TW200830385A - Silver particle dispersion liduid and method of manufacturing the same - Google Patents

Abstract

Provided is a silver particle dispersion liquid that is to disperse silver particles which are coated by an organic protective material on particles' surface and have an average particles size (DTEM) below 50nm, in an organic medium being non-polar or very low polarity and having a boiling point between 60 to 300 DEG C. The organic protective material is an amine compound containing at least one unsaturated bond per molecule. The silver particle dispersion liquid may be manufactured by reduction of a silver compound in the presence of amine compound having a molecular weight of 100 to 1000 and containing at least one unsaturated bond per molecule, by using one or more than two kinds liquid of alcohol or poly alcohol which exhibits a function as a reducing agent.

Description

200830385 ‘ 九、發明說明： - 【發明所屬之技街領域】 "本發明係有關使粒徑為奈米級（nanometer 〇rde :二粉末分散於有機化合物的液狀介質(簡稱液狀有機； 貝）中之銀粒子分散液及其製造法，詳言之，、 微細的電路圖案之配線形成用材料例如適合作：依：= (1 n k」e t)法之配線形成用材料的銀粒子的分散液及其製、: I本發明之銀粒子分散液’係適合作為本發明= 蠢SI(iarge seaie inte㈣iQn:大型龍電路）基板的配 FPD(flatpanel dispiay :平板顯示器)的形成用途、 細的溝渠㈣nch)、連通孔（via h〇le)、接觸孔（c〇niaet 的嵌入等的配線形成用途之材料者，亦可適用為 漆等的色料。 〃〜貝 【先前技術】 如固體物質的尺寸成為nm(奈米）級時，則由於比表面 #變得極大，因此本身雖為㈣，然氣體及液體之面極 馮大增。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（buik)者大為 降低，因此，較μ m (微米）級粒子者能進行精細的配線^描 繪，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，由於銀粒子粉末係低電阻且具有高的耐候性，又 金屬的償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nm級的銀粒子粉末之製造法可大致分為氣相法 318902 5 200830385 及液相法。氣相法一般係指氣體中的蒸發法，而專利文獻 1中係纪载於氦等的惰氣環境中且〇.5T〇rr (托）左右的低壓 下ί吏銀進仃瘵發之方法。關於液相法而言，專利文獻2中 係揭不在水相（waier phase)中使用胺將銀離子加以還原 後，將所得銀的微粒往經含有高分子量的分散劑之有機溶 剑相中移動，以製得銀的膠體（c〇n〇id)之方法。專利文獻3 f，則記載有在硫醇系的保護劑存在下於溶劑中使用還原 金屬氫化硼酸鹽或銨氫化硼酸鹽）進行鹵化銀之還 方法。 μ .專利文獻1 :日本特開2001_35255號公報 專利文獻2:曰本特開平u_319538號公報 專利文獻3 :日本特開2〇〇3·2533η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子，係粒徑在ι〇η江 分散液中的分散性良好者。然而，此種製法需要 特別的I置。因此，除了難以大量合成為量產用的銀^ 粒子之同時，銀粒子的收率亦低，以致由此種製法 粒子粉末價格不斐。 ^ 相對於此’液相法’基本上係適合於大量合成之方2 准在液中時，其奈米粒子之凝聚性極高，因此，有難 得分散為單-粒子之奈米粒子分散液之問題。—般二在 造奈米粒子時，作為分散介質而採用檸檬酸之例^較夕 而通常液中的金屬離子濃度，亦為極低至ig毫莫耳^ 328902 6 200830385 ㈣.01料/公升）以下。而此便成為產業應用上之瓶頸。 丄專利文獻2，係依液相法而藉自〇 2至〇 6 / 、及高原料飼給濃度而合成穩定分散之 萬二:：惟為抑制凝聚現象而使用數平均分子量為數 散劑：:如侧。在使用具高分子量的有機分 /、、匕作為色料使用時並無任何問題，惟用於帝 ，成用途時，則由於高分子量分散劑難於燃燒而在 二各易殘存、以及燒成後亦由於配線上容易發生細孔二 1而:二電阻升高或發生斷線之情形’故如欲依： ^成精細配線時便有問題。又，因使用高分子 叙關係，銀粒子分散液的黎度因增高而亦成為問題」 專利文獻3,係採周液相法，而飼給濃度亦以曾 ^公升以上的較高濃度進行反應以使所得之ι〇贿以下= =粒子分散於有機分散介質中，惟專利文獻3中則提幸分 系的分散劑。由於硫醇系的分版 Γ 因此在形成配線時，雖可.易於低溫燒成 4兩杜因含有硫⑻’而該硫成分會成為腐钱配線或其他 电子冬件之仙，因此並不適合為轉形成之用途。 因而’本發明之課題在於解決此種問題，而以廉價， ϋΓΓ方式製得適合精細的配線形成之用途、且低 血k、、、σ性良好的高分散性銀粒子的分散液。 (用以解決課題之手段） 八五為解決本發明之課題所開發之本發明提供一種銀粒子 刀政液’係使粒子表面以有機保護材被覆之平均粒徑 318902 7 200830385 (DTEM)5〇nm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（iiquid 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分子巾至少具有Η目以上的不飽和鍵之 胺化合物。此種胺化合物係使用分子量為1〇〇至1〇⑽者。 分散液尹的銀粒子，較佳為使用結晶粒徑（Dx)在5〇nm以 下，而單結晶化度（single crysiaIlinhy)(D测/Dx)在2 〇以 下者。分散液的銀濃度為5至90wt%，而其黏度為5〇mPa . _以下的牛頓流體（Newionian fluid)，表面張力可為 80mN’m以F，而pH為6.5以上。此種分散液，可通過具 凑叙粒子初冬的平均粒徑（DTEM)+2〇nm的孔徑之膜瀘器 (membrane filter)。依照本發明之銀粒子分散液中，並不含 有高分子量的黏合劑（binder)等，燒失量（ignUi〇ni〇ss)(3〇〇 c熱處理時的減量-⑽代熱處理時的減幻未滿，又， 在㈣下的燒結性良好，因而適合於依喷墨法之配線形成 |藉由塗佈之薄膜形成。 可用於依照本發明之銀粒子分散液之銀粒子粉末，可 ，照在液狀有機介質中還原銀化合物之液相法製造。此 時，作為該液狀有機介質，使用可發揮作為還原劑功能之 沸點在饥以上的醇或多元醇的1種或2種以上，然後， 可將該還原反應在有機化合物（胺化合物的！種或2種以上） 的存在下進行，經使所得之銀粒子粉末分散於彿點在6(TC 至30(TC的非極性或極性小的分散介質中之後，從其分散 液分離粗粒子，即可獲得依照本發明之銀粒子分散液。 318902 8 200830385 l •制=即，如依照本發明，則可提供-種銀粒子分散液之 二了、、特徵為.在發揮作為還原劑功能之醇或者多元 的1種或2種以上的液中進行銀化合物之還原時，在！ =中至少具有！個以上的不飽和鍵之分子量⑽至则 銀Γ早匕Γ物的共存下’進行前述的還原反應，並使所得之 =:粉末在_為6〇至3啊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） =本發明人依液相法重複進行銀粒子粉末之製造試驗之 如在沸點為Μ至MG的醇中，將硝酸銀在Μ C的溫度下(將所蒸發之醇回流於液相中之下)，例如 在分子4 1001400的胺化合物的共存下還原處理時 可得粒徑均句之球狀的銀的奈米粒子粉末，並記載於日本 2005-26305 ^ , 〇 或"L 或多元醇巾’絲化合物（代表性者為碟酸銀 g乳…’艮’在85 C以上的溫度下，例如在分子量⑽至 ,〇〇的脂肪酸的共存下還原處理時，則可得腐飿性化合物 少、粒徑均勻之球狀的銀的粒子粉末，並記载於 鳩纖6號說明書及圖面中。在任何情形，如將其= 子知末刀政祆非極性或者極性低的液狀有機介質中，則可 付銀粒子的分散液，並如從該分散液使用離心分離機 粗粒子時，即可得粒徑不均較少的（cv值（變異係數^ 偏差σ /個數平均粒子的百分比未滿4 〇 %以下）銀粒子=單 分散（monodispersed)之分散液。 、工 318902 9 200830385200830385 ' IX, invention description: - [Technology street field to which the invention belongs] " The invention relates to making the particle size nanometer (nanometer 〇rde: liquid medium in which two powders are dispersed in an organic compound (referred to as liquid organic; In particular, the material for forming a wiring of a fine circuit pattern is, for example, a silver particle of a material for wiring formation according to the method of: (1 nk"et). Dispersion and preparation thereof: I. The silver particle dispersion of the present invention is suitable for use as a FPD (flat panel disdisay) for the substrate of the present invention = iarge seaie inte (iQn: large-scale circuit) substrate, fine Ditch (four) nch), communication hole (via h〇le), contact hole (c〇niaet embedding, etc., which can be used as a material for wiring, etc., can also be applied to paints such as lacquer. 〃~贝 [Prior Art] such as solid matter When the size is changed to the nm (nano) level, since the specific surface # becomes extremely large, the surface itself is (4), and the surface of the gas and the 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 is much lower than that of a buick. Therefore, it is possible to perform fine wiring and drawing with a particle of μ m (micrometer) level, and it is possible to achieve low-temperature sintering or the like. Advantages. Especially among the metal particle powders, since the silver particle powder is low in electrical resistance and has high weather resistance, the metal compensation is also lower than other precious metals, and it is expected to be a generation with a fine wiring width. Wiring material. The manufacturing method of the silver particle powder of the known nm grade can be roughly classified into a gas phase method 318902 5 200830385 and a liquid phase method. The gas phase method generally refers to an evaporation method in a gas, and Patent Document 1 In the inert gas environment of Yu et al. and the low pressure of 〇.5T〇rr (Torr), the method of silver is introduced into the burst. In the liquid phase method, Patent Document 2 is not in the water phase. A method in which silver ions are reduced by using an amine, and the obtained silver particles are moved in an organic solution phase containing a high molecular weight dispersant to obtain a colloid of silver (c〇n〇id). 