TWI717433B - 配備對於溫度循環測試具有改良抗性之導電裝置的嵌裝玻璃 - Google Patents
配備對於溫度循環測試具有改良抗性之導電裝置的嵌裝玻璃 Download PDFInfo
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Abstract
本發明係關於嵌裝玻璃,其由至少一個基材所組成,該基材的一部分包含導電元件,該導電元件包含以含鉻的鋼製得的連接器,此連接器藉以錫、銀和銅為基礎的焊劑焊接至導電軌,其中該導電軌係藉由燒結包含銀粉和玻璃料之混合物之銀糊而形成,具有於25℃測定之低於或等於3.5μΩ.cm的電阻率和低於20%的孔隙度,該孔隙度係藉掃描式電子顯微術從通過該基材之含有該導電軌的部分且已先藉離子研磨而拋光的截面測得。
Description
本發明係關於包含電連接元件之嵌裝玻璃,其製程及其於汽車嵌裝玻璃領域中之用途。
本發明更特別地係關於具有電力功用的汽車嵌裝玻璃,例如受熱或化冰的嵌裝玻璃或甚至配備天線的嵌裝玻璃。存在於汽車嵌裝玻璃中的加熱電線、天線或其他感知器係由導電糊(例如含銀的糊,其經網版印在玻璃基板上)形成的導電軌,並藉焊至導電糊的連接器連接至電源供應器。因為這些系統中所用材料的熱膨脹係數不同,所以在這些嵌裝玻璃的製造和操作期間內出現應變或機械應力,產生弱點並在其中生成裂紋,特別是在這些連接器的區域中。目前使用的焊劑合金通常係以鉛為基礎並因此係以高延展性的金屬為基礎。此確保在進行製造商指定的耐受性試驗時,不會出現使得嵌裝玻璃不適用於所欲
用途的裂紋。歐洲目前直接禁止使用此類型之以鉛為基礎的合金且就尋求能夠代替以鉛為基礎的合金之其他焊劑合金投入更多的研究。以含有錫、銀和銅的合金達到一個良好的平衡點。這些合金不僅具有製成良好焊劑的性質,同時亦具有通過汽車製造商目前指定的試驗所須的堅強度。在此同時,以下關於自焊劑合金移除鉛,在連接器上進行老化試驗的問題變得更嚴格;特別地,溫度循環試驗的條件變得更嚴格。這些溫度循環試驗亦以其英文字首組合字TCT“溫度循環試驗(Temperature Cycling Test)”表示。這些試驗的目的是測定嵌裝玻璃是否能夠耐受溫度的連續迅速提高和降低且未弱化。這些試驗被開發用於加速系統的各種組份的熱行為差異所引發的外觀影響。新試驗指定溫度變化介於-40℃和+105℃之間,此範圍比先前試驗中所用的變化範圍(其限制至90℃)更大。亦改變循環數,由10次循環至最少60次循環。新的TCT條件亦要求在溫度提高的階段中之這些溫度變化的期間內施以14V的電壓,藉此對應於局部溫度(其可高達約120℃)而生成額外的熱。儘管連接器形狀和材料的最佳化,已知和目前使用的系統的耐受性不足且在這些更嚴格的試驗之後會生成裂紋和裂縫。特定言之,以錫、銀和銅為基礎之合金的剛性大於以鉛為基礎的合金,導致更多應力轉移至基材。這些合金的物理性質及較嚴格的TCT試驗導致嵌裝玻璃中產生更多的缺陷或裂紋。達到較高的溫度亦導致連接器和焊劑合金較大的熱膨脹,因此而將更多的應力施
於電連接元件整體上。配備此類型的連接器和合金之嵌裝玻璃因此不符合這些試驗指定的標準並因此而與製造商指定的標準不符。
本發明係關於一種嵌裝玻璃,其由包含電連接系統澱積於基材上之基材所組成,該電連接系統由至少一個電連接器、導電性金屬糊和焊劑合金所構成,由於在施以提高和降低溫度的試驗之後,出現於基材中的裂紋數明顯降低,所以該系統在溫度行為試驗中展現較佳堅強度。
1‧‧‧導電層
2‧‧‧淺灰色區域
3‧‧‧深灰色區域
4‧‧‧黑色區域
5‧‧‧琺瑯層
圖1是非根據本發明之樣品的掃描式電子顯微術觀察到的影像。
