201210426 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種形成多層印刷電路板、IC基板、用於 高頻應用之印刷電路板及可撓性基板之方法；因此獲得的 多層印刷電路板及IC基板’有機石夕烷結合混合物及使用包 3至J 一種無機矽酸鹽之組合物之處理。通常藉由將經成 像導電層（諸如含有銅者）與介電層（諸如部分固化之階段 树月曰（即，半固化膠片插入多層夾層中然後藉由施加熱 及壓力將之結合在一起而構成PCB&IC基板。由於具有光 滑銅表面之導電層不能與該半固化膠片良好地結合因此 已使用粗糙的銅表面以獲得與介電層之較佳結合。因此， 刀夕層PCB工業應用機械或化學粗縫化步驟以確保更佳 地結合。但是，由於電路圖案更精細，在此表面製備期間 物理損傷導體跡線之風險增加。業界改良導電層及介電層 之間之結合之其他方法係各種廣泛實踐於電鍍工業中之酮 表面氧化步驟以確保良好的界面黏合。 在另一方法中，使用有機矽烷增加銅表面及半固化膠片 表面之間之黏合。該等有機矽烷係於銅表面上沉積成薄層 中並在層壓期間該有機矽烷分子結合至環氧樹脂，即，半 固化膠片表面。爲了增加該有機矽烷及銅表面之間之黏 合，利用與有機矽烷反應之金屬（諸如錫）預塗佈該鋼表 面。s適當應用時，該有機矽烷處理係非常安定且對化學 钕蝕及層離具有抵抗力。該有機矽烷加工具有可在串聯加 工系統中裝設運輸帶之優點。 150386.doc 201210426 【先前技術】 文件EP 0 43 1 501 B 1揭示使用施加於經氧化之錫表面之 有機矽烷結合混合物製造多層印刷電路板之方法。該方法 無法製造細線1C基板。 專利申請案EP 1 978 024 A1揭示各種用於製造多層印刷 電路板之有機矽烷及膠狀矽石微粒之混合物及包含鹼性矽 酸鹽及膠狀矽石之結合混合物。 曰本專利申請案JP 200Ί 〇78〇揭示用於製造多層印刷電 路板之方法，其中有機矽烷黏合劑係施加於（例如）鈀層 上0 先前技術中描述之方法之主要缺點係有機矽烷層在某些 袤i兄下及在具有S20 μιη之特徵尺寸且使用SAp技術（半添 加法）製造之1C基板之製造中可能失效。 【發明内容】 因此，本發明之目的係爲了提供一種用於形成多層印刷 電路板或1C基板之方法，尤其藉由具有非常精細電路結構 之SAP技術製造者。該方法包含以下步驟 (a) 在介電層載體之表面上形成導電銅電路，且該電路 之厚度為至少4 μηι ; (b) 藉由將錫施加於該銅電路而在該銅電路上形成錫之 _物氫氧化物或其組合之層，藉此在施加期間或隨後 所施加的錫在其表面上轉化為氧化物、氫氧化物或其組合。 氧化物、氫氧化物或組合之層之厚度較佳不大於； (c) 將包含至少一種無機矽酸鹽之混合物施加於步驟 150386.doc 201210426 中形成之氧化物、氫氧化物或其組合之表面或施加於彳寺與 銅電路結合之絕緣層’該絕緣層包含部分固化之熱固.性I 合物組合物； (d) 將有機石夕炫結合混合物施加於步驟（c)中所形成之包 含至少一種無機矽酸鹽的層； (e) 重複步驟（a)、（b)、（c)及（d); (f) 將步驟（a)、（b)、（c)、（d)及（e)形成之材料結合成單 一物件，藉此有機矽烷塗層係在至少一種無機;5夕酸鹽層及 絕緣層之間’藉此結合期間固化部分固化之絕緣層；及視 需要 (g) 形成大量通過步驟（f)中形成的結合物件之孔洞； (h) 自通孔之相反開口金屬化通孔壁以形成導電通路以 形成多層電路板； 該方法之特徵為該有機矽烷結合混合物包含： (0至少一種具有式I結構之脲基石夕烧201210426 VI. Description of the Invention: [Technical Field] The present invention relates to a method of forming a multilayer printed circuit board, an IC substrate, a printed circuit board for high frequency applications, and a flexible substrate; The circuit board and the IC substrate 'organic ceramide coupling mixture and the treatment of the composition of the inorganic citrate of the package 3 to J. Typically by imaging an electrically conductive layer (such as a copper-containing layer) with a dielectric layer (such as a partially cured stage tree (ie, a semi-cured film is inserted into a multi-layered interlayer and then bonded by applying heat and pressure) Forming a PCB&IC substrate. Since a conductive layer having a smooth copper surface cannot be well bonded to the prepreg, a rough copper surface has been used to obtain a better bond with the dielectric layer. Therefore, the knive layer PCB industrial application machine Or a chemical roughing step to ensure better bonding. However, due to the finer circuit pattern, the risk of physically damaging the conductor traces during surface preparation increases. Other ways to improve the bond between the conductive layer and the dielectric layer The ketone surface oxidation step is widely practiced in the electroplating industry to ensure good interfacial adhesion. In another method, organic decane is used to increase the adhesion between the copper surface and the surface of the semi-cured film. The organic decane is attached to the copper surface. The organic decane molecule is deposited in a thin layer and bonded to the epoxy resin, ie, the surface of the semi-cured film during lamination. Increasing the adhesion between the organodecane and the copper surface, pre-coating the steel surface with a metal (such as tin) reactive with organic decane. When properly applied, the organodecane treatment is very stable and chemically etched and delaminated Resistant. The organodecane processing has the advantage of being able to be equipped with a conveyor belt in a tandem processing system. 150386.doc 201210426 [Prior Art] Document EP 0 43 1 501 B 1 discloses the use of organic decane applied to the surface of oxidized tin A method of producing a multilayer printed circuit board in combination with a mixture. The method is not capable of producing a thin-line 1C substrate. Patent application EP 1 978 024 A1 discloses various mixtures of organic decane and colloidal vermiculite particles for the production of multilayer printed circuit boards and contains alkaline A combination of bismuth citrate and colloidal vermiculite. The present patent application JP 200 Ί 〇 78 〇 discloses a method for producing a multilayer printed circuit board in which an organic decane binder is applied to, for example, a palladium layer. The main disadvantage of the method described is that the organodecane layer is under certain 及i brothers and has a feature size of S20 μη and uses SAp. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for forming a multilayer printed circuit board or a 1C substrate, particularly by having a very fine circuit. The SAP technology manufacturer of the structure. The method comprises the steps of: (a) forming a conductive copper circuit on the surface of the dielectric layer carrier, and the thickness of the circuit is at least 4 μm; (b) applying tin to the copper circuit A layer of tin hydroxide or a combination thereof is formed on the copper circuit whereby the tin applied during or subsequent application is converted to an oxide, hydroxide or a combination thereof on the surface thereof. The thickness of the hydroxide or combination layer is preferably no greater than; (c) applying a mixture comprising at least one inorganic cerate to the surface or application of the oxide, hydroxide or combination thereof formed in step 150386.doc 201210426 Insulation layer combined with copper circuit in Yu'er Temple', the insulating layer comprises a partially cured thermosetting composition; (d) applying an organic stone bonding mixture to step (c) a layer comprising at least one inorganic citrate; (e) repeating steps (a), (b), (c), and (d); (f) steps (a), (b), (c), The materials formed by (d) and (e) are combined into a single article, whereby the organodecane coating is cured between the at least one inorganic; bismuth acid layer and the insulating layer by the bonding of the partially cured insulating layer; (g) forming a plurality of holes through the bonded member formed in the step (f) as needed; (h) metallizing the through-hole walls from opposite openings of the through holes to form conductive paths to form a multilayer circuit board; The organodecane-binding mixture comprises: (0 at least one ureastone with a structure of formula I
式I 其中A係具有1至8個碳原子之伸烷基，B係羥基或具有1 至8個碳原子之烷氧基及η係1、2或3之整數，但若11係1 或2 ’則各個Β不需相同；及 (η)至少一種交聯劑，其選自由具有式π及式ΙΠ結構 之化合物及具有式II及III之化合物的混合物組成 之群， 150386.doc 201210426 OR. R,0Wherein A is an alkylene group having 1 to 8 carbon atoms, a B-based hydroxyl group or an alkoxy group having 1 to 8 carbon atoms and an integer of η, 1, 2 or 3, but if 11 is 1 or 2 'The individual oximes need not be the same; and (η) at least one crosslinking agent selected from the group consisting of a compound having the formula π and a fluorene structure and a mixture of compounds of the formulae II and III, 150386.doc 201210426 OR. R,0
式II R,〇—Si——R一Si——OR, 1 / \ 5 R3〇 or6 其中R!、R_2、R_3、R_4、Rs及R_6相互獨立係具有1至8個碳 原子之烧基’且其中R表示具有1至8個碳原子之伸烧 基，及Formula II R, 〇-Si——R-Si——OR, 1 / \ 5 R3〇or6 wherein R!, R_2, R_3, R_4, Rs and R_6 are independently of one another having 1 to 8 carbon atoms. And wherein R represents an alkylene group having 1 to 8 carbon atoms, and
Si(OR7)4 式 III 其中R?係選自由甲基、乙基及丙基組成之群， 及其中至少一種具有式I結構之脲基矽烷及至少一種交 聯劑之總濃度係1 g/Ι及50 g/Ι之間，and to circuit boards and IC substrates obtainable to the above process。 【實施方式】 本發明係關於一種如請求項1定義之用於形成多層印刷 電路板或1C基板之方法。該電路板具有介電材料之交替 層，其支撐經由中間層黏附至絕緣層之銅電路。該電路板 具有形成透過該板全部厚度之電路通道之通孔。 根據本發明之方法特別適用於具有50 μιη及甚至25 μιη或 更低之高密度互連特徵尺寸之細線抗蝕劑結構之電路。 1C基板通常係利用sAp技術製造並具有μπΐ2線及線 距特徵尺寸。1C基板係ic包裝件之基礎組件，其與裝配中 之其他電子組件結合，控制電子設備之功能。IC包裝件可 大體上分為單晶片模組（或SCM)及多晶片模組（或MCM)， 月J者3有單一 IC晶片之’及後者含有多個晶片及其他電子 裴置。 150386.doc 201210426 在夕層電路板或ic基板之形成中，可使用數十個導電層 及非導電層。同樣’對於形成多層電路板或lc基板而言， 需要鑽孔並可能由於緊鄰圍繞在孔周圍之區域中之層之層 ^出現缺陷。若在其中一層中存在缺陷或若發生層離，通 ㊉需丢棄整塊板或1C基板。因此在形成印刷電路板或^基 之各γ驟中，貝量對於商業化生產係必不可少。利用 該等技術可形成諸多物件。闡述性說明一種物件可依序包 含介電層’具有錫及位於錫之下之氧化物、氫氧化物或其 組合之層之銅電路，包含至少一種無機矽酸鹽之層，有機 矽烷結合混合物之層，絕緣層，第二介電層，具有第二層 錫、位於錫之下之氧化物、氫氧化物或其組合之層之第二 銅電路，第二層包含至少一種無機矽酸鹽之層，第二層有 機矽烷結合混合物之層及第二絕緣層。在以上物件中， (第一）絕緣層可直接或通過黏合層接觸至第二介電層。該 黏U劑在此項技術中已為人詳知，例如，高溫環氧樹脂。 在另一物件中，可不需要存在第二介電層且所有其他層具 有相同次序。在本發明另一實施例中，可存在介電層，在 其正反表面上具有銅電路。此後，在相反表面上施加各種 層，包括視需要之錫與位於錫之下之氧化物、氫氧化物或其 組合，無機矽酸鹽，有機矽烷結合混合物及絕緣層之層。 在本發明之方法中之起始材料係在一面或正反表面上包含 銅覆層之介電層。此銅層之厚度為至少丨μιη及更佳為15 μιη. 且其用於形成導電電路。可使用先前技術中熟知之技術以 形成該電路（諸如藉由感光抗蝕薄膜之可光成像技術隨後 I50386.doc 201210426 触刻銅之未受保護區域形成）。合適技術之實例係揭示於 美國專利3,469,982中。假如介電層之組合物具有電絕緣體 功能’其不起關鍵作用。有用的載體材料係揭示於美國專 利4,499，152中，諸如利用玻璃纖維增強之環氧樹脂。較佳 使用。Ρ刀固化之熱固性聚合物組合物’其在該技術中稱為 半固化膠片或「Β」階樹脂。 ’ 可藉由利用部分固化之樹脂（通常環氧樹脂（例如雙官能 基、四呂能基及多官能基環氧樹脂））浸潰玻璃織物增強材 料製備有用的介電基板或層。環氧樹脂係特別適合。本發 明之有機㈣組合物之優點係其等在基板材料之玻璃及樹 脂區域兩者上顯示極佳的黏合性，其通常係先前技術已知 之組合物之問題。 有用之树月曰之實例包括由甲醛及脲，或甲醛及三聚氰胺 反應製備之胺基型樹脂、聚醋、酚醛樹脂、聚矽氧、聚醯 胺、聚醯亞胺、鄰苯二甲酸二烯丙醋、苯基矽烷、聚苯並 米坐一笨醚、聚四氟乙烯、氰酸酯等。此等介電基板通 ㊉稱為半固化膠片。最新—代環氧樹脂基板係Ajinomoto GX-3及GX-13，其包含玻璃球纖維並亦可利用根據本發明 之方法處理。可藉由利用如以上描述之部分固化之樹脂浸 潰玻璃織物增強材料製備絕緣層及介電層。因此，絕緣層 亦可係半固化膠片。 在夕層印刷電路板或1C基板之形成中，可使用數層至少 一表面上具有導電金屬塗層或金屬電路之介電層及數層絕 緣層。 150386.doc 201210426 =電路後，通常需要形成氧化物、氫氧化物或 ^大二4外層。可藉由銅電路之氧化作用直接形成厚度 不大於1·5μηι及更佳不大於丨〇μπι之層。 在本發明—實施例中’導電層係由錫形成。將如下進行 更充分描述’塗層施加之較佳技術係藉由浸潰金屬锻層。 该金屬層之厚度較不重要且可係(例如)〇〇6至〇25…在 :加錫期間及隨後’形成其氧化物、氫氧化物或其組合之 缚塗層。由於此塗層可能非常薄，較佳不大於15 _或在 某些實例中僅單層厚度’可使用空氣氧化。在該情況中， 可在至下形成氧化物/氫氧化物，其中銅表面與周圍氧 氣及水蒸氣反應。其他用於形成氧化物/氫氧化物之技術 包括浸潰於或暴露至氧化性水浴中。 杈佳的浸潰錫塗層組合物包含硫脲化合物、錫鹽、還原 劑、酸及脲化合物。該錫鹽較佳包含亞錫鹽。儘管可使用 無機（礦物）酸或有機酸之亞錫鹽（例如，甲酸亞錫及乙酸亞 錫）’該錫鹽可包含礦物酸（諸如含硫酸、亞磷酸及氫鹵 酸’尤其是含硫酸（諸如硫酸或胺基績酸））之亞錫鹽。亦可 使用驗金屬錫酸鹽（諸如錫酸納或錫酸卸）及其該項技術中 已知之等效物。在一實施例中，硫酸亞錫、胺基磺酸亞錫 或乙酸亞錫係用作錫鹽。若沉積錫錯塗層，乙酸錯可用作 錯鹽。所使用之酸可係有機酸或基於硫、磷或自素之無機 酸（礦物酸）’以基於硫之酸較佳，諸如硫酸、曱項酸 (MS A)或胺基確酸。