TW201315685A - Fine silver particles, conductive paste containing fine silver particles, conductive film and electronic device - Google Patents

Fine silver particles, conductive paste containing fine silver particles, conductive film and electronic device Download PDF

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Publication number
TW201315685A
TW201315685A TW101127260A TW101127260A TW201315685A TW 201315685 A TW201315685 A TW 201315685A TW 101127260 A TW101127260 A TW 101127260A TW 101127260 A TW101127260 A TW 101127260A TW 201315685 A TW201315685 A TW 201315685A
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Taiwan
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fine particles
silver
silver fine
crystallite diameter
less
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TW101127260A
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Chinese (zh)
Inventor
Yosuke Yamamoto
Seiji Ishitani
Keisuke Iwasaki
Mineko Ohsugi
Hiroko Morii
Kazuyuki Hayashi
Yasuo Kakihara
Tetsuji Handa
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Toda Kogyo Corp
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Priority claimed from JP2011167364A external-priority patent/JP5773147B2/en
Priority claimed from JP2011167368A external-priority patent/JP5773148B2/en
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Publication of TW201315685A publication Critical patent/TW201315685A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Abstract

Provided are: fine silver particles suitable as a starting material for, e.g., a conductive paste which can be baked at a low temperature; a conductive paste containing said fine silver particles; a conductive film; and an electronic device. The fine silver particles according to the present invention are characterized by showing a ratio of the crystalline diameter at a Miller index in X-ray diffractometry of (111) to the crystalline diameter at a Miller index in X-ray diffractometry of (200) [crystalline diameter DX (111)/crystalline diameter DX (200)] of 1.40 or greater.

Description

銀微粒子及含有該銀微粒子之導電膏，導電膜及電子裝置 Silver microparticles and conductive paste containing the same, conductive film and electronic device

本發明係關於一種可較好地作為可低溫燒成之導電膏之原料用之平均粒徑100nm或平均粒徑未達100nm之銀微粒子及含有該銀微粒子之導電膏、導電膜及電子裝置。 The present invention relates to a silver fine particle having an average particle diameter of 100 nm or an average particle diameter of less than 100 nm which is preferably used as a raw material of a conductive paste which can be fired at a low temperature, and a conductive paste, a conductive film and an electronic device containing the silver fine particles.

電子裝置之電極或電路圖型之形成係使用含金屬粒子之導電膏，於基板上印刷電極或電路圖型後，經加熱燒成而使導電性膏中所含之金屬粒子燒成而進行，且依據加熱燒成溫度分類成燒成型膏與聚合物型膏。近年來，其加熱燒成溫度有低溫化之傾向。 The electrode or circuit pattern of the electronic device is formed by using a conductive paste containing metal particles, printing an electrode or a circuit pattern on the substrate, and then firing the metal particles contained in the conductive paste by heating and firing, and The heating firing temperature is classified into a baking paste and a polymer paste. In recent years, the heating and firing temperature tends to decrease.

燒成型膏一般係用於陶瓷基板上，且以金屬粒子與玻璃熔料、溶劑等作為主成分者，其加熱燒成溫度約為500℃以上。另一方面，聚合物型膏係使用於薄膜配線板或導電性接著劑等，係由使金屬粒子分散於樹脂、硬化劑、有機溶劑、分散劑等中之膏所組成，該導電性膏藉由網版印刷等於基板上形成特定之導體圖型，在高達250℃左右之溫度下加熱燒成而使用。 The baking paste is generally used on a ceramic substrate, and is preferably composed of metal particles, a glass frit, a solvent, or the like as a main component, and has a heating firing temperature of about 500 ° C or higher. On the other hand, the polymer type paste is used for a film wiring board, a conductive adhesive agent, or the like, and is composed of a paste in which metal particles are dispersed in a resin, a curing agent, an organic solvent, a dispersing agent, or the like, and the conductive paste is used. The screen printing is equivalent to forming a specific conductor pattern on the substrate, and is heated and fired at a temperature of up to about 250 ° C for use.

至於上述金屬粒子係使用銅粉以及銀粉，尤其於形成薄膜配線板之電路所使用之網版印刷用導電膏，係使用銀作為導電粒子。銀之缺點為容易引起遷移，但相較於具有相同程度之比電阻之銅，則較難氧化故容易作業，已被廣泛利用。 As the metal particles, copper powder and silver powder are used, and in particular, a conductive paste for screen printing used in a circuit for forming a thin film wiring board uses silver as a conductive particle. The disadvantage of silver is that it is easy to cause migration, but compared with copper having the same degree of specific resistance, it is difficult to oxidize and is easy to work, and has been widely used.

近年來，導電膏之加熱燒成溫度有低溫化之傾向。例如，電子裝置之安裝基板一般可加熱到300℃左右，為使耐熱性優異故使用聚醯亞胺製可撓性基板，但由於昂貴故最近檢討以較便宜之PET(聚對苯二甲酸乙二酯)基板或PEN(聚萘二甲酸乙二酯)基板作為替代材料。然而，PET基板或PEN基板與聚醯亞胺製可撓性基板相較耐熱性較低，尤其，使用於薄膜配線板之PET薄膜基板必須在150℃以下進行加熱燒成。 In recent years, the heating and baking temperature of the conductive paste tends to be lowered. For example, the mounting substrate of an electronic device can be generally heated to about 300 ° C. In order to make heat resistance excellent, a flexible substrate made of polyimide is used. However, due to the high cost, PET (polyethylene terephthalate) has been recently reviewed. A diester) substrate or a PEN (polyethylene naphthalate) substrate is used as an alternative material. However, the PET substrate or the PEN substrate has a lower heat resistance than the flexible substrate made of polyimide. In particular, the PET film substrate used for the film wiring board must be heated and fired at 150 ° C or lower.

且，若可在比200℃更低之溫度下進行加熱燒成，則亦可對聚碳酸酯或紙等之基板形成電極或電路圖型，可期待增廣各種電極材等之用途。 Further, if the heating can be performed at a temperature lower than 200 ° C, an electrode or a circuit pattern can be formed on a substrate such as polycarbonate or paper, and the use of various electrode materials and the like can be expected.

至於成為該可低溫燒成之導電膏原料之金屬粒子，期待有奈米等級之銀微粒子。其理由為金屬粒子之大小成為奈米等級時表面活性變高，由於熔點比金屬塊體者更降低，故成為可低溫燒結者之故。 As the metal particles which are the raw material of the conductive paste which can be fired at a low temperature, silver fine particles having a nanometer grade are expected. The reason for this is that the surface activity becomes high when the size of the metal particles becomes a nanometer level, and the melting point is lower than that of the metal block, so that it can be sintered at a low temperature.

又，奈米等級之銀微粒子可低溫燒結，同時一次燒結時可維持耐熱性，故亦可利用以往之焊料不具有之性質而期待作為無鉛之焊料替代材料。 Further, since the silver fine particles of the nanometer grade can be sintered at a low temperature and the heat resistance can be maintained at the time of primary sintering, it is expected to be a lead-free solder substitute material by utilizing properties not possessed by conventional solders.

迄今為止，已提案次微米至微米尺寸之銀微粒子作為成為電子裝置之配線材料或電極材料之銀微粒子，進而作為可低溫燒成之銀微粒子，銀微粒子已知有限定微晶直徑相對於BET比表面積之比之球狀銀粉(專利文獻1)，限定平均粒徑、微晶直徑及平均粒徑相對於微晶直徑之比之銀微粒子(專利文獻2)、限定敲實密度、雷射繞射法平 均粒徑及比表面積之銀粉(專利文獻3)、一次粒子之平均粒徑0.05~1.0μm、微晶直徑20~150nm之銀微粒子之製造方法(專利文獻4)、平均粒徑為0.1μm以上未達1μm，且粒度分布陡峭且為高分散性之球狀銀粉(專利文獻5)、一次粒徑為0.07~4.5μm，微晶直徑為20nm以上之高結晶銀粉(專利文獻6)、限定銀反應步驟中之溫度範圍，且一次粒徑為1~100nm之範圍之含有微小銀粒子之組成物(專利文獻7)等。 Heretofore, silver microparticles of a submicron to micron size have been proposed as silver fine particles which are wiring materials or electrode materials of an electronic device, and further, as silver fine particles which can be fired at a low temperature, silver fine particles are known to have a defined crystallite diameter with respect to a BET ratio. Spherical silver powder having a ratio of surface area (Patent Document 1), silver fine particles having a ratio of an average particle diameter, a crystallite diameter, and an average particle diameter to a crystallite diameter (Patent Document 2), a definition of a tap density, and a laser diffraction Silver powder having a normal particle diameter and a specific surface area (Patent Document 3), a method for producing silver fine particles having an average particle diameter of primary particles of 0.05 to 1.0 μm , and a crystallite diameter of 20 to 150 nm (Patent Document 4), and an average particle diameter of 0.1 μ m or more less than 1 μ m, and a particle size distribution is sharp and high dispersibility of a spherical silver powder (Patent Document 5), a primary particle diameter of 0.07 ~ 4.5 μ m, the crystallite diameter is 20nm or more high crystalline silver powder (Patent Document 6), a composition containing a small silver particle in a temperature range in the silver reaction step, and a primary particle diameter of 1 to 100 nm (Patent Document 7).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：特開2005-330529號公報 Patent Document 1: JP-A-2005-330529

專利文獻2：特開2006-183072號公報 Patent Document 2: JP-A-2006-183072

專利文獻3：特開2007-131950號公報 Patent Document 3: JP-A-2007-131950

專利文獻4：特開2008-31526號公報 Patent Document 4: JP-A-2008-31526

專利文獻5：特開2010-70793號公報 Patent Document 5: JP-A-2010-70793

專利文獻6：特開2007-16258號公報 Patent Document 6: JP-A-2007-16258

專利文獻7：特開2009-120949號公報 Patent Document 7: JP-A-2009-120949

前述專利文獻1至專利文獻6所揭示之銀微粒子雖均限定了平均粒徑及微晶直徑、BET比表面積值等，但均未考慮關於X射線繞射之密勒(Miller)指數(111)與(200) 之微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]，如後述之比較例所示，上述[微晶直徑Dx(111)/微晶直徑Dx(200)]未達1.40時，難以獲得具有良好低溫燒結性之銀微粒子。且，微晶直徑Dx(111)超過20nm時，由於銀微粒子之微晶直徑較大故成為銀微粒子內部之反應性亦低者，而不利於低溫燒結。 The silver fine particles disclosed in Patent Documents 1 to 6 each define an average particle diameter, a crystallite diameter, a BET specific surface area value, and the like, but do not consider a Miller index (111) regarding X-ray diffraction. The ratio of the crystallite diameter to (200) [crystallite diameter D x (111) / crystallite diameter D x (200)], as shown in the comparative example described later, the above [crystallite diameter D x (111) / micro When the crystal diameter D x (200)] is less than 1.40, it is difficult to obtain silver fine particles having good low-temperature sinterability. Further, when the crystallite diameter D x (111) exceeds 20 nm, since the crystallite diameter of the silver fine particles is large, the reactivity inside the silver fine particles is also low, which is disadvantageous for low-temperature sintering.

因此，本發明之技術課題為提供一種可較好地作為可低溫燒成之導電膏之原料用之銀微粒子。又，目的係獲得所得銀微粒子之平均粒徑為較廣範圍，尤其較好為30nm以上未達100nm以及100nm以上未達1μm之銀微粒子。 Therefore, the technical object of the present invention is to provide a silver fine particle which can be preferably used as a raw material of a conductive paste which can be fired at a low temperature. Further, it is an object to obtain a silver microparticle having an average particle diameter of a wide range, and particularly preferably 30 nm or more and less than 100 nm and 100 nm or more and less than 1 μm .

前述技術課題可藉由如下之本發明達成。 The above technical problems can be achieved by the present invention as follows.

亦即，本發明為一種銀微粒子，其特徵為X射線繞射之密勒指數(111)與(200)之微晶直徑比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上(本發明1)。 That is, the present invention is a silver fine particle characterized by a microcrystal diameter ratio of a Miller diffraction index (111) to (200) of an X-ray diffraction [crystallite diameter D x (111) / crystallite diameter D x (200 )] is 1.40 or more (Invention 1).

且，本發明係本發明1所記載之銀微粒子，其中平均粒徑(DSEM)為100nm以上未達1μm(本發明2)。 Further, the present invention is the silver fine particle according to the invention 1, wherein the average particle diameter (D SEM ) is 100 nm or more and less than 1 μm (Invention 2).

又，本發明係本發明1或2所記載之銀微粒子，其中密勒指數(111)之微晶直徑Dx(111)為20nm以下(本發明3)。 Further, the present invention is the silver fine particle according to the invention 1 or 2, wherein the crystallite diameter D x (111) of the Miller index (111) is 20 nm or less (Invention 3).

另外，本發明係本發明1~3所記載之銀微粒子，其中密勒指數(200)之微晶直徑Dx(200)為14nm以下(本發明4)。 Further, the present invention is the silver fine particles according to the first to third aspects of the present invention, wherein the Miller Index (200) has a crystallite diameter D x (200) of 14 nm or less (Invention 4).

又，本發明係本發明1~4中任一者所記載之銀微粒子，其中銀微粒子之粒子表面以由數平均分子量1,000以上之高分子系分散劑選出之一種或兩種以上被覆(本發明5)。 Further, the present invention is the silver fine particles according to any one of the present invention, wherein the surface of the particles of the silver fine particles is coated with one or two or more kinds selected from the group consisting of polymer-based dispersing agents having a number average molecular weight of 1,000 or more (the present invention) 5).

