TWI354323B - Silver particle dispersion liduid and method of ma - Google Patents

Description

^54323 九、發明說明： 【發明所屬之技術領域】 本發明係錢使粒徑4奈米級（nanometer order)的銀 粒子粉末分散於有機化合物的液狀介質（簡稱液狀有機介 質）中之銀粒子分散液及其製造法，詳言之，係有關為形成 微細的電路圖案之配線形成用材料例如適合作為依喷墨 (1 n k J e t)法之配線形成用材料的銀粒子的分散液及其製造 去。本發明之銀粒子分散液，係適合作為本發明之 LSI(large scale lntegrati〇n:大型積體電路）基板的配線或 FPD(flat panel display :平板顯示器）的形成用途、以及微 細的溝渠（trench)、連通孔（via h〇le)、接觸孔（c〇mact “⑹ 的嵌入等的配線形成用途之材料者，亦可適用為車輛 漆等的色料。 、 【先前技術】 如固體物質的尺寸成為nm(奈米）級時，則由於比 丨積變得極大’因此本身雖為固體，然氣體及液體之介面極 為大增1因此，其表面的特性將大大影響固體物質的性質。 已知如為金屬粒子粉末時，其熔點將較結塊卬⑴幻者大為 降低’因此，較# m (微米）級粒子者能進行精細的配線之描 緣，且將具備能達成低溫燒結等的優點。尤其金屬粒子粉 末之中，纟於銀粒子粉末係低電阻且具有高的耐候性，又 金屬的價格亦較其他貴金屬為低廉之故，而可望作為具有 精細的配線寬度之下世代的配線材料。 /、 已知_級的銀粒子粉末之製造法可大致分為氣相法 318902 5 叫4323 及液相法。氣相法-般係指氣體㈣蒸發法，而專利文獻 令係。己裁於氦等的惰氣環境中且G 5T⑽⑻左右的低 銀進行蒸發之方法。關於液相法而言，專利文獻2中 ’、不在水相（water Phase)中使用胺將銀離子加以還原 ί相銀的微，經含有高分子量的分散劑之有機溶 夕，以製得銀的膠體（colloid)之方法。專利文獻 中，則C载有在硫醇系的保護劑存在下於溶劑中使 劓（驗金屬氫化硼酸鹽或錢氫化蝴酸鹽）進行_化銀之還原 之方法。 ’、 專利文獻1 :日本特開2001_35255號公報 專利文獻2:日本特開平u_3i9538號公報 專利文獻3 :日本特開2〇〇3_253311號公報 【發明内容】 (發明所欲解決之課題） 以專利文獻1的氣相法所得之銀粒 在分散液中的分散性良好者。然而在，： :::二。因此，除了難以大量合成為量產用 ’、 ㈣，銀粒子的收率亦低，以致由此種f法所，/、 粒子粉末價格不斐。 去所得之 相對於此，液相法，基本上係適合 惟在液中時，其奈米粒子&之方法， ::散為單-粒子之奈米粒子分散液:問題此難: 造奈米粒子時，作兔八也人併 叙，在製 而、s * 分散介質而採用擰檬酸之例子齡夕 而心液中的金屬離子濃度，亦為極低至ι。毫莫^升 318902 6 13-54323 ㈣^莫耳/公升）以下。而此便成為產業應用上之瓶頸。 的獻2 ’係依液相法而藉由〇.2至〇.6莫耳/公升 銀=4濃度、及高原㈣給濃度而合成穩定分散之 萬抑制凝聚現象而使用數平均分子量為數 =的_子讀有機分散^在使用具高分子量 =劑者，如將此作為色料使用時並無任㈣題，惟用^ 路形成用途時，則由於古八2曰、# ； 子置分散劑難於燃燒而在燒成 ==及燒成後亦由於配線上容易發生細孔(㈣ 升^發生斷線之情形，故如欲依低溫燒成 句 配線時便有問題。又，因使用高分子量的分散 係’銀粒子分散液的黏度因增高而亦成為問題。 專利文獻3,係採用液相法，而飼料度亦以〇1莫 么升以上的較高濃度進行反應以使所得之以下的 ^子分肢錢分散介質巾，惟專利讀3 T使用硫醇系的分散劑。由於硫醇久 1低至200左古，+ π丄 π卞 •去除，惟因含有 》成配線時，雖可易於低溫燒成 電子零件之原因成分會成為腐餘配線或其他 '、 因此亚不適合為配線形成之用途。 大旦：二:：發明之課題在於解決此種問題，而以廉價， 溫製得適合精細的配線形成之用途、且低 1U良好“分散性銀粒子的分散液。 (用以解決課題之手段） 分气tn㈣之w題所開發之本發明提供—種銀粒子 刀月’，、使粒子表面以有機保護材被覆之平均粒徑 318902 7 1354323 * « (DTEM)50nm以下的銀粒子粉末，分散於沸點在6〇至3〇〇 °c的非極性或者極性低的液狀有機介質〇iquid state organic medium)中之銀粒子的分散液，其特徵為：前述的 有機保護材係在1分子中至少具有丨個以上的不飽和鍵之 胺化合物。此種胺化合物係使用分子量為1〇〇至ι〇〇〇者。 分散液中的銀粒子，較佳為使用結晶粒徑（Dx)在5〇nm以 下，而單結曰曰曰化度（singIe crystaIIinity)(DTEM/Dx)在2 〇以 下者。分散液的銀濃度為5至9〇wt%，而其黏度為5〇mPa. 眷s以下的牛頓流體（Newtonian fluid)，表面張力可為 8〇mN/m以下，而pH為6·5以上。此種分散液，可通過具 有銀粒子粉末的平均粒徑（DTEM)+2〇nm白々孔徑之膜濾哭 filter)。依照本發明之銀粒子分散液中，並不^ 有:分子量的黏合劑（binder)等，燒失量（igniti〇ni〇ss)(3〇〇 C熱處理時的減量·熱處理時的減幻未滿5%，又， 燒結性良好，因而適合於依喷墨法之配線形成 鲁或糟由塗佈之薄膜形成。 可用於依照本發日^之銀粒子分散液之銀粒子粉末，可 依如在液狀有機介質令衰 砵，你w 遇原銀化合物之液相法製造。此 沸點名价 ’負冑用可發揮作為還原劑功能之 相在85(:以上的醇或多元醇的"重 可將該還原反瘅在右嬙人& 上’ 後 的存在下：有機化合物(胺化合物的1種或2種以上） 至經使所得之銀粒子粉末分㈣點在机 =卿C的非極性或極性小的 液分離粗粒子，即 Μ之谩’仗其为散 I7丌獲侍依照本發明之銀粒子分散液。 318902 8 1354323 ★亦即，如依照本發明，則可提供一種銀粒子分散液之 表k法，其特徵為：在發揮作為還原劑功能之醇或者多元 醇的1種或2種以上的液中進行銀化合物之還原時在1 刀子中至少具有1個以上的不飽和鍵之分子量1〇〇至⑺㈧ 的胺化合物的共存下，進行前述的還原反應，並使所得之 銀粒子籾末在沸點為6〇至3〇〇°c的非極性或者極性低的液 狀有機介質中分散。 (發明之最佳實施形態） ^ I發明人恢液相法重複進行銀粒子粉末之製造試驗之 結果發現’如在滞點為85至15代的醇中，將石肖酸銀在Μ 至150 C的溫度下（將所蒸發之醇回流於液相中之下），例如 在=子量1〇〇至400的胺化合物的共存下還原處理時，則 可付粒輕均勻之球狀的銀的奈米粒子粉末，並記載於日本 特願20〇5·26805號說明書及圖面中。又發現，如在滞點為 85C以上的醇或多元醇中，將銀化合物（代表性者為碳酸銀 #或氧化銀），在阶以上的溫度下，例如在分子*⑽至 4〇〇的脂肪酸的共存下還原處理時，則可得腐餘性化合物 少、粒徑均勻之球狀的銀的粒子粉末，並記載於曰本特願 2005-26866纽明書及圖面中。在任何情形，如將其銀粒 Τ鳥末刀政於非極性或者極性低的液狀有機介質中，則可 仟銀粒子的分散液，並如從該分散液使用離心分離機去除 粗粒子時’即可得粒徑不均較少的（⑺值（變異係數卜標準 偏差σ/個數平均粒子的百分比未％ 4〇%以下）銀粒子經單 分散（monodispersed)之分散液。 318902 9 1354323 然而，在此專方法中，如提高反應溫度時 還原液中的銀離子，惟會引起粒子的燒結子有 致難於製得作為目的之⑽以下的銀粒子粉末而減 ，的銀離子的還原效率降低而減少收率，因此如：= 更進-步的改善。了的銀粒子粉末的製作時，則需要 對於此種課題發現’如作為有機化合 ⑼^上者，則即使提高反應溫度仍能防，里 =還原率且高效率製得5。_以下的銀粒子粉二 而發現，如採用大分子詈的古 本…、 ^ 的有機化合物時，而將其銀粒子 以液作為配線形成用之材料時，則出現在〇◦以下的 低溫下的燒結性會顯著降低之另一問題。 . 1 2述可知’如採用高分子量的有機化合物時，可以 =二生 —以下的銀粒子粉末、與其銀粒子分散液 的低4結性’完全係兩碼事而不能使其併存。 上不：以在30基：上使用有機薄膜等之電路等時，由於實質 自梦合☆ Μ 以上的，皿度燒成，因此，該分散液的用途 燒材料之電路基板中之低溫 ’、,美回該銀粒子分散液的價值之意。 鍵等的行研究之結果發現，如採用1分子内具有雙 併鍵1個以上之胺化合物時，且可達成前述之 並瘦由以/ 如在該還原處理令，階段性地提高溫度 卫、，&由以採用依多段及靡、、田 _ 反應/置度進仃還原之配方，或徹底實 318902 10 1354323. ' 施所得粒子懸浮液的洗滌及去除粗粒子的操作時，則更有 利達成前述之併存，而能以高收率製造銀奈米粒子經高度 分散之低溫燒結性良好的銀粒子分散液者。 以下，就本發明中所特定之事項加以說明。 [平均粒徑DTem] 本發明之銀粒子粉末，藉由TEM(transmission electron microscope，穿透式電子顯微鏡）觀察所測定之平均粒徑 (以DTEM表示）為200nm以下，較佳為lOOnm以下，更佳 #為50nm以下，再更佳為30nm以下，視情況為20nm以下。 因此，本發明之銀粒子粉末分散液係適合於精細配線之形 成者。在TEM觀察時，從經放大為60萬倍之影像測定未 重疊之獨立之粒子300個的直徑並求出其平均值。 [X射線結晶粒徑Dx] 本發明之銀粒子粉末，係結晶粒徑（以Dx表示）為 50nm以下者。銀粒子粉末的X射線結晶粒徑，可從X射 線繞射之結果，採用謝雷拉氏公式（Scherrer’s formula)而求 ¥得。其求出方法，係如下所示。 謝雷拉氏公式，可以下列一般式表示。^54323 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to dispersing a silver particle powder having a particle size of 4 nanometer order in a liquid medium (referred to as a liquid organic medium) of an organic compound. The silver particle dispersion liquid and the method for producing the same are, for example, a material for forming a wiring for forming a fine circuit pattern, for example, a dispersion of silver particles suitable as a material for forming a wiring by an inkjet method. And its manufacture goes. The silver particle dispersion liquid of the present invention is suitable for use as a wiring of an LSI (large scale integrated circuit) substrate of the present invention, a formation of an FPD (flat panel display), and a fine trench (trench) ), a communication hole (via h〇le), or a contact hole (c〇mact “(6)), etc., may be applied to a material such as a vehicle paint. [Previous technique] When the size becomes nm (nano), the ratio becomes extremely large. Therefore, although it is solid, the interface between gas and liquid is greatly increased. Therefore, the surface characteristics greatly affect the properties of the solid matter. When it is known that it is a metal particle powder, its melting point will be much lower than that of the agglomerate 1(1) illusion. Therefore, it is possible to perform fine wiring drawing than the #m (micron) class particle, and it is possible to achieve low-temperature sintering, etc. In particular, among the metal particle powders, the