TWI697355B - 具有增加穩定性之金屬分散液 - Google Patents
具有增加穩定性之金屬分散液 Download PDFInfo
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- TWI697355B TWI697355B TW105133903A TW105133903A TWI697355B TW I697355 B TWI697355 B TW I697355B TW 105133903 A TW105133903 A TW 105133903A TW 105133903 A TW105133903 A TW 105133903A TW I697355 B TWI697355 B TW I697355B
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- alkyl
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- 239000006185 dispersion Substances 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 12
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
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Abstract
Description
本發明係關於將具有50至80wt%之金屬粒子含量的金屬粒子溶膠穩定化的共聚物的用途。
在本發明之背景中,金屬粒子一詞涵蓋奈米粒子和次微米粒子。在本發明之背景中,奈米粒子係定義為至少一維小於100nm之粒子。微米粒子是三維的粒度皆在1μm與1000μm之間的粒子。次微米粒子係定義為三維皆大於100nm且至少一維小於1μm的粒子。溶膠或膠體是奈米或次微米粒子於液體中之分散液。
關於奈米級和次微米級之金屬粒子的性質和應用領域的重要準則包括平均粒度、粒度分佈、該分散液之膠體化學穩定性以及該等粒子之加工和物理化學性質。
多種製造金屬奈米粒子的方法係在先前技術中被揭示。一已知原則是在該液相中經溶解之金屬離子的直接化學還原。此方法之很多變化型尋求製造具有窄粒度分佈和界定之表面性質之金屬奈米粒子的膠體化學穩定的分散
液。
"膠體化學穩定的"一詞據了解意思是該膠體分散液的性質或該等膠體本身的性質在首次應用前之一般貯存期間或在二製造循環之間的暫停期間幾乎不改變。因此,例如,不應發生對產物品質會具有負面影響的該等膠體的實質聚集或絮凝。粒子之沉積/聚集一般藉由測定分散液上部之固體含量而確定。該固體含量之劇烈減少指明該分散液之低的膠體穩定性。
用於合成奈米級金屬分散液之必要成分是所用之分散用添加劑。該添加劑必須足量存在以分散該金屬粒子,但應在後續之應用中僅導致該等金屬功能之最少的損壞且因此理想上應以低濃度存在。該表面之過高的塗料可能另外負面地影響該金屬溶膠之物理化學性質。
金屬分散液尤其在微電子組件用來作為導體、半導體或用於屏蔽電磁場。該等金屬粒子必須以精細分散形式而無第一聚集下被應用且在固化程序後應形成連續層。對此固化程序特別有利的是a)耗費盡可能少的能量或b)減少固化時間。這意圖要允許溫度敏感性基材之使用。
水可分散之金屬分散液優於含溶劑之系統,特別是因安全理由,例如由於避免閃點。高度濃縮之金屬分散液之使用在此情況中因經濟和技術理由是需要的,因為此允許另外調配之極大自由度。
水性金屬分散液之製造在該文獻中廣泛地被描述。
因此,US-2,902,400(Moudry等人)揭示藉由以氫醌
和作為消毒劑之鞣酸將硝酸銀化學還原所得之微小銀粒子的用途。為穩定化,特殊的明膠產物被選擇且在分批程序中被反應。並沒有描述以清楚定義之聚合型分散輔助劑的連續合成。並不進行未經轉化之反應物或所形成之反應產物的移除。所得之濃度為0.6wt%的經分散的微粒子以去離子水稀釋至1:50000。
US-2,806,798描述一種供照相應用之黃色膠態銀溶膠的製造方法。聚乙二醇類或聚丙二醇類或甘油被描述為與聚乙烯醇、聚乙烯酯和縮醛類相關之穩定劑。在此文件中不使用由(甲基)丙烯酸系單體組成之共聚物。該等實例描述用於降低多種銀鹽類之毒性肼水合物。純化係藉由在丙酮中沉澱及在水中再分散而進行。由此所得之銀溶膠係包埋在光敏層中。此文件不討論經燒結之銀粒子的導電性。
在US-3,615,789中,使用膠態銀於濾色器系統和照相層。磺酸化之二胺基聯苯類被描述為絮凝助劑且明膠被使用以作為保護性膠體。二類物質皆包含硫且因此不適合作為用於製造純的銀化合物(AgS之形成)之添加劑。具有1.3-4.2%之銀的最終重量分率的膠態銀的製造係經由分批程序進行且包含多個複雜的純化步驟。然而,並未指明該銀粒子之溫度相依性。
