201203287 四、 指定代表圖： (一） 本案指定代表圖為：益。 *、、、 (二) 本代表圖之元件符號簡單說明：無。 五、 t案若有化學式時，請揭示最能顯示發明特徵的化學式 六、發明說明： 【發明所屬之技術領域】 包含導電生粉體的導電性 本發明係關於導電性粉體、 材料及導電性粒子的製造方法。 【先前技術】 先前，用於導電性接著劑、異向性導電膜、異向性 電接著劑等之導電性粉體’已知錄、銅、銀、金、焊錫等 的金屬粉末，·碳粉或碳纖維、碳片等的碳系材料；樹脂粒 子之表面以無電鍍鎳，披覆鎳之導電性粒子。 該等導電性粉體之中，於樹脂粒子之表面披覆鎳之導 電性粒子’鎖披膜容易被氧化，因此電阻有隨著時間增加 之情形。此外為進一步提高導電性為目的，通常在鎳』臈 上進一步形成鍍金披膜來使用。 由於金非常高價，使用其他的貴金屬代替金的研究被 進行。例如提案有將鈀作為最外層之導電性粉體（參照專利 文獻1〜3。）。但是，很難說具有與最外層為鍍金披膜之導 201203287 電性粒子同等的特性。 [先行技術文獻] [專利文獻] [專利文獻1 ]日本特開平1 1 -1 34936號公報 [專利文獻2]日本特開2007-194210號公報 [專利文獻3]日本特開2004-238738號公報 【發明内容】 [發明所欲解決的課題] 因此本發明之目的係在於提供，具有與具有鍍金披膜 作為最外層之先前技術之導電性粒子所組成之導電性粉體 同等或其以上之特性之導電性粉體。 [用以解決課題的手段] 為達成上述目的’本發明者們銳意研究的結果，發現 藉由使用：具有由鈀或鈀合金披膜的表面凸出，且與該披 膜呈連續體之凸起部，將該凸起部的高度，以及其個數等 凸起部的特性調整在特定範圍之鈀披覆粒子；鈀或鈀合金 披膜使用大體上不含有磷或，將磷含量調整在特定範圍以 下之彼獏；進一步作為導電性粉體調製大體上沒有凝聚粒 子之導電性粉體，可使之具有與具有鍍金披膜作為最外層 之先刚技術之導電性粒子所組成之導電性粉體同等或其以 上之優良的導電性，及電性可靠度者。 本發明係根據上述見識而完成者，提供一種導電性粉 體’其係於芯材粒子的表面形成鎳或鎳合金披膜之鎳被覆 201203287 粒子表面’進一步形成鈀或鈀合金披膜之導電性粒子所組 成者， 其特徵在於： 上述導電性粒子’具有：由鈀或鈀合金彼膜的表面凸 出，且與該鈀或鈀合金披膜呈連續體，在每1個粒子具有 5個以上高度為50nm以上之凸起部； 上述鈀或鈀合金彼膜中的磷含量為3重量％以下； 在於上述導電性粉體’導電性粒子之中，一次粒子所 佔比例，對導電性粉體的重量為85重量％以上。 此外，本發明提供一種導電性粒子之製造方法，其係 於芯材粒子的表面，形成鎳或鎳合金披膜，由該膜的表面 凸出，且與該披膜呈連續體’在每丨個粒子具有5個以上 高度為5〇nm以上之凸起部之鎳披覆粒子’於分散劑的存在 下，以下述（D1)至（D3)之任何一種方法，無電電鍍鈀處理。 (D1)以純鈀鍍浴做還原型無電電鍍鈀處理之方法。 (D2)在於使用亞磷酸或其鹽作為還原劑之還原型無電 電鍍把處理’使還原劑社離子之莫耳比為q.卜_做還 原型無電電鍍鈀處理之方法。 (D3)置換型無電電鍍鈀處理之方法。 [發明效果]201203287 IV. Designated representative map: (1) The representative representative of the case is: Yi. *, ,, (2) Simple description of the symbol of the representative figure: None. 5. If there is a chemical formula, please disclose the chemical formula which best shows the characteristics of the invention. 6. Description of the invention: [Technical field of the invention] Conductivity containing conductive powder The present invention relates to conductive powder, material and conductive Method for producing sexual particles. [Prior Art] Previously, conductive powders for conductive adhesives, anisotropic conductive films, anisotropic electrical adhesives, etc., known as metal powders of copper, silver, gold, solder, etc., carbon A carbon-based material such as powder or carbon fiber or carbon sheet; the surface of the resin particle is coated with nickel and electroless nickel-coated conductive particles. Among these conductive powders, the conductive particles coated with nickel on the surface of the resin particles are easily oxidized, so that the electric resistance may increase with time. Further, in order to further improve the conductivity, a gold-plated film is usually further formed on the nickel enamel. Since gold is very expensive, research using other precious metals instead of gold has been carried out. For example, a conductive powder having palladium as the outermost layer is proposed (see Patent Documents 1 to 3). However, it is difficult to say that it has the same characteristics as the 201203287 electrical particle whose outermost layer is a gold-plated film. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2004-194738 (Patent Document 3) SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a conductive powder having the same conductivity as that of a prior art conductive particle having a gold-plated film as the outermost layer. Conductive powder. [Means for Solving the Problem] In order to achieve the above object, the results of the intensive studies of the present inventors have been found to be convex by using a surface having a surface covered with palladium or a palladium alloy, and being convex with the film. The starting portion, the height of the convex portion, and the characteristics of the convex portion such as the number of the convex portion are adjusted to a specific range of palladium-coated particles; the palladium or palladium alloy is used without substantially containing phosphorus or phosphorus content. Other than the specific range; further, as the conductive powder, a conductive powder having substantially no agglomerated particles is prepared, and the conductive powder composed of the conductive particles having the gold-plated film as the outermost layer can be obtained. Excellent electrical conductivity and electrical reliability of powder equivalent or higher. The present invention has been completed based on the above findings, and provides a conductive powder which is formed by forming a nickel or nickel alloy overcoat on the surface of a core particle. The surface of the particle is further formed into a palladium or palladium alloy. In the case where the particles are composed of the particles, the conductive particles have a surface of a palladium or a palladium alloy and are continuous with the palladium or palladium alloy, and have five or more particles per one particle. a protrusion having a height of 50 nm or more; a phosphorus content in the palladium or palladium alloy film of 3% by weight or less; and a ratio of primary particles to conductive powder in the conductive powder 'conductive particles The weight is 85% by weight or more. Further, the present invention provides a method for producing conductive particles which is formed on a surface of a core material particle to form a nickel or nickel alloy film, which is protruded from the surface of the film, and is continuous with the film. Each of the particles has five or more nickel-coated particles having a height of 5 〇 nm or more in the presence of a dispersing agent, and is subjected to electroless plating of palladium in any of the following methods (D1) to (D3). (D1) A method of reducing electroless plating of palladium by a pure palladium plating bath. (D2) is a method in which a reductive electroless plating using phosphorous acid or a salt thereof as a reducing agent is used to treat the molar ratio of the reducing agent to q. (D3) A method of replacement type electroless plating palladium treatment. [Effect of the invention]
"、穴为兴具有鍍金披狀TP 外層之先前技術之導電性粒早 电f祖子所組成之導電性粉體同 其以上之導電性，及電性可貪 电炫『罪度者《此外，根據本發 製造方法，可容易地製造如此 故即此之導電性粉體。 4 201203287 【實施方式】 以下，基於較佳的實施形態說明本發明。本發明之導 電性粉體，係具有於芯材粒子的表面形成鎳或鎳合金彼膜 (以下，將該等僅統稱為「錄披膜」之錄被覆粒子表面， 進-步形成鈀或鈀合金披膜(以下’將該等僅統稱為「鈀披 膜」。）而成者。然後，本發明之導電性粉體，其特徵之一 在於.具有多數由鈀披膜的表面凸出之凸起部。以下，說 明該凸起部。 在於本發明，於導電性粒子之各個凸起部，係與㈣ 膜呈連續體，凸起部的最外層至少由纪披膜所構成。所謂 在此所豸連續體」係指鈀披膜與凸起部之間，並沒有接 縫等有損-體感之部位之存在的意思。因此，例如於怒材 粒子上形成纪披膜，使凸起部形成用核粒子附著於其上， 以該核粒子作為成長的起點形成之凸起部，並沒有與㈣ 膜形成連續體，故並不包含於本發明所述連續體。藉由凸 起部與趣披膜呈連續體，可確保凸起部之強度，故即使在 導電性粉體的使用時受到屢力並不容易使凸起部破損。結 果，可得良好的導電性。 在於本發明之導電性粉體之凸起部，其特徵之一在 於，以特定範圍存在具有特定以上高度者。即，本發明之 導電性粉體，每1個粒子具有5個以上高度為以上之 凸起部。# 1個粒子之高度為5nm以上的凸起部的個數上 限值’以1 〇 0 〇個以下w 下為佳。其理由係凸起部過多，則凸起 201203287 部與凸起部之間隔變窄’有降低做為凸起之效果之可能 性。特別是，每"固粒子之高度為50nm以上之凸起部之數 為5~3GG個’則可成為導電性特別優良者之點而佳。 高度為5〇nni以上的凸起部，以從粒子的表面放射狀延 伸之細長凸起為佳。該凸起部之高寬比以1〇以上為佳， 以1. 1以上更佳。其理由可認為係使用本發明之導電性粉 體導通電極時，於電極表面自然形成薄的氧化披膜，或有 故意形成電極之氧化披膜之情形，當凸起部的高寬 則容易突破該氧化披膜。此外，使用導電性粉體形成異向 性導電膜時’凸起部高寬比大’則樹脂排除性會變高，故 可認為導電性會變高。如此地，藉由使凸起部的高寬比為 1.0以上，即，使凸起部的形狀變細長，可使導電性非常 的高’在本發明者們的研究結果證明。特別是，在於後述 之實施例之實施例卜7與實施例8的對比明顯可知凸起 部的高寬比為U以上，則可有效地抑制長期保存於高 溫.南濕下後導電性的降低，本發明者們所知，使凸 起部的高寬比為i以上並不容易。在於先前的導電性粉體 的凸起部’可說具有-陀的形狀。高寬比的上限值，由於 凸起部受到塵力時有容易破損之傾向，故α 3.0以下為 佳。具有如此之大高寬比之凸起部之導電性粒子，例如可 藉由後述之方法製造。 在於本發明之高寬比’係指凸起部的高度Η與在於凸 起部之基部之ώ起部之寬度D之比，即以h/d定義之值。 由該定義明顯可知’高寬比係凸起部之細長度之尺寸者 6 201203287 其值越大意味著凸起部的形狀越細長。該高寬比，係表示 凸起部之高度為50nm以上之凸起部之平均值。 上述南寬比之測定古法1 丁· , 。藉由電子顯微鏡將導雷 性粉體之各個粒子放大觀R 电 卞裒大硯察。對於1個粒子至少針對", the hole is a gilded pedestal TP outer layer of the prior art conductive grain early morning electric progenitor composed of conductive powder with the above conductivity, and electrical can be greedy and stunned "criminal" Further, according to the production method of the present invention, the conductive powder thus obtained can be easily produced. 4 201203287 [Embodiment] Hereinafter, the present invention will be described based on preferred embodiments. The conductive powder of the present invention has a nickel or nickel alloy film formed on the surface of the core material particles (hereinafter, these surfaces are collectively referred to as "recorded film" on the surface of the coated particle, and palladium or palladium is further formed. The alloy film (hereinafter referred to as "palladium film" is collectively referred to as "palladium film"). Then, the conductive powder of the present invention is characterized in that it has a large surface which is protruded from the surface of the palladium film. In the present invention, the convex portions of the conductive particles are continuous with the (iv) film, and the outermost layer of the convex portion is composed of at least a film. The term "continuous body" refers to the existence of a portion between the palladium film and the convex portion and having no damage or body feeling such as a seam. Therefore, for example, a film is formed on the rag material to make the film convex. The nucleus particles for forming the starting portion are attached thereto, and the ridges formed by the nucleus particles as the starting point of growth do not form a continuum with the (IV) film, and thus are not included in the continuum of the present invention. The continuum is in a continuum with the fun mask to ensure the strength of the raised portion, so even When the conductive powder is used, it is not easy to damage the convex portion. As a result, good electrical conductivity can be obtained. The convex portion of the conductive powder of the present invention is characterized in that it is specific In the conductive powder of the present invention, the conductive powder of the present invention has five or more raised portions having a height of at least one. The number of raised portions of the height of #1 particles is 5 nm or more. The upper limit value is preferably 1 〇 0 〇 or less. The reason is that if the convex portion is excessive, the interval between the projection 201203287 and the convex portion is narrowed, which may reduce the effect of the projection. In particular, the number of the convex portions having a height of 50 nm or more per solid particle is 5 to 3 GG', which is preferable because the height is 5 〇 nni or more. The elongated protrusion extending radially from the surface of the particle is preferred. The aspect ratio of the convex portion is preferably 1 Å or more, more preferably 1.1 or more. The reason for using the conductive powder of the present invention is considered to be When the electrode is turned on, a thin oxide film is naturally formed on the surface of the electrode, or In the case where the oxide film of the electrode is intentionally formed, it is easy to break through the oxide film when the height of the convex portion is high. Further, when the conductive powder is used to form the anisotropic conductive film, the "high aspect ratio of the convex portion" is the resin. Since the exclusion property is high, it is considered that the conductivity is high. Thus, by making the aspect ratio of the convex portion 1.0 or more, that is, the shape of the convex portion is elongated, the conductivity can be made very high. The results of the research by the present inventors prove that, in particular, in the comparison between the embodiment 7 of the embodiment described later and the embodiment 8, it is apparent that the aspect ratio of the convex portion is U or more, and the long-term preservation can be effectively suppressed. It is known that the aspect ratio of the convex portion is i or more at a high temperature and a decrease in the electrical conductivity after the south wetness. The convex portion of the prior conductive powder can be said to have - The shape of the gyro. The upper limit of the aspect ratio tends to be easily broken when the raised portion is subjected to dust, so α 3.0 or less is preferable. The conductive particles having the convex portions having such a large aspect ratio can be produced, for example, by a method described later. The aspect ratio in the present invention means the ratio of the height Η of the convex portion to the width D of the ridge portion at the base portion of the convex portion, that is, a value defined by h/d. It is apparent from this definition that the size of the fine length of the boss portion of the aspect ratio is higher. 6 201203287 The larger the value, the more elongated the shape of the convex portion. The aspect ratio is an average value of the convex portions in which the height of the convex portion is 50 nm or more. The above-mentioned South-wide ratio is measured by the ancient method 1 Ding·. A magnifying view of each particle of the guided powder is observed by an electron microscope. For at least 1 particle
凸起部，測定其基部之長度D 夂阿度H。此時，在於觀察 像’比起存在於粒子中央的 ’、 r兴的凸起部，反而存在於粒子之周 緣之凸起部作為測定對象， ^ Λ 吨的測疋尺寸之觀點相當 重要。將如此之測定對至少？ η t至夕20個不同的粒子為對象進 將如此所得之複數高寬比 貝卄鼻術+均，以該值作為高 \° ，凸起部之橫斷面為異向性小的形狀（例如大致 2形)’故根據粒子的觀察角度使凸起部之基部之長"值 會變化之疑慮不大。 凸起部之高寬比如上所述， 位 ’、令該凸起部之基部之長 度D本身及凸起部之离谇 π π , 。又Η本身，關於基部的長度])為 〇. 〇5~0. 5# m，特別是以〇 ..4々m為佳，關於高度H以 〇. 05〜0. 5/z ，特別是以The raised portion is measured for the length of the base D 夂A degree H. In this case, it is important to observe that the image is present in the convex portion of the periphery of the particle rather than the convex portion existing in the center of the particle, and the convex portion of the particle is the measurement target. Will this be measured at least? η t to eve 20 different particles for the object to be obtained in the complex aspect ratio Behr Nasal +, with this value as high \ °, the convex portion of the cross section is a small anisotropy ( For example, it is roughly 2 in shape. Therefore, there is little doubt that the length of the base portion of the convex portion changes depending on the observation angle of the particle. The height and width of the convex portion are as described above, the position ', the length D of the base portion of the convex portion, and the distance 谇 π π of the convex portion. Η Η 〇 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ Take