3 f, it is recorded in thiol A further method of performing silver halide in the presence of a protective agent in a solvent using a reduced metal borohydride or ammonium borohydride. 。 。 。 。 。 。 。 。 。 。 。 。 。 专利 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ) ) ) ) ) ) ) ) ) ) ) ) The silver particles obtained by the vapor phase method of Patent Document 1 have a good dispersibility in the dispersion of the ι〇η River dispersion. However, this method requires a special I. Therefore, in addition to being difficult to synthesize a large amount of silver particles for mass production, the yield of silver particles is also low, so that the price of such a process particle powder is not high. ^ Relatively speaking, the 'liquid phase method' is basically suitable for a large amount of synthesis. When it is in a liquid, the nanoparticles have a very high degree of cohesiveness. Therefore, it is difficult to disperse into a single-particle nanoparticle dispersion. The problem. As for the case of making nano particles, the use of citric acid as a dispersion medium, and the concentration of metal ions in the liquid is also extremely low to ig millimolar ^ 328902 6 200830385 (4).01 material / liter )the following. This has become a bottleneck in industrial applications.丄 Patent Document 2, based on the liquid phase method, is synthesized from 〇2 to 〇6 / and high feedstock concentration to form a stable dispersion of the second:: the number average molecular weight is used to suppress the aggregation phenomenon. side. When using a high molecular weight organic component/, 匕 as a coloring material, there is no problem, but when it is used for emperor or in the case of use, the high molecular weight dispersing agent is difficult to burn and remains in the second and after firing. Also, since the fine holes 2 are easily generated on the wiring: the case where the second resistance is increased or the disconnection occurs is caused, so that it is problematic if it is fine wiring. In addition, due to the use of the polymer relationship, the concentration of the silver particle dispersion is also a problem due to the increase in the degree of liberation. Patent Document 3 is a liquid phase method in which the feed concentration is also carried out at a higher concentration of more than liters. In order to make the obtained ι 〇 bribe below = = particles are dispersed in the organic dispersion medium, but in Patent Document 3, the dispersing agent of the sub-system is fortunate. Because of the thiol-based Γ Γ Γ 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫 硫The purpose of the formation. Therefore, the object of the present invention is to solve such a problem, and to obtain a dispersion liquid of high-dispersion silver particles which is suitable for the formation of fine wiring and which has low blood k and good σ properties, which is inexpensive and sturdy. (Means for Solving the Problem) The present invention, which has been developed to solve the problems of the present invention, provides a silver particle knife solution "the average particle diameter of the particle surface coated with an organic protective material 318902 7 200830385 (DTEM) 5〇 a silver particle powder of less than nm, a dispersion of silver particles dispersed in a non-polar or low-polarity iiquid organic medium having a boiling point of 6 〇 to 3 〇〇 c, characterized by the aforementioned organic protection The material is an amine compound having at least an unsaturated bond of at least one element in a molecular towel. Such an amine compound is used in a molecular weight of from 1 Torr to 1 Torr (10). The silver particles of the dispersion Yin preferably have a crystal grain size (Dx) of 5 Å or less and a single crystallinity (Dx/Dx) of 2 Å or less. The silver concentration of the dispersion is 5 to 90% by weight, and the viscosity of the New Zealandian fluid having a viscosity of 5 〇 mPa or less may have a surface tension of 80 mN'm and an pH of 6.5 or more. Such a dispersion can be passed through a membrane filter having an average particle diameter (DTEM) of the particles in the early winter and an aperture of 2 〇 nm. The silver particle dispersion according to the present invention does not contain a high molecular weight binder, etc., and the loss on ignition (ignUi〇ni〇ss) (decrease in heat treatment at 3〇〇c - reduction in the heat treatment at (10) generation heat treatment It is not full, and it has good sinterability under (4), and is therefore suitable for wiring formation by an inkjet method|formed by a film to be coated. Silver particle powder which can be used for the silver particle dispersion according to the present invention, can be used A liquid phase method for reducing a silver compound in a liquid organic medium. In this case, one or two or more kinds of alcohols or polyols having a boiling point or higher in function as a reducing agent are used as the liquid organic medium. Then, the reduction reaction can be carried out in the presence of an organic compound (! or two or more kinds of amine compounds), and the obtained silver particle powder is dispersed in a point of 6 (TC to 30 (TC non-polar or polar) After dispersing the coarse particles from the dispersion in a small dispersion medium, the silver particle dispersion according to the present invention can be obtained. 