TWI286090B

TWI286090B - Highly crystalline silver powder and method for production thereof

Info

Publication number: TWI286090B
Application number: TW094103609A
Authority: TW
Inventors: Taku Fujimoto; Takuya Sasaki; Katsuhiko Yoshimaru; Hiroyuki Shimamura
Original assignee: Mitsui Mining & Smelting Co
Priority date: 2004-02-10
Filing date: 2005-02-04
Publication date: 2007-09-01
Also published as: WO2005075133A1; KR20070018025A; JP2005226094A; CN1925941A; EP1721690A1; US20090023007A1; JP4976642B2; TW200536636A; KR101215458B1

Abstract

A method for producing a highly crystalline silver powder is characterized in that a first aqueous solution containing silver nitrate, a dispersing agent and nitric acid is admixed with a second aqueous solution containing ascorbic acid, wherein the dispersing agent is preferably poly(vinyl pyrrolidone) or gelatin. A highly crystalline silver powder produced by the above method preferably has a D90/D10 of 2.1 to 5.0, a diameter of a crystallite greater than 300 Å, an average particle diameter D50 of 0.5 to 10 mum, and exhibits thermal shrinkage in the longitudinal direction at 700 DEG C of within ± 3%. The above highly crystalline silver powder is composed of fine particles with good dispersibility, broad particle size distribution, and large crystallites.

Description

-1286090 九、發明說明：【發明所屬之技術領域】本發明係有關於一種高結晶性銀粉及其製造方法。詳細說明之，係有關於一種高結晶性銀粉及其製造方法，其中將例如曰曰片元件、電漿顯示板等的電極或電路加以大幅精細化而能夠形成具有高密度及高精度且高可靠性者之導電性膏劑、特別是對微細的線路或薄層而平滑的塗膜等能 ==成具有高密度及高精度且高可靠性者之導電性膏劑的衣k…故較佳，由於係微粒、分散性良好、粒度分布不致 m而比較寬緩、微晶較大，故用作導電性膏劑的原料時，銀粉對膏劑的分散性以及銀粉在導電性膏劑中的填充性為相當優異，而能夠使由銀厚膜所形成的電極或電路等將由導電性膏劑所得到的銀厚膜製成耐熱相虽優異、同時比電阻（電阻率）較低者。【先前技術】一=往作為形成電子元件等的電極或電路之方法，一種導電性材料的銀粉分散於膏 ' ^ ^ Φ ^ ^ e W甲而形成導電性膏劑， =性印刷於基板後，藉由對該膏劑進行A ===:膜以製成電路的方法係習知者小型高密度二此，即電子… 粉，在製成導電性膏劑時，也期望劑的材料之银在真充性或分散性方面為相#優方面所謂分散性係，只要是未事 #者’於本發明中特別加以說明’則係指銀粉-1286090 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a highly crystalline silver powder and a method of producing the same. More specifically, the present invention relates to a highly crystalline silver powder and a method for producing the same, in which electrodes or circuits such as a chip element and a plasma display panel are greatly refined to form a high density, high precision, and high reliability. A conductive paste of a sexual person, in particular, a smooth coating film for a fine line or a thin layer, etc., can be made into a conductive paste having high density, high precision, and high reliability. The fine particles, the dispersibility are good, the particle size distribution is not gentle, and the crystallites are relatively wide. Therefore, when used as a raw material for the conductive paste, the dispersibility of the silver powder to the paste and the filling property of the silver powder in the conductive paste are excellent. In addition, the silver thick film obtained from the conductive paste can be made into a heat-resistant phase, and the specific resistance (resistivity) is low, such as an electrode or a circuit formed of a silver thick film. [Prior Art] As a method of forming an electrode or a circuit of an electronic component or the like, a silver powder of a conductive material is dispersed in a paste ' ^ ^ Φ ^ ^ e W A to form a conductive paste, and after being printed on the substrate, The method of making the circuit by A ===: film on the paste is a small high-density, that is, electronic... powder, when the conductive paste is prepared, the silver of the material of the agent is also expected to be true. In terms of chargeability or dispersibility, it is a so-called dispersive system. As long as it is not a problem, it is specifically described in the present invention.

2213-6834-PF 1286090 ㈢η丨的刀放性，意指銀粉的原始粒子之間凝聚的難易度。例如’所謂分散性良好的狀態係指原始粒子之間凝聚的：率較少或完全不凝聚的狀態；所謂分散性很差的狀態系才曰原始粒子之間凝聚的比率較多或完全凝聚的狀態。作為印刷著上述導電性膏劑的基板，通常使用於陶兗基板上ic的組件等放熱較大的部分等。然而，在此陶究基板^印刷導電性膏劑時，由於陶变基板的熱收縮率與由印刷者導電性膏劑所生成的銀厚膜之熱收縮率一般而言並不同故在丈。文堯¥陶兗基板和銀厚冑之間會有或剝離或基板本身發生變形之虞。因此，陶莞基板的熱收縮率與由印刷著導電性膏劑所形成的銀厚膜之熱收縮率儘量採取接近的值為較佳。作為在這樣焙燒時的上述銀厚膜的熱收縮之一項原因，-般認為係I電性膏劑中的銀粉在培燒時會引起燒結之故。亦即，-般認為銀粉係由微小的微晶所構成的多结晶體，為了形成銀厚膜而在對包含銀粉的導電性膏劑㈣焙燒時銀粉中的微小的微晶被燒結，於銀厚膜生成的前後發生尺寸改變而引起熱收縮。因此，對於得到含有熱收縮較小的銀粉之導電性膏劑，銀粉中的微晶儘可能大些，儘量不使微晶產生燒結較佳。並且’近年來電路的高頻特性之改善或使培燒前後的基板之尺寸精度更加提昇等都受到要求，因此，作為形成銀厚膜的基板，取代如上述一般的陶瓷基板而使甩 u⑽即erature c〇-fired Ceraraic :低溫共培燒陶竟） 2213-6834-PF 6 1286090 ·% '基板。甚且，該LTCC基板由於係對LTCC基板的生薄板| .包含銀粉等的低電阻導體之導電性膏劑同時進行燒結而得到者，故相較於使用上述一般的陶瓷基板並將導電性膏劑 =刷於其上而形成銀厚膜的電路之技術，則以較少的焙^ 人數即旎完成、容易控制陶瓷介電質膜厚、由導電性膏劑所形成#電路之導體電阻較低、纟易改善基板的表面 J·生，由這些觀點看來為較佳。然而，由於LTCC的尺寸穩定性非常優異，即使係使用於此LTCC的導電性膏劑的材料之銀粕亦強烈要求具更小的熱收縮，因而，銀粉中具較大的微晶更受到高度的期待。而且，如此銀粉中的微晶若較大，則一般而言銀粉的不純物含量會降低，基於此，由於銀厚膜所形成的電路之比電阻容易降低，故不僅是進行如上述的焙燒所形成的電路、而且即使是以非焙燒所形成的電路也可使用含有銀粉的導電性膏劑，由此觀點看來亦較佳。 _ 如上述，使用於導電性膏劑的銀粉期望其為微粒、分散性良好、粒度分布不致太窄峭而比較寬緩、微晶較大者。對此，曰本國專利申請案（特開2〇〇〇一 17〇6號公報）揭露，使硝酸銀水溶液與將丙烯酸單體溶解於L—抗壞血酸水溶液中的溶液進行混合並同時產生反應之高結晶體銀粒子的製造方法。若依據該方法，則可得到微晶尺寸為4〇〇 A以上、粒徑的範圍在2〜4 /z m的狹窄範圍之高結晶性銀粉。 ! 然而’曰本國專利申請案（特開2〇〇〇_ 17〇6號公報） 2213-6834-PF 7 Ϊ286090 斤述的銀粉，料微粒且微晶亦較大，但在例如·。c左彳…熱收縮率難以變得报小。此種銀粉雖然微晶非二，但在商溫的熱收縮率仍相當大，此理由推測係起因乂銀粉的_之範圍為2〜4“’粒度分布太窄，肖，基於粉之間形成空隙’致銀粉的填充性減低之故。因此，右使用於製成導電性膏劑以形成銀厚膜或利用l似基板二成電路，則在電路的形成前後之尺寸變化增大，而有板或LTa基板、特別是⑽基板报容易發生翻I曲的問題。 ^而’本發明的目的在於提供一種高結晶性銀粉及其 '广去，其中係微粒、分散性良好、粒度分布不致太窄峭而比較寬緩、微晶較大者。【發明内容】對於廷種實情’本發明者經專心致志研究的結果發王’若藉由將含有硝酸銀、分散劑以及賴之第^溶液、二含有抗壞血酸之第2水溶液加以混合的方法來製造銀秦，則能夠得到係微粒、粒度分布不致太窄嗜而比較寬緩、 ::晶較大、並可將由導電性膏劑所得到的銀厚膜製成耐熱收縮性相當優異者之高結晶性㈣成本發明。亦即，係-種高結晶性銀粉之製造方法，其特徵在於·· 對於含有確酸銀、分散劑以及硝酸之第工水溶液、與含有抗壞血酸之第2水溶液加以混合。 /、並且，提供一種高結晶性銀粉之製造方法，於上述高結晶性銀粉之製造方法中，其特徵在於：前述分散劑係二2213-6834-PF 1286090 (3) The knives of η丨 mean the ease of cohesion between the original particles of silver powder. For example, 'a state in which the dispersibility is good refers to a state in which the original particles are agglomerated: a state in which the rate is small or not aggregated at all; a state in which the dispersibility is poor is a ratio of cohesion between the original particles or a complete cohesion. status. As the substrate on which the conductive paste is printed, a portion having a large heat release such as a module of ic on a ceramic substrate is usually used. However, when the conductive paste is printed on the ceramic substrate, the heat shrinkage rate of the ceramic substrate is generally different from that of the silver thick film formed by the conductive paste of the printer. Wenyu ¥The pottery substrate and the silver thick enamel may be peeled off or the substrate itself is deformed. Therefore, it is preferable that the heat shrinkage ratio of the ceramic substrate and the heat shrinkage ratio of the silver thick film formed by printing the conductive paste are as close as possible. As a cause of heat shrinkage of the above-mentioned silver thick film at the time of such baking, it is generally considered that the silver powder in the electric paste of the first type causes sintering during firing. In other words, it is generally considered that the silver powder is a polycrystalline body composed of minute crystallites, and in order to form a silver thick film, fine crystallites in the silver powder are sintered when the conductive paste (4) containing silver powder is baked, and the silver crystal is thick. A change in size occurs before and after film formation to cause heat shrinkage. Therefore, in order to obtain a conductive paste containing silver powder having a small heat shrinkage, the crystallites in the silver powder are as large as possible, and it is preferable not to cause the crystallites to be sintered. In addition, in recent years, improvements in high-frequency characteristics of circuits and improvement in dimensional accuracy of substrates before and after firing have been demanded. Therefore, as a substrate for forming a silver thick film, 甩u(10) is replaced by the above-described general ceramic substrate. Erature c〇-fired Ceraraic: low temperature co-culture of pottery) 2213-6834-PF 6 1286090 ·% 'substrate. Further, the LTCC substrate is obtained by simultaneously sintering a conductive paste of a low-resistance conductor such as silver powder, which is a raw sheet of the LTCC substrate, and is compared with the use of the above-described general ceramic substrate and the conductive paste = The technique of brushing the circuit on which the silver thick film is formed is completed with a small number of baking, that is, the ceramic dielectric film thickness is easily controlled, and the conductive resistance is formed by the conductive paste. It is easy to improve the surface J of the substrate, which is preferable from these viewpoints. However, since the dimensional stability of the LTCC is very excellent, even the silver ruthenium of the material of the conductive paste used in the LTCC is strongly required to have a smaller heat shrinkage, and therefore, the larger crystallites in the silver powder are more highly subjected to the height. look forward to. Further, if the crystallites in the silver powder are large, the impurity content of the silver powder is generally lowered. Therefore, since the specific resistance of the circuit formed by the silver thick film is easily lowered, not only the calcination as described above is formed. It is also preferable to use a conductive paste containing silver powder even in a circuit formed by non-baking. _ As described above, the silver powder used for the conductive paste is desirably fine particles, good dispersibility, and the particle size distribution is not too narrow, and the shape is relatively wide and the crystallites are large. In this regard, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A method of producing silver particles. According to this method, a highly crystalline silver powder having a crystallite size of 4 Å A or more and a particle diameter ranging from 2 to 4 /z m can be obtained. However, the silver powder described in the National Patent Application (Japanese Patent Application Laid-Open No. Hei. No. Hei. No. 2, No. 6-6) 2213-6834-PF 7 Ϊ 286,090 is a large amount of fine particles and crystallites, but for example. c Left 彳... The heat shrinkage rate is difficult to become small. Although the silver powder is not two, the heat shrinkage rate at the commercial temperature is still quite large. This reason is presumed to be due to the fact that the range of 乂 silver powder is 2~4" 'the particle size distribution is too narrow, Xiao, based on the formation of powder The gap 'causes the filling property of the silver powder to be reduced. Therefore, when the right side is used to form a conductive paste to form a silver thick film or a substrate-like circuit is used, the dimensional change before and after the formation of the circuit is increased, and there is a plate. Or the LTa substrate, especially the (10) substrate, is prone to the problem of overturning. ^ And 'the object of the present invention is to provide a high crystalline silver powder and its 'exhaustion, in which the particles are fine, the dispersion is good, and the particle size distribution is not too narrow. It is sturdy and relatively lenient, and the crystallites are larger. [Summary of the invention] The result of the intent of the inventor's intent to study is that if the silver nitrate, the dispersing agent, and the second solution, the second containing When the second aqueous solution of ascorbic acid is mixed to produce silver ginseng, the fine particles can be obtained, the particle size distribution is not too narrow, and the granules are relatively narrow, and the crystals are larger, and the silver obtained by the conductive paste can be obtained. The film is made into a film having a high heat shrinkage resistance and is highly crystalline. (IV) The present invention is a method for producing a high-crystallinity silver powder, which is characterized in that it is an aqueous solution containing silver silicate, a dispersant, and nitric acid. And a second aqueous solution containing ascorbic acid is mixed. Further, a method for producing a highly crystalline silver powder is provided, and in the method for producing a high crystalline silver powder, the dispersant is

