TWI488928B - 水性導電組成物 - Google Patents
水性導電組成物 Download PDFInfo
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- TWI488928B TWI488928B TW097131367A TW97131367A TWI488928B TW I488928 B TWI488928 B TW I488928B TW 097131367 A TW097131367 A TW 097131367A TW 97131367 A TW97131367 A TW 97131367A TW I488928 B TWI488928 B TW I488928B
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- Taiwan
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- composition
- water
- acid
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- acrylic
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- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000002492 water-soluble polymer binding agent Substances 0.000 description 1
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Description
本發明係關於水性導電組成物,該等水性導電組成物可係塗敷於基板上如作為電路之使用之可印刷墨水,例如,智慧及活性包裝、測感器、及無線射頻辨識天線。
在以前,作為導電墨水使用之水性導電聚合物厚膜調配物,當於某些基板上印刷及固化時,及特定言之於撓性基板上時,通常已顯示低於最適之流變性、黏附、及撓性。作為可印刷之導電墨水使用之水性聚合之組成物係揭示,例如,於美國專利第5,286,415號及第5,389,403號(Advanced Products,Inc.)敘述一種包含熱塑性聚合物(諸如聚丙烯酸)、於水中之不溶於水之聚合物分散液、二醇化合物、導電填充劑、及水之水性導電聚合物組成物;美國專利第6,866,799號(Anuvu,Inc.)敘述一種包含與另一種聚合物諸如苯乙烯共聚合之水溶性丙烯酸系聚合物、導電填充劑、水溶性潤濕劑、水,及為了增大該組成物,水溶性彈性物之水性聚合之組成物;美國專利第5,492,653號(Heraeus,Inc.)敘述一種包含30至80重量%之經塗布之銀薄片、實質上完全水溶性聚合物黏合劑、二甘醇單丁基醚、及水之塗料組成物;及美國專利第5,658,499號(Heraeus,Inc.)中敘述一種實質上由30至80重量%之經塗布之銀薄片、實質上完全水溶性黏合劑、其他添加劑、及水組成之水性塗料組成物。然而,此等組成物不滿足於今日之導電墨水應用中需要之所有性能需求。
在以前已製備金屬粉末,諸如不規則地成形或球形之銀粉末,但是當調配、印刷及煅燒此等粉末時,造成相對地低之導電效率。此外,當以超過85%固體負荷調配時,由於過量之黏度,因此習用之薄片銀粉末時常顯示不良之篩網印刷特徵,其導致於乾燥後之印刷之圖案中之多孔性及缺陷。當以非薄片之粉末取代實質部分之薄片銀粉末時,達成實際上有用之黏度改良。然而,此種取代嚴重地損害導電效率。
因此,對於包含高含量之導電材料(諸如金屬薄片)、及當處理黏度以提供良好之印刷特性時維持優良之導電效率之水性導電塗料,依然需要。
本發明係關於一種水性導電組成物,其包含金屬薄片或粒子;於有效之溶合量之溶解丙烯酸共聚物之水及鹼中之可溶於鹼之丙烯酸或甲基丙烯酸共聚物;分散於水中之不溶於水之聚合物;及視需要,薄膜聚結(或潤濕)劑、塑化劑、或兩者。
