TWI453266B - 特別適用於結合電子組件與導體軌道之熱可活化膠帶 - Google Patents
特別適用於結合電子組件與導體軌道之熱可活化膠帶 Download PDFInfo
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- TWI453266B TWI453266B TW096130652A TW96130652A TWI453266B TW I453266 B TWI453266 B TW I453266B TW 096130652 A TW096130652 A TW 096130652A TW 96130652 A TW96130652 A TW 96130652A TW I453266 B TWI453266 B TW I453266B
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- adhesive tape
- acid
- block copolymer
- modified
- heat activatable
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
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Description
本發明係有關一種在高溫具低流動性之熱可活化黏著劑,其特別適合黏著撓性印刷導體軌道(撓性印刷電路板FPCB)。
如今撓性印刷電路板常用於多種電子裝置,例如手機、收音機、電腦、印表機等。其乃由銅層及高熔融抗性熱塑性塑料(大多數為聚醯亞胺,少數為聚酯)所構成。此等FPCB往往是由具特殊規格之膠帶所製得。一方面,為製得FPCB,銅箔須黏著於聚醯亞胺板;另方面,個別的FPCB亦須互相黏著,在此場合下,聚醯亞胺黏著聚醯亞胺。除此等應用外,FPCB亦黏著其他基材。
用於此等黏著任務之膠帶必須具有特殊規格。因為必須具備高黏著性能,所用膠帶通常為在高溫加工之熱可活化膠帶。此等膠帶在高溫(往往是約200℃之高溫)黏著FPCB時,必須不會釋出揮發性成分。為獲得高度內聚力,膠帶必須能在加熱時交聯。在黏合操作時之高壓,使得膠帶在高溫之流動性須低。亦即未交聯膠帶之黏度須高,或須快速交聯。此外,膠帶亦必須能耐軟焊料浴(solder bath),換句話說,膠帶必須能短暫耐288℃之高溫。
為此理由,採用純熱塑性樹脂並不合理,儘管它易熔,能確保黏合基材之潤溼,並可在數秒內快速黏合。然而在高溫下,它太軟以致於在黏合過程中加壓會擠出黏合線外。再者,它也不能耐軟焊料浴。
就可交聯膠帶而言,通常採用環氧樹脂或酚醛樹脂,其可和特殊硬化劑反應而得聚合物網狀結構。在本特殊場合下,不能採用酚醛樹脂,因在交聯硬化過程中會釋出脫除產物,而在硬化過程或最後在軟焊料浴導致起泡。
環氧樹脂主要用於結構黏合,經合適交聯劑固化後,產生非常脆的黏著劑,其雖有高黏合強度,但實質上無可撓性。
可撓性的提升乃應用於FPCB不可或缺的。一方面,黏合乃利用理想上成卷之膠帶;另方面,導體軌道須為撓性,可彎曲,例如膝上型個人電腦之導體軌道即須為撓性,其可折疊式螢幕乃利用FPCB連接其他電路。
可用兩種方法使環氧樹脂黏著劑可撓化。首先,已知利用彈性體鏈可使環氧樹脂可撓化,但由於彈性體鏈很短,故可撓化程度有限。獲得可撓性之另外方案是在黏著劑中加入彈性體。此案之缺點是彈性體未化學交聯,亦即只有在高溫仍保持高黏度之彈性體才能使用。
因膠帶通常乃由溶液製得,往往不易尋求同時具備在高溫不流動的足夠長的鏈及能溶解於溶液中之足夠短的鏈之彈性體。
雖然可利用熱熔膠操作(hotmelt operation),但在交聯系統中頗為困難,因必須在生產過程中防止太早的交聯。
