TW201511035A - Composite copper particles and production method therefor - Google Patents
Composite copper particles and production method therefor Download PDFInfo
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- H—ELECTRICITY
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- 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
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/068—Flake-like particles
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
Description
本發明係關於一種複合銅粒子及其製造方法。 The present invention relates to a composite copper particle and a method of producing the same.
薄片狀之銅粒子具有如下優點：因其扁平之形狀，故而比表面積較大，又粒子彼此之接觸面積較大，因此可藉由將該薄片狀之銅粒子添加於導電性組合物而使導電性提高，又可調整黏度。例如本案申請者首先提出了薄片銅粉及含有其之導電性膏(參照專利文獻1)。 The flaky copper particles have an advantage that the flat surface shape is large, and the contact area between the particles is large, so that the flaky copper particles can be electrically conductive by adding them to the conductive composition. Increased sex and adjustable viscosity. For example, the applicant of the present invention first proposed a thin copper powder and a conductive paste containing the same (see Patent Document 1).
於專利文獻1中記載有一種薄片銅粉，其係粒徑為10μm以下者，且粒度分佈之標準偏差SD與重量累積粒徑D50之比，即SD/D50之值為0.5以下，重量累積粒徑D90與重量累積粒徑D10之比，即D90/D10之值為4.0以下。又，於上述文獻中記載有一種薄片銅粉，其係粒徑為10μm以下者，且SD/D50之值為0.15~0.35，縱橫比([厚度]/[D50])之值為0.3~0.7。藉由具有此種構成之上述文獻所記載之薄片銅粉，而變得可形成精細圖案之電路。 Patent Document 1 discloses a copper flake having a particle diameter of 10 μm or less, and a ratio of a standard deviation SD of a particle size distribution to a weight cumulative particle diameter D 50 , that is, a value of SD/D 50 of 0.5 or less, and a weight. The ratio of the cumulative particle diameter D 90 to the weight cumulative particle diameter D 10 , that is, the value of D 90 /D 10 is 4.0 or less. Further, in the above document, a copper flake having a particle diameter of 10 μm or less and having a SD/D 50 value of 0.15 to 0.35 and an aspect ratio ([thickness]/[D 50 ]) of 0.3 is described. ~0.7. According to the sheet copper powder described in the above-mentioned document having such a configuration, a circuit capable of forming a fine pattern can be obtained.
[專利文獻1]日本專利特開2003-119501號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-119501
然而，伴隨著電子零件之進一步小型化及高性能化，而要求其所使用之材料進一步微細化。因此，針對作為導電性組合物之素材之薄片狀銅粉，亦要求其微粒化。然而，於由含有微粒化之薄片狀銅粉 之導電性膏形成導電膜之情形時，有膜之燒結時所產生之氣體不易逸出之傾向，因此，電極膜之連續性變差。 However, with the further miniaturization and high performance of electronic components, it is required to further reduce the materials used. Therefore, the flaky copper powder as the material of the conductive composition is also required to be microparticulated. However, in the form of flaky copper powder containing micronized When the conductive paste is formed into a conductive film, the gas generated during the sintering of the film tends not to escape, and thus the continuity of the electrode film is deteriorated.
因此，本發明之課題在於提供一種可消除上述先前技術所具有之各種缺陷之複合銅粒子及其製造方法。 Accordingly, an object of the present invention is to provide a composite copper particle which can eliminate various defects of the prior art described above and a method for producing the same.
本發明提供一種複合銅粒子，其係將扁平狀銅粒子與較該扁平狀銅粒子為微粒之複數個無機氧化物粒子複合化而成，且上述無機氧化物粒子於上述扁平狀銅粒子之表面分佈不均。 The present invention provides a composite copper particle obtained by combining flat copper particles with a plurality of inorganic oxide particles having fine particles as the fine particles, and the inorganic oxide particles are on the surface of the flat copper particles. uneven distribution.
又，本發明提供一種複合銅粒子之製造方法，其係使用珠粒，對球狀之原料銅粉與無機氧化物之粉體之混合粉進行分散處理，使該原料銅粉之銅粒子扁平地塑性變形，並且於該銅粒子之表面配置該無機氧化物之粒子者，且使用利用動態光散射式粒度分佈測定法之累積體積50容量%中之體積累積粒徑D50(nm)、與自BET比表面積換算之粒徑DBET之比，即D50/DBET為60以上者作為上述無機氧化物之粉體。 Moreover, the present invention provides a method for producing composite copper particles by using a bead to disperse a mixed powder of a spherical raw material copper powder and an inorganic oxide powder, and to flatten the copper particles of the raw material copper powder. Plastically deformed, and the particles of the inorganic oxide are disposed on the surface of the copper particles, and a volume cumulative particle diameter D 50 (nm) in a cumulative volume of 50% by volume using a dynamic light scattering type particle size distribution measurement method, and The ratio of the particle diameter D BET in terms of the BET specific surface area, that is, the powder having the D 50 /D BET of 60 or more is used as the powder of the above inorganic oxide.
圖1係表示對實施例1中所獲得之複合銅粒子進行銅之元素分佈分析(mapping)而獲得之結果的圖像。 Fig. 1 is an image showing the results obtained by subjecting the composite copper particles obtained in Example 1 to elemental distribution of copper.
圖2係表示對實施例1中所獲得之複合銅粒子進行鋯之元素分佈分析而獲得之結果的圖像。 Fig. 2 is an image showing the results obtained by performing elemental distribution analysis of zirconium on the composite copper particles obtained in Example 1.
圖3係表示對實施例1中所獲得之複合銅粒子進行鋁之元素分佈分析而獲得之結果的圖像。 Fig. 3 is a view showing an image obtained by performing elemental distribution analysis of aluminum on the composite copper particles obtained in Example 1.
