TWI643213B - 導電性微粒子及導電性微粒子的製造方法 - Google Patents
導電性微粒子及導電性微粒子的製造方法 Download PDFInfo
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Abstract
本發明之導電性微粒子係具有:含有丙烯酸系樹脂之核粒子、及在核粒子之表面上直接或隔著鎳層設置之銀層,銀層之表面被覆率為70%以上。
Description
本發明係關於導電性微粒子及導電性微粒子之製造方法。
異方導電性材料等係可使用導電性微粒子。就導電性微粒子而言,已知具有作為核粒子之樹脂粒子、及形成於核粒子上之金屬層之導電性微粒子。樹脂粒子係已知例如苯乙烯系樹脂或丙烯酸系樹脂。另一方面,金屬層一般係在成為基底之鎳層上設有金層之構成。
與上述相關者,例如日本專利第3561748號中係揭示一種在樹脂粒子上使鎳進行無電解鍍敷,然後使金進行無電解鍍敷而得之導電性粒子(參照實施例)。又,在日本特開平8-325543號公報及日本專利第3587398號中,記載著在樹脂粒子上形成鎳層,進一步在其上形成金層,藉此形成導電性粒子。
然而,金價昂貴,故持續尋求取代金之廉價替代材料。作為金之替代材料,可考慮銀。使用銀之導電性微粒子,例如日本專利第3832938號中揭示一種無電
解銀鍍敷粉體,其係具有鎳鍍敷皮膜基底層之經銅被覆的粒子作為基材,藉由銅與銀之取代反應形成銀皮膜之無電解鍍敷法,在基材之表面形成銀皮膜。
[專利文獻1]日本專利第3561748號
[專利文獻2]日本特開平8-325543號公報
[專利文獻3]日本專利第3587398號
[專利文獻4]日本專利第3832938號
然而,在核粒子上直接或隔著鎳層,難以藉鍍敷形成銀層。例如,如記載於日本專利第3832938號(專利文獻4),必須在鎳層與銀層之間設置銅層等。以如此之方法,為了設置銅層必須追加製造步驟,無法獲得廉價之導電性微粒子。
又,使用苯乙烯系樹脂作為核粒子時,可藉由藥品使樹脂粒子表面進行粗化,藉錨定效果而可提高於樹脂粒子上形成之金屬層之密著性。然而,苯乙烯系樹脂昂貴。而且,使用更廉價之丙烯酸系樹脂作為核粒子時,因丙烯酸系樹脂為高耐藥品性,故難以使樹脂微粒子適當粗化。
從此事實,使用丙烯酸系樹脂作為核粒子時,在樹脂粒子上直接或隔著鎳層形成緻密之銀層係更困難。
因此,本發明之課題在於提供一種導電性微粒子及其
製造方法,係在使用含有丙烯酸系樹脂之核粒子的導電性微粒子中,可在核粒子上隔著鎳層或直接形成緻密之銀層者。
本案之發明人等發現藉由含有界面活性劑之溶液處理含有丙烯酸系樹脂之核粒子,可解決上述課題。亦即,本發明係含有以下事項。
〔1〕一種導電性微粒子,具有:含有丙烯酸系樹脂之核粒子、以及在前述核粒子之表面上直接或隔著鎳層設置之銀層,前述銀層之表面被覆率為70%以上。
〔2〕如前述〔1〕項所述之導電性微粒子,其中,算數平均粒徑為1μm至100μm。
〔3〕一種導電性微粒子之製造方法,具備:藉由含有界面活性劑之溶液處理含有丙烯酸系樹脂之核粒子之步驟;以及在藉由前述界面活性劑處理過之核粒子上,使用無電解銀鍍敷液形成銀層之步驟。
〔4〕如〔3〕項所述之導電性微粒子之製造方法,更具備:在形成前述銀層之步驟前,在藉由前述界面活性劑處理過之核粒子上,使用無電解鎳鍍敷液形成鎳層之步驟。
〔5〕如前述〔3〕或〔4〕項所述之導電性微粒子之製造方法,其中,前述界面活性劑之濃度為0.5g/L至20g/L。
〔6〕如前述〔3〕至〔5〕中任一項所述之導電性微粒子之製造方法,其中,前述界面活性劑為胺基羧酸鹽。
〔7〕如前述〔3〕至〔6〕中任一項所述之導電性微粒子之製造方法,其中,前述無電解銀鍍敷液為非氰無電解銀鍍敷液。
若依據本發明,可提供一種在使用含有丙烯酸系樹脂之核粒子的導電性微粒子中,可在核粒子上隔著鎳層或直接形成緻密之銀層的導電性微粒子及其製造方法。
第1A圖係有關比較例之導電性微粒子之掃描型電子顯微鏡照片。
第1B圖係有關實施例之導電性微粒子之掃描型電子顯微鏡照片。
第2圖係表示有關比較例之導電性微粒子的表面被覆率之測定結果的圖。
第3圖係表示有關實施例之導電性微粒子的表面被覆率之測定結果的圖。
以下,說明有關本發明之實施態様。
(1)導電性微粒子