2213-6834-PF 8 -1286090 乙烯吼π各燒酮。又提供一種高結晶性银粉之製造方法，於上述高結晶性銀粉之製造方法中’其特徵在於：前述分散劑係明膠。而且’提供一種高#晶性銀粉之製造方&，於上述高結晶性銀粉之製造方法中，其特徵在於：_ i水溶液係，相對於硝酸銀100重量份，則調配聚乙烯吡咯烷酮5 重量份〜60重量份、硝酸35重量份~7〇重量份。並且，提供一種高結晶性銀粉之製造方法，於上結晶性銀粉之製造方法中，i特 ' 八符做在於·前述第1水溶液係，相對於确酸銀100重量份，則調配明膠0·5重量份〜10 重量份、硝酸35重量份〜70重量份。又提供-種高結晶性銀粉之製造方法，於上述高妹晶性銀粉之製造方法中，其特徵在於：對於前述帛i水溶液與前述第2水溶液係由相對於前述第丨水溶液中所調配的硝酸銀m重量份，則以第2水溶液中所調配的抗壞血酸 30重量份〜90重量份所形成的比率加以混合。而且，提供一種高結晶性銀粉之製造方法，於上述高結晶性銀粉之製造方法中’其特徵在於：對於前述第^ 溶液與前述第2水溶液係由相對於前述第2水溶液中所調配的抗壞血酸10 0重量份，則以第1 士、〜則弟1水溶液中所調配的硝酸40重量份〜150重量份所形成的比率加以混人。並且’提供-種高結晶性銀粉，其特徵在於：以上述高結晶性銀粉之製造方法加以製造。又為-種高結晶性銀粉’係於上述高結晶性銀粉之製 2213-6834-PF 9 •1286090 造方法所製造者，其特徵在於 y 祕日日徑係300 A以上。而且’係一種高結晶性银私甘& 、杨’其特徵在於：平均粒徑 D50 為 0·5/ζπι〜並且’係-種高結晶性銀粉，其特徵在於：於7。吖的熱收縮率為± 3%以内。又為一種高結晶性銀粉 ^ 其特徵在於·· Dw/Di。為 2.1 〜5.0。徑為的長2213-6834-PF 8 -1286090 Ethylene 吼 π each ketone. Further, a method for producing a highly crystalline silver powder, which is characterized in that the dispersant is gelatin, is produced in the method for producing a high crystalline silver powder. Further, the invention provides a method for producing a high-crystalline silver powder, which is characterized in that: in the aqueous solution of the high-crystalline silver powder, the aqueous solution of the aqueous solution is prepared by mixing 5 parts by weight of polyvinylpyrrolidone with respect to 100 parts by weight of silver nitrate. ～60 parts by weight, and 35 parts by weight of nitric acid to 7 parts by weight. Further, a method for producing a highly crystalline silver powder is provided. In the method for producing an upper crystalline silver powder, the first aqueous solution is in the first aqueous solution system, and the gelatin is blended with respect to 100 parts by weight of the acid silver. 5 parts by weight to 10 parts by weight, and 35 parts by weight of nitric acid to 70 parts by weight. Further, in the method for producing a high-crystallinity silver powder, the method for producing a high-crystal silver powder is characterized in that the aqueous solution of 帛i and the second aqueous solution are formulated with respect to the aqueous solution of the second aqueous solution. M parts by weight of silver nitrate is mixed at a ratio of 30 parts by weight to 90 parts by weight of ascorbic acid formulated in the second aqueous solution. Further, a method for producing a high crystalline silver powder is provided, wherein the method for producing a high crystalline silver powder is characterized in that the ascorbic acid is added to the second aqueous solution in relation to the second solution and the second aqueous solution. 10 parts by weight of the nitric acid is blended in a ratio of 40 parts by weight to 150 parts by weight of nitric acid prepared in the first aqueous solution of the first and second aqueous solutions. Further, a high crystalline silver powder is provided, which is produced by the above-described method for producing a highly crystalline silver powder. Further, a high-crystallinity silver powder is produced by the above-mentioned method for producing a highly crystalline silver powder, 2213-6834-PF 9 • 1286090, which is characterized in that it has a y-day diameter of 300 A or more. Further, 'a high crystalline silver granules &amp; yang' is characterized in that the average particle diameter D50 is 0·5/ζπι and the phylogenetic high-crystalline silver powder is characterized by 7.热 The heat shrinkage rate is within ± 3%. It is also a kind of highly crystalline silver powder ^ which is characterized by DW/Di. For 2.1 to 5.0. Long

而且’係-種高結晶性銀粉，其特徵在於：微晶 300 A以上、平均粒徑D5。為〇. 5㈣]—、於·。。度方向的熱收縮率為± 3%以内。其特徵在於：D9〇/D1Q為並且’係一種高結晶性銀粉， 2· 1 〜5· 0。發明效果：有關本發明的高結晶性銀粉由於係微粒、分散性良好、粒度分布不致太窄靖而比較寬缓、微晶較大，故用作導電性㈣的原料時，銀粉對㈣的分散性以及銀粉在導電性貧劑中的填充性為相當優異，而能夠使由銀厚膜所形成的電極或電路等更為精細化，可將由導電性膏劑所得到的銀厚膜製成耐熱收縮性相當優異、同時比電阻較低者。並且，有關本發明的高結晶性銀粉之製造方法能夠有效地製造上述有關本發明的高結晶性銀粉。【實施方式】 (有關本發明的高結晶性銀粉）有關本發明的高結晶性銀粉實質上係一種粒狀的粉Further, the present invention is characterized in that the crystallite has a crystallinity of 300 A or more and an average particle diameter D5. For 〇. 5(四)]—, 于·. . The thermal shrinkage in the direction of the direction is within ± 3%. It is characterized in that D9〇/D1Q is and is a high crystalline silver powder, 2·1 〜5·0. EFFECTS OF THE INVENTION The high-crystalline silver powder according to the present invention has a fine particle size, good dispersibility, and a narrow particle size distribution, and is relatively broad and has a large crystallite size. Therefore, when used as a raw material for conductivity (IV), dispersion of silver powder to (4) The filling property of the silver powder in the conductive poor agent is quite excellent, and the electrode or the circuit formed by the thick silver film can be made finer, and the thick silver film obtained from the conductive paste can be made into heat-resistant shrinkage. The sex is quite excellent, and the specific resistance is lower. Further, the method for producing a highly crystalline silver powder of the present invention can efficiently produce the above-described highly crystalline silver powder according to the present invention. [Embodiment] (Highly crystalline silver powder according to the present invention) The highly crystalline silver powder according to the present invention is substantially a granular powder.