圖4係表示對實施例1至3以及比較例1及2中所獲得之銅粒子進行熱機械分析之測定結果的圖表。 4 is a graph showing the results of measurement of thermomechanical analysis of the copper particles obtained in Examples 1 to 3 and Comparative Examples 1 and 2.
以下基於較佳之實施形態而對本發明進行說明。本發明之複合銅粒子係作為母材之銅粒子與複數個無機氧化物粒子複合化而構成。 作為母材之銅粒子係具有扁平之形狀之扁平狀銅粒子。與母材複合化之無機氧化物粒子係較作為母材之扁平狀銅粒子微粒者。 Hereinafter, the present invention will be described based on preferred embodiments. The composite copper particles of the present invention are composed of copper particles as a base material and a plurality of inorganic oxide particles. The copper particles as the base material are flat copper particles having a flat shape. The inorganic oxide particles compounded with the base material are compared with the flat copper particle particles as the base material.
關於本發明之複合銅粒子，於無機氧化物粒子向作為母材之扁平狀銅粒子複合化之狀態具有如下一個特徵。詳細而言，無機氧化物粒子於扁平狀銅粒子之表面分佈不均。所謂「於表面分佈不均」，係指遍及扁平狀銅粒子之表面整個面，無機氧化物粒子並非均勻地存在，無機氧化物粒子偏於表面中之一部分而進行分佈。即，扁平狀銅粒子之表面具有：無機氧化物粒子存在之區域，即無機氧化物粒子存在區域；與無機氧化物粒子實質上不存在之區域，即無機氧化物粒子不存在區域。就無機氧化物粒子於扁平狀銅粒子之表面分佈不均之情況而言，具有如下所述之優點。即，於使用本發明之複合銅粒子而製備導電性膏等導電性組合物，將該導電性組合物之塗膜進行煅燒而形成電子電路等時，若無機氧化物粒子於扁平狀銅粒子之表面分佈不均，則該分佈不均部位，即無機氧化物粒子存在區域與無機氧化物粒子不存在區域相比，變得難以引起複合銅粒子彼此之結合。該難以引起結合之部位作為煅燒時所產生之氣體之逸出通道而發揮作用。其結果，有效地防止煅燒時所產生之電極之鼓出。藉此，可抑制使用本發明之複合銅粒子而形成之電子電路等之電阻的上升，又表面平滑性變良好。相對於此，於使用無機氧化物粒子不存在於表面之扁平狀銅粒子之情形時，於煅燒時扁平狀銅粒子彼此容易以面結合，因此難以形成氣體之逸出通道。其結果，於煅燒時容易產生電極之鼓出。 The composite copper particles of the present invention have the following characteristics in a state in which inorganic oxide particles are composited into flat copper particles as a base material. Specifically, the inorganic oxide particles are unevenly distributed on the surface of the flat copper particles. The term "uneven surface distribution" means that the entire surface of the surface of the flat copper particles is present, the inorganic oxide particles are not uniformly present, and the inorganic oxide particles are distributed on one of the surfaces. That is, the surface of the flat copper particles has a region in which the inorganic oxide particles exist, that is, a region in which the inorganic oxide particles exist, and a region in which the inorganic oxide particles are not substantially present, that is, a region in which the inorganic oxide particles are not present. In the case where the inorganic oxide particles are unevenly distributed on the surface of the flat copper particles, there are advantages as described below. In other words, when a conductive composition such as a conductive paste is prepared by using the composite copper particles of the present invention, and the coating film of the conductive composition is fired to form an electronic circuit or the like, the inorganic oxide particles are in the form of flat copper particles. When the surface distribution is uneven, the uneven distribution portion, that is, the region where the inorganic oxide particles are present, becomes less likely to cause the composite copper particles to bond to each other than the region where the inorganic oxide particles are not present. The portion which is hard to cause bonding functions as an escape passage of the gas generated at the time of calcination. As a result, the bulging of the electrode generated at the time of firing is effectively prevented. Thereby, the increase in the electric resistance of the electronic circuit or the like formed by using the composite copper particles of the present invention can be suppressed, and the surface smoothness can be improved. On the other hand, when the inorganic oxide particles are not present on the surface of the flat copper particles, the flat copper particles are easily bonded to each other at the time of firing, and thus it is difficult to form a gas escape passage. As a result, bulging of the electrode is likely to occur at the time of firing.
本發明中，所謂無機氧化物粒子分佈不均，係指如下述之圖1至圖3所示般，對本發明之複合銅粒子進行UMT(Ultramicrotome，超薄切片機)加工而形成剖面，針對該剖面進行元素分佈分析(mapping)時，於複合銅粒子之周圍觀察到無機氧化物粒子存在區域及無機氧化物粒子不存在區域。相對於此，遍及複合銅粒子之周圍全部區域而觀 察到無機氧化物粒子存在區域之情形、或者反之遍及複合銅粒子之周圍全部區域而觀察到無機氧化物粒子不存在區域之情形並不符合「無機氧化物粒子分佈不均」。 In the present invention, the uneven distribution of the inorganic oxide particles means that the composite copper particles of the present invention are processed by UMT (Ultramicrotome) to form a cross section as shown in Figs. 1 to 3 below. When elemental distribution analysis was performed on the cross section, the region where the inorganic oxide particles exist and the region where the inorganic oxide particles did not exist were observed around the composite copper particles. In contrast, the entire area around the composite copper particles is observed. When the region in which the inorganic oxide particles are present is observed, or the region where the inorganic oxide particles are not observed is observed over the entire region around the composite copper particles, the "inorganic oxide particle distribution unevenness" is not satisfied.