silver particle powder is low in electrical resistance and has high weather resistance, and the price of the metal is lower than that of other precious metals, and is expected to be fine. The wiring material of the generation under the wiring width. /, The manufacturing method of the known silver particle powder can be roughly divided into the gas phase method 318902 5 called 4323 and the liquid phase method. The gas phase method refers to the gas (four) evaporation method. The patent document is a method in which the low silver of G 5T(10)(8) is evaporated in an inert gas environment such as 氦. For the liquid phase method, in Patent Document 2, 'not in the water phase The use of an amine to reduce silver ions, the micro-silver, and the organic solvent containing a high molecular weight dispersant, to obtain a colloid of silver. In the patent literature, C is contained in a thiol system. In the presence of a protective agent, ruthenium (metal hydride borate or hydroxyhydrogenate) is subjected to _ silver reduction. 'Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-35255 Patent Document 2: Japanese Patent Laid-Open SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The silver particles obtained by the vapor phase method of Patent Document 1 are excellent in dispersibility in a dispersion liquid. However, at: ::: two Therefore, in addition to the difficulty in mass synthesis into mass production ', (4), the yield of silver particles is also low, so that the particle powder is not expensive by this f method. In contrast, the liquid phase method, It is basically suitable for the method of nanoparticle & only when it is in liquid, :: dispersion of single-particle nanoparticle dispersion: the problem is difficult: when making nanoparticle, it is also a rabbit In the case of s* dispersion medium and the use of citric acid, the concentration of metal ions in the heart fluid is also extremely low to ι. 毫 ^ 318 902 6 13-54323 (4) ^ Mo / liter) the following. This has become a bottleneck in industrial applications. The contribution of 2' is based on the liquid phase method and the number of average molecular weights is determined by the concentration of 〇.2 to 6.6 mole/liter of silver=4 and the plateau (4). _Sub-reading organic dispersion ^When using a high molecular weight = agent, if you use this as a coloring material, there is no (4) problem, but when using the ^ road to form the use, it is due to the ancient eight 2 曰, # ; It is difficult to burn, and after firing == and after firing, the pores are likely to occur on the wiring ((4) rises and the wire breaks. Therefore, there is a problem if the wire is to be fired at a low temperature. Also, due to the use of high molecular weight. The dispersion of the silver particle dispersion is also a problem due to an increase in viscosity. Patent Document 3 uses a liquid phase method, and the feed rate is also reacted at a higher concentration of 〇1 mol or more to obtain the following. ^Sub-divided money disperses the media towel, but the patent reads 3 T uses a thiol-based dispersant. Since the thiol is as long as 200 to the left, + π丄π卞• is removed, but because it contains the wiring, although The component that can be easily burned into electronic parts at low temperatures becomes a residual wiring or other ', This sub-Asian is not suitable for the use of wiring formation. Dadan: 2: The object of the invention is to solve such problems, and it is cheap and warm to be suitable for fine wiring formation, and low 1U good dispersion of dispersive silver particles. (The means for solving the problem) The invention developed by the problem of the gas tn (four) provides a silver particle knives, and the average particle size of the particle surface coated with an organic protective material is 318902 7 1354323 * « (DTEM a silver particle powder of 50 nm or less, a dispersion of silver particles dispersed in a non-polar or low-polar liquid organic medium having a boiling point of 6 Torr to 3 〇〇 ° C, characterized in that: The organic protective material is an amine compound having at least one or more unsaturated bonds in one molecule. The amine compound is one having a molecular weight of from 1 Å to ι. The silver particles in the dispersion are preferably The crystal grain size (Dx) is below 5 〇 nm, and the single singularity (SingIe crysta IIinity) (DTEM/Dx) is below 2 。. The silver concentration of the dispersion is 5 to 9 〇 wt%, and Its viscosity is 5〇mPa. Newtonian fluid, surface tension can be 8 〇 mN / m or less, and pH is above 6.5. This dispersion can pass through the average particle size (DTEM) with silver particle powder + 2 〇 nm chalk aperture In the silver particle dispersion according to the present invention, there is no such thing as a molecular weight binder or the like, and the loss on ignition (igniti〇ni〇ss) (3 〇〇C heat treatment reduction) - The illusion of heat treatment is less than 5%, and the sinterability is good. Therefore, it is suitable for forming a film which is coated with a film according to an inkjet method. It can be used in the silver particle powder according to the silver particle dispersion according to the present day. It can be made in the liquid phase method of the original silver compound, for example, in the liquid organic medium. This boiling point name 'negative 可 can be used as a reducing agent function in the presence of 85 (: above the alcohol or polyol " heavy can be reversed in the presence of the right &人 & Compound (one or two or more kinds of amine compounds) until the obtained silver particle powder is divided into four (4) points, and the non-polar or polar liquid is separated by a small amount of liquid, that is, Μ之谩' The silver particle dispersion according to the present invention is obtained. 