適合使用於本發明中之金屬薄片或粒子係提供導電性之任何者。〝薄片〞係意表其主要形狀係薄片,如由掃描電子顯微術測定之材料。適合之金屬薄片及粒子包括任何之貴金屬,及於一種具體實施例中係銀薄片或粒子。於另一種具體實施例中,導電材料係具有3微米之平均質量直徑(D50)及8.8微米之90%直徑(D90)之雙模態銀薄片。〝平均質量直徑〞(D50)係於該直徑,以質量計50%之薄片具有比正在談論中之值較小之直徑,而以質量計50%具有較大之直徑。值D90係於該直徑,以質量計90%之薄片具有比正在談論中之值較小之直徑。可將金屬之粒子加入,以補充雙模態之薄片。
於一種具體實施例中,該金屬係銀(Ag)、或以銀塗布之銅,以油酸塗布者。於另一種具體實施例中,油酸係以於以重量計約0.05%至5%之範圍內之單分子層塗布於至少三分之二之薄片之表面上。
本發明之水性導電組成物之黏度直接地隨著金屬薄片之負荷變動。金屬薄片之負荷可係如金屬顏料(即薄片及粒子)對於黏合劑之比率表示。顏料對於黏合劑比率產生金屬薄片之數量相對於以酸安定化之水性聚合物乳液中之聚合物之數量。例如,包含2,000克之銀與500克之水性聚合物乳液(其包含40%固體)之水性導電組成物具有10之顏料對於黏合劑比率。
為了決定銀填充劑對於黏合劑比率之影響,製造具有於5至10之範圍內之銀填充劑對於黏合劑比率之一系列之水性導電組成物。以30微米敷料器(applicator)及10微米桿-塗布器將該等水性導電組成物塗敷於聚酯上,及測定電阻值。此等電阻值係於圖1及2中呈現。發現,對於兩種塗敷方法,最佳之(即最低之)電阻皆係以於約8至約10之間(較佳地約9)之銀填充劑對於黏合劑比率(即,於金屬填充劑與組成物之剩餘之固體內容物之間之比率)獲得。
適合之金屬薄片及粒子係市售的。較佳之金屬薄片及粒子係於調配之期間顯示高分散性以容許於水性導電組成物中之高固體含量者。
於本發明之水性導電組成物中可組合小數量之其他金屬粉末及/或薄片,以提供可印刷墨水之多種改質。例如,可將鎳粉末加入以修飾脫離性質(release properties)、物理強度、外觀及其他態樣。
於本發明中有用之適合之可溶於鹼之(甲基)丙烯酸共聚物包括丙烯酸或甲基丙烯酸(較佳地丙烯酸)與一種或一種以上之疏水性乙烯系不飽和之共聚單體(諸如苯乙烯、(甲基)丙烯酸烷基酯及其類似物)之共聚物。較佳者係苯乙烯。對於鹼溶度所需要之羧酸含量將視酸之選擇及視共聚單體之疏水性而定。於苯乙烯作為共聚單體之情況中,需要約30重量%之丙烯酸或約60%之甲基丙烯酸。可溶於鹼之成分之分子量將影響黏合劑之黏度,倘若所有其他條件皆相等,則較高之分子量明顯地產生較高之黏度。一種較佳之重量平均分子量(Mw)範圍係約1,000至10,000道耳吞,更佳地1,500至6,000,如經由使用聚苯乙烯標準之膠透層析術(GPC)而測定。然而,視印刷方法之黏度限制而定,較高分子量可溶於鹼之共聚物可係有用的,此對於熟習此項技藝者將係明白的。
當使用以安定化一種於不同情況下之不含界面活性劑之不溶性乳液聚合物時,以總乾燥聚合物(可溶成分加上不溶性成分)計算,可溶於鹼之共聚物之通常含量係約10至20重量%。當存在另外之界面活性劑安定化作用時,可使用較低之數量。倘若於不溶性聚合物成分之聚合作用後添加,則可使用較高之數量。以乾燥為基準計算,於導電墨水中存在之可溶於鹼之共聚物之數量將係於0.3至5重量%之範圍內,較佳地0.5至2重量%。
該(甲基)丙烯酸共聚物係經由適合數量之鹼之存在以中和該酸及使其於溶液中安定化而溶解於水中。達成中和作用之任何之鹼係合格的,但較佳之鹼係氫氧化銨,此係由於其揮發性之緣故。熟習此項技藝者將熟悉適合於中和丙烯酸共聚物並且具有揮發性之性質之相似之鹼性(鹼)材料。
適合之不溶於水之聚合物分散液之實例包括苯乙烯型、聚胺甲酸乙酯、丙烯酸型、聚酯及乙烯型樹脂聚合物於水中之分散液。有用者係苯乙烯與一種或一種以上之乙烯系不飽和之單體之共聚物。乙烯系不飽和之單體包括,但不限於,丙烯酸及甲基丙烯酸之酯類、丙烯醯胺、甲基丙烯醯胺、N-取代之醯胺類諸如第三丁基丙烯醯胺及N-乙烯基吡咯啶酮、腈類諸如丙烯腈、羧酸類諸如丙烯酸、甲基丙烯酸、伊康酸及其類似物。特別有用者係苯乙烯與丙烯酸或甲基丙烯酸C1