本實施態様之導電性微粒子係具有:含有丙烯酸系樹脂之核粒子、及設於核粒子之表面上的銀層。銀層係直接設於核粒子之表面上,或在銀層與核粒子之間亦可設有鎳層作為基底。
在此,銀層之表面被覆率為70%以上,較佳係80%以上,更佳係95%以上。具有如此之表面被覆率的導電性微粒子係可依據後述之製造方法獲得。
在本發明中,所謂「表面被覆率」係在核粒子之表面藉銀層被覆之區域之比例。表面被覆率係例如可藉由取得掃描型電子顯微鏡照片而求得。亦即,使用掃描型電子顯微鏡取得導電性微粒子之圖像,對於所取得之圖像進行2進位化處理,藉此,可求得藉銀層被覆之領域。而且,藉銀層被覆領域之面積除以核粒子全體之面積,可求得表面被覆率。
可使用來作為核粒子之丙烯酸系樹脂,係使含有(甲基)丙烯酸酸酯作為主成分(50重量%以上,較佳係70重量%以上,更佳係90重量%以上)之單體聚合而得之樹脂粒子。(甲基)丙烯酸酸酯係可舉例如選自由(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-丙酯、(甲基)丙烯酸氯-2-羥基乙基酯、二乙二醇單(甲基)丙烯酸酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯基酯及(甲基)丙烯酸異莰酯所構成之群中的至少1種之化合物。
又,丙烯酸系樹脂之單體成分係可含有少量之其他單體。如此之其他單體成分係可舉例如苯乙烯系單體。
導電性微粒子之算數平均粒徑係無特別限定,但例如為1μm至100μm。
本實施態様之導電性微粒子係因以高的表面被覆率藉銀層被覆核粒子,故具有極低之體積電阻值。因此,例如可用來作為異方導電性材料用之導電性微粒子。
(2)導電性微粒子之製造方法
本實施態様之導電性微粒子之製造方法係具備:藉由含有界面活性劑之溶液處理含有丙烯酸系樹脂之核粒子的步驟;及在經界面活性劑處理之核粒子上,使用無電解銀鍍敷液形成銀層之步驟。若依據此方法,藉由界面活性劑處理核粒子,可對核粒子賦予潤濕性。藉由賦予潤濕性,可提高在核粒子上形成之金屬層之密著性。
以下,說明銀層隔著鎳層形成於核粒子上之導電性粒子之製造方法。
1.前處理
首先,藉由含有界面活性劑之溶液處理成為原料之核粒子。具體上係將核粒子浸漬於含有界面活性劑之溶液,較佳係水溶液,進行攪拌。
界面活性劑係無特別限定,但可使用例如兩性界面活性劑、陰離子系界面活性劑、陽離子系界面活性劑、及非離子系界面活性劑,以使用兩性界面活性劑為較佳。
兩性界面活性劑係可舉例如胺基羧酸鹽、羧基甜菜鹼型、磺基甜菜鹼型、及咪唑啉鎓菜鹼型型、烷基胺氧化物,以使用胺基羧酸鹽為較佳。
陰離子系界面活性劑係可例示如聚氧乙烯烷基硫酸鹽、烷基或烯基硫酸鹽、聚氧乙烯烷基或烯基硫酸酯鹽、烷基磺酸鹽、α烯烴磺酸鹽、烷基苯磺酸鹽、烷基醚硫酸鹽或烯基醚硫酸鹽、烷基或烯基醚羧酸鹽等。
陽離子系界面活性劑係可舉例如烷基胺鹽類、第四級銨鹽類、聚氧乙烯烷基胺鹽類、及聚乙烯聚胺誘導體等。
非離子系界面活性劑係可舉例如聚氧乙烯烷基醚、聚氧乙烯甘油脂肪酸酯、乙二醇脂肪酸酯、聚氧乙烯脂肪酸醯胺等。
又,界面活性劑溶液中係可含有矽酸鹽等助劑。
溶液中之界面活性劑之濃度例如0.5g/L至20g/L,較佳係5g/L至15g/L。
又,界面活性劑溶液之溫度例如10至70℃,較佳係20至50℃,更佳係30至40℃。
以界面活性劑處理之時間例如1至60分,較佳係3至20分,更佳係5至15分。
又,以界面活性劑處理之前,可進行公知之其他前處理。如此之其他前處理係可舉例如使用醇水溶液之膨潤處理、使用鹼性水溶液之蝕刻處理、及使用酸性水溶液之蝕刻處理等。
使用於蝕刻處理之酸性水溶液可使用例如在硫酸水溶液中使氧化劑(例如過錳酸鉀等過錳酸鹽、或鉻酸鈉及鉻酸鉀等鉻酸鹽)溶解之水溶液。
2.觸媒化(catalyzing)
以界面活性劑進行處理後,對核粒子施予觸媒化處理。觸媒化處理之方法係無特別限定。例如使核粒子浸漬在氯化鈀及氯化錫之混合溶液之後,使用酸或鹼溶液選擇性除去錫,藉此,可於核粒子擔持鈀。又,觸媒化處理之後,藉由具有還原劑之水溶液處理核粒子,可使觸媒活性化。
3.無電解鎳鍍敷
然後,藉由使核粒子浸漬於無電解鎳鍍敷液,在核粒子上形成鎳層。無電解鎳鍍敷液係無特別限定,例如可使用含有作為鎳源之水溶性鎳鹽、pH調整劑、及還原劑等之水溶液。水溶性鎳鹽係可舉例如硫酸鎳、氯化鎳、酢酸鎳、次亞磷酸鎳等。pH調整劑可舉例如氨等。還原劑係可舉例如次亞磷酸鈉、氫氧化硼鈉、氫化硼鉀、二甲基胺硼烷、聯胺、及甲醛等。又,可在含有水溶性鎳鹽及pH調整劑之無電解鎳液中浸漬核粒子使鎳層析出後,將還原劑添加於水溶液中,進行還原處理。