318902 8 200830385 l • Preparation = that, according to the present invention, a silver particle dispersion can be provided Second, special When the silver compound is reduced in one or two or more kinds of liquids which function as a reducing agent or an alcohol, the molecular weight (10) of at least one or more unsaturated bonds in ! = to silver Γ The above-mentioned reduction reaction is carried out under the coexistence of the cockroaches, and the obtained =: the powder is dispersed in a non-polar or low-polar liquid organic medium having a _ of 6 Å to 3 Å. (Best embodiment of the invention) The present inventors repeated the production test of the silver particle powder by a liquid phase method, such as in an alcohol having a boiling point of Μ to MG, and silver nitrate at a temperature of Μ C (returning the evaporated alcohol under the liquid phase) For example, in the case of reduction treatment of the amine compound of the molecule 4 1001400, a spherical silver nanoparticle powder having a uniform particle size can be obtained, and is described in Japanese 2005-26305 ^ , 〇 or "L or polyol towel 'Silk compound (representatively, silver silicate g milk...'艮' at a temperature of 85 C or higher, for example, in the coexistence of a molecular weight (10) to a fatty acid of hydrazine, a less rot compound is obtained. a spherical silver particle powder having a uniform particle size, and It is described in the specification and drawing of Yanxian No. 6. In any case, if it is a non-polar or low-polarity liquid organic medium, it can be used as a dispersion of silver particles. When the coarse particles of the centrifugal separator are used from the dispersion, the particle size is less uneven (cv value (variation coefficient ^ deviation σ / percentage of average particles less than 4% by weight) silver particles = monodisperse Dispersion of (monodispersed)., 318902 9 200830385

A 然而，在此等方法中，如提高反應溫 ‘還原液t的銀離子，惟會引起教子又文，則有效地 致難於製得作為目的之50nm以下的二而袓粒子化，以 地，如降低反應溫度時，則雖可防止子粉末，而相反 中的銀離子的還原效率降低而減少^了^ ’惟由於液 '行作為目的之50nm以下的銀粒子制走如奴穷效進 更進一步的改善。 a不〇衣作時，則需要 =_發現，如作為有機化 #〇〇以上者，則即使提高反應溫度仍能防 使用刀子里 能以高還原率且高效率製得50_ :子其：果’ 而，現’如採用大分子量的有機:=二 分散液作為配線形成用之材料時，列 =銀粒子 低溫下的燒結性會顯著降低之另—問題。/ 0C以下的 高收::::。知’如採用高分子量的有機化合物時，可以 门收羊衣仔50細以下的銀粒子粉末、盘苴銀 P低溫燒結性，完全係兩碼事而不能使其併存。77攻 在基板上使用有機薄膜等之 上不能以300。(；以上的溫声 '才自於貝貝 自度k成，因此，該分散液的用途 自然胃文到限制，並在採用其 料之+ k 燒結性良好者4 材科之电路基板中之低溫 认B 係表不攸向该銀粒子分散液的價值之意。 ;疋再行研九之結果發現，如採用1分子内且有雔 鍵等的不飽和心個以上之胺介人^ 子雙 银六 $ 上之胺化合物時，且可達成前述之 者發現’如在該還原處理中，階段性地提高溫度 、’採用依多段反應溫度進行還原之配方，或徹底實. 318902 200830385 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(transmis si on 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2〇〇nm以下，較佳為100nm以下，更佳 _ 50nm以下，再更佳為3〇nm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。A However, in these methods, for example, increasing the silver ion of the reaction temperature 'reducing liquid t, but causing the teachings to be essay, effectively makes it difficult to produce the target of 50 nm or less, and the particles, For example, when the reaction temperature is lowered, the sub-powder can be prevented, and the reduction efficiency of the silver ion in the opposite direction is reduced, and the reduction of the silver particles of 50 nm or less, which is the purpose of the liquid, is carried out. Further improvement. If you don't wear clothes, you need to find =_, if you are more than #有机, if you increase the reaction temperature, you can prevent the use of a knife with high reduction rate and high efficiency to produce 50_: However, when a large molecular weight organic:=two dispersion liquid is used as a material for wiring formation, the column = the sinterability at the low temperature of the silver particles is remarkably lowered. / High below 0C::::. Knowing that if a high molecular weight organic compound is used, it is possible to collect the silver particle powder of less than 50 fine pieces of the sheep's clothes, and the low-temperature sinterability of the silver-plated silver P, which is completely different and cannot coexist. 77 attack No more than 300 can be used on the substrate using an organic film or the like. (The above-mentioned Wensheng' is derived from Babe's self-containedness. Therefore, the use of the dispersion is natural and limited, and it is used in the circuit board of the material of the material with good k + sinterability. The low temperature recognition B system does not mean the value of the silver particle dispersion. The results of the 疋 研 研 研 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九In the case of a double-silver-on-amine compound, it can be found that, as in the reduction treatment, the temperature is increased stepwise, and the formula is reduced by the reaction temperature according to the multi-stage reaction temperature, or completely. 318902 200830385 In the case of the washing of the particle suspension and the operation of removing the coarse particles, it is more advantageous to achieve the above-mentioned coexistence, and it is possible to produce a silver particle dispersion having a high degree of low-temperature sinterability with high dispersion of silver nanoparticles. The matters specified in the present invention are described. [Average particle diameter dtem] The silver particle powder of the present invention is observed by a TEM (transmissive electron microscope) observation of the average particle diameter (by DTEM) It is 2 〇〇 nm or less, preferably 100 nm or less, more preferably _ 50 nm or less, still more preferably 3 〇 nm or less, and optionally 20 nm or less. Therefore, the silver particle powder dispersion of the present invention is suitable for fine wiring. In the TEM observation, 300 diameters of independent particles which are not overlapped are measured from an image magnified 600,000 times, and the average value thereof is determined. [X-ray crystal grain size Dx] Silver particle powder of the present invention The crystal grain size (indicated by Dx) is 50 nm or less. The X-ray crystal grain size of the silver particle powder can be obtained by X-ray diffraction, and is obtained by Scherrer's formula. The method of obtaining is as follows. The Scherrer's formula can be expressed by the following general formula.