.U.4#m為佳。凸起部之基部 之長度D及凸起部之离_ H 度H在該範圍，則可更加提升導電 南度為50nm以上之Λ如加,. a , 上之凸起部，在每1個粒子存在上述數 目p可，加上如此之凸起部， ,n 、，_ 於導電性粒子中存在高度為 5 0nm以下之&起部，+ 士人丄_ 本發明並無妨。但是，高度為_ 以下的凸起部多數在尤 子在，則凸起部與凸起部 有降低做為凸起之效果 仏叉乍 生’故尚寬比滿足上述範圍 之凸起部之比例，對全f 于王體凸起數以40%以上為佳，以45% 201203287 以上更佳’進一步以50%以上為佳。 本發明之導電性粉體’其特徵在於含於鈀披膜之磷（p) 含量。詳言之’本發明者們研究的結果發現，於鈀披膜中 含有超過3重量％的磷，則對導電性，以及電性可靠度有影 響。因此，於本發明，鈀披膜中的磷含量以3重量％以下， 以2重量％以下為佳。磷含量的下限值並無特別限定，越小 越好。鈀彼膜中的磷含量，係以後述之實施例所記載的方 法測定。 關於位於鈀披膜下側之鎳披膜，含於該披膜中的磷含 量並無特別限制。 關於鈀披膜的厚度，過薄則導電性粉體難以顯現充分 的導電性，相反地過厚則容易從芯材粒子的表面剝離。由 此觀點，在不存在凸起部之部位之鈀披膜之厚度以5〜5 〇 〇⑽ 為佳’以10~300ηηι更佳。 鎳披膜，與鈀披膜同樣地，過薄則有導電性能並不充 分之情形，相反地過厚則粒子有容易凝聚之傾向，故其厚 度以10〜300nm，特別是以50〜250nm為佳。 在於導電性粒子之鈀彼膜之厚度及鎳彼膜之厚度，可 以後述之實施例所記載的方法測定。 位於鈀彼膜下側之鎳披膜，係將芯材粒子之表面披覆 形成鎳披覆粒子。該鎳披覆粒子，以對芯材粒子無電電鍍 鎳處理，於該芯材粒子表面形成鎳披臈的同時亦形成凸起 部者為佳。因為如此地形成之凸起部，可變得更不容易破 損。由此觀點，在於本發明之導電性粉體，在於各個粒子 8 201203287 之凸起部，以鎳或鎳合金所組成之凸起部芯體，及由披覆 該芯體表面之鈀或鈀合金所組成之凸起部披覆層所構成者 為佳。凸起部係如此之構造時，凸起部芯體’與位於鈀披 膜下側之錄披膜呈連續體為佳。此外，凸起部彼覆層，與 把披膜呈連續體為佳。 藉由上述鎳披膜披覆之芯材粒子，可使用由後述之各 種材質所組成者。特別是使用樹脂粒子作為芯材粒子，則 斤知導電1·生叙體之粒度分佈變的狹窄，又壓縮恢復特性 優良的觀點而特別佳。 在於本發明之導電性粉體，各個粒子的形狀以球形為 佳。在此所述粒子之形狀，係去除凸起部之粒子之形狀。 冰子為球形’則起因於具有凸起部，本發明之導電性粉體， 成為導電性高者。 此外本發明之導電粉體，在於與先前所述的凸起部個 數之關係、’以後述之柯爾特計數（CQulter_nter)法求得 之平均粒徑為卜5。“，特別是以卜細，尤其以 1.5〜30"之導電性粒子所構成者為佳。藉由該範立 :之導電性粒子’可…個粒子之凸起部數與凸起部的 雄度平衡，而可容易使導電度變高。 導電性粒子，其粒徑變小 團聚，則使用導電性粒子之異 不適。此外，為解開團聚而施 披膜剥離而成導電性降低之原 之導電性粉體，提高各個粒子 則有容易團聚的傾向。發生 向導電膜有容易引起短路之 以粉碎處理，則鈀彼膜及録 因。由此觀點，在於本發明 之分散性非常的重要。因此 201203287 在於本發明之導電性粉體，纟導電性粒子之中，—次粒子 所佔的比例，對於導電性粉體的重量為85重量％以上，以 90重量0/〇以上為佳，以92重詈 ”之… 重量以上更佳。為提高導電性 如體之刀散性，例如只要依照後述之方法製造導電性粒子 即可一次粒子所佔比例係以如下方法測定1導電性粉 體o.ig放入io〇mL的水以超音波均質儀分散i分鐘。接 著’以柯爾特計數法測定粒度分佈。由該結果算出一次 粒子之重量比例。 ^ 在於導電性粒子之鈀披膜係 了田缶屬鈀或鈀合金所構 成。於把合金’包含例如鈀-磷合金 ° ^鈀—磷合金，係於後 述之導電性粉體之製造，作為釦玷嗓 ^ 忭马鈀的還原劑使用次亞磷酸鈉 時所產生的合金。 此外，在於導電性粒子之鎳披膜，係由金屬錄或錄合 金所構成。於鎳合金’包含例如錄，合金。鎳—碟合金， 係於後述之導電性粉體之製造，作為 戸与螺的還原劑使用次亞 磷酸鈉時所產生的合金。 其次，說明本發明之導電性粉體 肢 < 艮好的製造方法。 於本製造方法，其係於芯材粒子的表 形烕鎳或鎳合金 披膜，由該膜的表面凸丨’且與該披膜呈連續體，在每i 個粒子具有5個以上高度為5〇nm以上之Λ如加 <凸起部之鎳披覆粒 子(以下，僅稱為「錦披覆粒子」。），於分散劑的存在下， 以下述(D1)至(D3)之任何一種方法，無電電鍍鈀處理。 ⑽以純㈣浴做還原型無電電㈣處理之方法。 (D2)在於使用亞鱗酸或其鹽作*费 乍為還原劑之還原型無電 10 201203287 100做還 電鍍鈀處理，使還原劑對鈀離子之莫耳比為0 原型無電電鍍鈀處理之方法。 (D3)置換型無電電鍍鈀處理之方法。 錄披覆粒子’係以如下(Μ)及⑽的2個之中的任一 用C二則凸起部的強度強，即使在導電性粉體的使 =到壓力，凸起部不容易破損，結果可得良電 性之觀點而佳。 (bl) :有丄將分散劑及包含鎳離子之無電電錄錄洛，與於 =擔持貴金屬之芯材粒子混合，於該芯材粒子的表面形 =初期薄膜層時，料1公升錄離子的濃度調整為 的0Η·_莫耳/公升之該無電電㈣浴，使用表面積 的總和成的量之該芯材粒子之αι步驟；及 將在於A1步驟所得，具有錄初期薄膜層之上述芯材粒 ^，及包含上迷分散劑之水性聚料，維持該分散劑顯現分 政效果之㈣圍，對該水性毁料，持續性添加相當於每小 時錄的析出量成25〜100nm之量的錄離子及還原劑之心 驟之方法（以下，稱為「bl之製造法」。）。 (b2) 具有：將芯材粒子之水性毁料添加於包含分散劑、錄 鹽、還原劑、錯化劑等之無電電鍍鎳浴，做無電電鍍錄處 理之B1步驟’接著對該無電電鍍鎳浴，將無電電鍍錄液之 構成成分至少分離成，分別同時且持續性添加 電鑛鎳處理之B2步驟之方法(以下，稱為… 11 201203287 法」。) 〇 用於上述bl及b2的製造法之芯材粒子之形狀，會對 目的之導電性粒子之形狀有很大的影響。如上所述’披覆 芯材赤iL ^ -¾. y <表面之鎳彼膜的厚度及鈀彼膜很薄，故芯材粒 子的形狀幾乎直接反映在導電性粒子的形狀。導電性粒子 以球形較佳以如先前所述，故芯材粒子之形狀亦以球形為 佳。 心材粒子為球形時，芯材粒子 • 伍a的〜卞电 粒子之粒徑有非常大的影響。如上所述，披覆芯材粒子 表面之錄披膜的厚度及纪披膜很薄，故芯材粒子的粒徑 乎直接反映在導電性粒子的粒徑。由此觀點，可知芯材: 子之粒l可與目的之導電性粒子之粒徑為相同程度。 體而言以柯爾特計數法所求之平均粒徑以卜50"，特; 是以卜40㈣，尤其以U〜3〇·〇㈣為佳。 ^由上述方法測定之芯材粉體之粒度分佈有個寬度 -般“，粉體的粒度分佈的寬 動係數所表示。 式U)所不的3 變動係數⑻=(標準偏差/平均粒徑)χΐ〇〇⑴ :變動係數大表示分佈有寬度，另 小則表示粒度分佈窄。於本發 變動係拿 變動係數為編下，特別广月’作為材粒子’使制 者為佳。其理由，係將本 膜中的導電粒子時，有可貢獻電性粒子用於異向導電 之利點。 於有效的連接之比例會變高 12 201203287 芯材粒子之具體例，無機物可舉，有金屬（含合金）、 玻璃、陶瓷、二氧化矽、碳、金屬或非金屬之氧化物（亦包 含含水物）、包含鋁矽酸鹽之金屬矽酸鹽、金屬碳化物、金 屬氮化物、金屬碳酸鹽、金屬硫酸鹽、金屬磷酸鹽、金屬 硫化物'金屬酸鹽、金屬函化物及碳等。有機物，可舉天 然纖維、天然樹脂、聚乙烯、聚丙烯、聚氣乙烯、聚苯乙 烯、聚丁烯、聚醯胺、聚丙烯酸酯、聚丙烯腈、聚縮醛、 離聚物、聚酯等的熱可塑性樹脂、醇酸樹脂、酚樹脂、尿 素樹脂'三聚氰胺樹脂、苯代三聚氰胺樹脂、三聚氰胺樹 脂、二甲苯樹脂、矽膠樹脂、環氧樹脂或苯二酸二烯丙酉旨 樹脂等。該等可單獨使用，亦可以2種以上的混合物使用。 此外，芯材粒子之其他物性，並無特別限定，惟芯材 粒子為樹脂粒子時，以下式（2)所定義之κ值，在於2〇t 在l〇kgf/_ i〇〇〇〇kgf/_之範圍，且1⑽壓縮變形後之 恢復率在於 於20t在1%〜1〇0%之範圍為佳。.U.4#m is better. The length D of the base portion of the convex portion and the distance _H degree H of the convex portion are in this range, so that the conductive south is 50 nm or more, for example, plus, the upper convex portion is in each one. The particles may have the above-mentioned number p, and such a convex portion may be added, and n, , _ may have a height of 50 nm or less in the conductive particles, and the starting point may be +, and the present invention may be omitted. However, most of the raised portions having a height of _ below are in the case of the Ueko, and the convex portion and the convex portion are reduced as the effect of the convex portion, and the ratio of the convex portion satisfying the above range is satisfied. For all f, the number of convex protrusions is preferably 40% or more, and 45% is better than 201203287. Further, 50% or more is preferred. The conductive powder of the present invention is characterized by a phosphorus (p) content contained in a palladium film. In particular, the results of studies by the present inventors have found that the inclusion of more than 3% by weight of phosphorus in the palladium mask affects electrical conductivity and electrical reliability. Therefore, in the present invention, the phosphorus content in the palladium coating film is preferably 3% by weight or less and preferably 2% by weight or less. The lower limit of the phosphorus content is not particularly limited, and the smaller the better. The phosphorus content in the palladium film is measured by the method described in the examples below. Regarding the nickel film located on the lower side of the palladium film, the phosphorus content contained in the film is not particularly limited. When the thickness of the palladium film is too thin, the conductive powder is less likely to exhibit sufficient conductivity, and if it is too thick, it is easily peeled off from the surface of the core particle. From this point of view, the thickness of the palladium film in the portion where the convex portion is not present is preferably 5 to 5 〇 〇 (10), and more preferably 10 to 300 ηη. The nickel film is the same as the palladium film. If it is too thin, the conductivity is not sufficient. On the contrary, if the film is too thick, the particles tend to aggregate. Therefore, the thickness is 10 to 300 nm, especially 50 to 250 nm. good. The thickness of the palladium film of the conductive particles and the thickness of the nickel film can be measured by the method described in the examples below. The nickel film located on the lower side of the palladium film covers the surface of the core material particles to form nickel coated particles. The nickel-coated particles are preferably treated by electroless nickel plating on the core material particles, and a nickel blister is formed on the surface of the core material particles, and a convex portion is also formed. Because of the raised portion thus formed, it becomes less susceptible to breakage. From this point of view, the conductive powder of the present invention resides in a raised portion of each particle 8 201203287, a raised core composed of nickel or a nickel alloy, and a palladium or palladium alloy coated with the surface of the core. It is preferred that the composed of the raised portion is composed of a raised layer. In the case where the projections are constructed in this way, it is preferable that the projection core body & the recording film on the lower side of the palladium film are continuous. In addition, it is preferable that the convex portion is covered with a layer and the continuous film is formed. The core material particles coated with the above nickel film can be composed of various materials described later. In particular, when resin particles are used as the core material particles, it is particularly preferable that the particle size distribution of the conductive material 1 is narrow, and the compression recovery property is excellent. In the conductive powder of the present invention, the shape of each particle is preferably a spherical shape. The shape of the particles herein is to remove the shape of the particles of the raised portion. The fact that the ice is spherical is caused by the convex portion, and the conductive powder of the present invention is highly conductive. Further, the conductive powder of the present invention is in the relationship with the number of the above-mentioned convex portions, and the average particle diameter determined by the Coulter counter method described later is 5. "In particular, it is better to use fine particles, especially 1.5~30" of conductive particles. By the Fan Li: the conductive particles can be... the number of convex portions of the particles and the convex portion The degree of conductivity is high, and the conductivity is increased. When the conductive particles are agglomerated, the conductive particles are disfigured. In addition, the film is peeled off to release the agglomeration and the conductivity is lowered. The conductive powder tends to agglomerate easily in the respective particles, and the pulverization treatment occurs when the conductive film is likely to cause a short circuit, and the palladium film and the cause of the recording are important. Therefore, 201203287 is a conductive powder of the present invention, and among the ruthenium conductive particles, the proportion of the secondary particles is preferably 85% by weight or more based on the weight of the conductive powder, and more preferably 90% by weight or more. It is more important than the weight of 92. In order to improve the electrical conductivity, such as the scalpel property of the body, for example, the conductive particles may be produced according to the method described later, and the ratio of the primary particles may be measured by the following method: 1 conductive powder o. The sonic homogenizer is dispersed for one minute. Next, the particle size distribution was measured by Colt's counting method. From this result, the weight ratio of the primary particles was calculated. ^ The palladium coating of the conductive particles is composed of palladium or palladium alloy. The alloy ', for example, a palladium-phosphorus alloy, palladium-phosphorus alloy, is produced by the production of a conductive powder described later, and is an alloy produced by using sodium hypophosphite as a reducing agent for ruthenium palladium. Further, the nickel film of the conductive particles is composed of a metal record or a gold alloy. The nickel alloy 'includes, for example, a film, an alloy. The nickel-dish alloy is produced by the production of a conductive powder described later, and is an alloy produced when sodium hypophosphite is used as a reducing agent for snails and snails. Next, a description will be given of a method for producing a conductive powder body of the present invention. In the present manufacturing method, the ruthenium-nickel or nickel alloy film of the core material particles is formed by the surface of the film and is continuous with the film, and has a height of 5 or more per i particles. 5 〇 nm or more, for example, a nickel-coated particle of a raised portion (hereinafter, simply referred to as "a brocade particle"), in the presence of a dispersing agent, the following (D1) to (D3) Either method, electroless plating palladium treatment. (10) A method of treating a reduced type of electricity (4) in a pure (four) bath. (D2) is a method of using a ruthenium acid or a salt thereof as a reducing agent to reduce the amount of electricity 10 201203287 100 and also performing electroplating palladium treatment so that the molar ratio of the reducing agent to palladium ions is 0. Prototype electroless plating palladium treatment method . (D3) A method of replacement type electroless plating palladium treatment. The recording of the coated particles is strong in any of the following two (C) and (10), and the strength of the convex portion is strong, and the convex portion is not easily broken even when the conductive powder is pressed to the pressure. The result is good from the viewpoint of good electricity. (bl): The dispersant and the electroless magnetic recording containing nickel ions are mixed with the core material particles of the noble metal, and the surface of the core material is the initial film layer, and the material is 1 liter. The concentration of ions is adjusted to 0 Η·_mol/liter of the electroless (four) bath, the total amount of surface area is used to form the amount of the core particles of the core layer; and the result of the step A1, having the initial film layer The core material particles and the aqueous polymer material containing the dispersing agent maintain the (4) circumference of the dispersing agent, and the continuous addition of the water-based material is equivalent to an amount of precipitation per hour of 25 to 100 nm. The method of recording the ions and the reducing agent (hereinafter referred to as "the manufacturing method of bl"). (b2) having: adding an aqueous residue of the core material particles to an electroless nickel plating bath containing a dispersing agent, a salt, a reducing agent, a distorting agent, etc., and performing a step B1 of electroless plating recording, and then the electroless electricity In the nickel plating bath, the constituents of the electroless plating bath are at least separated into a method of simultaneously and continuously adding the B2 step of the electro-mineral nickel treatment (hereinafter referred to as "11 201203287 method"). 〇 used for the above bl and b2 The shape of the core material particles of the manufacturing method has a great influence on the shape of the conductive particles of interest. As described above, the thickness of the nickel film on the surface and the palladium film are very thin, so the shape of the core particles is almost directly reflected in the shape of the conductive particles. The conductive particles are preferably spherical in shape as described above, so that the shape of the core particles is also preferably spherical. When the core material particles are spherical, the core material particles have a very large influence on the particle size of the particles. As described above, since the thickness of the film covering the surface of the core material particles and the film are thin, the particle diameter of the core particles is directly reflected in the particle diameter of the conductive particles. From this point of view, it is understood that the core material: the particles 1 can be the same as the particle diameter of the intended conductive particles. In terms of body, the average particle size obtained by Colt's counting method is preferably 50", especially; it is preferably 40(4), especially U~3〇·〇(4). ^The particle size distribution of the core powder measured by the above method has a width-like", which is expressed by the width coefficient of the particle size distribution of the powder. Equation 5) The coefficient of variation (8) = (standard deviation / average particle diameter) ) χΐ〇〇 (1): A large coefficient of variation indicates that the distribution has a width, and a small one indicates a narrow distribution of particle size. In the variation of the present invention, the coefficient of variation is used as a code, and in particular, the term "material as a material particle" is preferred. When the conductive particles in the film are used, there is a point that the conductive particles can be contributed to the anisotropic conduction. The ratio of the effective connection becomes high. 12 201203287 Specific examples of the core material particles, inorganic materials, metal (including alloys), glass, ceramics, ceria, carbon, metal or non-metal oxides (also containing hydrates), metal silicates containing aluminosilicates, metal carbides, metal nitrides, metal carbonates Salt, metal sulfate, metal phosphate, metal sulfide 'metal salt, metal complex and carbon, etc. Organic matter, natural fiber, natural resin, polyethylene, polypropylene, polyethylene, polystyrene, poly Butene Thermoplastic resin, polyalkyd resin, phenol resin, urea resin 'melamine resin, benzoguanamine resin, melamine resin, two Toluene resin, silicone resin, epoxy resin, or bismuth phthalate resin, etc. These may be used alone or in combination of two or more kinds. Further, other physical properties of the core material particles are not particularly limited. When the core material particles are resin particles, the κ value defined by the following formula (2) lies in the range of 2〇t in l〇kgf/_i〇〇〇〇kgf/_, and the recovery rate after 1(10) compression deformation lies in It is preferably in the range of 1% to 1% 0% at 20t.
