TW200936807A - Conductive particles and method for forming metal film - Google Patents

Abstract

Disclosed is a method for forming a metal coating film, which is characterized by forming a metal coating film on an electrically non-conductive particle having a particle diameter of 0.5 to 100 μm by electroless plating. The electroless plating is carried out after a pre-treatment for attaching a metal core to the electrically non-conductive particle is carried out, and can form a metal coating film made of silver in the presence of a silane compound having a thiol group. The metal coating film formed over the entire surface of the electrically non-conductive particle can impart electrical conductivity to the electrically non-conductive particle. The electrically non-conductive particle has a particle diameter ranging from 0.5 to 100 μm. The metal coating film is composed of a single silver layer.

Description

200936807 六、發明說明： 【發明所屬之技術領域】 本發明係關於可利用於例如導電材料、電磁波阻隔材料等之 導電性粒子，及於非導電性粒子上形成金屬薄膜之方法。' 【先前技術】 ❹ 作為於非導電性粒子上形成金屬薄膜之技術，已知有無電 解電鍍之方法可行。為促進無電解電鍍之反應，於非導電g粒 子之表面一般係施予使無電解電鍍起始之觸媒附著之前 理。於此前處理係例如使非導電性粒子接觸氯化亞錫之BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive particle which can be used for, for example, a conductive material, an electromagnetic wave blocking material, and the like, and a method of forming a metal thin film on a non-conductive particle. [Prior Art] ❹ As a technique for forming a metal thin film on non-conductive particles, a method of electroless plating is known. In order to promote the electroless plating reaction, the surface of the non-conductive g particles is generally applied to cause the catalyst to be attached before the electroless plating. Prior to the treatment, for example, the non-conductive particles were exposed to stannous chloride.

後，再使其與氣化鈀之水溶液接觸。藉此，因非導電性粒子之 表，所吸紅麟仅，轉飾alladiume()U 吸著於非導電性粒子之表面。鈀膠體係作為使盔電解電铲妒 之觸媒而作用。此外，無電解電鍍液係包含 ^二 ;二調：:严，另外，於進行上 之問^時屬義之厚度極不—致，有無法形成連續性薄膜 ，如日本特公平㈣爪號公報中有提出一種為 有強力蚊覆蓋力之金屬紐縣 胃_、ς 叉，及之後於芯材上進行無電解電鍍之 仵。於觸媒化步驟令，於貴金屬離子捕捉^斤， =鑛保有貴金屬。於無電 等溶液同時添加以進種溶液構成，並分別將此 號公報卜中係输 1厕-14409 金屬薄膜之技術。作為—般之置換為形成貴 電鑛形成基層，再嶋換嫩ί==== 200936807 因f田=調整電鍍液之pH值而添加次亞磷酸鈉(― yp〇ph〇sphlte monohydrate)、擰檬酸(dtric 扯⑷等。另一方面， ”為控制貴金屬薄膜之結晶構造，會添加 =膜包含祕及金具妓轉_讀金 銘等。 古導電率局之貴金屬已為人所知。銀*但比金有更 雜之物绿刊_制=卜 2ίίΐ成銀所組成之金屬薄膜時，將會形成作為基層之 錄層^銀層之至少包含二層之金膜。此等由複數層所组成 之金屬薄膜對於成本而言相當不利。對於非導電性粒;斤亦# 由於施予使用輕合劑(coupungagent)之前處理後進行無 電解電鑛’以使由銀所組狀金屬薄卿成之方法。另外，若 對於微米級之料錄子辭祕理，將無法於料電性粒子 上形成由銀組成之金屬薄膜，或僅能形成不連續之金屬薄膜。 ϋίΐϊ米、級之非導電性粒子’形成單層銀所組成之金屬 薄膜之技術實用性仍然有待加強。 ❹ 【發明内容】 本發明之發明者們對於微米級之非導電型粒子，係研究出 可連續形成單層由銀所組成之金屬_之技術。本發明之目的 ，提供-種使由銀所組成之金屬薄膜容易形成之金屬薄膜形 t法。齡’本㈣之目的健供—種具有優良導電性且低 成本之導電性粒子。 為解決上綱題，於本㈣ϋ樣巾係提供—種於0 5 之非導電性粒子上，以無電解電鑛形成金屬薄膜 ^金屬薄膜形成方法。無電解電鍍為於非導電性粒子上實施附 著金屬核之前處理之同時，於具有硫醇基之矽烷化合物之存在 下，使由銀所組成之金屬薄膜形成。 200936807 於述問題’於本發明之第二態樣中係提供一種藉由 i導電性粒子之全體表面形狀金屬薄膜，賦予其導電性之 ¥电性粒子。非導電性粒子之餘為…㈣〜鄭巾之範圍。 此外，金屬薄膜係由單層之銀所構成。 【實施方式】 以下將詳細說明本發明具體化之實施態樣。 <金屬薄膜形成方法>Thereafter, it is brought into contact with an aqueous solution of vaporized palladium. Thereby, due to the non-conductive particles, the red lining is only circulated, and the alladiume () U is sorbed on the surface of the non-conductive particles. The palladium gel system acts as a catalyst for the electric shovel of the helmet. In addition, the electroless plating solution contains ^2; the second tone:: strict, in addition, the thickness of the sense is not very high when the above is performed, and there is no way to form a continuous film, such as the Japanese special fair (four) claw number bulletin There is a proposal for a non-electrolytic plating on a core material of a metal New Zealand stomach with a strong mosquito cover. In the catalytic process, the precious metal ions are captured, and the mine has precious metals. In the absence of electricity, the solution is added at the same time as the seed solution, and the technique of transferring the 1 toilet-14409 metal film to the No. As a general replacement, the formation of a precious iron ore to form a base layer, and then change the tenderness. ί==== 200936807 Adding sodium hypophosphite (― yp〇ph〇sphlte monohydrate) and screwing the f field = adjusting the pH of the plating solution Citric acid (dtric (4), etc. On the other hand," in order to control the crystal structure of the precious metal film, it will add = the film contains the secret and the metal tool _ _ reading Jin Ming, etc. The precious metal of the ancient conductivity bureau is known. However, if there is a more complicated material than gold, the metal film composed of silver and silver will form a gold film containing at least two layers as the recording layer of the base layer. The composition of the metal film is quite unfavorable for the cost. For the non-conductive particles; Jin Yi # because of the application of the coupungagent before the treatment of electroless ore, so that the composition of the metal formed by the silver thin In addition, if the micron-sized material is recorded, it is impossible to form a metal thin film composed of silver on the electric material particles, or only to form a discontinuous metal thin film. ϋίΐϊ, the non-conductivity of the grade The particles 'form a metal composed of a single layer of silver The technical applicability of the film still needs to be strengthened. ❹ SUMMARY OF THE INVENTION The inventors of the present invention have studied a technique for continuously forming a single layer of a metal composed of silver for a micron-sized non-conductive particle. OBJECTIVE: To provide a metal film-shaped t method in which a metal thin film composed of silver is easily formed. The purpose of the age of (4) is to provide conductive particles having excellent conductivity and low cost. To solve the above problem, In the (4) ϋ ϋ 系 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供At the same time, a metal thin film composed of silver is formed in the presence of a thiol group-containing decane compound. 200936807 In the second aspect of the present invention, a whole surface of the i conductive particles is provided. The shape of the metal film, which gives the conductivity of the electric particles. The non-conductive particles are ... (4) ~ Zheng towel range. In addition, the metal film is composed of a single layer of silver [Embodiment] Hereinafter, an embodiment of the present invention will be described in detail. <Metal film forming method>