-C18
(較佳地C1
-C8
)烷基酯之共聚物。此等苯乙烯-(甲基)丙烯酸系共聚物可另外包含羧酸單體諸如丙烯酸或甲基丙烯酸。一種較佳不溶於水之聚合物分散液之實例係苯乙烯與丙烯酸2-乙基己酯之共聚物。乙烯型樹脂包括乙烯基單體(諸如乙酸乙烯酯、丙酸乙烯酯、柯赫酸乙烯酯(vinyl versatate)、氯乙烯及其類似物)與包括乙烯、丙烯酸烷基酯或甲基丙烯酸烷基酯、羧酸或其他乙烯系不飽和之單體之一種或一種以上單體之共聚物。
不溶於水之聚合物分散液可係以可溶於鹼之共聚物、以習用之陰離子及/或非離子界面活性劑、或兩者之組合安定化。
可溶於鹼之聚合物成分對於不溶於鹼之聚合物成分之比率將係由存在之羧酸之總含量決定。以總乾燥聚合物計算,較佳之含量係約1至10重量%,更佳地3至6重量%。以乾燥為基準計算,於導電墨水中存在之不溶於水之聚合物分散液之數量將係於1至15重量%之範圍內,較佳地2至10重量%,更佳地4至8重量%。
適合之塑化劑之實例包括多羧酸諸如酞酸、異酞酸、對酞酸、己二酸、壬二酸、癸二酸、及苯六甲酸之酯類。亦可使用磷酸酯類(諸如磷酸三辛酯、磷酸三甲苯酚酯、磷酸三甲苯酯及磷酸三甲苄酯)、及聚酯塑化劑類諸如聚月桂酸伸丙酯、黃豆油衍生之塑化劑類諸如環氧化之黃豆油及經氯化之石蠟。特別適合之塑化劑包括二羧酸之C2-14
烷基酯類,其等之實例包括酞酸二丁酯、酞酸二己酯、酞酸二辛酯、酞酸二異辛酯、酞酸二壬酯、酞酸二C7-9
烷基酯類之混合物、酞酸二(十三酯)、酞酸丁苄酯、己二酸二丁酯、己二酸二己酯、己二酸二辛酯、己二酸二異辛酯、癸二酸二丁酯及癸二酸二辛酯。高沸點二醇化合物諸如二丙二醇二苯甲酸酯亦係適合的。
適合之薄膜聚結或潤濕劑包括較低沸點二醇化合物,諸如,乙二醇單丁基醚。此種化合物具有優於較高分子量化合物之較大揮發性之利益。適合之二醇聚結劑之實例包括1,3-丁二醇、丙二醇及乙二醇。此等劑可係單獨地或與彼此共同地使用。
聚結劑及塑化劑之含量將係經由聚合物成分之玻璃轉移溫度而決定。倘若須要,則一般熟習者將選擇一種數量,該數量係足夠以於乾燥之後產生撓性,連續之薄膜,但不是太大致使於乾燥之後留下膠黏之塗層。
於後文中將提及於水中之可溶於鹼之丙烯酸共聚物、不溶於水之聚合物分散液、(倘若具有)二醇化合物、及(倘若具有)塑化劑之組合(無任何金屬之填充劑),作為用於金屬填充劑之黏合劑。
分散金屬薄片及/或粒子之一種方法係使用自MorehouseCowles或Charles Ross and Son Company可獲得之類型之高速率分散混合器。通常,加入之金屬薄片及/或粒子之數量係二至四(或更多)乘以黏合劑之重量。最初,混合係緩慢的,然後當導電材料之薄片係已完全組合入黏合劑中時,以較高之速率混合該分散液歷時短暫之時間,注意避免將空氣引進入混合物中。於一種具體實施例中,於混合之期間內,不容許分散液之溫度超過30-35℃。倘若需要,則可使用適合尺寸之絲網過濾器過濾最終之產物。混合方法製造一種視覺上均勻之於液體中之混合物。
可溶於鹼之聚合物協助導電填充劑之最初潤濕及組合,以產生粒子或薄片之均勻之分散液。其進一步發揮作用以避免填充劑於儲存之期間內之硬擠塞,及使任何沈降之粒子能經由攪拌或搖動而容易地再分散。
於另外之具體實施例中,本發明包含於基板上配置水性導電組成物作為導電塗布墨水,如一或多條狹窄之線,藉此於基板上形成至少一條導電之痕跡(trace),或配置如覆蓋該基板之至少一部分之表面之薄膜。
可印刷之導電體之黏度及印刷性質應係於印刷機上印刷之前調整,及於印刷之期間經由添加劑之適合之使用而維持常數。倘若需要,則此可係經由將氨水及最低數量之特別選擇之防沫劑加入而達成。視印刷方法及印刷運轉之期間而定,稀釋之氨及0.01-0.2體積%之防沫劑之添加可能係必要的。此種添加應係剛於印刷之前進行及良好地混合該組合物。其後添加之數量及頻率係視墨水性質、印刷機之結構、導電組成物之曝露之表面、周圍溫度、濕度、印刷速率及其他因素而定。對於維持印刷之電子導體之物理性質於常數,連接於緩慢之墨水循環泵之封閉之墨水再循環系統係最佳的。