，可使電極 充分地接觸。 。因為藉由滿足該 K 值（kgf/mm2) = (3/，2)xFxS-3/2xrl/2, the electrode can be brought into full contact. . Because by satisfying the K value (kgf/mm2) = (3/, 2) xFxS-3/2xrl/2
13 201203287 金屬離子螯合或作為鹽捕捉。例如於芯材粒子的表面，存 在胺基、亞胺基、醯胺基、醯亞胺基、氰基、氫氧基、腈 基、羧基等時，該芯材粒子表面具有貴金屬離子捕捉能。 將表面改質成具有責金屬離子捕捉能時，可使用例如日本 特開昭61-64882號公報所記載的方法。 使用如此之芯材粒子，於其表面擔持貴金屬。具體而 吕，將芯材粒子分散在如氣化鈀或硝酸銀之貴金屬鹽之稀 薄酸性水溶液。藉此將貴金屬離子捕捉於粒子的表面。貴 金屬鹽的濃度以粒子之表面積11〇2以1χ1(Γ7〜1χΐ〇_2莫耳的 範圍即充分。捕捉貴金屬離子之芯材粒子由系分離水洗。 接著，將芯材粒子㈣於水1此加入還原劑進行貴金屬 離子之還原處理。藉此於芯材粒子的表面擔持貴金屬。還 原劑，可使用例如次亞磷酸納、氫氧化、氫氧化棚钟、 二甲基胺硼烷、聯胺、福馬林等。 亦可在將貴金屬離子捕捉於芯材粒子的表面之前， 粒子的表面施以吸附錫離子之敏感化處理。於離子的表 吸附錫離子，例如只要將表面改質之芯材粒子投入氣化 錫水溶液攪拌特定時間即可。 、以下，更詳細地說明上述bl之製造方法。本製造 法可大分為(1)於芯材粒子的表面形成鎳初期薄膜層 A1步驟；及⑺使用A1步驟所得之粒子作為原料，形成 的之導電性粒子之A2步驟之2步驟。以下，說明各個步顯 在於A1步驟，將包含分散劑及鎳離 浴，及於表面擔持貴金屬之芯材粒子混合，於；= 14 201203287 表面，形成鎳初期薄膜層。 將上述芯材粒子，與 錄浴混合。無電電__ ㈣及鎳料之無電電鑛 之分散劑，可舉例如非 疋π其 ,,..a 隹離子界面活性劑、兩性離子界 性劑及/或水溶性高八工U T介面活 ^ 刀子。非離子界面活性劑，可使用聚r 一醇、聚氧乙婦烷醚、 « ^ . A 虱乙烯烷基笨醚等的聚氧烯醚争 界面活性劑。兩Μ蝕2田 尔 子界面活性劑，可使用烷基二甲基乙 I甜菜驗、院基二曱美雜 …f基竣甲基乙酸甜臬鹼、烷基二甲基胺 土 * I驗等的甜菜驗系界面活性劑。水溶性高分子， :使用聚乙稀醇、聚乙烯料咬、經乙基纖維素等。分散 劑的使用量，雖依其種一 貝 叙對液體（無電電鍍鎳浴）的 φ 〇·5〜30g/L。特別是，分散劑的使用量對液體（盔電 1錄浴）的體積為H〇g/L的範圍，則可提升錄披膜的密 者性之觀點而佳。 、含於無電電錢鎳浴之錄離子，使用水溶性錄鹽作其錄 源1^溶性㈣，可使用硫酸鎳或氣化錄，惟並非限定於 3於‘，，、電電鍍鎳浴之鎳離子之濃度為〇 . 0001U⑽ Ίΰ* , 、 么升，特別是以0.0001〜0.005莫耳/公升為佳。 於無電電鍍鎳浴，在上述成分之外亦可含有還原劑。 、原劑可使用與用於先前所述之責金屬離子之還原者相 151 束 , m ° 在於無電電鍍鎳浴之還原劑的濃度為4χ1〇-、2. 〇莫 耳/公升，特別是以2.0x10_3~0.2莫耳/公升為佳。 於無電電鍍鎳浴，可進一步含有錯化劑。藉由含有錯 化劑，可發揮抑制鍍液之分解之有利的效果。錯化劑，可 201203287 舉有機叛酸或其鹽，例如檸檬酸、乙醇酸、酒石酸、蘋果 酸、乳酸或者葡萄糖酸或其鹼金屬鹽或銨鹽。該等錯化劑 可使用1種或2種以上。在於無電電鍍鎳浴之錯化劑的濃 度為0.005〜6莫耳/公升，特別是以〇〇1~3莫耳/公升為佳。 混合把以刚處理之芯材粒子與無電電鍍鎳浴之方法， 並無特別限定。例如將無電電㈣浴，加熱至鎳離子可還 原的溫度，在該狀態下，將施以前處理之芯材粒子投入無 電電鍍錄浴中。藉由此操作，錄離子還原，藉由還原產生 •鎳在、材離子的表面形成初期薄膜層。初期薄膜層，其 厚度為G.卜1_，特別是以形成為G.卜5nm為佳。在此點、, 凸起部尚未形成。 子之量’與投入之芯材粒子之量之關係。具體而言，剑 公升錄離子的濃度調整為〇._ι〜〇·_莫耳/公升， 1Γ1" 005莫耳/公升之無電電鍍鎳浴，使用表面積 總和成ϋ以一量的芯材粒子。藉此，可: =二=度之初期薄膜層。此外，藉由使錄離 成初㈣以地防止 徑小時，例如師為3相團I此在於芯材粒子之: '拉k為3"m以下時特別有效。 完成鎳離子的還原，接著進 接著A1步驟進扞. A2步驟。A2步驟q ^ ㈣進仃。並不進行 薄膜層之芯㈣子由液體分㈣的之具有錄初； 具有錦初期薄膜層之芯材粒 此’在於㈣ f生槳枓令，殘存著A1步 16 201203287 驟所添加之分银·拖丨。γ & A n ^ 在於A2步驟’ A1步驟所得具有錄初 '薄膜層之芯材粒子，及用於ai步驟之含有分散劑之水性 漿料持’性地添加鎳離子及還原劑。所為「持續性地添 加二係指將錄離子及還原劑一口氣添加以外之意思花 ^疋時間連續地或斷斷續續地添加錄離子及還原劑之意 心。此時，添加鎳離子及還原劑之時機可完全一致，或先 行添加鎳離子，垃簞、 接者添加遇原劑亦可。亦可為其相反。再 者在於添加的終點，可先行結束㈣子的添加，而接著 結束還原劑的添加。亦可為其相反。 ;A2步驟之鎳離子之鎳源’可使用與用於A1步驟 所使用之鎳源相同者。關於還原劑亦相同。 離子的還原’首先於液中生成微 :鎳核粒+ 4吏該核粒子附著於Ai步驟所得之具有鎳初 期4膜層之芯材粒子之表面，以附著之核粒子作為起點使 ”成長开v成由錄所組成之凸起部芯體。藉由採用該方法， 可有效地防止粒子之^日χ闹 之相互團聚，且可容易地形成高度為 5〇nm以上高寬比為！以上的凸起部。 在於A2步驟之鎳離子之還原，將水性聚料，維持在 A1步驟所添加之分散劑（該分散劑亦殘存於A2步驟）顯現 分散效果之pH範圍非當& + * _ , 靶固非㊉的重要。藉此，可有效地防止粒子 4互團1於pH的5周整，邊觀察水性浆料的μ對水性聚 料添加各種礦酸等的酸或氫氧化鈉等的鹼即可。pH的調整 範圍，只要按照使用之分散劑採用適切的值即可。例如使 用非離子界面活性劑作发八 注劑作為分散劑時，將水性漿料的pH維持 17 201203287 在5〜10之範圍為佳。使用兩 時，將水性激料的仙维持在子界面活性劑作為分散劑 -\ 7 寺在5〜8之範圍為佳。使用此w w 商分子作為分散劑時，亦將 冑用水〉谷性 圍為佳。 毁抖的ΡΗ維持在5〜8之範 在於Α2步驟之鎳離子 工夕县n s 定原添加於水性漿料之錄雜 子之量及還原劑的量最為重要。 ·'、 -S· ，可首尾良好地形成 问寬比向的凸起部芯體。具體條件，係 1 性地以h小時相當於鎳析出量為2 ㈣持續 為佳之量之鎳離子及居和.“ nm，以40〜60nm # ' 、、诗。藉由採用如此之添加條件， 鎳的析出里，較初期薄臈層優先生 成高寬比高的凸起部芯體。 p 〇谷易地形 在於錄離子及還斤齋丨^^,天< — 還原㈣添加’亦可將水性漿料加埶為 寺疋的溫度，使藉由還原劑之錄離子之還原順利地進行。 在於錦離子及還原劑的添加，亦可將水性漿料授拌，使還 原之錄附著均句地產生。如此，可得目的之銻披覆粒子。 其次，更詳細地說明上$ b2之製造方法。在於本製造 方法之B1步驟，係將芯材粒子之水性焚料，與含有分散 劑、鎳鹽、還原劑及錯化劑之無電電鑛錄浴混合之無電電 鍵鎳步驟。於該B1步驟’在對芯材粒子形成錄披膜的同時 會發生鑛浴之自我分解。由於該自我分解係於芯材粒子的 附近發生’故在鎳披膜的形成時自我分解物被捕捉於芯材 粒子的表面’生成微小凸起之核，與其同時形成鎳披膜。 以生成之微小凸起之核作為基點，成長凸起部芯體。 於B1步驟，使上述之芯材粒子以1〜5〇〇g/L為佳，以 18 201203287 5,〇g/L更佳的範圍充分分 操作，可使用通常的授拌、高速攪拌=水性漿料。分散 儀等之剪斷分散裝置進行 3膠體磨或者均質 亦無妨。按照需要，於於分散操作併用超音波 散劑之情形。接著，對含==加界面活性劑等的分 添加劑之無電電鍍鎳浴， 八 種 水性锻料η · 仃刀政操作。添加芯材粒子之 水！生漿枓，進灯無電電鍍B1步驟。 上述之分散劑，可舉例如 卞界面活性劑、兩性離 子界面活性劑及/或水溶性 離 使用聚乙二醇、聚氧乙計J 離子界面活性劑’可 备 / 烯烷醚、聚氧乙烯烷基苯醚等的聚 氧烯醚系界面活性劑。兩 Λ 二曱基乙酸甜菜鹼、烷基烷基 疋丞一甲基羧甲基乙酸甜菜鹼、烷 -甲基胺基乙酸甜菜驗等的甜菜驗系界面活性劑。水溶性 :分子^使用聚乙稀醇1乙稀対咬、經乙基纖維素 =等刀散劑可以1種或組合2種以上使用。分散劑的 用1雖依其種類般對液體（無電電鍵鎳浴）的體積 為。.5耀。特別是，分散劑的使用量對液體(無電電鍍 鎳洛）的體積為H〇g/L的範圍，則可提升鎳彼膜的密著性 之觀點而佳。 鎳鹽’可使用例如氯化鎳、硫酸鎳或醋酸鎳，其濃度 以〇. 1〜50g/L之範圍為佳。還原劑，可使用例如次亞磷酸 鈉、二甲基胺硼烷、氫氧化棚納、氫氧化棚鉀或聯胺等， 其濃度以0. 5Og/L之範圍為佳。錯化劑，可舉檸檬酸、 乙醇酸、酒石酸、蘋果酸、乳酸或者葡萄糖酸或其鹼金屬 19 201203287 ΑΤΟ 鹽或銨鹽等的羧酸（鹽），甘胺酸等的胺基酸、乙二胺 _ 基胺4的胺酸、其他的敍、EDAT或焦填酸（鹽）等，對鎖離 子有錯化作用之化合物，該等可以丨種或2種以上。其濃 度以卜100g/L為佳，以5〜50g/L之範圍更佳。在此階段之 =電電鍍鎳浴較佳的pH在私14的範圍。無電電鍍錄反應， 當添加芯材粒子的水性漿料即迅速地開始，伴隨著氫氣的 產生。無電電鍍B1步驟，係以完全無法確認該氫氣的產生 時結束。 接著，在於B2步驟，接續上述M步驟，使用包含 鎳鹽、還原劑及鹼之中@ i種的第i水溶液，與含有剩下 的2種的第2水溶液；或⑴)含鎳鹽之第i水溶液，與含 有還原劑的第2水溶液，及含有驗㈣3水溶液將該等 水溶液分別同時且持續性地，添加㈣步驟之液進行無電 電鑛錦。添加該等液則電鑛反應再度開始，惟藉由調整其 添加量’可將形成之鎳披膜控制在所期望的膜厚。無電電 鍍鎳浴的添加結束後’直到完全無法確認氫氣的產生將液 溫保持一陣子繼續攪拌使反應完成。 鹼可使用例如氫氧 關於上述（i i)之情 於上述（Ο之情形，使用含錄鹽之第i水溶液，與含還 原劑及鹼之第2溶液為#，惟並非限定於此組合。此時， 於第1水溶液不含還原劑及驗，於第2水溶液不含錄鹽。 鎳鹽及還原劑，可使用先前所敘述者 化鈉或氫氧化鉀等鹼金屬的氫氧化物 形亦相同。 水溶液分別含有锦 於上述（ii)之情形，於第丨〜第 20 201203287 還原劑及驗，且於各水溶液不含該成分以外的其他2 成分。 、 或（U)之任一情形，水溶液中的鎳鹽的濃度為 5"。二’特別是以10(1〜3〇〇g/L為佳。還原劑的濃度為 '，特別是以50〜90〇g/L為佳。驗的濃度為 心卿卜特別是以2。娜L為佳。 B2步驟，可於B1步驟結束後連續進行惟亦可取代 此’將Β1步驟與Β2步驟斷斷續續進行 步驟後，藉由過遽等的方法，將芯材粒子與』: 離，將4材粒子重新分散於水調製水性 劑以卜100g/LA杜 r 対此將錯化 ’、’、〜5〇g/L更佳的濃度範圍溶解之水 >谷液添加1分散劑以。.5，g/L… 圍溶解調製水性總粗认斗， s ^丈佳的範 忒枓，於該水性漿料進行添加上述之各水 溶液之B2步驟之方沬I, κ合枣 方法。如此可得目的之銻披覆粒子。 再者’在於Μ及b2之掣i生方、车 做使用球磨之粉碎牛驟2 可對鎳披覆粒子’ 之鋅披覆粒子：粉碎步驟，可得單分散 …’藉由對該單分散之錄披覆粒子做後 纪披膜，此外，可將—次趣早…的表面也成均勾的鑛 比例，在於益電電铲鈀盧·-性粉體之重量所佔的 内。 更谷易地故疋於上述範圍 在於本發明，bl之製造方法，無關乎㈣ 可有效地使用，惟特別县料4 u < X小 符另丨疋對芯材粒子的平均粒徑 的微粒的芯材粒子做I電 ‘“ ^ 電電鍍錦，得到具有凸起部芯體之 21 201203287 效的方法。 鐮彼覆粒子之情形，係、特別有效的方法。另_方面，心 製造方法’對3，" m之相對較大的芯材粒子做無電電參 錄，得到具有凸起部芯體之錄披覆粒子之情形，係特別有又 子’於分散劑的存在下， 無電電鍍鈀處理，可得目 藉由對如此所得之鎳披覆粒 以下述（D1)至（D3 )的任一方法， 的之導電性粉體。 (D1)以純鈀鍍浴做還原型無電電鍍鈀處理之方法。 (D2)在於使用亞磷酸或其鹽作為還原劑之還原型無電 電鍍鈀處理，使還原劑對鈀離子之莫耳比為〇.丨〜丨做還 原型無電電鍍鈀處理之方法。 (D3)置換型無電電錄把處理之方法。 上述（D1)及（D2)之還原型無電電鍍鈀之方法，係將鍍 液中鈀離子藉由還原劑的作用，使鈀析出於鎳披膜上者。 然後，在（D1)的電鍍方法，藉由例如使用甲酸化合物做為 還原劑，可得純度9 9%以上的無電電鍍鈀披膜，另一方面， 於（D2)的還原型無電電鍍鈀的方法，藉由使用次亞磷酸鈉 或其鹽作為還原劑，可得鈀-磷合金所組成之電鍍披膜。 以下，說明以（D1)之純鈀鍍浴做還原型無電電鍍鈀處 理之方法。純鈀鍍浴’係由含有鈀化合物、還原劑及錯化 劑作為必須成分之水溶液所組成。於本發明，使純鈀鍍浴， 含有分散劑及上述鎳披覆粒子進行還原型無電電鍍鈀處 理。 上述纪化合物，只要是可溶於鑛液’可得特定濃度的 22 201203287 水溶液者’並無特別限定。可使用例如，硫酸鈀、氣化鈀、 硝酸鈀、醋酸鈀、乙二胺氣化鈀、四胺基二氣化鈀等的水 溶性鈀化合物等。該等可以1種或2種以上使用。此外， 把化σ物，亦可使用將把溶液化之把溶液。纪溶液，可使 用例如，乙二胺氣化鈀溶液或四胺基二氯化鈀溶液。純鈀 鍛浴之纪化合物的含量，鈀以〇·卜30g/L為佳，以 〇. 3〜1 〇g/L更佳。 還原劑使用甲酸或其鹽。在於純鈀鍍浴之還原劑的含 量，以〇· 1 00g/L為佳，以卜5〇g/L更佳。 錯化劑，可調合例如，乙二胺、二乙烯三胺等的胺類； 乙:胺二醋酸、乙二胺四醋酸、二乙烯三胺五醋酸等的胺 基夕竣酉文，該等之鈉鹽、鉀鹽、錄鹽；甘胺酸、丙胺酸、 亞胺基一醋酸、腈基三醋酸、左旋麩胺酸、左旋麩胺酸2 B ^左旋天冬胺酸、牛磺酸等的胺基酸、該等之鈉鹽、 :鹽、銨鹽；胺基三亞甲基膦酸、卜羥基亞乙基]，卜二膦 胺四亞甲基膦酸、該等的銨鹽、卸鹽、納鹽。錯 化Μ可以1種單獨或混合2種以上使用。在於純鈀鍍浴之 錯化劑的含量’以°. 5〜1()°g/L程度為佳，以5〜50g/L程度 更佳。 *政劑可舉例如非離子界面活性劑、兩性離子界面 一醇 欠'合丨生间分子。非離子界面活性劑，可使用聚乙 ，、A氧乙稀院醚、聚氧乙烯院基苯醚等的聚氧烯醚系 :面::性劑。兩性離子界面活性劑，可使用烷基二甲基乙 菜鹼、院基二甲基叛甲基乙酸甜菜驗、烧基二甲基胺 23 201203287 基乙酸甜菜鹼等的甜菜鹼系界面活性劑。水溶性高分子， 可使用聚乙烯醇、聚乙烯。比咯啶、羥乙基纖維素等。分散 劑的使用1，雖依其種類，一般對液體（純鈀鍍浴）的體積 為0. 5〜30g/L。特別是’分散劑的使用量對液體（純鈀鍍浴） 的體積為卜l〇g/L的範圍，則可提升鈀披膜的密著性，並 且抑制生成團聚粒子之效果高之觀點而佳。 上述無電電鍍鈀反應的pH為3〜10，特別是以4〜7，則 可得女疋的析出速度而佳。於pH的調整，可使用例如硫 酸、鹽酸、氫氧化鈉、氨水等。反應溫度為2〇〜9(rc，特 別是以40〜80t ,則可得平滑而緻密的彼膜之觀點而佳。 再者，純鈀鍍浴，亦可含有安定劑等的常用的添加劑。 含有如此之添加劑之純鈀鍍浴，亦可使用例如日本kanigen 株式會社小島化學藥品株式會社、中央化學產業株式會 社等所市售之市售品。 其次，說明（D2)之使用次亞磷酸或其鹽作為還原劑之 還原型無電電鍍把的方法。（D2)之鑛浴，使用㈣鐘浴。 該把-碳鍍浴，係由包含減合物、次亞磷酸或其鹽之還原 劑及錯化劑為必須成分之水溶液所組成。於本發明，將該 鈀-磷鍍浴，與分散劑及上述鎳披覆粒子混合，進行還原型 無電電鑛Ιε處理。 鈀化。物、還原劑、錯化劑及分散劑，可將與上述) 之還原型無電電鍵把的方法相同者，以同樣的添加量使用。 於（D2)的還原型鍵把的方法，藉由調整還原劑對把離 子之調合量在特定㈣，調㈣披膜中的磷含量。通常， 24 201203287 鈀披膜中的磷含量，隨著還原劑之次碟酸鈉或其鹽對纪離 子之調合量變多而變多。（D2)之還原型無電電鍍鈀，使還 原劑對鈀離子的莫耳比’設定於較先前為低的範圍為佳。 即’藉由將還原劑對鈀離子的莫耳比設定為〇.卜1〇〇做還 原型無電電鍍鈀處理，可使鈀彼膜中的峨含量為3重量％ 以下’調整為0· 5~3重量％為佳。還原劑對鈀離子的添加量 以莫耳比較0· 1少，則析出速度降低而並不實用，另一方 面’大過100,則如上所述鈀彼膜中的磷含量超過5重量％， 而無法得到磷含量為3重量％以下的鈀披膜。特別是，在本 發明’使還原劑對鈀離子的莫耳比以1〜3 〇之範圍為佳。 上述無電電鍍鈀-磷反應之pH’以5〜10為佳，以5 5〜9 更佳。藉由將pH設定於該範圍，可提高鍍液的安定性，此 外較不容易在鈀披膜產生龜裂等的缺陷。於pH的調整，可 使用例如硫酸、鹽酸、氫氧化鈉、氨水等。反應溫度為25〜8〇 °C，特別是以40~7(rc在可得平滑而緻密的披膜的觀點而 佳。 再者，鈀-磷鍍浴，亦可含有安定劑等的常用的添加 劑。含有如此之添加劑之鈀-磷鍍浴，亦可使用例如小島化 學藥品株式會社、石原藥品株式會社等所市售之市售品。 接著，說明（D3)之置換型無電電鍍鈀的方法。於⑶3) 之置換型無電電鍍鈀的方法，藉由鈀離子與鎳離子之置換 反應做置換型無電電鍍鈀於鎳彼覆粒子形成鍍鈀彼膜。、 置換型無電電鍍鈀浴，係由包含鈀化合物及錯化劑為 必須成分之水溶液所組成。於本發明，係對置換型無電電 25 201203287 鍵纪/谷含有分散劑及上述鎳彼覆粗子進行置換型無電電 錢叙處理。 纪化合物、錯化物及分散劑，可將與上述（D1)之還原 型無電電鍍鈀的方法相同者，以同樣的添加量使用。鈀化 合物，特別是使用四胺基鈀鹽時，可得緻密的鈀披膜而佳。 使置換型無電電鍍鈀反應，於pH3〜1()，特別是pH4~8 進订，則容易得到平滑而緻密的被膜而佳。於pH的調整， 可使用例如硫酸、鹽酸、氫氧化鈉、氨水等。反應溫度為 25〜8〇°C，特別是以30〜70t，可使反應速度成實用程度的 速度’此外容易得到緻密的鈀披膜之點而佳。 於上述（D1)〜（D 3 )的電鍵反應結束後，以常法過遽分 離、乾燥，得到導電性粉體。按照需要，亦可將導電性粉 體做上述鎳彼覆粒子之製法所述，使用球磨之粉碎步驟。 藉由該粕碎步驟，可更容易地將一次粒子對導電性粉體之 重量所佔的比例，設定在上述範圍内。 如此所得之本發明之導電性粒子，可良好地使用於例 如異向性導電膜（A C F)或熱封連接器（H s c)、將液晶顯示面 板的電極與驅動LSI晶片的電路基板連接之導電材料等。 特別是，本發明的導電性粉體，可良好地用於導電性接著 劑之導電性填充劑。 上述導電性接著劑，係配置於形成導電性基材之2片 基板間，藉由加熱加壓將上述導電性基材接著導通之異向 導電接著劑。該異向導電性接著劑，包含本發明之導電性 粒子與接著劑樹脂。接著劑樹脂，只要是絕緣性且可用於 26 201203287 作為接著劑樹脂者即可，可無特別限定地使用。以熱可塑 性樹脂及熱硬化性樹脂均可，以藉由加熱顯現接著性能者 為佳。於如此之接著劑樹脂，可舉例如熱可塑性型、熱硬 化性型、紫外線硬化型等。此外，顯示熱可塑性型與熱硬 化性型之中間的性質之所謂半熱硬化性型、熱硬化性型與 紫外線硬化型之複合型等。該等接著騎脂可配合被黏對 象之電路基板等的表面特性或使用型態適宜選擇。特別 是’包含熱硬化性樹脂而構成之接著劑樹脂，接著後的材 料強度優良之點而佳。 接著劑樹脂，具體而言’可舉選自由乙烯-醋酸乙烯酯 共聚物、缓基變性乙稀-醋酸乙婦自旨共聚物、乙稀_異丁基 丙烯酸醋共聚物、聚醯胺、聚醯亞胺、聚醋、$乙烯醚、 ㈣ '聚氨酯' SBS嵌段聚合物、竣基變性娜 共聚物、SIS共聚物、SEBS共聚物、馬來酸變性SEBS共聚 物、聚丁二稀橡膠、氣戊二稀橡膠、緩基變性氣戊二稀橡 夥、苯乙稀—丁二稀橡膠、異丁稀-異戊二烯共聚物、丙稀 猜-丁二烯橡膠（以下’以膽表示。）、缓基變性nbr、胺 變性NBR、環氧樹脂、環氧醋樹脂、丙烯酸樹月旨、盼樹脂 或石夕膠樹脂等《1種或2種以上的組合而得者作為主劑調 製者。該等之中，熱可塑性樹脂，以苯乙烯—丁二烯橡膠或 SEBS等在重工性優良而佳。熱硬化性樹脂，以環氧樹脂為 佳該等之中，由接著力高、耐熱性、電絕緣性優良’且 炫融黏度低，可以低壓力連接之優點，以環氧樹脂最佳。 上述環氧樹脂，只要是在i分子中具有2個以上的環 27 201203287 氧基之多元環氧樹脂，可使用一般被使用的環氧樹脂。具 體而言’可例示酚酚醛'曱酚酚醛等的酚醛樹脂'雙酚Α、 雙酚F、雙酚AD、間苯二酚、二羥基二苯基醚等的多元盼 類、乙二醇、新戊二醇、甘油、三亞甲基丙烷、聚丙二醇 等的多元醇類、乙二胺、三乙烯四胺、苯胺等的聚胺基化 合物、己二酸、鄰笨二曱酸、間苯二甲酸等的多元羧基化 合物等與環氧氣丙烷或2-甲基環氧氣丙烷反應而得之縮水 甘油型環氧樹脂。此外，二環戊二烯環氧化物、丁二烯二 聚二環氧化物等的脂肪族或脂環族環氧樹脂。該等可單獨 或混合2種以上使用。 再者，上述之各種接著樹脂，使用減少雜質離子（Na 或Cl等）或水解性氣等之高純度品，在防止離子遷移的觀 點而佳。 在於異向導電性接著劑之本發明之導電性粒子之使用 量’對接著劑樹脂成分100重量部通常為〇.丨〜30重量部， 以0.5〜25重量部為佳，以卜2〇重量部更佳。藉由導電性 粒子之使用量在於該範圍内，可抑制接觸電阻或熔融黏度 變尚，可提升連接可靠度，充分地確保連接的異向性。 於上述異向導電性接著劑，於上述之導電性粒子及接 著劑樹脂之外，在於該技術領域，可調合習知之添加劑， 其調合量亦可為該技術領域習知之範圍。其他的添加劑， 可例不例如，黏著賦予劑、反應性助劑、環氧樹脂硬化劑、 金屬氧化物、光起始劑、增感劑、硬化劑、加硫劑、惡化 防止劑、耐熱添加劑、熱傳導提升劑、軟化劑、著色劑' 28 201203287 各種偶合密I丨+、1 p 齊戍金屬惰性劑等。 松、、*梦㈣予劑可舉松香、松香衍生物、松油稀樹脂、 ·:酚樹脂、石油樹脂、古馬隆—茚樹脂、苯乙烯系樹脂' 、烯系樹脂、烷基酚樹脂、二甲苯樹脂等。反應性 劑’即做為架擦#|丨 H , 氰胺樹脂、尿素樹 :如多7、異I酸醋類、三聚 仏Μ /、、烏洛托品類、胺類、酸酐、過氧化 物等。環氧樹脂硬化劑，只要…分子中具有2個以上 的：11氫者可無特別限制地使用。具體而f，例如二乙烯 "—乙烯四胺、間笨二胺、雙氰胺、聚乙二胺等的聚 :基：合物4苯二甲酸酐、甲基納迪克酸酐、六氫鄰苯 -軒均苯四甲酸軒等的有機酸酐；紛盼搭、甲齡盼 酸等的_脂。該等可以單獨或…種以上使用。此 根據用途或按照需要亦可使用潛在性硬化劑。可使用 之潛在性硬化劑’可舉例如，咪唑系、醯肼系、三氟化硼― 胺錯合物、疏鹽、胺化醯亞胺、聚胺之鹽、雙氰胺等及該 等之變性物。該等可以單獨或以2種以上的混合體使用。 上述異向導電性接著劑，通常，可藉由在於該當業者 廣乏地使用之製造裝置，將本發明之導電性粒子及接著劑 樹知以及按照需要之硬化劑或各種添加劑調合，接著劑樹 脂為熱硬化性樹脂之情形，藉由在有機溶劑中混合，熱可 塑性樹脂之情形，則以接著劑樹脂之軟化點以上的溫度， 具體而言，以約50〜130。(：程度為佳，以約60〜110〇c程度更 佳’熔融混煉而製造。如此所得之異向導電性接著劑，可 以塗佈，亦可做成膜狀使用。 29 201203287 [實施例] 以下’以實施例更詳細地說明本發明。但是，本發明 的範圍，並非限定於該實施例。若無特別提及，「％」係「重 量％」的意思。 [鎳彼覆粒子試料N1之調製] (1)A1步驟 使用真比重為1.1之球狀苯乙烯_二氧化矽複合樹脂 [平均粒徑3//m’（株）日本觸媒製，商品名s〇u〇STAR，變 動係數=· V)3. 2%]作為芯材粒子（1L當量的表面積的總和 為5. 46m )。將其9g’邊攪拌投入4〇〇此調整劑水溶液 and HAAS 電子材料製之「CLEANER c〇nmti〇ner 23。）。 調整劑水溶液之澧；^4 n m/ τ、 晨度為40ml/L)。接者，於液溫6〇t邊施 加超音波搜拌30分鐘進行芯材粒子之表面改質及分散處 理。將水溶液過遽’將再漿水洗一次之芯材粒子作成賺 的聚料。對該浆料投入氯化亞踢水溶液2〇〇mi。該水溶液 的濃度為^、/卜以常溫心^分鐘，進行使錫離子 吸附於騎粒子表面之敏感化處理。接著將水溶液過濟， 再浆水洗一次。接著將芯材粒子作成舰的漿料，維持 在60C。併用超音波邊授拌 , 丁寸添加 2社 ’ 0. llm〇1/L 的 。維持授拌狀態5分鐘，進行於芯材粒子的 表面捕捉鈀離子之活化處理。 接著，將詩2Gg/L__、5.軌之 納、硫酸錄六水合物(無水換算為。.躺、聚 之水溶液所組成之無電電心3L^Am： / 30 201203287 Λ 電鍍浴，投入擔持鈀之芯材粒子9g，開始A1步驟。攪拌5 分鐘確認氫氣的發泡停止，完成A1步驟。 (2) A 2步驟13 201203287 Metal ions chelate or capture as a salt. For example, when an amine group, an imine group, a guanamine group, a quinone group, a cyano group, a hydroxyl group, a nitrile group or a carboxyl group is present on the surface of the core material particles, the surface of the core material particles has a noble metal ion trapping energy. When the surface is modified to have a metal ion trapping ability, for example, the method described in JP-A-61-64882 can be used. Using such core material particles, a precious metal is supported on the surface thereof. Specifically, the core material particles are dispersed in a dilute acidic aqueous solution of a noble metal salt such as gasified palladium or silver nitrate. Thereby, precious metal ions are captured on the surface of the particles. The concentration of the noble metal salt is such that the surface area of the particles is 11 〇 2 to 1 χ 1 (the range of Γ 7 〜 1 χΐ〇 2 摩尔 is sufficient. The core material particles for capturing the noble metal ions are separated by water washing. Next, the core material particles (four) are in water 1 The reducing agent is added to carry out the reduction treatment of the noble metal ions, whereby the precious metal is supported on the surface of the core material particles. For the reducing agent, for example, sodium hypophosphite, hydrogen hydroxide, oxidized greenhouse clock, dimethylamine borane, hydrazine can be used. , Formalin, etc.. Before the precious metal ions are trapped on the surface of the core particles, the surface of the particles is sensitized by adsorption of tin ions. The ions on the surface of the ions are adsorbed, for example, the core material is modified by the surface. The particles may be added to the vaporized tin aqueous solution for a predetermined period of time. Hereinafter, the method for producing the above bl will be described in more detail. The production method can be largely divided into (1) a step of forming a nickel initial film layer A1 on the surface of the core material particles; and (7) The second step of the A2 step of using the particles obtained in the step A1 as a raw material to form the conductive particles. Hereinafter, each step will be described in the step A1, and the dispersant and the nickel are separated from the bath. And mixing the core material particles supporting the precious metal on the surface, forming an initial film layer of nickel on the surface of == 201203287. Mixing the above core material particles with the bath. No electricity __ (4) and dispersion of nickel-free electroless ore The agent may, for example, be non-疋π,,..a 隹 ion interfacial surfactant, zwitterionic boundary agent and/or water-soluble high-eight UT interface knives. Non-ionic surfactant, poly-r- Polyoxyalkylene ethers, surfactants such as alcohols, polyoxyethylene ethers, « ^ . A 虱 vinyl alkyl phenyl ethers. Two etch 2 tartar surfactants, alkyl dimethyl I Beet test, hospital based 曱 曱 ... f f f f 竣 竣 竣 竣 竣 竣 竣 、 竣 竣 竣 竣 竣 f f f f f f f f f f f f f f f f f f f f f f f Polyethylene bite, ethyl cellulose, etc. The amount of dispersant used is φ 〇·5~30g/L depending on the type of liquid (electroless nickel plating bath). In particular, dispersant The amount of use of the liquid (helmet electric 1 recording bath) is in the range of H〇g/L, which can enhance the view of the denseness of the film. And good. Containing ions in the nickel bath without electricity and electricity, using water-soluble salt as the source of the source 1 ^ solubility (four), can be used nickel sulfate or gasification record, but not limited to 3, ',, electroplating The concentration of the nickel ion in the nickel bath is 〇. 0001U(10) Ίΰ* , 、, 升, particularly preferably 0.0001 to 0.005 mol/liter. In the electroless nickel plating bath, a reducing agent may be contained in addition to the above components. The original agent may be used in a 151 bundle with the reducing agent used for the metal ion previously described, and the concentration of the reducing agent in the electroless nickel plating bath is 4χ1〇-, 2. 〇mol/liter, especially 2.0x10_3~0.2 m/d is preferred. In the electroless nickel plating bath, it may further contain a distoring agent. By containing a distoring agent, an advantageous effect of suppressing decomposition of the plating solution can be exhibited. A dismuting agent, 201203287, may be an organic trestic acid or a salt thereof, such as citric acid, glycolic acid, tartaric acid, malic acid, lactic acid or gluconic acid or an alkali metal or ammonium salt thereof. These distorting agents may be used alone or in combination of two or more. The concentration of the distorting agent in the electroless nickel plating bath is 0.005 to 6 m/d, particularly preferably ~1 to 3 m/d. The method of mixing the core material to be treated and the electroless nickel plating bath is not particularly limited. For example, the electroless (four) bath is heated to a temperature at which nickel ions can be reduced, and in this state, the previously treated core material particles are placed in an electroless plating bath. By this operation, the ion reduction is performed, and reduction is caused by the formation of nickel. The initial film layer is formed on the surface of the material ions. The initial film layer has a thickness of G.b.1_, particularly preferably formed as G.b. 5 nm. At this point, the raised portion has not yet been formed. The relationship between the amount of sub- and the amount of core material that is input. Specifically, the concentration of the literary ion of the sword is adjusted to 〇._ι~〇·_m/L, 1Γ1" 005 m/L of the electroless nickel plating bath, using the total surface area to form a core particle . Thereby, it is possible to: = the initial film layer of two degrees. In addition, by preventing the recording from being separated from the beginning (four) to prevent the diameter from being small, for example, the division is a three-phase group I. This is in the core material particles: 'It is particularly effective when the pull k is 3" The reduction of nickel ions is completed, and then proceeds to step A1. Step A2. A2 step q ^ (four) into the 仃. The core of the film layer (4) is not recorded by the liquid (4); the core material with the initial film layer of the jin is in the (four) f raw paddle, and the silver added by the A1 step 16 201203287 remains. · Drag and drop. γ & A n ^ is a core material having a film layer of the beginning of the film obtained in the step A1 of the step A1, and an aqueous slurry containing a dispersing agent for the ai step is added with nickel ions and a reducing agent. The phrase "continuously adding the second system refers to the addition of the recording ion and the reducing agent, and the intention of adding the ion and the reducing agent continuously or intermittently. At this time, the nickel ion and the reducing agent are added. The timing can be exactly the same, or the nickel ion can be added first, and the raw material can be added to the raw material, or the opposite can be added. In addition, the end point of the addition can be terminated first (four), and then the reducing agent is finished. Adding. Alternatively, the nickel source of nickel ion in step A2 can be used in the same manner as the nickel source used in the step A1. The same is true for the reducing agent. The reduction of ions is first generated in the liquid: Nickel nucleus + 4 吏 核 附着 吏 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着body. By adopting this method, the agglomeration of the particles can be effectively prevented, and the aspect ratio of the height of 5 〇 nm or more can be easily formed! Above the raised portion. In the reduction of nickel ions in the A2 step, the aqueous polymer is maintained in the dispersant added in the step A1 (the dispersant also remains in the A2 step). The pH range in which the dispersion effect is exhibited is not & + * _ , target solid Ten important. In this way, it is possible to effectively prevent the particles 4 from being mixed with each other at pH 5, and to observe the acid of the aqueous slurry, and to add an acid such as various mineral acids or a base such as sodium hydroxide to the aqueous polymer. The pH adjustment range is as long as the appropriate value is used in accordance with the dispersant used. For example, when a nonionic surfactant is used as a dispersing agent, the pH of the aqueous slurry is maintained at 17 201203287, preferably in the range of 5 to 10. When using two, the water-based stimulant is maintained at the sub-interface active agent as a dispersant -\7 Temple is preferably in the range of 5 to 8. When using this w w quotient as a dispersing agent, it is also preferable to use 胄 water> gluten. The turbulent enthalpy is maintained at 5 to 8 in the 步骤2 step of nickel ion. The amount of the impurity added to the aqueous slurry and the amount of the reducing agent are most important. · ', -S· , can form the raised core of the width-to-width ratio well. The specific conditions are nickel ions and Kumhe, which are equivalent to a nickel precipitation amount of 2 (four) for a h hour, and "nm, 40 to 60 nm # ', and poetry. By using such an addition condition, In the precipitation of nickel, the core of the raised portion with higher aspect ratio is preferentially formed than the initial thin layer. p The valley is easy to be recorded in the ion and the jin ji 丨 ^ ^, day < — restore (four) add 'may also The water-based slurry is twisted to the temperature of the temple, so that the reduction of the recorded ions by the reducing agent proceeds smoothly. In addition to the addition of the cerium ions and the reducing agent, the aqueous slurry can also be mixed, so that the reduction is recorded. In this way, the object can be coated with particles. Secondly, the manufacturing method of the above $b2 is explained in more detail. In the B1 step of the manufacturing method, the aqueous material of the core material is mixed with the dispersant, Nickel salt, reducing agent and staggering agent without electro-electricity mining bath mixing electroless nickel bonding step. In the B1 step 'the formation of a film on the core material particles will occur at the same time as the self-decomposition of the mineral bath. Because of the self Decomposition occurs in the vicinity of the core material particles. At the time of formation, the self-decomposing material is trapped on the surface of the core material particle to generate a micro-protrusion core, and at the same time, a nickel film is formed. The core of the generated micro-protrusion is used as a base point to grow the convex core. The above-mentioned core material particles are preferably 1 to 5 〇〇g/L, and are sufficiently divided into 18 201203287 5 and more preferably 〇g/L. The usual mixing, high-speed stirring = aqueous slurry can be used. It is also possible to perform 3 colloidal grinding or homogenization by a shearing dispersing device such as a disperser, etc., as needed, in the case of dispersing operation and using ultrasonic powder. Next, electroless nickel plating with a sub-additive containing == addition of a surfactant, etc. Bath, eight kinds of water-based forging materials η · 仃 knife government operation. Add water of core material particles! Raw pulp 进, into the lamp electroless plating B1 step. The above dispersing agent, for example, 卞 surfactant, zwitterionic surfactant And/or a water-soluble polyoxyalkylene ether surfactant such as polyethylene glycol or polyoxyethylene J ion surfactant, which can be prepared with an enalkyl ether or a polyoxyethylene alkyl phenyl ether. Thioglycolic acid betaine, alkyl alkane A sugar beet test surfactant based on monomethyl carboxymethyl acetic acid betaine or alkane methyl amino acetic acid sugar beet. Water solubility: molecular ^ using polyethylene glycol 1 ethylene bite, ethyl The cellulose = the same amount of the granules may be used singly or in combination of two or more. The volume of the dispersing agent 1 is equivalent to the volume of the liquid (the electroless nickel bath). In particular, the use of the dispersing agent The amount of the liquid (electroless nickel plating) is in the range of H〇g/L, which is preferable from the viewpoint of improving the adhesion of the nickel film. The nickel salt can be used, for example, nickel chloride, nickel sulfate or acetic acid. Nickel, the concentration of which is preferably in the range of 1 to 50 g / L. The reducing agent may be, for example, sodium hypophosphite, dimethylamine borane, oxidized sulphate, potassium sulphate or hydrazine, etc. The concentration is preferably in the range of 0.50 g/L. The distoring agent may, for example, be citric acid, glycolic acid, tartaric acid, malic acid, lactic acid or gluconic acid or an alkali metal thereof. 