TWI458584B - 經可熱解聚合物塗覆的金屬粉末 - Google Patents
經可熱解聚合物塗覆的金屬粉末 Download PDFInfo
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Description
本發明係關於經聚合物塗覆的金屬粉末,諸如用於形成焊錫合金、球體及膏的金屬粉末。該等金屬粉末係由諸如氰基丙烯酸酯聚合物或二環戊二烯(「DCPD」)寡聚物的可熱解聚合物塗覆。
焊錫廣泛用於半導體封裝及半導體裝置之組裝。
例如焊錫球或球體用於諸如覆晶應用之半導體封裝之組裝。
焊錫膏通常用於將電子組件表面黏著(surface-mounted)焊接至電路板。可使用焊錫膏,此因其可由其膠粘特性而施用於電路板之選定區域之故,當該板穿過焊錫回流製程時,在無額外黏合劑下,該膠粘特性提供在形成永久黏合之前將電子組件固定於適當位置之能力。
焊錫膏一般包括焊錫粉末、諸如松香之含樹脂組份、諸如有機酸或胺之活化劑、流變性控制劑、增稠劑及溶劑。焊錫膏一般係藉由諸如網板印刷、佈膠及轉移印刷之技術而塗覆在電路板上。其後,將電子組件置於電路板上,並使焊錫膏回流,由此充分加熱焊錫以使其熔化,然後充分冷卻焊錫以使其固化。
一在使用焊錫膏之相關工業中的問題為其經常具有較短及不可預測之擱置壽命,例如一般為約一個月至六個月。擱置壽命之不可預測性至少部份係由自製造焊錫粉末至令其與助溶劑混合以形成焊錫膏之時間的滯後時間之變化而引起,從而導致焊錫粉末氧化程度之變化。該被氧化的粉末如未被氧化的粉末一樣不回流。此外,當焊錫粉末與本身腐蝕性助熔劑組合時,焊錫粉末經常與助熔劑反應,由此使粉末氧化並降低酸性,因此降低助熔劑之效果。結果,焊錫膏之性質經常經時而變壞。此外,焊錫粉末與助熔劑之間的反應一般導致焊錫膏之黏度實質上增加,其竟然無法依節距而變,而使焊錫膏難以印刷。
已藉由將焊錫膏儲存於冷凍條件嘗試降低焊錫粉末與助熔劑之間的反應速率,及由此增加焊錫膏的擱置壽命。然而,在將焊錫粉末併入焊錫膏之前,冷凍並不能有效補償焊錫粉末之不同氧化程度。
亦已報導使用不與焊錫膏反應的材料塗覆之焊錫粉末。例如美國專利第4,994,326號揭示可作為塗層使用的塗覆劑,其係不溶於或幾乎不溶於包含此類基於矽酮與氟之焊錫膏載劑,諸如矽酮油類、基於矽酮之高分子化合物、氟化矽酮油類、氟矽酮樹脂及基於氟化烴之高分子化合物。
該'326專利亦揭示相對大量施用於焊錫粉末的塗覆材料。雖然相對大量塗覆材料可有效抑制焊錫粉末之氧化,但通常而言,不期望具有大量塗覆材料,此因其等可產生阻止焊錫回流之障壁之故。此外,該等大量塗覆材料可造成物理阻礙及/或雜質,其導致較差回流特性,諸如助熔劑的不充分基質潤濕可造成焊錫之較差擴散及不連續焊錫連接。
此外,該'326專利揭示使用可於塗覆焊錫粉末中用作溶劑之氟化烴。目前,氟化烴被認為係環境污染物,故其之使用通常係不希望的。
美國專利第6,416,863號係關於及請求一種封包焊錫金屬粉末之方法,其中該粉末藉由在該焊錫粉末之表面進行聚合反應而具有薄聚合物保護膜,步驟如下:
a)製備粉末與疏水性液體之懸浮液,
b)藉由加入具有C1
至C20
之鏈長度的陽離子表面活性劑而在各金屬顆粒上生成一疏水性表面層,連續攪拌以在步驟(a)之疏水性層上形成一刷狀結構,
c)攪拌步驟a)及b)之混合物直至形成黏性均質體,
d)將自由基可聚合的單體加入步驟c)的均質體中,然後其形成具有玻璃化溫度Tg至少較焊錫粉末之固相線溫度低60℃的熱塑性聚合物,
e)加入有機引發劑以開始界面聚合反應,其併入步驟b)之疏水性層及形成一具有助熔劑特性之熱塑性聚合物的保護層,
f)藉由連續攪拌,將步驟e)的均質體引入含水製備品中,其中該製備品含有使懸浮液安定之乳化劑,並藉由將溫度調至50℃至90℃而控制聚合反應及維持此溫度至少120分鐘,及
g)冷卻、洗滌及回收步驟e)及f)之經封包的焊錫粉末。用於形成囊壁之適宜單體為自由基可聚合的單體,較佳為甲基丙烯酸-2-羥基乙基酯或甲基丙烯酸甲酯。
美國專利第5,328,522號係關於及請求一種焊錫膏,其包括
(i)助熔劑及