尤其是於無機氧化物粒子存在區域中，如下述之圖2所示般複數個無機氧化物粒子凝聚而形成凝聚體之情況就有效防止電極之連續性之方面而言較佳。 In particular, in the region where the inorganic oxide particles are present, as shown in Fig. 2, a plurality of inorganic oxide particles are aggregated to form an aggregate, and it is preferable to prevent the continuity of the electrode.
無機氧化物粒子例如藉由因其一部分被埋於扁平狀銅粒子之表面而產生之投錨效應而被配置於扁平狀銅粒子之表面。或者，無機氧化物粒子藉由無機氧化物粒子與扁平狀銅粒子之間所產生之凝聚力(表面能量)而被配置於扁平狀銅粒子之表面。又，亦有藉由無機氧化物粒子彼此間所產生之(表面能量)，而無機氧化物粒子彼此成為凝聚狀態之情形。 The inorganic oxide particles are disposed on the surface of the flat copper particles by, for example, a anchoring effect caused by a part of them being buried on the surface of the flat copper particles. Alternatively, the inorganic oxide particles are disposed on the surface of the flat copper particles by the cohesive force (surface energy) generated between the inorganic oxide particles and the flat copper particles. Further, there is a case where the inorganic oxide particles are in a state of aggregation by the (surface energy) generated between the inorganic oxide particles.
為了使無機氧化物粒子於扁平狀銅粒子之表面分佈不均，例如只要依據下述之製造方法而製造本發明之複合銅粒子即可。 In order to make the inorganic oxide particles unevenly distributed on the surface of the flat copper particles, for example, the composite copper particles of the present invention may be produced according to the following production method.
就使於使無機氧化物粒子在扁平狀銅粒子之表面分佈不均時所發揮之效果變明顯之觀點而言，無機氧化物粒子占本發明之複合銅粒子之比率較佳為0.001質量%以上且5.0質量%以下，進而較佳為0.01質量%以上且3.0質量%以下，進而更佳為0.01質量%以上且2.0質量%以下。無機氧化物粒子之比率例如可藉由電感耦合電漿發光分光分析裝置(ICP-AES)進行測定。 The ratio of the inorganic oxide particles to the composite copper particles of the present invention is preferably 0.001% by mass or more from the viewpoint that the effect of the inorganic oxide particles on the surface of the flat copper particles is uneven. Further, it is 5.0% by mass or less, more preferably 0.01% by mass or more and 3.0% by mass or less, and still more preferably 0.01% by mass or more and 2.0% by mass or less. The ratio of the inorganic oxide particles can be measured, for example, by an inductively coupled plasma emission spectroscopic analyzer (ICP-AES).
無機氧化物粒子只要僅存在於扁平狀銅粒子之表面即可，亦可不存在於扁平狀銅粒子之內部。但是於扁平狀銅粒子之內部存在無機氧化物粒子亦無妨。於使無機氧化物粒子在扁平狀銅粒子之表面分佈不均時，就使其所發揮之效果變明顯之觀點而言，存在於扁平狀銅粒子之內部之無機氧化物粒子之比率較少者較佳。就該觀點而言，本發明之複合銅粒子所含有之無機氧化物粒子中，存在於扁平狀銅粒子之 內部之無機氧化物粒子之比率較佳為1.0質量%以下，進而較佳為0.7質量%以下。該比率例如可藉由以本發明之複合銅粒子之剖面為對象之元素分佈分析而進行測定。所謂「存在於扁平狀銅粒子之內部之無機氧化物粒子」，係指於本發明之複合銅粒子之表面完全未露出之狀態之無機氧化物粒子。 The inorganic oxide particles may be present only on the surface of the flat copper particles, and may not be present inside the flat copper particles. However, it is also possible to have inorganic oxide particles in the interior of the flat copper particles. When the inorganic oxide particles are unevenly distributed on the surface of the flat copper particles, the ratio of the inorganic oxide particles existing inside the flat copper particles is small from the viewpoint that the effect exerted by the inorganic oxide particles becomes remarkable. Preferably. From this point of view, the inorganic oxide particles contained in the composite copper particles of the present invention are present in the flat copper particles. The ratio of the inorganic oxide particles in the interior is preferably 1.0% by mass or less, and more preferably 0.7% by mass or less. This ratio can be measured, for example, by elemental distribution analysis of the cross section of the composite copper particles of the present invention. The "inorganic oxide particles present in the interior of the flat copper particles" means inorganic oxide particles in a state in which the surface of the composite copper particles of the present invention is not exposed at all.
本發明之複合銅粒子具有反映作為母材之扁平狀銅粒子之形狀的扁平狀形狀。本發明之複合銅粒子之扁平程度於由作為板面之長徑d與厚度t之比之d/t，即縱橫比表示時，較佳為5以上且30以下，進而較佳為5以上且25以下，進而更佳為7以上且20以下。藉由本發明之複合銅粒子具有此種扁平程度，從而由本發明之複合銅粒子形成之電子電路等之緻密性變高，而有效地抑制電阻之上升。 The composite copper particles of the present invention have a flat shape reflecting the shape of the flat copper particles as the base material. The degree of flatness of the composite copper particles of the present invention is preferably 5 or more and 30 or less, more preferably 5 or more, in terms of d/t, which is a ratio of the major axis d to the thickness t of the plate surface, that is, the aspect ratio. 25 or less, more preferably 7 or more and 20 or less. When the composite copper particles of the present invention have such a flatness, the denseness of an electronic circuit or the like formed of the composite copper particles of the present invention is increased, and the increase in electrical resistance is effectively suppressed.
於對本發明之複合銅粒子之縱橫比進行測定之情形時，藉由電子顯微鏡觀察而對該粒子之板面之長徑d及厚度t進行測定。具體而言，使用掃描式電子顯微鏡(SEM)而拍攝粒子之照片後，自照片中之粒子之板面之長徑d與厚度t的比率而算出。 When the aspect ratio of the composite copper particles of the present invention was measured, the major axis d and the thickness t of the plate surface of the particles were measured by electron microscope observation. Specifically, after taking a photograph of the particles using a scanning electron microscope (SEM), the ratio of the major axis d to the thickness t of the plate surface of the particles in the photograph was calculated.
