TWI521025B - Resin composition and the use of its copper foil substrate and printed circuit board - Google Patents

Resin composition and the use of its copper foil substrate and printed circuit board Download PDF

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Publication number
TWI521025B
TWI521025B TW103100304A TW103100304A TWI521025B TW I521025 B TWI521025 B TW I521025B TW 103100304 A TW103100304 A TW 103100304A TW 103100304 A TW103100304 A TW 103100304A TW I521025 B TWI521025 B TW I521025B
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Taiwan
Prior art keywords
resin
epoxy resin
mouth
bisphenol
resin composition
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TW103100304A
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English (en)
Other versions
TW201508034A (zh
Inventor
Rongtao Wang
Yu Te Lin
Wenjun Tian
Ziqian Ma
Wenfeng Lv
Ningning Jia
Original Assignee
Elite Electronic Material Kunshan Co Ltd
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Publication of TW201508034A publication Critical patent/TW201508034A/zh
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Publication of TWI521025B publication Critical patent/TWI521025B/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
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    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G59/621—Phenols
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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Description

樹脂組成物及應用其之銅箔基板及印刷電路板
本發明係關於一種樹脂組成物，尤指一種應用於銅箔基板及印刷電路板之樹脂組成物。
習知技術使用DICY做為環氧樹脂之硬化劑，會有Tg低(DSC測試， Tg=140 ℃)及基板PCT耐熱性不佳的狀況。
習知技術使用了苯并[口咢][口井](Benzoxazine，Bz)樹脂做為環氧樹脂之硬化劑，然而苯并[口咢][口井]樹脂需要共硬化劑使苯并[口咢][口井]開環，然後再與環氧樹脂交聯。日立化成(CN1088727C)使用了苯酚酚醛樹脂與Bz樹脂協同作用，但使用苯酚酚醛樹脂會造成介電特性過高(Dk約4.4, Df約0.014@2GHz)，無法達到低介電銅箔基板之規格需求。