且，本發明係本發明1所記載之銀微粒子，其平均粒徑(DSEM)為30nm以上未達100nm(本發明6)。 Further, the present invention is the silver fine particle according to the first aspect of the invention, which has an average particle diameter (D SEM ) of 30 nm or more and less than 100 nm (Invention 6).

又，本發明係本發明1或6所記載之銀微粒子，其中密勒指數(111)之微晶直徑Dx(111)為25nm以下(本發明7)。 Further, the present invention is the silver fine particle according to the invention of claim 1 or 6, wherein the crystallite diameter D x (111) of the Miller index (111) is 25 nm or less (Invention 7).

又，本發明係本發明1、6、7之任一者所記載之銀微粒子，其中密勒指數(200)之微晶直徑Dx(200)為15nm以下(本發明8)。 Further, the present invention is the silver fine particles according to any one of the first to sixth aspects of the present invention, wherein the Miller Index (200) has a crystallite diameter D x (200) of 15 nm or less (Invention 8).

且，本發明係本發明1、6~8之任一者所記載之銀微粒子，其中銀微粒子之粒子表面以分子量10,000以上之高分子化合物被覆(本發明9)。 Further, the present invention is the silver fine particles according to any one of the first to sixth aspects of the present invention, wherein the surface of the particles of the silver fine particles is coated with a polymer compound having a molecular weight of 10,000 or more (Invention 9).

另外，本發明為一種導電膏，其包含如本發明1~9中任一者之銀微粒子(本發明10)。 Further, the present invention is a conductive paste comprising the silver fine particles according to any one of Inventions 1 to 9 (Invention 10).

另外，本發明為一種導電膜，其係使用如本發明10所記載之導電膏所形成(本發明11)。 Further, the present invention is a conductive film formed using the conductive paste as described in claim 10 of the present invention (Invention 11).

又，本發明為一種電子裝置，其具有如本發明11所記載之導電膜(本發明11)。 Moreover, the present invention is an electronic device comprising the conductive film according to Invention 11 (Invention 11).

本發明之銀微粒子由於X射線繞射之密勒指數(111)與(200)之微晶直徑之比[微晶直徑Dx(111)/微晶直徑 Dx(200)]為1.40以上，故可較好地作為可低溫燒成之導電膏等之原料。 The ratio of the crystallite diameter of the Miller diffraction index (111) to the crystallite diameter of (200) of the silver microparticles of the present invention [crystallite diameter D x (111) / crystallite diameter D x (200)] is 1.40 or more, Therefore, it can be preferably used as a raw material of a conductive paste which can be fired at a low temperature.

若更詳細說明本發明之構成則如下。 The structure of the present invention will be described in more detail as follows.

首先針對本發明相關之銀微粒子加以敘述。 First, the silver fine particles related to the present invention will be described.

本發明之銀微粒子之特徵為X射線繞射之密勒指數(111)與(200)之微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上之銀微粒子。 The silver microparticles of the present invention are characterized by a ratio of the Miller index of the X-ray diffraction (111) to the crystallite diameter of (200) [crystallite diameter D x (111) / crystallite diameter D x (200)] of 1.40. Silver particles above.

本發明之銀微粒子之平均粒徑可依據用途所需之條件於廣範圍內決定，但就製造方法之觀點而言，可分類成平均粒徑(DSEM)100nm以上(第一樣態)與平均粒徑(DSEM)未達100nm(第二樣態)之情況。 The average particle diameter of the silver fine particles of the present invention can be determined in a wide range depending on the conditions required for the use, but from the viewpoint of the production method, it can be classified into an average particle diameter (D SEM ) of 100 nm or more (the same state) and The average particle size (D SEM ) is less than 100 nm (second state).

首先針對上述第一樣態加以說明。第一樣態中，本發明之銀微粒子之平均粒徑(DSEM)為100nm以上，較好為100nm以上未達1μm，更好為100~500nm。藉由使平均粒徑(DSEM)在上述範圍內，而使朝配線與電極之微細化之對應變得容易。平均粒徑(DSEM)未達100nm時，即使在常溫下亦容易產生燒結，且會有使導電膏中之分散性及分散安定性下降之傾向，故有成為如第二樣態中所記載配方之必要的情況。平均粒徑(DSEM)超過1μm時，在低溫下之燒結性降低故較不佳。又，由於粒子尺寸過大，故使用其所得之電子裝置之微細化變得困難。 First, the above first state will be explained. In the first aspect, the average particle diameter (D SEM ) of the silver fine particles of the present invention is 100 nm or more, preferably 100 nm or more and less than 1 μm, more preferably 100 to 500 nm. By setting the average particle diameter (D SEM ) within the above range, it is easy to make the correspondence between the wiring and the electrode fine. When the average particle diameter (D SEM ) is less than 100 nm, sintering is likely to occur even at normal temperature, and the dispersibility and dispersion stability in the conductive paste tend to be lowered, so that it is as described in the second aspect. The necessary conditions for the formula. When the average particle diameter (D SEM ) exceeds 1 μm , the sinterability at a low temperature is lowered, which is not preferable. Moreover, since the particle size is too large, it becomes difficult to refine the electronic device obtained using the same.

本發明之第一樣態之銀微粒子之X射線繞射之密勒 指數(111)與(200)之微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上，較好為1.44以上，更好為1.48以上。藉由微晶直徑Dx(111)與微晶直徑Dx(200)之比成為1.40以上，可獲得低溫燒結性優異之銀微粒子。 The ratio of the Miller index (111) of the X-ray diffraction of the silver microparticles of the first aspect of the present invention to the crystallite diameter of (200) [crystallite diameter D x (111) / crystallite diameter D x (200) ] is 1.40 or more, preferably 1.44 or more, more preferably 1.48 or more. By the ratio of the crystallite diameter D x (111) to the crystallite diameter D x (200) is 1.40 or more, silver fine particles excellent in low-temperature sinterability can be obtained.

本發明之第一樣態之銀微粒子之X射線繞射之密勒指數(111)之微晶直徑Dx(111)較好為20nm以下，更好為10~19nm，又更好為10~18nm。微晶直徑Dx(111)超過20nm時，由於銀微粒子中之反應性降低，且會損及低溫燒結性故不佳。又，微晶直徑Dx(111)未達10nm時，銀微粒子變得不安定，即使在常溫下仍會開始產生部份燒結．熔著故不佳。 The crystallite diameter D x (111) of the Miller diffraction index (111) of the X-ray diffraction of the silver microparticles of the first aspect of the invention is preferably 20 nm or less, more preferably 10 to 19 nm, and more preferably 10~ 18nm. When the crystallite diameter D x (111) exceeds 20 nm, the reactivity in the silver fine particles is lowered, and the low-temperature sintering property is impaired, which is not preferable. Further, when the crystallite diameter D x (111) is less than 10 nm, the silver fine particles become unstable, and partial sintering starts to occur even at normal temperature. It is not good to melt.

本發明之第一樣態之銀微粒子之X射線繞射之密勒指數(200)之微晶直徑Dx(200)較好為14nm以下，更好為13nm以下，又更好為12nm以下。為使[微晶直徑Dx(111)/微晶直徑Dx(200)]成為1.40以上，微晶直徑Dx(200)較小者較佳。 The crystallite diameter D x (200) of the Miller diffraction index (200) of the X-ray diffraction of the silver fine particles of the first aspect of the present invention is preferably 14 nm or less, more preferably 13 nm or less, still more preferably 12 nm or less. In order to make the [crystallite diameter D x (111) / crystallite diameter D x (200)] 1.40 or more, the crystallite diameter D x (200) is preferably small.

本發明之第一樣態之銀微粒子之低溫燒結性係以後述之藉由加熱所致之微晶直徑之變化率[(於150℃加熱30分鐘後之銀微粒子之微晶直徑/加熱前之銀微粒子之微晶直徑)×100]進行評價，由150℃之加熱所致之微晶直徑之變化率較好為120%以上，更好為125%以上。微晶直徑之變化率未達120%時，難謂為低溫燒結性優異。本發明中，在210℃加熱30分鐘時，微晶直徑之變化率較好為150%以上，更好為170%以上。 The low-temperature sinterability of the silver fine particles of the first aspect of the present invention is a rate of change of the crystallite diameter by heating as described later [(the crystallite diameter of the silver fine particles after heating at 150 ° C for 30 minutes / before heating) The crystallite diameter of the silver fine particles was ×100], and the rate of change of the crystallite diameter by heating at 150 ° C was preferably 120% or more, more preferably 125% or more. When the rate of change of the crystallite diameter is less than 120%, it is difficult to be excellent in low-temperature sinterability. In the present invention, when heated at 210 ° C for 30 minutes, the rate of change of the crystallite diameter is preferably 150% or more, more preferably 170% or more.

本發明之第一樣態之銀微粒子之BET比表面積值較好為5m2/g以下。BET比表面積值超過5m2/g時，使用其所得之導電膏之黏度變得太高故而不佳。 The silver fine particles of the first aspect of the present invention preferably have a BET specific surface area value of 5 m 2 /g or less. When the BET specific surface area value exceeds 5 m 2 /g, the viscosity of the conductive paste obtained by using it becomes too high, which is not preferable.

本發明之第二樣態之銀微粒子之平均粒徑(DSEM)未達100nm，較好為30nm以上未達100nm，更好為35nm以上未達100nm。藉由使平均粒徑(DSEM)落在上述範圍，使利用其所得之電子裝置之微細化變得容易。平均粒徑(DSEM)未達30nm時，銀微粒子具有之表面活性變高，為了安定地維持該微細之粒徑故有必要附著大量之有機物等，故較不佳。 The average particle diameter (D SEM ) of the silver fine particles of the second aspect of the present invention is less than 100 nm, preferably 30 nm or more and less than 100 nm, more preferably 35 nm or more and less than 100 nm. By setting the average particle diameter (D SEM ) within the above range, it is easy to refine the electronic device obtained by the above. When the average particle diameter (D SEM ) is less than 30 nm, the surface activity of the silver fine particles is high, and in order to stably maintain the fine particle diameter, it is necessary to adhere a large amount of organic matter or the like, which is not preferable.

本發明之第二樣態之銀微粒子之X射線繞射之密勒指數(111)與(200)之微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上，較好為1.44以上，更好為1.48以上。藉由微晶直徑Dx(111)與微晶直徑Dx(200)之比成為1.40以上，可獲得低溫燒結性優異之銀微粒子。 The ratio of the Miller index (111) of the X-ray diffraction of the silver microparticles of the second aspect of the invention to the crystallite diameter of (200) [crystallite diameter D x (111) / crystallite diameter D x (200) ] is 1.40 or more, preferably 1.44 or more, more preferably 1.48 or more. By the ratio of the crystallite diameter D x (111) to the crystallite diameter D x (200) is 1.40 or more, silver fine particles excellent in low-temperature sinterability can be obtained.

本發明之第二樣態之銀微粒子之X射線繞射之密勒指數(111)之微晶直徑Dx(111)較好為25nm以下，更好為23~10nm，又更好為20~10nm。微晶直徑Dx(111)超過25nm時，銀微粒子中之反應性降低，且會損及低溫燒結性故而不佳。且，微晶直徑Dx(111)未達10nm時，銀微粒子變得不安定，即使在常溫下亦會開始產生部份燒結．熔著故而不佳。 The microcrystal diameter D x (111) of the Miller diffraction index (111) of the X-ray diffraction of the silver microparticles of the second aspect of the invention is preferably 25 nm or less, more preferably 23 to 10 nm, and even more preferably 20~ 10nm. When the crystallite diameter D x (111) exceeds 25 nm, the reactivity in the silver fine particles is lowered, and the low-temperature sintering property is impaired, which is not preferable. Moreover, when the crystallite diameter D x (111) is less than 10 nm, the silver fine particles become unstable, and partial sintering starts to occur even at normal temperature. It is not good to melt.

本發明之第二樣態之銀微粒子之X射線繞射之密勒指數(200)之微晶直徑Dx(200)較好為15nm以下，更好為 14nm以下，又更好為13nm以下。為使[微晶直徑Dx(111)/微晶直徑Dx(200)]成為1.40以上，微晶直徑Dx(200)越小越好。 The crystallite diameter D x (200) of the Miller diffraction index (200) of the X-ray diffraction of the silver fine particles of the second aspect of the invention is preferably 15 nm or less, more preferably 14 nm or less, still more preferably 13 nm or less. In order to make the [crystallite diameter D x (111) / crystallite diameter D x (200)] 1.40 or more, the smaller the crystallite diameter D x (200), the better.

本發明之第二樣態之銀微粒子之低溫燒結性係以後述之由加熱所致之微晶直徑之變化率[(於150℃加熱30分鐘後之銀微粒子之微晶直徑/加熱前之銀微粒子之微晶直徑)×100]進行評價，由150℃之加熱所致之微晶直徑之變化率較好為150%以上，更好為160%以上。微晶直徑之變化率未達150%時，難謂為低溫燒結性優異。本發明中，在210℃加熱30分鐘時，微晶直徑之變化率較好為180%以上，更好為200%以上。 The low-temperature sinterability of the silver fine particles of the second aspect of the present invention is a rate of change of the crystallite diameter by heating as described later [(the crystallite diameter of the silver fine particles after heating at 150 ° C for 30 minutes / the silver before heating) The crystallite diameter of the microparticles was ×100], and the rate of change of the crystallite diameter by heating at 150 ° C was preferably 150% or more, more preferably 160% or more. When the rate of change of the crystallite diameter is less than 150%, it is difficult to be excellent in low-temperature sinterability. In the present invention, when heated at 210 ° C for 30 minutes, the rate of change of the crystallite diameter is preferably 180% or more, more preferably 200% or more.