(ii)經塗覆之焊錫粉末,其包括由以經塗覆的焊錫粉末之總重量計約0.001重量%至約0.5重量%之量的聚對二甲苯(具有低於焊錫顆粒之熔點)塗覆的焊錫顆粒,且有效抑制在焊錫膏中的焊錫顆粒之氧化而實質上不會抑制經塗覆之焊錫粉末的回流特性。
美國專利第4,452,861號(Okamoto)描述由氰基丙烯酸酯聚合物包住的固體顆粒。將顆粒封包以防止因反應性或腐蝕性環境引起之降解。氰基丙烯酸酯聚合物係用於塗覆在陰極射線管或其類似物中用作塗層之磷光體顆粒及其類似物。鈰活化硫化鈣磷光體粉末係經塗覆的例示性材料。
美國專利申請公開案第2005/0171273號描述一種用於形成各向異性的導電性黏合劑之可固化組合物,其包括:
(i)某量之第一實質上未經固化之可固化組份;及
(ii)由第二可固化組份之固化產品塗覆的導電性顆粒,其中經塗覆之導電性顆粒分散於第一可固化組份內。
儘管有此技術狀態,但仍希望提供一種在金屬顆粒上作為塗層,尤其該等適宜用於焊錫膏之可固化組合物。
因此,本發明提供一種於其表面之至少一部份上塗覆有由至少一種反應性單體形成之可熱解聚合物的金屬粉末。
反應性單體之固化產品具有以物理上使金屬顆粒與諸如氧化及與助熔劑介質發生化學反應的環境降解隔離之目的作為其主要功能。通常,當儲存經塗覆金屬顆粒之金屬粉末及/或焊錫膏以供使用時,聚合物塗覆可作為對氧化之物理障壁。
對該塗覆所使用之反應性單體較佳為氰基丙烯酸酯。氰基丙烯酸酯在暴露於金屬顆粒時固化,且因此由易於固化之優點而言,其為保護劑之較佳選擇。當氰基丙烯酸酯聚合物分解時,例如在暴露於諸如在焊錫回流期間達到之溫度的處理溫度期間,其殘留部份僅為氰基丙烯酸酯單體。氰基丙烯酸酯聚合物具有一上限溫度,高於其時聚合物逆轉回產生其等之單體之溫度。然而,大多數聚合物具有較其等降解溫度高之上限溫度。因此在實務上,實際上不能觀察到該等聚合物之上限溫度。如氰基丙烯酸酯聚合物之其他聚合物具有極低上限溫度(經常在約120℃至約150℃之範圍內)。
氰基丙烯酸酯單體大體上可由下式所代表:
其中R1
係C1
-C40
烷基、C3
-C40
環烷基、或C2
-C40
烯基,可視需要與羥基或烷氧基官能基及/或醚鍵結。
適宜氰基丙烯酸酯單體為氰基丙烯酸之烷基、烯基及烷氧基酯,更特定言之其中該等酯類之烷基或烯基具有高達10個碳原子。氰基丙烯酸酯單體可選自氰基丙烯酸之甲基、乙基、正丙基、異-丙基、正丁基、異-丁基、第二-丁基、第三-丁基、正戊基、異戊基、正己基、異己基、正庚基、異庚基、正辛基、正壬基、烯丙基、甲氧基乙基、乙氧基乙基、3-甲氧基丁基及甲氧基異丙基酯。
氰基丙烯酸酯可進一步包含染料及顏料(與氰基丙烯酸酯可相容)以允許檢視塗層是否覆蓋在金屬顆粒上之程度或者塗層是否覆蓋在顆粒上程度。
適宜著色劑之實例包含1-羥基-4-[4-甲基苯基胺]-9,10蒽二酮(D+C紫色2號)、6-羥基-5-[(4-磺酸苯基)氧雜]-2-萘基磺酸二鈉鹽(FD+C黃色6號)、9-(o-羧基苯基)-6-羥基-2,4,5,7-四碘-3H-氧雜蔥-3-酮,二鈉鹽,一水合物(FD+C紅色3號)、2-(1,3-二氫-3-側氧基-5-磺基-2H-吲哚-2-亞基)-2,3-二氫-3-側氧基-1H-吲哚-5-磺酸二鈉鹽(FD+C藍色2號)、及酞菁(2-)銅。
固化加速劑可施用於氰基丙烯酸酯中,以使待塗覆之金屬顆粒減慢與氰基丙烯酸酯反應。此類包含揭示於國際專利申請公開案第WO 01/85861號中的加速劑,該案之全文以引用之方式併入本文。適宜用於本文中的固化加速劑之其他實例包含美國專利第6,475,331號(Grismala)及第6,294,629號(O’ Dwyer),兩者之全文均以引用之方式併入本文中。
其他聚合物亦可用作金屬粉末之保護劑,只須其等上限溫度低於聚合物之降解溫度並低於金屬顆粒之熔點即可。因此,具有適用上限溫度的聚合物具有在25℃-250℃範圍內的上限溫度。在金屬顆粒為焊錫粉末之情況下,可使用上限溫度在25℃-250℃範圍內的聚合物。上限溫度在80℃-200℃範圍內尤其可用。例如可使用DCPD聚合物。
在某些應用中,金屬顆粒可置於兩個基板之間,例如在半導體封裝應用中,其可在兩個導電性基板之間,以使顆粒必須未被充分塗覆以在其橋連之基板之間形成一導電性路徑。在該等情況下,使基板連在一起可足以「壓平」(因對其擠壓而變形)金屬顆粒而充分破壞塗層。