本實施態樣之金屬細形成方法為藉由無電解紐於粒徑 為〇.5#m〜50//m之非導電性粒子上形成金屬薄膜之方法。無 電解電鍍係於非導電性粒子上實施使金屬核附著之前處理之 同時’於具有硫醇基之矽烷化合物之存在下，形成由銀所組成 之金屬薄膜。 非導電性粒子為形成金屬薄膜之基材。作為非導電性粒子 1材質可列舉如選自一氧化碎、陶土(ceramics)、玻璃、樹 脂^中至少一種:作為二氧化矽，可列舉如完全結晶化之乾式 —氧化梦(方石英，cristobalite)、水分散型二氧化矽(膠體化二氧 =矽，colloidal silica)等。作為陶土，可列舉如礬i(alumina)、 藍寶石^sapphire)、富鋁紅柱石(muiite)、二氧化鈦(titania)、碳 化石夕、氮化石夕、氮化銘、氧化锆(zirc〇nia)等。作為玻璃，可列 舉BK7、SFn、Las歷等各種肖特玻璃(schott glass)、 光學冕玻璃(optical crown glass)、蘇打玻璃(s〇da glass)、低膨脹 爛石夕玻璃(borosilicate glass)等。作為樹脂類’可列舉如二氧化 脂、驗系樹脂、天然變性酚系樹脂、環氧樹脂、聚乙烯醇 系樹脂、纖維系(cellul〇se)樹脂’或聚烯烴系樹脂、苯乙烯系 樹脂、丙乙烯系樹脂等之變性物或經電暈放電(c〇r〇na discharge) 之表面處理物等。作為非導電性粒子，由粒徑不平均度小之觀 點而s，以選自二氧化石夕、陶土或玻璃中至少一種為佳，更佳 可列舉二氧化矽。作為非導電性粒子之形狀’可列舉如球狀、 200936807 2、板狀、針狀、中空狀等。若考慮非導電性粒子之分 導電性粒子之分散性料，料電性粒子之形狀以^ 非導電性粒子之粒徑為05〃m〜100/m之範圍。非 徑係由掃描式電子顯微鏡之照片測定。為此金屬薄膜 =方法所使狀非導雜粒子之平均粒徑以1/zm〜m 為仏’以l/zm〜2〇em為更佳。 ❹ φ 特別疋，若疋用於液晶顯示裝置用元件，有 =子之粒徑-致之必要。於此情況下，料 不之通式求得之cv值為1〇%以下為佳，以The metal thinning method of the present embodiment is a method of forming a metal thin film on a non-electroconductive particle having a particle diameter of 〇.5#m~50//m by electroless plating. The electroless plating is performed by forming a metal thin film composed of silver in the presence of a thiol compound having a thiol group on the non-electroconductive particles before the metal core is attached. The non-conductive particles are substrates on which a metal thin film is formed. Examples of the material of the non-conductive particles 1 include at least one selected from the group consisting of oxidized granules, ceramics, glass, and resin. As the cerium oxide, a dry-oxidized dream such as cristobalite, which is completely crystallized, can be cited. ), water-dispersed cerium oxide (colloidal silica). Examples of the clay include 矾i (alumina), sapphire (sapphire), mullite, titania, carbon carbide, nitriding, nitriding, zirconia, and the like. . Examples of the glass include various schott glass, optical crown glass, s〇da glass, and borosilicate glass such as BK7, SFn, and Las calendar. . Examples of the resin include, for example, a dioxide resin, a test resin, a naturally modified phenol resin, an epoxy resin, a polyvinyl alcohol resin, a cellulose resin, a polyolefin resin, or a styrene resin. A denatured product such as a vinylidene resin or a surface treated material by corona discharge or the like. The non-conductive particles are preferably at least one selected from the group consisting of silica, ceramsite, and glass, from the viewpoint of a small particle size unevenness, and more preferably cerium oxide. Examples of the shape of the non-conductive particles include a spherical shape, a 200936807 2, a plate shape, a needle shape, and a hollow shape. When the dispersible material of the electroconductive particles of the non-conductive particles is considered, the shape of the electro-chemical particles is such that the particle diameter of the non-electroconductive particles is in the range of from 0.05 μm to 100/m. The non-diameter system is determined by photographs of a scanning electron microscope. For this reason, the average particle diameter of the non-conductive particles of the metal thin film = method is preferably 1/zm to 2 〇em in the range of 1/zm to m. ❹ φ is particularly ambiguous. If 疋 is used for components for liquid crystal display devices, the particle size of = is necessary. In this case, it is preferable that the cv value obtained by the general formula is not less than 1% by weight.

X 10〇CV值(/°)—《[粒徑之標準誤差（em)]/[平均粒徑( 播非導電性粒子上附著金屬核之前處理後實 ί屬崎之金雜之錢，料會賦予成: 之賴細形成 人Α銀馬佳。作為刖處理，例如使含右石々Pi® ΐ後媒及金屬鹽之處理液與鱗電性粒子接i，X 10〇CV value (/°)—“[Standard error of particle size (em)]/[Average particle size (the amount of money that is processed after the metal core is attached to the non-conductive particles) Will be given to: The formation of the Α Α 马 。 。 。 。 。 。 。 。 。 。 。 。 。 。 , , , , , , , , , , , , , , , , , , , , , ,