Dx-K · λ//3 COS 0 式中，分別表示K : Scherrer常數，Dx :結晶粒徑， λ :測定用X射線波長，/3 :在X射線繞射所得峰值的半 高寬（FWHM : full width half maximum)，0 :繞射線的布 雷袼角（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 200830385Dx-K · λ//3 COS 0 where K: Scherrer constant, Dx: crystal grain size, λ: X-ray wavelength for measurement, /3: full width at half maximum of X-ray diffraction peak (FWHM) : full width half maximum), 0 : Bragg angle around the ray. 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 200830385

Dx=0.94x1.5405/β COS 〇 '[單結晶化度] 本發明之銀粒子粉末，係單結晶化度（Dtem/dx)為2 〇 以下者。因而，可形成精細的配線，其抗遷移性⑽㈣⑽ 亦優異。如單結晶化度在2‘0以上時，則多結晶化度(細hi crystamnity)增高而將在多結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] 本表明中，係使表面以有機保護枋被覆之銀粒子分散 機介質上而作成銀粒子分散液者，作為其有機保 =使用1分子中至少具有i個以上的不飽和鍵，而分 :、二00至1000，較佳為⑽竭的胺化合物。雖可 使用由於將此種具有不麵鍵之胺化合物作 ==還原反應中容易一齊產生银核之同時，發生能 %，：!:!!出之銀核的成長之現象，並如前述，可 物可在較低π下八~ /末由於該胺化合 ㈣Γ 政，因此可確保其銀粒子分散液的低溫 ^性;可財發财使用之代表性胺化合物而言，可例 舉.二：丙基鞍、油基胺、二油基胺 ；例 [液狀有機介質] τ 女寺 狀有述的有機保護材所被覆之銀粒子粉末分散之液 狀有機介質而言，係使 κ收 極性低的、、态# 士 ’、、 至3⑻C的非極性或者 的液狀有機介質。在此，「非極性或者極性低的」， 318902 12 200830385 ,2指在25下的相對介電常數(relative dielectric constant) 下八之意’較料5以下。如介電常數在15以上時， ^用、a、刀政性惡化而有沈降之情形而不宜。可按分散液 • 吏用各種液狀有機介質，其嫩氮系較適合使 .:十:疋可使用：異辛燒、正癸院、異十二烧、異己烧、 正十一烷、正十四检、τ丄— 的脂肪族烴、苯、甲苯、十三烧、己院、庚烧等 萘等的芳香族 7本'乙基苯'十氫萘'四氫 t生起Γ為如煤油(ker°sene)般的混合物。再者，為調整 切it; $合後㈣狀有機介質在坑下的介電 等=5以下之範圍内’添加醇系、調系 寺的極性有機介質。 卞 [醇或者多元醇] 的種=中4於發揮作為還原劑功能之醇或者多元·醇 液::r化合物之還原者，此種醇 %、第三丁醢r 知、正丁醇、異丁醇、第二丁 又，多_而、、巴豆醇（emyl相。1)、環戊醇等。 醇等知而§’可使用：二乙二醇、三乙二醇、四乙二 [黏度] 之分ίΓΓ發明之銀粒子粉末分散於液狀有機介質中 之：液因—種牛頓流體’在25。。下之黏度 法二二:Γ:銀粒子分散液，係〜^ 成用材科。依贺墨法進行配線形成時，為維持 318902 13 200830385 ‘配線的平坦性而欲求彈至基板上之液滴量的均勾性 、於本發明之銀粒子分散液係牛頓流體且黏度在50mPa.s 以下而在贺嘴無堵塞之下可順利排出液滴，因而可符合此 . 種需求。黏度之測定，可於身機產 ' 計RE55〇T ^•壯 （）製的R55〇型黏度 - 衣付錐形轉子（cone rotor；)0.8。者，& 25γ & 恆溫下進行。 在25C的 [表面張力] 本發明之銀粒子分散液，係在抑下的表面張 馨〇mN/m以下者。因此，適 為 純“丄 貝墨法之配線形成用之 枓。由於衣面張力大的分散液，在噴嘴前端的彎月面 ^lemscus)的形狀不穩定，因而難以控制排出量或排出時 ^广經W基板上之液滴的沾濕性(w伽础⑺不佳，而 線的平坦性變差之結果，惟由於本發明之銀粒子 ^又液之表面張力為8GmN/m以下而不會有上述之情況發 生而可進行品質良好的配線。表 x ^界面科學麵 張力之測疋，可使用協 而在25、温下測定。 本發明之銀粒子的分散液，可通過具有銀粒子粉末的 子簡)+2Gnm的孔徑之膜濾器。由於僅通過 =Π均粒捏％大2°_之孔徑 能 1不嘁$，而係各個粒子能在該液中流動之狀 二亦即，幾乎已完全呈分散之狀態。此種性質，亦表示 材ΓΓ艮粒子的分散液極適用為依喷墨法之配線形成用 材枓。如粒子中存在有凝聚之部分，則不僅容易發生噴嘴 318902 14 200830385 堵塞，並因所形成之配線的填充性不佳而在燒成時發生細 a 孔以致成為高電阻化或斷線的原因，惟此種情況，在才發 明之分散液則可避免。於膜濾器通過試驗中，作為孔护最 小的過濾器，可使用Whatman(懷特曼）社製阿諾脫普加 譯）25注射器過濾器（syringe filters)(孔徑2〇nm)。 [pH] 本發明之銀粒子分散液，係pH(氫離子濃度）為&$以 上者。因此，其特徵係··具有作為配線形成用材料時不致 餅腐#電路基板上的銅落，並難以引發配線間的遷移 (migration)。該分散液的_測定，可使用11〇反甩八(堀 場）(股）製Ph儀D-55T、及低導電性水·非水溶劑用pH電 極b377]〇D而實施。如依此種方法所測定之分散液的_ 未$ 6.5時，會因酸成分而引起電路基板上的銅箔腐蝕， 且容易發生配線間的遷移，以致降低電路的可靠性。 [燒失量] 、 φ銀粒子分散液之燒失量（％)，係指以下式表示之值。 燒失里 。 式中 W5〇、W3〇〇以及W10⑽，表示溫度在50。匚、3〇〇 C以及10001：下之分散液的重量。 旦本發明之銀粒子分散液的燒失量未滿5%。由於燒失 里未滿5 /〇’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、泉如k失里在5%以上時，則由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，有時 318902 15 200830385 Λ會阻礙到導電性，因而不宜。 、’曰可使用麥克科技/布爾卡埃伊克斯（音g TG撕測量器，依下列測定條件測定 • 試料重量：20±lmg， 升溫速度：HTC/分鐘， 氣體環境：大氣（無通氣）， 標準試料：氧化鋁20.0mg， 測定皿：（股）理學研究所製氧化鋁測定皿， 溫度範圍：50DC至1〇〇〇。〇 ^著，就本發明之銀粒子粉末之製造方法加以說明。 物（夂種錄子粉末，録醇❹7，將銀化合 鹽或銀氧化物），在有機化合物的共存下，在85 的溫度下進行還原處理即可製造。有機化合.物 ::子:=述]吏用1分子中具有1個以上的不餘和鍵 %== 则的胺化合物。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 :=大!:介質發揮功能者。醇而言，較佳= ==劑的蒸發與冷凝之回流條件下實施。供為還： / :而言，*:氯化銀、確酸銀、氧化銀、碳酸聲 酸銀。本發明之方限定於確 去中，反應時的液中# Ag(銀)離子濃 318902 16 200830385 ‘ 可* 50毫莫耳/公升以上之條件下進行。還原處理時， I段性地提高反應溫度，以多段反應溫度之 處理亦屬有利。 、彳丁逖原 反應後的銀粒子粉末的懸浮液(剛反應完成後的料漿 (slmry)) ’在經過洗滌·分 太鉻日日> w t 月又刀、、夂寻步驟後可作成依照 本4月之銀粒子的分散液，惟此等步驟的代表劑可 下。 [洗滌步驟] 籲υ將反應後的既定量的料聚，使用離^分離器（日立 (股）製的CF7D2)，以3000rpm實施固液分離 將上澄液棄去。 刀隹里，亚 ⑺於沈殿物中，添加與先前的料裝同量的甲醇 音波分散機加以分散。 亚ί之勝起 (3) 重複前述的（1)至（2)2次。 (4) 貫施前述的（1)，廢棄上澄液後取得沈澱物。 ’ [分散步驟] ^於前述的洗滌步驟中所得沈崎中添加液狀 所 ⑺接者’使用超音波分散機以製作銀粒子混濁γ貝 [分級步驟] / /乂。 ⑴將經分散步驟之銀粒子與液狀有機介質的混 同樣的離心分離器，以3_啊實施固液分離％八’使用 (2)回收上澄液。該上澄液即成為銀粒子分散液。刀、’里 [銀粒子分散液之濃度] 銀粒子分散液中的銀濃度，可依下述方式算出 318902 17 200830385 P (1)將前述的分級步驟所得之銀粒子分散液，移至已知重量 w 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 %w=267)185.83ml，及作為銀化合物之硝酸銀結晶（關東化 學（股）製）19.212g，使用磁力攪拌器（magnet stirrer)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（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的旋轉速度攪拌 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 200830385Dx = 0.94 x 1.5405 / β COS 〇 '[Single crystallinity] The silver particle powder of the present invention has a single crystallinity (Dtem/dx) of 2 Å or less. Therefore, fine wiring can be formed, and the migration resistance (10) (4) (10) is also excellent. When the degree of single crystallinity is 2 "0" or more, the degree of polycrystallization (fine h crystamnity) is increased, and impurities are easily contained between the polycrystalline particles, 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 invention, a silver particle dispersion liquid is formed on a silver particle disperser medium coated with an organic protective ruthenium, and as an organic material, at least one or more unsaturated substances are used in one molecule. The bond, and is divided into: 20 to 1000, preferably (10) depleted amine compound. It is possible to use a phenomenon in which the silver core is easily generated by the amine compound having the non-face bond as the == reduction reaction, and the growth of the silver core is generated by the energy %, :!:!! The material can be at a lower π -8 / / due to the amine compound (four) ,, so it can ensure the low temperature of its silver particle dispersion; can be cited as a representative amine compound for the use of wealth. : propyl saddle, oleylamine, dioleylamine; example [liquid