2213-6834-PF *ί286090 體。有關本發明的高結晶性銀粉係，平均粒徑^為〇. & ^1〇以^而lA計5uib較佳。平均粒徑Dse若在該範圍内則使用料f性㈣時，由於銀粉在導電性㈣巾的填充性相當優異，同時能夠使由銀厚膜所形成的電路等更為精細化，故較佳。另一方面，平均粒徑^若小於0 5=，月則由於銀粉的回收困難，故不佳；若超過1Mm，則由於2213-6834-PF *ί286090 Body. Regarding the highly crystalline silver powder of the present invention, the average particle diameter is preferably 〇. & ^1 〇 is preferably 5 μb. When the average particle diameter Dse is in the range of (f), the silver powder is excellent in the filling property of the conductive (four) towel, and the circuit formed by the silver thick film can be further refined. . On the other hand, if the average particle diameter ^ is less than 0 5 =, it is not preferable because the recovery of silver powder is difficult; if it exceeds 1 Mm,

銀粉之間凝聚情形相當多，故不佳。此處所謂平均粒徑L 係指以激光繞射散射法所求得的體積平均粒徑、亦即累積分布5 0 %的粒徑。、有關本發明的尚結晶性銀粉係微晶徑為A以上、而350 A〜600 A較佳。微晶徑若在該範圍内，則將含有該銀粉的導電性㈣塗布於陶£基板，力❹燒而形成了^ 銀厚膜所製成的電路等之時，培燒前後的銀厚膜之熱收縮率與陶竟基板的熱收縮率相接近，對於或是銀厚膜由陶竞There are quite a lot of cohesive conditions between the silver powder, so it is not good. Here, the average particle diameter L means a volume average particle diameter obtained by a laser diffraction scattering method, that is, a particle diameter of a cumulative distribution of 50%. Further, the crystalline silver powder of the present invention has a crystallite diameter of A or more and 350 A to 600 A. When the crystallite diameter is within this range, the conductivity (4) containing the silver powder is applied to a ceramic substrate, and when a circuit made of a silver thick film is formed by firing, a thick silver film before and after firing is formed. The heat shrinkage rate is close to that of the ceramic substrate, for the silver thick film by Tao Jing

基板剝離或是陶:£基板隨著銀厚膜尺寸的改變而變形的情形加以抑制的效果相當大，故較佳。另一方面，微晶徑若小於300 A，則將含有該銀粉的導電性膏劑塗布於陶究基板，加以梧燒而形成了由銀厚膜斤製成的電路等之4 ’由於培燒前後的銀厚膜之收縮比陶瓷基板的收縮還要大，目| | 4后、％疋受人則或疋銀厚膜容易由陶瓷基板剝離或是陶£基板容易隨著銀厚膜尺寸的改變而變形，故不佳。此處所謂微晶徑係指對銀粉試樣進行X射線繞射所得到的mB®的繞㈣之尖峰的半值寬度所求得的微晶徑之平均值。It is preferable that the substrate is peeled off or the substrate is deformed by the deformation of the silver thick film. On the other hand, if the crystallite diameter is less than 300 A, a conductive paste containing the silver powder is applied to a ceramic substrate, and calcined to form a circuit made of a silver thick film, etc. The shrinkage of the silver thick film is larger than the shrinkage of the ceramic substrate. After the film is removed, the thick film of the silver film is easily peeled off from the ceramic substrate or the substrate is easily changed with the thickness of the silver film. The deformation is not good. The term "microcrystalline diameter" as used herein refers to the average value of the microcrystal diameters obtained by the half value width of the peak of the winding (4) of mB® obtained by X-ray diffraction of the silver powder sample.

2213-6834-PF 11 1286090 有關本發明的高結晶性銀粉係，DwDi。通常為 2.卜5.0、而2.5〜4.7較佳。再者，於本發明中，心與^ 係各別表示基於激光繞射散射式粒度分布測定法之累積八容量%及9〇容㈣中值粒徑（㈣:制表： >差不齊的指標’ DWDl。若較大，則表示粒度分布的表差不齊程度較大。^心若在上述範圍内，則銀粉的粒度分布不致太窄峭而比較寬緩，2213-6834-PF 11 1286090 A highly crystalline silver powder system of the present invention, DwDi. Usually 2. b, and 2.5 to 4.7 is preferred. Further, in the present invention, the heart and the system respectively indicate the cumulative eight-volume% and the nine-volume (four) median diameter based on the laser diffraction scattering type particle size distribution measurement ((4): tabulation: > The index 'DWDl. If it is larger, it means that the particle size distribution is not uniform. If the heart is within the above range, the particle size distribution of the silver powder is not too narrow and relatively gentle.

若以使用該銀粉的導電性膏劑來形成電路，則由於銀粉的填充性相當優異’因此電路的耐熱收縮性易成為相當優異者、亦即在培燒前後的電路之尺寸改變易成為較小者’故較佳。，另一方面，D90/D10若小於，則銀粉的粒度分布太窄峭’以使用該銀粉的$電性膏劑來形成電路的#，由於銀粉的填充性很差，故電路的耐熱收縮性易成為不良者、亦即在焙燒前後的電路之尺寸改變易成為較大者，故不佳。籲並且，WDl°若超過5· 〇,則銀粉的粒度分布太過寬緩，以使用該銀粉的導電性膏劑來形成電路的話，由於銀粉的填充=很差，故電路的耐熱收縮性易成為不良者、亦即在培燒前後的電路之尺寸改變易成為較大者，故不佳。 σ 闕本發明的咼結晶性銀粉係，於700°C的長度方向的熱收縮率通常為± 3%以内、而± 2%以内較佳。#者，於本發明中，所謂±X%以内係意指_χ%〜+χ%。於本發明中: 所明於700 C的長度方向的熱收縮率係指對於將銀粉製成丸粒的試樣，利用熱機械分析（ΤΜΑ)所測定的丸粒之長度When the circuit is formed using the conductive paste of the silver powder, the filling property of the silver powder is relatively excellent. Therefore, the heat shrinkage resistance of the circuit is likely to be excellent, that is, the size change of the circuit before and after the firing is likely to be smaller. 'It is better. On the other hand, if D90/D10 is smaller than, the particle size distribution of the silver powder is too narrow. 'The electric paste using the silver powder is used to form the circuit #. Since the filling property of the silver powder is poor, the heat shrinkage resistance of the circuit is easy. It is not preferable to become a defective person, that is, a change in the size of a circuit before and after firing is likely to become a larger one. If the WDl° exceeds 5·〇, the particle size distribution of the silver powder is too broad, and if the conductive paste of the silver powder is used to form the circuit, since the filling of the silver powder is very poor, the heat shrinkage resistance of the circuit is likely to become It is not good for the bad, that is, the size change of the circuit before and after the burning is easy to become larger. σ 阙 The 咼 crystallized silver powder of the present invention has a heat shrinkage rate in the longitudinal direction of 700 ° C of usually within ± 3% and preferably within ± 2%. #者, In the present invention, the term "±X%" means _χ%~+χ%. In the present invention: the heat shrinkage ratio in the longitudinal direction of 700 C means the length of the pellet measured by thermomechanical analysis (ΤΜΑ) for a sample in which silver powder is pelletized.

2213-6834-PF 12 1286090 方向的熱收縮率。有關本發明的高結晶性銀粉係，在比較低溫、例如_ 曰燒隸塗膜之電阻率較低。亦即，即使在低溫使高結日日|±銀鳥U口，燒結物的電阻率容易成為較低者。再如此於3啊培燒的銀塗膜之電阻率較低的於微晶徑較大以致銀粉内的雷作、Η糸暴 Τ刀門的電子的移動較為順暢之故。有關本發明的高結晶性銀”， O.lOmVg〜1.0 mVg、❿ 〇 20mV η η 2 槓、吊為 g向1JJOni/g〜0.9〇mVg較佳。該比表面積右小於(M〇m2/g，則因基於銀厚膜的電極或電路之細化易發生困難，故不佳。並且，該比表面積若超過ι〇 ^ ’則由於銀粉的膏劑化易產生困難，故不於本發明中所謂比表面積係指BET比表面積。有關本發明的向結晶性銀粉係，輕敲密度（㈣通常為3.8g/cffi3以上、而4 〇g/cm3〜6 〇g/cjn3較佳。輕敲密度（tapdensity)若在該範圍内，則在製作導電性膏劑時高結晶性銀粉中的銀粉對膏劑之填充性良好，而 :易製侍導電性膏齊卜並且於形成導電性膏劑的塗膜時，精由在高結晶性銀粉之間形成適度的空隙而在焙燒塗膜時’由塗膜脫灰易於進行，培燒膜密度有所改善，此結果由於容易降低銀厚膜的電阻故較佳。有關本發明的高結晶性銀粉可藉由例如下述的方法來加以製造。 (有關本發明的高結晶性銀粉之製造方法）有關本發明的高結晶性銀粉之製造方法係，對於含有确酸銀、分散劑以及確酸之第！水溶液、與含有抗壞血酸2213-6834-PF 12 1286090 Thermal contraction rate in the direction. The highly crystalline silver powder of the present invention has a low electrical resistivity at a relatively low temperature, for example, a ruthenium-coated film. That is, even at a low temperature, the high-density day |± silver bird U port, the resistivity of the sintered material tends to be lower. In this way, the silver coating film which is burned at 3 Å has a lower resistivity and a larger crystallite diameter, so that the movement of electrons in the silver powder and the smashing of the smashing door are smoother. Regarding the highly crystalline silver of the present invention, O.lOmVg~1.0 mVg, ❿20mV η η 2 bar, and g is preferably 1JJOni/g to 0.9〇mVg. The specific surface area is smaller than (M〇m2/g). In the case where the thickness of the electrode or the circuit based on the silver thick film is difficult to be difficult, it is not preferable. The specific surface area refers to the BET specific surface area. Regarding the crystallized silver powder of the present invention, the tapping density ((4) is usually 3.8 g/cffi3 or more, and 4 〇g/cm3 to 6 〇g/cjn3 is preferable. In the range of the above, when the conductive paste is prepared, the silver powder in the high crystalline silver powder has good filling property with the paste, and is easy to prepare the conductive paste and forms a coating film of the conductive paste. Fineness is formed by forming a moderate void between the highly crystalline silver powders, and when the coating film is fired, it is easy to remove the ash by the coating film, and the density of the sintered film is improved. This is preferable because the resistance of the silver thick film is easily lowered. The highly crystalline silver powder according to the present invention can be used, for example, by the following The method for producing a highly crystalline silver powder according to the present invention relates to a method for producing a highly crystalline silver powder according to the present invention, which comprises an aqueous solution containing silver, a dispersing agent, and an acid, and an ascorbic acid.