某些可使用之有機酸包含單緩酸或具 有最多約六個碳原子之二羧酸（諸如曱酸、乙酸 '蘋果酸 150386.doc 201210426 及馬來酸）。由於使用氫_酸或函鹽將在所沉積之錫塗層 中產生齒化物殘留物，此等鹽干擾錫之電學性質並亦可作 為塗層中之腐触材料’故若可能的話較佳係不使用氫_酸 或鹵鹽。在本發明一實施例中’該浸潰錫塗層組合物進一 步包含至少一種螯合劑。特別佳之螯合劑包含胺基叛酸及 經基羧酸。某些可用於此態樣之特定胺基羧酸包含乙二胺 四乙酸、羥乙基乙二胺三乙酸、氮基三乙酸、N—二經基乙 基甘胺酸及伸乙基雙（羥基苯基甘胺酸）。可使用之經基叛 酸包含酒石酸、檸檬酸、葡萄糖酸及5_磺基水楊酸。 可使用之各種還原劑係此項技術中已知且通常包含具有 至多十個碳原子之飽和或不飽和、脂肪族或環狀之有機 醛。在此態樣中可使用具有至多六個碳原子之低碳數烷基 醛，諸如甲醛、乙醛、丙醛、丁醛及類似物。特別佳之醛 包含羥基脂肪族醛，諸如甘油醛；赤藻糖；異赤藻糖；阿 拉伯糖及其各種位置異構體及葡萄糖及其各種位置異構 體。已發現葡萄糖用於防止金屬鹽氧化至更高的氧化態， 例如，Sn(II)至Sn(I\〇,並且作為螯合劑且尤其用於此等 原因。可使用之界面活性劑包含任意非離子、陰離子、 陽離子或兩性界面活性劑。該非離子界面活性劑係特別 佳。 包含至少一種無機矽酸鹽之組合物係在步驟（c)中作為塗 料施加於氧化錫、氫氧化錫或组合，或施加於部分固化之 熱固性聚合物組合物（此項技術中亦稱為半固化膠片或 「B」階樹脂）。與構造為介電層相同的材料可用於稱為^ 150386.doc 201210426 緣層之層以更容易區別於其他層。至少—種無機矽酸鹽係 選自藉由通式慮2〇 · Si〇2 . nH2〇(其中以系！至4之間，較佳 1至3之間，η為〇至9之間及Μ係選自由Na+、Κ+&ΝΗ4+Μ成 之群）描述其特徵之水溶性無機矽酸鹽。至少一種無機石夕 酸鹽之濃度為0.05 §/1至50 g/1之間，較佳〇5 §/1至1〇 g/l之 間。遠混合物另外視需要包含至少一種水溶性磷酸鹽，其 係選自由磷酸鈉、磷酸鉀、磷酸銨、磷酸二鈉、磷酸三 鈉、磷酸二鉀、磷酸三鉀、磷酸二銨、磷酸三銨、三聚磷 酸鈉、三聚磷酸鉀及三聚磷酸銨及類似物組成之群。該至 少一種水溶性磷酸鹽之濃度為〇.〇5 g/丨至5〇 g/1之間，更佳 〇.5 g/Ι至 1〇 g/i之間。 包含至少一種無機矽酸鹽之組合物係藉由任意慣用的方 法（例如，藉由浸塗、喷塗、刷塗及浸潰）沉積於具有經氧 化之錫表面之銅層上。該組合物係在15<t至6〇<t，更佳 20 C至40 C之溫度下沉積於經氧化之錫表面上。 在本發月貫施例中，基板係在包含至少一種無機石夕酸 鹽之組合物中浸塗5秒至1〇〇秒，更佳1〇秒至3〇秒。 在另一實施例中，在有機矽烷結合混合物沉積前不乾燥 包含至少一種無機矽酸鹽之層。 然後，根據本發明之有機矽烷結合混合物係在步驟（d) 中作為塗料施加於包含至少—種無機石夕酸鹽之層。對於可 用於本土明中之有機矽烷結合混合物需要該有機矽烷結 口混σ物形成結合至包含至少—種無機矽酸鹽及部分固化 並轉化為凡全固化之絕緣層之黏著中間層。需要該包含至 150386.doc 201210426 少-種無機石夕酸鹽之層及有機石夕烧結合混合物發揮防止根 據如本文定義之熱應力測試之層離的功能。在較佳的模式: 中，具有完全固化之絕緣層之多層電路板滿足 55110D之所有規格。 :般認為脲基矽烷與有機矽烷之矽烷醇（SIGH)-基團形 成氫橋鍵及/或形成縮合反應中之共價金屬__鍵…般 認為該有機㈣通過經官能基取代之有機基團與鄰近層相 互作用以提供凡得瓦力相互作用（其係強極性力氫橋相互 作用）’或與介電樹脂形成共價鍵。一般認 基錢形成網路以降低所產生之黏著有機w = 性。本發明之防㈣著有機錢層係由具有以下作為其基 本組分之有機矽烷結合混合物製備。 ⑴至少一種具有根據式丨結構之脲基矽烷：Si(OR7)4 Formula III wherein R? is selected from the group consisting of methyl, ethyl and propyl, and the total concentration of at least one of the ureido decane having the structure of Formula I and at least one crosslinking agent is 1 g/ Between 50 g/Ι, and to circuit boards and IC substrates obtainable to the above process. [Embodiment] The present invention relates to a method for forming a multilayer printed circuit board or a 1C substrate as defined in claim 1. The board has alternating layers of dielectric material that support the copper circuitry adhered to the insulating layer via the intermediate layer. The board has through holes that form circuit passages through the entire thickness of the board. The method according to the invention is particularly suitable for circuits having a thin line resist structure having a high density interconnect feature size of 50 μηη and even 25 μηη or less. The 1C substrate is typically fabricated using sAp technology and has a μπΐ2 line and line feature size. The 1C substrate is the base component of the ic package that, in combination with other electronic components in the assembly, controls the functionality of the electronic device. IC packages can be broadly divided into single-chip modules (or SCMs) and multi-chip modules (or MCMs), which have a single IC chip and the latter contain multiple wafers and other electronic devices. 150386.doc 201210426 In the formation of a circuit board or an ic substrate, dozens of conductive layers and non-conductive layers can be used. Similarly, for forming a multilayer circuit board or an lc substrate, drilling is required and defects may occur due to the layer immediately adjacent to the layer surrounding the hole. If there is a defect in one of the layers or if delamination occurs, the entire board or 1C substrate needs to be discarded. Therefore, in the formation of a printed circuit board or a gamma step, the amount of scallops is indispensable for a commercial production system. Many of these objects can be formed using these techniques. Illustratively, an article may sequentially comprise a dielectric layer 'a copper circuit having a layer of tin and an oxide, hydroxide or combination thereof under tin, comprising at least one layer of inorganic silicate, an organic decane-binding mixture a layer, an insulating layer, a second dielectric layer, a second copper circuit having a second layer of tin, an oxide under the tin, a hydroxide or a combination thereof, the second layer comprising at least one inorganic bismuth salt The layer, the second layer of organic decane bonding mixture and the second insulating layer. In the above article, the (first) insulating layer may be in contact with the second dielectric layer directly or through the adhesive layer. Such adhesives are well known in the art, for example, high temperature epoxy resins. In another article, there may be no need to have a second dielectric layer and all other layers have the same order. In another embodiment of the invention, a dielectric layer may be present having a copper circuit on its front and back surfaces. Thereafter, various