖 3 1.57 48.4 0.47 136 >180 DICY/Bffl/|fct 5 1.60 41.2 0.41 136 >180 TEP/BEN/ltfch 3 1.60 53.1 288 0.46 135 >180 TEP/BEN/Itth 5 1.62 49.6 268 0.42 139 >180 曙臓 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。
0424-6591TWF;02900021;esmond.ptd 第14頁

Claims (1)

  1. 523532
    六、申請專利範^ 1 · 一種=氧樹脂/黏土奈米複合材料，包括·· 一包合％氧樹脂之高分子基質；以及 兮® =層狀黏土材料，均勻分散於上述高分子基質中，且 :r曰2 ί t材料經過⑴氣化节炫銨，以及（2)二氰胺或四 申乙基戊胺插層改質處理。 人如Ϊ請專利範圍第1項所述之環氧樹脂/黏土奈米複 口 ；' ，/、中含有〇·卜10重量％之層狀黏土材料。 人如t請專利範圍第2項所述之環氧樹脂/黏土奈米複 σ ; ’/、中含有0 ·5〜6重量％之層狀黏土材料。 人奸t如^專利範圍第1 ’所述之環氧樹脂/黏土奈米複 ；：'，、中該層狀黏土材料之陽離子交換當量為5 0〜2 0 0 ineq/ 1 〇〇g 〇 人姑5粗如! Ϊ專利範圍第1項所述之環氧樹脂/黏土奈米複 〇材枓，其中該層狀黏土材料係擇自 (tfcj (hall〇ySite)、絹雲母（SeriCite)、以及雲母 八2如！請專利範圍第1項所述之環氧樹脂/黏土奈米複 &。材料，其中該層狀黏土材料為蒙脫土u〇ntm〇ri"⑽… 人*Λ如申請專利範圍第1項所述之環氧樹脂，黏土夺米福 曰材料，其中該層狀黏土材料之層間距至少44 Α。”卡複 8 · —種印刷電路板用之預浸體，包括： 一環氧樹脂/黏土奈米複合材料，以 寸以及一玻璃纖維布
    六、申請專利範圍 含浸於該, • 长氧樹脂/黏土奈米複合材料，該複合材料包括 材一包含環氧樹脂之高分子基質；以及（b) 一層狀黏土 經捫钵Ϊ句分散於上述高分子基質中，且該層狀黏土材料 左過插層改質處理。 點9^如申請專利範圍第8項所述之預浸體，其中該層狀 i 材料係經過（1)氯化苄燒銨，以及（2)二氰胺或四伸乙 土戊胺插層改質處理。 士申清專利範圍第8項所述之預浸體’其中更包括 一硬化劑。 、 士 b Π ·如申請專利範圍第8項所述之預浸體，其中該環氧 樹脂/黏土奈米複合材料含有〇· 1〜丨〇重量％之層狀黏土材料 卜1 2 ·如申請專利範圍第1 1項所述之預浸體，其中該環 氧4丨爿9 /黏土奈米複合材料含有〇· 5〜6重量％之層狀黏土材 料。 1 3 ·如申請專利範圍第8項所述之預浸體，其中該層狀 黏土材料之陽離子交換當量為50〜2〇〇 me q/100g。 1 4·如申請專利範圍第8項所述之預浸體，其中該層狀 黏土材料係擇自下列所組成之族群：硅礬石類黏土 (smectite clay)、蛭石（vermicuiite)、管狀高嶺土 (hall〇ysite)、絹雲母（sericite)、以及雲母（mica)。 1 5 ·如申請專利範圍第8項所述之預浸體，其中該層狀 黏土材料為蒙脫土（montmorillonite)。 1 6 ·如申請專利範圍第8項所述之預浸體，其中該層狀
    0424-6591TWF;02900021;esmond.ptd 第16頁 523532 六、申請專利範圍 黏土材料之層間距至少44 A。 丄 17 ^ r H /積層板，由複數個申 • 種印刷電路基板，包括 ^. 請專利銘m结 A %会而成，且彡亥積層板之 月寸〜軏圍第8項所述之預浸體雙么 至少一面更疊合有一金屬層。 1 Ο » ,4, ·+[之印刷電路基板，其 1 8 ·如申請專利範圍第1 7項所也 中該金屬層為銅箔。 1 9 ·如申請專利範圍第1 7項所述之印刷電路基板，其 中該印刷電路基板在Tg前2_軸的熱膨脹係數小於60ppm/ 〇C。 2 〇 ·如申請專利範圍第1 7項所述之印刷電路基板，其 中該印刷電路基板在12〇 〇c二小時下的吸水率小於〇· 5wt0/〇
    0424-6591TWF;02900021;esmond.ptd 第17頁
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