就大體而論,本發明提供水性導電組成物以作為可印刷之導電體使用,其中可以用於多種之基板上印刷導電痕跡之現有,市售之印刷機使用此等導電組成物。於較佳之具體實施例中,導電性係經由於適合地混合於本文中敘述之黏合劑中之金屬銀或以銀塗布之銅之微細薄片之使用而達成,而生成之組成物係可利用於印刷機中之使用。
被使用之可印刷導電體之導電性係視多種因素而定,包括於沈積於基板上之組成物之內之金屬薄片及/或粒子之互相之位置、排列、及物理連結。薄膜乾燥方法、加熱/固化介質之施用或操作、及外部處理方法(諸如酸洗、施加壓力、及高能量光處理)影響導電性及安定性。
達成於金屬粒子中之適合之位向及接近之安置,而無粗厚之聚合物粒子表面潤濕層之形成,係良好的。此係經由原料之選擇及媒液之正確製備而達成。經由技術諸如粒子表面處理之使用而製備該金屬表面,亦係有益的。
對於在印刷方法之期間達成適合之粒子沈積,於金屬粒子表面之頂部上之黏合劑層之形成係良好的。黏合劑層亦協助粒子之黏附於基板材料,及增進於乾燥方法之後之粒子間之壓實。
由於金屬分散液中之液體之低百分率,因此於印刷之後,可印刷之導電體趨於快速地乾燥。通常調節水性導電組成物之pH到達於7.5至10.5之範圍內之pH;於另一種具體實施例中,到達於8至10之範圍內之pH;及於另一種具體實施例中,到達於8.5至9.5之範圍內之pH。於此等範圍內之一種具體實施例中,pH最初係於7.5至8.5,及當氨水蒸發時,於所有範圍內之pH降低。於此種方法之期間,聚合物系統自水溶性狀態轉變成不溶於水狀態。用周圍或略微提高之溫度空氣之強制對流可協助乾燥方法。於測定最終產物之導電性質中,此種方法發生作用。假設,由於本發明之組成物係快速乾燥的,因此當印刷以形成導電之痕跡時,印刷之痕跡快速地收縮及於金屬薄片或粒子之間產生壓縮。此種壓縮提高連接,因此,優於其他組成物之較高之導電性。
精確地稱重3克之鏈轉移劑,1-十二烷硫醇,及將其移至以攪拌器、冷凝器及加料漏斗裝備之三頸圓底燒瓶中。將106.7克之2-丙醇、94.0克之苯乙烯、40.3克之丙烯酸及4.5克之偶氮雙(異丁腈)引發劑(AIBN)之溶液加入此燒瓶中。於混合以確保均勻之後,將燒瓶沈浸於維持於82±2℃之水浴中及以120轉每分鐘(rpm)攪拌內容物。於達到回流溫度之後二小時,於30分鐘之期間內將23.4克之2-丙醇緩慢地並且均勻地加入。維持回流歷時另外之2.5小時。然後冷卻燒瓶內容物至50℃及將24克之氫氧化銨加入。於完成混合之後,於250轉每分鐘攪拌下,將400克之去離子(DI)水加入。然後以另外之氨調節pH至於8.5-9.0之範圍內。然後於攪拌下加熱燒瓶之內容物至70℃及經由真空而移出2-丙醇,直到固體含量達到24-26重量%、最後之pH達到8.0-9.0為止。以膠透層析術測定分子量,Mw,其係5,070道耳吞。
使用緩慢地加入之4.5克之AIBN及26.7克之2-丙醇,相似地製備第二種,較低分子量可溶於鹼之聚合物(膠體B)。以膠透層析術測定分子量,Mw,其係2,390道耳吞。
依循美國專利5,455,299之教導,使用來自實例1之可溶於鹼之聚合物溶液作為安定化之實體,製備乳液聚合物。
將230.8克之膠體溶液A、及116.0克之去離子水稱重進入以攪拌器、冷凝器及兩個加料漏斗裝備之三頸圓底燒瓶中。燒瓶係經由於液體表面下引進氮氣而除去氧。然後於維持於80℃之水浴中加熱燒瓶及以70轉每分鐘攪拌內容物。當內容物溫度到達70℃時,將4.2克之苯乙烯及1.8克之丙烯酸2-乙基己酯之混合物加入,及於77℃將0.03克之過氧硫酸銨(APS)於5.19克之去離子水中之引發劑溶液加入。於15分鐘溫度平衡之後,提高攪拌器攪拌至180轉每分鐘,及開始由0.25克之過氧硫酸銨於40.39克之去離子水中組成之引發劑溶液之均勻緩慢之添加。於230分鐘之期間內將引發劑加入。於同時,開始80.13克之苯乙烯與34.34克之丙烯酸2-乙基己酯之混合物之均勻緩慢之添加,及於210分鐘之期間內完成該添加。於遍及聚合作用中,維持反應溫度於80±2℃。於單體添加之後,將2.88克之去離子水通過單體加料漏斗加入,及維持內容物於80℃歷時另外之1.5小時。然後冷卻溫度至低於40℃,及以氨調節pH至9.1。