318902 8 1354323 ★ That is, according to the present invention, a silver particle dispersion liquid k method can be provided, which is characterized in that the alcohol functioning as a reducing agent or In the case where the silver compound is reduced in one or two or more kinds of liquids of the polyhydric alcohol, the above-mentioned reduction reaction is carried out in the presence of at least one or more unsaturated bonds having a molecular weight of from 1 to (7) (VIII). And dispersing the obtained silver particles in a non-polar or low-polar liquid organic medium having a boiling point of 6 〇 to 3 ° C. (Best embodiment of the invention) ^ I Inventor liquid phase method Repeated manufacturing test of silver particle powder It has been found that 'in the alcohol of 85 to 15 generations, the silver tartaric acid is refluxed at a temperature of C to 150 C (the evaporated alcohol is refluxed below the liquid phase), for example, at a sub-quantity of 1 In the case of the reduction treatment of the amine compound having a enthalpy of 400, it is possible to apply a spherical silver nanoparticle powder which is light and uniform, and is described in Japanese Patent Application No. 20〇5·26805 and the drawings. It has been found that, for example, in an alcohol or polyol having a hysteresis of 85 C or more, a silver compound (representatively, silver carbonate # or silver oxide), at a temperature above the order, for example, a fatty acid having a molecular weight of *(10) to 4 Å In the case of the reduction treatment in the coexistence, it is possible to obtain a spherical silver particle powder having a small amount of a rot residue and a uniform particle size, and is described in Japanese Patent Application No. 2005-26866, New Zealand, and the drawings. For example, if the silver ostrich is cut into a non-polar or low-polar liquid organic medium, the dispersion of silver particles can be smashed, and when the coarse particles are removed from the dispersion using a centrifugal separator, Particle size unevenness ((7) value (coefficient of variation, standard deviation σ / number of average particles) a fraction of not more than 4% by weight) a monodispersed dispersion of silver particles. 318902 9 1354323 However, in this specific method, for example, increasing the silver ion in the reducing solution at the reaction temperature causes the sintering of the particles. When it is difficult to obtain the silver particle powder of (10) or less which is the target, the reduction efficiency of the silver ions is lowered to reduce the yield, so that, for example, the improvement of the silver particle powder is performed. It is necessary to find out for such a problem, as in the case of organic compound (9), even if the reaction temperature is raised, it can be prevented, and the reduction ratio and the high efficiency are obtained. When an organic compound is used as an organic compound of 詈, and a silver particle is used as a material for wiring formation, there is another problem that the sinterability at a low temperature below 〇◦ is remarkably lowered. As can be seen from the above description, when a high molecular weight organic compound is used, the silver particle powder of the second generation or less can be completely combined with the low particle structure of the silver particle dispersion and cannot be combined. In the case of using a circuit such as an organic film on the basis of 30 or more, the film is burned by the above-mentioned substance, and therefore, the use of the dispersion is low in the circuit board of the material to be burned, The beauty of the value of the silver particle dispersion. As a result of the investigation of the bond or the like, it has been found that, if one or more amine compounds having a double bond in one molecule are used, and the above-mentioned one can be achieved, and the temperature is reduced, for example, in the reduction treatment, , & is more advantageous in the process of washing and removing coarse particles by using a multi-stage and 靡, _ _ reaction / set reduction, or completely 318902 10 1354323. By achieving the above-mentioned coexistence, it is possible to produce a silver particle dispersion having a high degree of low-temperature sinterability in which silver nanoparticle particles are highly dispersed in a high yield. Hereinafter, matters specific to the present invention will be described. [Average particle diameter DTem] The average particle diameter (indicated by DTEM) of the silver particle powder of the present invention measured by TEM (transmission electron microscope) is 200 nm or less, preferably 100 nm or less. Preferably, it is 50 nm or less, more preferably 30 nm or less, and it is 20 nm or less as the case may be. Therefore, the silver particle powder dispersion of the present invention is suitable for the formation of fine wiring. In the TEM observation, 300 diameters of independent particles which were not overlapped were measured from an image which was magnified 600,000 times, and the average value thereof was determined. [X-ray crystal grain size Dx] The silver particle powder of the present invention has a crystal grain size (indicated by Dx) of 50 nm or less. The X-ray crystal grain size of the silver particle powder can be obtained from the X-ray diffraction result using the Scherrer's formula. The method for determining the method is as follows. The Schererer's formula can be expressed in the following general formula.