organic medium] τ female temple-like organic protective material coated with silver particle powder dispersed liquid organic medium, Non-polar or liquid organic medium with low polarity, state #士, to 3(8)C. Here, "non-polar or low polarity", 318902 12 200830385, 2 means a relative dielectric constant at 25, which means less than 5. If the dielectric constant is above 15, it is not appropriate to use a, a, or a knife to deteriorate and settle. It can be used according to the dispersion liquid. It can be used in various liquid organic media. Its tender nitrogen system is suitable for use.: Ten: 疋 can be used: different simmering, simmering sputum, different twelve burning, different burning, n-undecane, positive Fourteen inspections, τ丄—aliphatic hydrocarbons such as aliphatic hydrocarbons, benzene, toluene, thirteen-burning, hexagram, and heptane, etc. The aromatic 7-ethyl benzene 'decahydronaphthalene' tetrahydrogen is produced as kerosene. a mixture of (ker°sene). Furthermore, in order to adjust the cutit;; after the (four) organic medium is in the range of the dielectric below the pit, etc. = 5 or less, the polar organic medium of the alcohol system and the modulating temple is added.卞[Alcohol or polyhydric alcohol] species = medium 4 is used as a reducing agent function alcohol or polyhydric alcohol solution: :r compound reduction, such alcohol%, third butyl sulfonate, n-butanol, iso Butanol, second dibutyl, poly-, and crotyl alcohol (emyl phase. 1), cyclopentanol and the like. Alcohol, etc. §' can be used: diethylene glycol, triethylene glycol, tetraethylene glycol [viscosity], the silver particle powder of the invention is dispersed in a liquid organic medium: liquid factor - Newtonian fluid 25. . Viscosity under the law 22: Γ: silver particle dispersion, system ~ ^ into the material section. When the wiring is formed by the Heha ink method, in order to maintain the flatness of the wiring of 318902 13 200830385, the uniformity of the amount of droplets to be ejected onto the substrate is required, and the silver particle dispersion of the present invention is a Newtonian fluid with a viscosity of 50 mPa. s The following can smoothly discharge the droplets without blocking the mouthpiece, thus meeting the needs of this. For the determination of viscosity, it can be used in the production of 'RE55〇T ^• Zhuang () R55 黏 type viscosity - clothing cone rotor (cone rotor;) 0.8. , & 25 γ & [Surface tension] at 25C The silver particle dispersion of the present invention is not less than the surface 张mN/m. Therefore, it is suitable for the formation of the wiring of the mussel ink method. The shape of the meniscus at the tip of the nozzle is unstable due to the dispersion of the coating surface tension, and it is difficult to control the discharge amount or discharge. The wettability of the droplets on the substrate of the wide warp W (when the base (7) is poor, and the flatness of the line is deteriorated, but the surface tension of the silver particles of the present invention is not more than 8 GmN/m. The above-mentioned situation can occur and the wiring can be made of good quality. Table x ^ The measurement of the interface scientific surface tension can be measured at 25 °C using the synergy. The dispersion of the silver particles of the present invention can have silver particles. a membrane filter with a pore size of +2Gnm of the powder. Since the pore diameter of the powder is only 1%, the particle diameter of the powder can be 1 or less, and the particles can flow in the liquid. It is almost completely dispersed. This property also indicates that the dispersion of the material particles is extremely suitable for the wiring forming material according to the inkjet method. If there is a coagulated portion in the particles, the nozzle 318902 is not only prone to occur. 200830385 Blockage and wiring due to the formation The filling property is not good, and the fine a hole occurs during firing, which causes high resistance or disconnection. However, in this case, the dispersion which was invented can be avoided. In the test of the membrane filter, it is used as a hole protector. The smallest filter can be a syringe filter (aperture 2 〇 nm) of Whatman (Whiteman). [pH] Silver particle dispersion of the present invention, pH ( The hydrogen ion concentration is equal to or higher than the above. Therefore, it is characterized in that it does not cause copper slip on the circuit board when it is used as a wiring forming material, and it is difficult to cause migration between wirings. The measurement can be carried out by using a 11-inch anti-deuterium (Earth) (Phase) Ph-meter D-55T and a low-conductivity water/non-aqueous solvent pH electrode b377] 〇D. When the dispersion _ is not 6.5, the copper foil on the circuit board is corroded due to the acid component, and the migration between the wirings is liable to occur, so that the reliability of the circuit is lowered. [Lost-loss], φ silver particle dispersion The loss on ignition (%) refers to the value expressed by the following formula. In the case of W5〇, W3〇〇 and W10(10), the weight of the dispersion at a temperature of 50 匚, 3〇〇C, and 10001: The loss of the silver particle dispersion of the present invention is less than 5%. If the loss is less than 5 /〇', therefore, when the wiring is fired, the organic protective material is burned in a short time without suppressing the sintering, and the good conductivity is obtained. In this case, since the organic protective material acts as a sintering inhibitor at the time of firing, the electric resistance of the wiring is increased, and sometimes 318902 15 200830385 阻碍 hinders the conductivity, and thus is not suitable. , '曰 can use Mike Technology / Burka Eyix (sound g TG tear measuring device, measured according to the following measurement conditions • sample weight: 20 ± lmg, heating rate: HTC / minute, gas environment: atmospheric (no ventilation) , Standard sample: alumina 20.0mg, measuring dish: (stock) Alumina measuring dish made by Institute of Science, temperature range: 50DC to 1〇〇〇. 