以膠體B依循相同之程序,使用第二種乳液(B)。
乳液聚合物之性質係於下列之表中提供:
將依循實例2之程序製備之1,000克之乳液A,稱重進入以攪拌器及加料漏斗裝備之二頸燒瓶中。於水浴中加熱內容物至40℃,及設定攪拌至100轉每分鐘。於10分鐘之期間內將一種較高沸點塑化劑,59.1克之二丙二醇二苯甲酸酯,加入。於另外之15分鐘之攪拌後,於30分鐘之期間內將45.5克之一種較低沸點塑化劑/聚結之溶劑,乙二醇單丁基醚,緩慢地加入,及繼續攪拌歷時另外之15分鐘。於冷卻至30℃之後,以氨調節pH至9.0。
經由相同之程序使用乳液B而製備第二種黏合劑,黏合劑B。
黏合劑之性質係於下列之表中提供:
將167.6克之黏合劑A稱重進入塑膠混合容器中。將一個Ross高速率分散混合器降下進入液體中,直到輪葉係位於剛剛高於容器之底部為止,及設定混合速率至500轉每分鐘。將500克之以油酸塗布之銀薄片緩慢地組合入黏合劑中。於此種方法之期間,再提升及降低輪葉高度,以確保銀之完全潤濕。然後提高混合速率至1,200轉每分鐘,及容許導電墨水混合歷時1小時。使用冷卻浴,以維持溫度低於30℃。於混合之完成後,使用第3號贊恩杯(no. 3 Zahn cup)測量黏度,發現其係265秒。認為,對於令人滿意之撓版輪轉印刷,此黏度係太高。然後以2.8%之氨稀釋該樣本至45秒之黏度及約81%之總固體含量。以乾燥為基準,生成之墨水,墨水A,包含89.7%之銀,因此銀對於黏合劑比率係8.7:1。
依循以上程序但使用168.8克之黏合劑B以製備第二種導電墨水(墨水B),俾能達成以乾燥為基準計算之相同之銀對於黏合劑比率。於此種情況中,於氨稀釋前之黏度係80秒。以2.8%之氨稀釋該樣本至33秒之黏度,總固體約82%。
以乾燥為基準計算,此等墨水具有下列之組成:
自實質上與黏合劑B相似之組成但具有39重量%之固體含量及235mPa.s之布魯克菲爾德黏度(Brookfield viscosity)之黏合劑(黏合劑C)製備一種墨水。此種黏合劑係依循實例4之程序但使用147克之黏合劑C而調配成為導電墨水,俾能達成以乾燥為基準計算之相同之銀對於黏合劑比率。將13.6毫升之2.8%之氨加入,以達成84.4重量%之總固體含量及32秒之第三號贊恩杯黏度。對於促進較快速之乾燥,較高之固體含量係良好的。
性質係如下:
其中1密耳(mil)係25微米。
其中1密耳係25微米。
其中1密耳係25微米。
其中1密耳係25微米。
使用油漆攪拌器歷時5分鐘,於17個月儲存後之墨水能再還原。墨水係良好地分散,具有良好之外觀及維持其導電度。
以下認明之成分之於水中之85%分散液係於如上述之高速率分散混合器中製備及顯示下列之性能:
於2個月儲存後,於油漆攪拌器中之五次5分鐘搖動之後,組成物之品質係劣的:似糊劑、含砂的及很黏性的。
以下認明之成分之於水中之85%溶液係於如上述之高速率分散混合器中製備及顯示下列之性能:
其中1密耳係25微米。
自9.80克之可溶於鹼之苯乙烯/丙烯酸共聚物與苯乙烯丙烯酸酯乳液(不溶的)之混合物、10.00克之聚(氯乙烯)乳液(來自Nisshin Kagaku Kogyo K.K.之Viniblan270)、0.20克之阿拉伯膠、及56克之銀薄片製備一種乳液。試驗調配物之性能,及於實例10之表中記載結果,如調配物1。
製備數種導電之水性調配物,以試驗於周圍及提高之溫度及於濕度條件下之電阻發展,及比較本發明之調配物相對於比較調配物之適印刷性(printability)及撓性。所有調配物係如下經由於室溫摻合成分而製備:將乳液裝載進入適合之容器中及攪拌,同時將任何添加劑、水及氨加入;然後於攪拌下將銀薄片加入,及繼續攪拌歷時10分鐘。使用下拉延(draw down)塗敷或照相凹版輪轉印刷(rotogravure)塗敷,將最後調配物塗布於Melinex O聚對酞酸伸乙酯(PET)基板上。