本發明之第二樣態之銀微粒子之BET比表面積值較好為10m2/g以下，更好為8m2/g以下。BET比表面積值超過10m2/g時，使用其所得之導電膏之黏度變高故而不佳。 The silver fine particles of the second aspect of the invention preferably have a BET specific surface area value of 10 m 2 /g or less, more preferably 8 m 2 /g or less. When the BET specific surface area value exceeds 10 m 2 /g, the viscosity of the conductive paste obtained by using it becomes high, which is not preferable.

本發明之第一及第二樣態之銀微粒子之粒子形狀較好為球狀或粒狀。 The particle shape of the silver fine particles of the first and second aspects of the present invention is preferably spherical or granular.

本發明之銀微粒子較好以由高分子系分散劑選出之一種或兩種以上被覆。本發明之第一樣態之銀微粒子及第二樣態之銀微粒子中，高分子系分散劑較好依據數平均分子量而靈活使用。 The silver fine particles of the present invention are preferably coated with one or two or more selected from the group consisting of polymer dispersants. In the silver fine particles of the first aspect of the present invention and the silver fine particles of the second aspect, the polymer-based dispersant is preferably used flexibly depending on the number average molecular weight.

本發明之第一樣態之銀微粒子較好為銀微粒子之粒子表面以由數平均分子量1,000以上之高分子系分散劑選出之一種或兩種以上被覆。分散劑之數平均分子量較好為 1,000以上，更好為1,000~150,000，又更好為5,000~100,000。以數平均分子量未達1,000之分散劑進行表面處理之銀微粒子粉末，其分散劑處理之效果不足，在隨後之粉碎處理中，有銀粒子凝聚之傾向。另一方面，數平均分子量超過150,000時分散劑之黏度變高，難以對銀粒子之表面進行均一處理。 In the silver fine particles of the first aspect of the present invention, it is preferred that the surface of the particles of the silver fine particles is coated with one or two or more selected from the group consisting of polymer-based dispersing agents having a number average molecular weight of 1,000 or more. The average molecular weight of the dispersant is preferably 1,000 or more, more preferably 1,000 to 150,000, and even more preferably 5,000 to 100,000. The silver fine particle powder surface-treated with a dispersing agent having a number average molecular weight of less than 1,000 has insufficient effect of dispersing agent treatment, and silver particles tend to aggregate in the subsequent pulverization treatment. On the other hand, when the number average molecular weight exceeds 150,000, the viscosity of the dispersant becomes high, and it is difficult to uniformly treat the surface of the silver particles.

本發明之第二樣態之銀微粒子較好為銀微粒子之粒子表面以分子量10,000以上之高分子化合物(高分子系分散劑)被覆。分子量未達10,000時，在隨後進行之粉碎處理中會產生凝聚塊，所得銀微粒子在導電高中之分散性變困難故而不佳。且，高分子系分散劑之分子量上限為100,000左右，分子量比其高時黏度變高，難以對銀粒子之表面進行均一處理。 The silver fine particles of the second aspect of the present invention are preferably coated with a polymer compound (polymer dispersant) having a molecular weight of 10,000 or more on the surface of the particles of the silver fine particles. When the molecular weight is less than 10,000, agglomerates are generated in the subsequent pulverization treatment, and the dispersion of the obtained silver fine particles in the high conductivity is difficult, which is not preferable. Further, the upper limit of the molecular weight of the polymer-based dispersant is about 100,000, and when the molecular weight is higher than that, the viscosity is high, and it is difficult to uniformly treat the surface of the silver particles.

使用上述任一種分子量之高分子系分散劑時，若考慮高分子化合物對銀微粒子表面之處理均一性及處理效果，則作為分散劑較好為具有酸價與胺價二者(具有酸性官能基與鹼性官能基二者之官能基)之分散劑，或併用具有酸價之分散劑與具有胺價之分散劑。 When the polymer-based dispersant of any of the above molecular weights is used, it is preferable to have both an acid value and an amine value (having an acidic functional group) as a dispersing agent in consideration of the treatment uniformity and treatment effect of the polymer compound on the surface of the silver fine particles. A dispersing agent having a functional group with both basic functional groups, or a dispersing agent having an acid value and a dispersing agent having an amine value.

分散劑之被覆量係依銀微粒子之BET表面積值而定，但相對於銀微粒子粉末較好為0.1~3.0重量%，更好為0.2~2.5重量%。未達0.1重量%時，分散劑之處理量不足，在隨後之粉碎處理中，會有銀微粒子粉末凝聚之傾向。超過3.0重量%時，雖可抑制銀微粒子粉末之凝聚，但與未參與導電性之有機物成分增加故而不佳。 The coating amount of the dispersant is determined by the BET surface area value of the silver fine particles, but is preferably 0.1 to 3.0% by weight, more preferably 0.2 to 2.5% by weight based on the silver fine particle powder. When the amount is less than 0.1% by weight, the amount of the dispersant to be treated is insufficient, and in the subsequent pulverization treatment, the silver fine particle powder tends to aggregate. When it exceeds 3.0% by weight, aggregation of the silver fine particle powder can be suppressed, but it is not preferable because the organic component which does not participate in conductivity increases.

至於前述高分子系分散劑可使用市售者作為一般顏料分散劑，具體而言列舉為ANTI-TERRA-U、ANTI-TERRA-205、DISPERBYK-101、DISPERBYK-102、DISPERBYK-106、DISPERBYK-108、DISPERBYK-109、DISPERBYK-110、DISPERBYK-111、DISPERBYK-112、DISPERBYK-116、DISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-161、DISPERBYK-162、DISPERBYK-163、DISPERBYK-164、DISPERBYK-166、DISPERBYK-167、DISPERBYK-168、DISPERBYK-170、DISPERBYK-171、DISPERBYK-174、DISPERBYK-180、DISPERBYK-182、DISPERBYK-183、DISPERBYK-184、DISPERBYK-185、DISPERBYK-2000、DISPERBYK-2001、DISPERBYK-2008、DISPERBYK-2009、DISPERBYK-2022、DISPERBYK-2025、DISPERBYK-2050、DISPERBYK-2070、DISPERBYK-2096、DISPERBYK-2150、DISPERBYK-2155、DISPERBYK-2163、DISPERBYK-2164、BYK-P104、BYK-P104S、BYK-P105、BYK-9076、BYK-9077、BYK-220S(日本BYK化學股份有限公司製造)；EFKA 4008、EFKA 4009、EFKA 4046、EFKA 4047、EFKA 4010、EFKA 4015、EFKA 4020、EFKA 4050、EFKA 4055、EFKA 4060、EFKA 4080、EFKA 4300、EFKA 4330、EFKA 4400、EFKA 4401、EFKA 4402、EFKA 4403、EFKA 4406、FFKA 4800、EFKA 5010、 EFKA 5044、EFKA 5244、EFKA 5054、EFKA 5055、EFKA 5063、EFKA 5064、EFKA 5065、EFKA 5066、EFKA 5070(日本BASF股份有限公司製造)；SOLSPERSE 3000、SOLSPERSE 13240、SOLSPERSE 13940、SOLSPERSE 16000、SOLSPERSE 17000、SOLSPERSE 18000、SOLSPERSE 20000、SOLSPERSE 21000、SOLSPERSE 24000SC、SOLSPERSE 24000GR、SOLSPERSE 26000、SOLSPERSE 27000、SOLSPERSE 28000、SOLSPERSE 31845、SOLSPERSE 32000、SOLSPERSE 32500、SOLSPERSE 32550、SOLSPERSE 34750、SOLSPERSE 35100、SOLSPERSE 35200、SOLSPERSE 36000、SOLSPERSE 36600、SOLSPERSE 37500、SOLSPERSE 38500、SOLSPERSE 39000、SOLSPERSE 41000(日本Lubrizol股份有限公司製造)；AJISPER PB821、AJISPER PB822、AJISPER PB881、AJISPER PN-411、AJISPER PA-111(味之素精密化學股份有限公司製造)；DISPARLON KS-860、DISPARLON KS-873N、DISPARLON 7004、DISPARLON 1831、DISPARLON 1850、DISPARLON 1860、DISPARLON DA-7301、DISPARLON DA-325、DISPARLON DA-375、DISPARLON DA-234(楠本化成股份有限公司製造)；FLOREN DOPA-15B、FLOREN DOPA-17HF、FLOREN DOPA-22、FLOREN DOPA-33、FLOREN G-700、FLOREN G-820、FLOREN G-900(共榮社化學股份有限公司製造)等。該等分散劑可使用一種或組合兩種以上使用。 As the above-mentioned polymer-based dispersant, a commercially available one can be used as a general pigment dispersant, specifically, ANTI-TERRA-U, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-106, DISPERBYK-108. DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK -164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000 , DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK -P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (manufactured by BYK Chemical Co., Ltd.); EFKA 4008, EFKA 4009, EFKA 4046, EFKA 4047, EFKA 4010, EFKA 4015, EFKA 4020, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4080, EFKA 4300, EFKA 4330, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4406, FFKA 4800, EFKA 5010, EFKA 5044, EFKA 5244, EFKA 5054, EFKA 5055, EFKA 5063, EFKA 5064, EFKA 5065, EFKA 5066, EFKA 5070 (manufactured by BASF, Japan); SOLSPERSE 3000, SOLSPERSE 13240, SOLSPERSE 13940, SOLSPERSE 16000, SOLSPERSE 17000, SOLSPERSE 18000, SOLSPERSE 20000, SOLSPERSE 21000, SOLSPERSE 24000SC, SOLSPERSE 24000GR, SOLSPERSE 26000, SOLSPERSE 27000, SOLSPERSE 28000, SOLSPERSE 31845, SOLSPERSE 32000, SOLSPERSE 32500, SOLSPERSE 32550, SOLSPERSE 34750, SOLSPERSE 35100, SOLSPERSE 35200, SOLSPERSE 36000, SOLSPERSE 36600 , SOLSPERSE 37500, SOLSPERSE 38500, SOLSPERSE 39000, SOLSPERSE 41000 (manufactured by Lubrizol Co., Ltd.); AJISPER PB821, AJISPER PB822, AJISPER PB881, AJISPER PN-411, AJISPER PA-111 (manufactured by Ajinomoto Precision Chemical Co., Ltd.) ;DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1831, DISPARLON 1850, DISPARLON 1860, DISPARLON DA-7301, DISPARLON DA-325, DISPARLON DA-375, DISPARLON DA-234 (made by Nanben Chemical Co., Ltd.) ); FLOREN DOPA-15B, FLOREN DOPA-17HF, FLOREN DOPA-22, FLOREN DOPA-33, FLOREN G-700, FLOREN G-820, FLOREN G-900 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. These dispersing agents can be used singly or in combination of two or more.

接著，針對本發明之銀微粒子之製造方法加以敘述。 Next, a method of producing the silver fine particles of the present invention will be described.

本發明之銀微粒子可藉由將含有還原劑之水溶液添加於含銀鹽錯合物之水溶液中，使銀微粒子還原析出之銀微粒子之製造方法，或將硝酸銀水溶液添加於還原液中使銀微粒子還原析出之銀微粒子之製造方法之任一種獲得。另外，本發明之第二種樣態之平均粒徑(DSEM)未達100nm之銀微粒子之製造方法亦可採用將銀錯合物之醇溶液添加於還原劑溶液中使銀微粒子還原析出之於溶劑反應系中之銀微粒子之製造方法。不管任一種狀況，重要的是自反應至乾燥之全部步驟均在30℃以下之溫度範圍中進行。 The silver fine particles of the present invention can be produced by adding an aqueous solution containing a reducing agent to an aqueous solution containing a silver salt complex to reduce silver fine particles by precipitation, or adding a silver nitrate aqueous solution to the reducing liquid to form silver fine particles. Any one of the methods for producing the precipitated silver fine particles is obtained. In addition, in the second aspect of the present invention, the method for producing silver fine particles having an average particle diameter (D SEM ) of less than 100 nm may be carried out by adding an alcohol solution of a silver complex to a reducing agent solution to reduce and precipitate silver fine particles. A method for producing silver microparticles in a solvent reaction system. In either case, it is important that all steps from reaction to drying are carried out in a temperature range below 30 °C.

將含有還原劑之水溶液添加於含有銀錯合物之水溶液中使銀微粒子還原析出製造銀微粒子之方法之情況，係分別預先調製含有銀鹽錯合物之水溶液與含有還原劑之水溶液。 In the case where a solution containing a reducing agent is added to an aqueous solution containing a silver complex to reduce and precipitate silver fine particles to produce silver fine particles, an aqueous solution containing a silver salt complex and an aqueous solution containing a reducing agent are prepared in advance.