金屬顆粒可為單一大小,即實質上相同尺寸。若形成之帶隙為半導體封裝或組裝,則其可能十分重量,例如期望有特定大小。然而,可使用具有變化尺寸之顆粒,以具有關於一平均值的直徑之相對寬分佈,諸如在至少一維方向中,約0.5μm至100μm,較佳約3μm至約50μm之平均值。特定言之,希望經塗覆之顆粒形狀為球體。
較佳地,在顆粒上之塗覆少於約3μm,更特定言之在約0.001μm至約0.2μm的範圍內,諸如0.004μm至約0.4μm,例如自約0.01μm至約0.1μm。在顆粒上之塗覆亦可以在塗覆製程後的顆粒上獲得之重量為函數而確定。
該金屬顆粒上之聚合物塗覆對金屬顆粒賦予安定性,且對其中使用有該塗覆金屬顆粒之調配物而言,藉由減少顆粒對環境污染之反應性而賦予其安定性,或在調配物如銲錫膏之例中,藉由減少顆粒與用以形成該調配物之其他組份之反應性而對該調配物賦予安定性。
就焊錫回流製程而言,施用焊錫膏以後,至少一些金屬顆粒之聚合物塗層之至少一部份藉由暴露於在回流期間達到的高溫而被去除,以暴露出金屬顆粒(即本文為焊錫粉末)之表面。聚合物塗層亦可藉由物理破壞而至少部份被去除,例如藉由將足夠壓力施用於顆粒以使其變形,從而造成塗層之破壞。
經聚合物塗覆的金屬顆粒可施用於許多應用中。一種主要終用途大體上為電子工業,及特定言之為諸如在覆晶應用及焊錫球體應用中之焊錫膏。
經聚合物塗覆的金屬顆粒及調配物,諸如使用其製造之焊錫膏,及焊錫球體尤其可用於在半導體晶片及基板之間建立電子互連。
可使用任何類型/形狀的金屬顆粒。特定言之,顆粒可為球形或趨於球形。金屬顆粒之適宜金屬包含諸如錫、銀、銅、鉛、鋅、銦、鉍、及稀土金屬之元素金屬或諸如錫/銀/銅、錫/鉍、錫/鉛及錫/銦/鉍合金之合金。
本發明亦係關於一種在金屬顆粒上形成聚合物塗層之方法,其包括以下步驟:
a)提供複數個金屬顆粒;
b)在適宜條件下,施用氰基丙烯酸酯或諸如DCPD聚合物之其他可熱解聚合物以實質上塗覆大多數金屬顆粒表面之至少一部份;及
c)就丙烯酸酯而言,使丙烯酸酯固化以作為在該等金屬顆粒上之聚合物塗層。
本發明亦係關於一種形成焊錫膏之方法,其包括以下步驟:
a)提供經氰基丙烯酸酯或諸如DCPD聚合物之其他可熱解聚合物塗覆的焊錫粉末;
b)提供二或多種選自松香、活化劑、流變性控制劑、增稠劑、或溶劑之銲錫膏組份;及
c)令經氰基丙烯酸酯或諸如DCPD聚合物之其他可熱解聚合物塗覆的焊錫粉末與焊錫膏組份混合以形成焊錫膏。
藉由將金屬顆粒暴露於丙烯酸酯組份之蒸氣中,可在顆粒表面上形成經聚合的氰基丙烯酸酯的均勻塗層。使待施用於顆粒之均勻塗層氣相沉積。例如該等顆粒可暴露於在周圍溫度出現之任何適宜蒸氣中,或可適度升高溫度以產生蒸氣。在氰基丙烯酸酯之情況下,令蒸氣與顆粒表面接觸可足以使反應性單體聚合。可使用流體化床反應器以製備經塗覆之金屬顆粒。可將反應性單體之蒸氣注入反應器之流體化床體中。一般性塗層一般小於1μm厚度。熟習此項技術者顯然應瞭解施用反應性單體以形成聚合物塗層之其他方法,諸如將顆粒置於實質上未固化量的反應性單體中。
參考以下非限制性實例,現描述本發明。
設計氰基丙烯酸酯塗覆方法以不包括任何外部觸媒以使聚合反應可由金屬其自身表面引發,以使待形成之氰基丙烯酸酯聚合物在金屬表面上生長。
將500g類型4焊錫粉末(錫、Cu與Ag合金)(平均大小30μm)與1L無水甲苯一起置於2L大小圓底燒瓶中。然後引入0.2g氰基丙烯酸丁酯,然後將燒瓶置於旋轉蒸發器上,以100rpm旋轉燒瓶而使混合均勻。1小時後,過濾反應混合物以去除溶劑且焊錫粉末以新鮮甲苯洗滌兩次以移除未直接形成在銲錫粉末上之任何殘留氰基丙烯酸酯聚合物。使經塗覆的焊錫粉末在室溫下乾燥。
將經塗覆的焊錫粉末(類型4;錫、Cu及Ag合金),其中一些(經氰基丙烯酸酯塗覆的焊錫顆粒,類似於該等在實例1中所描述者),與助熔劑及其他焊錫膏組份組合以形成焊錫膏。一些焊錫膏係由經聚合物塗覆的焊錫粉末製備得到,其中聚合物塗層在一實例中係由甲基丙烯酸甲酯製得,而在另一實例中係由馬來醯亞胺製得。
藉由兩種方法測試超過擱置壽命、儲存壽命之焊錫膏的性能,其中各描述如下:
經由不鏽鋼刻花模板使焊錫膏印刷在載玻片上,然後使其回流,並檢查焊錫球之跡象。
1.使用一刮鬍刀片作為一擠塗器,利用一刻花模板將膏體印刷於載玻片上。刻花模板為0.1mm厚,具有3個直徑約5mm之洞,沿著該刻花模板間距均等。