Dx=K · λ / β COS θ 式中，分別表示K : Scherrer常數，Dx :結晶粒徑， λ :測定用X射線波長，冷：在X射線繞射所得峰值的半 高寬（FWHM : full width half maximum)，Θ :繞射線的布 - .* · « 1 雷格角（Bragg angle)。如K採用0.94的值，X射線的管球 使用Cu(銅）時，則前式可改寫為如下式。 11 318902 1354323Dx=K · λ / β COS θ where K: Scherrer constant, Dx: crystal grain size, λ: X-ray wavelength for measurement, and cold: half-height of peak value obtained by X-ray diffraction (FWHM : full Width half maximum),Θ: cloth around the ray - .* · « 1 Bragg angle. If K uses a value of 0.94 and the X-ray tube uses Cu (copper), the former formula can be rewritten as follows. 11 318902 1354323

Dx=〇.94x1.5405/^ COS ^ [單結晶化度] 本發明之銀粒子粉末，係單結晶化度（D雇版）為2 〇 以下者。因而，可形成精細的配線，其抗遷移性(——η) 亦優異。如單結晶化度在2·〇以上時，則多結晶化度（muid crystamnhy)增高而將在多肖晶粒子間容易含有不純物，燒 成時容易產生細孔而難以形成精細配線而不宜。又，由於 多結晶粒子間的不純物，因而亦會降低遷移性。 [有機保護材] 本發月中係使表面以有機保護材被覆之銀粒子分散 於液狀有機介質上而作成銀粒子分散液者，作為 護㈣使用1分子中至少具有工個以上的不飽和鍵，而分 子里為100至1000,較佳為100至4〇〇的胺化合物。雖可 ^則為由於將此種具有不鮮鍵之胺化合物作為有機保護 才使用，於還原反應中容易一齊產生銀核之同時 全體均勾抑制所析出之銀核的成長之現象，並如前述，可 2 =製得5〇nm以下之銀粒子粉末’且由於該胺化合 低溫下分散’因此可確保其銀粒子分散液的低溫 性:可於本發明中使用之代表性胺化合物而言，可例 二办—士㈣基胺、油基胺、二油基胺、油基伸丙基二胺等。 [液狀有機介質] 狀有有機保護材所被覆之銀粒子粉末分散之液 極性低的二Γs，係使用彿點在60至3〇ot的非極性或者 低的液狀有機介質。在此，「非極性或者極性低的」， 318902 12 ί 指在 25°C 下的相對介電常數（relative dielectric constant) 二15以下之意，較佳為5以下。如介電常數在15以上時， 本子的刀散性惡化而有沈降之情形而不宜。可按分散液 =用途而使用各種液狀有機介f，其t碳化氫系較適合使 寺别疋可使用.異辛烧、正癸垸、異十二烧、異己燒、 十一燒 ' 正十四嫁、ff 士一 h t 正十一烷、十三烷'己烷、庚烷等 :月曰肪知烴、[甲苯、二甲笨 萘等的芳香族庐箄。士笪、六也士 11 、二荨此荨液狀有機介質可使用1種或2種 :’亦可為如煤油(ker〇sene)般的混合物。再者，為調整 =士，亦可在混合後的液狀有機介質在坑下的介電 、15以下之範圍内，添加醇系、酮系、醚系、酯季 等的極性有齡質。 U S曰糸 [醇或者多元醇] 的ιίί7中’係於發揮作為還原劑功能之醇或者多元醇 而一㈣上的液中進行銀化合物之還原者，此種醇 可使用：丙醇、異丙醇、正丁醇、異丁醇、第二二 醇、第二丁醇、歸丙醇、ρ 少… —巴丑知（cr〇tyl alcohol)、環戊醇等。 又，夕兀醇而言，可使用： 醇等。 己一知、一乙一醇、四乙二 [黏度] 、。使依照本發明之銀粒子粉末分散於液狀 之分散液，係一種牛楠β駚备 π恢"貝中 s以下。因奸Π 在25C下之黏度為50_· 下因此，本發明之銀粒子分散液，係谪 + 法之配線形成用材料。依嘴 ’、為依噴墨 依嘴墨法進行配線形成時，為維持 318902 13 1354323 配，的平坦性而欲轉至基板上之液滴量的均勻性 :=之銀粒子分散液係牛頓流體且黏度在M s =在:嘴無堵塞之下可順利排出液滴，因而可符合此 黏度之測定，可於東機產業(股)製的㈣型黏度 怪溫下進行。 _ r〇t〇r)〇.8。者，在25°C的 [表面張力] 本發明之銀粒子分散液，係在抑下的表面張力為 下者。因此，適用為依喷墨法之配線形成用之 ，料。由於表面張力大的分散液，在噴嘴前端的彎月面 2_US)的形狀不穩定，因而難以控制排出量或排出時 而、，&彈至基板上之液滴的沾濕性（贈刚丨办)不佳，而 f為使配線的平坦性變差之結果，惟由財發明之銀粒子 $散液之表面張力為8GmN/maT而不會有上述之情況發 :可進行品質良好的配線。表面張力之測定，可使用協 鲁和界面科學（股）製造# CBVp心而在坑的怔溫下測定。 [膜濾器之通過直徑] 、，本發明之銀粒子的分散液，可通過具有銀粒子粉末的 平均粒徑（DTEM)+2Gnm #孔徑之㈣器。由於僅通過較銀 粒子的平均粒徑〜⑽大2〇nm之孔徑，故可知其分散液中 =銀粒子並不凝聚，而係各個粒子能在該液中流動之狀 心亦即，幾乎已完全呈分散之狀態。此種性質，亦表示 本發明之銀粒子的分散液極適用為依噴墨法之配線形成用 材料如粒子中存在有凝聚之部分，則不僅容易發生喷嘴 318902 14 1354323 . 堵塞，並因所形成之配線的填充性不佳而在燒成時發生細 孔以致成為向電阻化或斷線的原因》惟此種情況，在本發 明之分散液則可避免。於膜濾器通過試驗中，作為孔徑最 小的過濾器，可使用Whatman(懷特曼）社製阿諾脫普加（音 譯）25注射器過濾器（syringe filters)(孔徑20nm)。 [pH] 本發明之銀粒子分散液，係PH(氫離子濃度）為6 5以 上者。因此，其特徵係：具有作為配線形成用材料時不致 鲁於腐钱電路基板上的銅箔’並難以引發配線間的遷移 (migration)。該分散液的PH測定，可使用h〇rIBA(堀 場）(股）製Ph儀D-55T、及低導電性水·非水溶劑用pH電 極b377-10D而實施。如依此種方法所測定之分散液的pH 未滿6.5時，會因酸成分而引起電路基板上的銅箔腐蝕’ 且谷易發生配線間的遷移’以致降低電路的可靠性。 [燒失量] 銀粒子分散液之燒失量（％) ’係指以下式表示之值。 燒失量（％)=100x[(W50-W300)/W5(r(W5〇_w嶋)/W5〇] 。式中，W5〇、W3〇〇以及w]000，表示溫度在5〇ΐ、3〇〇 C以及1000 °c下之分散液的重量。 ^本發明之銀粒子分散液的燒失量未滿5¾。由於燒失 量未滿5%，因此，在進行配線之燒成時在短時間内燃燒 有機保護材而不需要抑制燒結之下可得具有良好導電性之 配線。如燒失量在5%以上時，料於在燒成時有機保護 材會發揮燒結抑制劑之作用，以致配線的電阻增高，有^ 318902 15 I3M323 會阻礙到導電性，因而不宜。 丁〇-上失二可:，:2科:’布爾卡埃伊克斯(音譯)社製 試料重量心二列測定條件測定。 升溫速度：l〇t/分鐘， 氣體環境：大氣（無通氣）， 標準試料：氧化鋁20.0mg， 測定皿··（股）理學研究所製氧化銘測定皿， 溫度範圍：50。〇至i00(rc f者’林發明之銀粒子/粉末之製造方法加以說明。 發明之銀粒子粉末，係在醇或多元醇中，將銀化入 物（各種銀鹽或銀氧化物），在有機化合物的共存下，、在^ 2 150°C的溫度下進行還原處理即可製造。有機化合物Dx=〇.94x1.5405/^ COS ^ [Single crystallinity] The silver particle powder of the present invention has a single crystallinity (D employment version) of 2 Å or less. Therefore, fine wiring can be formed, and the migration resistance (-η) is also excellent. When the degree of single crystallinity is at least 2 〇, the degree of polycrystallization (muid crystamnhy) is increased, and impurities are easily contained between the plurality of grains, and fine pores are likely to occur during firing, and it is difficult to form fine wiring. Further, since the impurities between the polycrystalline particles are also reduced, the mobility is also lowered. [Organic protective material] In the present month, silver particles coated with an organic protective material are dispersed on a liquid organic medium to form a silver particle dispersion, and as a protective material (four), at least one or more unsaturated substances are used in one molecule. A bond, and an amine compound in the molecule of from 100 to 1,000, preferably from 100 to 4 Å. However, it is possible to use such an amine compound having a non-fresh bond as an organic protection, and it is easy to generate a silver core in the reduction reaction while suppressing the growth of the precipitated silver core. 2 = can produce a silver particle powder of 5 〇 nm or less and, because the amine compound is dispersed at a low temperature, thereby ensuring the low temperature property of the silver particle dispersion: a representative amine compound which can be used in the present invention, For example, it can be carried out by using a compound such as a sulphate, an oleylamine, a dioleylamine or an oleylpropylamine. [Liquid organic medium] A liquid dispersion of silver particle powder coated with an organic protective material. The dioxane s having a low polarity is a non-polar or low liquid organic medium having a point of 60 to 3 Torr. Here, "non-polar or low polarity", 318902 12 ί means a relative dielectric constant of 25 or less at 25 ° C, preferably 5 or less. When the dielectric constant is 15 or more, the knife-off property of the present article is deteriorated and it is not preferable to have a sedimentation. Various liquid organic media can be used according to the dispersion = use, and the t hydrocarbon is more suitable for use in temples. It can be used in different places. It is different from Xinxin, Zhengyi, XII, Iso, and eleven. Fourteen marry, ff, ht, n-undecane, tridecane, hexane, heptane, etc.: hydrocarbons, [aromatics such as toluene, dimethyl stannonaphthalene, etc.). Glutinous, six-seven, and sputum. The liquid organic medium can be used in one or two types: 'It can also be a mixture such as kerosene. Further, in order to adjust the concentration of the liquid organic medium in the range of 15 or less, the polarity of the alcoholic, ketone, ether or ester season may be added to the liquid organic medium after mixing. In the ιίί7 of US曰糸[alcohol or polyol], it is used to reduce the silver compound in a liquid which acts as an alcohol or a polyol of a reducing agent function, and the alcohol can be used: propanol, isopropyl Alcohol, n-butanol, isobutanol, second diol, second butanol, propylene glycol, ρ less...