現有技術為了達到銅箔基板之低介電特性(Dk ≤ 4.1, Df≦ 0.01 @2GHz)，一般使用原料成本昂貴的氰酸酯樹脂，但氰酸酯樹脂之原料成本約為環氧樹脂之八倍以上，因此成本高昂造成產品競爭性不佳。
綜上所述，本領域缺乏一種無需使用氰酸酯樹脂亦能達到低介電特性且兼具了基板高耐熱特性的樹脂組成。
因此，本領域迫切需要開發一種無需使用氰酸酯樹脂亦能達到低介電特性且兼具了基板高耐熱特性的樹脂組成。
本發明的第一目的在於：為了克服此成本之困境，本發明揭露了無需使用氰酸酯樹脂亦能達到低介電特性的樹脂組成物，且兼具了基板高耐熱特性。
本發明的第二目的在於獲得應用本發明樹脂組成物的半固化膠片。
本發明的第三目的在於獲得應用本發明樹脂組成物的銅箔基板。
本發明的第四目的在於獲得應用本發明樹脂組成物的印刷電路板。
在本發明的第一方面，提供了一種樹脂組成物，其包含： (A)100重量份的環氧樹脂； (B)10至80重量份的苯并[口咢][口井]樹脂； (C)10至50重量份的雙環戊二烯苯酚樹脂；以及 (D)0.5至5重量份的胺類硬化劑； 所述樹脂組成物中不含二烯丙基雙酚A(DABPA)。
在本發明的一個具體實施方式中，所述雙環戊二烯苯酚樹脂選自如下結構式的化合物：， 其中n為1～5的正整數，Z為選自-H及-CH3 之其一者或其組合。
在本發明的一個具體實施方式中，該胺類硬化劑係選自下列群組中之至少一者：二胺基二苯碸、二胺基二苯基甲烷、二胺基二苯醚、二胺基二苯硫醚及雙氰胺。
在本發明的一個較佳實施方式中，所述胺類硬化劑為雙氰胺(DICY)。
在本發明的一個具體實施方式中，該環氧樹脂係選自下列群組中之至少一者：雙酚A環氧樹脂、雙酚F環氧樹脂、雙酚S環氧樹脂、雙酚AD環氧樹脂、雙酚A酚醛環氧樹脂、鄰甲酚酚醛環氧樹脂、三官能基環氧樹脂、四官能基環氧樹脂、雙環戊二烯型環氧樹脂、含DOPO之環氧樹脂、含DOPO-HQ之環氧樹脂、對二甲苯環氧樹脂、萘型環氧樹脂、苯并哌喃型環氧樹脂、聯苯酚醛環氧樹脂、異氰酸酯改質環氧樹脂、酚苯甲醛環氧樹脂及酚基苯烷基酚醛環氧樹脂。
在本發明的一個具體實施方式中，該苯并[口咢][口井]樹脂係選自下列群組中之至少一者：雙酚A型苯并[口咢][口井]樹脂、雙酚B型苯并[口咢][口井]樹脂、二胺基二苯醚型苯并[口咢][口井]樹脂及酚酞型苯并[口咢][口井]樹脂。
在本發明的一個具體實施方式中，其進一步包含30至70重量份的阻燃劑，該阻燃劑係選自下列無鹵阻燃劑及鹵素阻燃劑中之至少一者：雙酚聯苯磷酸鹽、聚磷酸銨、對苯二酚-雙-(聯苯基磷酸鹽)、雙酚A-雙-(聯苯基磷酸鹽)、三(2-羧乙基)膦、三(異丙基氯)磷酸鹽、三甲基磷酸鹽、二甲基-甲基磷酸鹽、間苯二酚雙二甲苯基磷酸鹽、磷氮基化合物、m-苯甲基膦、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯及三-羥乙基異氰尿酸酯、9,10-二氫-9-氧雜-10-磷菲-10-氧化物(DOPO)、含DOPO酚樹脂、乙基-雙(四溴苯鄰二甲醯亞胺)、乙烷-1,2雙(五溴苯)和2,4,6-三-(2,4,6-三溴苯氧基)-1,3,5-三嗪。
在本發明的一個具體實施方式中，所述阻燃劑可以採用物理混合或是通過化學法交聯到組分(A)的環氧樹脂，或是其它樹脂上。例如所述9,10-二氫-9-氧雜-10-磷菲-10-氧化物(DOPO)可以交聯到環氧樹脂，形成含DOPO環氧樹脂。
本發明的第二方面提供一種半固化膠片，其包含本發明所述的樹脂組成物。
本發明的第三方面提供一種銅箔基板，其包含本發明所述的半固化膠片。
本發明的第四方面提供一種印刷電路板，其包含本發明所述的銅箔基板。
本發明人經過廣泛而深入的研究，通過改進製備工藝，獲得了一種無需使用氰酸酯樹脂亦能達到低介電特性且兼具了基板高耐熱特性的樹脂組成，因此可以減少氰酸酯用量甚至不使用氰酸酯，在此基礎上完成了本發明。
本發明出於降低成本的原因可以不使用氰酸酯樹脂也能夠達到低介電及高耐熱性的要求，但並不表示本發明將氰酸酯樹脂排除在配方之外。
本發明中，術語“含有”或“包括”表示各種成分可一起應用於本發明的混合物或組合物中。因此，術語“主要由...組成”和“由...組成”包含在術語“含有”或“包括”中。