圖2和3是根據本發明之樣品的掃描式電子顯微術觀察到的影像。
本發明的一個標的是一種嵌裝玻璃,其由至少一部分包含導電元件之基材所組成,該導電元件包含以含鉻的鋼製得的連接器,此連接器藉以錫、銀和銅為基礎的焊劑焊接至導電軌,其中該導電軌以銀為基礎,具有於25℃測定之低於或等於3.5μΩ.cm的電阻率和低於20%的
孔隙度,該孔隙度係藉掃描式電子顯微術從通過該基材之含有該導電軌的部分且已先藉離子研磨而拋光的截面測得。根據本發明之嵌裝玻璃係耐得住在介於-40℃和+105℃之間的溫度變化,在溫度提高的階段內於14V的電壓下60次連續循環的TCT之嵌裝玻璃。
本發明者已顯示,令人訝異地,藉由選擇特別的材料用於連接器,特定類型的焊劑合金和含銀的導電糊兼具低孔隙度和低比電阻,能夠得到能夠耐得住新的TCT條件之用於汽車嵌裝玻璃的導電系統。
當顧及導電糊之燃燒,考慮在空氣下在包含介於550℃和700℃的溫度熱處理2至10分鐘,得以將銀導電糊固定在基材上。在燃燒之後進行用於定出導電糊特徵之測定。
以銀為基礎的導電軌係含銀粉和玻璃料之混合物之經燒結的銀糊。有利地,銀糊包含一些具有不同尺寸的粒子,其中有尺寸低於500nm的小粒子存在。在燃燒和離子研磨之後,在經銀導電軌塗覆的基材的截面影像上測定銀粒子的尺寸和形式,並自掃描式電子顯微鏡得到。
有利地,存在於導電糊中的銀粒子之粒徑分析為平均直徑D10低於1.1μm,直徑D10代表10%的粒子具有低於此值的直徑。較佳地,直徑D10低於0.8μm,粒徑分析之測定以雷射粒徑分析儀(例如Mastersizer MS2000)進行。
導電銀軌的孔隙度係以藉網版印刷在基材的至少一部分上的銀糊層之微分析定出。在掃描式電子顯微鏡下觀察經該導電軌塗覆之基材的一部分的截面。藉掃描式電子顯微鏡(SEM)得到的影像含有淺灰色區域,其對應於銀糊,深灰色區域,對應於存在於導電糊中的玻璃料,及黑色區域,其為層之孔隙的指標。層的孔隙度係藉由處理選定區域的影像,測定黑色區域的百分比而計算。例如,可觀察基材截面的50μm長度,影像係藉SEM放大5000倍和10kV電壓得到。孔隙度以%表示且係對於於觀察10個不同的位置之後得到之各個孔隙度的值之平均的值。
因此,測定本發明中所用之導電軌的方法如下:1)在電子顯微鏡下對該基材之塗覆有該導電軌的部分之經離子研磨而拋光的截面觀察約50μm的長度;2)藉影像處理所觀察到之代表孔隙的黑區域的量以定出黑區域相對於所觀察區域整體之百分比而定出孔隙度;3)以至少10個不同之經拋光截面的區域重複步驟1和2以得到至少10個孔隙度值;4)計算所得孔隙度值的平均。
基本上,導電軌之裂紋的傳播限於“並非極多孔”,即,其孔隙度低於20%。
較佳地,以銀為基礎的導電軌所具有的孔隙
度分佈為90%的孔隙的最長長度低於6μm。孔的尺寸係藉掃描式電子顯微術於該基材之包含該燃燒後的導電軌的部分之已先藉離子研磨而拋光的截面測得。
除了與層的孔隙度相關的條件以外,銀導電軌亦須具有於25℃測定之低於或等於3.5μΩ.cm的電阻率。電阻率低於3.5μΩ.cm得以確保銀導電糊和以鉻為基礎的鋼製成的焊劑合金之間之良好的相容性。電阻率p,以ohms.cm表示,係藉由測定銀製的導電線的電阻R(單位為ohms)並將長度l(單位是m)和電線截面積S(單位是m2)列入考量而得。
電線的截面係例如使用接觸或無接觸表面測平方法(profilometry)測定。電阻率測定通常以1m長的電線進行。
用於網版印刷導電軌之導電性銀糊有利地含有介於90和97重量%之間的銀,餘者是玻璃料。此銀含量對應於導電糊燃燒之後的含量。燃燒之後測得之導電銀軌的厚度變化介於2和30μm之間且較佳地介於5和15μm之間。