〇^,, the manufacturing method of the silver particle powder of the present invention is explained The product (the sputum seed powder, the alcohol sputum 7, the silver compound salt or the silver oxide) can be produced by the reduction treatment at a temperature of 85 in the presence of an organic compound. Organic compound::: = 吏 吏 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺Also: = large!: The medium functions. For alcohol, it is better to = == the evaporation and condensation of the agent is carried out under reflux conditions. For the sake of: / :, *: silver chloride, silver acetate, Silver oxide, silver acid sour acid. The invention is limited to In the middle of the reaction, the solution in the liquid #Ag (silver) ion concentration 318902 16 200830385 ' can be carried out under conditions of 50 millimoles / liter or more. During the reduction treatment, the reaction temperature is increased in stages, in a plurality of reaction temperatures. The treatment is also advantageous. The suspension of the silver particle powder after the reaction of the ruthenium ruthenium (slurry after the completion of the reaction) is "washed and divided into too chrome day" > wt month knives, 夂After the step is found, a dispersion of silver particles according to this April can be prepared, but the representative agent of these steps can be used. [Washing step] υ υ υ 既 既 既 既 既 既 既 既 既 既 既 既 ( ( CF7D2), which is subjected to solid-liquid separation at 3000 rpm, and the supernatant is discarded. In the shovel, Ya (7) is placed in the sect, and the same amount of methanol sonic disperser is added to disperse it. (3) Repeat the above (1) to (2) twice. (4) After the above (1) is applied, the precipitate is obtained after discarding the supernatant. '[Dispersion step] ^ In the aforementioned washing step The obtained sinking liquid was added to the liquid (7) and the ultrasonic wave disperser was used to make the silver particles turbid. Shell [Classification Step] / /乂. (1) The same centrifugal separator as the silver particles in the dispersion step and the liquid organic medium are mixed, and the solid-liquid separation is performed at 3 ah. The supernatant liquid is a silver particle dispersion. The concentration of silver in the silver particle dispersion of the knife, 'Li [concentration of silver particle dispersion] can be calculated as follows: 318902 17 200830385 P (1) The above classification step The obtained silver particle dispersion is transferred to a container having a known weight w. (2) The container is charged in a vacuum dryer, and sufficient attention is paid to prevent bumping while raising the degree of vacuum and temperature to carry out concentration. • Drying, after the liquid was not observed, it was dried in a vacuum at 200 ° C 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. 185.83 ml of oleylamine having an unsaturated bond in the molecule (%w=267, manufactured by Wako Pure Chemical Industries, Ltd.), and 19.212 g of silver nitrate crystal (manufactured by Kanto Chemical Co., Ltd.) as a silver compound, using a magnetic stirrer (magnet stirrer) is stirred 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 stirred and heated at a rotational speed of OO rpm, and refluxed at a temperature of 10 ° C for 2 hours and 30 minutes. Then, increase the temperature to l〇8 ° C, carry out 2 hours and 30 minutes of reflux 18 318902 200830385

後完成反應。此時，至1 0 Π1Z 為2口分鐘。 及至之升溫速度均作成 杰=反應完成後的料漿分取40〇11，並實施本文所記載之 洗滌步驟、分散步驟只及分έ 刀、及步驟後，製得銀粒子的分散 液。此％，於分散步驟中作 1 马/夜狀有機溶劑而添加煤油 40ml以製作混濁液，而對於 分級步驟所得之銀粒子分散 液，依本文中所記载之方法电 力忐貝施各特性的評價。 其結果’所仔之銀粒子，技 一 ^ 係平均粒徑DTEM=12.3nm， _吉晶粒控Dx= 15·0ϋΐη，輩έ士曰儿— 響 早…日日化度（DTEM/Dx)=0.82，就其 銀粒子分散液而言，銀粒子澧厣 ^ 了 卞辰度一5wt%，黏度= ll.mpa· s， 表面張力=25.4mN/m，^ P心86 ’燒失量二3.1%，而順利通 過Whatman社製阿諾脫普力 打肌g加25注射器過濾器（孔徑 2〇nm)，分散性良好且並無凝聚現象。 [實施例2] 於作為液狀有機介質兼還原, 你釗的兴丁醇（和光純藥（股） 製的特級品）120ml中5添加作兔士、 、 隱 』乍為成有機保護材之化合物之 分子中具有1個不飽和鍵之油其此w止u ’由基fee ( f光純藥（股）繫 及作為銀化合物之石肖酸銀結晶⑽〔 學（股）製）20.59g，使用磁力攪拌器攪拌，以使確酸銀溶解。 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10〇rpm的旋轉速度攪拌芎容、、夜 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之升溫速度均作成為2它/分鐘。 318902 19 200830385 β 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烷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。