本發明的發明構思在於：本發明使用苯并[口咢][口井]、雙環戊二烯苯酚樹脂及胺類硬化劑作為環氧樹脂的硬化劑，並且不含二烯丙基雙酚A，藉由環氧樹脂與三種硬化劑間的協同作用使本發明之樹脂組成物具有低介電性及高基板耐熱性。
以下對本發明的各個方面進行詳述：
綜述
本發明提供一種樹脂組成物，其包含： (A)100重量份的環氧樹脂； (B)10至80重量份的苯并[口咢][口井]樹脂； (C)10至50重量份的雙環戊二烯苯酚樹脂；以及 (D)0.5至5重量份的胺類硬化劑； 所述樹脂組成物中不含二烯丙基雙酚A(DABPA)。
本發明利用了樹脂組分(A)環氧樹脂與樹脂組分(B)苯并[口咢][口井]樹脂、樹脂組分(C)雙環戊二烯苯酚樹脂及樹脂成分(D)胺類硬化劑之間的協同作用，獲得低介電特性且兼具了基板高耐熱特性的樹脂組成物。上述樹脂組分中需不含二烯丙基雙酚A(DABPA)，否則可能導致基板耐熱性(T288)變差。
樹脂組分(A) ：環氧樹脂
如前所述，本發明採用樹脂組分(A)環氧樹脂、第一硬化劑組分(B)苯并[口咢][口井]樹脂、第二硬化劑組分(C)雙環戊二烯苯酚樹脂以及第三硬化劑成分(D)胺類硬化劑作為樹脂成分，利用其協同作用達到低介電性及高基板耐熱性。
普通的環氧樹脂一般均可與其餘組分構成協同作用，因此所述環氧樹脂沒有具體限制，只要不對本發明的發明目的產生限制即可。
本發明之樹脂組成物中，該成分(A)環氧樹脂係為下列其中一者或其組合：雙酚A (bisphenol A)環氧樹脂、雙酚F (bisphenol F)環氧樹脂、雙酚S (bisphenol S)環氧樹脂、雙酚AD (bisphenol AD)環氧樹脂、雙酚A酚醛(bisphenol A novolac)環氧樹脂、鄰甲酚酚醛(o-cresol novolac)環氧樹脂、三官能基(trifunctional)環氧樹脂、四官能基(tetrafunctional)環氧樹脂、雙環戊二烯型(dicyclopentadiene type, DCPD type)環氧樹脂、含DOPO之環氧樹脂、含DOPO-HQ之環氧樹脂、對二甲苯環氧樹脂(p-xylene epoxy resin)、萘型(naphthalene type)環氧樹脂、苯并哌喃型(benzopyran)環氧樹脂、聯苯酚醛(biphenyl novolac)環氧樹脂、異氰酸酯改質(isocyanate modified)環氧樹脂、酚苯甲醛(phenol benzaldehyde epoxy)環氧樹脂及酚基苯烷基酚醛(phenol aralkyl novolac)環氧樹脂。其中，DOPO環氧樹脂可為DOPO-PN環氧樹脂、DOPO-CNE環氧樹脂、DOPO-BPN環氧樹脂，DOPO-HQ環氧樹脂可為DOPO-HQ-PN環氧樹脂、DOPO-HQ-CNE環氧樹脂、DOPO-HQ-BPN環氧樹脂。
第一硬化劑：組分(B) ：苯并 [口咢][口井] 樹脂
本發明充分利用了三種硬化劑之間的協同作用。具體而言，本發明之樹脂組成物中，該成分(B)苯并[口咢][口井]樹脂係下列其中一者或其組合：雙酚A型苯并[口咢][口井]樹脂、雙酚B型苯并[口咢][口井]樹脂、二胺基二苯醚型苯并[口咢][口井]樹脂及酚酞型苯并[口咢][口井]樹脂。更具體而言，其較佳係選自下列通式(1)至(3)之至少一者：其中X1 及X2 係分別獨立為R或Ar或-SO2 -；R係選自-C(CH3 )2 -、-CH(CH3 )-、-CH2 -及經取代或未經取代之雙環戊二烯基；Ar係選自經取代或未經取代之苯、聯苯、萘、酚醛、雙酚A、雙酚A酚醛、雙酚F官能基。如Huntsman販賣之商品名LZ-8270、LZ-8280、LZ-8290、MT 35700、MT 35800。
在本發明的一個具體實施方式中，該苯并[口咢][口井]樹脂係選自下列群組中之至少一者：雙酚A型苯并[口咢][口井]樹脂、雙酚B型苯并[口咢][口井]樹脂、二胺基二苯醚型苯并[口咢][口井]樹脂及酚酞型苯并[口咢][口井]樹脂。
本發明之樹脂組成物，以100重量份之環氧樹脂為基準，係添加10至80重量份之苯并[口咢][口井]樹脂，於此添加範圍內之苯并[口咢][口井]樹脂含量，可使該樹脂組成物達到預期之低介電損耗值(Df)，若苯并[口咢][口井]樹脂不足10重量份，則達不到預期之低介電損耗值要求，若超過80重量份，則該樹脂組成物製作之基板耐熱性變差。