-cr〇tyl alcohol, cyclopentanol, and the like. Further, as the sorbitol, an alcohol or the like can be used. Known, one ethyl alcohol, four ethylene two [viscosity],. The dispersion of the silver particle powder according to the present invention in a liquid dispersion is hereinafter referred to as a bovine 駚 駚 & & 。 。. Since the viscosity at 25C is 50%, the silver particle dispersion of the present invention is a material for forming a wiring of the 谪 + method. According to the mouth, when the wiring is formed by the inkjet inkjet method, the uniformity of the amount of droplets to be transferred to the substrate in order to maintain the flatness of 318902 13 1354323: = silver particle dispersion is Newtonian fluid And the viscosity is in M s =: the nozzle can be discharged smoothly without being blocked, so the viscosity can be measured, which can be carried out under the (4) type viscosity temperature of the Dongji Industry Co., Ltd. _ r〇t〇r)〇.8. [Surface tension] at 25 ° C The silver particle dispersion of the present invention has the surface tension to be suppressed. Therefore, it is suitable for the formation of wiring by the inkjet method. Due to the dispersion of the surface tension, the shape of the meniscus 2_US at the tip of the nozzle is unstable, so it is difficult to control the amount of discharge or discharge, and the wetness of the droplets on the substrate (gives It is not good, and f is the result of the deterioration of the flatness of the wiring. However, the surface tension of the silver particles of the invention is 8 GmN/maT, which does not have the above-mentioned situation: good quality wiring can be performed. . The measurement of the surface tension can be carried out at the temperature of the pit using the #CBVp core manufactured by Xielu and Interface Science Co., Ltd. [Medium Diameter of Membrane Filter] The dispersion of the silver particles of the present invention can be passed through a device having an average particle diameter (DTEM) + 2 Gnm # pore diameter of the silver particle powder. Since only the average particle diameter of the silver particles is larger than (10) and the pore diameter is 2 〇 nm, it is understood that the silver particles in the dispersion do not aggregate, and the centroids in which the respective particles can flow in the liquid are almost Completely dispersed. This property also indicates that the dispersion of the silver particles of the present invention is extremely suitable for the wiring forming material according to the ink jet method, such as a portion in which particles are agglomerated, which is not only prone to nozzles 318902 14 1354323. The filling property of the wiring is not good, and pores are generated at the time of firing so as to cause resistance or disconnection. However, in this case, the dispersion of the present invention can be avoided. In the test of the membrane filter, as the filter having the smallest pore diameter, Whatno (Chipman) 25 syringe filter (aperture 20 nm) can be used. [pH] The silver particle dispersion of the present invention has a PH (hydrogen ion concentration) of 65 or more. Therefore, the feature is that it does not cause the copper foil on the circuit board of the rotted circuit when it is used as a material for forming a wiring, and it is difficult to cause migration between wirings. The pH of the dispersion can be measured using a pH meter D-55T manufactured by h〇rIBA (manufactured by Konica Minolta Co., Ltd.) and a pH electrode b377-10D made of a low conductivity water/nonaqueous solvent. When the pH of the dispersion measured by this method is less than 6.5, the copper foil on the circuit board is corroded by the acid component, and the migration between the wirings is liable to occur, so that the reliability of the circuit is lowered. [Amount Loss] The loss on ignition (%) of the silver particle dispersion is a value represented by the following formula. Loss on ignition (%)=100x[(W50-W300)/W5(r(W5〇_w嶋)/W5〇]. In the formula, W5〇, W3〇〇 and w]000 indicate that the temperature is 5〇ΐ The weight of the dispersion at 3 ° C and 1000 ° C. The loss on ignition of the silver particle dispersion of the present invention is less than 53⁄4. Since the loss on ignition is less than 5%, when the wiring is fired, Burning the organic protective material in a short time without suppressing the wiring having good conductivity under sintering. If the loss on ignition is more than 5%, it is expected that the organic protective material will act as a sintering inhibitor during firing. Therefore, the resistance of the wiring is increased, and there are ^ 318902 15 I3M323 will hinder the conductivity, so it is not suitable. Ding Wei - on the second can be:,: 2: "Burka Eyix (transliteration) system sample weight two Measurement of the column conditions. Heating rate: l〇t/min, gas atmosphere: atmosphere (no aeration), standard sample: alumina 20.0mg, measuring dish ··(shares) Institute of Science and Technology, oxidation meter, temperature range: 50. 〇 to i00 (rc f 'the method of manufacturing silver particles / powder of the invention. The silver particle powder of the invention is In an alcohol or a polyhydric alcohol, an inorganic compound (various silver salts or silver oxides) is produced by a reduction treatment at a temperature of 2 150 ° C in the presence of an organic compound.