2.在250℃下,在焊錫浴上加熱載玻片5秒鐘或直至其回流。
3.自該浴移除該載玻片並自該載玻片上滾轉出主要球體,然後將其冷卻。
4.藉由點數在各印痕上之焊錫球之數目,以×10之倍率在雙目顯微鏡上評價該載玻片。
5.取較低兩個印痕之平均並在下表中比較。
Brookfield黏度計採用旋轉式黏度測定原理:藉由檢測以固定速度旋轉浸入樣品中之T棒轉軸所需之扭矩來測量黏度。扭矩與在經浸入的轉軸上形成之黏性阻力成比例,且因而與膏之黏度成比例。在特定溫度下,於由規定方法製備之焊錫膏上進行測試。
1.將樣品置於25℃下6個小時。
2. 6小時後,自25℃去除樣品,打開並移除內部栓塞。刮下任何黏附於栓塞上之膏體並將其加入樣品中。
3.使用抹刀,輕輕攪拌膏體30秒,務必避免引入空氣。
4.使用在附有TF轉軸之升降支架上的Brookfield黏度計RVDA-II+。設定旋轉速度為5rpm。
5.設定升降行徑之底部低於膏體表面40mm。設定轉軸低於膏體表面3mm。
6.啟動轉軸旋轉並降下升降支架。
7.在降至最低點處記錄黏度。
焊錫粉末係由甲基丙烯酸甲酯及馬來醯亞胺聚合物以類似於以上針對氰基丙烯酸酯,即丙烯酸丁酯所描述之方法而塗覆。在經如此塗覆的焊錫粉末上執行焊錫成球測試,其顯示該等焊錫粉末不適宜用於焊錫膏調配物中,此因聚合物非可熱解及在達到其等上限溫度之前開始降解之故。將未經塗覆的焊錫粉末作為對照。
結果顯示,較之對照組,經甲基丙烯酸甲酯塗覆的銲錫粉末根據銲錫成球測試為不合格,然而由氰基丙烯酸酯形成之聚合物塗層作為銲錫粉末之保護劑表現佳,此因氰基丙烯酸酯聚合物在銲錫回流溫度下可熱解之故。
參考下表,較之對照組,經甲基丙烯酸甲酯聚合物塗覆的焊錫粉末在黏度測試中並無改良性質。
參考下表,較之對照組,經氰基丙烯酸辛酯聚合物塗覆的焊錫粉末顯示經時有利黏度積累,且可耐受5週的黏度測試而不失效,而對照組則否。
Claims (13)
- 一種在其表面之至少一部份上經可熱解聚合物塗覆的金屬顆粒,其中該可熱解聚合物具有低於該可熱解聚合物之降解溫度及低於該金屬顆粒之熔點的上限溫度,其中該可熱解聚合物為氰基丙烯酸酯聚合物或二環戊二烯聚合物;其中塗覆於該金屬顆粒上之聚合物的厚度介於約0.0001μm至約3.0μm之間。
- 如請求項1之金屬顆粒,其中該氰基丙烯酸酯聚合物係由以下結構所包括之氰基丙烯酸酯單體製得,
- 如請求項2之金屬顆粒,其中該氰基丙烯酸酯係選自由氰基丙烯酸之甲基、乙基、正丙基、異-丙基、正丁基、異丁基、第二-丁基、第三-丁基、正戊基、異戊基、正己基、異己基、正庚基、異庚基、正辛基、正壬基、烯丙基、甲氧基乙基、乙氧基乙基、3-甲氧基丁基及甲氧基異丙基酯組成之群。
- 如請求項1之金屬顆粒,其中該金屬顆粒為焊錫。
- 如請求項1之金屬顆粒,其中該金屬顆粒係由元素金屬製得。
- 如請求項1之金屬顆粒,其中該金屬顆粒係由合金製 得。
- 如請求項1之金屬顆粒,其中該金屬顆粒係由選自由錫、銀、銅、鉛、鋅、銦、鉍、及稀土金屬組成之群的元素金屬製得。
- 如請求項1之金屬顆粒,其中該金屬顆粒係由選自由錫/銀/銅、錫/鉍、錫/鉛、及錫/銦/鉍合金組成之群的合金製得。
- 一種包括如請求項1之經塗覆的金屬顆粒之焊錫膏組合物。
- 如請求項9之焊錫膏組合物,其中該經塗覆的金屬顆粒係以相對於總組份之約10重量%至約98重量%之量存在。
- 如請求項1之金屬顆粒,其中塗覆於該金屬顆粒上之聚合物的厚度小於約5μm。
- 如請求項1之金屬顆粒,其中塗覆於該金屬顆粒上之聚合物的厚度介於約0.001μm至約1μm之間。
- 一種形成經聚合物塗覆的金屬顆粒之方法,其包括以下步驟:a)提供複數個金屬顆粒;b)在適宜條件下,施用單體或可熱解聚合物以實質上塗覆大多數金屬顆粒表面之至少一部份;及c)就單體而言,使單體固化以作為在該等金屬顆粒上之聚合物塗料。
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JP6455508B2 (ja) * | 2014-03-25 | 2019-01-23 | 住友金属鉱山株式会社 | 被覆はんだ材料およびその製造方法 |