第二硬化劑：組分(C) 雙環戊二烯苯酚樹脂
本發明之樹脂組成物，以100重量份之環氧樹脂為基準，係添加10至50重量份之雙環戊二烯苯酚樹脂，於此添加範圍內之雙環戊二烯苯酚樹脂含量，可使該樹脂組成物達到預期之低介電常數值(Dk)，若雙環戊二烯苯酚樹脂不足10重量份，則達不到預期之低介電常數值要求，基板耐熱性變差(T288, Tg)，若超過50重量份，則該樹脂組成物製作之基板玻璃轉化溫度亦變低(Tg)。
本發明之樹脂組成物，以100重量份環氧樹脂為基準，較佳係添加10至40重量份雙環戊二烯苯酚樹脂。
硬化劑組分中二烯丙基雙酚A(DABPA) 的排除
所述硬化劑組成物中不含二烯丙基雙酚A(DABPA)。
發明人在以往實驗曾經發現，在環氧樹脂中添加二烯丙基雙酚A樹脂(DABPA)可使該樹脂組成物達到良好的交聯性，並提升Tg及提升樹脂與銅箔拉力值。
但是本發明人進一步實驗意外發現，當去除所述二烯丙基雙酚A(DABPA)而僅採用雙環戊二烯苯酚樹脂時，反而更有助於提高基板耐熱性(T288)。
第三硬化劑：組分(D) 胺類硬化劑
本發明之樹脂組成物中，該成分(D)胺類硬化劑係具有胺基官能基(amino)之樹脂，較佳係具有雙胺官能基(diamino)之樹脂。更具體而言，胺類硬化劑係可為二胺基二苯碸(diamino diphenyl sulfone)、二胺基二苯基甲烷(diamino diphenyl methane)、二胺基二苯醚(diamino diphenyl ether)、二胺基二苯硫醚(diamino diphenyl sulfide)、雙氰胺(dicyandiamide, DICY)之其一者或其組合。其中，所述胺類硬化劑較佳係4,4’-二胺基二苯碸(4,4’-diamino diphenyl sulfone)、4,4’-二胺基二苯基甲烷(4,4’-diamino diphenyl methane)、4,4’-二胺基二苯醚(4,4’-diamino diphenyl ether)、4,4’-二胺基二苯硫醚(4,4’-diamino diphenyl sulfide)、雙氰胺(dicyandiamide, DICY)之其一者或其組合。
在本發明的一個具體實施方式中，該胺類硬化劑係選自下列群組中之至少一者：二胺基二苯碸、二胺基二苯基甲烷、二胺基二苯醚、二胺基二苯硫醚及雙氰胺。
所述胺類硬化劑更佳為雙氰胺(DICY)。
本發明之樹脂組成物，以100重量份之環氧樹脂為基準，係添加0.5至5重量份之胺類硬化劑，於此添加範圍內之胺類硬化劑含量，係可使該樹脂組成物提升與銅箔之拉力值，若胺類硬化劑之含量不足0.5重量份，則達不到預期之拉力，若超過5重量份，會造成該樹脂組成物製作之基板吸濕性增加，造成基板PCT測試(不含銅基板之壓力鍋蒸煮試驗)爆板(delamination, fail)。
本發明之樹脂組成物，以100重量份環氧樹脂為基準，較佳係添加0.5至3重量份胺類硬化劑。
進一步，本發明之樹脂組成物，以100重量份環氧樹脂為基準，更佳係添加0.5至3重量份雙氰胺。
三種組分的協同關係
三種硬化劑組分的配比如下： (B)10至80重量份的苯并[口咢][口井]樹脂； (C)10至50重量份的雙環戊二烯苯酚樹脂；以及 (D)0.5至5重量份的胺類硬化劑。
因此三種組分的配比依次為(10～80)：(10～50)：(0.5～5)；為了獲得更好的協同效果，較佳苯并[口咢][口井]樹脂：雙環戊二烯苯酚樹脂：胺類硬化劑為（10～60）：（15～35）：（0.5～3）。
如前所述，發明人發現當去除所述二烯丙基雙酚A(DABPA)而採用雙環戊二烯苯酚樹脂時，反而使得所述基板耐熱性能進一步提高(T288)。
進一步的，本發明較佳使用的是第三硬化劑成分(D)DICY與其它硬化劑組合。習知技術認為使用DICY做為環氧樹脂之硬化劑，會有Tg低(DSC測試 Tg=140 ℃)及基板PCT耐熱性不佳的狀況。而本發明人發現，通過第一硬化劑組分(B)苯并[口咢][口井]樹脂、第二硬化劑組分(C)雙環戊二烯苯酚樹脂以及第三硬化劑成分(D)DICY之間的協同作用，可以獲得更佳的效果。如本發明的實施例E13所示，雖然也達到較好的效果，但是採用DDS反而不如採用DICY；在實施例7中，DICY增加，拉力也增加，且Tg可滿足要求。從對比例C14以及實施例E14可知，當去除所述二烯丙基雙酚A(DABPA)而採用雙環戊二烯苯酚樹脂時，反而使得所述含銅基板耐熱性(T288)進一步提高。