2213-6834-PF 13 1286090 之弟2水溶液加以混合者。於本發明中所謂第i水溶液係指含有硝酸銀、分散劑 t及硝酸的水溶液。作為調製第1水溶液所使用的水係純水、離子交換水、超純水等，由於防止不純物混入銀粉中，故^圭。作為本發明所使用的硝酸銀並未特別加以限定，固悲者以及調製成水溶液者之任一種皆可使用。作為本發明所使用的分散劑，可舉出例如：聚乙㈣钱嗣（剛、明膠、聚乙二醇、聚乙婦醇等。再者，於本發明中所謂明膠係以包含骨膠的概念來加以使用。於本發明所使用的分散劑之中，聚乙烯吼钱酮、明谬由於特別能夠提昇銀粉的耐熱收縮性，故較佳。於本發明中，藉 ^將分散劑調配於第1水溶液，可改善銀粉的分散性，^ =銀粉係微粒並有使其粒度分布不致太^肖而比較寬緩的作用。作為本發明所使用的碟酸並未特別加以限定，可使用 =酸、稀石肖酸的任一種。於本發明中，藉由將頌酸調配水溶液’由於可加以控制使得從銀離子生成銀的反應速度變得比較慢，故有使銀粉的粒度分布不致太窄崎而 :較寬緩、且增大微晶的作用。再者，若未調配硝酸而製 ^銀粉，則由於從銀離子生成銀的反應速度太快，反應立 P !生&相卓乂於如本發明調配確酸來製造的情形，則得到的銀粉容易成為粒徑較小、且微晶徑較小者。第1 X /合液係，为散劑為聚乙烯吡咯烷酮時，相石肖酸銀1〇0重量份’則通常含有聚乙婦H炫酉同5重量份2213-6834-PF 13 1286090 Brother 2 aqueous solution is mixed. In the present invention, the i-th aqueous solution means an aqueous solution containing silver nitrate, a dispersant t, and nitric acid. As the water-based pure water, ion-exchanged water, ultrapure water or the like used for preparing the first aqueous solution, since impurities are prevented from being mixed into the silver powder, it is used. The silver nitrate used in the present invention is not particularly limited, and any one of the sorrower and the aqueous solution can be used. The dispersing agent to be used in the present invention may, for example, be a polyethylene (tetra) ketone (glycol, gelatin, polyethylene glycol, polyglycol, etc. Further, in the present invention, the term "gelatin" includes the concept of inclusion of bone glue. Among the dispersants used in the present invention, polyethylene ketone and alum are preferred because they can particularly improve the heat shrinkage resistance of the silver powder. In the present invention, the dispersant is formulated in the first embodiment. 1 The aqueous solution can improve the dispersibility of the silver powder, and the silver powder-based fine particles have a function of making the particle size distribution less versatile and more relaxed. The dish acid used in the present invention is not particularly limited, and acid can be used. Any one of the dilute sulphuric acid. In the present invention, by adjusting the aqueous solution of citric acid, the reaction rate of silver generated from silver ions becomes relatively slow, so that the particle size distribution of the silver powder is not too narrow. Saki: It is more lenient and increases the effect of crystallites. Furthermore, if silver powder is not prepared by blending nitric acid, the reaction rate of silver from silver ions is too fast, and the reaction is vertical. In accordance with the present invention, the acid is formulated In the case of production, the obtained silver powder is likely to be smaller in particle size and smaller in crystallite diameter. The first X/liquid system is a powder of polyvinylpyrrolidone, and the phase stone is 1 〇0 parts by weight of silver. Then usually contains Polyethylene Women H Hyun and 5 parts by weight

2213-6834-PF 1286090 〜60旦重量份、而15重量份，重量份較佳、2〇重量份〜心重里伤更佳。聚乙烯吡咯烷_的調配量若在該範圍内由於銀粉的分散性右折拎呈 ^ ^ ' 有所改σ，同時銀粉的粒度分布容易成 =致太窄-比較寬缓，故較佳。另—方面，聚乙㈣咯:元？的調配里若小於5重量份，則由於所得到的銀粉容 Κ，讀過6G重量份，則由於所得到的銀粉 =:度容“高、容㈣環境、生產成本容易2213-6834-PF 1286090 to 60 parts by weight, and 15 parts by weight, preferably 2 parts by weight to 2 parts by weight. If the blending amount of polyvinylpyrrolidine _ is within this range, the dispersion of the silver powder is changed to σ by ^ ^ ', and the particle size distribution of the silver powder is easily too narrow - relatively broad, which is preferable. On the other hand, Poly B (4) is: Yuan? If the amount of the silver powder is less than 5 parts by weight, the 6 g parts by weight of the obtained silver powder are obtained, because the obtained silver powder =: the capacity is high, the volume (four) environment, and the production cost are easy.

=1水，讀係，分㈣為明料，相對於頌酸銀重…則通常含有明膠〇·5重量份，重量份、而U 2在8二置:較佳、2重量份〜6重量份更佳。明膠的調配里右在…内’則由於銀粉的分散性有粉的粒度分布容易成為不致太窄靖而比較寬缓，故2 =方面，明㈣調配量若小於G.5重量份到的銀粉^凝聚，故不佳；若超過重量份，則由^ 付到的銀粉中的不純物濃度容、產成本容易偏高，故不佳。小染環境、生第1水溶液係’分散劑為聚乙稀吼錢酮時，相對於水100重量份，則通常含有明^重量份,重量份、而；重篁份〜4重量份較佳。聚乙稀口比口各貌剩的調配量若在卜 ==於銀粉的分散性有所改善，同時銀粉的粒度：布合易成為不致太窄峭而比較寬緩，故較佳。聚乙稀π比洛貌鲷的調配量若小於i重量份，則由二’ 的銀粉容易凝聚，故不佳1超過1Q重量份，則由於戶==1 water, reading system, sub- (4) is a clear material, relative to silver citrate weight... usually contains gelatin 〇 · 5 parts by weight, parts by weight, and U 2 at 8 two: preferably, 2 parts by weight to 6 weight Better. In the blending of gelatin, the particle size distribution of the powder due to the dispersibility of the silver powder tends to be too narrow and not too narrow, so 2 = aspect, the amount of the silver (4) is less than G.5 parts by weight to the silver powder. ^Cohesion, it is not good; if it exceeds the weight, the impurity concentration and production cost of the silver powder paid by ^ are likely to be high, so it is not good. In the case of the small-dyeing environment and the raw first aqueous solution, the dispersing agent is polyethylene ketone, it is usually contained in parts by weight, and parts by weight, based on 100 parts by weight of water; . If the blending amount of the polyethylene mouth is better than that of the silver powder, and the particle size of the silver powder: the cloth is easy to be too narrow and relatively gentle, it is preferable. If the blending amount of the polyethylene π is more than i parts by weight, the silver powder of the two particles is easily aggregated, so the poor 1 exceeds 1Q by weight, because the household =

2213-6834-PF 15 * Ϊ286090 到的銀粉中的不純物濃廑成本容易偏高，故不佳。偏㊉、容易污染環境、生產第1水溶液係，分散劑份，則通常含有明膠〇」重旦2膠時，相對於水100重量〜2曾景_ 里77〜5重量份、而〇 _ 4重量份重里伤較仫。明膠的調配的分,祕女私外至右在該乾圍内，則由於銀粉的刀政性有所改善，同時銀粉 % ^ ^ UU ^ ^ ^ 的叔度刀布谷易成為不致太乍峭而比較寬緩，故較佳。2213-6834-PF 15 * Ϊ286090 The impurity in the silver powder is concentrated. The cost is easy to be high, so it is not good. Tenth, easy to pollute the environment, produce the first aqueous solution system, and the dispersant portion usually contains gelatin 〇 "heavy denier 2 gel, compared with water 100 weight ~ 2 jingjing _ 77 to 5 parts by weight, and 〇 _ 4 Heavy weight injuries are more serious. The distribution of gelatin, the secret woman to the right outside the dry circumference, because the knife-likeness of the silver powder has improved, while the silver powder% ^ ^ UU ^ ^ ^ of the uncle knife Kugu is not too sloppy It is more lenient, so it is better.