19 201203287 carboxylic acid (salt) such as salt or ammonium salt, amino acid such as glycine, and A compound of a diamine-aminoamine 4, an amine, an EDAT or a pyrophoric acid (salt), which has a staggering effect on a locked ion, and these may be used in two or more kinds. The concentration is preferably 100 g/L, more preferably 5 to 50 g/L. At this stage = the preferred pH of the electroplated nickel bath is in the range of 14 private. The electroless plating reaction, when the aqueous slurry of the core particles is added, starts rapidly, accompanied by the generation of hydrogen. The electroless plating B1 step was completed when it was completely impossible to confirm the generation of the hydrogen gas. Next, in step B2, the M step is followed by using an i-th aqueous solution containing a nickel salt, a reducing agent, and a base, and a second aqueous solution containing the remaining two kinds; or (1) a nickel-containing salt. The aqueous solution of i, the second aqueous solution containing the reducing agent, and the aqueous solution containing the test (IV) 3 are simultaneously and continuously added to the liquid of the step (IV) to carry out the electroless gold ore. When the liquid is added, the electromineral reaction starts again, but the formed nickel coating can be controlled to a desired film thickness by adjusting the amount of addition. After the addition of the electroless nickel plating bath was completed, it was not until the hydrogen gas generation was completely confirmed, and the liquid temperature was maintained for a while, and stirring was continued to complete the reaction. For the base, for example, the above-mentioned (ii) may be used. In the case of the above, the first aqueous solution containing the recorded salt is used, and the second solution containing the reducing agent and the alkali is #, but is not limited thereto. When the first aqueous solution does not contain a reducing agent and the test, the second aqueous solution does not contain a salt. The nickel salt and the reducing agent can be the same as the hydroxide of the alkali metal such as sodium or potassium hydroxide described above. The aqueous solution contains the above-mentioned (ii), in the second to the 20th 201203287 reducing agent, and in each of the two components other than the component in the aqueous solution, or (U), the aqueous solution The concentration of the nickel salt is 5 ". The second 'is especially 10 (1~3〇〇g/L is preferred. The concentration of the reducing agent is ', especially 50~90〇g/L is preferred. The concentration is in the heart of the Qing, especially in the case of 2. L. The step B2 can be carried out continuously after the end of the step B1, but it can also be replaced by the method of "interrupting the steps 1 and 2", , the core material particles and 』:, the 4 material particles are redispersed in the water to prepare the aqueous agent Bu 100g / LA Du r 対 This will be mis-', ', ~ 5 〇 g / L better concentration range of dissolved water> gluten solution added 1 dispersant to .. 5, g / L... The total rough confession, s ^ zhang Jia's Fan Wei, in the aqueous slurry is added to the above-mentioned respective aqueous solution of the B2 step of the 沬 I, κ 枣 jujube method. Thus can be obtained 锑 锑 粒子 particles. 'In the Μ and b2 掣i raw side, the car is made using a ball milled pulverized bovine 2 can be coated with zinc particles of nickel's granules: the pulverization step, can be monodispersed... 'by recording the monodisperse The coated particles are used as the post-discipline film, and in addition, the surface of the first-time fun... can also be the proportion of the ore, which lies in the weight of the electric power shovel palladium---the powder. Therefore, the above range is in the present invention, and the manufacturing method of bl does not depend on (4) it can be effectively used, but in particular, the material of the core material of the average particle diameter of the core material particles is 4 u < Do I electric '" ^ electroplating brocade to obtain a method with a raised core 21 201203287 effect. Another effective method. Another _ aspect, the heart manufacturing method 'for 3, " m relatively large core particles to do electro-electricity recording, to obtain a case with a raised core of the coated particles, special Further, in the presence of a dispersing agent, electroless plating of palladium is carried out, and the conductive powder of any of the following (D1) to (D3) can be obtained by the nickel-coated granules thus obtained. (D1) A method of reducing electroless palladium plating by a pure palladium plating bath. (D2) is a reduction type electroless plating palladium treatment using phosphorous acid or a salt thereof as a reducing agent, so that the molar ratio of the reducing agent to palladium ions is 〇 . 丨 ~ 丨 to do a reduction-type electroless plating palladium treatment method. (D3) A method of replacing the type of electroless recording. The above-mentioned (D1) and (D2) reduced electroless palladium plating method is a method in which palladium ions in a plating solution are deposited on a nickel film by a action of a reducing agent. Then, in the plating method of (D1), an electroless plating palladium film having a purity of 9 9% or more can be obtained by using, for example, a formic acid compound as a reducing agent, and on the other hand, a reduced electroless palladium plating of (D2) By using sodium hypophosphite or a salt thereof as a reducing agent, a plated film composed of a palladium-phosphorus alloy can be obtained. Hereinafter, a method of performing reduction-type electroless plating of palladium by a pure palladium plating bath of (D1) will be described. The pure palladium plating bath is composed of an aqueous solution containing a palladium compound, a reducing agent and a distoring agent as essential components. In the present invention, a pure palladium plating bath containing a dispersing agent and the above nickel-coated particles is subjected to a reduction-type electroless plating palladium treatment. The above-mentioned compound is not particularly limited as long as it is soluble in the mineral liquid and can be obtained at a specific concentration of 22 201203287 aqueous solution. For example, a water-soluble palladium compound such as palladium sulfate, palladium vapor, palladium nitrate, palladium acetate, palladium ethylenediamine or palladium tetraamine di palladium can be used. These may be used alone or in combination of two or more. Further, the sigma may be used as a solution which will be solutionized. For the solution, for example, an ethylenediamine vaporized palladium solution or a tetraamine palladium dichloride solution can be used. The content of the pure palladium forging bath compound, palladium is preferably 〇· Bu 30g/L, preferably 〇. 3~1 〇g/L. The reducing agent is used with formic acid or a salt thereof. The content of the reducing agent in the pure palladium plating bath is preferably 〇·100 g/L, more preferably 5 〇g/L. a distorting agent, for example, an amine such as ethylenediamine or diethylenetriamine; and an amine group such as amine diacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc., Sodium salt, potassium salt, recorded salt; glycine acid, alanine, imino-monoacetic acid, nitrile triacetic acid, L-glutamic acid, L-glutamic acid 2 B ^ L-aspartic acid, taurine, etc. Amino acid, such sodium salt, : salt, ammonium salt; aminotrimethylene phosphonic acid, hydroxyethylidene], diphosphonium tetramethylene phosphonic acid, such ammonium salts, unloading Salt, sodium salt. The oxime may be used singly or in combination of two or more. The content of the distorting agent in the pure palladium plating bath is preferably from 5 to 1 (degree) g/L, more preferably from 5 to 50 g/L. * The administrator may, for example, be a nonionic surfactant, a zwitterionic interface, an alcohol owing to an intercondylar molecule. As the nonionic surfactant, a polyoxyalkylene ether such as polyethylene, an oxyethylene ether, or a polyoxyethylene phenyl ether can be used. As the zwitterionic surfactant, a betaine-based surfactant such as alkyldimethylcarbamate, a hospital-based dimethyl betacetic acid beet test, or a dimethyl dimethylamine 23 201203287-based acetic acid betaine can be used. As the water-soluble polymer, polyvinyl alcohol or polyethylene can be used. Bilobidine, hydroxyethyl cellulose, and the like. 5〜30克/L。 The volume of the liquid (pure palladium plating bath) is 0. 5~30g / L. In particular, the amount of the dispersant used in the liquid (pure palladium plating bath) is in the range of l〇g/L, which improves the adhesion of the palladium film and suppresses the effect of producing agglomerated particles. good. The pH of the electroless plating palladium reaction is preferably from 3 to 10, particularly from 4 to 7, so that the precipitation rate of the privet is good. For the adjustment of pH, for example, sulfuric acid, hydrochloric acid, sodium hydroxide, aqueous ammonia or the like can be used. The reaction temperature is preferably 2 to 9 (rc, particularly 40 to 80 t, which is preferable from the viewpoint of a smooth and dense film. Further, the pure palladium plating bath may contain a usual additive such as a stabilizer. For the pure palladium plating bath containing such an additive, commercially available products such as Koji Co., Ltd., Koji Chemical Co., Ltd., and Chuo Chemical Industry Co., Ltd., etc., may be used. Next, the use of hypophosphorous acid or (D2) may be described. a method of reducing electroless plating using a salt as a reducing agent. (D2) a mineral bath using a (four) clock bath. The carbon-plating bath is a reducing agent comprising a reducing compound, hypophosphorous acid or a salt thereof, and The distorting agent is composed of an aqueous solution of an essential component. In the present invention, the palladium-phosphorus plating bath is mixed with a dispersing agent and the nickel-coated particles to carry out a reduction-type electroless ore Ι ε treatment. Palladium. The distoring agent and the dispersing agent can be used in the same manner as in the method of reducing the electroless key of the above). The method of reducing the bond of (D2) is carried out by adjusting the amount of phosphorus in the mask of the reducing agent to adjust the amount of ions in a specific (four). In general, 24 201203287 The phosphorus content in the palladium mask increases as the amount of the sodium sulfonate or its salt of the reducing agent increases. The reduced electroless plating of palladium (D2) makes it preferable to set the molar ratio of the reducing agent to palladium ions to a range lower than the previous one. That is, 'by adjusting the molar ratio of the reducing agent to the palladium ion to 〇. 