本發明之銀鹽錯合物可藉由混合作為銀原料之硝酸銀或乙酸銀，與氨水、銨鹽或螯合物化合物等而獲得。氨之添加量，由於胺錯合物中之氨之配位數為2，故相對於銀1莫耳較好添加2莫耳以上之氨。若考慮生產安定性或所得銀微粒子之粒度分布之改善，則氨之添加量較好為每1莫耳之銀為4莫耳以上，更好為10莫耳以上。 The silver salt complex of the present invention can be obtained by mixing silver nitrate or silver acetate as a silver raw material with ammonia water, an ammonium salt or a chelate compound or the like. The amount of ammonia added is preferably 2 mol or more of ammonia relative to silver 1 mol because the coordination number of ammonia in the amine complex is 2. When the production stability or the improvement of the particle size distribution of the obtained silver fine particles is considered, the amount of ammonia added is preferably 4 moles or more per 1 mole of silver, more preferably 10 moles or more.

本發明之還原劑可使用由異抗壞血酸(erythorbic acid)、抗壞血酸、烷醇胺、氫醌、葡萄糖、連苯三酚、聯胺、過氧化氫水溶液及甲醛選出之一種或兩種以上。就提高所得銀微粒子於導電膏中之分散性之觀點而言，較好使用有機系還原劑，更好使用異抗壞血酸或抗壞血酸。 The reducing agent of the present invention may be one or more selected from the group consisting of erythorbic acid, ascorbic acid, alkanolamine, hydroquinone, glucose, pyrogallol, hydrazine, aqueous hydrogen peroxide, and formaldehyde. From the viewpoint of improving the dispersibility of the obtained silver fine particles in the conductive paste, an organic reducing agent is preferably used, and isoascorbic acid or ascorbic acid is preferably used.

還原劑之添加量相對於銀1莫耳較好添加1.0莫耳以上，更好為1.0~2.0莫耳。尤其，使用抗壞血酸或異抗壞血酸作為還原劑時，相對於銀1莫耳超過2.0莫耳時，生成之銀微粒子會有彼此凝聚之傾向故而不佳。 The amount of the reducing agent added is preferably 1.0 mol or more, more preferably 1.0 to 2.0 mol, based on the silver 1 molar. In particular, when ascorbic acid or erythorbic acid is used as the reducing agent, when the silver 1 mol exceeds 2.0 mol, the generated silver fine particles tend to aggregate with each other, which is not preferable.

將硝酸銀水溶液添加於還原液中使銀微粒子還原析出之銀微粒子之製造方法之情況，亦可分別預先調製還原液與硝酸銀水溶液。 In the case where a silver nitrate aqueous solution is added to the reducing liquid to prepare a silver fine particle for reducing and depositing silver fine particles, the reducing liquid and the silver nitrate aqueous solution may be prepared in advance.

本發明之硝酸銀水溶液可藉由混合硝酸銀與離子交換水或純水獲得。水溶液中之硝酸銀之濃度較好為0.08~2.0mol/l之範圍，更好為0.1~1.8mol/l。 The aqueous silver nitrate solution of the present invention can be obtained by mixing silver nitrate with ion-exchanged water or pure water. The concentration of silver nitrate in the aqueous solution is preferably in the range of 0.08 to 2.0 mol/l, more preferably 0.1 to 1.8 mol/l.

還原液可藉由混合．攪拌氨水與離子交換水或純水及還原劑而獲得。又，還原液中使用之還原劑可使用前述之還原劑。 The reducing solution can be mixed by. It is obtained by stirring ammonia water with ion exchange water or pure water and a reducing agent. Further, as the reducing agent used in the reducing solution, the aforementioned reducing agent can be used.

還原劑之添加量相對於銀1莫耳較好添加1.0莫耳以上，更好為1.0~2.0莫耳。尤其，使用抗壞血酸或異抗壞血酸作為還原劑時，相對於銀1莫耳超過2.0莫耳時，會有生成之銀微粒子彼此凝聚之傾向故而不佳。 The amount of the reducing agent added is preferably 1.0 mol or more, more preferably 1.0 to 2.0 mol, based on the silver 1 molar. In particular, when ascorbic acid or erythorbic acid is used as the reducing agent, when the silver 1 mol exceeds 2.0 mol, the generated silver fine particles tend to aggregate with each other, which is not preferable.

含有銀錯合物之水溶液、含有還原劑之水溶液、還原液及硝酸銀水溶液，在調液時較好使液溫保持在18℃以下 ，在混合．攪拌含有銀鹽錯合物之水溶液與含有還原劑之水溶液或還原液與硝酸銀水溶液時，較好調整至使液溫不超過20℃。反應溫度超過20℃時，銀微粒子之微晶直徑Dx(111)變大，同時使微晶直徑Dx(111)/微晶直徑Dx(200)之比變成未達1.40，損及低溫燒結性故而不佳。 An aqueous solution containing a silver complex, an aqueous solution containing a reducing agent, a reducing solution, and an aqueous solution of silver nitrate are preferably kept at a temperature below 18 ° C during the liquid adjustment. When the aqueous solution containing the silver salt complex and the aqueous solution containing the reducing agent or the reducing solution and the aqueous silver nitrate solution are stirred, it is preferably adjusted so that the liquid temperature does not exceed 20 °C. When the reaction temperature exceeds 20 ° C, the crystallite diameter D x (111) of the silver fine particles becomes large, and the ratio of the crystallite diameter D x (111) / crystallite diameter D x (200) becomes less than 1.40, which impairs the low temperature. Sinterability is not good.

含還原劑之水溶液對含銀鹽錯合物水溶液之添加或含硝酸銀水溶液對還原液之添加較好儘可能在短時間內進行，更好為20秒以內，又更好為15秒以內。含有還原劑之水溶液對含有銀鹽錯合物之水溶液之添加時間，或硝酸銀水溶液對還原液之添加時間太長時，會有引起生成之銀微粒子彼此凝聚，粒子尺寸變大，同時粒度分布變大之傾向。 The addition of the aqueous solution containing the reducing agent to the aqueous solution containing the silver salt complex or the addition of the silver nitrate-containing aqueous solution to the reducing solution is preferably carried out in a short time as much as possible, more preferably within 20 seconds, and even more preferably within 15 seconds. When the aqueous solution containing the reducing agent is added to the aqueous solution containing the silver salt complex, or when the silver nitrate aqueous solution is added to the reducing liquid for too long, the generated silver fine particles are agglomerated with each other, the particle size becomes large, and the particle size distribution becomes Big tendency.

含有還原劑之水溶液對含有銀鹽錯合物之水溶液之添加後，或硝酸銀水溶液對還原液添加後，以使生成之銀微粒子彼此不產生凝聚之方式緩慢地進行攪拌．混合後，依據慣用方法進行過濾．水洗。此時，進行洗淨至濾液之導電度成為60μS/cm以下為止。 After the aqueous solution containing the reducing agent is added to the aqueous solution containing the silver salt complex, or the aqueous silver nitrate solution is added to the reducing solution, the generated silver fine particles are slowly stirred without causing aggregation. After mixing, filter according to the usual method. Washed. At this time, washing is performed until the conductivity of the filtrate is 60 μS /cm or less.

使所得銀微粒子之濾餅再分散於親水性有機溶劑中，將銀微粒子表面之水分置換成親水性有機溶劑後，使以慣用方法過濾之銀微粒子在溫度30℃以下，使用乾燥機或真空乾燥進行乾燥。乾燥溫度超過30℃時，銀微粒子之微晶直徑Dx(111)變大，同時微晶直徑Dx(111)/微晶直徑Dx(200)之比未達1.40，損及低溫燒結性故而不佳。藉由將銀微粒子表面之水分置換成親水性有機溶劑，可防止乾 燥後之銀微粒子成為彼此強固凝聚之狀態，使隨後之粉碎處理或表面處理、粉碎處理等變容易。 The filter cake of the obtained silver fine particles is redispersed in a hydrophilic organic solvent, and the water on the surface of the silver fine particles is replaced with a hydrophilic organic solvent, and then the silver fine particles filtered by a conventional method are dried at a temperature of 30 ° C or lower, using a dryer or vacuum drying. Dry. When the drying temperature exceeds 30 ° C, the crystallite diameter D x (111) of the silver microparticles becomes large, and the ratio of the crystallite diameter D x (111) / crystallite diameter D x (200) is less than 1.40, which impairs the low-temperature sinterability. It is not good. By replacing the moisture on the surface of the silver fine particles with a hydrophilic organic solvent, it is possible to prevent the silver fine particles after drying from being strongly agglomerated with each other, and to facilitate subsequent pulverization treatment, surface treatment, pulverization treatment, and the like.

至於親水性有機溶劑可使用甲醇、乙醇、丙醇等醇類及丙酮等。若考慮藉由乾燥進行溶劑之去除，則以甲醇及乙醇較佳。 As the hydrophilic organic solvent, an alcohol such as methanol, ethanol or propanol, acetone or the like can be used. When it is considered to remove the solvent by drying, methanol and ethanol are preferred.

上述水性反應系統之製造方法可製造第一及第二種樣態任一種之平均粒徑之銀微粒子，但控制粒徑之方法列舉為硝酸銀水溶液中硝酸銀濃度之調整，或還原液中之氨水濃度調整。例如藉由提高硝酸銀水溶液中之硝酸銀濃度，且降低還原液中之氨水濃度，可製造主要為第一樣態之平均粒徑之銀微粒子，相反地，藉由降低硝酸銀水溶液中之硝酸銀濃度，且提高還原液中之氨水濃度，可製造主要為第二樣態之平均粒徑之銀微粒子。 The above method for producing an aqueous reaction system can produce silver particles having an average particle diameter of any of the first and second forms, but the method of controlling the particle size is exemplified by adjusting the concentration of silver nitrate in the aqueous solution of silver nitrate or the concentration of ammonia in the reducing solution. Adjustment. For example, by increasing the concentration of silver nitrate in the aqueous solution of silver nitrate and lowering the concentration of ammonia in the reducing solution, silver fine particles having an average particle diameter of the first state can be produced, and conversely, by reducing the concentration of silver nitrate in the aqueous solution of silver nitrate, and By increasing the concentration of the ammonia in the reducing solution, silver fine particles having an average particle diameter mainly in the second form can be produced.

將銀鹽錯合物之醇溶液添加於還原劑溶液中使銀微粒子還原析出之溶劑反應系統中之銀鹽錯合物之醇溶液，可藉由在醇溶液中混合硝酸銀與為水溶性或水可溶性之碳數2~4之脂肪族胺之一種以上而獲得。脂肪族胺相對於硝酸銀1莫耳較好為2.0~2.5莫耳，更好為2.0~2.3莫耳。脂肪族胺之量相對於硝酸銀1莫耳未達2.0莫耳時，會有容易生成較大粒子之傾向。 Adding the alcohol solution of the silver salt complex compound to the alcohol solution of the silver salt complex in the solvent reaction system for reducing and depositing the silver fine particles in the reducing agent solution, by mixing the silver nitrate in the alcohol solution with water solubility or water It is obtained by dissolving one or more kinds of aliphatic amines having 2 to 4 carbon atoms. The aliphatic amine is preferably 2.0 to 2.5 moles, more preferably 2.0 to 2.3 moles, relative to silver nitrate. When the amount of the aliphatic amine is less than 2.0 mol per mol of silver nitrate, there is a tendency that large particles are easily formed.

碳數2~4之脂肪族胺重要的是使用水溶性或水可溶性者，具體而言可使用乙胺、正丙胺、異丙胺、正丁胺、異丁胺等，但若考慮銀微粒子之低溫燒結性及操作性，則以正丙胺及正丁胺較佳。 The aliphatic amine having 2 to 4 carbon atoms is important to use water-soluble or water-soluble ones, specifically, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, etc., but considering the low temperature of silver microparticles For sinterability and workability, n-propylamine and n-butylamine are preferred.

溶劑反應系統中之醇可使用具有與水之相溶性者。具體而言可使用甲醇、乙醇、丙醇及異丙醇等，較好使用甲醇及乙醇。該等醇類可單獨使用亦可混合使用。 The alcohol in the solvent reaction system can be used to have compatibility with water. Specifically, methanol, ethanol, propanol, isopropanol or the like can be used, and methanol and ethanol are preferably used. These alcohols may be used singly or in combination.

溶劑反應系統中之還原劑溶液可藉由使抗壞血酸或異抗壞血酸溶解於水中，或使抗壞血酸或異抗壞血酸溶解於水中後添加醇類並經混合而獲得。抗壞血酸或異抗壞血酸相對於硝酸銀1莫耳較好為1.0~2.0莫耳，更好為1.0~1.8莫耳。抗壞血酸或異抗壞血酸鋅對於硝酸銀1莫耳超過2.0莫耳時，會有生成之銀微粒子彼此凝聚之傾向故而不佳。 The reducing agent solution in the solvent reaction system can be obtained by dissolving ascorbic acid or erythorbic acid in water, or dissolving ascorbic acid or erythorbic acid in water, adding an alcohol, and mixing. Ascorbic acid or erythorbic acid is preferably 1.0 to 2.0 moles, more preferably 1.0 to 1.8 moles, relative to silver nitrate. When ascorbic acid or zinc erythorbate is less than 2.0 moles of silver nitrate, the tendency of the generated silver fine particles to agglomerate with each other is not preferable.