其它組分
在本發明的一個具體實施方式中，還包含30至70重量份的阻燃劑。所述阻燃劑既可選自鹵素阻燃劑，又可選自無鹵阻燃劑。
該鹵素阻燃劑可以是溴系阻燃劑，並且無特別限制，較佳選自以下阻燃劑中的至少一種：乙基-雙(四溴苯鄰二甲醯亞胺) (如購自Albemarle的SAYTEX BT-93)、乙烷-1,2雙(五溴苯) (如購自Albemarle的SAYTEX 8010)和2,4,6-三-(2,4,6-三溴苯氧基)-1,3,5-三嗪(如購自ICL Industrial公司的FR-245)。
該無鹵阻燃劑係可使用含氮阻燃劑或含磷阻燃劑，所述無鹵阻燃劑係可選擇性添加下列至少一種化合物，但並不以此為限：雙酚聯苯磷酸鹽(bisphenol diphenyl phosphate)、聚磷酸銨(ammonium poly phosphate)、對苯二酚-雙-(聯苯基磷酸鹽)(hydroquinone bis-(diphenyl phosphate))、雙酚A-雙-(聯苯基磷酸鹽)(bisphenol A bis-(diphenylphosphate))、三(2-羧乙基)膦(tri(2-carboxyethyl)phosphine, TCEP)、三(異丙基氯)磷酸鹽、三甲基磷酸鹽(trimethyl phosphate, TMP)、二甲基-甲基磷酸鹽(dimethyl methyl phosphonate, DMMP)、間苯二酚雙二甲苯基磷酸鹽(resorcinol dixylenylphosphate, RDXP，如PX-200)、磷氮基化合物(phosphazene，如SPB-100)、m-苯甲基膦(m-phenylene methylphosphonate, PMP)、聚磷酸三聚氰胺(melamine polyphosphate)、三聚氰胺氰尿酸酯(melamine cyanurate)及三-羥乙基異氰尿酸酯(tri-hydroxy ethyl isocyanurate)等，但並不以此為限。此外，無鹵阻燃劑亦可使用9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO)、含DOPO酚樹脂(如DOPO-HQ、DOPO-PN、DOPO-BPN)等，其中DOPO-BPN可為DOPO-BPAN、DOPO-BPFN、DOPO-BPSN等雙酚酚醛化合物。
本發明之樹脂組成物，可再進一步包含無機填充物(filler)、硬化促進劑(curing accelerator)、偶合劑(silane coupling agent)、增韌劑(toughening agent)、溶劑(solvent)之其中一者或其組合。
本發明之樹脂組成物進一步添加無機填充物之主要作用，在於增加樹脂組成物之熱傳導性、改良其熱膨脹性及機械強度等特性，且無機填充物較佳係均勻分佈於該樹脂組成物中。其中，無機填充物可包含二氧化矽(熔融態、非熔融態、多孔質或中空型)、氫氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、氮化硼、碳化鋁矽、碳化矽、二氧化鈦、氧化鋅、雲母、勃姆石(boehmite, AlOOH)、煆燒滑石、滑石、氮化矽、煅燒高嶺土，且無機填充物可為球型、纖維狀、板狀、粒狀、片狀或針鬚狀，並可選擇性經由矽烷偶合劑預處理。
本發明之樹脂組成物，以100重量份之環氧樹脂為基準，係添加10至150重量份之無機填充物。若無機填充物之含量不足10重量份，則無顯著之熱傳導性，且未改善熱膨脹性及機械強度等特性；若超過150重量份，則該樹脂組成物之填孔流動性變差，PCB鑽孔製程鑽針磨耗大。更具體而言，本發明之樹脂組成物，較佳係添加30至70重量份之無機填充物。