layers are applied to the opposite surface, including optionally tin and an oxide, hydroxide or combination thereof under tin, an inorganic silicate, an organic decane-bonding mixture, and a layer of an insulating layer. The starting material in the method of the present invention comprises a copper clad dielectric layer on one or both of the front and back surfaces. The copper layer has a thickness of at least 丨μηη and more preferably 15 μηη. and it is used to form a conductive circuit. The circuit can be formed using techniques well known in the art (such as photoimageable by photoresist film followed by I50386.doc 201210426 to form an unprotected area of copper). An example of a suitable technique is disclosed in U.S. Patent 3,469,982. If the composition of the dielectric layer has an electrical insulator function, it does not play a key role. Useful carrier materials are disclosed in U.S. Patent 4,499,152, which is incorporated herein by reference. It is better to use. A sickle-cured thermosetting polymer composition, which is referred to in the art as a semi-cured film or a "ruthenium" grade resin. A useful dielectric substrate or layer can be prepared by impregnating a glass fabric reinforcement with a partially cured resin, typically an epoxy resin (e.g., a bifunctional, tetralenyl, and polyfunctional epoxy). Epoxy resin is particularly suitable. An advantage of the organic (4) compositions of the present invention is that they exhibit excellent adhesion to both the glass and resin regions of the substrate material, which is generally a problem with compositions known in the prior art. Examples of useful tree sapphire include amine-based resins prepared by reacting formaldehyde and urea, or formaldehyde and melamine, polyacetal, phenolic resin, polyoxymethylene, polyamine, polyimine, phthalic acid diene Propylene vinegar, phenyl decane, polybenzoic acid sit on a stear ether, polytetrafluoroethylene, cyanate ester and the like. These dielectric substrates are referred to as semi-cured films. The latest generation of epoxy resin substrates are Ajinomoto GX-3 and GX-13, which comprise glass sphere fibers and can also be treated by the method according to the invention. The insulating layer and the dielectric layer can be prepared by impregnating the glass fabric reinforcing material with a partially cured resin as described above. Therefore, the insulating layer can also be a semi-cured film. In the formation of a printed circuit board or a 1C substrate, a plurality of dielectric layers having a conductive metal coating or a metal circuit and a plurality of insulating layers on at least one surface may be used. 150386.doc 201210426 = After the circuit, it is usually necessary to form an oxide, hydroxide or ^2 outer layer. The layer having a thickness of not more than 1·5 μηι and more preferably not more than 丨〇μπι can be directly formed by oxidation of the copper circuit. In the present invention - an embodiment, the conductive layer is formed of tin. A more complete description will be made as follows. A preferred technique for coating application is by impregnating a metal forged layer. The thickness of the metal layer is less critical and can be, for example, from 〇〇6 to 〇25... during the tinning and subsequent formation of an oxide coating of the oxide, hydroxide or combination thereof. Since this coating may be very thin, preferably no more than 15 _ or in some instances only a single layer thickness may be oxidized using air. In this case, an oxide/hydroxide can be formed at the bottom, wherein the copper surface reacts with the surrounding oxygen and water vapor. Other techniques for forming oxides/hydroxides include impregnation or exposure to an oxidizing water bath. A preferred dip tin coating composition comprises a thiourea compound, a tin salt, a reducing agent, an acid, and a urea compound. The tin salt preferably comprises a stannous salt. Although inorganic (mineral) acids or stannous salts of organic acids (for example, stannous formate and stannous acetate) can be used, the tin salt can contain mineral acids (such as sulfuric acid, phosphorous acid and hydrohalic acid), especially sulfuric acid. A stannous salt (such as sulfuric acid or an amine based acid). Metal stannates (such as sodium stannate or stannic acid) and their equivalents known in the art can also be used. In one embodiment, stannous sulfate, stannous sulfonate or stannous acetate is used as the tin salt. If a tin coating is deposited, acetic acid is used as a wrong salt. The acid to be used may be an organic acid or an inorganic acid (mineral acid) based on sulfur, phosphorus or self-priming, preferably a sulfur-based acid such as sulfuric acid, an acid (MS A) or an amino acid. Some organic acids which may