為^土藉此’可藉由益電解雷參播冬麗键摇f> _tA 二=物，合劑，係:=== 屬5物(拙)之官能基之矽烷耦合劑。 屬紅金屬形絲合物之官能基，可列舉極性 ==基錄具體而言，以選自氮原子、硫原子及以= 之原子之官能基為佳。作為該等官能基， -S〇〇H ^ -OPO(〇h)2 . 豳。若官種上之目此基。此等官能基亦可形成 孤右 S 月,基為-0H、_SH、_s〇2〇H、_s〇〇H、伽(〇h〔成 6 200936807 jOOH等酸性基時，作為該鹽，可列舉納鉀、鐘等驗金屬 旦，或銨鹽等。另一方面，若為视2等驗性基時，作為該鹽， 可列舉氯酸、硫酸、硝酸等無機酸鹽，及甲酸(f〇nnk add)、 • f酸、丙酸㈣ionic acid)、三氟醋酸扣胸職咖add)等有 機酸鹽。 . 夕烷耦合劑為具有藉由加水分解產生矽醇基之加水分解性 官能基之化合物。作為加水分解性官能基，可列舉如與別原 f直接結合之烷氧基(_〇R)等。作為構成上述烷氧基之R，以 炭^為1〜6之直鍊狀、分枝狀、環狀中任一種烷基為佳，具體 ❹ *言，可列舉甲基、乙基、η-丙基、異丙基、n_丁基、異丁基、 sec_丁基、tert-丁基、戊基、己基、環戊基、環己基等。 作為矽烷耦合劑之具體例，可列舉如3_胺丙烷基三甲氧基 矽，(3-ammopropyl 仕imethoxysiiane，APTMS)、3_胺丙烷基三 乙氧基矽烷(3-aminopropyl triethoxysilane，APTES)、N-2-(胺乙 $ f .)-3-胺丙烧基三甲氧基石夕烧 (NJ-QmmoethylH-aminopn^ trimeth〇xysilane)、N 2 (胺乙 2基A胺丙烧基三乙氧基石夕烧 (N-2-(aminoethyl)-3_amin〇pr〇pyl trieth〇xysUane)等。作為矽烷 輕合劑’從成本及易於處理之觀點而言，以3_胺丙烧基三甲氧 D 基石夕烧(3-aminopropyl trimethoxysilane，APTMS)為特佳。 加水分解觸媒係促進上述加水分解性官能基之加水分解。 1為加水分解觸媒，可列舉例如無水醋酸、冰醋酸、丙酸、檸 振酸甲fee草知_等有機酸，醋酸烧基|g(aiuminium %技伽） 等鋁螫合化β合物(aluminium chelates) ’氨水等無基鹼性化合物 等。其中，若考慮與作為3-胺丙烷基三甲氧基石夕烷之矽烧耦合 劑之良好反應性及成本，以氨水為佳。 對於/莫耳之矽烷耦合劑之加水分解觸媒之使用量，以 0.5〜5.0莫耳為佳，以15〜2 5莫耳為更佳。此外，對於i莫耳 之矽烷耦合劑之金屬鹽之使用量，以〇 〇〇5〜〇 〇5莫耳為佳，、以 0.015〜0.025莫耳為更佳。更進一步地，對於工莫耳之金屬鹽 200936807 之還原劑之使用量，以0.025MX25莫耳為佳，以0.075〜〇 125 莫耳為更佳。 作為前處理之處理液，可列舉水或水性溶媒。水性溶媒為 ^與有機溶媒之混合溶媒。作為有機溶媒，可列舉如甲醇、乙 醇、丙醇、丁醇等低級醇類，或丙酮等酮類。此等有機溶媒 單獨使用，或組合使用複數種。 無電解電鍍係於具有硫醇基之矽烷化合物之存在下，形成 由銀所組成之金屬薄膜。具有硫醇基之石夕烷化合物係如下列通 式(1)所示。 ❹ Xtn(Y)3-mSi(CH2)nSH …⑴ (於通式(1)中，X為碳數為1〜6之烷基、γ為碳數為i〜6之 烧氧基、m為0或1、η為1〜5之整數） X所示之烷基為直鏈狀、分歧狀及環狀中任一烷基，例如 曱基、乙基、η-丙基、異丙基、η-丁基、異丁基、sec_丁基、tert_ 丁基、戊基、己基、環戊基、環己基等。γ所示之烷氧基係以 -OR表示’作為構成該烧氧基之r為直鏈狀、分歧狀及環狀中 ⑩ 任一烧基’例如曱基、.乙基、.n-丙基、'異丙基、η-丁基、異丁 基、sec-丁基、tert-丁基、戊基、己基、環戊基、環己基等。 作為通式(1)所示之硫醇基(mercaptans)化合物，從可安定地形 成金屬薄膜之觀點而言，以3-硫醇丙基三乙氧基矽燒 (3 _mercaptopropyl triethoxy silane)為佳。 銀除了具有較金高之導電率以外，亦相當便宜。因此，其 作為具有非導電性粒子與其表面之由銀所組成之金屬薄膜係 有高度利用價值。作為無電解電鍍，係適用使用金屬鹽、還原 劑等周知之無電解電鍍法。作為還原劑，係使用如四氫硼酸鈉 (sodium tetrahydroborate)等氫化棚酸鹽(蝴氫化鈉等驗金屬氫 化棚酸鹽類、，氫化錢類等），聯氨(hydrazine)系化合物類、次 200936807 氯酸鹽等無機系還原劑’甲醛、檸檬酸、檸檬酸納等有機系還 原，。此等還原劑可單獨使用，亦可組合兩種以上使用。作為 無電解電鍍’以兼顧優良反應安定性及將雜質在可能範圍中降 ，最低之觀點而言’以使用銀鏡反應為佳。銀鏡反應係將銀之 氨錯合物(ammine complex)以還原劑予以還原而析出銀之反 ，應。具體而言，其係藉由於硝酸銀之氨水溶液中添加福馬林等 還原劑’使銀得以析出於非導電性粒子之表面。 無電解電鍍係於具有硫醇基之矽烷化合物與水之混合液與 非導電性粒子接觸後開始為佳。藉此，石夕燒化合物可安定地作 ❹ 用。此外，考慮矽烧化合物之溶解性，亦可將與水相容之有機 溶媒與水混合。使用此方式製成之混合液之無電解電鍍之溫度 條件、反應時間等等，係對應無電解電鍍中之通常做法設定。 田對於1莫耳之具有硫醇基之矽烷化合物之金屬鹽之使用 量，以0.005〜0·05莫耳為佳，以0.015〜0.025莫耳為更佳。更 ，步地’對於1莫耳之金屬鹽之還原劑使用量，以〇 〇25〜〇 25 莫耳為佳，以0.075〜0.125莫耳為更佳。 精由本發明之金屬薄膜形成方法所獲得之金屬薄膜，具有 較金屬之塊材或以習知之無電解電鍍法所形成之金屬薄&低 之密度。詳細而言，本發明之金屬薄膜相對於金屬之塊材之密 ® 5比((1〇.5g/cm3)x100) ’雖然稱有不平均，大致為50%〜85%之 範圍’更具體而言’為50%〜7〇%。因此，例如於將含有金屬 =覆層之基材配置於相面對之電極間、使兩電極接近而壓縮基 ^之情^下，因金屬薄膜之密度低，將容易變形。結果，電極 ，金屬^膜之接地面積將增大，提升經由金屬薄膜導通極 間之可靠性。 <導電性粒子> 非導電性粒子之表面全體係形成有金屬薄膜。導電性 係因該金屬薄膜被賦予導電性。非導電性粒子之粒徑 5 m〜50# m之範圍。金屬薄膜係由單層之銀所組成。 金屬薄膜係由連續之銀微粒子之集合體所組成。亦即，金 9 200936807 =膜係由細錄狀賴奸所軸之_性細。 二銀微粒子之集合體·_掃描式紗涵倍〜 ϊί倍ί·之情況τ，以無法觀測出不賴之金屬_之程 =細_列之集合體。金屬_之厚度從獲得安 觀點而言’以50nm以上為佳。 & 於本實施例中之金屬薄膜，在螢光χ光 J性:子所含之元素之外之元素，以僅檢=、=: ΪΪί ΐ粒徑i以適合作為液晶顯示元件用材料或異向Ϊ導 “材料之觀點而言’以GMm〜HK)難之範圍為佳，更佳 =2曰〇=之Ϊ圍。藉此獲得之導電性粒子係適合用於例如^ ^液曰曰扣70件之封合劑外，亦適合用於各種異向導電性材 藉由以上詳述之本實施態樣可獲得以下之效果。 ⑴^為金屬細形成方法之無電解紐係 屬核附著於非導電性粒子上之前處理之同時：於^ 之石夕烧化合物之存在下形成由銀所組成2金 m (2) 成金屬雜之_、Γΐ f ΐ寸之非導電性粒子形 植之if况下，仍可輕易地構成單層之銀。 ⑶ ίιΐΐΐ基^石夕烧化合物與水之混合液接觸非導 2性^子後’開始無電解電鑛。藉此可提高魏化5 物之作用，安定地形成金屬薄膜。 σ 例如，使用3-硫醇丙基三乙氧基魏 ⑷ 表=應實施無電解電二 觸無 ί 二: 金屬析出，使金屬核ίί至 進藉:提=可平均地 更進^提呵金屬薄膜之表 200936807 面平均性 ❹ ❹ 此，將難以對於形成金屬 3 導雜產生林辟，可蚊地形成金屬 金顧膜係由單層之銀所組成。因 子。此等導電性粒子因具有安定之導 二:用於例如液晶顯示元件之封合劑、螢ΐx光分析中，作為非導電性粒子 :二ίϊ素，以僅檢出金、銀及硫為佳，於 此ί月況下’導電性粒子之電性得以確實地發揮。、 鑛η導電性粒子上形成貴金屬薄膜之技 二+屬無電解鎳電鍍形成基層，再將鎳置換 ，，不安定。另-方面，二氧化石夕：i、s對於熱或座度則非常安定。因此，藉tin陶瓷、玻璃作為構成本發明之導電 W： # 士 電粒子，可提升對於熱或溼度之安定 ^:精可提供適合用於熱安定性為必要之導電性粒 另外，上述實施態樣亦可如下述予以變更。 成之靖膜雖為以單層構 ί由:此外’由银所組成之金屬薄膜可 藉由1 -人無電解電細滅，亦可藉由複數次無電解魏形成。 (實施例） (A)前處理 π 2 ^〇mL 1一角燒瓶中放入1〇g之二氧化石夕粒子(平均粒 仏../zm’ V值:0.96% ’藉由掃描式電子顯微鏡照片測 (5) ⑹ ⑺ ⑻ 11 200936807 定70個粒子之粒徑所獲得”加入63g之異丙醇(IPA)，進 行10分鐘之超音波處理。再加入63g之曱醇以電磁攪拌器 擾拌10分鐘’加入5〇g之25%氨水溶液、於3(TC之油槽中 攪拌1〇分鐘，以調製成A液。 將〇,23g之氣金酸(HAuCl4.4H20)加入50mL之曱醇中， 以電磁授拌器攪拌10分鐘後’藉由進一步加入4.5mL之 3-氨基丙基三甲氧基甲矽烷 (3-aminopropyltrimethoxysilane)，予以授拌 1〇 分鐘，以調製 成B液。矽 借此 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 。 。 。 。 。 。 。 。 The functional group of the red metal-shaped linear compound may, for example, be a polar group. The base is preferably a functional group selected from the group consisting of a nitrogen atom, a sulfur atom and an atom having an atom of =. As such functional groups, -S〇〇H ^ -OPO(〇h)2 . If the official kind of this purpose. These functional groups may also form a solitary right S month, and the base is -OH, _SH, _s〇2〇H, _s〇〇H, gamma (〇h [to 6 200936807 jOOH and other acidic groups, as the salt, may be enumerated In the case of a potassium salt, a clock, or the like, an ammonium salt or an ammonium salt is used. On the other hand, in the case of a second-order test group, inorganic salts such as chloric acid, sulfuric acid, and nitric acid, and formic acid (f〇) are mentioned as the salt. Nnk add), • f acid, propionic acid (tetra) ionic acid), trifluoroacetate buckle chest service add) and other organic acid salts. The oxane coupling agent is a compound having a hydrolyzable functional group which generates a sterol group by hydrolysis. The hydrolyzable functional group may, for example, be an alkoxy group (_〇R) which is directly bonded to an indifferent f. The R which constitutes the alkoxy group is preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and specific examples thereof include methyl group, ethyl group and η-. Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl and the like. Specific examples of the decane coupling agent include, for example, 3-aminopropane trimethoxysilane, (3-ammopropyl imethoxysiiane, APTMS), 3-aminopropyl triethoxysilane (APTES), N-2-(amine B$f.)-3-amine-propenyl-trimethoxysulfonate (NJ-QmmoethylH-aminopn^ trimeth〇xysilane), N 2 (amine B-based A-amine propylene-based triethoxy N-2-(aminoethyl)-3_amin〇pr〇pyl trieth〇xysUane), etc. As a decane light mixture agent, from the viewpoint of cost and ease of handling, 3-aminopropenyl trimethoxy D base stone 3-aminopropyl trimethoxysilane (APTMS) is particularly preferred. The hydrolyzed catalyst promotes hydrolysis of the hydrolyzable functional group. 1 is a hydrolyzed catalyst, and examples thereof include anhydrous acetic acid, glacial acetic acid, propionic acid, and citrate. Acidic feie grass knows _ and other organic acids, acetic acid alkyl group | g (aiuminium % gamma) and other aluminum chelates (aluminium chelates) 'a basic water and other basic compounds such as ammonia, etc. -Good reactivity and cost of amine-propane-based trimethoxy oxalate oxime coupling agent, with ammonia Preferably, the amount of the water-decomposing catalyst used for the /mole decane coupling agent is preferably 0.5 to 5.0 moles, more preferably 15 to 2 5 moles. Further, for the i mole sterane coupling agent The amount of the metal salt used is preferably 〇〇〇5 to 〇〇5 mol, and more preferably 0.015 to 0.025 mol. Further, the amount of the reducing agent for the metal salt 200936807 of the Momo Preferably, 0.025 MX25 mole is used, and 0.075 to 〇125 mole is more preferable. As the treatment liquid for the pretreatment, water or an aqueous solvent is used. The aqueous solvent is a mixed solvent of organic solvent, and can be used as an organic solvent. Examples thereof include lower alcohols such as methanol, ethanol, propanol, and butanol, and ketones such as acetone. These organic solvents are used singly or in combination of multiple kinds. Electroless plating is carried out in the presence of a decane compound having a thiol group. A metal thin film composed of silver is formed. The oxalyl compound having a thiol group is represented by the following formula (1): ❹ Xtn(Y)3-mSi(CH2)nSH (1) (in the formula (1) In the formula, X is an alkyl group having a carbon number of 1 to 6, and γ is an alkoxy group having a carbon number of i to 6, m 0 or 1, η is an integer of 1 to 5) The alkyl group represented by X is a linear, divalent or cyclic alkyl group such as an anthracenyl group, an ethyl group, an η-propyl group, or an isopropyl group. , η-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, and the like. The alkoxy group represented by γ is represented by -OR. 'As a constituent of the alkoxy group, r is linear, divergent, and cyclic, and any of the alkyl groups, such as fluorenyl, ethyl, and n-propyl. Base, 'isopropyl, η-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, and the like. As a mercaptans compound represented by the formula (1), 3-mercaptopropyl triethoxy silane is preferred from the viewpoint of stably forming a metal thin film. . In addition to being more conductive than gold, silver is also quite cheap. Therefore, it is highly valuable as a metal thin film composed of silver having non-conductive particles and its surface. As the electroless plating, a known electroless plating method such as a metal salt or a reducing agent is used. As the reducing agent, a hydrogenated shed acid salt such as sodium tetrahydroborate or a metal hydrazine sulfonate such as hydrogenated sodium hydride or a hydrazine compound is used. 200936807 An inorganic reducing agent such as chlorate is reduced by organic compounds such as formaldehyde, citric acid and sodium citrate. These reducing agents may be used singly or in combination of two or more. As the electroless plating, it is preferable to use a silver mirror reaction from the viewpoint of achieving both excellent reaction stability and lowering of impurities in a possible range. The silver mirror reaction reduces the silver ammine complex by a reducing agent to precipitate the silver. Specifically, silver is precipitated on the surface of the non-conductive particles by adding a reducing agent such as formalin to the aqueous ammonia solution of silver nitrate. The electroless plating is preferably carried out after the mixture of the decane compound having a thiol group and water is contacted with the non-conductive particles. In this way, the Shixi burning compound can be used safely. Further, in consideration of the solubility of the calcined compound, a water-compatible organic solvent may be mixed with water. The temperature conditions, reaction time, and the like of the electroless plating of the mixed solution prepared in this manner are set in accordance with the usual practice in electroless plating. The amount of the metal salt of the silane compound having a thiol group of 1 mole is preferably from 0.005 to 0.05 mm, more preferably from 0.015 to 0.025 moles. Further, the amount of the reducing agent used for the metal salt of 1 mole is preferably 〇 25 〇 25 摩尔, preferably 0.075 to 0.125 摩尔. The metal film obtained by the method for forming a metal thin film of the present invention has a thinner metal and a lower density than a metal block or a conventional electroless plating method. In detail, the ratio of the metal film of the present invention to the metal block is less than 5 ((1〇.5g/cm3)x100)' although it is uneven, and is generally in the range of 50% to 85% 'more specific In terms of '50% to 7〇%. Therefore, for example, when the substrate containing the metal layer is disposed between the opposing electrodes and the electrodes are brought close to each other to compress the group, the metal film is easily deformed because of its low density. As a result, the ground contact area of the electrode and the metal film is increased to improve the reliability of the conduction between the electrodes via the metal film. <Electrically conductive particles> A metal thin film is formed on the entire surface of the non-conductive particles. Conductivity is imparted to the metal thin film by conductivity. The particle size of the non-conductive particles is in the range of 5 m to 50 # m. The metal film is composed of a single layer of silver. The metal thin film is composed of a collection of continuous silver fine particles. That is, gold 9 200936807 = film system by the fine record of the razor axis. The assembly of two silver microparticles _ scanning yarn culvert ~ ϊ ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί The thickness of the metal _ is preferably 50 nm or more from the viewpoint of obtaining an ampere. & the metal thin film in the present embodiment, which is an element other than the element contained in the fluorescent luminescent J: substrate, and is only suitable for use as a material for a liquid crystal display element or a particle size i It is preferable that the heterogeneous enthalpy "from the viewpoint of the material" is GMm to HK), and more preferably = 2 曰〇 = the circumference. The conductive particles obtained thereby are suitable for use, for example, in liquid helium. In addition to the sealing agent of 70 pieces, it is also suitable for use in various anisotropic conductive materials. The following effects can be obtained by the above-described embodiment of the present invention. (1) The electroless nucleus of the metal thinning method is attached to the nucleus. On the non-conductive particles, the pre-treatment is carried out: in the presence of the compound of the ceremonial compound, the formation of 2 gold m (2) into a metal miscellaneous Γΐ, Γΐ f ΐ Under the circumstance, it is still easy to form a single layer of silver. (3) ί ΐΐΐ ΐΐΐ ^ 石 石 夕 夕 化合物 化合物 化合物 化合物 化合物 化合物 化合物 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触 接触Function, stable formation of a metal film. σ For example, using 3-thiol propyl triethoxy Wei (4) table = should be implemented without electricity Electric two-touch no ί two: metal precipitation, so that the metal core ίί to borrow: mention = can be even more into the ^ metal film table 200936807 surface average ❹ ❹ This, it will be difficult to form a metal 3 derivative The metal film formed by the mosquito can be composed of a single layer of silver. The conductive particles have a stable conductivity: used in, for example, a liquid crystal display element sealing agent, fluoranthene x-ray analysis, as Non-conductive particles: It is preferable to detect only gold, silver, and sulfur. In this case, the electrical properties of the conductive particles are reliably exhibited. The noble metal film is formed on the η conductive particles. Technology II + is electroless nickel plating to form the base layer, and then nickel is replaced, which is not stable. On the other hand, the dioxide dioxide: i, s is very stable for heat or seat. Therefore, by using tin ceramics, glass as a composition The conductive W of the present invention: #士士电颗粒, can enhance the stability to heat or humidity ^: Fine can provide conductive particles suitable for thermal stability. In addition, the above embodiment can also be modified as follows. Although the film is a single In addition, the metal film composed of silver can be quenched by electrolysis without being electrolyzed by one person, or by multiple electroless Wei. (Example) (A) Pretreatment π 2 ^ 〇 mL 1 〇g of cerium oxide particles (average enthalpy ../zm' V value: 0.96%' was measured in a corner flask by scanning electron microscopy (5) (6) (7) (8) 11 200936807 The particle size obtained was obtained by adding 63 g of isopropyl alcohol (IPA) for 10 minutes of ultrasonic treatment. Then adding 63 g of sterol to the magnetic stirrer for 10 minutes to add 5 〇g of 25% aqueous ammonia solution. 3 (Stir in the oil bath of TC for 1 minute to prepare the liquid A. Add 23 g of gas gold acid (HAuCl 4.4H20) to 50 mL of methanol and stir for 10 minutes with an electromagnetic stirrer' by further adding 4.5 mL of 3-aminopropyltrimethoxymethane (3- Aminopropyltrimethoxysilane), was mixed for 1 minute to prepare into solution B.