下拉延(draw down)塗敷係以25微米金屬線桿塗布50毫米×10毫米長方形(5個正方形)而進行。於周圍溫度於5、15、30、60及120分鐘之後,測量及記錄電阻。於周圍溫度5分鐘、於70℃1分鐘、於120℃1分鐘、及於150℃1分鐘之後,測量及記錄第二塗層之電阻。電阻係以歐姆/正方形/25微米之方式使用式(電阻測量
×以微米表示之厚度)/(25微米×正方形之數目)計算。
照相凹版輪轉印刷塗敷係以具有54條線每厘米之雕刻之圓筒及220毫米×53毫米之長方形(4.15個正方形)之Saueressig color proofer 90/200進行。測量及計算電阻,如用於下拉延塗層,但使用4.15個正方形之線條(track)。
為了試驗乾燥之導電塗層之撓性,經由照相凹版輪轉印刷而於125微米厚之聚對酞酸伸乙酯基板上印刷一種塗層,其後於150℃乾燥該塗層歷時1分鐘。自該基板切割出尺寸為100毫米×2毫米之線條及以歐姆之方式測量電阻,其後圍繞一個2毫米心軸彎曲該線道(tract)及再測量電阻。於撓性之另一試驗中,線條係經由以塗層向內折疊(180度彎曲)及以2公斤重量滾壓該皺摺線而皺摺。然後線條以塗層於外側上以不同方向折疊(180度彎曲)及再以2公斤重量滾壓該皺摺。測量及記錄電阻。
亦於經歷於85℃、及85%相對濕度(RH)之溫度及濕度調節歷時24小時後,測量電阻。製造於對酞酸伸乙酯之50毫米×10毫米線條上之下拉延塗層,及於150℃乾燥歷時1分鐘。於自該溫度及濕度調節移出之後1小時,測量電阻。
以重量份數表示之用於導電水性組成物之配方係於表1、圖3中記載。對於彼等調配物之電阻值係於表2、圖4中記載,及係關於該塗層之厚度報導及規格化。
除了於表1、圖3中記載之調配物以外,作兩種嘗試以組成包含14.98份之來自ICI之專賣之苯乙烯丙烯酸酯乳液、2.38份之聚(丙烯酸)、1.34份之乙二醇單丁基醚、1.29份之二丙二醇二苯甲酸酯、及1.50份之10%之氨水之調配物(實例7)。隨著聚(丙烯酸)之添加,該等組成物變稠及變成難以處理。
結果之討論:實例A及I係本發明之實例及皆包含可溶於鹼之苯乙烯/丙烯酸共聚物、及不溶之苯乙烯/丙烯酸酯共聚物。實例1另外包含乙烯型乳液及塑化劑。於周圍及提高之溫度及於溫度及濕度條件下,兩種樣本皆顯示導電性之很良好之發展,及很良好之適印刷性。對於實例A,撓性係良好的,及對於實例1係很良好的。
實例B不包含可溶於鹼之成分及顯示不良之適印刷性(於印刷後於導電性中之降低)、及不良之撓性(導電性於皺摺後之重大之損失)。
實例C不包含不溶之成分及顯示不良之適印刷性(於印刷後於導電性中之降低)、及無撓性(不能圍繞心軸彎曲而不斷裂)。
實例D包含不溶之成分及可溶之(酸)成分;然而,該酸係於其後加入該不溶之成分中,而非加入以安定化該不溶之乳液。此種墨水不是可印刷的。
實例E包含一種含聚合物之以氨中和之酸,及雖然其顯示良好之導電性及適印刷性,但是其於撓性試驗中斷裂。
實例F係相似於實例E但包含塑化劑,以嘗試提高撓性。此種樣本顯示不良之適印刷性(於印刷後於導電性中之降低),及於撓性試驗中斷裂。
實例G包含不溶之聚合物乳液及一種含聚合物之可溶之酸,具有彈性物以取代塑化劑。樣本顯示不良之適印刷性(於印刷後於導電性之降低)。
除了使用塑化劑以取代彈性物之外,實例H包含相同於實例G之成分。此種樣本顯示不良之適印刷性(於印刷後於導電性中之降低)。
實例A及I,包含本發明之導電水性調配物,於導電性、適印刷性、及撓性之發展中顯示最佳之總性能。
調配物J及K係以聚(氯乙烯)乳液之添加入苯乙烯/丙烯酸共聚物(可溶於鹼)及苯乙烯丙烯酸酯乳液(不溶的)中而製備,兩種樣本皆固化以產生於周圍溫度及於熱固化之後之良好之導電性。調配物K提供於印刷之後、於撓性試驗之後、及於溫度/濕度調節之後之較佳之導電性。
雖然本發明係已於以上參考其特定具體實施例敘述,但是於不脫離於本文中揭示之本發明之理念下可作多種改變、修飾及變動,此係明顯的。於是,希望涵蓋於附隨之申請專利範圍之精神及寬廣範圍內之所有此等改變、修飾及變動。