JP6455187B2 (ja) * | 2015-01-29 | 2019-01-23 | 住友金属鉱山株式会社 | 被覆はんだワイヤおよびその製造方法 |
MY192419A (en) * | 2016-11-16 | 2022-08-19 | Shoei Chemical Ind Co | Method for producing metal powder |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1079929A (zh) * | 1992-02-21 | 1993-12-29 | 联合碳化化学品及塑料技术公司 | 涂有聚对亚二甲苯基的焊剂粉末 |
US5281388A (en) * | 1992-03-20 | 1994-01-25 | Mcdonnell Douglas Corporation | Resin impregnation process for producing a resin-fiber composite |
CN1103172A (zh) * | 1993-07-28 | 1995-05-31 | 惠普公司 | 用于液体静电照相调色剂的螯合正电荷导向剂 |
WO2006009643A2 (en) * | 2004-06-17 | 2006-01-26 | Henkel Corporation | Ultra low density thermally clad microspheres |
JP4179628B2 (ja) * | 1994-05-27 | 2008-11-12 | スクリンプ システムズ エル.エル.シー. | 減圧バッグ、その製造方法および、その使用方法 |
Family Cites Families (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975422A (en) | 1972-11-21 | 1976-08-17 | Johnson & Johnson | Preparation of bis (2-cyanoacrylate)monomers |
US4012402A (en) | 1974-10-04 | 1977-03-15 | Johnson & Johnson | Modified cyanoacrylate monomers and methods for preparation |
US4452861A (en) * | 1982-05-20 | 1984-06-05 | Rca Corporation | Solid particles encapsulated with cyanoacrylate polymer |
DE3433851A1 (de) | 1984-09-14 | 1986-03-27 | Gurit-Essex, Freienbach | Chemisch haertbare harze aus 1-oxa-3-aza-tetralin-gruppen enthaltenden verbindungen und cycloaliphatischen epoxid-harzen, verfahren zu deren herstellung und haertung sowie die verwendung solcher harze |
US5290825A (en) * | 1985-05-17 | 1994-03-01 | Lazar Warren G | Composition and method for inhibiting the cure of cyanoacrylate adhesives and cure inhibited cyanoacrylate adhesive compositions |
JP2564152B2 (ja) | 1987-10-27 | 1996-12-18 | タムラ化研株式会社 | はんだペースト |