將 〇. 107g 之硼氫化鈉（s〇dium tetrahydroborate, NaBH4 ) 加入50mL之曱醇，藉由以電磁攪拌器攪拌1〇分鐘，以 製成C液。 液加入A液中，以3(TC攪拌5分鐘後，於緩緩滴入 C液犄，反應物將變化成紅色。於c液滴入後，將油槽加 熱至拌3小時。停止麟錢行三次甲醇萃取 後藉由吸引過濾採收形成有金屬核之二氧化 ，之乾燥烤箱(0職)予以乾燥3小時，戶斤獲得二=呈= 色0 、 片J i 氧切粒子之掃描式電子顯微鏡之照 士電子顯微鏡照片。參照第二圖’二氧切:$ 均 妹_雜齡布程度 -JiJ) 0.97 平均粒徑(am) 6.42 (B)金屬薄膜之形成107. 107 g of sodium borohydride (NaBH4) was added to 50 mL of decyl alcohol, and stirred by a magnetic stirrer for 1 Torr to prepare a liquid C. The liquid was added to the A solution, and after 3 minutes of TC stirring, the liquid was gradually dropped into the liquid c. The reaction product was changed to red. After the liquid droplet was introduced, the oil tank was heated to mix for 3 hours. After three times of methanol extraction, the metal nucleus is formed by suction filtration, and the drying oven (0 position) is dried for 3 hours, and the household is obtained by scanning electrons of the color = 2 and the film J i oxygen-cut particles. Electron microscopy photo of the microscope. Refer to the second figure 'dioxotomy: $ 均妹_how old cloth degree-JiJ) 0.97 average particle size (am) 6.42 (B) formation of metal film