在FPCB製造及加工領域之許多應用中,膠帶乃自通常用於保護膠帶之離型介質取出,然後貼到欲黏合之基材上。在此場合下,於操作前往往已模切之膠帶必須確保在剝開離型介質時,或貼合到基材時不會變形。因為剝開離型介質時須施一點力量,膠帶的彈性模數必須足夠大,才不會受力而產生任何延伸或其他變形。既然所用之產物須儘可能的薄,就不易在膠帶中添加載體;事實上,一般而言,膠帶只合一層黏著劑。因此,該黏著劑必須具足夠高的彈性模數,而不會延伸。
美國專利第5,369,167A號有提及基於酸酐改質之嵌段共聚物及環氧樹脂之黏著劑;以及此複合配方之製法。此外,須用交聯劑使環氧樹脂進行交聯。但該專利中,並未提到膠帶。
類似的黏著劑於日本專利第57/149369 A1亦有記載。其環氧樹脂亦需要硬化劑。其中並未揭示膠帶
歐洲專利第1,311,559A2號記載著利用螯合劑使順丁烯二酸酐改質之嵌段共聚物交聯,其中提到嵌段共聚物混合物之內聚力有提升。儘管在高溫有螯合劑和環氧樹脂交聯,但未提及熱活化膠帶之製法。
此外,螯合劑與例如酸改質之丙烯酸酯黏著劑交聯記載於例如美國專利第4,005,247A號或美國專利第3,769,254A號。
德國專利第10-2004-031-188A1號揭示黏合電子元件及可撓性導體軌道之膠帶,乃由至少一種酸改質或酸酐改質之乙烯基芳基嵌段共聚物及環氧樹脂。但其中未提及金屬螯合劑。
德國專利第10-2004-007-258A1號揭示的用於黏著性條狀片之黏著劑包含下列組成:-酸改質或酸酐改質之乙烯基芳基嵌段共聚物,-如下式所示之金屬螯合劑:(R1
O)n
M(XR2
Y)m
式中M乃選自週期表主族元素第二、三、四、五週期之金屬或過渡金屬;R1
乃烷基或芳基;n乃零或更大之整數;X及Y乃氧或氮,其均可利用雙鍵連接R2
;R2
乃連接X及Y之伸烷基,其可為分枝的,或在鏈中含氧或其他雜原子;m乃至少1之整數。-增黏樹脂。
黏著性片條(adhesive sheet strip)可藉由在黏合線(bondline)方向進行延展性拉伸而分離。
其中並未提及添加含環氧化物之化合物。
有鑑於此,本發明之目的在提供一種熱可活化膠帶,其受熱會交聯,加熱時黏度低,對聚醯亞胺之黏著性佳,在未交聯狀態可溶於有機溶劑,且在室溫有高彈性模數。
令人驚奇的是利用申請專利範圍獨立項所述之膠帶即可實現此目的。申請專利範圍附屬項提供本發明標的物之有利發展及可能的應用。
特別適合黏合電子元件和導體軌道之熱活化性黏著劑至少包含a)酸改質或酸酐改質之乙烯基芳族嵌段共聚物,b)含環氧基化合物,c)金屬螯合劑。
在本發明中所言之”膠帶”包含所有片狀結構,例如二維延展的片或片材、寬度有限而長度伸長之帶、帶材、模切材等。
所用之黏著劑較佳為嵌段共聚物,其包含較佳為苯乙烯之乙烯基芳族嵌段(A嵌段),及主要由較佳為丁二烯及異戊間二烯之1,3-二烯聚合而得之嵌段(B嵌段)。依本發明,均聚物及共聚物嵌段均可使用。所得嵌段共聚物可含相同或不同嵌段B,其可部分、選擇性或完全地氫化。嵌段共聚物可呈線型A-B-A結構。亦可採用輻射構型之嵌段共聚物、星形及線形多嵌段共聚物。其他可存在的成分尚包含A-B二嵌段共聚物。依本發明,乙烯基芳族化合物和異丁烯之嵌段共聚物亦可用。所有前述聚合物可單獨使用或互相混合使用。
至少一些所用的嵌段共聚物必須經酸改質或酸酐改質,改質操作主要是利用不飽和單羧酸及多羧酸或酸酐的自由基插枝共聚合:例如富馬酸、衣康酸、檸康酸、丙烯酸、馬來酐、衣康酐、檸康酐,較佳為馬來酐。酸或酸酐之用量較佳為佔嵌段共聚物重量的0.5至4重量%。
可採用市售之嵌段共聚物,例如Shell之KratonTM
FG1901及KratonTM
FG1924或Asahi之TuftecTM
M1913及TuftecTM
M1943。
一般的瞭解,環氧樹脂為每分子具一個以上環氧基之單體或寡聚物。其可為縮水甘油酯或表氯醇和雙酚A或雙酚F或此兩者之混合物之反應產物。同樣適用的有環氧酚醛樹脂,其乃酚及甲醛之反應產物再和表氯醇進行反應而得。亦可採用具兩個或以上環氧末端基之單體化合物做為環氧樹脂之稀釋劑。亦可用彈性改質之環氧樹脂或環氧改質之彈性體,例如環氧化苯乙烯嵌段共聚物(如Daicel公司之Epofriend)。