圖1係經由30微米敷料器塗敷之不同之顏料對於黏合劑(P/B)比率塗層之電阻值之圖。
圖2係經由10微米桿塗布器塗敷之不同之P/B比率塗層之電阻值之圖。
圖3係導電水性調配物之表。
圖4係對於彼等調配物之電阻值之表。
Claims (14)
- 一種水性導電組成物,其包含(i)金屬薄片或粒子;(ii)於有效溶合量之溶解丙烯酸或甲基丙烯酸共聚物之水及鹼中之可溶於鹼之丙烯酸或甲基丙烯酸共聚物;(iii)分散於水中之不溶於水之聚合物;及(iv)視需要,聚結劑、塑化劑、或兩者;其中該分散於水中之不溶於水之聚合物係選自苯乙烯、聚胺甲酸乙酯、丙烯酸型聚合物、聚酯、及乙烯型聚合物組成之群;且該金屬薄片或粒子係選自銀、銅、鎳、以銀塗布之材料、以銅塗布之材料、以鎳塗布之材料、及其混合物組成之群。
- 如申請專利範圍第1項之組成物,其中該可溶於鹼之(甲基)丙烯酸共聚物係苯乙烯-丙烯酸共聚物。
- 如申請專利範圍第1項之組成物,其中該分散於水中之不溶於水之聚合物係聚(氯乙烯)。
- 如申請專利範圍第3項之組成物,其中該金屬薄片或粒子係以油酸塗布之雙模態金屬薄片。
- 如申請專利範圍第4項之組成物,其中該雙 模態金屬薄片係銀及具有3微米之平均質量直徑(D50)。
- 如申請專利範圍第4項之組成物,其中該雙模態金屬薄片係銀及其中90%質量比之雙模態金屬薄片具有小於8.8微米之直徑。
- 如申請專利範圍第3項之組成物,其中該金屬薄片或粒子對於該組成物之剩餘固體含量之比率係於約8至約10之範圍內。
- 如申請專利範圍第1項之組成物,其中該聚結劑係存在及係選自乙二醇單丁基醚、1,3-丁二醇、丙二醇、及乙二醇組成之群。
- 如申請專利範圍第1項之組成物,其中該塑化劑係存在及係選自二丙二醇二苯甲酸酯、酞酸二丁酯、酞酸二己酯、酞酸二辛酯、酞酸二異辛酯、酞酸二壬酯、酞酸二C7-9 烷基酯類之混合物、酞酸二(十三酯)、酞酸丁苄酯、己二酸二丁酯、己二酸二己酯、己二酸二辛酯、己二酸二異辛酯、癸二酸二丁酯及癸二酸二辛酯組成之群。
- 如申請專利範圍第1項之組成物,其中該不溶於水之聚合物係分散於水中及係包含苯乙烯與丙烯酸2-乙基己酯單體之共聚物。
- 一種配置於撓性基板上經由印刷及乾燥如申請專利範圍第1項之組成物而形成之導電 塗層。
- 一種包含如申請專利範圍第11項之導電塗層之無線射頻辨識(RFID)天線。
- 如申請專利範圍第1項之組成物,其中該金屬薄片或粒子對於該組成物之剩餘固體含量之比率係於約8至約10之範圍內。
- 如申請專利範圍第1項之組成物,其中該分散於水中之不溶於水之聚合物包含苯乙烯及一或多種選自由丙烯酸及甲基丙烯酸之酯類、丙烯醯胺、甲基丙烯醯胺、正丁基丙烯醯胺、N-乙烯基吡咯啶酮、丙烯腈、丙烯酸、甲基丙烯酸、依康酸及其組合組成之群組的乙烯系不飽和單體。
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US87676406P | 2006-12-22 | 2006-12-22 | |
PCT/US2007/083445 WO2008127397A2 (en) | 2006-12-22 | 2007-11-02 | Waterborne conductive compositions |
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US7857998B2 (en) * | 2008-11-24 | 2010-12-28 | E. I. Du Pont De Nemours And Company | High conductivity polymer thick film silver conductor composition for use in RFID and other applications |
WO2012102304A1 (ja) * | 2011-01-26 | 2012-08-02 | ナミックス株式会社 | 導電性ペースト及びその製造方法 |