用以將電連接器焊至導電銀軌之合金係以錫、銀和銅為基礎的合金。被視為“無鉛”的合金符合歐洲規範指定的標準。用以將連接器焊至根據本發明之嵌裝玻璃的合金係包含90至99.5重量%的錫,較佳由93至99重量%的錫且更佳由95至98重量%的錫之合金。亦包
含,除了錫以外,0.5至5重量%的銀和0至5重量%的銅。此合金亦含有鉍、銦、鋅和/或錳。更佳地,此焊劑合金係包含96.5重量%的錫、3重量%的銀和0.5重量%的銅之合金。此焊劑合金置於電連接器底部之上。焊劑合金層的厚度較佳地低於或等於600μm且更佳地介於150和600μm之間。
電連接器製自含鉻的鋼。極佳地,此電連接器製自不銹鋼,即,製自包含至少10.5重量%的鉻的鋼。此類型的連接器具有與以錫、銅和銀為基礎的焊劑合金相容的優點。特定言之,各種材料所具有的熱膨脹係數須使得彼等能夠併用,沒有產生導致易碎性和裂紋傳播之過高的機械應力的風險。鋼製的連接器之熱膨脹係數是約25至30W/mK,其高於例如以鈦為基礎的合金製之連接器所具有者。此較高的導熱性因為促進更均勻的加熱,所以有助於焊接程序。不銹鋼連接器具有膨脹低於例如以銅為基礎的連接器的優點。特別推薦的不銹鋼合金是,例如,根據標準EN 10 088-3之不銹鋼1.4016、1.4113、1.4509和1.4510。此連接器較佳地具有介於0.1和2mm之間,更佳地介於0.2和1mm之間且又更佳地介於0.3和0.8mm之間的厚度。
此連接器的表面上任意地具有潤濕層或以鎳、銅、鋅、錫、銀、金或其合金為基礎的塗層與焊劑合金接觸。較佳地,此塗層以鎳和/或銀為基礎。此塗層中之鎳的厚度較佳地介於0.1μm和0.3μm之間,而銀的厚
度較佳地介於3至20μm之間。
根據一個具體實施例,該連接器的底面(即,欲被置於基材上的面)上具有至少兩個微坑或至少一個間隔器,以便確保介於連接器和導電銀層之間的連接準確地由焊劑合金達成。這些微坑或間隔器因為有助於含有合金及防止區域含有不均勻量的焊劑合金(此將導致在各種元件之間的區域之黏著欠佳)形成而使得系統更堅強。這些微坑或間隔器亦降低會在連接器元件和基材之間產生的機械應力。其有利地具有圓形且特別述於專利申請案US 2014/0110166。這些微坑或間隔器較佳地具有介於0.5×10-4m和10×10-4m之間的寬度及介於0.5×10-4m和5×10-4m之間的高度。這些微坑或間隔器之存在特別得以控制置於連接器下方的焊劑合金的厚度。由於應變隨著厚度提高,所以有利地能夠使得合金厚度儘量均勻以避免將會形成特別弱的區域的任何凝塊。
連接器亦可配置至少一個接觸凸點使其較易焊接。此接觸凸點位於連接器的待焊區中。
電連接系統置於其上的基材較佳地製自玻璃,且更特別地製自平板玻璃,例如,使用飄浮法(其中,熔融的玻璃倒在熔融的金屬浴上)製造者。其可例如為石英玻璃、硼矽酸鹽玻璃、鋁矽酸鹽玻璃和/或鈉鈣玻璃。此基材亦可具聚合性,且可包含聚乙烯、聚丙烯、聚碳酸酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚丁二烯、聚腈、聚酯、聚胺甲酸酯、聚氯乙烯、聚丙烯酸酯、聚醯
胺、聚伸乙基對酞酸酯和/或彼等之共聚物或摻合物。此基材較佳地透明。其具有介於0.5mm和25mm之間的厚度,且較佳地藉於0.5和10mm之間的厚度。
此基材可為經回火之玻璃或未經回火之玻璃。在經回火之玻璃中,表層經強化並因此而較強,藉此使得電連接系統之存在而產生的弱化效果更容易被觀察到。