4.無電解銀鍍敷
然後,在無電解銀鍍敷液中浸漬核粒子,形成銀層。無電解銀鍍敷液係無特別限定,可使用市售之液。例如,無電解銀鍍敷液係可使用含有作為銀離子源之水溶性銀鹽、及錯化劑之液體。水溶性銀鹽係可舉例如硝酸銀、硫酸銀鹽、及氰化銀等。但,更佳係可使用硝酸銀及硫酸銀等非氰銀鹽。
錯化劑係無特別限定,可舉例如甲醯胺、乙醯胺、草
醯胺酸、琥珀醯亞胺、亞硫酸、亞硫酸鹽、檸檬酸及氨等。
依據以上說明之方法,可獲得在核粒子上隔著鎳層形成銀層之導電性微粒子。又,在觸媒化處理步驟(catalysing)之後,不進行無電解鎳鍍敷,若實施無電解銀鍍敷步驟,亦可獲得在核粒子上直接形成銀層之導電性微粒子。
若依據本實施態様之方法,藉由以界面活性劑處理核粒子,可在核粒子上形成密著性高之緻密金屬層。其結果,可獲得以高的表面被覆率形成銀層之導電性微粒子,可明顯降低導電性微粒子之電阻值。
繼而,為更詳細說明本發明,以相關實施例進行說明。
在甲醇水溶液中浸漬作為核粒子之算數平均粒徑為6.5μm之丙烯酸樹脂粒子,使其膨潤。膨潤後,添加氫氧化鈉水溶液,使核粒子之表面進行預蝕刻。
然後,過濾分離核粒子,浸漬於80℃之酸性水溶液中80分鐘,進行攪拌,藉此,蝕刻核粒子之表面。酸性水溶液係使用於純水192.4ml中混合硫酸8.0ml及過錳酸鉀2.4g之溶液。
過濾分離後,進一步以酸性水溶液(鹽酸及過酸化氫水溶液)進行酸洗浄。使酸洗浄後之核粒子浸漬於界面活性劑水溶液中,以35℃攪拌10分鐘之後,過濾分離核粒子。界面活性劑水溶液係使用將含有10%之胺基羧酸鹽及5%
之矽酸鹽之水溶液進一步稀釋成為100ml/L者。
然後,將核粒子浸漬於觸媒溶液(氯化鈀及氯化錫之混合溶液)之後,使用鹽酸水溶液進行處理,藉此,在核粒子擔載鈀作為觸媒。其後,過濾分離核粒子。
然後,在含有鎳鹽及還原劑之市售鎳鍍敷液中浸漬核粒子,在核粒子上使鎳層析出。鎳層析出後,加入還原劑,使析出之鎳層還原。還原後,過濾分離粒子。
其後,在市售之非氰無電解銀鍍敷液中浸漬粒子,在鎳層上形成銀層。使已形成銀層之粒子過濾分離,以甲醇洗浄之後,使其乾燥,獲得實施例之導電性微粒子。
使用與實施例同様之方法,獲得比較例之導電性微粒子。但是未進行使用酸性水溶液(硫酸及過錳酸鉀水溶液)之蝕刻處理、及以界面活性劑水溶液之處理。
藉掃描型電子顯微鏡觀察實施例及比較例之導電性微粒子。第1A圖係表示比較例之導電性微粒子的掃描型電子顯微鏡照片,第1B圖係表示實施例之導電性微粒子的掃描型電子顯微鏡照片。如第1A圖所示,在比較例之導電性微粒子中一部分銀層從核粒子剥離,粒子之表面不均勻。相對於此,如第1B圖所示,實施例之導電性微粒子係核粒子之全體被銀層均勻被覆。亦即,瞭解到藉由以界面活性劑處理核粒子,可獲得緻密且密著性高之銀層。
又,對於各導電性微粒子之SEM圖像進行二值化(又
稱二元化)處理,求出在二值化處理圖像中黑畫素之比例作為未鍍著率。第2圖係表示比較例之測定結果之圖,第3圖係表示實施例之測定結果之圖。又,有關比較例2係進行3次測定。其結果,比較例之未鍍著率係31.5至49.0%(亦即,表面被覆率為51.0至68.5%),相對於此,實施例之未鍍著率係0.0%(表面被覆率為100%)。
繼而,計測實施例及比較例之導電性微粒子之電阻值。詳細係採取試料之導電性微粒子0.58ml,以一對之電極板夾持,以施加20kgf之荷重的狀態,對電極間施加電壓,測定導電性微粒子之電阻值。測定係對於各試料各實施3次,求出平均值作為結果。其結果,實施例之導電性微粒子之電阻值係159mΩ,相對於此,比較例之導電性微粒子之電阻值係4436mΩ。亦即,實施例之導電性微粒子具有較比較例小10倍以上小之電阻值,可確認具有良好之導電特性。
Claims (9)
- 一種導電性微粒子,具有:含有丙烯酸系樹脂且擔持有觸媒之核粒子、以及在擔持有前述觸媒之核粒子之表面上直接或隔著鎳層設置之銀層;其中,前述銀層之表面被覆率為70%以上,前述核粒子上未設置有錫層。
- 如申請專利範圍第1項所述之導電性微粒子,其中,算數平均粒徑為1μm至100μm。