環氧樹脂例如有Ciba Geigy公司之AralditeTM
6010、CY-281TM
、ECNTM
1273、ECNTM
1280、MY720、RD-2;Dow化學公司之DERTM
331、732、736、DENTM
432;Shell化學公司之EponTM
812、825、826、828、830等及HPTTM
1071、1079;Bakelite公司之BakeliteTM
EPR161、166、172、191、194等。
市售脂族環氧樹脂例如二氧化乙烯環己烷(如Union Carbide公司之ERL-4206、4221、4201、4298或0400)。
彈性化彈性體可得自如Noveon公司之Hycar。
環氧稀釋劑(含兩個或以上環氧基之單體)例如Bakelite公司之BakeliteTM
EPD KR、EPD Z8、EPD HD、EPD WF等或UCCP公司之PolypoxTM
R9、R12、R15、R19、R20等。
雖然如前述,不一定要加交聯劑,但是仍可再加硬化劑。在此所用的硬化劑必須只是具酸基或酸酐基之物質,因主要用於環氧交聯反應之胺及胍和酸酐反應,而减少反應基之數目。
除了已經談到之酸改質酸酐改質之乙烯基芳基嵌段共聚物,亦可再加酸或酸酐以獲得較高的交聯度,故進一步改善內聚力。在此情況下,如美國專利第3,970,608A號所述,可用單體酸酐及酸,酸改質或酸酐改質之聚合物,以及酸酐共聚物,如聚乙烯甲醚-馬來酐共聚物,例如是ISP公司之GantrezTM
。
金屬螯合劑中之金屬可為週期表主族元素第二、三、四及五週期之金屬及過渡金屬。特別合適的是鋁、錫、鈦、鋯、鉿、釩、鈮、鉻、錳、鐵、鈷及鈰。特佳為鋁及鈦。
各種金屬螯合劑可用於螯合交聯,並可用下式表示:(R1
O)n
M(XR2
Y)m
式中M係如前述之金屬,R1
係烷基或芳基,如甲基、乙基、丁基、異丙基或苄基,n係零或更大整數,X及Y係氧或氮,其均可利用雙鍵連接R2
,R2
係連接X及Y之伸烷基,其可呈分枝狀,或在鏈中含氧或其他雜原子,m係整數,但至少為1。
較佳之螯合配位基乃由下列化合物反應而得:三乙醇胺、2,4-戊二酮、2-乙基-1,3-己二醇或乳酸。特佳之交聯劑為乙醯丙酮酸鋁及乙醯丙酮酸鈦。
所選酸及/或酸酐基對乙醯丙酮基的比必須約相同,以便獲得最適交聯,經發現交聯劑少許過量是正面的。雖然為得適當的交聯,酐基及乙醯丙酮基中之任一基均不可有5倍的莫耳過量,但是此兩基的比是可變化的。
環氧樹脂和彈性體之化學交聯可在黏著性薄膜中產生很高的強度。其對聚醯亞胺的黏合強度亦明確地很高。
為提升黏著性,亦可添加能和嵌段共聚物中彈性體鏈段相容的增黏劑。
可用於本發明壓敏性黏著劑之增黏劑例如基於松香或松香衍生物之未氫化、部分氫化或完全氫化之樹脂,二環戊二烯的氫化聚合物,基於C5
、C5
/C9
或C9
單體流之未氫化、部分氫化、選擇性或完全氫化之樹脂,基於α-蒎烯及/或β-蒎烯及/或δ-薴烯之聚萜烯樹脂,和較佳為純C8
及C9
芳族的氫化聚合物。前述之增黏劑樹脂可單獨或混合使用。
其他適用之添加劑典型上包含:-主抗氧化劑,如位阻酚-次級抗氧化劑,如亞磷酸酯或硫醚-製程安定劑,如C-自由基補獲劑-光安定劑,如紫外線吸收劑或位阻胺-加工助劑-末端嵌段補強樹脂-填充料,如二氧化矽、玻璃(經研磨的或顆粒)、氧化鋁、氧化鋅、碳酸鈣、二氧化鈦、碳黑、金屬粉末等-顏料、染料及光學增亮劑-必要時,其他聚合物,較佳為本質為彈性體者。
本發明系統的優點是很低之軟化溫度,其乃來自嵌段共聚物末端嵌段中的聚苯乙烯之軟化點。因在交聯反應過程中,彈性體引入聚合物網絡,在典型上用於黏合FPCB之高溫(高至200℃)下,此反應很快,在黏合線上沒有黏著劑滲出之現象。藉由添加所謂的催速劑可進一步提升反應速度。
可用的促進劑例如:-三級胺,例如苄二甲胺、二甲胺甲酚、三(二甲胺甲基)酚-三鹵化硼-胺錯合物-被取代之咪唑-三苯膦