”之前述「⑷前處理」中所獲得之粒子中加W 12 200936807 之水’以超音波處理10分鐘後，加入〇.〇15mL之3-硫醇丙 基二乙氧基石夕烧(3-mercaptopropyl triethoxysilane)，以電磁 授拌器携:摔5分鐘。再加入〇.65g之硝酸銀’更進一步授摔 1 〇分鐘。接著於加入13mL之25%之氨水溶液後，添加zomL 之〇.24mmol/L之福馬林溶液攪拌5分鐘。以吸引過遽採收 沉澱之覆有銀層之二氧化矽粒子，以曱醇洗淨後，於7〇它 之乾燥烤箱中乾燥3小時。"The water obtained in the above-mentioned "(4) pre-treatment" was added to the water of W 12 200936807. After ultrasonic treatment for 10 minutes, 15 mL of 3-thiol propyl diethoxy sulphur was added. Mercaptopropyl triethoxysilane), carried with an electromagnetic stirrer: fell for 5 minutes. Add 〇.65g of silver nitrate and further drop for 1 〇 minutes. Then, after adding 13 mL of a 25% aqueous ammonia solution, zomL of 24.24 mmol/L of the formalin solution was added and stirred for 5 minutes. The cerium oxide particles coated with the silver layer which attracted the precipitate were collected, washed with decyl alcohol, and dried in a drying oven at 7 Torr for 3 hours.

第三圖係顯示形成有金屬薄膜之二氧化矽粒子之掃描式 電子顯微鏡照片。參照第三圖，二氧化矽粒子之全體砉 係形成有金屬_。 以掃描式電子顯微鏡測定70個粒子之平均粒徑，並求出 顯示粒徑分布程度之CV值。該結果係顯示於表2。 (表2) 平均粒徑（xzm) CV 值(％) __ 6.64 1.45 金屬薄膜之厚度為0.11 。 <於樹脂中之分散性評量> l〇g之樹脂(商品名：STRUCT BOND)以混煉機攪拌！ 卞鐘。於此樹脂中加入0 2g之實施例丨之導電性粒子並攪 拌/ ^鐘。將混合有導電性粒子之樹脂塗抹至載玻片上， ，蓋蓋玻片後以光學顯微鏡觀察。光學顯微鏡之照片係 示於第四圖。 ” 藉由光學顯微鏡之觀察，於3〇2個粒子中，僅產生4個 2.32%)有2個以上之粒子互相粘著之狀況，可知其於樹脂 中之分散性為非常良好。 <螢光X光分析>The third figure shows a scanning electron micrograph of cerium oxide particles formed with a metal thin film. Referring to the third figure, the entire structure of the cerium oxide particles is formed with a metal _. The average particle diameter of 70 particles was measured by a scanning electron microscope, and the CV value indicating the degree of particle size distribution was determined. The results are shown in Table 2. (Table 2) Average particle diameter (xzm) CV value (%) __ 6.64 1.45 The thickness of the metal film was 0.11. <Dispersibility Evaluation in Resin> The resin of L〇g (trade name: STRUCT BOND) is stirred by a kneader! Cuckoo clock. To the resin, 0 2 g of the conductive particles of Example 并 was added and stirred for +/- hr. The resin mixed with the conductive particles was applied onto a glass slide, and the coverslip was covered and observed under an optical microscope. The photograph of the optical microscope is shown in the fourth figure. According to observation by optical microscopy, only two (2.32% of the 3 〇 2 particles were produced), and two or more particles adhered to each other, and it was found that the dispersibility in the resin was very good. Light X-ray analysis>

於實施例1中所獲得之導電性粒子係使用全自動螢光X 13 200936807 光分析裝置(SPECTORIES公司製、PW2400型、燈管：职、 測定元素:Na〜U、照射面積:25mm p)進行定性分析。 採集約2g之導電絲子，使其均勻覆蓋於 製膜片上2著，將麵片載置於全自動螢先^ 置上，以氦氣置換測定部。藉由於可檢出Na〜U元之 ί ί 5騎行掃描來測定元素。絲檢出之元素 僅有&、銀及金二種’並無檢測出此三種元素之 螢光X光分析_於第五圖至第七圖巾顯示。另外，第五 螢光x光分析圖’第六圖為顯示檢出金 ❹ 2先X光讀圖，而第七圖為顯示檢出硫之螢光χ光分 柯圖。 <電阻值之測定> =微小壓縮測試機(島津製作所製），測定20個實施例 之導電錄子之餘值縣得其平均值 標準誤差值-同麵於表3。 贿之、，，。果係與The conductive particles obtained in Example 1 were subjected to a fully automatic fluorescent X 13 200936807 optical analysis apparatus (manufactured by SPECTORIES, PW2400, lamp: position, measuring element: Na to U, irradiation area: 25 mm p). Qualitative analysis. Approximately 2 g of the conductive filaments were collected to uniformly cover the film, and the wafer was placed on the fully automatic fluorescent device to replace the measuring portion with helium gas. The element is determined by the detection of the Na~U ί ί 5 riding scan. The elements detected by the silk are only &, silver and gold. 'The fluorescent X-ray analysis of these three elements is not detected _ is shown in the fifth to seventh figures. In addition, the sixth fluorescent x-ray analysis chart is shown in Fig. 6 as the first X-ray reading of the detected gold ❹ 2, and the seventh picture is the fluoroscopy of the detected sulfur. <Measurement of Resistance Value> = Micro-compression tester (manufactured by Shimadzu Corporation), and the average value of the conductivity records of the 20 examples was measured. The standard error value - the same as in Table 3. Bribe,,,. Fruit system

一_平均電阻值(Ω) _________ 3.9 「 —~~— _差值 2.2 -1 · 圓 -J ❹ (實施例2) 以Πϊ用二氧化石夕粒子(平均粒徑：4.22_、WU3%) 化石^粒^用與實施例1同樣之方式製成覆蓋有銀層之二氧 <耐濕熱評量> 製)對之導€絲子，使藏驗溫帥㈣公司 八圖二-C、9。％四、2顿之條件下進行濕熱試驗。第 3係顯不於濕熱試驗前之導電性粒子之掃描式電子雛 200936807 =微=則;性粒子之掃描式 前後之銀層狀態並無觀及弟九圖後’於濕熱試驗 求得檢；個:電性粒子之電阻值’分別 獲得之結果係於表4 粒子之贿與平均電阻值，所 ❹A _ average resistance value (Ω) _________ 3.9 "-~~- _ difference 2.2 -1 · circle -J ❹ (Example 2) 二 二 二 ( ( (average particle size: 4.22_, WU 3%) In the same manner as in the first embodiment, in the same manner as in the first embodiment, the dioxin <moisture-resistance evaluation> which is covered with a silver layer is used to make the guide wire, so that the Tibetan inspection is gentle (four) company eight figure two-C The wet heat test was carried out under the conditions of 9% and 4%. The third system was not able to scan the electrons of the conductive particles before the damp heat test. 200936807 = micro = then; the state of the silver layer before and after the scanning of the particles After the observation of the nine figures, the results of the test in the damp heat test; the resistance value of the electric particles are obtained in Table 4, the bribe of the particles and the average resistance value.