本發明亦係關於一種用於製造由至少一個具有電連接系統的基材所組成之嵌裝玻璃之方法,該方法包含以下步驟:a)將以錫、銅和銀為基礎的焊劑合金施於以鉻為基礎的鋼所製得的電連接器的至少一個接觸區;b)將配備該焊劑合金的電連接器置於澱積於該經塗覆或未經塗覆的基材上之銀導電軌上,該導電軌具有於25℃測定之低於或等於3.5μΩ.cm的電阻率和低於20%的孔隙度,該孔隙度係藉掃描式電子顯微術從該基材之含有該電連接系統之部分經離子研磨而拋光的截面測得;及c)將該連接器的接觸區焊接至該導電銀軌。
較佳地,在步驟a)中,小量的焊劑合金,墊或扁平液滴形式,澱積在連接器的接觸區上。澱積的合金的形狀、體積和厚度經預設。較佳地,澱積的焊劑-合金墊的厚度小於或等於0.6mm。其形狀較佳地與接觸區的形狀相同,以確保後者與導電軌的整個區域接觸。
導電銀軌係藉澱積得到,使用嫻於此技術者
已知的方法,例如藉網版印刷,導電銀糊(以銀為基礎的琺瑯)在基材上。導電銀糊層之澱積係在步驟a)中獨立地進行,但其可於步驟a)之前,之時或之後進行。銀糊層可直接澱積於基材上,或澱積於基材上的層上。因此,導電銀糊層可澱積於澱積在基材上的黑色琺瑯上且基本上用以防止自嵌裝玻璃外部看到電連接系統。
一旦澱積,導電糊層之後於約150℃乾燥,之後在空氣中於介於550℃和700℃的溫度燃燒2至10分鐘(燒結步驟)。藉此燒結之以銀為基礎的琺瑯為固體。接觸終端或連接器可經焊接以使得導電線被供以電力。
連接器可藉衝壓(stamping)、柱塞焊接(piston soldering)、微燄焊接(micro-flame soldering)、雷射焊接、熱空氣焊接、感應焊接(induction soldering)、阻抗焊接(resistive soldering)和/或超音波焊接。
本發明亦係關於前述包含至少一個電連接系統的嵌裝玻璃於建築或載具且特別是汽車載具、軌道載具或飛機之用途。此嵌裝玻璃特別作為受熱的擋風玻璃、側窗、後擋風玻璃或車頂或、在嵌裝玻璃上或在嵌裝玻璃中配備天線或配備任何其他電功能的擋風玻璃、側窗、後擋風玻璃或車頂。
以下實例非限制地說明本發明。
這些循環的期間內,未控制測定槽中的濕度。樣品進行至少60次連續循環。14V(+/- 0.2)的電壓於溫度提高階段施於樣品(標準VW80101)。
圖1是非根據本發明之樣品的掃描式電子顯微術觀察到的影像,其中觀察到導電層(1)具有高孔隙度(高於20%)。
圖2和3是根據本發明之樣品的掃描式電子顯微術觀察到的影像,其中觀察到導電層(1)具有低孔隙度(低於20%)。
這些照片中,淡灰色區域(2)對應於銀導電層(1),深灰色區域(3)對應於玻璃料,黑色區域(4)對應於銀層的孔隙。
這些圖中,導電層(1)澱積於琺瑯層(5)上。
以下實例中,在銀糊分散於丙酮中之後,粒度測定以MAstersizer MS2000粒度測定器進行,其以He-Ne雷射型的紅光源和LED型的藍光源操作。欲製備樣品,50mg的銀糊稀釋於20mL丙酮中。
孔隙尺寸之測定及特定言之,其最長長度之測定,係在導電糊燃燒之後,以掃描式電子顯微鏡下觀察到的影像進行。
藉由將導電銀糊層澱積在已事先澱積黑色琺瑯層區之玻璃基材區域上而製得複數個樣品。此糊的銀粒基本上為尺寸介於0.5和10μm之間的薄片形式。銀粒子的粒度測定得知平均直徑D10是1,25μm。銀糊層和琺瑯層藉網版印刷以自聚酯線梭織之77.55-網目織品製的網版澱積。此銀糊於150℃乾燥,之後在640℃的溫度在空氣下燒結140秒,之後,藉此塗覆的基材經淬冷。藉此得到的樣品經切割並置於離子研磨機中以拋光截面。此拋光以Hitachi IM4000研磨機在氬流下,以6kV的電壓進行,拋光循環持續2小時。之後在掃描式電子顯微術中,藉偵測回散射的電子,以放大5000倍和10kV的壓力觀察樣品。觀察50μm長度的區域。藉由以軟體套裝Image Pro分析所得影像,定出所研究樣品之黑色區域的百分比,評估孔隙度。藉掃描式電子顯微術測定,藉此得到的導電軌所具有的孔係度為30%。孔的最長長度是8.5μm。