理想上酸改質及/或酸酐改質之彈性體和環氧樹脂之用量比例乃使環氧基和酐基之莫耳分率正好相等。若只用稍微改質之彈性體及具低環氧化物當量的低分子量環氧樹脂,則結果只得很少量-低於10重量%之環氧樹脂,百分率係所用之環氧樹脂的對改質苯乙烯嵌段共聚物而言。
雖然為得足夠的交聯,酐基和環氧基均不可大於4倍的莫耳過量,但是此兩基的比例可在廣範圍內變化。
為製造膠帶,黏著性成分較佳為溶於合適溶劑,例如甲苯或萘70/90及丙酮之混合物;並使溶液塗於附有離型層(如離型紙或離型薄膜)之撓性基板上;乾燥塗層,使得組成物又能容易自基板再次移除。經合適的加工、模切,乃在室溫製得輥狀或其他形狀產物。然後較佳為在高溫將對應形狀黏著於欲黏合之基板(如聚醯亞胺)上。
亦可直接將黏著劑塗在聚醯亞胺基板上。然後此種黏著劑片可用於罩蓋FPCB中之銅導體軌道。
不一定須在單一製程中完成貼合操作。膠帶可先以熱層合黏附於兩基板之一。在實際上和第二基板(第二聚醯亞胺片或銅箔)熱黏合操作中,樹脂接著完全或部分硬化,並使黏合線獲得高黏合強度。
所混合的環氧樹脂較佳在層合溫度時應先不進行任何化學反應,而是在熱貼合時與酸或酸酐反應。
本發明黏著劑之優點是彈性體事實上和樹脂化學結合;不必在環氧樹脂中加入硬化劑,因為彈性體本身即硬化劑。
由於製程中乾燥操作產生和金屬螯合物之交聯,所以本發明黏著劑明顯硬化,彈性模數也提高。
令人驚奇的是儘管彈性體之酸基及/或酐基和金屬螯合物在室溫交聯,通常在高於150℃之熱活化會使得改質彈性體和環氧樹脂交聯,產生高度內聚力及高黏合強度。金屬螯合物並不會妨害第二階段之交聯。
玆以非限制本發明範圍之實施例進一步說明本發明。
在甲苯中溶解92.5克KratonTM
FG1901(馬來酐改質之苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物,其中具30重量%聚苯乙烯嵌段及約2重量%馬來酐)、7.5克BakeliteTM
EPR191(環氧樹脂)及2克乙醯丙酮酸鋁之混合物,並將所得溶液塗於1.5克/米3
矽酮化離型紙上,在110℃乾燥塗層15分鐘。黏著層厚度為25微米。
在甲苯中溶解87.4克KratonTM
FG1901、2.6克BakeliteTM
EPR161(環氧樹脂)、10克RegaliteTM
R1100((Eastman)公司之氫化烴樹脂,軟化點約100℃)及1.5克乙醯丙酮酸鋁之混合物,並將所得溶液塗於1.5克/米3
矽酮化離型紙上,在110℃乾燥塗層15分鐘。黏著層厚度為25微米。
在甲苯中溶解92.5克KratonTM
FG1901(馬來酐改質之苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物,其中具30重量%聚苯乙烯嵌段及約2重量%馬來酐)及7.5克BakeliteTM
EPR191(環氧樹脂)之混合物,並將所得溶液塗於1.5克/米3
矽酮化離型紙上,在110℃乾燥塗層15分鐘。黏著層厚度為25微米。
FPCB和所得膠帶之黏合
利用實施例1至3所得膠帶各黏合兩片FPCB。為此目的,在100℃將膠帶層合於聚醯亞胺/銅箔FPCB層合板中之聚醯亞胺片上。然後將另一FPCB之聚醯亞胺片黏合於膠帶,並將整個組合放入可加熱之Brkle壓機中,於180℃加壓1.3MPa經歷30分鐘。
測試方法
前面實施例所得黏著劑板係以下列測試方法測其性質: FPCB之T-剝離試驗
利用拉力試驗機(Zwick公司製),以180°角及50毫米/分鐘之速率剝離前面製程所得之FPCB/膠帶/FPCB之複合體,測量所需的力量(牛頓/厘米)。在20℃及50%相對溼度下,進行測試。每一測試值均測定三次。
在5%伸長率之力量
因為如此高可撓性薄材料往往不易測定其彈性模數,所以改測在5%伸長率之力量。其藉由自黏著條衝切1厘米寬及10厘米長黏著劑;並夾於拉力試驗機,以300毫米/分鐘之速率拉伸該條,記錄在5%伸長率之力量。結果以牛頓/厘米記錄。
軟焊料浴耐性