The reaction is completed afterwards. At this time, to 1 0 Π 1Z is 2 minutes. And the heating rate is made into a gel. After the completion of the reaction, the slurry is taken up to 40〇11, and the washing step and the dispersing step described herein are carried out only after the splitting knife and the step, and a dispersion of silver particles is obtained. %%, in the dispersion step, 1 horse/night organic solvent is added and 40 ml of kerosene is added to prepare a turbid liquid, and for the silver particle dispersion obtained in the classification step, the characteristics of the electric 忐 are applied according to the method described herein. Evaluation. The result is 'the silver particle, the average particle size DTEM = 12.3nm, _ JI grain control Dx = 15·0ϋΐη, the generation of gentleman — children - ring early... daytime degree (DTEM / Dx) =0.82, in terms of its silver particle dispersion, the silver particle 澧厣^ has a 卞 度 一 5 wt%, viscosity = ll.mpa· s, surface tension = 25.4 mN / m, ^ P heart 86 'burning loss two 3.1% And smoothly through the Whatman company's Arnold's muscle muscle g plus 25 syringe filter (pore size 2 〇 nm), good dispersion and no agglomeration. [Example 2] As a liquid organic medium and reduction, it is added to the 120ml of the chlorinated butyl alcohol (special grade product made by Wako Pure Chemical Co., Ltd.) as a kind of organic protective material. An oil having one unsaturated bond in the molecule of the compound is obtained from the base fee (f-pure pure drug (stock) system and as a silver compound, silver silicate silver crystal (10) [manufactured by the company), 20.59 g, Stir using a magnetic stirrer to dissolve the acid silver. 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 a magnetic stirrer was used at a rotation speed of 10 rpm. The mixture was stirred, heated at night, and refluxed at a temperature of 108 ° C for 5 hours to complete the reaction. At this time, the temperature increase rate up to 108 ° C was made 2 it / minute. 318902 19 200830385 β The total amount of the slurry after completion of the reaction is subjected to a washing step, a dispersion step, and a classification step as described herein to prepare a dispersion of silver particles. At this time, 6.28 g of dodecane was added as a liquid organic solvent in the dispersion step 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.

I 其結果，所得之銀粒子，係平均粒徑DTEM=8.01nm， 結晶粒徑〇x=4.69nm，單結晶化度（DTEM/Dx)二1.71，就其 銀粒子分散液而言，銀粒子濃度=65.4wt%，黏度= 10mPa · •，表面張力=25.0mN/m，pH二8·61，燒失量二4.8%，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) 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)l99· 11ml、及作為銀化合物之石肖酸銀結、晶（關東化 % (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1 OOrpm的旋轉速度擾拌該溶液 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 · 200830385 時’於分散步驟中作丄 ，以製作混濁液，而對、啕機溶劑而添加十四烷2.43g 依本文中所記幾之;分級步驟所得之銀粒子分散液， 其結果，施各特性的評價。 •結晶粒徑¥6.02nm 曰係平均粒徑腿， 资粒子八今六 ·、'、° B日化度（dtem/Dx)=；L50，就其 銀粒子分散液而 一18 7 p 銀被子濃度二75.8wt%，黏度 一 18.3mPa · s，表面張力 -4 Ω〇/ · mH/m ’ ΡΗ=8·50，燒失量 一4·0/〇,而順利通過Wh ★ π, 一 、加恤⑽社製阿諾脫普加25注射器過 ^ , 】】’ /It% 凝聚現象。 (比較例1、2) 貝％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υ、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 見使用十四炊》作為为政介質並依既定方法嘗試製作油 墨·，惟未能觀察任何經分散:^·油墨中之粒子。I. As a result, the obtained silver particles have an average particle diameter DTEM=8.01 nm, a crystal grain size 〇x=4.69 nm, and a single crystallinity (DTEM/Dx) of 1.71, and in terms of the silver particle dispersion, silver particles Concentration = 65.4wt%, viscosity = 10mPa · •, surface tension = 25.0mN/m, pH 2: 8.61, loss on ignition of 2.8%, smoothly passed through the Whatman company's Arnoldup plus 25 syringe filter (pore size 20nm ), good dispersion and no agglomeration. (Example 3) In 120 ml of isobutanol (a special product manufactured by Wako Pure Chemical Industries, Ltd.) as a liquid organic medium and a reducing agent, a compound having an organic protective material is added to have a single unsaturated bond in a molecule. An oil-based amine (Mw=267) of the pure chemical (manufactured by Kokusai Co., Ltd.) l99·11 ml, and a silver succinic acid silver salt and a crystal (manufactured by Kanto Chemical Co., Ltd.) 20.59 g as a silver compound, and stirred using a magnetic stirrer. In order to dissolve the 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 was agitated at a rotation speed of 100 rpm using a magnetic stirrer. The solution was mixed and heated, and the reaction was completed after refluxing at a temperature of 108 ° C for 5 hours. 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. The 20 318 902 · 200830385 'in the dispersion step to make a turbid liquid to make a turbid liquid, and to add a tetradecane 2.43 g to the solvent, according to the following; the silver particle dispersion obtained by the classification step, As a result, evaluation of each characteristic was performed. • Crystalline particle size ¥6.02nm 曰 series average grain size leg, particle particle 八六六, ', ° B degree (dtem/Dx) =; L50, its silver particle dispersion and a 18 7 p silver quilt The concentration is 25.8wt%, the viscosity is 18.3mPa · s, the surface tension is -4 Ω〇 / · mH/m ' ΡΗ=8·50, the loss on ignition is 4·0/〇, and the smooth passage of Wh ★ π, I. Plus (10) the system of Arnold's plus 25 syringes ^, 】] ' / It% condensation phenomenon. (Comparative Examples 1 and 2) In the case of Example 1, a cyclohexylamine (Comparative Example, ethylhexylamine (Comparative Example 2)) was used instead of the oleylamine as the organic compound having no unsaturated bond. 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 were not confirmed. For the sake of caution, the use of the fourteen 炊 as a medium of administration and attempting to produce ink according to the established method was performed. However, it was not possible to observe any particles dispersed in the ink.