be used include mono-acids or dicarboxylic acids having up to about six carbon atoms (such as capric acid, acetic acid 'malic acid 150386.doc 201210426 and maleic acid). Since the use of hydrogen-acids or so-called salts will result in the formation of tooth residue in the deposited tin coating, these salts interfere with the electrical properties of tin and can also act as a corrosion-resistant material in the coating', so if possible No hydrogen-acid or halogen salt is used. In an embodiment of the invention, the impregnated tin coating composition further comprises at least one chelating agent. Particularly preferred chelating agents comprise an amino acid and a carboxylic acid. Certain specific aminocarboxylic acids which can be used in this aspect include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrogen triacetic acid, N-di-propylethylglycine, and ethylidene bis ( Hydroxyphenylglycine). The rhodamines which can be used include tartaric acid, citric acid, gluconic acid and 5-sulfosalicylic acid. Various reducing agents which can be used are those known in the art and generally comprise a saturated or unsaturated, aliphatic or cyclic organic aldehyde having up to ten carbon atoms. Low carbon number alkyl aldehydes having up to six carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like can be used in this aspect. Particularly preferred aldehydes include hydroxyaliphatic aldehydes such as glyceraldehyde; erythroglucose; isoerythrocyanine; arabinose and its various positional isomers and glucose and its various positional isomers. Glucose has been found to prevent oxidation of metal salts to higher oxidation states, for example, Sn(II) to Sn(I\〇, and as a chelating agent and especially for such reasons. Surfactants that can be used contain any non- An ionic, anionic, cationic or amphoteric surfactant. The nonionic surfactant is particularly preferred. The composition comprising at least one inorganic cerate is applied as a coating to tin oxide, tin hydroxide or a combination in step (c), Or applied to a partially cured thermosetting polymer composition (also known in the art as a pre-cured film or a "B" grade resin). The same material as the dielectric layer can be used to be referred to as ^150386.doc 201210426 The layers are more easily distinguished from the other layers. At least one type of inorganic citrate is selected from the group consisting of 2〇·Si〇2.nH2〇 (wherein the system is between 4 and 4, preferably 1 to 3) The water-soluble inorganic citrate characterized by η being between 〇 and 9 and the lanthanoid series being selected from the group consisting of Na+, Κ+&ΝΗ4+. The concentration of at least one inorganic oxalate is 0.05 § Between /1 and 50 g/1, preferably 5 §/1 to 1〇g/l The far mixture additionally contains at least one water-soluble phosphate, which is selected from the group consisting of sodium phosphate, potassium phosphate, ammonium phosphate, disodium phosphate, trisodium phosphate, dipotassium phosphate, tripotassium phosphate, diammonium phosphate, and triammonium phosphate. a group consisting of sodium tripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate, and the like. The concentration of the at least one water soluble phosphate is between 〇5 丨 5 g / 丨 to 5 〇 g / 1, more preferably 〇5g/Ι to 1〇g/i. The composition comprising at least one inorganic bismuth salt is deposited by any conventional method (for example, by dip coating, spray coating, brushing, and dipping) On the copper layer having the surface of the oxidized tin, the composition is deposited on the surface of the oxidized tin at a temperature of 15 < t to 6 〇 < t, more preferably 20 C to 40 C. In one embodiment, the substrate is dip coated in a composition comprising at least one inorganic mineral acid salt for from 5 seconds to 1 second, more preferably from 1 second to 3 seconds. In another embodiment, in the organic germane. The layer comprising at least one inorganic ceric acid salt is not dried prior to deposition of the combined mixture. Then, the organic decane according to the invention The combined mixture is applied as a coating to the layer comprising at least one inorganic ceric acid salt in step (d). The organodecane junction sigma is required to form a bond to the organic decane-binding mixture that can be used in the local ambition. An inorganic citrate and partially cured and converted into an adhesive intermediate layer of a fully cured insulating layer. It is required to prevent the inclusion of a layer of inorganic-phosphorus acid salt and an organic stone sulphur-smelting mixture to 150386.doc 201210426 The function of delamination according to the thermal stress test as defined herein. In the preferred mode: a multilayer circuit board with a fully cured