將前面製程黏合所得FPCB複合體放入溫度為288℃之軟焊料浴10秒。若不會產生氣泡引起FPCB中聚醯亞胺層膨脹,則表示本黏合能耐軟焊料浴。然而即使略有氣泡產生,均列為失敗。
溫度安定性
彷照前面所述T-剝離試驗,依據上述所揭示之方式所製得之FPCB複合體之一端被懸吊起來,而另一端吊著500克之重物。在70℃做靜態剝離試驗。測量單位時間靜態剝離之距離(毫米/小時)。
試驗結果
為評估前述諸例的黏著劑,先做T-剝離試驗。結果列於表1中。
由此可知實施例1及實施例3均同樣可得高黏著強度。
膠帶之溫度安定性可用靜態剝離試驗評估,結果列於表2中。
實施例1及3並無大差異;只是實施例2採用樹脂摻混料,剝離略多。在5%伸長率下的拉力列於表3。
以螯合劑交聯明顯提升拉伸膠帶所需的力量。
此三例均通過金屬熔化液測試。
Claims (13)
- 一種熱可活化膠帶,其具有至少包含下列成分之黏著劑:a)酸改質或酸酐改質之乙烯基芳基嵌段共聚物,b)含環氧基之化合物,c)金屬螯合劑作為交聯劑,該黏著劑在兩個分別的交聯步驟中可被交聯,第一步驟係在室溫下且第二步驟係在高於150℃下進行。
- 如申請專利範圍第1項所述之熱可活化膠帶,其中乙烯基芳基嵌段共聚物為苯乙烯嵌段共聚物。
- 如申請專利範圍第1項所述之熱可活化膠帶,其中含環氧基之化合物為環氧樹脂、環氧化聚合物、或其組合。
- 如申請專利範圍第1項所述之熱可活化膠帶,其中在第二交聯步驟中環氧基和乙烯基芳基嵌段共聚物之酸基或酸酐基進行交聯。
- 如申請專利範圍第1項所述之熱可活化膠帶,其中該金屬螯合劑係以下式表示:(R1 O)n M(XR2 Y)m 式中M係週期表主族元素第二、三、四或五週期之金屬或過渡金屬,R1 係烷基或芳基,n係零或大於零的整數,X及Y係氧或氮,其均可利用雙鍵連接R2 ,R2 係連接X及Y之伸烷基,其可呈分枝狀,或可含氧或其他雜原子, m係整數,但至少為1。
- 如申請專利範圍第1項所述之熱可活化膠帶,其中金屬螯合劑係乙醯丙酮酸鋁或乙醯丙酮酸鈦。
- 如申請專利範圍第1項所述之熱可活化膠帶,其中膠帶包含其他酸酐、其他彈性體、增黏樹脂、催速劑、染料、碳黑、金屬粉末、或其組合。
- 如申請專利範圍第1至7項中任一項所述之熱可活化膠帶,其中該酸改質或酸酐改質之乙烯基芳基嵌段共聚物及該含環氧基之化合物存在之含量為,該含環氧基之化合物存在的含量不大於酸改質及/或酸酐改質之乙烯基芳基嵌段共聚物存在的含量之10重量%。
- 如申請專利範圍第8項所述之熱可活化膠帶,其中該含環氧基之化合物存在的含量不大於酸改質及/或酸酐改質之乙烯基芳基嵌段共聚物存在的含量之5重量%。
- 一種以黏著劑黏合塑膠元件之方法,其中該塑膠元件係以如申請專利範圍第1至9項中任一項之熱可活化膠帶所黏合,該熱可活化膠帶具有包含至少酸改質及/或酸酐改質之乙烯基芳基嵌段共聚物及環氧樹脂的黏著劑。
- 一種如申請專利範圍第1至9項中任一項之熱可活化膠帶的用法,其係用於黏合塑膠元件。
- 一種如申請專利範圍第1至9項中任一項之熱可活化膠帶的用法,其係用於黏合電子元件及/或撓性印刷電路板(FPCB)。
- 一種如申請專利範圍第1至9項中任一項之熱可活化膠帶的用法,其係用於黏合聚醯亞胺。
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DE102012206265A1 (de) * | 2012-04-17 | 2013-10-17 | Tesa Se | Temperaturstabile vernetzbare Klebemasse mit Hart- und Weichblöcken |
JP6018461B2 (ja) * | 2012-08-21 | 2016-11-02 | パナック株式会社 | 自己粘着性フィルム、これを用いた飛散防止ガラスの製造方法、及び自己粘着性熱可塑性エラストマー組成物 |