本發明所述之硬化促進劑係可包含路易士鹼或路易士酸等觸媒(catalyst)。其中，路易士鹼可包含咪唑(imidazole)、三氟化硼胺複合物、氯化乙基三苯基鏻(ethyltriphenyl phosphonium chloride)、2-甲基咪唑(2-methylimidazole, 2MI)、2-苯基咪唑(2-phenyl-1H-imidazole, 2PZ)、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole, 2E4MI)、三苯基膦(triphenylphosphine, TPP)與4-二甲基胺基吡啶(4-dimethylaminopyridine, DMAP)中之一者或多者。路易士酸係可包含金屬鹽類化合物，如錳、鐵、鈷、鎳、銅、鋅等金屬鹽化合物，如辛酸鋅、辛酸鈷等金屬觸媒。
本發明所述之偶合劑，係可包含矽烷化合物(silane)及矽氧烷化合物(siloxane)，依官能基種類又可分為胺基矽烷化合物(amino silane)、胺基矽氧烷化合物(amino siloxane)、環氧基矽烷化合物(epoxy silane)及環氧基矽氧烷化合物(epoxy siloxane)。
本發明所述之增韌劑係選自：橡膠(rubber)樹脂、聚丁二烯丙烯腈(carboxyl-terminated butadiene acrylonitrile rubber, CTBN)、核殼聚合物(core-shell rubber)等添加物。
本發明所述之溶劑係可選自甲醇、乙醇、乙二醇單甲醚、丙酮、丁酮(甲基乙基酮)、甲基異丁基酮、環己酮、甲苯、二甲苯、甲氧基乙基乙酸酯、乙氧基乙基乙酸酯、丙氧基乙基乙酸酯、乙酸乙酯、二甲基甲醯胺、丙二醇甲基醚等溶劑或其混合溶劑。
本發明所述之樹脂組成物，可再進一步包含下列樹脂之其一者或其組合：聚苯醚(polyphenylene ether)樹脂、氰酸酯(cyanate ester)樹脂、異氰酸酯(isocyanate ester)樹脂、馬來醯亞胺(maleimide)樹脂、聚酯(polyester)樹脂、苯乙烯(styrene)樹脂、丁二烯(butadiene)樹脂、苯氧(phenoxy)樹脂、聚醯胺(polyamide)樹脂、聚醯亞胺(polyimide)樹脂。
半固化膠片
本發明提供一種半固化膠片，其包含本發明所述的組成物。
本發明之再一目的在於揭露一半固化膠片(prepreg)，其具有低介電常數、低介電損耗、耐熱及難燃等特性。據此，本發明所揭露之半固化膠片可包含一補強材及前述之樹脂組成物，其中該樹脂組成物係以含浸等方式附著於該補強材上，並經由高溫加熱形成半固化態。其中，補強材係可為纖維材料、織布及不織布，如玻璃纖維布等，其係可增加該半固化膠片之機械強度。此外，該補強材可選擇性經由矽烷偶合劑或矽氧烷偶合劑進行預處理，如經矽烷偶合劑預處理之玻璃纖維布。
前述之半固化膠片經由高溫加熱或高溫且高壓下加熱可固化形成固化膠片或是固態絕緣層，其中樹脂組成物若含有溶劑，則該溶劑會於高溫加熱過程中揮發移除。
銅箔基板
本發明提供一種銅箔基板，其包含本發明所述的半固化膠片。
本發明之又一目的在於揭露一種銅箔基板(copper clad laminate)，其具有低介電特性、耐熱性、難燃性等特性，且特別適用於高速度高頻率訊號傳輸之電路板。據此，本發明提供一種銅箔基板，其包含兩個或兩個以上之銅箔及至少一絕緣層。其中，銅箔可進一步包含銅與鋁、鎳、鉑、銀、金等至少一種金屬之合金；絕緣層係由前述之半固化膠片於高溫高壓下固化而成，如將前述半固化膠片疊合於兩個銅箔之間且於高溫與高壓下進行壓合而成。
本發明所述之銅箔基板至少具有以下優點之一：低介電常數與低介電損耗、優良的耐熱性及難燃性。該銅箔基板進一步經由製作線路等製程加工後，可形成一電路板，且該電路板與電子元件接合後於高溫、高濕度等嚴苛環境下操作而並不影響其質量。
印刷電路板
本發明提供一種印刷電路板，其包含本發明所述的銅箔基板。
本發明之再一目的在於揭露一種印刷電路板(printed circuit board)，其具有低介電特性、耐熱性及難燃性等特性，且適用於高速度高頻率之訊號傳輸。其中，該電路板係包含至少一個前述之銅箔基板，且該電路板係可由習知之製程製作而成。
如無具體說明，本發明的各種原料均可以通過市售得到，或根據本領域的常規方法製備得到。除非另有定義或說明，本文中所使用的所有專業與科學用語與本領域具有通常知識者所熟悉的意義相同。此外，任何與所記載內容相似或均等的方法及材料皆可應用於本發明中。