銀鹽錯合物之醇溶液對溶劑反應系統中之還原劑溶液之添加係藉由將上述銀錯合物之醇溶液滴加於還原液中進行。還原反應中之反應溫度為15~30℃之範圍，更好為18~30℃。反應溫度超過30℃時，微晶直徑變大故不佳。且，滴加速度較好為3ml/分鐘以下。滴加時間短時，會有粒子尺寸及微晶直徑變大之傾向故而不佳。 The addition of the alcohol solution of the silver salt complex to the reducing agent solution in the solvent reaction system is carried out by dropwise adding the alcohol solution of the above silver complex to the reducing solution. The reaction temperature in the reduction reaction is in the range of 15 to 30 ° C, more preferably 18 to 30 ° C. When the reaction temperature exceeds 30 ° C, the diameter of the crystallites becomes large, which is not preferable. Further, the dropping rate is preferably 3 ml/min or less. When the dropping time is short, the particle size and the crystallite diameter tend to become large, which is not preferable.

滴加結束後，持續攪拌1小時以上後，利用靜置使銀微粒子沉降，藉由傾析去除上澄液後，依據慣用方法使用醇類及水進行過濾．水洗。此時，進行洗淨直到濾液之導電度成為60μS/cm以下。 After the completion of the dropwise addition, the mixture was continuously stirred for 1 hour or more, and the silver fine particles were allowed to settle by standing, and the supernatant liquid was removed by decantation, and then filtered using an alcohol and water according to a conventional method. Washed. At this time, washing is performed until the conductivity of the filtrate becomes 60 μS /cm or less.

洗淨之銀微粒子在溫度30℃以下乾燥，或者真空乾燥後，以慣用方法粉碎可獲得本發明之銀微粒子。乾燥溫度超過30℃時，銀微粒子之微晶直徑Dx(111)變大，同時微晶直徑Dx(111)/微晶直徑Dx(200)之比未達1.40，會損及 低溫燒結性故而不佳。 The washed silver fine particles are dried at a temperature of 30 ° C or lower, or dried in a vacuum, and then pulverized by a conventional method to obtain silver fine particles of the present invention. When the drying temperature exceeds 30 ° C, the crystallite diameter D x (111) of the silver microparticles becomes large, and the ratio of the crystallite diameter D x (111) / crystallite diameter D x (200) is less than 1.40, which may impair the low-temperature sintering. Sex is not good.

任一種製造方法中，乾燥後之銀微粒子亦可藉由慣用方法粉碎獲得本發明之銀微粒子。 In any of the manufacturing methods, the dried silver fine particles can also be pulverized by a conventional method to obtain the silver fine particles of the present invention.

本發明之銀微粒子較好在粉碎處理前預先以高分子分散劑進行表面處理。本發明之第一樣態中，較好以由如上述之數平均分子量1,000以上之高分子系分散劑選出之一種或兩種以上進行表面處理。以分子量1,000以上之高分子化合物之被覆量相對於銀微粒子較好為0.1~3.0重量%，更好為0.2~2.5重量%。藉由使高分子化合物之處理量落在上述範圍，可藉由粉碎處理獲得足夠之處理效果。又，本發明之第二樣態中，較好以如上述之分子量10,000以上之高分子化合物進行表面處理。分子量10,000以上之高分子化合物之被覆量相對於銀微粒子較好為0.2~4重量%，更好為0.3~3重量%。藉由使高分子化合物之處理量落在上述範圍，可藉由粉碎處理獲得足夠之處理效果。藉由以高分子化合物預先進行表面處理，在隨後進行之粉碎處理中可獲得高的粉碎處理效果，且更均一之粉碎處理成為可能。另一方面，將高分子化合物添加於銀微粒子之還原析出反應中時，處理量及處理效果之均一性會有問題，在隨後進行之粉碎處理中產生凝聚塊，所得銀微粒子在導電膏中之分散性變得困難故而不佳。 The silver fine particles of the present invention are preferably surface-treated with a polymer dispersant before the pulverization treatment. In the first aspect of the invention, it is preferred to carry out a surface treatment by one or two or more selected from the group consisting of polymer-based dispersants having an average molecular weight of 1,000 or more as described above. The coating amount of the polymer compound having a molecular weight of 1,000 or more is preferably from 0.1 to 3.0% by weight, more preferably from 0.2 to 2.5% by weight, based on the silver fine particles. By reducing the amount of the polymer compound to be in the above range, a sufficient treatment effect can be obtained by the pulverization treatment. Further, in the second aspect of the invention, it is preferred to carry out surface treatment with a polymer compound having a molecular weight of 10,000 or more as described above. The coating amount of the polymer compound having a molecular weight of 10,000 or more is preferably 0.2 to 4% by weight, more preferably 0.3 to 3% by weight based on the silver fine particles. By reducing the amount of the polymer compound to be in the above range, a sufficient treatment effect can be obtained by the pulverization treatment. By subjecting the polymer compound to surface treatment in advance, a high pulverization treatment effect can be obtained in the subsequent pulverization treatment, and a more uniform pulverization treatment becomes possible. On the other hand, when the polymer compound is added to the reduction precipitation reaction of the silver fine particles, there is a problem in the uniformity of the treatment amount and the treatment effect, and agglomerates are generated in the subsequent pulverization treatment, and the obtained silver fine particles are in the conductive paste. Dispersibility becomes difficult and not good.

以高分子化合物進行之銀微粒子之表面處理係使以親水性有機溶劑置換．乾燥後之銀微粒子再分散於使高分子化合物溶解於有機溶劑中而成之高分子化合物溶液中，緩 慢攪拌30~300分鐘後，去除有機溶劑，使用乾燥機或真空乾燥在30℃以下進行乾燥。 The surface treatment of the silver microparticles by the polymer compound is replaced by a hydrophilic organic solvent. The dried silver fine particles are redispersed in a polymer compound solution obtained by dissolving the polymer compound in an organic solvent. After slowly stirring for 30 to 300 minutes, the organic solvent is removed, and drying is carried out at 30 ° C or lower using a dryer or vacuum drying.

藉由高分子化合物進行表面處理之銀微粒子之粉碎較好使用噴射式粉碎機。 The pulverization of the silver fine particles surface-treated by the polymer compound is preferably carried out using a jet mill.

接著，針對含本發明之銀微粒子之導電膏加以敘述。 Next, the conductive paste containing the silver fine particles of the present invention will be described.

本發明之導電膏可為燒成型膏及聚合物型膏之任一種形態，燒成型膏時，由本發明之銀微粒子及玻璃熔料所成，且亦可視需要調配黏結劑樹脂、溶劑等其他成分。又，聚合物型膏時，係由本發明之銀微粒子及溶劑所成，且亦可視需要調配黏結劑樹脂、硬化劑、分散劑、流變調整劑等其他成分。 The conductive paste of the present invention may be in the form of any of a baking paste and a polymer paste. When the paste is fired, it is formed by the silver fine particles and the glass frit of the present invention, and the adhesive resin, solvent, etc. may be blended as needed. Other ingredients. Further, in the case of the polymer type paste, it is formed of the silver fine particles and the solvent of the present invention, and other components such as a binder resin, a curing agent, a dispersing agent, and a rheology adjusting agent may be blended as needed.

黏結劑樹脂可使用該領域中習知者，列舉為例如乙基纖維素、硝基纖維素等纖維素系樹脂，聚酯樹脂、胺基甲酸酯改質之聚酯樹脂、環氧改質之聚酯樹脂、丙烯酸改質之聚酯等各種改質之聚酯樹脂，聚胺基甲酸酯樹脂、氯化乙烯．乙酸乙烯酯共聚物、丙烯酸樹脂、環氧樹脂、酚樹脂、醇酸樹脂、丁醛樹脂、聚乙烯醇、聚醯亞胺、聚醯胺醯亞胺等。該等黏結劑可單獨使用或併用兩種以上。 As the binder resin, those known in the art can be used, and examples thereof include cellulose resins such as ethyl cellulose and nitrocellulose, polyester resins, urethane-modified polyester resins, and epoxy modification. Polyester resin, acrylic modified polyester and other modified polyester resin, polyurethane resin, vinyl chloride. Vinyl acetate copolymer, acrylic resin, epoxy resin, phenol resin, alkyd resin, butyral resin, polyvinyl alcohol, polyimide, polyamidimide, and the like. These binders may be used alone or in combination of two or more.

至於溶劑可使用該領域中習知者，列舉為例如十四烷、甲苯、二甲苯、乙基苯、二乙基苯、異丙基苯、胺基苯、對-異丙基甲苯(p-cymene)、四氫萘及石油系芳香族烴混合物等烴系溶劑；乙二醇單乙基醚、乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丁基醚、丙二醇單第三丁基醚、二乙二醇單乙基醚、二乙二醇單 丁基醚、二丙二醇單甲基醚、二丙二醇單丁基醚、三丙二醇單甲基醚等醚或二醇醚系溶劑；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等二醇酯系溶劑；甲基異丁基酮、環己酮等酮系溶劑；松油醇(terpineol)、沉香醇(linalool)、香葉醇(geraniol)、香茅醇(citronellol)等萜烯醇；正丁醇、第二丁醇、第三丁醇等之醇系溶劑；乙二醇、二乙二醇等二醇系溶劑；γ-丁內酯及水等。溶劑可單獨使用或併用兩種以上。 As the solvent, those skilled in the art can be used, and are exemplified by, for example, tetradecane, toluene, xylene, ethylbenzene, diethylbenzene, cumene, aminobenzene, p-isopropyltoluene (p- Hydrocarbon solvent such as cymene), tetrahydronaphthalene and petroleum aromatic hydrocarbon mixture; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl Ethyl ether, propylene glycol mono-telebutyl ether, diethylene glycol monoethyl ether, diethylene glycol single Ether or glycol ether solvent such as butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether or tripropylene glycol monomethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl a glycol ester solvent such as ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate; methyl isobutyl ketone, cyclohexanone Ketone solvents; terpineol, linalool, geraniol, citronellol, etc.; n-butanol, second butanol, third butanol, etc. Alcohol solvent; glycol solvent such as ethylene glycol or diethylene glycol; γ-butyrolactone and water. The solvent may be used singly or in combination of two or more.

導電膏中之銀微粒子之含量係依據用途而不同，但例如形成配線用途之情況等較好儘可能接近100重量%。 The content of the silver fine particles in the conductive paste varies depending on the application, but it is preferably as close as possible to 100% by weight, for example, in the case of forming a wiring.

本發明之導電膏可藉由使用擂潰機、罐研磨機、三軸輥研磨機、旋轉式混合機、二軸混練機等各種混練機、分散機，使各成分分散．混合而獲得。 The conductive paste of the present invention can be dispersed by using various kneading machines and dispersing machines such as a kneader, a can grinder, a triaxial roll grinder, a rotary mixer, and a two-axis kneading machine. Obtained by mixing.

本發明之導電膏可適用於網版印刷、噴墨法、凹版印刷、轉印印刷、輥塗、流動塗佈、噴霧塗裝、旋轉塗佈、浸漬、刮板塗佈、電鍍等各種塗佈方法。 The conductive paste of the present invention can be applied to various coatings such as screen printing, inkjet printing, gravure printing, transfer printing, roll coating, flow coating, spray coating, spin coating, dipping, blade coating, electroplating, and the like. method.

又，本發明之導電膏可使用作為FPD(平板顯示器)、太陽能電池、有機EL等之電極形成或LSI基板之配線形成，以及微細凹槽、貫穿孔、接觸孔之埋入等之形成配線之材料。又，層合陶瓷電容或層合電感器之內部電極形成用等之在高溫下燒成之用途，當然亦可低溫燒成，故可較好地使用作為可撓基板或IC卡、於其他基板上之配線形成材料及電極形成材料。且，亦可使用於電磁波遮蔽膜 或紅外線反射遮蔽等中作為導電性被膜。在電子安裝中亦可使用作為零件安裝用接合材。 In addition, the conductive paste of the present invention can be formed by forming an electrode such as an FPD (flat panel display), a solar cell, or an organic EL, or a wiring of an LSI substrate, and forming a wiring such as a fine groove, a through hole, or a buried hole of a contact hole. material. Further, the use of a laminated ceramic capacitor or a laminated inductor for forming an internal electrode or the like for firing at a high temperature can of course be performed at a low temperature, so that it can be preferably used as a flexible substrate or an IC card on other substrates. The wiring forming material and the electrode forming material. Also, it can also be used in electromagnetic shielding films. Or as a conductive film in infrared reflection shielding or the like. It is also possible to use a bonding material for component mounting in electronic mounting.

〈作用〉 <effect>

本發明中重點為X射線繞射之密勒指數(111)與(200)之微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上之銀微粒子係可低溫燒成之事實。因此，該銀微粒子之平均粒徑(DSEM)較好為30nm以上且未達1μm，可選擇極為廣範圍之平均粒徑。 The focus of the present invention is that the ratio of the Miller index (111) of the X-ray diffraction to the crystallite diameter of (200) [the crystallite diameter D x (111) / crystallite diameter D x (200)] is 1.40 or more. The fact that microparticles can be fired at low temperatures. Therefore, the average particle diameter (D SEM ) of the silver fine particles is preferably 30 nm or more and less than 1 μm , and an extremely wide average particle diameter can be selected.

本發明之銀微粒子之低溫燒結性優異之理由並不清楚，但本發明人等進行多項實驗之結果，發現低溫下燒結性優異之銀微粒子均具有微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上之值。此認為是微晶直徑Dx(111)與微晶直徑Dx(200)之比愈大則晶格之變形愈大且不安定，而顯示銀微粒子具活性者。 The reason why the low-temperature sinterability of the silver fine particles of the present invention is excellent is not clear. However, as a result of a number of experiments, the present inventors have found that silver fine particles excellent in sinterability at low temperatures have a ratio of crystallite diameters [crystallite diameter D x ( 111) / crystallite diameter D x (200)] is a value of 1.40 or more. It is considered that the larger the ratio of the crystallite diameter D x (111) to the crystallite diameter D x (200), the larger the deformation of the crystal lattice and the more unstable, and the silver fine particles are active.