夕二t前所述，㈣1分子中具有1個以上的不餘和鍵 为1 100至1000的胺化合物。該有機化合物爾後即 構成銀粒子粉末的有機保護材。 醇或者多元醇，係作為銀化合物的還原劑，或作為反 應系的液狀有機介質發揮功能者。醇而言，較佳為異丁醇、 =丁醇等。還原反應較佳為在加熱下依重複此種液狀有機 W質兼還原劑的蒸發與冷凝气回流條件下實施。供為還原 ，銀化合物而言，有：氣化銀、硝酸銀、氧化銀、碳酸銀 等彳欠工業上來看，較佳為硝酸銀，惟並不特別限定於硝 酸銀。本發明之方法中，反應時的液中的Ag(銀）離子濃 318902 16 1354323 . 度，可在50毫莫耳/公升以上之條件下進行。還原處理時， 階段性地提高反應溫度，以多段反應溫度之方式進行還原 處理亦屬有利。 〃 反應後的銀粒子粉末的懸浮液（剛反應完成後的料漿 (slurry))，在經過洗滌.分散.分級等步驟後可作成依照 本發明之銀粒子的分散液，惟此等步驟的代表劑可列舉如 下。 [洗滌步驟]As described in the first day of the second, (4) one or more of the amine compounds having 1 to 100 bonds in the first molecule. This organic compound then constitutes an organic protective material of the silver particle powder. The alcohol or the polyol functions as a reducing agent for the silver compound or as a liquid organic medium as a reaction system. The alcohol is preferably isobutanol, =butanol or the like. The reduction reaction is preferably carried out under the conditions of evaporation of the liquid organic-based reducing agent and reflux of the condensation gas under heating. For the reduction, the silver compound is: silver hydride, silver nitrate, silver oxide, silver carbonate, etc., which is industrially preferable, and is preferably silver nitrate, but is not particularly limited to silver nitrate. In the method of the present invention, the Ag (silver) ion concentration in the liquid at the time of the reaction is 318902 16 1354323 degrees, and can be carried out under conditions of 50 mmol/liter or more. In the reduction treatment, it is also advantageous to gradually increase the reaction temperature and carry out the reduction treatment in the form of a plurality of reaction temperatures.悬浮 a suspension of the silver particle powder after the reaction (slurry after the completion of the reaction), after washing, dispersing, grading, etc., a dispersion of silver particles according to the present invention may be prepared, but the steps are Representative agents can be enumerated below. [washing step]

(1)將反應後的既定量的料聚，使用離心分離器（日立工機 (股）製的CF7D2)，以3000rpm實施固液分離3〇分鐘， 將上澄液棄去。 ’並使用超 (2) 於沈澱物中，添加與先前的料漿同量的甲醇 音波分散機加以分散。 (3) 重複前述的（1)至（2)2次。 (4)實施前述的（1)，廢棄上澄液後取得沈澱物。 [分散步驟] ⑴於前述的洗滌步料所得沈澱物中添加錄有 (2)接著，使用超音波分散機以製作銀粒子混 、 [分級步驟] 0= 經分好驟之録子與㈣有機介#心㈣ :樣的離心分離器，以3 _rpm實施固液分離3 〇分鐘。 (2)回收上澄液。該上澄液即成為銀粒子分散液。 [銀粒子分散液之濃度] 月之0 銀粒子分散液中的銀濃度，可依下述方式算出。 318902 17 1354323 . ' (1)將前述的分級步驟所得之銀粒子分散液，移至已知重量 之容器中。 (2) 將該容器裝付於真空乾燥機中，充分注意防止暴沸 (bumping)而一邊提升真空度及溫度以實施濃縮·乾燥，待 觀察不到液體後，在真空狀態200°C下實施乾燥6小時。 (3) 冷卻至室溫後從真空乾燥機取出容器並測定重量。 (4) 從前述（3)的重量減去容器重量，以求出銀粒子分散液中 的銀粒子的重量。 • (5)從前述（4)的重量及銀粒子分散液的重量，算出分散液中 的銀粒子濃度。 【實施方式】 [實施例] (實施例1) 於作為液狀有機介質兼還原劑的異丁醇（和光純藥（股） 製的特級品）140ml中，添加作為成有機保護材之化合物之 分子中具有1個不飽和鍵之油基胺（和光純藥（股）製 鲁Mw=267)185.83m卜及作為銀化合物之硝酸銀結晶（關東化 學（股）製）19.212g，使用磁力擾拌器（magnet stirrer)擾拌， 以使硝酸銀溶解。 將此溶液移至附有回流器之容器中並載置於油浴（oil bath)上，對容器内將作為惰性氣體之氮氣以400ml/分鐘的 流量吹入，並使用磁力擾拌器以1 OOrpm的旋轉速度授拌 該溶液並加熱，在l〇〇°C的溫度下實施回流2小時30分 鐘。然後，提高溫度至l〇8°C，實施2小時30分鐘的回流 18 318902 1354323 將反應完成後的料漿的全量，經本文所記載之洗滌步 驟、分散步驟以及分級步驟後，製得銀粒子的分散液。此 時，於分散步驟中作為液狀有機溶劑而添加十二烧6.28g 以製作混濁液，而對於經分級步驟所得之銀粒子分散液， 依本文所記載之方法實施各特性的評價。 其結果，所得之銀粒子，係平均粒徑DTEM=8.01 nm，(1) A predetermined amount of the material after the reaction was collected, and a solid-liquid separation was carried out at 3000 rpm for 3 minutes using a centrifugal separator (CF7D2 manufactured by Hitachi Ltd.), and the supernatant was discarded. And use super (2) in the precipitate, and add the same amount of methanol sonic dispersion machine as the previous slurry to disperse. (3) Repeat the above (1) to (2) twice. (4) The above (1) is carried out, and a precipitate is obtained after discarding the supernatant liquid. [Dispersion step] (1) Adding to the precipitate obtained in the above-mentioned washing step is recorded (2) Next, using an ultrasonic disperser to prepare silver particles, [grading step] 0 = recording of the good points and (4) organic Introduction #心(四) : A sample centrifugal separator that performs solid-liquid separation at 3 rpm for 3 〇 minutes. (2) Recover the supernatant. This supernatant liquid becomes a silver particle dispersion. [Concentration of Silver Particle Dispersion] Month 0 The silver concentration in the silver particle dispersion can be calculated as follows. 