電阻率測定係使用Tailor Hobson Talysurf 50表面測平計進行以定出電線之1m長度的截面積。導電軌於25℃測得的電阻率是4.5μΩ.cm。
不銹鋼連接器(對照編號1.4016)藉
Sn96.5Ag3Cu0.5合金感應焊接至導電銀軌。此焊接步驟之前,玻璃基材預熱至60℃且導電軌表面以鋼毛刷刷過。
電連接器已焊接至彼的玻璃基材之後連續進行所述的溫度循環超過60次。
這些試驗之後,在所有製得的樣品中觀察實質破裂情況。此樣品未符合溫度循環式樣的標準。
以與實例1所述相同方式製得樣品,但使用不同的導電銀糊。所用琺瑯與實例1中者相同。此糊的銀粒基本上為尺寸介於1和6μm之間的薄片形式和尺寸介於140和400μm之間的球形式。此銀粒的粒度測定得知平均直徑D10是0,46μm。自此銀糊得到的導電軌具有16%的孔隙度和於25℃測得之3.2μΩ.cm的電阻率。孔的最長長度是3.5μm。
所用焊劑合金和連接器亦與實例1中者相同。在各種樣品上測試兩種類型的焊接(感應焊接和電阻焊接)。樣品之後在與實例1中所述之相同的條件下進行溫度循環試驗。
所有的樣品成功地通過試驗且無裂紋顯現。
以與實例1中所述之相同的方式製得樣品,
但使用不同的導電銀糊。所用琺瑯與實例1中者相同。此糊的銀粒基本上為尺寸介於1.2和2.4μm之間的球形式和尺寸介於70和400μm之間的較小粒子形式。此銀粒的粒度測定得知平均直徑D10是0.43μm。自此銀糊得到的導電軌具有15%的孔隙度和於25℃測得之2.8μΩ.cm的電阻率。孔的最長長度是1.8μm。
所用焊劑合金和連接器亦與實例1中者相同。在各種樣品上測試兩種類型的焊接(感應焊接和電阻焊接)。樣品之後在與實例1中所述之相同的條件下進行溫度循環試驗。
所有的樣品成功地通過試驗且無裂紋顯現。
使用與實例2中所用之不同的黑色琺瑯製得與實例2中所述之相同的樣品。系統的其他組份與實例2中所述者完全相同。藉此得到的所有樣品成功地通過試驗且無裂紋顯現。
Claims (23)
- 一種嵌裝玻璃,其由至少一部分包含導電元件之基材所組成,該導電元件包含以含鉻的鋼製得的電連接器,此電連接器藉以錫、銀和銅為基礎的焊劑焊接至導電軌,其中該導電軌以銀為基礎,具有於25℃測定之低於或等於3.5μΩ.cm的電阻率和低於20%的孔隙度,該孔隙度係藉掃描式電子顯微術從通過該基材之含有該導電軌的部分且已先藉離子研磨而拋光的截面測得。
- 如請求項1之嵌裝玻璃,其中該導電軌係包含銀粉和玻璃料之混合物的經燒結銀糊。
- 如請求項1或2之嵌裝玻璃,其中該以銀為基礎的導電軌所具有的孔隙度分佈為90%的孔隙的最長長度低於6μm。
- 如請求項2之嵌裝玻璃,其中該經燒結銀糊包含具不同尺寸的銀粒子,這些粒子中有尺寸低於500nm的小粒子存在。
- 如請求項4之嵌裝玻璃,其中該等小粒子具有直徑低於500nm的球形。
- 如請求項4之嵌裝玻璃,其中存在於該經燒結銀糊中的銀粒子之粒徑分析為直徑D10低於1.1μm,直徑D10代表10%的粒子具有低於此值的直徑。
- 如請求項1或2之嵌裝玻璃,其中該焊劑係包含90至99.5重量%的錫之合金。
- 如請求項1或2之嵌裝玻璃,其中該焊劑係包含 93至99重量%的錫之合金。
- 如請求項1或2之嵌裝玻璃,其中該焊劑係包含95至98重量%的錫之合金。
- 如請求項7之嵌裝玻璃,其中該焊劑亦包含0.5至5重量%的銀和0至5重量%的銅。