EP-A-1493780提出氧化銀奈米粒子之合成及彼等轉化成金屬銀。該導電性組成物包含顆粒狀銀化合物和黏合劑和隨意地還原劑和黏合劑。氧化銀、碳酸銀、乙酸銀及
類似者被利用以作為顆粒狀銀化合物。乙二醇、二乙二醇、二乙酸乙二醇酯及其他二醇類被利用以作為該還原劑。具有20nm至5μm之平均粒徑的熱可固化樹脂(諸如多價苯乙烯樹脂或聚對苯二甲酸伸乙二酯)的精細粉末被利用以作為該黏合劑。該顆粒狀銀化合物在該黏合劑中,於150℃以上之溫度下,被還原成元素銀,其互相聚結。然而,EP-A-1493780不揭示銀奈米粒子之高度濃縮的水性分散液如何在150℃以下之溫度產生導電層。
Ruy等人之關鍵工程材料(Key Engineering Materials)264-268冊141-142頁教示使用均聚型銨鹽合成奈米級銀粒子。硝酸銀以硼氫化鈉或肼轉變成元素銀。這提供不多於10%之粒度<20nm之銀的水性分散液。此文件沒有指出在低於130℃之低溫下的貯存穩定性和燒結行為。
US-8,227,022描述在二階段方法中金屬奈米粒子之水性分散液的製造。為此目的,在第一子步驟中,經溶解之金屬鹽以水溶性聚合物進行初步還原且以還原劑進行完全還原。在第二子步驟中,該奈米粒子被濃縮且藉由第二分散劑再分散。所述之製造方法以小的實驗量實施且提供具有不多於18%之Ag比例的銀分散液。分散劑相對銀的比例在最佳情況中被確認為5.7%。在表4中所報告之值顯示:即使在60℃以上之相對低溫下也產生導電性。這是缺點,因為由於基材之印刷方法或印刷媒介之加熱中的廢熱,此種狀況導致該金屬粒子之過早燒結及因此導致所用之機器的故障。
US-8,460,584描述一種方法,藉此方法,可使用低分子量(C4-C20碳鏈長度)羧酸類製備銀奈米粒子。在該等粒子沉澱後,該等粒子可被分散在有機溶劑(甲苯)和油酸中。並不描述生態健康之在水中的分散液。為測定導電性,將產物施加至玻璃片且在210℃之溫度下燒結。導電性被報告為2.3 E04 S/cm(=2.3 E06 S/m)。
在WO 2007/118669中描述一種製造濃縮奈米級金屬氧化物分散液的方法和彼在製造奈米級金屬粒子中之另外的用途。其中,使用甲醛,將金屬氧化物還原成元素銀。該等金屬粒子藉由添加分散輔助劑被分散在水相中。該金屬粒子溶膠和其氧化物先質由於該分散輔助劑之使用而顯現出高的膠體化學穩定性。
在WO 2007/118669的一具體例中,分散輔助劑係選自包含烷氧化物、烷基醇醯胺類、酯類、胺氧化物、烷基聚醣苷類、烷基酚類、芳基烷基酚類、水溶性均聚物、隨機共聚物、嵌段共聚物、接枝聚合物、聚氧化乙烯、聚乙烯醇類、聚乙烯醇類和聚乙酸乙烯酯類之共聚物、聚乙烯基吡咯啶酮類、纖維素、澱粉、明膠、明膠衍生物、胺基酸聚合物、聚離胺酸、聚天冬胺酸、聚丙烯酸酯類、聚伸乙基磺酸酯類、聚苯乙烯磺酸酯類、聚甲基丙烯酸酯類、芳香族磺酸與甲醛之縮合產物、萘磺酸酯類、木質磺酸酯類、丙烯酸系單體之共聚物、聚伸乙基亞胺、聚乙烯基胺類、聚烯丙基胺類、聚(2-乙烯基吡啶類)及/或聚二烯丙基二甲基銨氯化物。該文件並沒有給予與所製造之溶膠
的穩定性和導電性相關的指示。
WO-2012/055758揭示一種以外來元素摻雜之金屬粒子的製備方法以在低燒結溫度下獲得導電性。在本發明之實例中,製造Ag溶膠,其在140℃下1小時後展現4.4 E+06 S/m之導電性。沒有摻雜RuO2之比較用樣品在140℃下1小時後獲得1 S/m之比導電性。
US-2006/044384申請案描述甲基丙烯酸之隨機和三元聚合物和聚甲基丙烯酸乙二醇酯(PEGMA)的用途。以羥基為端基之具有256g/mol或360g/mol之分子量的PEGMA被用在實例中。[0009]段提示:該非離子部分應具有低於1000g/mol之鏈長度。以有毒的肼還原成元素銀。具有至高30wt%之濃度的Ag溶膠被製造。需要10至100wt%(以銀為基準計)之分散劑以確保足夠之粒子穩定性。偵測導電性,但既沒揭示參數(層厚度、溫度)也沒揭示單位。沒有調查所製造之粒子的貯存穩定性。
所有經描述之用於製造奈米和次微米級金屬粒子的方法具有決定性缺點。因此,例如,所描述之方法不能以工業規模複製或所製造之粒子具有極高之分散劑含量。若意圖使該等粒子產生導電性,燒結僅在至少140℃之相對高溫下進行且因此不適合施加在溫度敏感性之聚合物基材上。
因此以下本發明之目的是要發現一種分散劑,其允許
高度濃縮之金屬分散液的工業規模製造且甚至在至高60℃下的貯存期間確保高的膠體化學穩定性。在塗覆方法以及熱或光子處理之後,由此所製造之分散液甚至在自90℃之相對低溫下應變為導電且因此應可應用於溫度敏感性之塑膠基材。另外目標是要產生比該先前技術更好之導電性,同時保留相同之燒結溫度和時間。