挺個) 46/50 _ 42/50~~~ 2表4之絲可 粒子之個數差僅為4個。 H邮電阻值之 (實施例3) 2〇ΓτΐΕΛ實施例1「(A)前處理」巾所獲得之粒子十加入 3 甲以其超音波處理1〇分鐘後，加入〇.〇15mL之 φ 3:硫知丙基f基二甲氧基矽烷*職卿_ dmiethoxys—e) ’以辆鮮器游5分鐘。再加入⑽y 之，酸銀’更進-步_ 1G分鐘。接著於加人i3mL之^I =虱水溶紐，添加2GmL之〇.24mmGi/L之福馬林溶液授 ^ 5分鐘„過_收沉殿之覆有銀層之二氧化石夕粒 子’以甲醇洗淨後，於7〇t之乾燥烤箱中乾燥3小時。 第十圖係顯示形成有金屬薄膜之二氧化石夕粒子 電子顯微鏡照片。參照第十圖，二氧切粒 幾乎均形成有金屬薄膜。 衣 (實施例4) 於lg之實施例1「(A)前處理」中所獲得之粒子中加入 200mL之水，以超音波處理10分鐘後，加入〇 〇15扯之 15 200936807 .醇丙基二甲氧基石夕燒（3-mercaptopropyl t^nethoxysilane) ’以電磁授摔器獅5分鐘。再加入〇 銀更進一步携拌10分鐘。接著於加入13mL之25% =水= 夜後’添加2〇mL之〇 24mm〇1/L之福馬林溶液攪 ^为釦二以吸引過濾採收沉澱之覆有銀層之二氧化矽粒 二以甲醇洗淨彳，’於7。。(：之乾燥烤箱中乾燥3小時。 =十-_齡形成有金屬_之二氧化雜子之掃描 ^電子顯微鏡照片。參照第十—圖，二氧化雜子之全體 表面幾乎均形成有金屬薄膜。 ❹ φ (比較例1) 於lg之實施例1「(A)前處理」中所獲得之粒子中加入 200mL之水，以超音波處理1〇分鐘後，加入〇 65g之 銀麟10分鐘。接著於加入13mL之抓之氨水溶液後， 添加20mL之〇.24mmol/L之福馬林溶液攪拌5分鐘。以 引過濾採收沉澱之覆有銀層之二氧化矽粒子，以 後，於70°C之乾燥烤箱中乾燥3小時。 ' 第十一圖係顯示形成有金屬薄膜之導電性粒子之 電子顯微鏡照片。參·十二圖，非導電性粒 & 一部分並無形成金屬薄膜。 衣面有 (比較例2) (A)表面處理 一於500mL之三角燒瓶中放入1〇g之作為非導電性粒子之 一氧化矽粒子(平均粒徑：6.40e m，以COULTER公司少 MUpiSIZER II測定）’加入63g之異丙醇(岡，以 ^器攪拌10分鐘，再藉由加入50g之25%氨水溶液、於 。(:之油槽中攪拌1〇分鐘，以調製成A液。 、 於A液中加入4.5mL之3_硫醇丙基三乙氧基矽It is quite a) 46/50 _ 42/50~~~ 2 The silk of Table 4 can only be 4 pieces of difference. H-mail resistance value (Example 3) 2 〇Γ ΐΕΛ ΐΕΛ Example 1 "(A) pre-treatment" towel obtained by adding 10 particles of A, after ultrasonic treatment for 1 minute, adding 〇. 〇 15mL of φ 3 : sulphur propyl f-dimethoxy decane * Secretary _ dmiethoxys - e) 'Swim for 5 minutes. Adding (10)y, the acid silver is further advanced - 1G minutes. Then add i3mL of ^I = water soluble solution, add 2GmL of 〇.24mmGi / L of the formalin solution for 5 minutes „ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ After drying, it was dried in a drying oven at 7 Torr for 3 hours. The tenth graph shows an electron micrograph of a cerium dioxide particle formed with a metal thin film. Referring to the tenth graph, the dioxy dicing particles are almost all formed with a metal thin film.衣衣 (Example 4) 200 mL of water was added to the particles obtained in Example 1 "(A) Pretreatment", and after ultrasonic treatment for 10 minutes, 〇〇151515 200936807 was added. 3-mercaptopropyl t^nethoxysilane 'Electrically disarmed lions for 5 minutes. Add 〇 silver and carry it for another 10 minutes. Then, after adding 13 mL of 25% = water = after night, add 2 〇 mL of 〇 24 mm 〇 1 / L of the humulus solution to stir the two to attract the filter to collect the precipitated silver-coated cerium oxide particles. Wash the mash with methanol, 'at 7. . (: Drying in a dry oven for 3 hours. = Scanning electron micrograph of metal-doped dioxins formed at ten-years. Referring to the tenth-graph, almost all of the surface of the dioxins are formed with a metal film. φ φ (Comparative Example 1) 200 mL of water was added to the particles obtained in Example 1 "(A) Pretreatment" of lg, and ultrasonic treatment was carried out for 1 minute, and then 65 g of silver lining was added for 10 minutes. Then, after adding 13 mL of the ammonia aqueous solution, 20 mL of the hydrazine solution of 24 mmol/L was added and stirred for 5 minutes. The precipitated silver dioxide-coated cerium oxide particles were collected by filtration, and then, at 70 ° C. Drying in a dry oven for 3 hours. 'The eleventh figure shows an electron micrograph of conductive particles formed with a metal thin film. The twelve-electrode, non-conductive particles & part of the metal film is not formed. (Comparative Example 2) (A) Surface treatment - 1 〇g of a non-conductive particle of cerium oxide particles (average particle diameter: 6.40em, measured by COULTER MUpiSIZER II) was placed in a 500 mL Erlenmeyer flask. Add 63g of isopropyl alcohol (Oka, stir 10 minutes, by adding 50g of 25% ammonia aqueous solution, (:: the oil tank is stirred for 1 ,, to prepare a liquid A. Add 4.5mL of 3- thiol propyl triethoxylate in the liquid A Base

Omercaptopropyltriethoxysilane) ’ 於油槽中加溫 16 200936807 ' 攪拌j小時。停止攪拌並進行三次甲醇萃取後，藉由吸引 過濾採收以硫醇進行表面處理後之二氧化石夕粒子，以7〇。〇 之乾燥烤箱予以乾燥3小時。Omercaptopropyltriethoxysilane) ' Heating in the oil bath 16 200936807 ' Stir for 1 hour. After the stirring was stopped and methanol extraction was performed three times, the cerium oxide particles after surface treatment with mercaptan were recovered by suction filtration to 7 Torr. Dry in a dry oven for 3 hours.

、/坌屬溥膜之形成 、將lg由(八)表面處理所獲得之粒子中加入2〇〇11^之水， ^超2處理1。分鐘後’加入G 65g之確酸銀授拌1〇分 =^者於加人13rnL之25%之氨水溶液後，添加20mL ❹ ❿ 之福馬林雜餅5分鐘。以吸引過遽採收 i乾燥烤箱中粒子’以甲醇洗淨後，於7〇°c 電屬2膜之導電性粒子之掃描式 無銀之覆ί。 十二圖’二氧化雜子之表面並 (比較例3) 广|層，並對於藉由將 3.如m、CV ^ 4 物绿子(平均粒徑： 量。第十巴係_ 2進仃一上述同條件下之耐濕熱評 片，第十五顯微鏡照 態較渴五圖’ _試驗後之金屑層之狀 於濕熱試驗之前後測定5〇個 (表5)/ / is the formation of the enamel film, lg from (8) surface treatment of the particles obtained by adding 2 〇〇 11 ^ water, ^ super 2 treatment 1. After the minute, 'G 65g was added to the acid silver and 1 〇 is divided into ^ 2. After adding 13 rnL of 25% ammonia solution, 20 mL of 福 ❿ fumarin cake was added for 5 minutes. In order to attract the sputum, the particles in the drying oven are washed with methanol, and then the scanning particles of the electroconductive particles of the two films are irradiated at 7 〇 °c. Twelve graphs of the surface of the dioxins and (Comparative Example 3) broad | layer, and for the green matter by means of 3. such as m, CV ^ 4 (average particle size: quantity. Tenth Bar System _ 2仃The above-mentioned moisture-resistant heat evaluation film under the same conditions, the fifteenth microscope is more thirsty than the five pictures' _ the shape of the gold chip after the test is measured 5 times before the damp heat test (Table 5)