W 318902 21W 318902 21

Claims (1)

200830385 十、申請專利範圍： •、，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)5〇nm以下的銀粒子粉末，分散於沸點 在60至300°C的非極性或者極性低的液狀有機介質中 =銀粒子的分散液，其特徵為：前述的有機保護材係1 刀子中至少具有1個以上不飽和鍵之胺化合物。 2‘如申請專利範圍第！項之銀粒子分散液，其中銀粒子的 結晶粒徑（Dx)在5〇nm以下，而單結晶化度（D窗/Dx) I 在2 · 0以下。 如申明專利範圍第1項或第2項之銀粒子分散液 Mi Ιτί * 、〜舉，J 刀狀/ 有機保護材係分子量為1〇〇至1〇⑽的胺化合物 4.如申請專利範圍第卜2項或第3項之銀粒子分散液 、中刀放液的銀濃度為5至9〇wt%。 5’如申請專利範_丨項至第4項中任—項之銀粒子分 液’其係黏度為50mPa. s以下的牛頓流體。 ^如申請專利範圍第1項至第5項中任-項之銀粒子分 液，其中表面張力為8〇mN/m以下。 7· ^申請專利範圍第丨項至第6項中任—項之銀粒子分 =’其中可通過具有銀粒子粉末的平均粒徑⑴聰 〇nm的孔徨的膜濾器者。 =申請專鄉㈣丨項至第7射任—項之絲 液’其中pH為6.5以上者。 9·=申請專利範圍第〗項至第8項中任—項之銀粒子分負 /之’其中燒失量未滿5〇/0者。 318902 22 200830385 、1 0· —種申請專利範圍第i項之銀粒子分散液之製造法，其 11 #寸欲為：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分子中 至 > 具有1個以上不飽和鍵之分子量〗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。 U 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丨種 或^種以上的液中進行銀化合物之還原時，在^分子中 至少具有1個以上不飽和鍵之分子量100至圆的胺 化合物的共存下，谁> 乂 仃刖迷的逛原反應，並使所得之銀 粒子粉末在沸點為6〇 ^ ^ . M 300 c的非極性或者極性低的 液/μν有機介質中分散。200830385 X. Patent application scope: •, a silver particle dispersion, which is a silver particle powder having an average particle diameter (DTEM) of 5 〇 nm or less coated on an organic protective material, dispersed at a boiling point of 60 to 300 ° C. In the liquid organic medium having a low polarity or a low polarity, a dispersion of silver particles, wherein the organic protective material is an amine compound having at least one unsaturated bond in the first knife. 2 ‘If you apply for a patent range! The silver particle dispersion of the silver particles has a crystal grain size (Dx) of 5 Å or less and a single crystallinity (D window/Dx) I of 2 or less. For example, the silver particle dispersion of the first or second aspect of the patent scope Mi Ιτί *, 〜, J knife-shaped / organic protective material is an amine compound having a molecular weight of 1 〇〇 to 1 〇 (10). The silver concentration of the silver particle dispersion and the medium knife discharge liquid of the item 2 or the third item is 5 to 9% by weight. 5', as in the application of the patents _ 至 to 4, the silver particle liquid distribution' is a Newtonian fluid having a viscosity of 50 mPa·s or less. ^ A silver particle separation according to any one of the items 1 to 5 of the patent application, wherein the surface tension is 8 〇 mN/m or less. 7. The silver particle fraction of any of the items in the scope of the application of the second to sixth items is a membrane filter having pores of an average particle diameter (1) of the silver particle powder. = Apply for the hometown (4) item to the 7th line - the silk liquid of the item, where the pH is 6.5 or higher. 9·=Applicable to the scope of the patent range from item 〖 to item -8, the silver particles are divided into / / where the loss on ignition is less than 5 〇 / 0. 318902 22 200830385 , 1 0 · A method for producing a silver particle dispersion of the invention patent range, the 11 # inch desire is: one or two or more kinds of alcohols or polyols which function as a reducing agent When the reduction of the silver compound is carried out in the liquid, the above-mentioned reduction reaction is carried out in the presence of an amine compound having a molecular weight of one or more unsaturated bonds in one molecule to 1 Torr. U. The method for producing a silver particle dispersion according to the first aspect of the invention, characterized in that, when a silver compound is reduced in a liquid or a liquid of an alcohol or a polyol which functions as a reducing agent, In the coexistence of an amine compound having a molecular weight of at least one unsaturated bond having at least one unsaturated bond in the molecule of 100 to a circle, which is entangled in the original reaction, and the obtained silver particle powder has a boiling point of 6 〇 ^ ^ . Disperse in 300 c of non-polar or low polarity liquid/μν organic medium. 318902 23 200830385 七、指定代表圖：本案無圖式 -(一）本案指定代表圖為：第（）圖。 (二）本代表圖之元件符號簡單說明： 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 本案無代表化學式318902 23 200830385 VII. Designated representative map: There is no schema in this case - (1) The representative representative map of this case is: (). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 4 3189024 318902