318902 17 1354323 . ' (1) The silver particle dispersion obtained in the above classification step is transferred to a container of known weight. (2) The container is placed in a vacuum dryer, and sufficient attention is paid to prevent the bumping, and the degree of vacuum and temperature are raised to carry out concentration and drying. After the liquid is not observed, the vacuum is carried out at 200 ° C. Dry for 6 hours. (3) After cooling to room temperature, the container was taken out from the vacuum dryer and the weight was measured. (4) The weight of the container was subtracted from the weight of the above (3) to determine the weight of the silver particles in the silver particle dispersion. (5) Calculate the concentration of silver particles in the dispersion from the weight of the above (4) and the weight of the silver particle dispersion. [Examples] [Examples] (Example 1) A compound which is an organic protective material was added to 140 ml of isobutyl alcohol (a special product manufactured by Wako Pure Chemical Industries, Ltd.) as a liquid organic medium-reducing agent. An oleylamine having an unsaturated bond in the molecule (Wu Pure Chemical Co., Ltd., Lu Mw=267), 185.83 m, and a silver nitrate crystal (manufactured by Kanto Chemical Co., Ltd.) 19.212 g, using magnetic interference The magnet stirrer is disturbed to dissolve the silver nitrate. The solution was transferred to a vessel with a reflux vessel and placed on an oil bath, and nitrogen gas as an inert gas was blown into the vessel at a flow rate of 400 ml/min, and a magnetic stirrer was used. The solution was mixed at a rotational speed of OO rpm and heated, and refluxed at a temperature of 10 ° C for 2 hours and 30 minutes. Then, the temperature is raised to 10 ° C, and the reflux is performed for 2 hours and 30 minutes. 18 318902 1354323 The total amount of the slurry after the completion of the reaction is obtained by the washing step, the dispersing step and the classification step described herein to obtain silver particles. Dispersion. At this time, in the dispersion step, 6.28 g of twelve-burning was added as a liquid organic solvent to prepare a turbid liquid, and the silver particle dispersion obtained by the classification step was evaluated for each characteristic by the method described herein. As a result, the obtained silver particles have an average particle diameter DTEM=8.01 nm,

結晶粒徑Dx=4.69nm，單結晶化度（DTEM/Dx) = l .71，就其 銀粒子分散液而言，銀粒子漢度=65.4wt%，黏度=10mPa · s，表面張力=25.0mN/m，pH=8.61，燒失量=4.8%，順利通 過Whatman社製阿諾脫普加25注射器過濾器（孔徑 20nm)，分散性良好且並無凝聚現象。 (實施例3)The crystal grain size Dx=4.69 nm, the degree of single crystallinity (DTEM/Dx) = 1.41, and in terms of its silver particle dispersion, the silver particle degree is 65.4 wt%, the viscosity is 10 mPa · s, and the surface tension is 25.0. mN/m, pH=8.61, loss on ignition = 4.8%, and smoothly passed through an Arnoldup Plus 25 syringe filter (pore size 20 nm) manufactured by Whatman Co., Ltd., and the dispersibility was good and there was no aggregation. (Example 3)

I 於作為液狀有機介質兼還原劑的異丁醇（和光純藥（股） 製的特級品）120ml中，添加作為成有機保護材之化合物之 分子中具有1個不飽和鍵之油基胺（和光純藥（股）製 Mw=267)199.11ml、及作為銀化合物之硝酸銀結晶（關東化 學（股）製）20.59g，使用磁力攪拌器攪拌，以使硝酸銀溶解。 將此溶液移至附有回流器之容器中並載置於油浴上， 對容器内將作為惰性氣體之氮氣以400ml/分鐘的流量吹 入，並使用磁力攪拌器以lOOrpm的旋轉速度攪拌該溶液 並加熱，在108°C的溫度下實施回流5小時後完成反應。 此時，至108°C之升溫速度作成2°C/分鐘。 將反應完成後的料漿的全量，經本文所記載之洗滌步 驟、分散步驟以及分級步驟後，製得銀粒子的分散液。此 20 318902 1354323 時，於分散步驟中作為液狀有機溶劑而添加十四烧2.43g 以製作混濁液，而對於經分級步驟所得之銀粒子分散液， 依本文中所記載之方法實施各特性的評價。I oleylamine having one unsaturated bond in a molecule which is a compound of an organic protective material, is added to 120 ml of isobutyl alcohol (a special product of Wako Pure Chemical Industries, Ltd.) as a liquid organic medium and a reducing agent. (Mw=267) 199.11 ml (manufactured by Wako Pure Chemical Co., Ltd.) and 20.59 g of silver nitrate crystal (manufactured by Kanto Chemical Co., Ltd.) as a silver compound, and stirred with a magnetic stirrer to dissolve silver nitrate. The solution was transferred to a vessel equipped with a reflux vessel and placed on an oil bath, and nitrogen gas as an inert gas was blown into the vessel at a flow rate of 400 ml/min, and stirred using a magnetic stirrer at a rotation speed of 100 rpm. The solution was heated and refluxed at a temperature of 108 ° C for 5 hours to complete the reaction. At this time, the temperature increase rate to 108 ° C was 2 ° C / min. The entire amount of the slurry after completion of the reaction is subjected to a washing step, a dispersing step, and a classification step as described herein to obtain a dispersion of silver particles. In the case of 20 318 902 1354323, 2.43 g of tetradecene is added as a liquid organic solvent in the dispersing step to prepare a turbid liquid, and for the silver particle dispersion obtained by the fractionation step, various characteristics are carried out according to the methods described herein. Evaluation.