本發明之複合銅粒子除扁平外，較佳為微粒。藉由為扁平且為微粒，從而使用本發明之複合銅粒子而形成之電子電路等之緻密性進一步變高，而進一步有效地抑制電阻之上升。就該觀點而言，關於本發明之複合銅粒子，其利用雷射繞射散射式粒度分佈測定法之累積體積50體積%中之體積累積粒徑D50較佳為0.1μm以上且10μm以下，進而較佳為0.2μm以上且9.0μm以下，進而更佳為0.3μm以上且7.0μm以下。 The composite copper particles of the present invention are preferably fine particles in addition to being flat. The density of the electronic circuit or the like formed by using the composite copper particles of the present invention is further increased by being flat and fine particles, and the increase in resistance is further effectively suppressed. From the viewpoint of the composite copper particles of the present invention, the volume cumulative particle diameter D 50 in the cumulative volume of 50% by volume of the laser diffraction scattering particle size distribution measurement method is preferably 0.1 μm or more and 10 μm or less. Further, it is preferably 0.2 μm or more and 9.0 μm or less, and more preferably 0.3 μm or more and 7.0 μm or less.
銅之粒子通常有如下傾向：若其粒徑變小，則伴隨著粒徑變小而燒結起始溫度降低。該傾向亦適用於本發明之複合銅粒子。然而，根據本發明之複合銅粒子之具體用途，有不期望燒結起始溫度降低之情形。關於該方面，於本發明之複合銅粒子中，因於作為母材之扁平 狀銅粒子之表面存在無機氧化物粒子，故而燒結起始溫度之降低得到抑制。換言之，本發明之複合銅粒子雖然為微粒，但可維持與先前所使用之銅粉之燒結起始溫度相同程度之燒結起始溫度。 The copper particles generally have a tendency to decrease in the sintering initiation temperature as the particle diameter becomes smaller as the particle diameter becomes smaller. This tendency also applies to the composite copper particles of the present invention. However, according to the specific use of the composite copper particles of the present invention, there is a case where the sintering initiation temperature is not expected to be lowered. In this aspect, in the composite copper particles of the present invention, due to the flatness as the base material Since the inorganic oxide particles are present on the surface of the copper particles, the decrease in the sintering initiation temperature is suppressed. In other words, although the composite copper particles of the present invention are fine particles, the sintering initiation temperature can be maintained to the same extent as the sintering initiation temperature of the previously used copper powder.
本發明之複合銅粒子除為扁平外，較佳為具有較寬之粒度分佈。若具有扁平形狀之本發明之複合銅粒子之粒度分佈較寬，則由本發明之複合銅粒子形成之電子電路等之緻密性變高。其結果發揮如下有利之效果，即有效地抑制電阻之上升。就該觀點而言，於採用利用雷射繞射散射式粒度分佈測定法之最大粒徑Dmax與D50之比，即Dmax/D50之值作為粒度分佈之寬窄之參數的情形時，該值較佳為3以上且10以下，進而較佳為3以上且9以下，進而更佳為3以上且8以下。 The composite copper particles of the present invention preferably have a broad particle size distribution in addition to being flat. When the composite copper particles of the present invention having a flat shape have a wide particle size distribution, the denseness of an electronic circuit or the like formed of the composite copper particles of the present invention becomes high. As a result, the advantageous effect of effectively suppressing the increase in resistance is exhibited. From this point of view, when the ratio of the maximum particle diameter D max to D 50 by the laser diffraction scattering particle size distribution measurement, that is, the value of D max /D 50 is used as a parameter of the width and width of the particle size distribution, The value is preferably 3 or more and 10 or less, more preferably 3 or more and 9 or less, and still more preferably 3 or more and 8 or less.
為了使本發明之複合銅粒子具有上述範圍之粒度分佈，例如只要於下述之本發明之複合銅粒子之較佳製造方法中，適當設定使原料銅粉為扁平時之條件即可。 In order to make the composite copper particles of the present invention have a particle size distribution in the above range, for example, in the preferred production method of the composite copper particles of the present invention described below, the conditions for making the raw material copper powder flat may be appropriately set.
構成本發明之複合銅粒子之作為母材之扁平狀銅粒子之尺寸係與上述本發明之複合銅粒子之尺寸相同。另一方面，關於無機氧化物粒子之尺寸，係將較扁平狀銅粒子微粒設為條件，且自BET比表面積換算之粒徑(以下亦稱為「BET換算粒徑」)較佳為1nm以上且500nm以下，較佳為1nm以上且400nm以下，進而較佳為1nm以上且300nm以下。藉由將具有該範圍之大小之無機氧化物粒子與扁平狀銅粒子進行複合化，而可有效地抑制電極之鼓出，並且有效地抑制燒結起始溫度之降低。 The size of the flat copper particles as the base material constituting the composite copper particles of the present invention is the same as the size of the composite copper particles of the present invention described above. On the other hand, the size of the inorganic oxide particles is set to be a condition of the flat particles of the copper particles, and the particle diameter in terms of the BET specific surface area (hereinafter also referred to as "BET-converted particle diameter") is preferably 1 nm or more. Further, it is 500 nm or less, preferably 1 nm or more and 400 nm or less, and more preferably 1 nm or more and 300 nm or less. By combining the inorganic oxide particles having the above-described range with the flat copper particles, the bulging of the electrode can be effectively suppressed, and the decrease in the sintering initiation temperature can be effectively suppressed.