本發明的其它方面由於本文的公開內容，對本領域具有通常知識者而言是顯而易見的。
下面結合具體實施例，進一步闡述本發明。應理解，這些實施例僅用於說明本發明而不用於限制本發明的範圍。下列實施例中未註明具體條件的實驗方法，通常按照國家標準測定。若沒有對應的國家標準，則按照通用的國際標準、常規條件、或按照製造廠商所建議的條件進行。除非另外說明，否則所有的份數為重量份，所有的百分比為重量百分比，所述的聚合物分子量為數均分子量。
實施例1～14和對比例1～14 SEC-365：異氰酸酯改性環氧樹脂，購自Shin-A； EXA-9900：含萘環的環氧樹脂，購自大日本油墨化學(D.I.C.)； HP-7200H: 雙環戊二烯苯酚環氧樹脂，購自大日本油墨化學(D.I.C.)； NC-3000：聯苯環氧樹脂，購自日本化藥(Nippon Kayaku)； LZ 8280：雙酚F型苯并[口咢][口井]樹脂，購自Huntsman； MT 35700：雙酚A型苯并[口咢][口井]樹脂，購自Huntsman； MT 35800：酚酞型苯并[口咢][口井]樹脂，購自Huntsman； PF-3500：二胺基二苯醚型苯并[口咢][口井]樹脂，購自長春樹脂； PD-9110：雙環戊二烯苯酚樹脂，購自長春樹脂； Dicy：雙氰胺，購自勤裕； DDS：4,4-二胺基二苯碸，購自Atul LTD； SPB-100：磷腈化合物，購自大塚化學； XZ92741：含磷阻燃劑，購自陶氏化學； PX-200：縮合磷酸酯，購自大八化學； 8010：乙烷-1,2-雙(五溴苯)，購自Albemarle公司； BT-93：乙基-雙(四溴苯鄰二甲醯亞胺)，購自Albemarle公司； Fused silica：熔融態二氧化矽，購自矽比科； 2PZ：2-苯基咪唑，購自四國化成； 6020：胺基矽烷，購自道康寧。
所述實施例1～14和對比例1～14的配方如下表1和表2所示。實施例的樣品以E1～E14示出；對比例的樣品以C1～C14示出。
將上述實施例1至14及對比例1至14之樹脂組成物，分批於攪拌槽中混合均勻後置入一含浸槽中，再將玻璃纖維布通過上述含浸槽，使樹脂組成物附著於玻璃纖維布，再進行加熱烘烤成半固化態而得半固化膠片。
將上述分批製得的半固化膠片，取同一批之半固化膠片四張及兩張18 μm銅箔，依銅箔、四片半固化膠片、銅箔之順序進行疊合，再於真空條件下經由200 ℃壓合2小時形成銅箔基板，其中四片半固化膠片固化形成兩銅箔間之絕緣層。
分別將上述含銅箔基板及銅箔蝕刻後之不含銅基板做物性量測，物性量測項目包含玻璃轉化溫度(Tg, DSC示差掃描熱量分析儀器，differential scanning calorimetry)、耐熱性T-288 (含銅基板測試，288攝氏度下受熱不爆板的時間，以熱機械分析儀(Thermomechanical analysis, TMA)測試含銅基板於288 ℃下耐熱性，以受熱不爆板的時間結果評判耐熱性，越長越好)、PCT (2 atm/3 hours) (不含銅基板之壓力鍋蒸煮試驗，在121 ℃高壓蒸煮(pressure cooking at 121℃)3小時吸濕後浸錫測試，在288 ℃錫爐內浸錫測試，20秒觀看有無爆板)、銅箔與基板間拉力(peeling strength(剝離強度，以萬能拉力機測量), P/S, half ounce copper foil(半盎司銅箔)，銅箔與基板間拉力越高越好)、含銅基板浸錫測試(solder dip，S/D，288℃，10秒，測耐熱回數)、介電常數(dielectric constant, Dk，Dk值越低越好，以AET 微波誘電分析儀測量不含銅基板Dk值))、介電損耗(dissipation factor, Df，Df值越低越好，以AET 微波誘電分析儀測量不含銅基板Df值)、耐燃測試(flaming test，UL94，其中等級優劣排列為V-0 ＞ V-1 ＞ V-2)。分別將實施例1至14之樹脂組成物之量測結果列表於表1，對比例1至14之樹脂組成物之量測結果列表於表2。
表1
結論：
實施例E1-E14中苯并[口咢][口井]、雙環戊二烯苯酚樹脂及胺類固化劑共用，使基板能夠同時滿足耐熱(T288，Tg，S/D)、耐濕熱(PCT)、銅箔拉力(P/S)、低介電(Dk & Df)及阻燃性的要求。