其結果，所得之銀粒子，係平均粒徑E>TEM=9.〇5nm， 結晶粒徑Dx=6.02nm，單結晶化度（DTEM/Dx)=l .50，就其 銀粒子分散液而言，銀粒子濃度=75.8wt%，黏度 = 18.3mPa . s，表面張力=23_5mN/m，pH=8.50，燒失量 =4.0%，而順利通過Whatman社製阿諾脫普加25注射器過 濾器（孔徑20nm)，分散性良好且並無凝聚現象。 (比較例1、2) 實施例1中，係使用不具有不飽和鍵之有機化合物之 環己基胺（比較例1)、乙基己基胺（比較例2)以取代油基 胺。其餘則在與實施例1同樣條件下進行實驗。其結果， 並未見到粒子之生成，甚至未能確認粒子物性。為慎重起 見，使用十四烷作為分散介質並依既定方法嘗試製作油 墨，惟未能觀察任何經分散於油墨中之粒子。 21 318902As a result, the obtained silver particles have an average particle diameter E > TEM = 9. 〇 5 nm, a crystal grain size Dx = 6.02 nm, and a single crystallinity (DTEM / Dx) = 1.5, which is a silver particle dispersion. 』, silver particle concentration = 75.8wt%, viscosity = 18.3mPa. s, surface tension = 23_5mN / m, pH = 8.50, loss on ignition = 4.0%, and smoothly through the Whatman company's Arnoldup plus 25 syringe filter (Polar diameter: 20 nm), good dispersibility and no agglomeration. (Comparative Examples 1 and 2) In Example 1, a cyclohexylamine (Comparative Example 1) or ethylhexylamine (Comparative Example 2) which is an organic compound having no unsaturated bond was used in place of the oleylamine. The rest of the experiment was carried out under the same conditions as in Example 1. As a result, no particle formation was observed, and even the physical properties of the particles could not be confirmed. For the sake of caution, tetradecane was used as a dispersion medium and an attempt was made to produce an ink according to a predetermined method, but any particles dispersed in the ink were not observed. 21 318902

Claims (1)

135432 申請專利範圍 100. V. 2 8~~~— 年月日修正本 第96101215號專利申請案 1〇〇年7月28曰修正替換頁 、種銀粒子分散液，係使粒子表面經有機保護材被覆之 平均粒徑（DTEM)50nm以下的銀粒子粉末，分散於 在60至30(TC而且具有25。〇時之介電常數為15以下的 液狀有機介質中之銀粒子的分散液，其特徵為：前述的 有機保護材係1分子中至少具有“固以上不飽和鍵之胺 化合物。 2.135432 Patent application scope 100. V. 2 8~~~- Year, month and day revision of the patent application No. 96101215, July 28, 1st, revised replacement page, silver particle dispersion, the particle surface is organically protected a silver particle powder having an average particle diameter (DTEM) of 50 nm or less coated with a material, and dispersed in a dispersion of silver particles in a liquid organic medium having a dielectric constant of 15 or less at 60 to 30 (TC and having a dielectric constant of 15 or less). The above-mentioned organic protective material has at least one amine compound having one or more unsaturated bonds in one molecule. 如申請專職圍第i項之絲子分驗，其巾銀粒子的 、=晶粒徑㈣在50nm以下，而單結晶化度（d簡 在2.0以下。For example, if the silkworm of the i-term of the full-time occupation is applied, the silver particle size of the towel is = 50 nm or less, and the degree of single crystallinity (d is less than 2.0). 3. 如申請專利範圍第丨項之銀粒子分散液， 材係分子量為100至1〇〇〇的胺化合物。 4. 如申請專韻Μ丨項线粒子分散液， 銀;辰度為5至9〇wt%。 如申請專利範圍第1項之銀粒子分散液 5〇mPa. s以下的牛頓流體。 6· ^申請專利_第1項之絲子分散液， 為80mN/m以下。 7.=請專㈣㈣丨奴絲子分數液， t粒子粉末的平均粒徑（D 碰 其中有機保護 其中分散液的 其係黏度為 其中表面張力 其中可通過具 的孔徑的膜濾 項之銀粒子分散液，其t pH為6.5 8，如申請專利範圍第 以上者。 9·如申請專利範圍第 項至第8項中任一項之銀粒子分散 318902(修正版) 22 1354323 . — 第96101215號專利申請案 • . 100年7月28曰修正替換頁 液，其中燒失量未滿5%者。 • 10. 一種申請專利範圍第1項之銀粒子分散液之製造法，其 - 特徵為··在發揮作為還原劑功能之醇或者多元醇的1種 或2種以上的液中在85t：至15CTC之溫度範圍内以每分 鐘2C之昇溫速度進行銀化合物之還原時，在丨分子中 至少具有1個以上不飽和鍵之分子量1〇〇至1〇〇〇的胺 化合物的共存下，進行前述的還原反應。 11.-種申請專利範圍第i項之銀粒子分散液之製造法，其 特徵為.在發揮作為還原劑功能之醇或者多元醇的丨種 或2。種以上的液中在85〇c至15〇。匸之溫度範圍内以每分 鐘2°C之昇溫速度進行銀化合物之還原時，在1分子中 至夕具有1個以上不飽和鍵之分子量100至1000的胺 化合物的共存下’進行前述的㈣反應，並使所得之銀 粒子粉末在沸點為60 5 k 。 机丄 ϋ至30〇C的具有25。(：時之介電常 數為15以下的液狀有機介質中分散。 318902(修正版) 233. A silver particle dispersion according to the scope of the patent application, which is an amine compound having a molecular weight of 100 to 1 Torr. 4. If you apply for a special rhyme-item particle dispersion, silver; the degree is 5 to 9 〇 wt%. For example, the silver particle dispersion of claim 1 is a Newtonian fluid of 5 〇 mPa·s or less. 6· ^ Apply for a patent _ Item 1 of the silk dispersion, which is 80mN / m or less. 7.= Please special (4) (4) 丨 丨 子 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分 分a dispersion having a t pH of 6.5, as described in the patent application. 9. A silver particle dispersion according to any one of claims 8 to 8 (revised edition) 22 1354323 . — No. 96101215 Patent Application • . July 28, 100, revised replacement page liquid, in which the loss of ignition is less than 5%. • 10. A method for manufacturing a silver particle dispersion according to item 1 of the patent application, which is characterized by - When reducing a silver compound at a temperature increase rate of 2 C per minute in a temperature range of 85 t: to 15 CTC in one or two or more liquids of an alcohol or a polyhydric alcohol functioning as a reducing agent, at least in the ruthenium molecule The above-mentioned reduction reaction is carried out in the presence of an amine compound having a molecular weight of 1 Å to 1 Å having one or more unsaturated bonds. 11. A method for producing a silver particle dispersion of the invention of claim i, Features are. When the silver compound is reduced at a temperature increase rate of 2 ° C per minute in a temperature range of 85 〇 c to 15 发挥, which is an alcohol or a polyol of a reducing agent function, or a liquid of 2 or more types In the coexistence of an amine compound having a molecular weight of 100 to 1000 having one or more unsaturated bonds in one molecule, the above-mentioned (four) reaction is carried out, and the obtained silver particle powder has a boiling point of 60 5 k. 〇C has a dispersion of 25 in liquid organic medium having a dielectric constant of 15 or less. 318902 (Revised Edition) 23