為了求出無機氧化物粒子之BET換算粒徑而進行之BET比表面積之測定例如以下述方式進行。即，使用自吸附於表面之氣體量算出比表面積之氣體吸附法而進行測定。作為具體之測定裝置，例如可使用Yuasa-ionics公司製造之MONOSORB。 The measurement of the BET specific surface area obtained by determining the BET equivalent particle diameter of the inorganic oxide particles is carried out, for example, in the following manner. That is, the measurement was carried out by a gas adsorption method in which a specific surface area was calculated from the amount of gas adsorbed on the surface. As a specific measuring device, for example, MONOSORB manufactured by Yuasa-ionics Co., Ltd. can be used.
作為無機氧化物粒子，就於下述之本發明之複合銅粒子之較佳 製造方法中，使該無機氧化物粒子容易配置於扁平狀銅粒子之表面之方面而言，較佳為使用硬度高於銅者。所謂硬度，係指使用莫氏硬度計而測定之材料之硬度。 As the inorganic oxide particles, the composite copper particles of the present invention described below are preferred. In the production method, in order to facilitate the arrangement of the inorganic oxide particles on the surface of the flat copper particles, it is preferred to use a hardness higher than that of copper. The term "hardness" refers to the hardness of a material measured using a Mohs hardness tester.
若考慮上述事項，則作為無機氧化物粒子較佳之物質，例如為氧化鋁、氧化鋯、二氧化矽、鈦酸鋇、氧化釔、氧化鋅等。該等物質可單獨使用1種，或者可組合2種以上使用。 In view of the above, preferred examples of the inorganic oxide particles include alumina, zirconia, ceria, barium titanate, cerium oxide, zinc oxide, and the like. These may be used alone or in combination of two or more.
與無機氧化物粒子複合化之扁平狀銅粒子亦可僅由銅構成，或者亦可除含有銅外，亦包含其他金屬元素或半金屬元素(以下，為了方便起見而將該等統稱為「金屬元素」)。於扁平狀銅粒子包含其他金屬元素之情形時，作為該金屬元素，例如可使用鋁、鋯、釔、矽等顯示與銅不同之燒結行為之材料等。該等金屬元素可單獨使用1種，或者組合2種以上使用。藉由扁平狀銅粒子含有其他金屬元素，從而發揮如下有利之效果，即可控制銅之燒結行為。 The flat copper particles combined with the inorganic oxide particles may be composed only of copper, or may contain other metal elements or semi-metal elements in addition to copper (hereinafter, these are collectively referred to as "for convenience". metal element"). In the case where the flat copper particles contain other metal elements, as the metal element, for example, a material exhibiting a sintering behavior different from copper such as aluminum, zirconium, hafnium or tantalum can be used. These metal elements may be used alone or in combination of two or more. By the fact that the flat copper particles contain other metal elements, the following advantageous effects can be exerted, and the sintering behavior of copper can be controlled.
扁平狀銅粒子所含有之其他金屬元素亦可以金屬單體之狀態存在，或者亦可以與銅之合金之狀態、或金屬元素之化合物(例如氧化物)存在。就使藉由含有其他金屬元素而發揮之上述效果進一步變明顯之觀點而言，其他金屬元素較佳為以氧化物等金屬元素之化合物之狀態含於扁平狀銅粒子中。 The other metal element contained in the flat copper particles may be present in the state of a metal monomer, or may be present in a state of an alloy of copper or a compound of a metal element (for example, an oxide). From the viewpoint of further enhancing the above-described effects by the inclusion of other metal elements, the other metal element is preferably contained in the flat copper particles in the state of a compound of a metal element such as an oxide.
其他金屬元素可均勻地存在於扁平狀銅粒子中，或者亦可偏在於特定部位。本發明者研究之結果，明確其他金屬元素較佳為偏在於扁平狀銅粒子之表面。本發明者認為其原因在於：表面附近容易對燒結行為產生影響。 Other metal elements may be uniformly present in the flat copper particles, or may be biased at specific sites. As a result of studies by the inventors, it has been clarified that other metal elements are preferably biased on the surface of the flat copper particles. The inventors believe that the reason is that the vicinity of the surface easily affects the sintering behavior.
於其他金屬元素偏在於扁平狀銅粒子之表面之情形時，該金屬元素較佳為遍及扁平狀銅粒子之表面整個面大致均勻地存在。因成為此種存在狀態，故而可容易地控制煅燒時之燒結行為，且結合使用較寬範圍之粒徑之扁平狀銅粒子，而變得容易進行電極之膜厚之設計， 故而較佳。 In the case where the other metal element is biased on the surface of the flat copper particles, the metal element preferably exists substantially uniformly over the entire surface of the flat copper particles. Since it is in such a state of existence, the sintering behavior at the time of firing can be easily controlled, and the flat copper particles having a wide range of particle diameters can be used in combination, and the film thickness of the electrode can be easily designed. Therefore, it is better.
關於其他金屬元素之含有比率，相對於本發明之扁平銅粒子中之銅之質量，較佳為0.001質量%以上且5.0質量%以下，進而較佳為0.01質量%以上且3.0質量%以下，進而更佳為0.05質量%以上且1.0質量%以下。藉由以該範圍之比率含有其他金屬元素，從而使藉由含有該金屬元素而發揮之上述效果進一步變明顯。 The content ratio of the other metal element is preferably 0.001% by mass or more and 5.0% by mass or less, more preferably 0.01% by mass or more and 3.0% by mass or less, based on the mass of the copper in the flat copper particles of the present invention. More preferably, it is 0.05 mass% or more and 1.0 mass% or less. By including other metal elements in the ratio of the range, the above effects exerted by the inclusion of the metal elements are further enhanced.