實施例 Example

以下例示本發明之實施例，並具體說明本發明，但本發明並不受限於以下之實施例。又，以下諸例中，實施例1-1~1-9、比較例1-1~1-5、實施例2-1~2-9、比較例2-1~2-5、實施例3-1~3-9及比較例3-1~3-5為本發明之第一樣態之例，實施例4-1~4-13、比較例4-1~4-7、實施例5-1~5-13及比較例5-1~5-7為本發明第二樣態之例。 The embodiments of the present invention are exemplified below, and the present invention is specifically described, but the present invention is not limited to the following examples. Further, in the following examples, Examples 1-1 to 1-9, Comparative Examples 1-1 to 1-5, Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-5, and Example 3 -1 to 3-9 and Comparative Examples 3-1 to 3-5 are examples of the first aspect of the present invention, Examples 4-1 to 4-13, Comparative Examples 4-1 to 4-7, and Example 5 -1 to 5-13 and Comparative Examples 5-1 to 5-7 are examples of the second aspect of the present invention.

銀微粒子之平均粒徑係使用掃描型電子顯微鏡照相「 S-4800」(HITACHI製造)攝影粒子之照片，且使用該照片針對100個以上之粒子測定粒徑，算出其平均值作為平均粒徑(DSEM)。 The average particle diameter of the silver fine particles is a photograph of the photographic particles of "S-4800" (manufactured by HITACHI) using a scanning electron microscope, and the particle diameter is measured for 100 or more particles using the photograph, and the average value is calculated as the average particle diameter ( D SEM ).

銀微粒子之比表面積係以「Monosorb MS-11」(Quantachrome股份有限公司製造)，利用BET法測定之值表示。 The specific surface area of the silver fine particles is represented by "Monosorb MS-11" (manufactured by Quantachrome Co., Ltd.) and measured by the BET method.

銀微粒之微晶直徑Dx(111)及微晶直徑Dx(200)係使用X射線繞射裝置「RINT2500」(RIGAKU股份有限公司製造)，以Cu之Kα線作為線源，求得面指數(1,1,1)面及(2,0,0)面之波峰之半寬值，且以Scherrer之式計算微晶直徑。 The crystallite diameter D x (111) and the crystallite diameter D x (200) of the silver particles were obtained by using an X-ray diffraction device "RINT 2500" (manufactured by RIGAKU Co., Ltd.), and using the Kα line of Cu as a line source. The half-width of the peak of the index (1,1,1) plane and the (2,0,0) plane, and the crystallite diameter is calculated by the Scherrer formula.

銀微粒子之X射線繞射之密勒指數(111)與(200)之微晶直徑之比係使用上述微晶直徑Dx(111)及微晶直徑Dx(200)，由[微晶直徑Dx(111)/微晶直徑Dx(200)]求得。 The ratio of the Miller index (111) of the X-ray diffraction of the silver particles to the crystallite diameter of (200) is the above crystallite diameter D x (111) and the crystallite diameter D x (200), from [crystallite diameter D x (111) / crystallite diameter D x (200)] was obtained.

銀微粒子之因加熱所致之微晶直徑之變化率(%)係使用在150℃下加熱銀微粒子30分鐘後之微晶直徑Dx(111)與加熱前之銀微粒子之微晶直徑Dx(111)，依據下述數1算出之值。又，將加熱條件改變成在210℃下30分鐘之情況亦同樣求得微晶直徑之變化率。 Change in crystallite diameter of the silver fine particles due to heating by the rate (%) was constructed using the silver fine particles was heated for 30 minutes the crystallite diameter D x (111) and silver microparticles before the crystallite diameter D x of heating at 150 ℃ (111), the value calculated based on the following number 1. Further, the rate of change of the crystallite diameter was also determined by changing the heating conditions to 210 ° C for 30 minutes.

〈數1〉微晶直徑之變化率(%)=加熱後之銀微粒子之微晶直徑/加熱前之銀微粒子之微晶直徑×100 <Number 1> Change rate of crystallite diameter (%) = crystallite diameter of heated silver microparticles / crystallite diameter of silver microparticles before heating × 100

使用本發明之第一樣態之例之燒成型膏之導電性塗膜之特性係以下述方法求得。亦即，將後述之燒成型導電膏塗佈於氧化鋁基板上，在120℃預乾燥30分鐘後，針對在200℃、300℃、400℃、500℃、600℃加熱30分鐘獲得之導電性膜，使用四端子電阻測定裝置「LORESTA GP/MCP-T600」(三菱化學Analytech股份有限公司製造)測定，由薄片電阻及膜厚算出比電阻，以圖之橫軸設為溫度，縱軸設為薄片比電阻予以作圖，且以薄片比電阻成為1×10-5 Ω．cm以下之溫度表示。又，顯示在120℃、200℃及400℃分別加熱30分鐘時之導電性膜之薄片比電阻。 The characteristics of the conductive coating film of the fire-forming paste using the example of the first aspect of the present invention are obtained by the following method. That is, a conductive molding paste to be described later is applied onto an alumina substrate, and preliminarily dried at 120 ° C for 30 minutes, and then electrically conductive at 200 ° C, 300 ° C, 400 ° C, 500 ° C, and 600 ° C for 30 minutes. The film was measured using a four-terminal resistance measuring device "LORESTA GP/MCP-T600" (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the specific resistance was calculated from the sheet resistance and the film thickness. The horizontal axis of the graph was set to the temperature, and the vertical axis was set. The specific resistance of the sheet is plotted, and the specific resistance of the sheet is 1 × 10 -5 Ω. The temperature below cm is expressed. Further, the sheet specific resistance of the conductive film when heated at 120 ° C, 200 ° C, and 400 ° C for 30 minutes was shown.

另外，聚合物型膏之情況，係顯示將後述導電性聚合物型之導電膏塗佈於膜厚50μm之聚醯亞胺薄膜上之導電膜在120℃、210℃及300℃下分別加熱30分鐘時之導電性膜之薄片比電阻。 Further, in the case of a polymer type paste, a conductive film of a conductive polymer type described later is applied onto a polyimide film having a film thickness of 50 μm at 120 ° C, 210 ° C and 300 ° C, respectively. The sheet specific resistance of the conductive film when heated for 30 minutes.

本發明之第一樣態之例之導電性塗膜之比電阻係將後述之導電性膏塗佈於聚醯亞胺薄膜上，在120℃下預乾燥後，在150℃、210℃及300℃之各溫度下加熱硬化30分鐘獲得之導電性膜，分別使用四端子電阻測定裝置「LORESTA GP/MCP-T600」(三菱化學Analytech股份有限公司製造)測定，由薄片電阻及膜厚算出比電阻。 The specific resistance of the conductive coating film of the example of the first aspect of the present invention is applied to a polyimide film by a conductive paste to be described later, and pre-dried at 120 ° C at 150 ° C, 210 ° C and 300. The conductive film obtained by heat-hardening for 30 minutes at each temperature of °C was measured by a four-terminal resistance measuring device "LORESTA GP/MCP-T600" (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the specific resistance was calculated from the sheet resistance and the film thickness. .

〈實施例1-1：銀微粒子之製造〉 <Example 1-1: Production of silver fine particles>

於50L之反應塔中添加作為還原劑之異抗壞血酸 739g(相對於銀1mol為1.5mol)、純水32.3L及氨水(25%)780g(相對於銀1mol為4.1mol)後，邊冷卻至18℃以下邊進行混合．攪拌，調整還原液。另外，將硝酸銀475g與純水6,300g添加於20L之聚乙烯容器後，邊冷卻至18℃以下邊進行混合．攪拌，調整硝酸銀水溶液。 Adding ascorbic acid as a reducing agent to a 50L reaction column 739 g (1.5 mol with respect to 1 mol of silver), 32.3 L of pure water, and 780 g of ammonia water (25%) (4.1 mol with respect to 1 mol of silver) were mixed while cooling to below 18 ° C. Stir and adjust the reducing solution. In addition, 475 g of silver nitrate and 6,300 g of pure water were added to a 20 L polyethylene container, and then cooled to 18 ° C or lower for mixing. Stir and adjust the aqueous solution of silver nitrate.

接著，一方面使反應系統冷卻至20℃以下，一方面邊攪拌邊將硝酸銀水溶液添加於還原液中(添加時間為10秒以下)。添加結束後，攪拌30分鐘後，靜置30分鐘使固體成分沉降。以傾析去除上澄液後，使用濾紙抽氣過濾，接著使用純水進行洗淨．過濾直到濾液之導電度成為7μS/cm為止。 Next, on the one hand, the reaction system was cooled to 20 ° C or lower, and on the other hand, an aqueous solution of silver nitrate was added to the reducing solution while stirring (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes, and then allowed to stand for 30 minutes to precipitate a solid component. After decanting to remove the supernatant, filter it with a filter paper and then wash it with pure water. Filtration until the conductivity of the filtrate became 7 μS/cm.

使所得銀微粒子之濾餅再分散於甲醇溶液中，使銀微粒子表面之水分置換成甲醇並經過濾後，在真空乾燥機中於25℃下乾燥6小時。接著，將所得銀微粒子300g添加於將2.4g之高分子化合物「DISPERBYK-106」(商品名：日本BYK化學股份有限公司製造)分散於純水與甲醇之混合用液(水：甲醇比為1：10)中而成之溶液中(相對於銀微粒子為0.8重量%)，且在真空乾燥機中於25℃乾燥12小時後，以噴射式粉碎機粉碎，獲得實施例1-1之銀微粒子。 The filter cake of the obtained silver fine particles was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol and filtered, and then dried in a vacuum dryer at 25 ° C for 6 hours. Then, 300 g of the obtained silver fine particles were added to 2.4 g of the polymer compound "DISPERBYK-106" (trade name: manufactured by Japan BYK Chemical Co., Ltd.) in a mixed liquid of pure water and methanol (water: methanol ratio was 1). :10) In the solution (0.8% by weight with respect to the silver fine particles), and dried in a vacuum dryer at 25 ° C for 12 hours, and then pulverized by a jet mill to obtain silver fine particles of Example 1-1. .

所得銀微粒子之粒子形狀為粒狀，平均粒徑(DSEM)為268nm，微晶直徑Dx(111)為14.2nm，微晶直徑Dx(200)為9.0nm，Dx(111)/Dx(200)為1.58，BET比表面積值為1.5m2/g，微晶直徑之變化率(150℃×30分鐘)為 128%，微晶直徑之變化率(210℃×30分鐘)為179%。 The particle shape of the obtained silver fine particles was granular, the average particle diameter (D SEM ) was 268 nm, the crystallite diameter D x (111) was 14.2 nm, and the crystallite diameter D x (200) was 9.0 nm, D x (111) / D x (200) is 1.58, the BET specific surface area value is 1.5 m 2 /g, the rate of change of crystallite diameter (150 ° C × 30 minutes) is 128%, and the rate of change of crystallite diameter (210 ° C × 30 minutes) is 179%.

〈實施例2-1：導電膏之製造(燒成型膏)〉 <Example 2-1: Production of conductive paste (baking paste)>

對實施例1-1之銀微粒子100重量份添加乙基纖維素樹脂2.5重量份、無鉛玻璃熔料2.5重量份、苯二甲酸二正丁酯3.0重量份及2,2,2-三甲基-1,3-戊二醇單異丁酸酯(Texanol)/1-苯氧基-2-丙醇(1：1)15.4重量份，使用自轉．公轉混練機「AWATORY練太郎ARE-310」(THINKY公司製造，註冊商標)進行預混合後，使用三軸輥進行均勻混練．分散處理，獲得實施例2-1之導電膏(燒成型膏)。 2.5 parts by weight of ethyl cellulose resin, 2.5 parts by weight of lead-free glass frit, 3.0 parts by weight of di-n-butyl phthalate, and 2,2,2-trimethyl group were added to 100 parts by weight of the silver fine particles of Example 1-1. -1,3-pentanediol monoisobutyrate (Texanol) / 1-phenoxy-2-propanol (1:1) 15.4 parts by weight, using rotation. The remixing machine "AWATORY ritaro ARE-310" (manufactured by THINKY Co., Ltd., registered trademark) was premixed and then uniformly kneaded using a triaxial roller. The conductive paste (baking paste) of Example 2-1 was obtained by dispersion treatment.

將上述獲得之導電膏(燒成型膏)塗佈於氧化鋁基板上，在120℃預乾燥30分鐘後，藉由在200℃、300℃、400℃、500℃、600℃加熱30分鐘，獲得導電性膜。 The conductive paste (baking paste) obtained above was applied onto an alumina substrate, pre-dried at 120 ° C for 30 minutes, and then heated at 200 ° C, 300 ° C, 400 ° C, 500 ° C, 600 ° C for 30 minutes. A conductive film was obtained.