〇〇1 〇〇 to reduce the electroless palladium treatment, the ruthenium content in the palladium film can be adjusted to 3% by weight or less. ~3% by weight is preferred. When the amount of the palladium ion added to the reducing agent is less than 0.1 in the molar ratio, the precipitation rate is lowered and it is not practical. On the other hand, when the amount is larger than 100, the phosphorus content in the palladium film is more than 5% by weight as described above. However, a palladium film having a phosphorus content of 3% by weight or less was not obtained. In particular, in the present invention, it is preferred that the molar ratio of the reducing agent to palladium ions is in the range of 1 to 3 Torr. The pH of the above electroless plating palladium-phosphorus reaction is preferably 5 to 10, more preferably 5 5 to 9. By setting the pH in this range, the stability of the plating solution can be improved, and defects such as cracks in the palladium film are less likely to occur. For the adjustment of pH, for example, sulfuric acid, hydrochloric acid, sodium hydroxide, ammonia water or the like can be used. The reaction temperature is 25 to 8 ° C, especially 40 to 7 (rc is preferable from the viewpoint of obtaining a smooth and dense film. Further, the palladium-phosphorus plating bath may also contain a stabilizer, etc. For the palladium-phosphorus plating bath containing such an additive, commercially available products such as Komaki Chemical Co., Ltd. and Ishihara Pharmaceutical Co., Ltd., etc., may be used. Next, a method of replacing electroless plating of palladium according to (D3) will be described. In the method of replacing electroless palladium electroplating in (3) 3), a substitutional electroless plating palladium is formed by displacement of palladium ions and nickel ions to form a palladium-plated film on the nickel-coated particles. The replacement electroless plating palladium bath is composed of an aqueous solution containing a palladium compound and a distoring agent as essential components. In the present invention, the replacement type non-electricity is used. The 2012-03287 key/valley contains a dispersing agent and the above-mentioned nickel-coated rough is subjected to a replacement type without electricity and electricity. The compound, the compound, and the dispersing agent may be used in the same manner as in the method of reducing electroless palladium electroplating of the above (D1). A palladium compound, particularly a tetraamine-based palladium salt, is preferred because a dense palladium film is obtained. The substitution type electroless plating palladium reaction is preferably carried out at pH 3 to 1 (), particularly at pH 4 to 8, to obtain a smooth and dense film. For the adjustment of pH, for example, sulfuric acid, hydrochloric acid, sodium hydroxide, ammonia water or the like can be used. The reaction temperature is 25 to 8 ° C, particularly 30 to 70 t, and the reaction rate can be made practical, and it is preferable to obtain a dense palladium film. After the completion of the above-mentioned (D1) to (D3) key-bonding reaction, the mixture was separated and dried by a usual method to obtain a conductive powder. If necessary, the conductive powder may be used as the method for producing the above-mentioned nickel-coated particles, and a pulverization step of a ball mill may be used. By the mashing step, the ratio of the weight of the primary particles to the conductive powder can be more easily set within the above range. The conductive particles of the present invention thus obtained can be suitably used for, for example, an anisotropic conductive film (ACF) or a heat seal connector (H sc), and an electrode for connecting an electrode of a liquid crystal display panel to a circuit substrate for driving the LSI wafer. Materials, etc. In particular, the conductive powder of the present invention can be suitably used as a conductive filler for a conductive adhesive. The conductive adhesive is an anisotropic conductive adhesive which is disposed between two substrates on which a conductive substrate is formed and which is electrically connected to the conductive substrate by heat and pressure. The anisotropic conductive adhesive comprises the conductive particles of the present invention and an adhesive resin. The binder resin may be used as an adhesive resin as long as it is insulating and can be used as an adhesive resin, and can be used without particular limitation. Both the thermoplastic resin and the thermosetting resin may be used to exhibit the subsequent properties by heating. Examples of such an adhesive resin include a thermoplastic type, a heat-hardening type, and an ultraviolet curing type. Further, a so-called semi-thermosetting type, a thermosetting type, and an ultraviolet curing type which are intermediate between the thermoplastic type and the heat-hardening type are shown. These subsequent riding can be suitably selected in accordance with the surface characteristics or the type of use of the circuit substrate or the like to be adhered. In particular, it is preferable that the adhesive resin is composed of a thermosetting resin and the material is excellent in strength. The binder resin, specifically, may be selected from the group consisting of ethylene-vinyl acetate copolymer, buffer-based modified ethylene-acetate copolymer, ethylene-isobutyl acrylate copolymer, polyamine, poly醯imine, polyester, vinyl ether, (iv) 'polyurethane' SBS block polymer, fluorenyl modified copolymer, SIS copolymer, SEBS copolymer, maleic acid modified SEBS copolymer, polybutylene rubber, Air pentylene rubber, slow-base denaturing gas pentane rubber, styrene-butadiene rubber, isobutylene-isoprene copolymer, propylene guess-butadiene rubber (hereinafter referred to as biliary .), a combination of a slow-denatured nbr, an amine-denatured NBR, an epoxy resin, an epoxy vinegar resin, an acrylic tree, a resin, or a lye resin, etc. By. Among these, the thermoplastic resin is excellent in reworkability such as styrene-butadiene rubber or SEBS. The thermosetting resin is preferably an epoxy resin because it has a high adhesion force, excellent heat resistance and electrical insulating properties, and has a low viscous viscosity and can be connected at a low pressure. As the epoxy resin, as long as it is a polyvalent epoxy resin having two or more ring 27 201203287 oxy groups in the i molecule, an epoxy resin generally used can be used. Specifically, 'polyphenols such as phenolic phenolic phenolic phenolic phenolic phenol, bisphenol fluorene, bisphenol F, bisphenol AD, resorcinol, dihydroxy diphenyl ether, and the like can be exemplified, and ethylene glycol is used. Polyols such as neopentyl glycol, glycerin, trimethylenepropane, and polypropylene glycol, polyamine compounds such as ethylenediamine, triethylenetetramine, and aniline, adipic acid, o-dibenzoic acid, and isophthalic acid A glycidyl type epoxy resin obtained by reacting a polyvalent carboxyl compound such as formic acid with epoxy propylene or 2-methyl epoxide. Further, an aliphatic or alicyclic epoxy resin such as a dicyclopentadiene epoxide or a butadiene dipolyoxide. These may be used alone or in combination of two or more. Further, as the above-mentioned various resin, a high-purity product which reduces impurity ions (such as Na or Cl) or a hydrolyzable gas is used, and it is preferable to prevent ion migration. The amount of the conductive particles of the present invention in the case of the anisotropic conductive adhesive is generally 〇. 30 to 30 parts by weight of the adhesive resin component, preferably 0.5 to 25 parts by weight, and the weight of the weight is 2 Better department. When the amount of the conductive particles used is within this range, the contact resistance or the melt viscosity can be suppressed, the connection reliability can be improved, and the anisotropy of the connection can be sufficiently ensured. In addition to the above-mentioned conductive particles and the binder resin, the above-mentioned anisotropic conductive adhesive may be a conventional additive in the technical field, and the blending amount thereof may be within the range known in the art. Other additives may, for example, be an adhesion-imparting agent, a reactive auxiliary agent, an epoxy resin hardener, a metal oxide, a photoinitiator, a sensitizer, a hardener, a vulcanizing agent, a deterioration inhibitor, and a heat-resistant additive. , heat conduction enhancer, softener, colorant ' 28 201203287 various coupling dense I 丨 +, 1 p Qi Qi metal inert agent. Pine, and *Dream (four) pre-agents can be rosin, rosin derivatives, pine oil thin resin, ·: phenol resin, petroleum resin, coumarone - enamel resin, styrene resin', olefinic resin, alkyl phenol resin , xylene resin, etc. Reactive agent 'is used as frame rub #|丨H, cyanamide resin, urea tree: such as 7, iso-acid vinegar, trimeric hydrazine /, urotropine, amines, acid anhydride, peroxidation Things and so on. The epoxy resin hardener can be used without particular limitation as long as it has two or more molecules: 11 hydrogen. Specifically, f, for example, divinyl"-ethylenetetramine, m-diamine, dicyandiamide, polyethylenediamine, etc., poly(alkyl) phthalic anhydride, methyl nadic anhydride, hexahydroortho An organic acid anhydride such as benzene-xanthene tetracarboxylic acid hydrazine; These may be used alone or in combination of the above. This can also be used as a latent hardener depending on the application or as needed. Examples of the latent curing agent that can be used include imidazole, anthraquinone, boron trifluoride-amine complex, sparing salt, amidated imine, salt of polyamine, dicyandiamide, and the like. Denatures. These may be used singly or in combination of two or more kinds. In the above-mentioned anisotropic conductive adhesive, the conductive particles and the adhesive of the present invention can be blended with a curing agent or various additives as needed, and the adhesive resin can be usually used in a manufacturing apparatus which is widely used by the manufacturer. In the case of a thermosetting resin, the thermoplastic resin is mixed in an organic solvent at a temperature higher than the softening point of the adhesive resin, specifically, about 50 to 130. (It is preferably a degree of about 60 to 110 〇c. It is produced by melt-kneading. The anisotropic conductive adhesive obtained in this manner can be applied or used as a film. 29 201203287 [Examples] The present invention will be described in more detail by way of examples. However, the scope of the present invention is not limited to the examples. Unless otherwise specified, "%" means "% by weight". (1) The A1 step uses a spherical styrene-cerium oxide composite resin having a true specific gravity of 1.1 [average particle size 3//m', manufactured by Nippon Shokubai Co., Ltd., trade name s〇u〇STAR, The coefficient of variation = · V) 3. 2%] as the core material particles (the total surface area of 1 L equivalent is 5.46 m). Stir the 9g' into the 4" aqueous solution of the modifier and the "CLEANER c〇nmti〇ner 23" made of HAAS electronic material. The enthalpy of the aqueous solution of the regulator; ^4 nm / τ, morning density of 40 ml / L) Then, the surface of the core material particles is modified and dispersed by applying ultrasonic waves for 30 minutes at a liquid temperature of 6 〇t. The aqueous solution is passed through a core material which is washed once and washed again to make a profit. The slurry was subjected to a chlorinated aqueous solution of 2 〇〇mi. The concentration of the aqueous solution was 、, /, at room temperature for a minute, and the sensitization treatment was performed to adsorb the tin ions on the surface of the riding particles. Then wash the water again, then use the core material particles as the slurry of the ship, keep it at 60C, and mix it with ultrasonic wave, add 2 to '0. llm〇1/L. Keep the mixing state for 5 minutes. The activation treatment of palladium ions is captured on the surface of the core material particles. Next, the poems 2Gg/L__, 5. the rails of the nanometer, and the sulfuric acid recorded hexahydrate (the water-free electroless core 3L consisting of the aqueous solution ^Am: / 30 201203287 电镀 Electroplating bath, put into the core material of palladium 9g, step A1 starts. Confirmed stirring for 5 minutes the hydrogen bubbling ended, the completion of the step A1. (2) A 2 step