繼而，對本發明之微粒子集合體之較佳製造方法進行說明。於本製造方法中，使用珠粒，對球狀之原料銅粉與無機氧化物之粉體之混合粉進行分散處理。藉由該分散處理，而使原料銅粉之銅粒子扁平地塑性變形，並且於該銅粒子之表面配置該無機氧化物之粒子。此時重要的是使用凝聚程度較高者作為無機氧化物之粉體。藉由使用凝聚程度較高之無機氧化物之粉體，而可於將球狀之原料銅粉與無機氧化物之粉體複合化時，使無機氧化物粒子分佈不均。就該觀點而言，有利的是使用利用動態光散射式粒度分佈測定法之累積體積50容量%中之體積累積粒徑D50(nm)、與自BET比表面積換算之粒徑DBET之比，即D50/DBET為60以上者作為無機氧化物之粉體。D50/DBET係表示粉體之凝聚程度之指標，該值越大，表示粉體之凝聚程度變得越高。而且，藉由使用D50/DBET為60以上之無機氧化物之粉體，從而其凝聚狀態被反映至作為目標物之複合銅粒子，從而無機氧化物粒子以分佈不均之狀態被配置於扁平狀銅粒子之表面。 Next, a preferred method of producing the fine particle assembly of the present invention will be described. In the present production method, the beads are used to disperse the mixed powder of the spherical raw material copper powder and the inorganic oxide powder. By this dispersion treatment, the copper particles of the raw material copper powder are plastically deformed flat, and the particles of the inorganic oxide are disposed on the surface of the copper particles. At this time, it is important to use a powder having a higher degree of aggregation as an inorganic oxide. By using a powder of an inorganic oxide having a high degree of aggregation, it is possible to make the inorganic oxide particles unevenly distributed when the spherical copper powder of the raw material is combined with the powder of the inorganic oxide. From this point of view, it is advantageous to use a ratio of the volume cumulative particle diameter D 50 (nm) in the cumulative volume 50% by volume of the dynamic light scattering type particle size distribution measurement to the particle diameter D BET converted from the BET specific surface area. That is, a powder having an inorganic oxide of D 50 /D BET of 60 or more. D 50 /D BET is an index indicating the degree of aggregation of the powder. The larger the value, the higher the degree of aggregation of the powder. In addition, by using a powder of an inorganic oxide having a D 50 /D BET of 60 or more, the aggregated state is reflected to the composite copper particles as a target, and the inorganic oxide particles are disposed in a state of uneven distribution. The surface of flat copper particles.
就使無機氧化物粒子於扁平狀銅粒子之表面分佈不均之觀點而言，較佳為D50/DBET之值較大，但若該值過大，則有變得難以將球狀之原料銅粉與無機氧化物之粉體進行混合之傾向。就該觀點而言，D50/DBET之值較佳為60以上且300以下，進而較佳為60以上且100以下。 From the viewpoint of uneven distribution of the inorganic oxide particles on the surface of the flat copper particles, the value of D 50 /D BET is preferably large, but if the value is too large, it becomes difficult to obtain a spherical material. The tendency of copper powder to be mixed with inorganic oxide powder. From this point of view, the value of D 50 /D BET is preferably 60 or more and 300 or less, and more preferably 60 or more and 100 or less.
使用珠粒，對球狀之原料銅粉與無機氧化物之粉體之混合粉進 行分散處理時，使用直徑較佳為0.005mm以上且1.0mm以下，進而較佳為0.05mm以上且0.5mm以下，進而更佳為0.05mm以上且0.3mm以下者作為珠粒。關於珠粒之材質，只要為硬度高於銅及無機氧化物粒子者即可，例如較佳為使用氧化鋁、氧化鋯、二氧化矽等。 Using beads, a mixture of spherical copper powder and inorganic oxide powder In the case of the dispersion treatment, the diameter is preferably 0.005 mm or more and 1.0 mm or less, more preferably 0.05 mm or more and 0.5 mm or less, and still more preferably 0.05 mm or more and 0.3 mm or less. The material of the beads may be any hardness higher than that of copper and inorganic oxide particles. For example, alumina, zirconia, cerium oxide or the like is preferably used.
關於珠粒之使用量，相對於成為處理對象之處理機之容量，較佳為50質量%以上且90質量%以下，進而較佳為60質量%以上且85質量%以下，進而更佳為65質量%以上且85質量%以下。 The amount of use of the bead is preferably 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less, and still more preferably 65%, based on the capacity of the processing device to be treated. The mass% or more and 85% by mass or less.
於使用珠粒之分散處理中，例如可使用珠磨機。於使用珠磨機之情形時，分散處理所需之時間雖亦取決於處理機之容量等，但於通常使用容量為0.1L以上且300L以下之珠磨機之情形時，針對銅粉1kg，較佳為將上述分散處理所需之時間設為5分鐘以上且90分鐘以下，進而較佳為設為10分鐘以上且70分鐘以下。藉由採用該條件，而可一定程度維持無機氧化物之粉體之凝聚狀態，並且使球狀之原料銅粉始終良好地扁平化，並且可將處於凝聚狀態之無機氧化物之粉體配置、固定於扁平狀銅粒子之表面。 In the dispersion treatment using beads, for example, a bead mill can be used. In the case of using a bead mill, the time required for the dispersion treatment depends on the capacity of the processor, etc., but in the case of a bead mill having a capacity of 0.1 L or more and 300 L or less, for 1 kg of copper powder, The time required for the dispersion treatment is preferably 5 minutes or longer and 90 minutes or shorter, and more preferably 10 minutes or longer and 70 minutes or shorter. By using this condition, the aggregation state of the powder of the inorganic oxide can be maintained to some extent, and the spherical copper powder of the raw material can be uniformly flattened at all times, and the powder of the inorganic oxide in a state of aggregation can be disposed. Fixed to the surface of flat copper particles.