ES2088905T3 (es) | 1988-07-18 | 1996-10-01 | Gurit Essex Ag | Resinas endurecibles para formar plasticos dificilmente inflamables y resistentes a altas temperaturas y procedimientos para su fabricacion. |
US5180752A (en) | 1990-03-08 | 1993-01-19 | Pierce & Stevens Corporation | Process for making dry microspheres |
JPH0420650U (zh) | 1990-06-04 | 1992-02-20 | ||
EP0493310A1 (de) | 1990-12-21 | 1992-07-01 | Gurit-Essex AG | Zu schwerentflammbaren Kunststoffen härtbare Harzmischungen und deren Verwendung |
US5234757A (en) | 1991-04-30 | 1993-08-10 | The Dexter Corporation | Expandable films and molded products therefrom |
US5369192A (en) | 1993-06-28 | 1994-11-29 | Minnesota Mining And Manufacturing Company | Binder resin for resin transfer molding preforms |
US5480603A (en) | 1994-05-19 | 1996-01-02 | The Dow Chemical Company | Method for preparing preforms for molding processes |
BR9507927A (pt) | 1994-06-06 | 1997-11-11 | Henkel Kgaa | Processo para a preparação de bis-cianoacrilatos |
US5569508A (en) | 1995-01-03 | 1996-10-29 | The Boeing Company | Resin transfer molding with honeycomb core and core filler |
US5567499A (en) | 1995-01-03 | 1996-10-22 | The Boeing Company | Resin transfer molding in combination with honeycomb core |
US5736074A (en) * | 1995-06-30 | 1998-04-07 | Micro Fab Technologies, Inc. | Manufacture of coated spheres |
US5677048A (en) | 1996-03-04 | 1997-10-14 | Gateway Technologies, Inc. | Coated skived foam and fabric article containing energy absorbing phase change material |
US5902535A (en) | 1997-07-30 | 1999-05-11 | Mcdonnell Douglas Corporation | Resin film infusion mold tooling and molding method |
DE19826756C2 (de) * | 1998-06-15 | 2002-04-18 | Juergen Schulze | Verfahren zum Verkapseln von feinen Lotmetallpulvern und danach hergestellte Lotmetallpulver |
US6207786B1 (en) | 1998-11-10 | 2001-03-27 | Edison Polymer Innovation Corporation | Ternary systems of benzoxazine, epoxy, and phenolic resins |