分別使用300mL包含224g/L的硫酸鎳水溶液、210g/L 次亞磷酸鈉及80g/L氫氧化鈉之混和水溶液，將該等對Αι 步驟所得之芯材粒子之漿料，以定量幫浦分別連續添加， 開始無電電鍍A2步驟。添加速度均為2. 5mL/分。再者， 由開始滴入時至結束滴入之pH為5. 8〜6. 2，每i小時之鎳 析出量為48nm。將液全量添加後，保持於7〇°c的溫度持續 攪拌5分鐘。接著將液過濾，將過濾物清洗3次後以i 〇 〇 C的真空乾燥機乾燥，得到具有錄_鱗合金披膜之鎳彼覆粒 子試料N1。 [鎳披覆粒子試料N2之調製] (1)B1步驟 對用於製作N1時之芯材粒子進行與a 1步驟相同的表 面改質處理，進行於芯材粒子的表面捕捉鈀之活化處理。 接著’將溶解20g/L的酒石酸鈉、4.5g/L之硫酸錄六水合 物、5.4g/L之次亞磷酸鈉、及5g/L之聚乙二醇之水溶液 所組成之無電電鍍浴3 L升溫為7 0 °C，對該無電電鑛浴， 投入擔持鈀之芯材粒子9g，開始B1步驟。授拌5分鐘破 認氫氣的發泡停止，完成B1步驟。 (2)B2步驟Using 300 mL of a mixed aqueous solution containing 224 g/L of a nickel sulfate aqueous solution, 210 g/L of sodium hypophosphite, and 80 g/L of sodium hydroxide, respectively, the slurry of the core particles obtained by the steps of the above steps was quantitatively pumped separately. Add continuously and start electroless plating A2 step. 5毫升每分。 The addition speed is 2. 5mL / min. The amount of nickel precipitated per hour was 48 nm, from the time of the start of the dropwise addition to the end of the pH of 5. 8~6. After the whole amount of the solution was added, the mixture was kept at a temperature of 7 ° C for 5 minutes. Then, the liquid was filtered, and the filtrate was washed three times, and then dried in a vacuum dryer of i 〇 〇 C to obtain a nickel-coated particle sample N1 having a film of a scale alloy. [Preparation of nickel-coated particle sample N2] (1) Step B1 The core material particles used for the production of N1 were subjected to the same surface modification treatment as in the a1 step, and the activation treatment of palladium on the surface of the core material particles was carried out. Then, an electroless plating bath 3 which dissolves 20 g/L of sodium tartrate, 4.5 g/L of sulfuric acid recorded hexahydrate, 5.4 g/L of sodium hypophosphite, and 5 g/L of polyethylene glycol is prepared. The temperature of L was increased to 70 ° C, and 9 g of palladium core material particles were charged into the electroless ore bath, and the step B1 was started. The mixing of the hydrogen gas was stopped for 5 minutes to complete the B1 step. (2) Step B2
分別使用300mL包含224g/L的硫酸鎳水溶液、21〇g/L 认亞鱗納及80g/L風乳化納之混和水溶液，將該等對μ 31 201203287 步驟所得之芯材粒子之漿料，以定量幫浦分別連續添加， 開始無電電鍍B2步驟。添加速度均為2 5mL/分。將液全 量添加後，保持於7 〇 C的溫度持續攪拌5分鐘。接著將液 過濾，將過濾物清洗3次後，以1 〇〇t：的真空乾燥機乾燥， 得到具有鎳-磷合金彼膜之鎳披覆粒子試料N2。 [鎳披覆粒子試料N 3之調製（比較品）] 對用於製作N1時之芯材粒子進行與A1步驟相同的表 面改質處理，於芯材粒子的表面捕捉鈀後，邊攪拌投入加 溫為65°C之裝有20g/L酒石酸鈉及5g/L聚乙二醇之水溶 液3L，充分攪拌分散調製水性漿料後，分別使用3〇〇π^包 含224g/L的硫酸鎳水溶液、21〇g/L次亞磷酸鈉及8〇g/L 氫氧化鈉之混和水溶液。添加速度為5mL/分。將液全量添 加後，保持70°C的溫度持續攪拌5分鐘。接著將液過濾， 將過濾物清洗3次後，以1 〇〇t的真空乾燥機乾燥，得到 具有鎳-磷合金披膜之鎳彼覆粒子試料N3。以該方法得到 平滑性優良的披膜。 [鎳彼覆粒子試料N4之調製（比較品）] 對用於製作N1時之芯材粒子進行與A1步驟相同的表 面改質處理，進行於芯材粒子的表面捕捉|巴之活化處理。 接著，於鍍液中不添加聚乙二醇以外，以與製作N2時同樣 的操作，得到具有鎳_磷合金彼膜之鎳披覆粒子試料N4。 [鎳披覆粒子之物性評估] 分別將鎳披覆粒子N卜N4之平均粒徑，鎳彼膜之厚 度，鎳披膜之密著性測定，評估。此外，分別測定高度為 32 201203287 之凸起部芯 。將該等之 5〇nm以上的凸起部芯體的個數，高度為5〇nm 體之高寬比。各物性的評估係以如下方法進行 結果不於表1。 [鎳披膜之厚度] 於王水將鎳披膜溶解，將披膜的 以下式（3)及（4)算出鎳披膜的厚 將錄披覆粒子，浸潰 成分以ICP或化學分析， 度0 A=[(r + t)3-r3]d1/r3d2 ⑻ A=W/(l〇〇-W) (4) 式中，r為芯材粒子之半徑（以…，t為鎳披膜的厚度， di為鎳披膜的比重’ d2為芯材粒子之比重，w為鎳含率（重 量％)。 [凸起部芯體的個數及高寬比] 使用SEM，將鎳披覆粒子放大3〇〇〇〇倍以觀察1〇視野， 算出鎳披覆粒子之1個所具有的高度5〇nffl以上之凸起部芯 體之個數，及高度50nm以上之凸起部芯體之高寬比之平均 值0 [鎳披膜之密著性] 於lOOmL燒杯放入2g鎳彼覆粒子及90g直徑lmm的氧 化锆球，進一步放入10mL甲苯。以攪拌裝置攪拌1〇分鐘 後，將氧化锆球與漿料分離乾燥。將乾燥後的鎳披覆粒子， 使用SEM放大為2000倍觀察10視野，算出藉由攪拌所生 成之剝離片之個數之平均值。剝離片之個數未滿1〇個以 〇’ 1 0〜3 0個以△，超過3 0個以X評估。 33 201203287Using 300 mL of a mixed aqueous solution containing 224 g/L of a nickel sulfate aqueous solution, 21 〇g/L of sub-squamous sodium and 80 g/L of air-emulsified sodium, respectively, the slurry of the core material particles obtained by the step 51 201203287 is used. The quantitative pumps are continuously added separately, and the electroless plating B2 step is started. The addition rate was 2 5 mL/min. After the whole amount of the solution was added, the mixture was kept at a temperature of 7 〇 C for 5 minutes. Subsequently, the solution was filtered, and the filtrate was washed three times, and then dried in a vacuum dryer of 1 〇〇t: to obtain a nickel-coated particle sample N2 having a nickel-phosphorus alloy film. [Preparation of nickel-coated particle sample N 3 (Comparative product)] The core material particles used for the production of N1 were subjected to the same surface modification treatment as in the step A1, and palladium was trapped on the surface of the core material particles, and then stirred and added. The aqueous solution containing 20 g/L sodium tartrate and 5 g/L polyethylene glycol at a temperature of 65 ° C is fully stirred and dispersed to prepare an aqueous slurry, and then each of 3 π π contains 224 g/L of a nickel sulfate aqueous solution. A mixed aqueous solution of 21 〇g/L sodium phosphite and 8 〇g/L sodium hydroxide. The addition rate was 5 mL/min. After the entire amount of the solution was added, the temperature was maintained at 70 ° C for 5 minutes. Then, the solution was filtered, and the filtrate was washed three times, and then dried in a vacuum dryer of 1 Torr to obtain a nickel-coated particle sample N3 having a nickel-phosphorus alloy coating. In this way, a film having excellent smoothness is obtained. [Preparation of nickel-coated particle sample N4 (Comparative product)] The core material particles used for the production of N1 were subjected to the same surface modification treatment as in the step A1, and subjected to surface activation of the core material particles. Next, a nickel-coated particle sample N4 having a nickel-phosphorus alloy film was obtained in the same manner as in the case of producing N2 except that polyethylene glycol was not added to the plating solution. [Evaluation of physical properties of nickel-coated particles] The average particle diameter of the nickel-coated particles Nb, N4, the thickness of the nickel film, and the adhesion of the nickel film were measured and evaluated. In addition, the raised cores with a height of 32 201203287 were measured separately. The number of the raised cores of 5 〇 nm or more and the height is the aspect ratio of the body of 5 〇 nm. The evaluation of each physical property was carried out in the following manner. The results are not shown in Table 1. [Thickness of Nickel Film] The nickel film is dissolved in Wangshui, and the thickness of the nickel film is calculated by the following formulas (3) and (4) of the film, and the coated particles are coated, and the impregnated components are analyzed by ICP or chemical analysis. Degree 0 A=[(r + t)3-r3]d1/r3d2 (8) A=W/(l〇〇-W) (4) where r is the radius of the core particle (with ..., t is nickel) The thickness of the film, di is the specific gravity of the nickel film, d2 is the specific gravity of the core material particles, and w is the nickel content (% by weight). [Number and height-to-width ratio of the core of the raised portion] Nickel is coated with SEM The coated particles were magnified 3 times to observe a 1 〇 field of view, and the number of raised cores having a height of 5 〇 nff or more of one of the nickel coated particles and the height of the raised portion having a height of 50 nm or more were calculated. Average value of aspect ratio 0 [Adhesion of nickel film] 2 g of nickel-coated particles and 90 g of zirconia balls of 1 mm diameter were placed in a 100 mL beaker, and 10 mL of toluene was further added. After stirring for 1 minute, the stirring device was used. The zirconia balls and the slurry were separated and dried, and the dried nickel-coated particles were magnified by SEM to 2000 times to observe 10 fields of view, and the average value of the number of peeling sheets produced by stirring was calculated. In less than a few square 1〇 '0 to 1 0~3 △, 0 to more than 3 X evaluation. 33201203287
[表1] 鎳彼覆粒子試料 N1 N2 N3 N4 平均粒徑（y π〇 3.2 3.2 3.2 3.8 鎳披膜之厚度(nm) 96 97 95 96 鎳披膜的密著性 〇 〇 〇 Δ 50nm以上的 凸起部芯體 個數 20 8 0 7 高寬比 1.23 0.65 一 0.65 [實施例1至3 ] 調製由 10g/L 的 EDTA-2Na、10g/L 檸檬酸-2Na 及 20g/L 的四胺基二氯化鈀（Pd(NH3)4Cl2)溶液（以鈀為2g/L)、叛曱 基纖維素（分子量250000，醚化度0. 9)10 Oppm所組成之無 電電鑛纪液。將該錄把液0.65公升（實施例1)，1.3公升（實 施例2) ’ 2. 6公升（實施例3)加熱為70。(：。將此邊攪拌， 添加1 0g上述所得鎳披覆粒子試料（N1)。藉此於粒子的表 面進行無電電鍍處理。處理時間為6〇分鐘。處理結束後， 將液過濾’將過濾物再漿3次。接著以11 〇它的真空乾燥 機乾燥。如此地’於鎳-磷合金披膜上施以鍍鈀披覆處理。 [實施例4 ] 調製由10g/L乙二胺、i〇g/L曱酸鈉及2〇g/L四胺二 氣化鈀（Pd(NH3)4Cl2)溶液（以鈀為2g/L)、羧甲基纖維素（分 子量250000,醚化度0.9)1 〇 〇ppm所組成之無電電鍍鈀液。 將該鍍鈀液1.3公升加熱為7(rc。將此邊攪拌，添加1〇g 上述所得鎳彼覆粒子試料（N1)。藉此於粒子的表面進行無 電電鍍處理。處理時間為30分鐘。處理結束後，將液過渡， 之後進行與實施例1同樣的步驟，於鎳_磷合金披膜上施以 34 201203287 y 鍍鈀披覆處理。 [實施例5 ] 調製由10g/L乙二胺、50g/L次亞磷酸鈉及2〇g/L四 胺二氯化鈀（Pd(NH3)4Cl2)溶液（以鈀為2g/L)、羧甲基纖維 素（分子量250000，醚化度〇.9)100ppm所組成之無電電鍍 鈀-磷液。將該鍍鈀液1.3公升加熱為5〇t。將此邊攪拌: 添加l〇g上述所得鎳披覆粒子試料（N1)。藉此於粒子的表 面進行無電電鍍處理。處理時間為3〇分鐘。處理結束後， 將液過濾，之後進行與實施例丨同樣的步驟，於鎳_磷合金 披膜上施以鍍鈀披覆處理。 [實施例6及7 ] 使次亞磷酸鈉的濃度為10g/L(實施例6)，25g/L(實施 例7)以外，進行與實施例5同樣的操作，於鎳合金披膜上 施以鍵把-填彼覆處理。 [實施例8至1 〇 ] 使鎳披覆粒子為N 2以外，進行與實施例2、實施例4、 實施例5同樣的操作，於鎳—磷合金披膜上施以鍍鈀彼覆處 理。 [比較例1至3 ] 使鎳彼覆粒子為N3以外，進行與實施例2、實施例4、 實施例5同樣的操作，於鎳—磷合金披膜上施以鍍鈀彼覆或 鑛把-填披覆處理。 [比較例4至6 ] 使鎳彼覆粒子為N4以外，進行與實施例2、實施例4、 35 201203287 實施例5同樣的操作’於鎳_磷合金披膜上施以鍍鈀披覆或 鍍鈀-磷披覆處理。 [比較例7 ] 使人亞磷k納的濃度為2 〇 〇 g / [以外，進行與實施例5 同樣的操作，於鎳合金披臈上施以鍍鈀_磷披覆處理。 [參考例1(鍍金）] 調製由10g/L的EDTA_4Na、1〇g/L獰檬酸_2Na及 9g/L的氰化金鉀（以金為2.〇g/L)所組成之無電電鍍金 液。將該鍍金液2公升加熱為79t。將此邊攪拌，添加1〇g 錄披覆粒子N卜藉此於粒子的表面進行無電電鍍處理。處 理時間為2G分鐘。處理結束後，將液過減，將過遽物再聚 3次。接著以U〇t的真空乾燥機乾燥。如此地，於鎳-磷 〇金披膜上施以鐘金披覆處理。 [導電性粉體之物性評估] 將實施例、比較例及參考例所得導電性粒子之平均粒 徑、錄披膜的厚度、把披膜的厚度、金披膜的厚度、纪披 膜中的磷含量、高度50nm以上的凸起部的個數、高度50nra 5上的凸起部的高寬比、—次粒子所佔比例，分別測定. 评估。將該等結果’示於以下表2。此外，分別測定砰 T披膜或金披膜的密著性、導電性、短路的發生（電性可 罪度）、電阻值。將續笼处里，_# 值將该專結果，π於以下表3。再者 Π = Γ高度5°nm以上的凸起部的個數、高度5 — 以上的凸起部的高窗比、^妯 门見比鈀披臊或金披膜的密著性# 上述鎖被膜同樣的方法測定，。此外，鎖披膜的:;與 36 201203287 鈀披膜的厚度、金披膜的厚度、鈀披膜中的磷含量、導電 I1生短路的發生（電性可靠度）、電阻值係如下測定.評估。 [鑛把或鍍金後的鎳披膜的厚度] 將導電性粒子，浸潰於王水將金屬彼膜溶解，將披膜 的成分以ICP或化學分析，以下式（5)及（6)算出鎳披膜的 厚度。 A=[(r + t)3-r3]di/r3d2 ⑸ A=W/(l〇〇-X) (6) 式中，r為芯材粒子之半徑（# m)，t為鎳披膜的厚度， 心為鎳彼膜的比重，&為芯材粒子之比重，w為鎳含率（重 量％) ’ X為金或纪之含率。 [金披膜.鈀彼膜之厚度] 將導電性粒子，浸潰於王水將金或鈀披膜溶解，將披 膜的成分以ICP或化學分析，以下式（7)及（8)算出金或鈀 彼膜的厚度。 B=[(r + t + u)3-(r + t)3]d3/(r + t)3d4] (7) B=X/(100-X) (8) 式中，u為金或鈀之含率（重量％)，心為金或鈀披膜的 比重，eh為Νι品之比重，X為金或鈀之含率（重量。在 此，N1品的比重&係使用計算式。比重係以如下（9)的計 算式所算出。 d4=100/[(W/d.)+(l〇〇-ff)/d2] (9) [鈀披膜中的磷含量] 將紀披覆前的鎳粒子浸潰於王水使鎳彼膜溶解，將披 37 201203287 膜成分以ICP或化學分析，算出金 π…干 進—步將ΐε枯 覆厚的粒子之鎳、纪披膜溶解後， τ散犋成分以ICP或化 學分析’算出金屬化率，以如下式苴 下式算出鈀披膜t的磷含量。 錄披覆粒子中的峨含量（g) C = VxYi/l 〇〇 (10) 鈀披覆粒子中的磷含量（g) D=V/(l-ff/l〇〇)xY2/i〇〇 (11) 把披覆粒子中的I巴含量（g) E=V/(l-W/l〇〇)-V (12) 因此Ιε披膜中的碌含率E(重量％)為 F=(D-C)/(D-C+E)xl〇〇 (13) 在此，V係鈀處理前的鎳披覆粒子之重量（g) , L係鎳 披覆粒子之碟含率（重量％)，[係㈣覆粒子之璘含率^重 量%)’ 麵之金屬化率。惟在此，由於來自錄披膜之録 及磷的溶出非常的少’故當作〇計算。 [導電性、短路的發生（電性可靠度）、電阻] 將環氧樹脂1 〇 〇部、硬化劑i 5 〇部、甲笨7 〇部混合， 令製、邑緣陡接著劑。對此調合導電性粒子】5部得到糊料。 :用棒土佈機’將該糊料塗佈於矽膠處理之聚酯膜上使之 乾燥。使用所得塗層膜’與於全面以紹蒸鑛之玻璃及形成 5〇 # m間距之銅圓案之聚醯亞胺膜基板之間連接。然後藉 由測定電極間的導通電阻，評估導電性粒子之導電性。評 估係以電阻值2Ω以下為〇，以2~5Ω 4Δ，5Ω以上為X。 匕外亦觀察有無短路。再者，以85t . 85%RH的條件保 38 201203287 I 持50Oh後，亦測定電阻值。 [表2] 平均 粒徑 (//m) Ni披膜 的厚度 (nm) Pd彼膜 的厚度 (nm) Au披膜 的厚度 (nm) Pd彼膜中 的P含量 (重量％) 高度50nm以上的凸起部 一次粒子 之比例 (%) 個數 基部長度D (#m) 高度Η (μπι) 南寬比 實 例 1 3.2 80 10 0 N. D. 20 0.145 0.178 1.23 92 2 3.2 63 25 0 N.D. 13 0.163 0.186 1.14 94 3 3.3 38 50 0 N.D. 19 0.184 0.217 1.18 93 4 3.2 94 25 0 N.D. 14 0.183 0.205 1.12 93 5 3.2 95 24 0 2.7 17 0.135 0.169 1.25 92 6 3.3 95 25 0 0.9 19 0.165 0.185 1.12 95 7 3.1 95 24 0 1.7 13 0.142 0.170 1.20 92 8 3.2 64 24 0 N. D. 7 0.135 0.088 0. 65 93 9 3.2 95 24 0 N.D. 8 0.183 0.137 0.75 92 10 3.2 95 23 0 2.8 7 0.196 0.141 0.72 94 參 考 例 1 3.2 74 0 25 N.D. 12 0.172 0.213 1.24 93 比 較 例 1 3.2 62 25 0 N. D. 0 - - - 92 2 3.2 95 25 0 N. D. 0 - - - 90 3 3.2 96 24 0 2.7 0 - - - 90 4 3.9 62 25 0 N. D. 8 0.112 0. 