關於無機氧化物粒子，於與扁平狀銅粉複合化之前後，其粒徑(一次粒徑)未產生變化。因此，用作原料之無機氧化物之粉體之粒徑係與本發明之複合銅粒子所含有的無機氧化物粒子之粒徑相同。另一方面，用作原料之原料銅粉係藉由使用珠粒之分散處理而扁平化，因此於複合化之前後，形狀及尺寸產生變化。於分散處理前之狀態中，原料銅粉包含球狀之銅粒子之集合體，且就容易獲得微粒之複合銅粒子之方面而言，較佳為使用利用雷射繞射散射式粒度分佈測定法之累積體積50容量%中之體積累積粒徑D50為0.03μm以上且8μm以下、尤其是為0.05μm以上且7μm以下者。再者，亦可使用球狀以外之形狀之銅粒子作為原料銅粉，但於該情形時，有難以獲得所需之具有扁平形狀之複合銅粒子之情形。又，球狀之銅粒子就與其他形狀之銅粒子 相比容易製造之方面而言有利。 Regarding the inorganic oxide particles, the particle diameter (primary particle diameter) did not change after being combined with the flat copper powder. Therefore, the particle diameter of the powder of the inorganic oxide used as the raw material is the same as the particle diameter of the inorganic oxide particles contained in the composite copper particles of the present invention. On the other hand, the raw material copper powder used as a raw material is flattened by dispersion treatment using beads, and thus the shape and size are changed after the compositing. In the state before the dispersion treatment, the raw material copper powder includes an aggregate of spherical copper particles, and in terms of easily obtaining composite copper particles of the fine particles, it is preferable to use a laser diffraction scattering type particle size distribution measurement method. The volume cumulative particle diameter D 50 in the cumulative volume of 50% by volume is 0.03 μm or more and 8 μm or less, and particularly preferably 0.05 μm or more and 7 μm or less. Further, copper particles having a shape other than a spherical shape may be used as the raw material copper powder. However, in this case, it is difficult to obtain a desired composite copper particle having a flat shape. Further, the spherical copper particles are advantageous in that they are easier to manufacture than copper particles of other shapes.
原料銅粉較佳為其凝聚程度較高。藉此，可使所獲得之複合銅粒子之凝聚程度變高。就該觀點而言，針對原料銅粉測定之利用雷射繞射散射式粒度分佈測定法之最大粒徑Dmax與D50之比，即Dmax/D50之值較佳為2以上且15以下，進而較佳為3以上且13以下，進而更佳為3以上且10以下。具有此種粒度分佈之原料銅粉只要適當設定藉由霧化等乾式法、或濕式還原而製造原料銅粉時之條件即可。或者，可藉由將利用該等方法所製造之銅粉進行混合、或進行分級而獲得。 The raw material copper powder is preferably highly agglomerated. Thereby, the degree of aggregation of the obtained composite copper particles can be made high. From this point of view, the ratio of the maximum particle diameter D max to D 50 of the laser diffraction scattering particle size distribution measurement for the raw material copper powder measurement, that is, the value of D max /D 50 is preferably 2 or more and 15 Hereinafter, it is more preferably 3 or more and 13 or less, and still more preferably 3 or more and 10 or less. The raw material copper powder having such a particle size distribution may be subjected to a condition in which a raw material copper powder is produced by a dry method such as atomization or a wet reduction. Alternatively, it can be obtained by mixing or classifying the copper powder produced by the methods.
於設為目標之複合銅粒子中含有銅以外之其他金屬元素之情形時，有利的是使該金屬元素事先含於原料銅粉中。例如於使用鋁元素作為其他金屬元素之情形時，可採用下述方法。例如於乾式法中，於熔融之銅之熔液中混合鋁。於濕式法中於銅之還原途中添加氧化鋁等鋁氧化物。於藉由該等方法而製造之原料銅粉中，鋁元素主要存在於粒子中之表面附近之位置。 In the case where the target composite copper particles contain a metal element other than copper, it is advantageous to include the metal element in the raw material copper powder in advance. For example, when aluminum is used as the other metal element, the following method can be employed. For example, in the dry process, aluminum is mixed in a molten copper melt. In the wet method, an aluminum oxide such as alumina is added during the reduction of copper. In the raw material copper powder produced by these methods, aluminum element is mainly present at a position near the surface in the particle.
藉由進行如上所述之分散處理，可獲得設為目標之複合銅粒子。以上述方式獲得之複合銅粒子係以含有該複合銅粒子之導電性組合物之形態使用。例如以導電性膏或導電性油墨之形態使用。該導電性膏係例如含有本發明之複合銅粒子、有機媒劑、及玻璃料者。該有機媒劑含有樹脂成分與溶劑。作為樹脂成分，例如可列舉：丙烯酸系樹脂、環氧樹脂、乙基纖維素、羧基乙基纖維素等。作為溶劑，可列舉：松油醇及二氫松油醇等萜烯系溶劑、或乙基卡必醇及丁基卡必醇等醚系溶劑。作為玻璃料，可列舉：硼矽酸玻璃、硼矽酸鋇玻璃、硼矽酸鋅玻璃等。導電性膏中之微粒子集合體之比率較佳為設為36~97.5質量%。玻璃料之比率較佳為設為1.5~14質量%。有機媒劑之比率較佳為設為1~50質量%。作為該導電性膏中之導電性成分，亦可僅使用本發明之複合銅粒子，或者亦可將該微粒子集合體與其他銅微 粒子組合使用。藉由將本發明之複合銅粒子與其他銅微粒子組合使用，而變得容易進一步精確地進行膏之黏度調整。 By performing the dispersion treatment as described above, the target composite copper particles can be obtained. The composite copper particles obtained in the above manner are used in the form of a conductive composition containing the composite copper particles. For example, it is used in the form of a conductive paste or a conductive ink. The conductive paste is, for example, a composite copper particle, an organic vehicle, and a glass frit of the present invention. The organic vehicle contains a resin component and a solvent. Examples of the resin component include an acrylic resin, an epoxy resin, ethyl cellulose, and carboxyethyl cellulose. Examples of the solvent include terpene-based solvents such as terpineol and dihydroterpineol, and ether solvents such as ethyl carbitol and butyl carbitol. Examples of the glass frit include borosilicate glass, bismuth borosilicate glass, and zinc borosilicate glass. The ratio of the fine particle aggregate in the conductive paste is preferably 36 to 97.5 mass%. The ratio of the glass frit is preferably set to 1.5 to 14% by mass. The ratio of the organic vehicle is preferably from 1 to 50% by mass. As the conductive component in the conductive paste, only the composite copper particles of the present invention may be used, or the fine particle assembly may be combined with other copper micro-particles. Particles are used in combination. By using the composite copper particles of the present invention in combination with other copper microparticles, it becomes easy to further accurately adjust the viscosity of the paste.