於0·1重量份，則由於所得到：方面二明膝的調配量若小 ^ 的銀粉容易凝聚，故不佳；右超過5重量份，則由於所备傯古+日七、^到的銀粉中的不純物濃度容易偏网、谷易污染環境、 — 玍產成本各易偏高，故不佳。第1水溶液係’相對於硝酸銀1〇〇重量份，則通常含有硝酸35重量份〜70重量份、而40重^份〜6〇重量份較 L、48重量份〜54重量份f社 .^ ^ 里知更锃。硝酸的調配量若在該範圍内，則由於銀粉的粒度分布，㈤布烕為不致太乍峭而比較寬緩、 =微晶增大的效果較大’故較佳。另-方面，確酸的調配^小於35重量份，則由於銀粉的結晶性容易偏低，故不佺，若超過70重量份，則由於所得到的銀粉容易凝聚，故不佳。再者’於本發明中，所謂硝酸的調配量係指換曾為濃度61%的濃硝酸之調配量。斤於本發明中所謂第2水溶液係指含有抗壞血酸的水溶液。作為調製第2水溶液所使用的水係純水、離子交換水超純水等，由於防止不純物混入銀粉中，故較佳。作為本考X明所使用：的抗壞血酸可使用左旋體、右旋體的任一種'In the case of 0.1 part by weight, it is obtained because: the amount of the second knee is small, and the silver powder is easy to aggregate, so it is not good; if the right is more than 5 parts by weight, it is due to the preparation of the ancient + day seven, ^ to The concentration of impurities in the silver powder tends to be partial to the net, the valley is easy to pollute the environment, and the cost of production is easy to be high, so it is not good. The first aqueous solution is usually contained in an amount of 35 parts by weight to 70 parts by weight based on 1 part by weight of silver nitrate, and 40 parts by weight to 6 parts by weight, more than L, 48 parts by weight to 54 parts by weight. ^ Know more. If the amount of nitric acid is within this range, it is preferable because the particle size distribution of the silver powder is (5) the coating is not too sturdy and relatively gentle, and the effect of increasing the crystallites is large. On the other hand, when the acidity is less than 35 parts by weight, the crystallinity of the silver powder tends to be low, so that if it exceeds 70 parts by weight, the obtained silver powder tends to aggregate, which is not preferable. Further, in the present invention, the amount of nitric acid to be blended means the blending amount of concentrated nitric acid having a concentration of 61%. In the present invention, the second aqueous solution means an aqueous solution containing ascorbic acid. Water-based pure water, ion-exchanged water, ultrapure water, and the like used for preparing the second aqueous solution are preferred because they prevent impurities from being mixed into the silver powder. As the ascorbic acid used in this test, any of the left-handed and right-handed bodies can be used.

有關本發明的製造方法，混合上述第1水溶液與第 2213-6834-PF 16 1286090 水溶液’在混合液中使高結晶性銀粉析可舉出例如··攪拌妥第〗作為混合形態，規讦文弟1水溶液第】水溶液的方法。在這種情況下作二2 =液添加於此方法，可將全部的第2水溶液—併添水洛液的添加可將第2水，、容笼名 Α σ於第1水溶液，亦將弟2水冷液母次以少量緩緩添加於第 π 第1水溶液中的分散劑為聚乙她燒綱時二用再者，部的第2水溶液一併添加於第！水溶液的方、去右全易得到係微粒且粒度分布則由於容故較佳·第1 士較寬緩的銀粉， 7 /合液中的分散劑為明膠時，若水溶液每次以少量緩緩添加等第、示1不/谷液的方法，谷易控制銀粉的粒徑，故較佳。、；於混合第1水溶液與第2水溶液係，相對 1水溶液的硝酸銀100重量份，；W ·:弟 w 則調配於第2水滚饬由从抗壞血酸通常以3〇重量份〜9〇重、 & 里里切、而40重量份〜8〇曹篁份較佳、50重量份〜75重量份為更佳人丨五的比率加以混合。相對於硝酸銀之抗壞血酸的調配量若在該範圍内銀粉的收率容易增多，故較佳。另一、、 1ΠΠ . ^ yv 々φ 相對於硝酸銀 100重罝份之抗壞血酸的調配量若小抑、利重罝份，則由於逛原不足致銀粉的收率容易偏低，故不佳；相對於硝酸銀 ⑽重量份之抗壞血酸的調配量若超過90重量份，則由於容易污染環境、生產成本容易偏高，故不佳。並且，於混合第1水溶液與第2水溶液係，所得到的混合液中的銀離子濃度通常以10g/1〜80g/卜而30g/1〜65 g/1較佳的比率加以混合。混合液中的銀離子濃度若在該 2213-6834-PF 17 1286090 範圍内，則由於銀粉的收率較高且所得聚，故較佳。另-方面，銀離子濃度若小於1〇銀粉難以凝於銀粉的生產性容易變差，故不佳；銀離子=，則由 g/l ’則由於所得到的銀粉容易凝聚，故不佳右超過80 又於混合第！水溶液與第2水溶液係第2水溶液的抗壞血酸1〇〇重量份，則調配二= 中的《通常以40重量份〜15〇重量份、而Μ =液重量份較佳、65重量份〜⑽重量合。相對於抗壞也酸之確酸的調配量匕率加以混於銀粉的收率容易增多，故較佳。另以乾圍内’則由血酸100重量份之石肖酸的調配量若小於4〇面重^對於抗壞難以使所得到的銀粉之微晶徑變得报大，里; 抗壞血酸100重量份之紘舻从咕 1土，相對於刀之为酸的调配量若超過150重量份，則由於所得到的銀粉容易凝聚，故不佳。基於混合第1水溶液與第2水溶液’在混合在第1水溶液與第2水溶液混合完成後，若再，混合通常是3分鐘以上、最好是5分鐘二 =1的银粉成長，則銀粉的粒徑及粒度分布與 I二佳。ΓΓ易成為有關本發明的銀粉的特定範圍内者， t車父佳。在混合液中所等的過❹η 例如制努採漏斗、…'置來加以過遽之後，以純水清洗滤渣，施予乾知，則可得财ϋ本發明的高結晶性銀粉。一=有關本發明的南結晶性銀粉能夠用作可形成例如曰曰W、電聚顯示板、玻璃陶兗組件、陶究滤波器等的In the production method of the present invention, the first aqueous solution and the 2123-6834-PF 16 1286090 aqueous solution are mixed, and the high crystalline silver powder is precipitated in the mixed solution, for example, by stirring, as a mixed form, Method of aqueous solution of aqueous solution 1 In this case, the second 2 = liquid is added to the method, and the second aqueous solution can be added to the second aqueous solution, and the second water can be added to the first aqueous solution. The water-cooling solution is added to the first aqueous solution of the π-th aqueous solution in a small amount, and the second aqueous solution of the second aqueous solution is added to the second! In the case of the aqueous solution, it is easy to obtain the fine particles, and the particle size distribution is better because of the tolerance. The first silver powder is relatively gentle. When the dispersing agent in the liquid/liquid is gelatin, the aqueous solution is slowly reduced by a small amount. It is preferable to add the first step and the method of showing the 1st/column solution, and the grain control is controlled by the grain size of the silver powder. And mixing the first aqueous solution and the second aqueous solution with 100 parts by weight of silver nitrate in one aqueous solution; W ·: the second water is mixed with the second water, usually from 3 parts by weight to as little as 3 parts by weight of ascorbic acid. & Riccione, and 40 parts by weight of ~8 〇 Cao 篁 parts are preferred, and 50 parts by weight to 75 parts by weight are mixed for a better ratio of 丨5. The blending amount of ascorbic acid with respect to silver nitrate is preferable because the yield of silver powder tends to increase in this range. The other, 1 ΠΠ . ^ yv 々 φ relative to the silver nitrate 100 罝之抗抗抗抗若若若若若硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸硝酸When the amount of the ascorbic acid (10 parts by weight) of silver nitrate is more than 90 parts by weight, the production is easily contaminated and the production cost is likely to be high, which is not preferable. Further, when the first aqueous solution and the second aqueous solution are mixed, the concentration of silver ions in the obtained mixed solution is usually mixed at a preferred ratio of 10 g / 1 to 80 g / b and 30 g / 1 to 65 g / 1. When the concentration of silver ions in the mixed solution is in the range of 2213-6834-PF 17 1286090, it is preferable because the yield of the silver powder is high and the polymerization proceeds. On the other hand, if the silver ion concentration is less than 1 〇 silver powder is difficult to condense on the silver powder, the productivity tends to be poor, so it is not good; if the silver ion =, then the silver powder is easily condensed by g/l ', so the poor right exceeds 80 is mixed again! In the aqueous solution and the second aqueous solution, the second aqueous solution of ascorbic acid is used in an amount of 40 parts by weight to 15 parts by weight, and preferably Μ = liquid by weight, and 65 parts by weight to (10) by weight. Hehe. It is preferred that the yield of the silver powder is increased in comparison with the amount of the acid which is resistant to acid and acid. In addition, in the dry circumference, the amount of the sulphuric acid of 100 parts by weight of the blood acid is less than 4 〇. The resistance is difficult to make the microcrystalline diameter of the obtained silver powder large, and the ascorbic acid 100 weight When the amount of the acid is more than 150 parts by weight with respect to the scallop, the obtained silver powder is easily aggregated, which is not preferable. After the mixing of the first aqueous solution and the second aqueous solution is completed, the mixing of the first aqueous solution and the second aqueous solution is completed, and if the silver powder is usually mixed for 3 minutes or longer, preferably 5 minutes and 2 = 1, the silver powder is grown. The diameter and particle size distribution are better than I. It is easy to become a specific range of the silver powder of the present invention. The high-crystallized silver powder of the present invention can be obtained by washing the filter residue with pure water and drying it after the excess ❹n in the mixed solution, for example, the nucleus funnel. A = South crystalline silver powder according to the present invention can be used as, for example, 曰曰W, an electropolymer display panel, a glass ceramic component, a ceramic filter, or the like.