如現在已經發現的,令人意外地,以混合烷氧基化的(甲基)丙烯酸衍生物和丙烯酸系單體為底質的共聚物極適合作為用於製造奈米級金屬粒子的分散劑。與已知之均質烷氧基化的甲基丙烯酸衍生物相比,以根據本發明之共聚物製造之水性奈米級金屬分散液展現在室溫下(尤其在至高60℃下)明顯更好的貯存穩定性。然而,在高溫下意外地發現穩定性之反轉而結果是:以根據本發明之聚合物所製造之粒子在如90℃一般低之溫度以上進行燒結。
這例如使可能甚至在低燒結溫度下獲得下述良好導電性:至少1.8 E06 S/m,尤其在90℃下2.0 E06 S/m,至少2.9 E06 S/m,尤其在110℃下3.1 E06 S/m,及至少5.2 E06 S/m,尤其在130℃下5.4 E06 S/m。根據本發明之金屬分散液因此也允許使用溫度敏感性之基材作為印刷存料,但同時達成迄今尚未以該已知之金屬分散液達成之良好導電性。
這使可能使用溫度敏感性之基材。同樣可達成與減低之時間需求配合的經改良的導電性。
圖1顯示根據本發明所製造之銀奈米粒子樣品之按體
積計的粒度分佈;且圖2顯示根據本發明所製造之銀奈米粒子樣品之透射電子顯微照片。
在下文中描述之本發明的具體例係關於該用途:R 在本發明之較佳具體例中是氫或甲基。
A和B是C2-C4伸烷基基團,條件是A和B不同。此意思是:式(1)之結構單元可以用至多200個C2-C4-烷氧基單元烷氧化,其中可以涉及以環氧乙烷、環氧丙烷或環氧丁烷之至少二者逐段(blockwise)烷氧化或以環氧乙烷、環氧丙烷或環氧丁烷之至少二者(隨機)混合烷氧化。
當A和B是伸乙基或伸丙基基團時是較佳的。當A是伸丙基基團且B是伸乙基基團時是特佳的。特別地,A是伸丙基基團且B是伸乙基基團,其中m=2至7且n=50至200,較佳地m=2至6且n=50至200,極佳地m=3至6且n=50至200。
以式(1)之結構單元為底質之巨單體可藉由烷氧化丙烯酸或甲基丙烯酸衍生物(丙烯酸一詞在下文中據了解也包含甲基丙烯酸)之聚合獲得。這些可藉由下述物質之烷氧化獲得:丙烯酸或2-烷基丙烯酸或乙二醇、丙二醇或丁二醇之丙烯酸單酯類(丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯或丙烯酸2-羥基丁酯)或乙二醇、丙二醇或丁二
醇之2-烷基丙烯酸單酯類(2-烷基丙烯酸2-羥基乙酯、2-烷基丙烯酸2-羥基丙酯或2-烷基丙烯酸2-羥基丁酯)。
該烷氧化之丙烯酸衍生物特佳係藉由丙烯酸2-羥基丙酯或2-烷基丙烯酸2-羥基丙酯之經DMC催化的烷氧化製造,特別是藉由2-甲基丙烯酸2-羥基丙酯之經DMC催化的烷氧化製造。與傳統之經鹼催化的烷氧化相反,DMC催化允許具有精確定義之性質的單體的極選擇性合成且避免無用的副產物。DE-102006049804和US-6034208教示DMC催化之優點。
以下列述含有與以上合成描述類似之較佳合成實例:當式(1)之結構單元的組成相當於下列聚二醇類之至少一者時是較佳的:聚二醇1 聚甲基丙烯酸伸烷二醇酯(式(1),m=2,n=12-13;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約750g/mol聚二醇2 聚甲基丙烯酸伸烷二醇酯(式(1),m=2,n=17-19;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約1000g/mol聚二醇3 聚甲基丙烯酸伸烷二醇酯(式(1),m=5,n=38-40;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約2000g/mol聚二醇4 聚甲基丙烯酸伸烷二醇酯(式(1),m=5,n=95-105;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約5000g/mol
聚二醇5 聚甲基丙烯酸伸烷二醇酯(式(1),m=5,n=190-200;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約12000g/mol。
合適之式(2)的結構單元較佳是衍生自下列者:苯乙烯磺酸、丙烯醯胺甲基丙烷磺酸(AMPS)、乙烯基磺酸、乙烯基膦酸、烯丙基磺酸、甲基烯丙基磺酸、丙烯酸、甲基丙烯酸及順丁烯二酸或其酸酐、以及上述酸類與單或二價相對離子之鹽類、還有2-乙烯基吡啶、4-乙烯基吡啶、乙烯基咪唑、乙酸乙烯酯、甲基丙烯酸環氧丙酯、丙烯腈、四氟乙烯和DADMAC。可被提及之另外的實例包括N-乙烯基甲醯胺、N-乙烯基甲基甲醯胺、N-乙烯基甲基乙醯胺、N-乙烯基乙醯胺、N-乙烯基吡咯啶酮(NVP)、5-甲基-N-乙烯基吡咯啶酮、N-乙烯基戊內醯胺及N-乙烯基己內醯胺。在一較佳具體例中,式(2)之結構單元衍生自N-乙烯基咪唑、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、丙烯酸及甲基丙烯酸。