- 如請求項1或2之嵌裝玻璃,其中該焊劑係包含96.5重量%的錫、3重量%的銀和0.5重量%的銅之合金。
- 如請求項1或2之嵌裝玻璃,其中該電連接器製自不銹鋼。
- 如請求項1或2之嵌裝玻璃,其中該電連接器的底面上具有至少兩個微坑或間隔器,該底面係將被置於該基材上。
- 如請求項1或2之嵌裝玻璃,其中在燒結之後所測得該以銀為基礎的導電軌的厚度介於2和30μm之間。
- 如請求項1或2之嵌裝玻璃,其中在燒結之後所測得該以銀為基礎的導電軌的厚度介於5和15μm之間。
- 如請求項1或2之嵌裝玻璃,其中該基材係經回火之玻璃。
- 如請求項1或2之嵌裝玻璃,其中該基材係非經回火之玻璃。
- 一種用於製造由至少一個具有電連接系統的基材所組成之嵌裝玻璃之方法,該方法包含以下步驟:a)將以錫、銅和銀為基礎的焊劑合金施於以鉻為基礎的鋼所製得的電連接器的至少一個接觸區; b)將配備該焊劑合金的電連接器置於澱積於經塗覆或未經塗覆的該基材上之銀導電軌上,該銀導電軌具有於25℃測定之低於或等於3.5μΩ.cm的電阻率和低於20%的孔隙度,該孔隙度係藉掃描式電子顯微術從一通過該基材之含有該銀導電軌的部分且已先藉離子研磨而拋光的截面測得;及c)將該連接器的接觸區焊接至該銀導電軌。
- 如請求項18之方法,其中在步驟a)中,將厚度小於或等於0.6mm的墊或扁平小滴澱積於該連接器的接觸區上。
- 如請求項18或19之方法,其中該連接器藉衝壓(stamping)、柱塞焊接(piston soldering)、微燄焊接(micro-flame soldering)、雷射焊接、熱空氣焊接、感應焊接(induction soldering)、阻抗焊接(resistive soldering)、使用焊鐵(soldering iron)、或以超音波方式而焊接至該銀導電軌。
- 一種如請求項1至17中任一項之嵌裝玻璃之用途,其用於建築物或載具。
- 如請求項21之用途,其中該載具是汽車載具、軌道載具或飛機。
- 如請求項21或22之用途,其作為受熱的擋風玻璃、側窗、後擋風玻璃、或車頂,或作為配備天線或配備任何其他電功能在嵌裝玻璃上或嵌裝玻璃中的擋風玻璃、側窗、後擋風玻璃或車頂。
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FR1562116A FR3044962B1 (fr) | 2015-12-10 | 2015-12-10 | Vitrage muni d'un dispositif conducteur electrique et possedant une resistance amelioree aux tests cycliques de temperature. |
FR1562116 | 2015-12-10 |
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FR3103809B1 (fr) * | 2019-11-29 | 2022-05-27 | Saint Gobain | Procédé d’obtention de vitrages munis de motifs électroconducteurs |
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TW201414120A (zh) * | 2012-06-06 | 2014-04-01 | Saint Gobain | 帶有電連接元件之玻璃板 |