2213-6834-PF 18 1286090 電極或電路之導電性膏劑的原料，特別是利用銀粉的熱收縮率非常小，不僅是能夠適用作一般的陶竟基板以作為形成電路的基板、而且是能夠適用作LTCC基板用的導電性膏劑的原料。並且，有關本發明的高結晶性銀粉之製造方法能夠使用於有關本發明的高結晶性銀粉之製造。以下雖係以實施例來表示，但本發明並不限於這些實施例所作的解釋。【實施例1】於常溫的純水500g中置入PVP (κ值·· 3〇) 1〇g、硝酸銀50g及濃石肖酸（濃度61%) 24·6 g，加以授拌使溶解以調製第1水溶液（第！水溶液A)。另一方面，於常溫的純水500g中置入抗壞血酸35 8g，加以攪拌使溶解以調製第 2水溶液（第2水溶液A)。帛！水溶液與第2水溶液的組成如第1表及第2表所示。其次，在攪拌第1水溶液A的狀態下，將第2水溶液八一併添加至該第1水溶液U，自添加完成後再授拌5 分鐘使混合液中的粒子成長，停止攪拌，使混合液中的粒子沈降後丟棄混合液的上層澄清液，利用努採漏斗來過濾混合液’以純水清洗濾渣，施予乾燥，而得到高結晶2213-6834-PF 18 1286090 The raw material of the conductive paste of the electrode or the circuit, especially the silver powder, has a very small heat shrinkage rate, and can be applied not only as a general ceramic substrate but also as a substrate for forming a circuit, and is applicable. A raw material of a conductive paste for a LTCC substrate. Further, the method for producing a highly crystalline silver powder according to the present invention can be used for the production of the highly crystalline silver powder of the present invention. Although the following is shown by way of example, the invention is not limited to the explanation of the embodiments. [Example 1] PVP (κ value··3〇) 1〇g, silver nitrate 50g, and concentrated stone acid (concentration 61%) 24·6 g were placed in 500 g of pure water at room temperature, and mixed to dissolve The first aqueous solution (the first aqueous solution A) was prepared. On the other hand, 35 g of ascorbic acid was placed in 500 g of pure water at normal temperature, and the mixture was stirred and dissolved to prepare a second aqueous solution (second aqueous solution A). silk! The composition of the aqueous solution and the second aqueous solution is as shown in Tables 1 and 2. Next, the second aqueous solution was added to the first aqueous solution U in a state where the first aqueous solution A was stirred, and after the addition was completed, the particles in the mixed solution were grown for 5 minutes, and the stirring was stopped to form a mixed solution. After the particles in the sediment are settled, the supernatant liquid of the mixed liquid is discarded, and the mixture is filtered by a Nunch funnel. The filter residue is washed with pure water and dried to obtain high crystallinity.

性銀粉。 M 對於所得到的銀粉利用下述方法來測定d】。、d 5。、仏。 -。、仰、微晶徑、比表面積、輕敲密度、熱收縮率以及電阻率’算出WDle。結果如第3表〜第6表所示。 (n、D9„、DlDe、SD):使用日機裝股份公司類Silver powder. M For the obtained silver powder, d] was measured by the following method. , d 5. Oh. -. WDle was calculated as the pitch, the crystallite diameter, the specific surface area, the tap density, the heat shrinkage rate, and the resistivity. The results are shown in Tables 3 to 6. (n, D9„, DlDe, SD): use Nikkei Co., Ltd.

2213-6834-PF 19 1286090 .microtrac-hra以激光繞射散射法所求得的累積分布在 .1〇%、50%、90%及100%的時點之粒徑，將這些粒徑各別設為 e(#m) Di。。（ # m )，將所得到的粒度分布的標準偏差設為SD。 (微晶徑）··利用Rigaku股份公司製χ射線繞射裝置 RINT2000PC來進行粉末χ射線繞射的分析，由所得到的各晶面之繞射角的尖峰之半值寬度以求得微晶徑。 (比表面積）··利用YUASA I〇nics股份公司製來測定BET比表面積，而使用此BET比表面積。 (輕敲密度）··利用藏持科學機械製造廠製輕敲機藉由對試樣輕敲來測定輕敲密度。 (熱收縮率）：壓固銀粉以製作圓柱形的丸粒，利用2213-6834-PF 19 1286090 .microtrac-hra The particle size of the cumulative distribution at .1〇%, 50%, 90%, and 100% obtained by laser diffraction scattering method. For e(#m) Di. . ( # m ), the standard deviation of the obtained particle size distribution is set to SD. (Microcrystal diameter)······························································· path. (Specific surface area) · The BET specific surface area was measured by using YUASA I〇nics Co., Ltd., and this BET specific surface area was used. (Tap density) · The tapping density was measured by tapping the sample using a tapping machine made by a Scientific Machinery Factory. (heat shrinkage rate): compressing silver powder to make cylindrical pellets, utilizing

Seiko Instruments Inc·股份公司製 TMA/SS6300，對於該丸粒，在空氣中，以昇溫速度1(rc/min由常溫至85〇艺為止的範圍來進行TMA分析，測定丸粒的長度方向的熱收縮 _ 率。測定溫度設為30(rc、5〇(rc及70(rc。 (電阻率）：將蔥品醇95重量份與乙基纖維素5重量份加以混合以調製混合溶劑，將該混合溶劑丨5重量份與粉體試樣85重量份加以混合來製作膏劑，將該膏劑在3〇(rc 焙燒以製作具有數左右厚度的銀塗膜。並且，除了取代300°C的培燒温度而設為4〇〇。〇及5〇〇°c之外，與上述同樣地施行以製作銀塗膜。其次，利用（Hewlett-Packard股份公司製MILL10ΗΜ METER) ’以四端網絡法來測定上述銀塗膜的電阻（Ω )之TMA/SS6300 manufactured by Seiko Instruments Inc., Ltd., TMA analysis was carried out in the air at a temperature increase rate of 1 (rc/min from room temperature to 85 °C), and the heat in the longitudinal direction of the pellet was measured. The shrinkage rate is set to 30 (rc, 5 〇 (rc and 70 (rc) (resistance): 95 parts by weight of onion alcohol and 5 parts by weight of ethyl cellulose are mixed to prepare a mixed solvent, 5 parts by weight of the mixed solvent and 85 parts by weight of the powder sample were mixed to prepare a paste, and the paste was calcined at 3 rpm to prepare a silver coating film having a thickness of several or so. In the same manner as above, a silver coating film was produced in the same manner as described above, and the temperature was changed to 4 〇 and 5 〇〇 ° C. Next, it was measured by a four-terminal network method (MILL10 ΗΜ METER, manufactured by Hewlett-Packard Co., Ltd.). The resistance of the above silver coating film (Ω)

2213-6834-PF 20 l286〇9〇後’由銀塗膜的截面積與端子之間的長度以求得電阻率p (Ω · m)。【實施例2】於常溫的純水500g中置入PVP ( K值·· 30 ) 20g、硝酸銀5〇g及濃硝酸（濃度61%) 24· 6 g，加以攪拌使溶解以 °氣弟1水/谷液（苐1水溶液B)。另一方面，於常溫的純夂5〇〇g中置入抗壞血酸35· 8g，加以攪拌使溶解以調製第 2水溶液（第2水溶液A)。第}水溶液與第2水溶液的組成如第1表及第2表所示。其次，在攪拌第1水溶液B的狀態下，將第2水溶液併添加至該第丨水溶液B中，自添加完成後再攪拌5 分鐘使混合液中的粒子成長。其後停止攪拌，使混合液中的粒子沈降後丢棄混合液的上層澄清液，#用努採漏斗來 k濾此口液，以純水清洗濾渣，施予乾燥，而得到高結晶性銀粉。 1同樣地實施，利用上述 SD、微晶徑、比表面積、 ’算出mo/Di。。結果如第2213-6834-PF 20 l286〇9〇 The resistivity p (Ω · m) was determined from the cross-sectional area of the silver coating film and the length between the terminals. [Example 2] PVP (K value · · 30 ) 20 g, silver nitrate 5 〇 g, and concentrated nitric acid (concentration 61%) 24·6 g were placed in 500 g of pure water at room temperature, and stirred to dissolve Water / gluten solution (苐1 aqueous solution B). On the other hand, 35. 8 g of ascorbic acid was placed in a pure 夂 5 〇〇g at room temperature, and stirred to dissolve to prepare a second aqueous solution (second aqueous solution A). The composition of the aqueous solution and the second aqueous solution is as shown in Tables 1 and 2. Next, while stirring the first aqueous solution B, the second aqueous solution was added to the second aqueous solution B, and after the completion of the addition, the particles in the mixed solution were grown by stirring for 5 minutes. Thereafter, the stirring is stopped, the particles in the mixed solution are allowed to settle, and the supernatant liquid of the mixed liquid is discarded. # The liquid is filtered by a Knockout funnel, and the residue is washed with pure water and dried to obtain a highly crystalline silver powder. . 1 was carried out in the same manner, and the above-mentioned SD, microcrystal diameter, specific surface area, and 'calculated mo/Di were used. . Result as

對於所得到的銀粉與實施例方法來測定Dh、d5〇、D9。、Dm、輕敲密度、熱收縮率以及電阻率 3表〜第6表所示。【比較例1】於常溫的純水500g中置入PVP (K值：30) l〇g及硝酸銀50g，加以攪拌使溶解以調製第丄水溶液（第i水溶液c>另一方面;，於常溫的純水5〇〇g中置入抗壞血酸26g，加以授拌使溶^製第2水溶液（第2水溶液b)。第】The obtained silver powder and the method of the examples were used to measure Dh, d5, and D9. , Dm, tapping density, heat shrinkage rate, and resistivity are shown in Table 3 to Table 6. [Comparative Example 1] PVP (K value: 30) l〇g and 50 g of silver nitrate were placed in 500 g of pure water at room temperature, and stirred to dissolve to prepare a second aqueous solution (i-th aqueous solution c>; on the other hand; at room temperature 26 g of ascorbic acid was placed in 5 g of pure water, and the second aqueous solution (second aqueous solution b) was dissolved by mixing.

2213-6834-PF 21 1286090 溶液與第2水溶液的組成如第！表及第2表所示。 R其次，在授拌第1水溶液c的狀態下，將第2水、^ B-併添力，第！水溶液c中，自添加完成==液分鐘使混合液中的粒子成長。其後停止授拌，使混：二5 的粒子沈降後丢辛混人涪的、之中人— 層澄清液，制努採漏斗來慮以純水清洗滤逢，施予乾燥，而得到銀粉。2213-6834-PF 21 1286090 The composition of the solution and the second aqueous solution is as follows! Table and Table 2. R, in the state where the first aqueous solution c is being mixed, the second water and the ^B- are added together, and the first! In the aqueous solution c, the particles in the mixed solution were grown from the completion of the addition == liquid. After that, the mixing is stopped, so that the particles of the mixture of 2:5 are settled, and then the human-layer clear liquid is poured into the funnel, and the funnel is cleaned to wash the filter with pure water, and dried to obtain silver powder. .