IES990974A2 (en) | 1998-11-23 | 2000-05-31 | Loctite R & D Ltd | Cyanoacrylate Compositions |
JP2000208889A (ja) * | 1999-01-13 | 2000-07-28 | Toppan Printing Co Ltd | 低誘電配線基板用樹脂組成物及びそれを用いた低誘電配線基板 |
JP2001228602A (ja) * | 1999-12-07 | 2001-08-24 | Fuji Photo Film Co Ltd | 平版印刷版用原版 |
CN1432053A (zh) | 2000-05-12 | 2003-07-23 | 洛克泰特(R&D)有限公司 | 氰基丙烯酸酯粘合剂的活化剂组合物 |
AU2001290266A1 (en) * | 2000-10-25 | 2002-05-06 | Harima Chemicals, Inc. | Electroconductive metal paste and method for production thereof |
US6475331B1 (en) | 2001-06-26 | 2002-11-05 | Henkel Loctite Corporation | Cyanoacrylate compositions |
KR20050086725A (ko) | 2002-11-18 | 2005-08-30 | 허니웰 인터내셔날 인코포레이티드 | 솔더 구체, 분말 및 예비성형품용 코팅 조성물, 이의제조방법 및 용도 |
US20050042961A1 (en) | 2003-08-18 | 2005-02-24 | Henkel Loctite Corporation | Curable compositions for advanced processes, and products made therefrom |
IE20040065A1 (en) * | 2004-02-02 | 2005-08-10 | Loctite R & D Ltd | Rapidly curing formulations including a conductive component |
JP4750670B2 (ja) * | 2006-10-26 | 2011-08-17 | 電気化学工業株式会社 | セラミックス回路基板の製造方法 |
CN100556950C (zh) * | 2006-12-28 | 2009-11-04 | 上海交通大学 | 一种聚合物/金属纳米复合材料的制备方法 |
US8212369B2 (en) * | 2007-01-31 | 2012-07-03 | Henkel Ag & Co. Kgaa | Semiconductor wafer coated with a filled, spin-coatable material |
EP2370219B8 (en) | 2008-11-21 | 2014-09-10 | Henkel US IP LLC | Thermally decomposable polymer coated metal powders |
DE102009000861A1 (de) | 2009-02-13 | 2010-08-19 | Henkel Ag & Co. Kgaa | Verfahren zur Herstellung von Cyanacrylsäureestern |
-
2009
- 2009-11-20 EP EP09828281.7A patent/EP2370219B8/en active Active
- 2009-11-20 TW TW098139663A patent/TWI458584B/zh active
- 2009-11-20 JP JP2011537646A patent/JP5546551B2/ja active Active