7.5 試驗 44/50 17 200936807 濕熱試驗後7.5 Test 44/50 17 200936807 After the damp heat test

"主 -—~~ ____________ J/3U ，從表5之結材知，於雜試 粒子之健差為39個，麟驗後之檢料僅脚H (比較例4) 由‘雷立均粒徑· 6.42/m、CV値:0·70%)上藉 全以ίίίίίΐ ’並對於藉由將鎳與金置換之置換 ，電鑛所獲侍之導電性粒子(平均粒徑：675細 ❹ 〇一·77%)進行與上述同條件下之耐濕熱評量。第十六顯 不濕熱試驗前之掃描式電子顯微鏡照片，第十七圖、顧二"Main--~~ ____________ J/3U, from the material of Table 5, the difference between the miscellaneous test particles is 39, and the test after the Lin test is only the foot H (Comparative Example 4) from 'Lei Lijun Particle size · 6.42/m, CV 値: 0·70%) borrowed all by ί ί ί ' ' and replaced by nickel and gold, the conductive particles obtained by the electric ore (average particle size: 675 fine ❹ 〇·77%) The moisture heat resistance evaluation under the same conditions as above was carried out. Sixteenth visible scanning electron micrograph before the damp heat test, the seventeenth figure, Gu Er

=濕熱試驗後之掃描式電子顯微鏡照片。參照第十六'‘圖I *第L七圖二濕熱試驗後之金屬層之狀態較濕熱試驗^有大 =:其係變得十分粗糙。此-現象為鎳之氧化= 、於濕熱試驗之前後測定50個導電性粒子之電阻值，八 求得檢測出電阻值之導電性粒子之個數與平均了 獲得之結果係於表6中顯示。 平均電阻值(Ω) 檢測出電阻值之個數ΓΛΓΜίίΠ 濕熱試驗前 7.5 46/50 濕熱試驗後 10.4 — 6/50 υ〜、、，口不j π爪，热热瑪鳅則後無檢測出電阻值之 粒子之個數差為40個’於試驗後之檢出率僅12%(6/5〇個^ Φ (比較例5) 於lg之實施例1「(A)前處理」中所獲得之粒子中加入 200mL之水’以超音波處理1〇分鐘後，加入〇 之 2-硫醇乙醇(2-mercaptoethanol)’以電磁攪拌器攪拌5分鐘。 接著加入0.65g之硝酸銀並再攪拌1〇分鐘，於加入13mL 之25 /ί>之氣水溶液後’添加20mL之〇.24mrnol/L之福馬林 200936807 拌5分鐘。以吸引過濾採收峨之財銀層之 $粒子，以曱醇洗淨後，於贼之乾燥烤箱中乾燥3小 第十八圖係顯示形成有金屬薄膜之導電性粒子之 片。參照第十八圖，二氧化雜子之二 (比較例6)= Scanning electron micrograph after the damp heat test. Referring to the sixteenth ''Figure I * L L Figure 2 two wet heat test state of the metal layer is greater than the damp heat test ^ =: its system becomes very rough. This phenomenon is the oxidation of nickel =, the resistance value of 50 conductive particles is measured before and after the damp heat test, and the number of conductive particles which are obtained by detecting the resistance value and the average result are shown in Table 6. . Average resistance value (Ω) The number of resistance values detected ΓΛΓΜίίΠ 7.5 46/50 before damp heat test 10.4 — 6/50 after wet heat test 、~, ,, mouth not j π claw, no heat detected after heat and heat The difference between the number of particles of the value is 40. The detection rate after the test is only 12% (6/5〇^ Φ (Comparative Example 5) obtained in Example 1 "(A) Pretreatment" of lg Add 200 mL of water to the particles. After ultrasonic treatment for 1 minute, add 2-mercaptoethanol to stir with a magnetic stirrer for 5 minutes. Then add 0.65 g of silver nitrate and stir for 1 〇. Minutes, after adding 13 mL of 25 /ί> of the aqueous solution of water, add 20 mL of 24.24mrnol/L of Formalin 200936807 for 5 minutes to attract the particles of the silver layer of the sputum, and wash it with decyl alcohol. Then, it is dried in a dry oven of a thief. The small eighteenth figure shows a sheet of conductive particles formed with a metal thin film. Referring to the eighteenth figure, the second of the dioxins (Comparative Example 6)