對於所得到的銀粉與實施例1同樣地實施，利用上、千、 :法來……5。、一、SD、微晶捏、比表面積述輕破密度、熱收縮率以及電阻率，算丨“/心。結果如 3表〜第6表所示。【實施例3】一。於韦皿的純水25〇g中置入明膠（新田GELAnN股份公司製）1· Og、硝酸銀5〇g及濃硝酸（濃度61%) 26·紅，藉由力:熱至5G°C並加以攪拌使溶解間製第1水溶液（第！欠’合液D)。另一方面，於常溫的純水250g中置入抗壞血酸26· 4=，加以攪拌使溶解以調製第2水溶液（第2水溶液C)第1水洛液與第2水溶液的組成如第1表及第2表所示。 ^其久，在50 C攪拌第1水溶液D的狀態下，將常溫的第2水溶液c經3 0分鐘緩緩添加至該第丨水溶液D中，自添加完成後再攪拌5分鐘使混合液中的粒子成長。其後停止攪拌’使混合液中的粒子沈降後丟棄混合液的上層澄清液，利用努採漏斗來過濾混合液，以純水清洗濾渣，施予乾燥’而得到高結晶性銀粉。The obtained silver powder was carried out in the same manner as in Example 1, and the upper, the thousand, and the following were used. 1, SD, microcrystalline kneading, specific surface area, light density, heat shrinkage rate and electrical resistivity, calculated as "/heart. The results are shown in Table 3 ~ Table 6. [Example 3] 25 g of pure water was placed in gelatin (made by Xintian GELAnN Co., Ltd.) 1 · Og, silver nitrate 5 〇 g and concentrated nitric acid (concentration 61%) 26 · red, by force: heat to 5 G ° C and stirred The first aqueous solution (the undeployed 'liquid D) was prepared by dissolving. On the other hand, ascorbic acid 26·4 was placed in 250 g of pure water at normal temperature, and the mixture was stirred and dissolved to prepare a second aqueous solution (second aqueous solution C). The composition of the first aqueous solution and the second aqueous solution is as shown in the first table and the second table. ^ For a long time, the second aqueous solution c at normal temperature is passed through for 30 minutes while the first aqueous solution D is stirred at 50 C. Slowly added to the aqueous solution D of the second aqueous solution, and the mixture was stirred for 5 minutes, and the particles in the mixed solution were allowed to grow. Thereafter, the stirring was stopped, and the particles in the mixed solution were allowed to settle, and the supernatant liquid of the mixed liquid was discarded. The funnel was used to filter the mixed solution, and the filter residue was washed with pure water and subjected to drying to obtain a highly crystalline silver powder.

2213-6834-PF 22 1286090 對於所得到的銀粉與實施例1同樣地實施，利用上述方法來測定Dh、D5〇、D9。、Dm、SD、微晶徑、比表面積、輕敲密度、熱收縮率以及電阻率，算出D9G/Dl()。結果如第 3表〜第6表所示。【實施例4】於常溫的純水500g中置入明膠（新田GELATIN股份公司製）3· 〇g、硝酸銀5〇g及濃硝酸（濃度61%) 24. 6g，藉由加熱至5 0 °c並加以攪拌使溶解以調製第1水溶液（第1 水洛液E)。另一方面，於常溫的純水5〇〇g中置入抗壞血酸25· 9g，加以攪拌使溶解以調製第2水溶液（第2水溶液D )。第1水溶液與第2水溶液的組成如第1表及第2表所示。 ^ ^人，在5 0 c攪拌第1水溶液E的狀態下，將常溫的第2水洛液D經30分鐘缓缓添加至該第1水溶液£中，自 >加=成後再攪拌5分鐘使混合液中的粒子成長。其後停 _止攪拌，使混合液中的粒子沈降後丟棄混合液的上層澄清液:利用努採漏斗來過濾混合液，以純水清洗濾」查，施予乾燥，而得到高結晶性銀粉。、τ狖所侍到的銀粉與實施例1同樣地實施，利用_ 二去來測（Dh、1)5。、D9。、Dl。。、SD、微晶徑、比表面, 輕敲密度、熱收縮率以及電阻率，算…D1。。結心 3表〜第6表所示。2213-6834-PF 22 1286090 The obtained silver powder was carried out in the same manner as in Example 1, and Dh, D5〇, and D9 were measured by the above method. Dm, SD, microcrystalline diameter, specific surface area, tapping density, heat shrinkage rate, and electrical resistivity, and D9G/Dl() was calculated. The results are shown in Tables 3 to 6. [Example 4] Gelatin (manufactured by Shinoda GELATIN Co., Ltd.) 3·〇g, silver nitrate 5〇g, and concentrated nitric acid (concentration: 61%) were placed in 500 g of pure water at room temperature. 24.6 g by heating to 50 The mixture was stirred and dissolved to prepare a first aqueous solution (the first aqueous solution E). On the other hand, 25 g of ascorbic acid was placed in 5 g of pure water at a normal temperature, and the mixture was stirred and dissolved to prepare a second aqueous solution (second aqueous solution D). The compositions of the first aqueous solution and the second aqueous solution are shown in Tables 1 and 2. ^^人, in the state where the first aqueous solution E is stirred at 50 c, the second aqueous solution D at normal temperature is slowly added to the first aqueous solution for 30 minutes, and is stirred by adding > Minutes allow the particles in the mixture to grow. Thereafter, the stirring is stopped, the particles in the mixed solution are allowed to settle, and the supernatant liquid of the mixed liquid is discarded: the mixture is filtered by a nucleus funnel, washed with pure water, and dried to obtain a highly crystalline silver powder. . The silver powder served by τ狖 was carried out in the same manner as in Example 1, and (Dh, 1) 5 was measured by _2. , D9. , Dl. . , SD, microcrystalline diameter, specific surface, tapping density, heat shrinkage rate and resistivity, calculate...D1. . The knot is shown in Table 3 to Table 6.

2213-6834-PF 23 12860902213-6834-PF 23 1286090

【第1表】水 (g) 分散劑的種類分散劑 (g) 硝酸銀 ω 濃硝酸 (g) 第1水溶液的種類實施例1 500 PVP 10 50 24.6 A 實施例2 500 PVP 20 50 24.6 B 比較例1 500 PVP 10 50 0 C 實施例3 250 明膠 1.0 50 26.4 D 實施例4 500 明膠 3.0 50 24.6 E[Table 1] Water (g) Dispersant type Dispersant (g) Silver nitrate ω Concentrated nitric acid (g) Type of first aqueous solution Example 1 500 PVP 10 50 24.6 A Example 2 500 PVP 20 50 24.6 B Comparative example 1 500 PVP 10 50 0 C Example 3 250 Gelatin 1.0 50 26.4 D Example 4 500 Gelatin 3.0 50 24.6 E