待根據本發明使用之聚合物包含例如99至70、較佳地95至75、特佳地90至80wt%之式(1)的結構單元。
在一較佳具體例中,式(1)之結構單元和式(2)之結構單元加總至100%。
待根據本發明被使用之聚合物的製造係藉由使用合適自由基起始劑,在50與150℃之間的溫度下,單體的自由基聚合進行。這些聚合物之分子量可在6000至1×106g/mol,較佳地15000至800000之範圍內變化,然而
以在20000與600000g/mol之間的分子量為極佳的。
適合之醇溶劑包括水溶性單或二醇類,例如丙醇、丁醇、乙二醇及乙氧化之單醇類,諸如丁基乙二醇、異丁基乙二醇和丁基二乙二醇。然而,也可能單獨使用水作為溶劑。在該聚合後,通常形成澄清溶液。
因此製造之分散劑溶液也可包含其他物質,例如殺生劑、UV穩定劑、抗氧化劑、金屬鈍化劑、IR吸收劑、阻燃劑及類似者,其量為0.01-1.0wt%,較佳地0.01-0.5wt%且極佳地0.1-0.25wt%。
在較佳具體例中,該奈米級金屬粒子係以連續方式在微反應工廠中遵照WO 2007/118669之[0027]至[0056]段製造。因此獲得之金屬粒子溶膠係利用薄膜過濾純化且濃縮成具有50-80wt%、較佳地51-79wt%且特佳地52-78wt%之銀粒子的固體含量。該等銀粒子之粒度較佳在至少一維上是在5與100nm之間。該分散劑含量是1-9wt%,較佳是2-8wt%且特佳是3-7wt%。根據本發明所製造之銀奈米粒子樣品的透射電子顯微照片及對應之按體積計的粒度分佈係顯示於圖(1)和(2)中。
該共聚物之合成係進行如下:配備攪拌器、迴流冷卻器、內部溫度計及氮入口的燒瓶以在下表中所報告之重量分率之在溶劑中的式(1)之聚二醇和式(2)之丙烯酸系單體以及分子量調節劑初步填充,同時導入氮。溫度隨後
在攪拌下升至80℃且該起始劑之溶液在1小時期間被計量入。該混合物係在此溫度下攪拌另外二小時。後續可計量入另外的添加劑。該共聚物之組成摘述於下表中。
該奈米級金屬粒子係以連續方式在微反應工廠中遵循EP-2010314之[0027]至[0056]段製造。因此所得之金屬粒子溶膠係利用薄膜過濾純化且濃縮至50-80wt%之金屬含量。該分散劑含量被測定為1-9wt%。
為供比較,金屬奈米粒子係遵循US-20060044382(Lexmark,實例A[0019]和實例[0023])、WO-2012/055758(Bayer Technology Services/BTS,實例1)和US-8227022製造且被包括以作為比較用實例1、2、3和4。
所得之銀溶膠係在室溫下貯存且該分散液之固體含量(=銀和分散劑含量總和)係在不攪拌樣品下以4、8和16週之間隔測定。固體含量之降低指向該銀粒子之沉澱,從而降低該分散液之穩定性。
如上表顯明的,所有以本發明之聚合物為底質之銀溶膠顯現出比先前技術之銀溶膠(比較1-4)明顯更高之在室溫下的穩定性。
為供電試驗,所得之金屬溶膠係藉由旋轉塗覆以0.1與10μm(較佳在0.5與5μm)之間的層厚而施加至18×18mm玻璃片。然後該玻璃板在每一情況中在限定溫度下進行熱燒結60分鐘且表面電阻係藉由四點方法被測量,單位是[Ohm/平方]。在測定該層厚度之後,測定比導電性,單位是[S/m]。
如由上表顯明的,所有以根據本發明之聚合物所製造之銀溶膠在熱燒結後在絕對值及該燒結溫度之開始方面超過該比較用產物之導電性。這意思是:需要降低之能量輸入以在成品中達成相當的導電性。這也使可作為印刷用儲料的熱敏性基材的範圍加寬。
Claims (13)
- 如申請專利範圍第1項之金屬分散液,其中A及/或B是伸乙基基團或伸丙基基團或A是伸丙基基團且B是伸乙基基團。
- 如申請專利範圍第1或2項之金屬分散液,其中m=2至7且n=50至200。
- 如申請專利範圍第1或2項之金屬分散液,其中存在水溶性單-或二醇類或乙氧基化之單醇類作為另外的溶劑。
- 如申請專利範圍第1或2項之金屬分散液,其中式(1)之結構單元的組成對應於下列聚二醇類之至少一者:聚二醇1 聚甲基丙烯酸伸烷二醇酯(式(1),m=2,n=12-13;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約750g/mol聚二醇2 聚甲基丙烯酸伸烷二醇酯(式(1),m=2,n=17-19;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約1000g/mol聚二醇3 聚甲基丙烯酸伸烷二醇酯(式(1),m=5,n=38-40;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約2000g/mol聚二醇4 聚甲基丙烯酸伸烷二醇酯(式(1),m=5,n=95-105;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約5000g/mol 聚二醇5 聚甲基丙烯酸伸烷二醇酯(式(1),m=5,n=190-200;(A-O)是[CH2CH(CH3)O)];(B-O)是(CH2CH2O));莫耳質量約12000g/mol。