KR102195294B1 (ko) | 2012-12-28 | 2020-12-24 | 엔티에이치 디그리 테크놀로지스 월드와이드 인코포레이티드 | 니켈 잉크 및 내산화성이며 전도성인 코팅 |
US20140374672A1 (en) * | 2013-06-24 | 2014-12-25 | Xerox Corporation | Conductive metal inks with polyvinylbutyral binder |
KR102524435B1 (ko) * | 2015-12-23 | 2023-04-24 | 헨켈 아게 운트 코. 카게아아 | 전도성 조성물을 위한 결합제로서의 중합체 에멀젼 |
EP3385342B1 (en) * | 2017-04-03 | 2020-03-25 | Nano and Advanced Materials Institute Limited | Water-based conductive ink for rapid prototype in writable electronics |
US10984921B2 (en) * | 2017-06-30 | 2021-04-20 | Sekisui Chemical Co., Ltd. | Conductive paste |
KR102622747B1 (ko) * | 2023-01-16 | 2024-01-09 | 주식회사 대안데칼 | 투톤 헬멧 전사지 |
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- 2007-11-02 JP JP2009542991A patent/JP5220029B2/ja not_active Expired - Fee Related
- 2007-11-02 WO PCT/US2007/083445 patent/WO2008127397A2/en active Application Filing
- 2007-11-02 CN CN2007800473249A patent/CN101595534B/zh active Active
- 2007-11-02 ES ES07873584T patent/ES2378582T3/es active Active
- 2007-11-02 KR KR1020097015363A patent/KR101434256B1/ko active IP Right Grant
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EP2097908B1 (en) | 2012-02-01 |
JP5220029B2 (ja) | 2013-06-26 |
US20120061623A1 (en) | 2012-03-15 |
CN101595534B (zh) | 2012-07-18 |
EP2097908A4 (en) | 2010-03-10 |
EP2097908A2 (en) | 2009-09-09 |
EP2097908B2 (en) | 2017-08-23 |
WO2008127397A3 (en) | 2009-03-26 |
ATE544162T1 (de) | 2012-02-15 |
ES2378582T3 (es) | 2012-04-16 |
CN101595534A (zh) | 2009-12-02 |
JP2010513682A (ja) | 2010-04-30 |
WO2008127397A2 (en) | 2008-10-23 |
TW200925227A (en) | 2009-06-16 |
KR101434256B1 (ko) | 2014-08-27 |
KR20090098896A (ko) | 2009-09-17 |
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