insulating layer meets all specifications of 55110D. It is generally considered that the urea decane and the decyl alcohol (SIGH)- group of the organic decane form a hydrogen bridge and/or form a covalent metal in the condensation reaction, and the organic group is considered to be substituted by the functional group. The cluster interacts with adjacent layers to provide a van der Waals interaction (which is a strong polar hydrogen bridge interaction)' or forms a covalent bond with the dielectric resin. Generally, the basic money forms a network to reduce the adhesive organic w = sex produced. The prevention (4) organic money layer of the present invention is prepared from an organic decane-bonded mixture having the following basic components. (1) at least one urea-based decane having a structure according to the formula:
/B(4-n)/B(4-n)
式I ，、中A係具有丨至8個碳原子之伸烷基，b係羥基或具有丄至 8個碳原子之烧氧基，及_、2或3之整數，但若祕2或 3則B不需要相同；及（π)至少—種交聯劑選自由具有 根據式II結構之化合物，具有式爪化合物及具有式Η及⑴ 化合物之混合物組成之群Formula I, wherein A is an alkylene group having from 丨 to 8 carbon atoms, b is a hydroxyl group or an alkoxy group having from 丄 to 8 carbon atoms, and an integer of _, 2 or 3, but if secret 2 or 3 Then B does not need to be the same; and (π) at least one crosslinking agent is selected from the group consisting of a compound having the structure according to formula II, a compound having a formula and a mixture of a compound having the formula and (1)
严4 Si—OR, \ 5 0RCStrict 4 Si-OR, \ 5 0RC
式II ^0 R20-^Si—R-R30 150386.doc -12- 201210426 2 R3 R4、R5及R0相互獨立地係具有i至8個碳 原子之烷基且R表示具有丨至8個碳原子之伸烷基 Si(OR7)4 式 ΠΙ 其中R?係選自由甲基、乙基及丙基組成之群。 若存在多於一_基團，式I中各個B基團較佳係相同。 同樣Rl R2、R3、R4、尺5及R6較佳係相同。在脲基矽烷 中伸烧基A較佳係二價伸乙基或伸丙基及院氧基B較佳 係甲氧基或乙氧基。特別佳之脲基料係γ_脲基丙基三乙 氧基。在根據式„之交聯财，烧基較佳❹基或乙 基及伸烷基R較佳係二價伸乙基或伸丙基。根據仙之特 別佳之交聯劑係六甲氧基二甲矽烷基乙烷。矽烷結合混合 物之组分濃度可能廣泛變化以滿足特定應狀需要。因此 脲基石夕院對交聯劑之重量比率可係99:1a1:99之間。腺基 石夕烧及交聯劑之重量比率較佳係1(}:1及1:1之間。通常使二 單—腺基㈣與單-交聯劑，但是，該㈣結合混合物中 使用如上定義之兩種或多種脲基矽烷及/或如上定義之兩 種或多種交聯劑係在本發明之範圍内。在本發明之實踐 中’ β亥有機石夕烧結合混合物可作為液體溶液施加於包含至 ^種無機矽酸鹽之層或絕緣層表面。在此實例中，該有 機矽烷結合混合物包含用於脲基矽烷及交聯劑之互溶劑。 有機石夕燒之總濃度為！ §/1及5〇 g/1之間，更佳2 g/m g/i 之間。藉由任意慣用的方法（例如，藉由浸塗、喷塗、刷 塗及浸潰）施加該溶液。 可對如以上描述製備之多層印刷電路板或IC基板施以慣Formula II ^0 R20-^Si-R-R30 150386.doc -12- 201210426 2 R3 R4, R5 and R0 are each independently an alkyl group having from 1 to 8 carbon atoms and R represents from 丨 to 8 carbon atoms The alkyl group Si(OR7)4 formula wherein R? is selected from the group consisting of methyl, ethyl and propyl groups. If more than one group is present, each of the B groups of formula I is preferably the same. Similarly, Rl R2, R3, R4, ruler 5 and R6 are preferably the same. The excipient A in the ureido decane is preferably a divalent ethyl or propyl group and a ethoxy group B is preferably a methoxy group or an ethoxy group. A particularly preferred urea base is gamma-ureidopropyltriethoxy. In the cross-linking formula according to the formula, the alkyl group or the ethyl group and the alkyl group R are preferably a divalent ethyl group or a propyl group. The cross-linking agent is preferably a hexamethoxy dimethyl group. The concentration of the component of the decane-ethane-blending mixture may vary widely to meet the specific requirements. Therefore, the weight ratio of the urea-based stone to the cross-linking agent may be between 99:1a1:99. The weight ratio of the crosslinking agent is preferably between 1 (}: 1 and 1:1. Usually two mono-glycosyl (tetra) and a single-crosslinking agent are used, but the (four) binding mixture is used in two or more of the above definitions. Urea-based decane and/or two or more cross-linking agents as defined above are within the scope of the present invention. In the practice of the present invention, the β-organic zephyr-baked combination can be applied as a liquid solution to the inorganic a layer of tantalate or an insulating layer. In this example, the organodecane-binding mixture comprises a mutual solvent for the urea-based decane and the crosslinking agent. The total concentration of the organic stone is §/1 and 5〇g Between /1, preferably between 2 g/mg/i, by any conventional method (for example, by Coating, spraying, brushing and dipping) the solution is applied may be as described above for the multilayer printed circuit board or an IC board applied inertia Preparation of