- 如申請專利範圍第1或2項之金屬分散液,其中式(2)之單體係選自由N-乙烯基咪唑、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、丙烯酸或甲基丙烯酸所組成之群組。
- 如申請專利範圍第1或2項之金屬分散液,其中該分散液包含1-9wt%之該分散劑。
- 如申請專利範圍第1或2項之金屬分散液,其中該分散液包含0.1至1.0wt%之量的另外的添加劑。
- 如申請專利範圍第1或2項之金屬分散液,其中該銀粒子之粒度在至少一維上是在5與100nm之間。
- 如申請專利範圍第1或2項之金屬分散液,其中至少1.8 E06 S/m之導電值係藉由在90℃之溫度下燒結而達成。
- 一種如申請專利範圍第1至10項中任一項之金屬分散液的用途,其係用於製造墨液組成物、油漆、塗料或圖形印刷物質。
- 一種如申請專利範圍第1至10項中任一項之金屬分散液的用途,其係用於製造導電塗料。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104254418A (zh) * | 2011-11-03 | 2014-12-31 | 克拉里安特国际有限公司 | 用于制备金属纳米颗粒分散体的方法、金属纳米颗粒分散体及其用途 |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2806798A (en) | 1953-07-08 | 1957-09-17 | Du Pont | Process for preparing yellow colloidal silver |
| US2902400A (en) | 1956-05-08 | 1959-09-01 | Moudry Zdenek Vaclav | Methods for producing liquid oligodynamic compositions |
| CH467475A (de) | 1966-06-28 | 1969-01-15 | Ciba Geigy | Verfahren zur Herstellung von angereichertem Kolloidsilber |
| US4888248A (en) * | 1986-07-01 | 1989-12-19 | Hidefumi Hirai | Colloidal metal dispersion, and a colloidal metal complex |
| US5854386A (en) | 1997-08-25 | 1998-12-29 | Arco Chemical Technology, L.P. | Stabilizers for polymer polyols |
| KR100479847B1 (ko) * | 2002-04-16 | 2005-03-30 | 학교법인 포항공과대학교 | 우수한 안정성, 균일한 모양 및 나노미터 크기의 좁은입자 분포를 갖는 금속 콜로이드 및 그의 제조 방법 |
| EP1383597A4 (en) * | 2001-04-30 | 2006-09-06 | Postech Foundation | COLLOIDAL SOLUTION OF METAL NANOPARTICLES, METAL-POLYMER-NANOVER-BASED MATERIALS AND METHOD FOR THE MANUFACTURE THEREOF |
| JPWO2002094954A1 (ja) * | 2001-05-21 | 2004-09-09 | 日本ペイント株式会社 | 金属コロイド高濃度溶液の製造方法 |
| TWI251018B (en) | 2002-04-10 | 2006-03-11 | Fujikura Ltd | Electroconductive composition, electroconductive coating and method of producing the electroconductive coating |
| US7402627B2 (en) * | 2003-08-18 | 2008-07-22 | Columbia Insurance Company | Precursor colorant composition for latex paint |
| US20060044382A1 (en) * | 2004-08-24 | 2006-03-02 | Yimin Guan | Metal colloid dispersions and their aqueous metal inks |