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JP4014547B2 (ja) * | 2003-08-07 | 2007-11-28 | 信越ポリマー株式会社 | 配線体形成材料、配線体及び配線体の製造方法 |
US7573630B2 (en) * | 2006-06-02 | 2009-08-11 | Exatec, Llc | Photochromatic effect for polycarbonate glazing applications |
WO2011010659A1 (ja) * | 2009-07-21 | 2011-01-27 | 日亜化学工業株式会社 | 導電性材料の製造方法、その方法により得られた導電性材料、その導電性材料を含む電子機器、および発光装置 |
JP4870223B1 (ja) * | 2010-09-02 | 2012-02-08 | ニホンハンダ株式会社 | ペースト状銀粒子組成物、金属製部材接合体の製造方法および金属製部材接合体 |
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JP5819751B2 (ja) * | 2012-02-29 | 2015-11-24 | 三ツ星ベルト株式会社 | 導電性積層体並びにその製造方法及び前駆体 |
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US20180368268A1 (en) | 2018-12-20 |
KR20180091879A (ko) | 2018-08-16 |
TW201736124A (zh) | 2017-10-16 |
FR3044962B1 (fr) | 2017-12-22 |
RU2018121047A (ru) | 2020-01-10 |
JP2019505458A (ja) | 2019-02-28 |
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AR107024A1 (es) | 2018-03-14 |
BR112018006137A2 (pt) | 2018-10-23 |
MX2018006945A (es) | 2018-08-01 |
WO2017098164A1 (fr) | 2017-06-15 |
BR112018006137B1 (pt) | 2022-03-03 |
EP3386747B1 (fr) | 2022-06-15 |
HUE059196T2 (hu) | 2022-10-28 |
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PL3386747T3 (pl) | 2022-09-12 |
ES2923871T3 (es) | 2022-10-03 |
CA2999950C (fr) | 2023-08-01 |
DK3386747T3 (da) | 2022-08-01 |
KR102662932B1 (ko) | 2024-05-07 |
EP3386747A1 (fr) | 2018-10-17 |
CA2999950A1 (fr) | 2017-06-15 |
FR3044962A1 (fr) | 2017-06-16 |
US10512169B2 (en) | 2019-12-17 |
PT3386747T (pt) | 2022-08-16 |
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