- 如申請專利範圍第1或2項所述之導電性微粒子,其中,前述核粒子係擔持鈀作為前述觸媒。
- 一種導電性微粒子之製造方法,具備:藉由含有界面活性劑之溶液處理含有丙烯酸系樹脂之核粒子之步驟;於經前述含有界面活性劑之溶液處理過之核粒子擔持觸媒之步驟;以及在擔持有前述觸媒之核粒子上,不設置錫層,而使用無電解銀鍍敷液形成銀層之步驟。
- 如申請專利範圍第4項所述之導電性微粒子之製造方法,更具備:在形成前述銀層之步驟前,在擔持有前述觸媒之核粒子上,使用無電解鎳鍍敷液形成鎳層之步驟。
- 如申請專利範圍第4或5項所述之導電性微粒子之製造方法,其中,前述界面活性劑之濃度為0.5g/L至20g/L。
- 如申請專利範圍第4或5項所述之導電性微粒子之製造方法,其中,前述界面活性劑為胺基羧酸鹽。
- 如申請專利範圍第4或5項所述之導電性微粒子之製造方法,其中,前述無電解銀鍍敷液為非氰無電解銀鍍敷液。
- 如申請專利範圍第4或5項所述之導電性微粒子之製造方法,其中,前述擔持觸媒之步驟係具備下列步驟:將經前述界面活性劑處理過之核粒子浸漬於含有氯化鈀及氯化錫之觸媒溶液的步驟;以及在前述浸漬之步驟後,使用酸或鹼溶液從前述核粒子除去錫的步驟。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200929266A (en) * | 2007-08-02 | 2009-07-01 | Hitachi Chemical Co Ltd | Circuit connection material, and connection structure of circuit member and connection method of circuit member using the circuit connection material |
TW201232562A (en) * | 2010-11-22 | 2012-08-01 | Nippon Chemical Ind | Conductive powder, conductive material including the same, and manufacturing method for the same |
TW201241072A (en) * | 2011-01-25 | 2012-10-16 | Nippon Catalytic Chem Ind | Conductive microparticle, resin particle, and anisotropic conductive material using same |
EP2607520A1 (en) * | 2010-08-20 | 2013-06-26 | Mitsubishi Materials Corporation | Silver-coated spherical resin, method for producing same, anisotropically conductive adhesive containing silver-coated spherical resin, anisotropically conductive film containing silver-coated spherical resin, and conductive spacer containing silver-coated spherical resin |
JP2013129856A (ja) * | 2011-12-20 | 2013-07-04 | Adeka Corp | 無電解めっき前処理剤及び該前処理剤を用いた無電解めっき前処理方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3045880B2 (ja) * | 1991-12-04 | 2000-05-29 | 哲人 中島 | プラスチック鏡及びその製造方法 |
US20070269603A1 (en) * | 2004-08-05 | 2007-11-22 | Sekisui Chemical Co., Ltd. | Conductive Fine Particle, Method for Producing Conductive Fine Particle and Electroless Silver Plating Liquid |