| US20060044384A1 (en) | 2004-08-25 | 2006-03-02 | Eastman Kodak Company | Inkjet recording element comprising aluminosilicate and acetoacetylated poly(vinyl alcohol) |
| JP2008527169A (ja) | 2005-01-10 | 2008-07-24 | イシウム リサーチ デベロップメント カンパニー オブ ザ ヘブリュー ユニバーシティー オブ イエルサレム | 金属ナノ粒子の水系分散物 |
| CN101137730B (zh) * | 2005-03-11 | 2011-11-16 | 东洋油墨制造株式会社 | 导电性油墨、导电电路及非接触性介质 |
| US20070078190A1 (en) * | 2005-09-30 | 2007-04-05 | Distefano Frank V | Use of 2,3-dihydroxynaphthalene-6-sulfonic acid salts as dispersants |
| CN1958653A (zh) * | 2005-09-30 | 2007-05-09 | 气体产品与化学公司 | 2,3-二羟基萘-6-磺酸盐作为分散剂的应用 |
| DE102006017696A1 (de) | 2006-04-15 | 2007-10-18 | Bayer Technology Services Gmbh | Verfahren zur Herstellung von Metallpartikeln, hieraus hergestellte Metallpartikel und deren Verwendung |
| DE102006049804A1 (de) | 2006-10-23 | 2008-04-24 | Clariant International Limited | Wasserlösliche hydroxyfunktionelle, copolymerisierbare Polyalkylenglykol-Makromonomere, deren Herstellung und Verwendung |
| US7560052B2 (en) * | 2007-03-30 | 2009-07-14 | Lexmark International, Inc. | Silver ink compositions containing a cationic styrene/acrylate copolymer additive for inkjet printing |
| DE102007021868A1 (de) * | 2007-05-10 | 2008-11-20 | Clariant International Limited | Nichtionische wasserlösliche Additive |
| CN104785163B (zh) * | 2008-08-22 | 2018-04-13 | 日产化学工业株式会社 | 由具有铵基的支链高分子化合物构成的金属微粒分散剂 |
| US8460584B2 (en) | 2008-10-14 | 2013-06-11 | Xerox Corporation | Carboxylic acid stabilized silver nanoparticles and process for producing same |
| EP2204249A1 (en) * | 2008-12-16 | 2010-07-07 | Akzo Nobel Coatings International B.V. | Aqueous dispersions of metallic particles |
| WO2011048876A1 (ja) * | 2009-10-20 | 2011-04-28 | Dic株式会社 | 金属ナノ粒子含有複合体、その分散液、及びこれらの製造方法 |
| DE102010009493A1 (de) * | 2010-02-26 | 2011-09-29 | Clariant International Limited | Polymere und ihre Verwendung als Dispergiermittel mit schaumhemmender Wirkung |