- 2009-11-20 KR KR1020117014134A patent/KR101517087B1/ko active IP Right Grant
- 2009-11-20 CN CN200980151795.3A patent/CN102264491B/zh active Active
- 2009-11-20 ES ES09828281.7T patent/ES2498718T3/es active Active
- 2009-11-20 WO PCT/US2009/065296 patent/WO2010059924A2/en active Application Filing
- 2009-11-20 PL PL09828281T patent/PL2370219T3/pl unknown
- 2009-11-20 PT PT98282817T patent/PT2370219E/pt unknown
-
2011
- 2011-05-23 US US13/113,716 patent/US8486498B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1079929A (zh) * | 1992-02-21 | 1993-12-29 | 联合碳化化学品及塑料技术公司 | 涂有聚对亚二甲苯基的焊剂粉末 |
US5281388A (en) * | 1992-03-20 | 1994-01-25 | Mcdonnell Douglas Corporation | Resin impregnation process for producing a resin-fiber composite |
CN1103172A (zh) * | 1993-07-28 | 1995-05-31 | 惠普公司 | 用于液体静电照相调色剂的螯合正电荷导向剂 |
JP4179628B2 (ja) * | 1994-05-27 | 2008-11-12 | スクリンプ システムズ エル.エル.シー. | 減圧バッグ、その製造方法および、その使用方法 |
WO2006009643A2 (en) * | 2004-06-17 | 2006-01-26 | Henkel Corporation | Ultra low density thermally clad microspheres |
Also Published As
Publication number | Publication date |
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CN102264491A (zh) | 2011-11-30 |
EP2370219B8 (en) | 2014-09-10 |
CN102264491B (zh) | 2014-11-26 |
JP2012509991A (ja) | 2012-04-26 |
EP2370219A2 (en) | 2011-10-05 |
US8486498B2 (en) | 2013-07-16 |
US20110265913A1 (en) | 2011-11-03 |
PL2370219T3 (pl) | 2015-03-31 |
WO2010059924A2 (en) | 2010-05-27 |
KR20110089352A (ko) | 2011-08-05 |
KR101517087B1 (ko) | 2015-05-04 |
PT2370219E (pt) | 2014-10-03 |
JP5546551B2 (ja) | 2014-07-09 |
ES2498718T3 (es) | 2014-09-25 |
TW201026421A (en) | 2010-07-16 |
EP2370219A4 (en) | 2012-08-22 |
EP2370219B1 (en) | 2014-06-25 |
WO2010059924A3 (en) | 2010-08-26 |
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