S 150386.doc •13· 201210426 用的層壓溫度及層壓壓力板之間之壓力。在此方法中，層 麼操作通常將涉及1_72 MPa至5·17 MPa之間之壓力， 130 C至約350 C之間之溫度及層壓循環為3〇分鐘至2小時。 或者，真空層壓方法係用於IC基板中之BilUd_up Film。層 壓板係置於銅表面上，於l〇0〇c下層壓且以3 kg/cm2壓製3〇 秒。 根據本發明之優點包括增強之黏合性、增強之抗氧化性 及增強之防潮性，對於高密度互連線及1(：基板尤其明顯。 實例 用於實驗之測試樣品係： (i)由0·8mm厚度之標準FR4材料層與厚度35μm之銅層 製備之全銅平板且尺寸為31〇x5〇〇 mm (π)具有厚1.6 mm FR4單側經結構化之側面與厚度35 μηι銅之結構化平板且尺寸2〇〇χ15〇 (111)具有厚度 32 ㈣之 ABF 薄膜（Ajinomoto GX13) ,在串聯式喷塗系統中測試樣品⑴及（ii)之鋼表面係經化 學清洗，利用浸潰錫組合物及有機矽烷結合混合物處理， 及視*要在利用有機矽烷結合混合物處理 料鹽之組合物處理’並對EP0435()1 B1之實例^述= 樣时A(即在有機矽烷結合混合物沉積前不利用無機矽酸鹽 處理）進行評估。 在所有實例巾所使用之化學清洗及利用浸潰錫組合物之 處理係在表1中概述： 150386.doc 14 201210426 加工步驟 溫度[°c] 加工時間[s] 組合物 化學清洗： 酸洗 UC (Atotech Deutschland GmbH 之產品） 35 17 酸性清潔劑 沖洗 25 35 水 根據步驟(b)之浸潰錫處理： Secure Enhancer MSA (Atotech Deutschland GmbH 之產品） 包含Sn2+離子、 MSA及硫脲 沖洗 25 35 水 沖洗 25 17 DI水 應用於實例1至5中之加工步驟（c)至（d)係在表2中概述： 加工步驟 溫度[°C] 加工時間[S] 組合物 根據步驟(C)之利 用無機矽酸鹽處理： 40 25 偏石夕酸納(x= 1) 沖洗 25 17 水 根據步驟(d)之牙1 用有機矽烷結合混合物處理 35 20 3-[三（乙氧基/曱氧基）曱矽烷 基]丙基]脲及2-雙(三乙氧基曱 石夕烧基)乙烧之混合物 乾燥 65 35 在所有實驗中，類型⑴或（Π)之平板係在施加無機矽酸 鹽及有機矽烷結合混合物後與ABF薄膜層壓。層壓前，在 65°C下預熱平板5分鐘。利用熱軋層壓機及在1 00°C輥輪溫 度下以1 m/分鐘之層壓速度進行層壓。平板兩側面之層壓 需要兩步層壓步驟。然後移除PET覆蓋箔片。 層壓後，在利用空氣循環之烘箱中於1 80°C固化層壓板 30分鐘。 150386.doc -15· 201210426 然後’利用去膠渣加工處理所有平板兩次，此後實施通 過穿孔之鍍覆加工，其中銅係利用無電鍍鋼加工沉積且利 用10 μηι電錢銅增強。 在經銅電鍛後應用熱退火。應用三階段退火處理：第一 階段在180°C下退火60分鐘’第二階段在20(Tc下退火6〇分 鐘及第三階段在200。(：下退火60分鐘。 然後藉由樣品之光學檢測對氣泡計數。觀察到兩種類型 的氣泡：類型一係由ABF薄膜與錫層部分層離引起（即增黏 劑層失效），另一種係由鍍銅層與FR4基礎材料層離引起。 實例1至5期間僅考慮類型1之氣泡。 實例1(對照物） 在此實例中’如EP 043 501 B1之實例1中之樣品a描述 之包含1.0重量。/〇 3-[三（乙氧基/曱氧基）曱矽烷基]丙基]脲 及0_2重量。/。2-雙（三乙氧基甲矽烷基）乙烷之相同之有機矽 烧結合混合物係沉積在經氧化之錫表面上。不應用步驟（c) 之處理類型。 觀察到氣泡。 實例2(對照物） 利用步驟（d)中之包含1_〇重量％之3 [三（乙氧基/曱氧基） 甲矽烷基]丙基]脲及1.0重量％之2_雙（三乙氧基甲.矽烷基） 乙烷之有機矽烷結合混合物處理平板。不應用根據步驟（c) 之處理。 觀察到氣泡。 實例3 150386.doc 16- 201210426 應用如實例1中使用之相同的有機矽烷結合混合物。在 應用該有機料結合混合物前，利用如2至3頁中描述之根 據加工次序之步驟⑷之包含2 g/1偏石夕酸納㈣）之組合物 處理平板。 未銳察到氣泡。 實例4 利用如2至3頁中描述之加工次序之步驟（c)中之包含2 g/i 偏矽酸鈉（x=l)之組合物及步驟（(1)47之包含丨〇重量％之3_ [三（乙氧基/甲氧基）甲矽烷基]丙基]脲及丨〇重量％之2雙 (乙氧基甲矽烷基）乙烷之有機矽烷結合混合物處理平板。 未觀察到氣泡。 實例5 此實例顯示若在有機矽烷結合混合物沉積前於經氧化之 矽表面上沉積無機矽酸鹽層，該經氧化錫表面對於有機矽 烧結合混合物之可濕性增加原因。 根據表1中概述之方法處理具有銅表面之FR4基板。然 後，包含2 g/ι偏矽酸鈉0=1)之組合物係沉積在經氧化之錫 表面上（在T=35°C，t=30秒下沉積）、沖洗並乾燥。使用甘 油作為測試液體藉由停滴測試方法比較經清洗之銅表面、 經氧化之錫表面及經偏矽酸鈉塗佈之經氧化之錫表面之可 濕性。 1〇〇秒後對甘油之接觸角分別係85。（經清洗之銅表面）、 50°(經氧化之錫表面）及35。（利用包含偏矽酸鈉之組合物塗 佈之經氧化之錫表面）。 150386.doc •17· 201210426 對甘油所產生之接觸角越小，對於有機魏結合混合物 之表面可濕性越佳。 實例6 在應用壓力鋼測試之前及之後’藉由測定具有銅表面之 F R 4基礎基板及A B F薄膜之間之界面之剝離強度證明根據 本發明之方法製備之層壓物之防潮性增加。 根據表1及2製備對照組樣品，但不施加無機石夕酸鹽塗 料。根據表1及2中描述之方法製備根據本發明之方法之樣 品0 然後兩種樣品進行根據Jedec Standard JESD22-A102-C 之壓力鍋測試（121°C，100% RH，205 kPa為時24小時）。 根據1卩(：-丁1^-650第2.4.8號測定其剝離強度。 層壓後兩種樣品之剝離強度係13.33 N/cm及壓力鍋測試 後對照樣品為10.75 N/cm及根據本發明之方法製備之樣品 為 11.96 N/cm。 150386.docS 150386.doc •13· 201210426 The pressure used between the lamination temperature and the laminated pressure plate. In this method, the layer operation will typically involve a pressure between 1 and 72 MPa to 5.17 MPa, a temperature between 130 C and about 350 C and a lamination cycle of 3 to 2 minutes. Alternatively, the vacuum lamination method is applied to BilUd_up Film in an IC substrate. The laminate was placed on a copper surface, laminated at 10 ° C and pressed at 3 kg/cm 2 for 3 seconds. Advantages in accordance with the present invention include enhanced adhesion, enhanced oxidation resistance, and enhanced moisture resistance for high density interconnects and 1 (: substrates are particularly pronounced. Examples of test samples used in experiments: (i) by 0 · 8mm thick standard FR4 material layer and 35μm copper layer prepared with copper plate and 31〇x5〇〇mm (π) with a thickness of 1.6 mm FR4 single-sided structured side and thickness 35 μηι copper structure A flat sheet of 2〇〇χ15〇(111) ABF film (Ajinomoto GX13) having a thickness of 32 (4). The steel surfaces of the samples (1) and (ii) were chemically cleaned in a tandem spray system using a dipping tin. Treated with the composition and the organodecane-bonded mixture, and treated according to the composition of the organic decane-binding mixture treatment salt and 'as for the example of EP0435()1 B1 = A (ie, deposited in the organic decane-bonded mixture) The evaluation was carried out without prior treatment with inorganic citrate. The chemical cleaning used in all the examples and the treatment using the immersion tin composition are summarized in Table 1: 150386.doc 14 201210426 Processing step temperature [°c] Processing Time [s] Chemical cleaning of the composition: Pickling UC (product of Atotech Deutschland GmbH) 35 17 Acid cleaner rinse 25 35 Water impregnation tin according to step (b): Secure Enhancer MSA (product of Atotech Deutschland GmbH) Contains Sn2+ Ion, MSA and thiourea rinse 25 35 Water rinse 25 17 DI water The processing steps (c) to (d) used in Examples 1 to 5 are summarized in Table 2: Processing step temperature [°C] Processing time [S The composition is treated according to step (C) using inorganic citrate: 40 25 bismuth sodium hydride (x = 1) rinsing 25 17 water according to step (d) tooth 1 treated with organic decane binding mixture 35 20 3- Mixture of [tris(ethoxy/decyloxy)decyl]propyl]urea and 2-bis(triethoxycarbosulfanyl)ethyl bromide 65 35 In all experiments, type (1) or The plate of the crucible is laminated with the ABF film after applying the inorganic cerate and the organic decane-bonding mixture. The plate is preheated at 65 ° C for 5 minutes before lamination. Using a hot-roll laminator and at 100 ° C Lamination at a roll speed of 1 m/min at the roll temperature. The pressure requires a two-step lamination step. The PET cover foil is then removed. After lamination, the laminate is cured in an air circulating oven at 180 ° C for 30 minutes. 