| ES2495390T3 (es) * | 2010-03-12 | 2014-09-17 | Clariant International Ag | Producción de revestimientos de superficie conductivos con dispersión con nanopartículas de plata estabilizadas de forma electrostática |
| EP2444148A1 (de) | 2010-10-25 | 2012-04-25 | Bayer Material Science AG | Metallpartikelsol mit dotierten Silbernanopartikeln |
| KR101828605B1 (ko) * | 2011-03-31 | 2018-02-13 | 주식회사 케이씨씨 | 마이크로겔 및 이의 제조 방법, 그리고 수용성 도료 조성물 |
| US8734949B2 (en) * | 2011-08-10 | 2014-05-27 | Basf Se | Method for passivating metallic surfaces using carboxylate-containing copolymers |
| EP2608217B1 (en) * | 2011-12-21 | 2014-07-16 | Agfa-Gevaert | A dispersion comprising metallic, metal oxide or metal precursor nanoparticles, a polymeric dispersant and a sintering additive |
| CN104470659B (zh) * | 2012-07-19 | 2016-01-27 | 日油株式会社 | 银纳米微粒及其制备方法、银纳米微粒分散液及形成银成分的基材 |
-
2016
- 2016-10-12 CA CA3003504A patent/CA3003504A1/en not_active Abandoned
- 2016-10-12 CN CN201680063487.5A patent/CN108348884A/zh active Pending
- 2016-10-12 JP JP2018521423A patent/JP2018535321A/ja active Pending
- 2016-10-12 WO PCT/EP2016/074424 patent/WO2017071949A1/de not_active Ceased
- 2016-10-12 EP EP16781113.2A patent/EP3368204A1/de not_active Withdrawn
- 2016-10-12 KR KR1020187015438A patent/KR20180077252A/ko not_active Withdrawn
- 2016-10-12 US US15/771,757 patent/US20180340083A1/en not_active Abandoned
- 2016-10-20 TW TW105133903A patent/TWI697355B/zh not_active IP Right Cessation
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2018
- 2018-04-16 IL IL258734A patent/IL258734A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104254418A (zh) * | 2011-11-03 | 2014-12-31 | 克拉里安特国际有限公司 | 用于制备金属纳米颗粒分散体的方法、金属纳米颗粒分散体及其用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180340083A1 (en) | 2018-11-29 |
| WO2017071949A1 (de) | 2017-05-04 |
| IL258734A (en) | 2018-06-28 |
| KR20180077252A (ko) | 2018-07-06 |
| CN108348884A (zh) | 2018-07-31 |
| JP2018535321A (ja) | 2018-11-29 |
| TW201731587A (zh) | 2017-09-16 |
| EP3368204A1 (de) | 2018-09-05 |
| CA3003504A1 (en) | 2017-05-04 |
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