JP2007242307A (ja) * | 2006-03-06 | 2007-09-20 | Sekisui Chem Co Ltd | 導電性微粒子及び異方性導電材料 |
CN1936078A (zh) * | 2006-09-01 | 2007-03-28 | 烟台硕德新材料有限公司 | 一种新型复合导电微球及其制备方法 |
CN101245148B (zh) * | 2007-02-13 | 2012-05-23 | 镇江爱邦电子科技有限公司 | 单分散性高性能导电银颗粒 |
JP4961315B2 (ja) * | 2007-09-28 | 2012-06-27 | Dowaエレクトロニクス株式会社 | 金属被覆ニッケル粉の製造方法 |
JP5151920B2 (ja) * | 2008-02-05 | 2013-02-27 | 日立化成工業株式会社 | 導電粒子及び導電粒子の製造方法 |
GB2505035B (en) * | 2012-05-29 | 2014-10-29 | Conpart As | Isotropic conductive adhesive |
JP6210723B2 (ja) * | 2013-05-08 | 2017-10-11 | 三井金属鉱業株式会社 | 銀コートニッケル粒子及びその製造方法 |
CN104789948A (zh) * | 2015-03-26 | 2015-07-22 | 谢振西 | 一种在微米级聚丙烯酸微球上镀覆镍和银的方法 |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200929266A (en) * | 2007-08-02 | 2009-07-01 | Hitachi Chemical Co Ltd | Circuit connection material, and connection structure of circuit member and connection method of circuit member using the circuit connection material |
EP2607520A1 (en) * | 2010-08-20 | 2013-06-26 | Mitsubishi Materials Corporation | Silver-coated spherical resin, method for producing same, anisotropically conductive adhesive containing silver-coated spherical resin, anisotropically conductive film containing silver-coated spherical resin, and conductive spacer containing silver-coated spherical resin |
TW201232562A (en) * | 2010-11-22 | 2012-08-01 | Nippon Chemical Ind | Conductive powder, conductive material including the same, and manufacturing method for the same |
TW201241072A (en) * | 2011-01-25 | 2012-10-16 | Nippon Catalytic Chem Ind | Conductive microparticle, resin particle, and anisotropic conductive material using same |
JP2013129856A (ja) * | 2011-12-20 | 2013-07-04 | Adeka Corp | 無電解めっき前処理剤及び該前処理剤を用いた無電解めっき前処理方法 |
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