所得導電性塗膜之薄片比電阻成為1.0×10-5 Ω．cm以下之溫度為195℃。且，在120℃加熱處理30分鐘時之比電阻為7.7×10-5 Ω．cm，在200℃加熱處理30分鐘時之比電阻為9.1×10-6 Ω．cm，在400℃加熱處理30分鐘時之比電阻為4.7×10-6 Ω．cm， The sheet of the obtained conductive coating film has a specific resistance of 1.0×10 -5 Ω. The temperature below cm is 195 °C. Moreover, the specific resistance at 1200 ° C for 30 minutes is 7.7 × 10 -5 Ω. Cm, the specific resistance at 1200 × C heat treatment for 30 minutes is 9.1 × 10 -6 Ω. Cm, the specific resistance when heated at 400 ° C for 30 minutes is 4.7 × 10 -6 Ω. Cm,

〈實施例3-1：導電膏之製造(聚合物型膏)〉 <Example 3-1: Production of conductive paste (polymer type paste)>

對實施例1-1之銀微粒子100重量份添加聚酯樹脂11.0重量份及硬化劑1.4重量份，以使導電膏中之銀微粒子之含量成為70wt%之方式添加二乙二醇單乙基醚，進 行預混合後，使用三軸輥進行均勻混練．分散處理，獲得實施例3-1之導電膏。 To 100 parts by weight of the silver fine particles of Example 1-1, 11.0 parts by weight of a polyester resin and 1.4 parts by weight of a curing agent were added, and diethylene glycol monoethyl ether was added so that the content of the silver fine particles in the conductive paste became 70% by weight. In After pre-mixing, use a three-axis roller for uniform mixing. The conductive paste of Example 3-1 was obtained by dispersion treatment.

將上述獲得之導電膏(聚合物型膏)塗佈於膜厚50μm之聚醯亞胺薄膜上，且在120℃、210℃及300℃下分別加熱30分鐘，獲得導電性塗膜。 The conductive paste (polymer type paste) obtained above was applied onto a polyimide film having a film thickness of 50 μm , and heated at 120 ° C, 210 ° C, and 300 ° C for 30 minutes to obtain a conductive coating film.

所得導電性塗膜在120℃加熱處理30分鐘時之比電阻為3.7×10-4 Ω．cm，在210℃加熱處理30分鐘時之比電阻為2.8×10-6 Ω．cm，在300℃加熱處理30分鐘時之比電阻為9.8×10-6 Ω．cm。 The specific resistance of the obtained conductive coating film after heat treatment at 120 ° C for 30 minutes is 3.7 × 10 -4 Ω. Cm, the specific resistance at 270 ° C for 30 minutes is 2.8 × 10 -6 Ω. Cm, the specific resistance when heated at 300 ° C for 30 minutes is 9.8 × 10 -6 Ω. Cm.

依循前述實施例1-1、實施例2-1及實施例3-1製作銀微粒子及導電膏。列示各製造條件及所得銀微粒子末及導電膏之諸特性。 Silver fine particles and a conductive paste were produced in accordance with the above Example 1-1, Example 2-1, and Example 3-1. The properties of each of the production conditions and the obtained silver fine particles and the conductive paste are listed.

〈實施例1-2~1-4及比較例1-1~1-2〉 <Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-2>

藉由變更銀微粒子之各種生成條件，獲得銀微粒子。又，比較例1-5之粒子為市售之微米尺寸之銀粒子粉末。此時之製造條件示於表1，所得銀微粒子之諸特性示於表3。 Silver fine particles are obtained by changing various production conditions of silver fine particles. Further, the particles of Comparative Example 1-5 were commercially available micron-sized silver particle powders. The manufacturing conditions at this time are shown in Table 1, and the characteristics of the obtained silver fine particles are shown in Table 3.

〈實施例1-6：銀微粒子之製造〉 <Example 1-6: Production of Silver Microparticles>

於50L之反應塔中添加作為銀原料之硝酸銀595g、純水38L及氨水(25%)2,381g(相對於銀1mol為10.0mol)後，邊冷卻至10℃以下邊進行混合．攪拌，調整銀鹽錯合物水溶液。另外，將作為還原劑之異抗壞血酸 925g(相對於銀1mol為1.5mol)與純水8,333g添加於20L之聚乙烯容器中後，邊冷卻至10℃以下邊進行混合．攪拌，調整含有還原劑之水溶液。 595 g of silver nitrate as a silver raw material, 38 L of pure water, and 2,381 g of ammonia water (25%) (10.0 mol with respect to 1 mol of silver) were added to a reaction column of 50 L, and the mixture was cooled to 10 ° C or lower and mixed. Stir and adjust the aqueous solution of the silver salt complex. In addition, ascorbic acid as a reducing agent 925 g (1.5 mol with respect to 1 mol of silver) and 8,333 g of pure water were added to a 20 L polyethylene container, and then cooled to below 10 ° C for mixing. Stir and adjust the aqueous solution containing the reducing agent.

接著，一方面使反應系統冷卻至10℃以下，一方面邊攪拌邊將含有還原劑之水溶液添加於銀鹽錯合物水溶液中(添加時間為10秒以下)。添加結束後，攪拌30分鐘後，靜置30分鐘使固體成分沉降。以傾析去除上澄液後，使用濾紙抽氣過濾，接著使用純水進行洗淨．過濾直到濾液之導電度成為20μS/cm為止。 Next, on the one hand, the reaction system was cooled to 10 ° C or lower, and on the one hand, an aqueous solution containing a reducing agent was added to the aqueous solution of the silver salt complex with stirring (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes, and then allowed to stand for 30 minutes to precipitate a solid component. After decanting to remove the supernatant, filter it with a filter paper and then wash it with pure water. Filter until the conductivity of the filtrate became 20 μS /cm.

將所得銀微粒子之濾餅再分散於甲醇溶液中，使銀微粒子表面之水分置換成甲醇並經過濾後，在真空乾燥機中於25℃乾燥6小時。接著，將所得銀微粒子300g添加於將3.6g之高分子化合物「DISPERBYK-106」(商品名：日本BYK化學股份有限公司製造)分散於純水與甲醇之混合用液(水：甲醇比為1：10)中而成之溶液中(相對於銀微粒子為1.2重量%)，且在真空乾燥機中於25℃乾燥12小時後，以噴射式粉碎機粉碎，獲得實施例1-6之銀微粒子。 The obtained silver fine particle filter cake was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol, filtered, and dried in a vacuum dryer at 25 ° C for 6 hours. Then, 300 g of the obtained silver fine particles were added to 3.6 g of the polymer compound "DISPERBYK-106" (trade name: manufactured by Japan BYK Chemical Co., Ltd.) in a mixed liquid of pure water and methanol (water: methanol ratio was 1). :10) in a solution (1.2% by weight with respect to silver fine particles), and dried in a vacuum dryer at 25 ° C for 12 hours, and then pulverized by a jet mill to obtain silver fine particles of Examples 1-6. .

〈實施例1-7~1-9及比較例1-3~1-4〉 <Examples 1-7 to 1-9 and Comparative Examples 1-3 to 1-4>

藉由變更銀微粒子之各種生成條件，獲得銀微粒子。 Silver fine particles are obtained by changing various production conditions of silver fine particles.

此時之製造條件示於表2，所得銀微粒子之諸特性示於表3。 The manufacturing conditions at this time are shown in Table 2, and the characteristics of the obtained silver fine particles are shown in Table 3.

〈導電膏(燒成型膏)之製造〉 <Manufacture of conductive paste (baking paste)> 〈實施例2-2~2-9及比較例2-1~2-5〉 <Examples 2-2 to 2-9 and Comparative Examples 2-1 to 2-5>

除變更銀微粒子之各種種類以外，餘遵循前述實施例2-1之導電膏(燒成型膏)之製作方法製造導電膏及導電性塗膜。 A conductive paste and a conductive coating film were produced in the same manner as in the production method of the conductive paste (baking paste) of the above-described Example 2-1 except for changing various types of silver fine particles.

此時之製造條件及所得導電塗膜之諸特性示於表4。 The production conditions at this time and the characteristics of the obtained conductive coating film are shown in Table 4.

〈導電膏(聚合物型膏)之製造〉 <Manufacture of Conductive Paste (Polymer Paste)> 〈實施例3-2~3-9及比較例3-1~3-5〉 <Examples 3-2 to 3-9 and Comparative Examples 3-1 to 3-5>

除變更銀微粒子之各種種類以外，餘遵循前述實施例3-1之導電膏(聚合物型膏)之製作方法製造導電膏及導電性塗膜。 A conductive paste and a conductive coating film were produced in the same manner as in the production method of the conductive paste (polymer type paste) of Example 3-1 except that various types of silver fine particles were changed.

此時之製造條件及所得導電塗膜之諸特性示於表5。 The production conditions at this time and the characteristics of the obtained conductive coating film are shown in Table 5.

〈實施例4-1：銀微粒子之製造〉 <Example 4-1: Production of silver fine particles>

於50L之反應塔中添加作為還原劑之異抗壞血酸 739g(相對於銀1mol為1.5mol)、純水33.4L及氨水(25%)3,808g(相對於銀1mol為20mol)後，邊冷卻至18℃以下邊進行混合．攪拌，調整還原液。另外，將硝酸銀475g與純水1,900g添加於20L之聚乙烯容器中後，邊冷卻至18℃以下邊進行混合．攪拌，調整硝酸銀水溶液。 Adding ascorbic acid as a reducing agent to a 50L reaction column 739 g (1.5 mol with respect to 1 mol of silver), 33.4 L of pure water, and 3,808 g of ammonia water (25%) (20 mol with respect to 1 mol of silver) were mixed while cooling to below 18 ° C. Stir and adjust the reducing solution. In addition, 475 g of silver nitrate and 1,900 g of pure water were added to a 20 L polyethylene container, and then cooled to 18 ° C or lower for mixing. Stir and adjust the aqueous solution of silver nitrate.

接著，一方面使反應系統冷卻至20℃以下，一方面邊攪拌邊將硝酸銀水溶液添加於還原液中(添加時間為10秒以下)。添加結束後，攪拌30分鐘後，靜置30分鐘使固體成分沉降。以傾析去除上澄液後，使用濾紙抽氣過濾，接著使用純水進行洗淨．過濾直到濾液之導電度成為38μS/cm為止。 Next, on the one hand, the reaction system was cooled to 20 ° C or lower, and on the other hand, an aqueous solution of silver nitrate was added to the reducing solution while stirring (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes, and then allowed to stand for 30 minutes to precipitate a solid component. After decanting to remove the supernatant, filter it with a filter paper and then wash it with pure water. Filter until the conductivity of the filtrate became 38 μS /cm.

使所得銀微粒子之濾餅再分散於甲醇溶液中，使銀微粒子表面之水分置換成甲醇並經過濾後，在真空乾燥機中於25℃乾燥6小時。接著，對所得銀微粒子300g添加分散於甲醇溶液中之4.2g高分子化合物「DISPERBYK-106」(商品名：日本BYK化學股份有限公司製造)(相對於銀微粒子為1.4重量%)，經攪拌．混合90分鐘後，蒸餾去除甲醇。接著且在真空乾燥機中於25℃乾燥6小時後，以噴射式粉碎機粉碎，獲得實施例4-1之銀微粒子。 The filter cake of the obtained silver fine particles was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol and filtered, and then dried in a vacuum dryer at 25 ° C for 6 hours. Next, to the 300 g of the obtained silver fine particles, 4.2 g of a polymer compound "DISPERBYK-106" (trade name: manufactured by Japan BYK Chemical Co., Ltd.) (1.4% by weight with respect to silver fine particles) dispersed in a methanol solution was added and stirred. After mixing for 90 minutes, methanol was distilled off. Subsequently, it was dried in a vacuum dryer at 25 ° C for 6 hours, and then pulverized by a jet mill to obtain silver fine particles of Example 4-1.

所得銀微粒子之粒子形狀為粒狀，平均粒徑(DSEM)為86.0 nm，微晶直徑Dx(111)為15.4nm，微晶直徑Dx(200)為9.5nm，Dx(111)/Dx(200)為1.62，BET比表面積值為2.9m2/g，微晶直徑之變化率(150℃×30分鐘)為118%，微晶直徑之變化率(210℃×30分鐘)為145%。 The particle shape of the obtained silver microparticles was granular, the average particle diameter (D SEM ) was 86.0 nm, the crystallite diameter D x (111) was 15.4 nm, and the crystallite diameter D x (200) was 9.5 nm, D x (111) /D x (200) is 1.62, the BET specific surface area value is 2.9 m 2 /g, the rate of change of crystallite diameter (150 ° C × 30 minutes) is 118%, and the rate of change of crystallite diameter (210 ° C × 30 minutes) It is 145%.

〈實施例5-1：導電膏之製造〉 <Example 5-1: Production of Conductive Paste>

對實施例4-1之銀微粒子100重量份添加聚酯樹脂11.0重量份及硬化劑1.4重量份，及使導電膏中之銀微粒子之含量成為70wt%之方式添加二乙二醇單乙基醚，使用自轉．公轉混練機「AWATORY練太郎ARE-310」(THINKY公司製造，註冊商標)進行預混合後，使用三軸輥進行均勻混練．分散處理，獲得導電膏。 To 100 parts by weight of the silver fine particles of Example 4-1, 11.0 parts by weight of a polyester resin and 1.4 parts by weight of a curing agent were added, and diethylene glycol monoethyl ether was added so that the content of silver fine particles in the conductive paste was 70% by weight. , use rotation. The remixing machine "AWATORY ritaro ARE-310" (manufactured by THINKY Co., Ltd., registered trademark) was premixed and then uniformly kneaded using a triaxial roller. Dispersion treatment to obtain a conductive paste.