實施例E6與E7相比較，E7使用較多的DICY，使得銅箔拉力(P/S)有所增強。
對比例C1-C2使用了二烯丙基雙酚A樹脂(DABPA)導致基板耐熱性明顯變差(T288)。而實施例E14由於不含二烯丙基雙酚A樹脂(DABPA)，導致基板耐熱性(T288)明顯優於對比例C14。
對比例C3-C13由於配方中某個組分不在本發明所限制的相應組分含量範圍內，因此導致C3-C13不能同時兼顧耐熱(T288，Tg，S/D)、耐濕熱(PCT)、銅箔拉力(P/S)、低介電(Dk & Df)及阻燃性的要求。
以上所述僅為本發明的較佳實施例而已，並非用以限定本發明的實質技術內容範圍，本發明的實質技術內容是廣義地定義於申請的申請專利範圍中，任何他人完成的技術實體或方法，若是與申請專利範圍所定義的完全相同，抑或是一種等效的變更，均將被視為涵蓋於該申請專利範圍之中。
在本發明提及的所有文獻都在本申請中引用作為參考，就如同每一篇文獻被單獨引用作為參考一樣。此外，應理解的是，在閱讀了本發明的上述內容之後，本領域具有通常知識者可以對本發明作各種改動或修改，這些等價形式同樣落於本申請所附申請專利範圍所限定的範圍。

Claims (11)

  1. 一種樹脂組成物，其包含： (A)100重量份的環氧樹脂； (B)10至80重量份的苯并[口咢][口井]樹脂； (C)10至50重量份的雙環戊二烯苯酚樹脂；以及 (D)0.5至5重量份的胺類硬化劑； 其中，所述樹脂組成物中不含二烯丙基雙酚A(DABPA)。
  2. 如請求項1所述的樹脂組成物，其中，所述苯并[口咢][口井]樹脂：雙環戊二烯苯酚樹脂：胺類硬化劑的配比為（10～60）：（15～35）：（0.5～3），所述配比為重量比例。
  3. 如請求項1所述的樹脂組成物，其中，所述雙環戊二烯苯酚樹脂選自如下結構式的化合物：， 其中n為1～5的正整數，Z為選自-H及-CH3 之其一者或其組合。
  4. 如請求項1所述的樹脂組成物，其中，該胺類硬化劑係選自下列群組中之至少一者：二胺基二苯碸、二胺基二苯基甲烷、二胺基二苯醚、二胺基二苯硫醚及雙氰胺。
  5. 如請求項1所述的樹脂組成物，其中，該環氧樹脂係選自下列群組中之至少一者：雙酚A環氧樹脂、雙酚F環氧樹脂、雙酚S環氧樹脂、雙酚AD環氧樹脂、雙酚A酚醛環氧樹脂、鄰甲酚酚醛環氧樹脂、三官能基環氧樹脂、四官能基環氧樹脂、雙環戊二烯型環氧樹脂、含DOPO之環氧樹脂、含DOPO-HQ之環氧樹脂、對二甲苯環氧樹脂、萘型環氧樹脂、苯并哌喃型環氧樹脂、聯苯酚醛環氧樹脂、異氰酸酯改質環氧樹脂、酚苯甲醛環氧樹脂及酚基苯烷基酚醛環氧樹脂。
  6. 如請求項1所述的樹脂組成物，其中該苯并[口咢][口井]樹脂係選自下列群組中之至少一者：雙酚A型苯并[口咢][口井]樹脂、雙酚B型苯并[口咢][口井]樹脂、二胺基二苯醚型苯并[口咢][口井]樹脂及酚酞型苯并[口咢][口井]樹脂。
  7. 如請求項1至6中任一項所述的樹脂組成物，其進一步包含30至70重量份的阻燃劑，該阻燃劑係選自下列無鹵阻燃劑及鹵素阻燃劑中之至少一者：雙酚聯苯磷酸鹽、聚磷酸銨、對苯二酚-雙-(聯苯基磷酸鹽)、雙酚A-雙-(聯苯基磷酸鹽)、三(2-羧乙基)膦、三(異丙基氯)磷酸鹽、三甲基磷酸鹽、二甲基-甲基磷酸鹽、間苯二酚雙二甲苯基磷酸鹽、磷氮基化合物、m-苯甲基膦、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯及三-羥乙基異氰尿酸酯、9,10-二氫-9-氧雜-10-磷菲-10-氧化物(DOPO)、含DOPO酚樹脂、乙基-雙(四溴苯鄰二甲醯亞胺)、乙烷-1,2雙(五溴苯)以及2,4,6-三-(2,4,6-三溴苯氧基)-1,3,5-三嗪。
  8. 如請求項1所述的樹脂組成物，其進一步包含無機填充物、硬化促進劑、偶合劑、增韌劑、溶劑之其中一者或其組合。
  9. 一種半固化膠片，其包含如請求項1至8中任一項所述的樹脂組成物。
  10. 一種銅箔基板，其包含如請求項9所述的半固化膠片。
  11. 一種印刷電路板，其包含如請求項10所述的銅箔基板。
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