JP2014040498A (ja) * | 2012-08-21 | 2014-03-06 | Panac Co Ltd | 自己粘着性フィルム、これを用いた飛散防止ガラスの製造方法 |
KR101797723B1 (ko) * | 2014-12-08 | 2017-11-14 | 셍기 테크놀로지 코. 엘티디. | 접착용 수지 조성물, 접착용 필름 및 연성 금속 적층체 |
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- 2006-10-06 DE DE102006047738A patent/DE102006047738A1/de not_active Withdrawn
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2007
- 2007-08-20 TW TW096130652A patent/TWI453266B/zh not_active IP Right Cessation
- 2007-09-24 DE DE502007005081T patent/DE502007005081D1/de active Active
- 2007-09-24 JP JP2009530845A patent/JP2010505978A/ja active Pending
- 2007-09-24 CN CNA2007800374281A patent/CN101522844A/zh active Pending
- 2007-09-24 KR KR1020097009340A patent/KR101496787B1/ko active IP Right Grant
- 2007-09-24 EP EP07820503A patent/EP2079815B1/de not_active Not-in-force
- 2007-09-24 US US12/440,276 patent/US9273231B2/en not_active Expired - Fee Related
- 2007-09-24 AT AT07820503T patent/ATE481459T1/de active
- 2007-09-24 WO PCT/EP2007/060096 patent/WO2008043660A1/de active Application Filing
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Also Published As
Publication number | Publication date |
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DE502007005081D1 (de) | 2010-10-28 |
KR101496787B1 (ko) | 2015-02-27 |
ATE481459T1 (de) | 2010-10-15 |
EP2079815B1 (de) | 2010-09-15 |
TW200817489A (en) | 2008-04-16 |
US20100012271A1 (en) | 2010-01-21 |
US9273231B2 (en) | 2016-03-01 |
CN101522844A (zh) | 2009-09-02 |
KR20090088873A (ko) | 2009-08-20 |
DE102006047738A1 (de) | 2008-04-10 |
EP2079815A1 (de) | 2009-07-22 |
WO2008043660A1 (de) | 2008-04-17 |
JP2010505978A (ja) | 2010-02-25 |
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