065 0.58 68 5 4 95 24 0 N.D. 6 0.115 0.071 0.62 60 6 4 95 25 0 2.6 9 0.125 0.081 0.65 70 7 3.2 94 23 0 6.2 15 0.132 0.162 1.23 92 [表3] 皮膜的 密著性 導電性 短路的 發生 初期 電阻值 (Ω) 85。。， 85°/〇RH > 500h後的 電阻值（Ω) 實施例1 〇 〇 Μ »*»> 1.8 2.0 實施例2 〇 〇 益 t *»> 1.6 2.1 實施例3 〇 〇 益 »»»、 0.9 1.6 實施例4 〇 〇 無 0.9 1.2 實施例5 〇 〇 益 1.7 2.0 實施例6 〇 〇 無 1.2 1.5 實施例7 〇 〇 益 #»»、 1.4 1.7 實施例8 〇 〇 無 1.8 3.2 實施例9 〇 〇 無 1.9 3.0 實施例10 〇 〇 益 1.7 3.3 39 201203287 參考例 〇 〇 無 0.7 1.5 比較例1 〇 X 無 6.3 10.3 比較例2 〇 X 無 7.0 15.2 比較例3 〇 X 益 «»»> 9.0 9.5 比較例4 Δ Δ 有 2.3 3.3 比較例5 Δ Δ 有 2.5 3.2 比較例6 Δ Δ 有 3.0 3.8 比較例7 〇 Δ 無 3.0 5.8 【圖式簡單說明】 無。 【主要元件符號說明】 無。 40[Table 1] Nickel-coated particle sample N1 N2 N3 N4 Average particle size (y π 〇 3.2 3.2 3.2 3.8 Thickness of nickel film (nm) 96 97 95 96 Nickel film adhesion 〇〇〇 Δ 50 nm or more Number of raised cores 20 8 0 7 Aspect ratio 1.23 0.65 - 0.65 [Examples 1 to 3] Modulation of 10 g/L of EDTA-2Na, 10 g/L of citric acid-2Na and 20 g/L of tetraamine An electroless ore-free mineral solution consisting of palladium dichloride (Pd(NH3)4Cl2) solution (palladium 2g/L) and trespassyl cellulose (molecular weight 250,000, etherification degree 0.9) 10 Oppm. Recording liquid 0.65 liters (Example 1), 1.3 liters (Example 2) ' 2. 6 liters (Example 3) was heated to 70. (:. Stirring, adding 10 g of the above-mentioned nickel-coated particle sample (N1), thereby performing electroless plating treatment on the surface of the particles. The treatment time is 6 〇 minutes. After the treatment is finished, the liquid is filtered 'the filter is repulped 3 times. Then dried in a vacuum dryer of 11 Torr. The ground is applied to the nickel-phosphorus alloy coating by palladium plating. [Example 4] The preparation is made up of 10 g/L ethylenediamine, i〇g/L sodium citrate and 2〇g/L tetraamine. Palladium An electroless plating palladium solution consisting of Pd(NH3)4Cl2) solution (palladium 2g/L), carboxymethylcellulose (molecular weight 250,000, etherification degree 0.9) 1 〇〇ppm. The palladium plating solution is heated at 1.3 liters. 7 (rc), the mixture was stirred, and 1 〇g of the obtained nickel-coated particle sample (N1) was added. Thereby, electroless plating treatment was performed on the surface of the particles. The treatment time was 30 minutes. After the treatment, the liquid was transferred. Thereafter, the same procedure as in Example 1 was carried out, and a palladium plating treatment of 34 201203287 y was applied to the nickel-phosphorus alloy film. [Example 5] The preparation was carried out by 10 g/L of ethylenediamine and 50 g/L of sodium hypophosphite. And 2〇g/L tetraamine palladium dichloride (Pd(NH3)4Cl2) solution (palladium 2g/L), carboxymethyl cellulose (molecular weight 250,000, etherification degree 9.9) 100ppm The palladium-phosphorus solution was electroplated, and 1.3 liters of the palladium plating solution was heated to 5 Torr. This was stirred: 1 g of the obtained nickel-coated particle sample (N1) was added, whereby electroless plating treatment was performed on the surface of the particles. The treatment time was 3 minutes. After the treatment, the liquid was filtered, and then the same procedure as in Example , was carried out, and the nickel-phosphorus alloy was applied to the film. The palladium plating treatment was carried out. [Examples 6 and 7] The same operation as in Example 5 was carried out except that the concentration of sodium hypophosphite was 10 g/L (Example 6) and 25 g/L (Example 7). Apply a key to the nickel alloy mask. [Examples 8 to 1] The same operations as in Example 2, Example 4, and Example 5 were carried out except that the nickel-coated particles were N 2 , and the nickel-phosphorus alloy coating was subjected to palladium plating treatment. . [Comparative Examples 1 to 3] The same operations as in Example 2, Example 4, and Example 5 were carried out except that the nickel-coated particles were N3, and a palladium-plated coating or a bead was applied to the nickel-phosphorus alloy coating. - Fill and cover. [Comparative Examples 4 to 6] The same operation as in Example 2, Example 4, and 35 201203287 Example 5 was carried out except that the nickel-coated particles were N4, and palladium plating was applied to the nickel-phosphorus alloy film or Palladium-plated-phosphorus coating treatment. [Comparative Example 7] The same procedure as in Example 5 was carried out except that the concentration of human phosphorous kna was 2 〇 〇 g / [, and a palladium plating-phosphorus coating treatment was applied to the nickel alloy ruthenium. [Reference Example 1 (gold plating)] The preparation consists of 10 g/L of EDTA_4Na, 1〇g/L citric acid 2Na, and 9 g/L of gold potassium cyanide (with gold of 2.〇g/L). Electroplating gold liquid. The gold plating solution was heated to 2 liters of 2 liters. This was stirred, and 1 g of the coated particles N was added to perform electroless plating treatment on the surface of the particles. The processing time is 2G minutes. After the end of the treatment, the liquid was reduced and the mixture was re-aggregated three times. It was then dried in a vacuum dryer of U〇t. Thus, a nickel-platinum coating was applied to the nickel-phosphorus ruthenium film. [Evaluation of Physical Properties of Conductive Powder] The average particle diameter of the conductive particles obtained in the examples, the comparative examples, and the reference examples, the thickness of the film, the thickness of the film, the thickness of the gold film, and the film in the film The phosphorus content, the number of the convex portions having a height of 50 nm or more, the aspect ratio of the convex portion at a height of 50 nra 5, and the proportion of the secondary particles were measured and evaluated. These results are shown in Table 2 below. Further, the adhesion, conductivity, occurrence of a short circuit (electrical susceptibility), and resistance value of the 砰T or gold film were measured. Will be in the cage, _# value will be the special result, π in Table 3 below. Furthermore, Π = the number of protrusions with a height of 5° nm or more, the height ratio of the protrusions with a height of 5 — 5 or more, and the adhesion of a palladium or gold film. The film was measured in the same manner as the film. In addition, the lock film:; and 36 201203287 palladium mask thickness, gold film thickness, phosphorus content in the palladium film, the occurrence of conductive I1 short circuit (electrical reliability), resistance value is determined as follows. Evaluation. [Thickness of nickel cover after gold or gold plating] The conductive particles are immersed in aqua regia to dissolve the metal film, and the components of the film are analyzed by ICP or chemical analysis, and the following formulas (5) and (6) are calculated. The thickness of the nickel film. A=[(r + t)3-r3]di/r3d2 (5) A=W/(l〇〇-X) (6) where r is the radius of the core particle (# m) and t is the nickel The thickness of the core is the specific gravity of the nickel film, & is the specific gravity of the core particles, and w is the nickel content (% by weight) 'X is the gold or the content of the grain. [Golden film. Thickness of palladium film] The conductive particles are immersed in aqua regia to dissolve gold or palladium, and the components of the film are analyzed by ICP or chemical analysis, and the following formulas (7) and (8) are calculated. The thickness of the gold or palladium film. B=[(r + t + u)3-(r + t)3]d3/(r + t)3d4] (7) B=X/(100-X) (8) where u is gold or The content of palladium (% by weight), the center of gravity is the specific gravity of gold or palladium, eh is the specific gravity of Νι, and X is the content of gold or palladium (weight. Here, the specific gravity of N1 & The specific gravity is calculated by the following formula (9): d4=100/[(W/d.)+(l〇〇-ff)/d2] (9) [Phosphorus content in palladium mask] The nickel particles before the coating are immersed in the aqua regia to dissolve the nickel film, and the film composition of the 201203287 can be ICP or chemically analyzed to calculate the gold π... dry-step ΐ ε 枯 thick layer of nickel, Ji film After the dissolution, the τ-dispersion component was calculated by ICP or chemical analysis to calculate the metallization ratio, and the phosphorus content of the palladium film t was calculated by the following formula: The content of ruthenium in the coated particles (g) C = VxYi/l 〇 〇(10) Phosphorus content in palladium-coated particles (g) D=V/(l-ff/l〇〇)xY2/i〇〇(11) I bar content in coated particles (g) E= V/(lW/l〇〇)-V (12) Therefore, the depletion ratio E (% by weight) in the Ιε film is F=(DC)/(D-C+E)xl〇〇(13) , the weight of nickel-coated particles before V-palladium treatment (g ), the dishing ratio (% by weight) of the L-based nickel-coated particles, and the metallization ratio of the surface of the coating. However, since the recording from the film and the dissolution of phosphorus are very small, it is calculated as 〇. [Electrical Conductivity, Short-Circuit Generation (Electrical Reliability), and Resistance] The epoxy resin 1 〇 〇 part, the hardener i 5 〇 part, and the 笨 7 7 〇 part are mixed, and the 邑 陡 。 。 。. In this case, the conductive particles were blended into five parts to obtain a paste. The paste was applied to a silicone-treated polyester film by a bar soil cloth machine to be dried. The obtained coating film ' was used for connection between a glass which was fully vaporized with a glass and a polyimide film having a copper circle of 5 Å. Then, the conductivity of the conductive particles was evaluated by measuring the on-resistance between the electrodes. The evaluation is based on a resistance value of 2 Ω or less, 2 to 5 Ω 4 Δ, and 5 Ω or more. There are also short circuits observed outside the raft. In addition, the condition was maintained at 85t. 85% RH. 38 201203287 I After 50Oh, the resistance value was also measured. [Table 2] Average particle diameter (//m) Thickness of Ni film (nm) Thickness of Pd film (nm) Thickness of Au film (nm) PP content of P film (% by weight) Height 50 nm or more Proportion of primary particles (%) Number of base lengths D (#m) Height Η (μπι) South aspect ratio Example 1 3.2 80 10 0 ND 20 0.145 0.178 1.23 92 2 3.2 63 25 0 ND 13 0.163 0.186 1.14 94 3 3.3 38 50 0 ND 19 0.184 0.217 1.18 93 4 3.2 94 25 0 ND 14 0.183 0.205 1.12 93 5 3.2 95 24 0 2.7 17 0.135 0.169 1.25 92 6 3.3 95 25 0 0.9 19 0.165 0.185 1.12 95 7 3.1 95 24 0 1.7 13 0.142 0.170 1.20 92 8 3.2 64 24 0 ND 7 0.135 0.088 0. 65 93 9 3.2 95 24 0 ND 8 0.183 0.137 0.75 92 10 3.2 95 23 0 2.8 7 0.196 0.141 0.72 94 Reference example 1 3.2 74 0 25 ND 12 0.172 0.213 1.24 93 Comparative example 1 3.2 62 25 0 ND 0 - - - 92 2 3.2 95 25 0 ND 0 - - - 90 3 3.2 96 24 0 2.7 0 - - - 90 4 3.9 62 25 0 ND 8 0.112 0. 065 0.58 68 5 4 95 24 0 ND 6 0.115 0.071 0.62 60 6 4 95 25 0 2.6 9 0.125 0.081 0.65 70 7 3.2 94 23 0 6.2 15 0.132 0.162 1. 23 92 [Table 3] Adhesion of the film Conductivity Short-circuit occurrence Initial resistance value (Ω) 85. . , 85°/〇RH > Resistance value after 500h (Ω) Example 1 〇〇Μ »*»> 1.8 2.0 Example 2 〇〇益t *»> 1.6 2.1 Example 3 〇〇益»» », 0.9 1.6 Example 4 〇〇 No 0.9 1.2 Example 5 1.7 1.7 2.0 Example 6 〇〇 No 1.2 1.5 Example 7 〇〇益#»», 1.4 1.7 Example 8 〇〇 No 1.8 3.2 Example 9 〇〇 No 1.9 3.0 Example 10 1.7 1.7 3.3 39 201203287 Reference Example 〇〇 No 0.7 1.5 Comparative Example 1 〇X No 6.3 10.3 Comparative Example 2 〇X No 7.0 15.2 Comparative Example 3 〇X 益«»»> 9.0 9.5 Comparative Example 4 Δ Δ has 2.3 3.3 Comparative Example 5 Δ Δ has 2.5 3.2 Comparative Example 6 Δ Δ has 3.0 3.8 Comparative Example 7 〇 Δ No 3.0 5.8 [Simple description of the diagram] None. [Main component symbol description] None. 40