將上述獲得之導電膏塗佈於膜厚50μm之聚醯亞胺薄膜上，分別在120℃、210℃及300℃加熱30分鐘，獲得導電性塗膜。 The conductive paste obtained above was applied onto a polyimide film having a film thickness of 50 μm , and heated at 120 ° C, 210 ° C, and 300 ° C for 30 minutes to obtain a conductive coating film.

使所得導電性塗膜在120℃加熱處理30分鐘時之比電阻為1.5×10-5 Ω．cm，在210℃下加熱處理30分鐘時之比電阻為6.8×10-6 Ω．cm，在300℃下加熱處理30分鐘時之比電阻為3.1×10-6 Ω．cm。 The specific electrical resistance of the obtained conductive coating film at 120 ° C for 30 minutes is 1.5 × 10 -5 Ω. Cm, the specific resistance at 270 ° C for 30 minutes is 6.8 × 10 -6 Ω. Cm, the specific resistance at 300 ° C for 30 minutes is 3.1 × 10 -6 Ω. Cm.

遵照前述實施例4-1及實施例5-1製作銀微粒子及導電膏。列示各製造條件及所得銀微粒子末及導電膏之諸特性。 Silver fine particles and a conductive paste were produced in accordance with the above Examples 4-1 and 5-1. The properties of each of the production conditions and the obtained silver fine particles and the conductive paste are listed.

〈實施例4-2~4-5及比較例4-1~4-2〉 <Examples 4-2 to 4-5 and Comparative Examples 4-1 to 4-2>

藉由變更銀微粒子之各種生成條件，獲得銀微粒子。 Silver fine particles are obtained by changing various production conditions of silver fine particles.

此時之製造條件示於表6，所得銀微粒子之諸特性示於表9。 The manufacturing conditions at this time are shown in Table 6, and the characteristics of the obtained silver fine particles are shown in Table 9.

〈實施例4-6：銀微粒子之製造〉 <Example 4-6: Production of Silver Microparticles>

於50L之反應塔中添加作為銀原料之硝酸銀475g及氨水(25%)3,808g(相對於銀1mol為20mol)後，邊冷卻至8℃以下邊進行混合．攪拌，調整銀鹽錯合物水溶液。另外，將作為還原劑之異抗壞血酸739g(相對於銀1mol為1.5mol)與純水3,530g添加於20L之聚乙烯容器中後，邊冷卻至9℃以下邊進行混合．攪拌，調整含有還原劑之水溶液。 475 g of silver nitrate as a silver raw material and 3,808 g of ammonia water (25%) (20 mol with respect to 1 mol of silver) were added to a reaction column of 50 L, and then mixed while cooling to 8 ° C or less. Stir and adjust the aqueous solution of the silver salt complex. Further, 739 g of isoascorbic acid (1.5 mol with respect to 1 mol of silver) and 3,530 g of pure water as a reducing agent were added to a 20 L polyethylene container, and then cooled to 9 ° C or lower for mixing. Stir and adjust the aqueous solution containing the reducing agent.

接著，一方面使反應系統冷卻至10℃以下，一方面邊攪拌邊將含有還原劑之水溶液添加於銀鹽錯合物水溶液中(添加時間為10秒以下)。添加結束後，攪拌30分鐘後，靜置30分鐘使固體成分沉降。以傾析去除上澄液後，使用濾紙抽氣過濾，接著使用純水進行洗淨．過濾直到濾液之導電度成為15μS/cm為止。 Next, on the one hand, the reaction system was cooled to 10 ° C or lower, and on the one hand, an aqueous solution containing a reducing agent was added to the aqueous solution of the silver salt complex with stirring (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes, and then allowed to stand for 30 minutes to precipitate a solid component. After decanting to remove the supernatant, filter it with a filter paper and then wash it with pure water. Filtration until the conductivity of the filtrate became 15 μS/cm.

使所得銀微粒子之濾餅再分散於甲醇溶液中，使銀微粒子表面之水分置換成甲醇並經過濾後，在真空乾燥機中於25℃乾燥6小時。接著，對所得銀微粒子300g添加分散於甲醇溶液中之4.2g高分子化合物「DISPERBYK-106」(商品名：日本BYK化學股份有限公司製造)(相對於銀微粒子為1.4重量%)，經攪拌．混合90分鐘後，蒸餾去除甲醇。接著，在真空乾燥機中於25℃乾燥6小時後，以噴射式粉碎機粉碎，獲得實施例4-6之銀微粒子。 The filter cake of the obtained silver fine particles was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol and filtered, and then dried in a vacuum dryer at 25 ° C for 6 hours. Next, to the 300 g of the obtained silver fine particles, 4.2 g of a polymer compound "DISPERBYK-106" (trade name: manufactured by Japan BYK Chemical Co., Ltd.) (1.4% by weight with respect to silver fine particles) dispersed in a methanol solution was added and stirred. After mixing for 90 minutes, methanol was distilled off. Subsequently, it was dried in a vacuum dryer at 25 ° C for 6 hours, and then pulverized by a jet mill to obtain silver fine particles of Examples 4 to 6.

〈實施例4-7~4-9及比較例4-3~4-4〉 <Examples 4-7 to 4-9 and Comparative Examples 4-3 to 4-4>

藉由變更銀微粒子之各種生成條件，獲得銀微粒子。 Silver fine particles are obtained by changing various production conditions of silver fine particles.

此時之製造條件示於表7，所得銀微粒子之諸特性示於表9。 The manufacturing conditions at this time are shown in Table 7, and the characteristics of the obtained silver fine particles are shown in Table 9.

〈實施例4-10：銀微粒子之製造〉 <Example 4-10: Production of Silver Microparticles>

於2L燒杯中添加硝酸銀160g與甲醇800mL後，邊以水浴冷卻邊添加正丁基胺151.6g後，邊冷卻至18℃以下邊混合．攪拌，調製A液。另外，將異抗壞血酸248.8g量取於5L燒杯中，添加水1600mL攪拌溶解後，添加甲醇800mL且邊冷卻至18℃以下邊進行混合．攪拌，調製B液。 After adding 160 g of silver nitrate and 800 mL of methanol to a 2 L beaker, 151.6 g of n-butylamine was added while cooling in a water bath, and then the mixture was cooled to 18 ° C or lower and mixed. Stir and prepare solution A. In addition, 248.8 g of erythorbic acid was weighed in a 5 L beaker, and 1600 mL of water was added thereto to stir and dissolve. Then, 800 mL of methanol was added and the mixture was cooled to 18 ° C or lower for mixing. Stir and prepare solution B.

接著，攪拌B液，一面以使反應系統成為20℃以下之方式冷卻，一面於1小時20分鐘內將A液滴加於B液中。滴加結束後，攪拌14小時後，靜置30分鐘使固體成分沉澱。傾析上澄液並經去除後，使用濾紙抽氣過濾，接著使用甲醇與純水洗淨．過濾。 Next, the liquid B was stirred, and the reaction liquid was cooled to 20 ° C or lower, and A liquid droplets were added to the liquid B over 1 hour and 20 minutes. After completion of the dropwise addition, the mixture was stirred for 14 hours, and then allowed to stand for 30 minutes to precipitate a solid component. After decanting the supernatant and removing it, it is filtered with a filter paper and then washed with methanol and pure water. filter.

使所得銀微粒子之固成分在真空乾燥機中於30℃乾燥6小時後，對所得銀微粒子24g添加分散於甲醇溶液中之0.48g高分子化合物「DISPERBYK-106」(商品名：日本BYK化學股份有限公司製造)(相對於銀微粒子為2.0重量%)，經攪拌．混合90分鐘後，蒸餾去除甲醇。接著，在真空乾燥機中於25℃乾燥6小時後，以噴射式粉碎機粉碎，獲得實施例4-10之銀微粒子。 After the solid content of the obtained silver fine particles was dried in a vacuum dryer at 30 ° C for 6 hours, 0.48 g of a polymer compound "DISPERBYK-106" (trade name: Japan BYK Chemical Co., Ltd.) dispersed in a methanol solution was added to 24 g of the obtained silver fine particles. Made by Ltd. (2.0% by weight relative to silver microparticles), stirred. After mixing for 90 minutes, methanol was distilled off. Subsequently, it was dried in a vacuum dryer at 25 ° C for 6 hours, and then pulverized by a jet mill to obtain silver fine particles of Examples 4 to 10.

此時之製造條件示於表8，所得銀微粒子之諸特性示 於表9。 The manufacturing conditions at this time are shown in Table 8, and the characteristics of the obtained silver fine particles are shown. In Table 9.

〈實施例4-11~4-13及比較例4-5~4-6〉 <Examples 4-11 to 4-13 and Comparative Examples 4-5 to 4-6>

藉由變更銀微粒子之各種生成條件，獲得銀微粒子。 Silver fine particles are obtained by changing various production conditions of silver fine particles.

此時之製造條件示於表7，所得銀微粒子之諸特性示於表9。 The manufacturing conditions at this time are shown in Table 7, and the characteristics of the obtained silver fine particles are shown in Table 9.

〈導電性塗料之製造〉 <Manufacture of Conductive Coatings> 〈實施例5-2~5-13及比較例5-1~5-7〉 <Examples 5-2 to 5-13 and Comparative Examples 5-1 to 5-7>

除變更銀微粒子之各種種類以外，餘遵循前述實施例5-1之導電性塗料之製作方法製造導電性塗料及導電性膜。 A conductive coating material and a conductive film were produced in the same manner as in the production method of the conductive coating material of Example 5-1 except that various types of silver fine particles were changed.

此時之製造條件及所得導電性塗膜之諸特性示於表10。 The production conditions at this time and the properties of the obtained conductive coating film are shown in Table 10.

[產業上利用之可能性] [Possibility of industrial use]

本發明相關之銀微粒子由於X射線繞射之密勒指數 (111)與(200)之微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上，故可較好地作為可低溫燒成之導電膏等之原料。 The silver microparticles according to the present invention have a ratio of crystallite diameters of the Miller diffraction index (111) to (200) of the X-ray diffraction [crystallite diameter D x (111) / crystallite diameter D x (200)] of 1.40 or more. Therefore, it can be preferably used as a raw material for a conductive paste which can be fired at a low temperature.

Claims (12)

一種銀微粒子，其特徵為X射線繞射之密勒指數(Miller)(111)與(200)之微晶直徑之比[微晶直徑Dx(111)/微晶直徑Dx(200)]為1.40以上。 A silver microparticle characterized by the ratio of the Miller index (111) of the X-ray diffraction to the crystallite diameter of (200) [crystallite diameter D x (111) / crystallite diameter D x (200)] It is 1.40 or more. 如申請專利範圍第1項之銀微粒子，其平均粒徑(DSEM)為100nm以上未達1μm。 For example, the silver fine particles of the first application of the patent range have an average particle diameter (D SEM ) of 100 nm or more and less than 1 μm . 如申請專利範圍第1或2項之銀微粒子，其中密勒指數(111)之微晶直徑Dx(111)為20nm以下。 The silver fine particles of claim 1 or 2, wherein the Miller index (111) has a crystallite diameter D x (111) of 20 nm or less. 如申請專利範圍第1~3項中任一項之銀微粒子，其中密勒指數(200)之微晶直徑Dx(200)為14nm以下。 The silver fine particles according to any one of claims 1 to 3, wherein the Miller index (200) has a crystallite diameter D x (200) of 14 nm or less. 如申請專利範圍第1~4項中任一項之銀微粒子，其中銀微粒子之粒子表面被由數平均分子量1,000以上之高分子系分散劑選出之一種或兩種以上被覆。 The silver fine particles according to any one of the first to fourth aspects of the present invention, wherein the surface of the particles of the silver fine particles is coated with one or more selected from the group consisting of polymer-based dispersants having a number average molecular weight of 1,000 or more. 如申請專利範圍第1項之銀微粒子，其平均粒徑(DSEM)為30nm以上未達100nm。 The silver fine particles of the first aspect of the patent application have an average particle diameter (D SEM ) of 30 nm or more and less than 100 nm. 如申請專利範圍第1或6項之銀微粒子，其密勒指數(111)之微晶直徑Dx(111)為25nm以下。 The silver microparticles of the first or sixth aspect of the patent application have a Miller index (111) having a crystallite diameter D x (111) of 25 nm or less. 如申請專利範圍第1、6、7項中任一項之銀微粒子，其中密勒指數(200)之微晶直徑Dx(200)為15nm以下。 The silver fine particles according to any one of claims 1, 6, and 7, wherein the Miller index (200) has a crystallite diameter D x (200) of 15 nm or less. 如申請專利範圍第1、6~8項中任一項之銀微粒子，其中銀微粒子之粒子表面係以分子量10,000以上之高分子化合物被覆。 The silver fine particles of any one of the above-mentioned items, wherein the particle surface of the silver fine particles is coated with a polymer compound having a molecular weight of 10,000 or more. 一種導電膏，其包含如申請專利範圍第1~9項中 任一項之銀微粒子。 A conductive paste comprising the items 1 to 9 of the patent application scope Any of the silver particles. 一種導電膜，其係使用如申請專利範圍第10項之導電膏所形成。 A conductive film formed using a conductive paste as in claim 10 of the patent application. 一種電子裝置，其具有如申請專利範圍第11項之導電膜。 An electronic device having a conductive film as in claim 11 of the patent application.
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