150386.doc -15· 201210426 Then 'use the glue The slag was processed to treat all the plates twice, after which plating was performed by perforation, in which the copper system was deposited by electroless steel processing and reinforced with 10 μηι. Thermal annealing is applied after copper forging. A three-stage annealing treatment is applied: the first stage is annealed at 180 ° C for 60 minutes 'the second stage is at 20 (6 ° annealed at Tc and 200 at the third stage. (: 60 minutes under annealing. Then by optical optics) The bubble count was detected. Two types of bubbles were observed: the type was caused by partial delamination of the ABF film from the tin layer (i.e., the adhesion promoter layer failed), and the other was caused by the delamination of the copper plating layer from the FR4 base material. Only the bubbles of type 1 were considered during the examples 1 to 5. Example 1 (Control) In this example, the sample a as described in Example 1 of EP 043 501 B1 contains 1.0 weight. /〇3-[three (ethoxy) The same organic sulphur-bonded mixture of bis-(oxy)alkyl) propyl]urea and 0-2 by weight of bis(triethoxycarbenyl)ethane is deposited on the surface of oxidized tin No. The type of treatment of step (c) is not applied. Air bubbles are observed. Example 2 (Control) Using 3% by weight of the step (d) [3 (ethoxy/decyloxy) formane And propyl]urea and 1.0% by weight of 2_bis(triethoxymethyl decyl) ethane organic decane The mixture was treated with a plate. The treatment according to step (c) was not applied. Air bubbles were observed. Example 3 150386.doc 16-201210426 The same organic decane-binding mixture as used in Example 1 was applied. Before applying the organic material-binding mixture, use The plates were treated with a composition comprising 2 g/1 of sodium sulphate (4) according to step (4) of the processing sequence as described in pages 2 to 3. No bubbles were observed. Example 4 utilizes the description as described on pages 2 to 3. The composition and the step of the step (c) comprising 2 g/i sodium metasilicate (x = 1) and the step ((1) 47 comprising 丨〇% by weight of _3_[three (ethoxy/methoxy) The plate was treated with an organic decane-bonded mixture of carbaryl-propyl]urea and hydrazine in an amount of 2% by weight of bis(ethoxymethyl decyl) ethane. No bubbles were observed. Example 5 This example shows the presence of organic decane. The inorganic silicate layer is deposited on the surface of the oxidized ruthenium prior to deposition of the combined mixture, and the wettability of the tin oxide surface for the organic bismuth-sintering mixture increases. The FR4 substrate having a copper surface is treated according to the method outlined in Table 1. Then, including 2 g/ι partial The composition of sodium citrate 0 = 1) was deposited on the surface of oxidized tin (deposited at T = 35 ° C, t = 30 seconds), rinsed and dried. Using glycerol as a test liquid by stopping the test method Comparing the wettability of the surface of the cleaned copper, the surface of the oxidized tin and the surface of the oxidized tin coated with sodium metasilicate. The contact angle of glycerol after 1 sec is 85. (Cleaved copper Surface), 50° (oxidized tin surface) and 35. (oxidized tin surface coated with a composition containing sodium metasilicate) 150386.doc •17· 201210426 The more contact angles produced by glycerol Small, the surface wettability of the organic Wei-binding mixture is better. Example 6 The peel strength of the interface between the F R 4 base substrate having a copper surface and the A B F film was measured before and after the application of the pressure steel test to demonstrate an increase in moisture resistance of the laminate prepared according to the method of the present invention. A control sample was prepared according to Tables 1 and 2, but no inorganic silicate coating was applied. Sample 0 according to the method of the present invention was prepared according to the methods described in Tables 1 and 2. The two samples were then subjected to a pressure cooker test according to Jedec Standard JESD22-A102-C (121 ° C, 100% RH, 205 kPa for 24 hours) . The peel strength was measured according to 1卩(:-丁1^-650#.4.8. The peel strength of the two samples after lamination was 13.33 N/cm and the control sample after the pressure cooker test was 10.75 N/cm and according to the present invention The sample prepared by the method was 11.96 N/cm. 150386.doc