於lg之實施例1「(A)前處理」中所獲得之粒子中加入 200mL之水’以超音波處理10分鐘後，加入〇.〇15mL之 2-硫醇乙基辛烷(2_mercapt〇ethyi 〇ctane，2 ME 以 俨 ^器祕10分鐘。接著加人〇.65g之猶銀並再授摔^ 分鐘’於加入13mL之25。/。之氨水溶液後，添加2〇mL之 0f4mm〇l/L之福馬林溶液攪拌5分鐘。以吸引過滤採收沉 澱之覆有銀層之二氧化矽粒子，以曱醇洗淨後，於7〇£)(：之 乾燥烤箱中乾燥3小時。 ' 第十九圖係顯示形成有金屬薄膜之導電性粒子之掃描式 電子顯微鏡照片。參照第十九圖，二氧化石夕粒子之表面並 無覆蓋銀膜。 (比較例7) 於lg之實施例1「(A)前處理」中所獲得之粒子中加入 200mL之水，以超音波處理10分鐘後，加入〇.〇13g之三 水合硫醇醋酸約(calcium mercaptoacetate)，以電磁擾拌器授 拌5分鐘。接著加入〇.65g之硝酸銀並再攪拌10分鐘，於 加入13mL之25%之氨水溶液後，添加2〇mL之0.24mmol/L 之福馬林溶液攪拌5分鐘。以吸引過濾採收沉澱之覆有銀 層之二氧化矽粒子，以甲醇洗淨後，於7〇〇c之乾燥烤箱中 乾燥3小時。 第二十圖係顯示形成有金屬薄膜之導電性粒子之掃描式 19 200936807 二氧化梦粒子之表面有 電子顯微鏡照片。參照第二十圖 一部分並無覆蓋銀膜。 (比較例8) 於lg之實施例1「(A)前處理」中所獲得之粒子争加入 2〇〇mL之水，以超音波處理1〇分鐘後，加入0.015mL之 3-胺丙烧基三甲氧基矽烷（3_amin〇pr ❹ ❹ tmneth〇XyS1lane)，以電磁攪拌器攪拌5分鐘。接著加入〇 之硝酸銀並再攪拌1〇分鐘，於加入13mL之25%之氨水溶 液後，添加20mL之〇.24mmol/L之福馬林溶液攪拌5分鐘。 以吸引過濾採收沉澱之覆有銀層之二氧化矽粒子，以甲 洗淨後’於70°C之乾燥烤箱中乾燥3小時。 第二十一圖係顯示形成有金屬薄膜之導電性粒子之 式電子顯微鏡照片。參照第二十一圖，非導電性粒子之= 面有一部分並無形成金屬薄膜。 對於所獲得之導電性粒子進行於樹脂中之分散性評量。 弟一十二圖係分散性評量中所使用之光學顯微鏡照片。表 照第二ί二圖，可觀察出導電性粒子凝結之狀態，'此一i 果係顯示，其作為液晶顯示元件封合劑之單分散導 子之產率相當低。 【圖式簡單說明】 第一圖為實施例1中所使用之二氧化矽粒子之掃描式 顯微鏡照片。 第二圖為於實施例1中施以前處理之非導電性粒子之 式電子顯微鏡照片。 第三圖為實施例1之導電性粒子之掃描式電子顯微鏡照片。 第四圖為顯示實施例1之導電性粒子於樹脂中之分散 之光學顯微鏡照片。 〜 第五圖為顯示實施例1之導電性粒子中檢測出銀之螢光χ 20 200936807 光分析圖。 光分析1之導電性粒子巾檢測出金之螢光χ 光分析^顯讀細1之料錄？巾檢咖硫之榮光χ 前之狀侦濕熱試驗 二氧化雜子於濕熱試驗 訂圖例3之導電餘子之掃描式電子顯微鏡照片。 片。 4實細之轉味子讀料電子顯微鏡照 照片第忙料之錄例1之導電錄仅式電子顯微鏡 片第十三_比較例2之導概粒子之掃描式f子顯微鏡照 掃概奸料賊麟之狀態之 ❿ 掃觸纖之狀態之 掃^之料錄子概賊麟之狀態之 掃描第之料錄奸聽雜後之狀態之 第十八圖為比侧5之導紐好之掃描式t子顯微鏡照 第十九圖為比侧6之導電錄仅掃喊奸顯微鏡照 第二十_錄例7之導電錄子之掃描錢子顯微鏡照 200936807 第二十一圖為比較例8之導電性粒子之掃描式電子顯微鏡 照片。 第二十二圖為顯示比較例8之導電性粒子於樹脂中之分散 狀態之光學顯微鏡照片。 【主要元件符號說明】 無Add 200 mL of water to the particles obtained in Example 1 "(A) Pretreatment" in lg. After ultrasonic treatment for 10 minutes, add 15 mL of 2-thiol ethyl octane (2_mercapt〇ethyi). 〇ctane, 2 ME to 俨^器秘10分钟. Then add 〇.65g of yin silver and then give a drop ^ minutes' after adding 13mL of 25% ammonia solution, add 2〇mL of 0f4mm〇l /L of the marinal solution was stirred for 5 minutes. The precipitated silver dioxide-coated cerium oxide particles were collected by suction filtration, washed with decyl alcohol, and dried in a dry oven for 3 hours. Fig. 19 is a scanning electron micrograph showing conductive particles on which a metal thin film is formed. Referring to Fig. 19, the surface of the silica dioxide particles is not covered with a silver film. (Comparative Example 7) Example of lg 1 Add 200 mL of water to the particles obtained in (A) Pretreatment. After ultrasonic treatment for 10 minutes, add 13 g of calcium mercaptoacetate to the electromagnetic stirrer. Mix for 5 minutes. Then add 65.65g of silver nitrate and stir for another 10 minutes, add 13mL of 25% ammonia water. After the solution, 2 mL of a 0.24 mmol/L solution of Formalin was added and stirred for 5 minutes. The precipitated silver dioxide-coated cerium oxide particles were collected by suction, washed with methanol, and dried at 7 ° C. Drying in the oven for 3 hours. Figure 20 shows the scanning pattern of conductive particles formed with a metal film. 200936807 The surface of the dioxide dioxide particles has an electron micrograph. Part of the twentieth figure does not cover the silver film. Example 8) The particles obtained in Example 1 "(A) Pretreatment" of lg were added to 2 mL of water, and after ultrasonic treatment for 1 minute, 0.015 mL of 3-aminopropenyl was added. Oxydecane (3_amin〇pr ❹ ❹ tmneth〇XyS1lane), stir for 5 minutes with a magnetic stirrer. Then add silver nitrate and stir for another 1 minute. After adding 13 mL of 25% ammonia solution, add 20 mL of hydrazine. 24 mmol/L of the formalin solution was stirred for 5 minutes. The precipitated silver dioxide-coated cerium oxide particles were collected by suction filtration, and then washed with a 'drying oven' at 70 ° C for 3 hours. The figure shows conductive particles formed with a metal film Electron micrograph of the type. Referring to the twenty-first figure, a part of the surface of the non-conductive particles is not formed with a metal thin film. The dispersion of the obtained conductive particles in the resin is evaluated. It is an optical microscope photograph used in the dispersibility evaluation. According to the second diagram, the state of condensation of the conductive particles can be observed, which is shown as a monodisperse guide of the liquid crystal display element sealing agent. The yield of the child is quite low. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a scanning micrograph of cerium oxide particles used in Example 1. The second figure is an electron micrograph of the non-conductive particles previously treated in Example 1. The third graph is a scanning electron micrograph of the conductive particles of Example 1. The fourth graph is an optical micrograph showing the dispersion of the electroconductive particles of Example 1 in a resin. ~ The fifth figure is a fluorescence analysis chart showing the detection of silver in the conductive particles of Example 1. Light-sensitive analysis of the conductive particle towel detected gold fluorescent χ light analysis ^ display fine 1 material record? The scent of the sulphur sulphur is detected by the smear of the sulphur. The smear of the smear of the smear of the dioxins in the damp heat test. sheet. 4, the fine-grained taste reading material, the electron microscope, the photograph, the busy material, the record 1, the conductive recording, the electron microscope, the thirteenth _ comparative example 2, the scanning particle, the sub-microscope, the scanning material The state of the thief's state 扫 触 触 之 ^ ^ ^ ^ ^ ^ ^ 概 概 概 概 概 概 概 概 概 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第The t-micrograph of the t-microscope is the comparison of the conductive recordings of the side 6 and the scanning of the microscope. The twentieth _ record 7 of the conductive recording of the magnetic book microscope photo 200936807 The twenty-first figure is the comparison example 8 Scanning electron micrograph of conductive particles. Fig. 22 is an optical micrograph showing the state of dispersion of the electroconductive particles of Comparative Example 8 in the resin. [Main component symbol description] None

22twenty two

Claims (1)

200936807 七、申請專利範圍： 1. 一種於粒禋為〇.5"m〜i〇0//m之非導電性粒子上藉由無 電解電鍍形成金屬薄膜之金屬薄膜形成方法，其特徵為： 於，金屬核附著至前述非導電性粒子上之前處理時，同時實 施前述無電解電鑛，於具有硫醇基之石夕烧化合物之存在下形 成由銀所組成之前述金屬薄膜。 2·如申請專利範圍第丨項所述之金屬薄膜形成方法，其中於前 述具有硫醇基之矽烷化合物與水之混合液接觸前述非導電性 粒子後，開始前述無電解電鑛。 ❹ 3. ίΪΐ專利範圍第1項或第2項所述之金屬薄卿成方法， ，、中則述具有硫醇基之矽烷化合物為3_硫醇丙基三乙氧基矽 烷(3-mercaptopropyl triethoxysilane) 〇 4· !!範圍第1項或第2項所述之金屬_形成方法， 其中别述無電解電鍍係藉由銀鏡反應實施。 5. 第1項或第2項所述之金屬薄卿成方法， 係使含有魏偶合劑、加水分解觸媒及金屬鹽之 述非導電性粒子接觸後，藉由還原劑析出前述金 之金屬，使金屬核得以附著，其特徵為： 金屬以金屬會形成整合物 6· 1項或第2項所述之金屬薄膜形成方法， 其中則述金屬核之金屬為金或銀。 7‘ 粒子之全體表面形成之金屬薄膜而獲得 前述金屬薄膜係由單層之銀所構成。 8. ϊΓϋΞίΙϋ，述之導電性粒子，其特徵為：於前 > ^ I之ί光X光分析中，前述非導電性粒子所含元 素以外之凡素，僅檢測出金、銀及硫。 9. 如申請專利範圍第7項或第8項所述之導電性粒子其係作 23 200936807 為液晶顯示元件之封合劑使用。 10.如申請專利範圍第7項或第8項所述之導電性粒子，其係 作為異方性導電性材料使用。200936807 VII. Patent application scope: 1. A method for forming a metal thin film formed by electroless plating on a non-electroconductive particle of 禋.5"m~i〇0//m, characterized in that: When the metal core is attached to the non-conductive particles, the electroless ore is simultaneously applied, and the metal thin film composed of silver is formed in the presence of a thiol-containing compound. 2. The method for forming a metal thin film according to the above aspect of the invention, wherein the electroless ore is started after the non-conductive particles are contacted with a mixture of a decane compound having a thiol group and water. ❹ 3. 金属 金属 Ϊΐ Ϊΐ Ϊΐ Ϊΐ Ϊΐ 金属 金属 金属 金属 金属 金属 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- Triethoxysilane) The metal-forming method described in the first or second aspect, wherein the electroless plating is carried out by a silver mirror reaction. 5. The metal thinning method according to Item 1 or 2, wherein the non-conductive particles containing a Wei coupling agent, a hydrolyzing catalyst and a metal salt are contacted, and the metal of the gold is precipitated by a reducing agent. The metal core is attached, and the metal is formed by a metal to form a metal thin film forming method according to the above item or the second item, wherein the metal of the metal core is gold or silver. 7' The metal thin film formed on the entire surface of the particle is obtained. The metal thin film is composed of a single layer of silver. 8. 导电ίΙϋ, the conductive particles described above, characterized in that in the X-ray analysis of the former > ^ I, only the elements other than the elements contained in the non-conductive particles are only gold, silver and sulfur. 9. The conductive particles described in claim 7 or 8 are used as a sealing agent for liquid crystal display elements. 10. The conductive particle according to claim 7 or 8, which is used as an anisotropic conductive material. 24twenty four