【第2表】水 (g) 抗壞血酸 (g) 第2水溶液的種類實施例1 500 35.8 A 實施例2 500 35.8 A 比較例1 500 26.0 B 實施例3 250 26.4 C 實施例4 500 25.9 D 【第3表】 Dio (βΐη) D50 (//m) D90 (//m) D100 (βΐη) D90/D10 SD 實施例1 2.97 6.35 10.75 22.0 3.6 3.01 實施例2 1.30 3.03 5.67 15.6 4.4 1.59 比較例1 2.14 2.83 4.08 9.3 1.9 0.71 實施例3 2.72 4.36 7.33 18.5 2.7 1.71 實施例4 0.76 1.27 2.28 4.6 3.0 0.57 【第4表】微晶徑（A) 比表面積（m2/g) 輕敲密度（g/cm3) 實施例1 441 0.30 4.1 實施例2 377 0.62 4.0 比較例1 258 0.62 3.8 實施例3 545 0.20 4.4 實施例4 441 0.72 4.8 2213-6834-PF 24 •1286090 【第5表】於300°C的熱收縮率 (%) 於500°C的熱收縮率 (%) 於700°C的熱收縮率 (%) 實施例1 0.13 一 113 一2.2 實施例2 0.09 —2.68 -2.9 比較例1 0.84 一 4.02 -7.82 實施例3 0.27 1.08 1.13 實施例4 一 0.58 一 1_51 一 1.35 【第6表】於300°C焙燒的銀塗膜的電阻率ρ (Ω · m) 於400°C焙燒的銀塗膜的電阻率ρ (Ω ·ιη) 於500°C焙燒的銀塗膜的電阻率Ρ (Ω · m) 實施例1 4.1 xl〇·5 2.0 xlO*5 9.9 xlO-6 實施例2 5.2 χ ΙΟ'5 1.5 xlO'5 1.2 xlO*5 比較例1 7.2 xlO*4 8.9 xlO·6 4.8 xlO'5 實施例3 9.4 xlO'6 8.3 xlO-6 9·9χ10·6 實施例4 1.0 xlO*5 8.8x10'6 4.8 xlO*5 由第1表〜第5表可判斷，使用分散劑及硝酸所製作的銀粉係’微晶徑較大而具高結晶性，在7〇〇的熱收縮率較小。並且可判斷，使用明膠作為分散劑者，特別是在7〇〇 C的熱收縮率較小。又由第6表可判斷，使用分散劑及硝酸所製作的銀粉比起不使用硝酸所製作的銀粉，在3〇〇艺焙燒的銀塗膜的電阻率p較低。此理由推測係基於微晶徑較大致銀粉内的電子的移動變得較為順暢之故。二產業上可利用性：有關本毛月的鬲結晶性銀粉及高結晶性銀粉之製造方法能夠用作可形成例如晶片元件、電漿顯示板、玻璃組件、陶錢波器等的電極或電路之導電性膏劑的原料，特別是能夠適用作咖基板用的導電性膏劑的原料。[Table 2] Water (g) Ascorbic acid (g) Type of second aqueous solution Example 1 500 35.8 A Example 2 500 35.8 A Comparative Example 1 500 26.0 B Example 3 250 26.4 C Example 4 500 25.9 D [Part 1] 3 Table] Dio (βΐη) D50 (//m) D90 (//m) D100 (βΐη) D90/D10 SD Example 1 2.97 6.35 10.75 22.0 3.6 3.01 Example 2 1.30 3.03 5.67 15.6 4.4 1.59 Comparative Example 1 2.14 2.83 4.08 9.3 1.9 0.71 Example 3 2.72 4.36 7.33 18.5 2.7 1.71 Example 4 0.76 1.27 2.28 4.6 3.0 0.57 [Table 4] Microcrystalline diameter (A) Specific surface area (m2/g) Tap density (g/cm3) Example 1 441 0.30 4.1 Example 2 377 0.62 4.0 Comparative Example 1 258 0.62 3.8 Example 3 545 0.20 4.4 Example 4 441 0.72 4.8 2213-6834-PF 24 • 1286090 [Table 5] Thermal Shrinkage at 300 ° C ( %) Thermal shrinkage at 500 ° C (%) Thermal shrinkage at 700 ° C (%) Example 1 0.13 - 113 - 2.2 Example 2 0.09 - 2.68 -2.9 Comparative Example 1 0.84 - 4.02 - 7.82 Example 3 0.27 1.08 1.13 Example 4 A 0.58 A 1_51 A 1.35 [Table 6] Resistance of a silver coating film baked at 300 ° C ρ (Ω · m) resistivity ρ (Ω · ιη) of the silver coating film fired at 400 ° C. Resistivity Ρ (Ω · m) of the silver coating film fired at 500 ° C. Example 1 4.1 xl 〇·5 2.0 xlO*5 9.9 xlO-6 Example 2 5.2 χ 5'5 1.5 xlO'5 1.2 xlO*5 Comparative Example 1 7.2 xlO*4 8.9 xlO·6 4.8 xlO'5 Example 3 9.4 xlO'6 8.3 xlO-6 9·9χ10·6 Example 4 1.0 xlO*5 8.8x10'6 4.8 xlO*5 From the first table to the fifth table, it can be judged that the silver powder produced by using a dispersant and nitric acid has a large crystallite diameter and is high. Crystallinity, the heat shrinkage rate at 7 较小 is small. Further, it can be judged that gelatin is used as a dispersing agent, and in particular, the heat shrinkage rate at 7 〇〇 C is small. Further, from the sixth table, it can be judged that the silver powder produced by using the dispersant and the nitric acid has a lower resistivity p of the silver coating film calcined at 3 Å than the silver powder produced without using nitric acid. This reason is presumed to be based on the fact that the movement of electrons in the silver powder is relatively smooth based on the large crystallite diameter. Secondary industry availability: The manufacturing method of the bismuth crystalline silver powder and the high crystalline silver powder relating to the present month can be used as an electrode or a circuit which can form, for example, a wafer element, a plasma display panel, a glass component, a ceramic wave device, or the like. The raw material of the conductive paste can be suitably used as a raw material for a conductive paste for a coffee substrate.

2213-6834-PF 25 1286090 【圖式簡單說明】無【主要元件符號說明】無2213-6834-PF 25 1286090 [Simple description of the diagram] None [Key component symbol description] None

2213-6834-PF 262213-6834-PF 26

Claims

•1286090 十、申請專利範圍： 1_-#胃結晶性銀粉之製造方法’其特徵在於·對於含有硝酸銀、分散南丨以$姑减政J以及力酸之第1水溶液、與含有抗壞血酉文之第2水溶液加以混合。、2_如申％專利範圍第j項所述的高結晶性銀粉之製造方法，其中前述分散劑係聚乙輯嘻㈣。、3.如中請專利範圍第1項所述的高結晶性銀粉之製造方法，其中前述分散劑係明膠。• 1286090 X. Patent application scope: 1_-# Method for producing gastric crystalline silver powder' is characterized by the inclusion of silver nitrate, the dispersion of Nanxun, the first aqueous solution of the acid and the acid, and the inclusion of ascorbic acid. The second aqueous solution of the text is mixed. 2. The method for producing a highly crystalline silver powder according to item j of the patent application of the present invention, wherein the dispersing agent is a polytetracycline (IV). 3. The method for producing a highly crystalline silver powder according to claim 1, wherein the dispersing agent is gelatin.

' 申明專利範圍第2項所述的高結晶性銀粉之製造 /、中别述第1水溶液係，相對於硝酸銀1 〇〇重量份，則調配聚乙輪院酉同5重量份〜6〇重量份、瑣酸Μ重量伤〜7 0重量份。量份申明專利範圍第3項所述的高結晶性銀粉之製造套、中別述第1水溶液係，相對於確酸銀工〇〇重量份，則調配明膠G.5重1份〜1G重量份、硝酸35重量份〜r^重、6·如申明專利乾圍第1項所述的高結晶性銀粉之製造方法其中對於剧述第！水溶液與前述第2水溶液係由相對於刖述第1水/合液中所調配的硝酸銀⑽重量份，則以第2水洛液中所調配的抗壞血酸3〇重量份，重量份所形成的比率加以混合。 7 ·如申請專利範，视阁弟1項所述的高結晶性銀粉之製造方法，其中對於前述第〗士 w 昂1水溶液與前述第2水溶液係由相對於前述第2水溶液中辦▲田 τ所调配的抗壞血酸1 〇〇重量份， 2213-6834-PF 27 •1286090 确酸40重量份〜150重量份所形以第1水溶液中所調配的成的比率加以混合。，其特徵在於··利用如申請專利以製造。 8項所述的高結晶性銀粉，其中 10·如申請專利範圍第8馆糾、+、& _ ^ 8項所述的尚結晶性銀粉，其中平均粒徑D5〇為0· 5// m〜10# m。Γ η'The production of the high crystalline silver powder described in the second paragraph of the patent scope, and the first aqueous solution of the above-mentioned patent range, the weight of the silver nitrate is adjusted to 5 parts by weight to 6 parts by weight with respect to 1 part by weight of silver nitrate. , 琐 Μ Μ weight loss ~ 70 0 parts by weight. The manufacturing kit of the high crystalline silver powder described in item 3 of the patent scope and the first aqueous solution system described in the third paragraph are formulated to have a gelatin G.5 weight of 1 part to 1 G weight relative to the weight fraction of the silver acetate. Parts, 35 parts by weight of nitric acid ~ r ^ heavy, 6 · The method for producing high-crystalline silver powder according to claim 1 of the patent dry circumference, which is for the drama! When the aqueous solution and the second aqueous solution are used in a ratio of 10 parts by weight of the silver nitrate prepared in the first water/liquid mixture, the ratio of the weight fraction of the ascorbic acid in the second water solution is 3 parts by weight. Mix it. (7) The method for producing a high crystalline silver powder according to the above, wherein the aqueous solution of the first aqueous solution and the second aqueous solution are based on the second aqueous solution. The ascorbic acid 1 〇〇 by weight of τ, 2213-6834-PF 27 • 1286090 The acid is 40 parts by weight to 150 parts by weight and mixed in a ratio prepared in the first aqueous solution. It is characterized in that it is manufactured by applying for a patent. The high crystalline silver powder according to item 8, wherein 10% of the crystallized silver powder as described in the eighth section of the patent application scope, +, & _ ^ 8 wherein the average particle diameter D5 〇 is 0·5// m~10# m. Γ η

8 · —種高結晶性銀粉範圍第1項所述的方法加 9·如申請專利範圍第微晶徑係300 A以上。 u * (而D5G係表示基於激光繞射政射式粒度分布測定法的f 岡系積分布50容量％之中值粒徑 (β m)) 11 ·如申請專利範圍第8 jf辦、+、&古& a ’所述的间結晶性銀粉，其中於700 °C的熱收縮率為± 3%以内。 12. 如申請專利範圍第8項所述的高結晶性銀粉，其中 IWD】。為2·卜5. 〇。（而於前式令，仏。及D9。係各別表示基於激光繞射散射式粒度分布測定法的累積分布1〇容量％及 90谷篁％之中值粒徑（am)) 13. —種高結晶性銀粉，其特徵在於··微晶徑為3〇〇 a 以上、平均粒徑β5()為〇· 5 // m〜;[〇 # m、於7〇(rc的長度方向的熱收縮率為± 3 %以内。 14 ·如申凊專利範圍第13項所述的高結晶性銀粉，其中Dgo/lho為2· 1〜5· 0。（而於前式中，Di〇及D9。係各別表示基於激光繞射散射式粒度分布泪彳定法的累積分布1 〇容量％及90容量％之中值粒徑（# m)) < 2213-6834-PF 288 · Highly crystalline silver powder The method described in the first item is added. 9. The patented range has a microcrystalline diameter of 300 A or more. u * (While D5G is a median particle size (β m) based on the fractal distribution of the laser diffraction particle size distribution method. 50% of the median diameter (β m)) 11 & an < a < a ' described as a crystalline silver powder, wherein the heat shrinkage at 700 ° C is within ± 3%. 12. The high crystalline silver powder as described in claim 8 of the patent application, wherein IWD]. For 2. Bu. 5. 〇. (And in the former order, 仏. and D9. The respective means the cumulative distribution based on the laser diffraction scattering particle size distribution method 1% capacity% and 90% 之中% median particle size (am)) 13. A high crystalline silver powder characterized in that the microcrystal diameter is 3 〇〇 a or more, and the average particle diameter β 5 () is 〇 · 5 // m 〜 ; [〇# m, at 7 〇 (the length direction of rc The heat shrinkage rate is within ± 3 %. 14 · The high crystalline silver powder according to claim 13 of the patent application, wherein Dgo/lho is 2·1 to 5·0. (In the former formula, Di〇 and D9. The cumulative distribution of lacrimal method based on laser diffraction scattering particle size distribution 1 〇 capacity % and 90 vol% median diameter (# m)) < 2213-6834-PF 28