以下，藉由實施例而對本發明進而詳細地進行說明。然而，本發明之範圍並不受該等實施例限制。只要未特別事先說明，則「%」及「份」分別意指「質量%」及「質量份」。 Hereinafter, the present invention will be described in detail by way of examples. However, the scope of the invention is not limited by the embodiments. "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise stated.
使用三井金屬礦業公司製造之CB-3000作為原料銅粉。關於該原料銅粉，其Dmax/D50之值為3.5，D50為3.2μm。D50及Dmax係使用日機裝公司製造之Microtrac X-100而進行測定。該原料銅粉係含有0.25%之鋁者。鋁係以單體之狀態存在於粒子中之內表面。 CB-3000 manufactured by Mitsui Mining & Mining Co., Ltd. was used as raw material copper powder. Regarding the raw material copper powder, the value of D max / D 50 was 3.5, and the D 50 was 3.2 μm. D 50 and D max were measured using a Microtrac X-100 manufactured by Nikkiso Co., Ltd. The raw material copper powder contains 0.25% aluminum. Aluminum is present on the inner surface of the particles in a monomer state.
使用氧化鋯之粉體作為無機氧化物之粉體。關於該粉體，其D50/DBET之值為70，BET換算粒徑DBET為15nm。D50係使用Malvern Instruments公司製造之Zetasizer ZS而進行測定。DBET係使用Yuasa-ionics公司製造之MONOSORB而進行測定。 A powder of zirconia is used as the powder of the inorganic oxide. The powder had a D 50 /D BET value of 70 and a BET equivalent particle diameter D BET of 15 nm. The D 50 was measured using a Zetasizer ZS manufactured by Malvern Instruments. D BET was measured using MONOSORB manufactured by Yuasa-ionics.
將原料銅粉1000g與無機氧化物之粉體100g投入至珠磨機，進行混合而製成混合粉，進而亦投入至直徑0.2mm之氧化鋯製之珠粒，進行分散處理。珠粒之量相對於處理機之容量，設為70%。珠磨機之容積為2L，分散處理時間設為20分鐘。藉此，獲得設為目標之複合銅粒子。利用上述方法對無機氧化物粒子占複合銅粒子之比率進行測定，結果為0.5%。 1000 g of the raw material copper powder and 100 g of the inorganic oxide powder were placed in a bead mill and mixed to prepare a mixed powder, which was further poured into beads of zirconia having a diameter of 0.2 mm, and subjected to dispersion treatment. The amount of beads was set to 70% with respect to the capacity of the processor. The volume of the bead mill was 2 L, and the dispersion treatment time was set to 20 minutes. Thereby, the target composite copper particles are obtained. The ratio of the inorganic oxide particles to the composite copper particles was measured by the above method and found to be 0.5%.
針對所獲得之複合銅粉，藉由UMT(Ultramicrotome，超薄切片機)加工而切出剖面，針對該剖面，進行利用STEM(Scanning Transmission Electron Microscopy，掃描穿透電子顯微鏡)-EDS(Energy Dispersive Spectroscopy，能量色散光譜)之元素分佈分析。作分佈分析之元素為銅、鋯及鋁。將其結果示於圖1至圖3。自該等圖可明確，複合銅粒子呈扁平形狀，且於其表面氧化鋯之粒子分佈不均。尤其是明確氧化鋯之粒子複數個凝聚而形成凝聚體。又，明確於作為母材之扁平狀銅粒子中，鋁偏在於偏平狀銅粒子之表面而並非粒子內部。 With respect to the obtained composite copper powder, a cross section is cut by UMT (Ultramicrotome) processing, and STEM (Scanning) is used for the cross section. Transmission Electron Microscopy, EDS (Energy Dispersive Spectroscopy) element distribution analysis. The elements for distribution analysis are copper, zirconium and aluminum. The results are shown in Figures 1 to 3. As is clear from the figures, the composite copper particles have a flat shape, and the particles of zirconia are unevenly distributed on the surface thereof. In particular, it is clear that a plurality of particles of zirconia are aggregated to form an aggregate. Further, it is clear that in the flat copper particles as the base material, aluminum is biased on the surface of the flat copper particles and not inside the particles.
使用氧化鋁之粉體代替實施例1中所使用之氧化鋯之粉體。關於該粉體，其D50/DBET之值為60，BET換算粒徑DBET為10nm。除此以外，以與實施例1相同之方式獲得複合銅粒子。利用上述方法對無機氧化物粒子占複合銅粒子之比率進行測定，結果為0.5%。 The powder of alumina was used in place of the powder of zirconia used in Example 1. The powder had a D 50 /D BET value of 60 and a BET equivalent particle diameter D BET of 10 nm. Except for this, composite copper particles were obtained in the same manner as in Example 1. The ratio of the inorganic oxide particles to the composite copper particles was measured by the above method and found to be 0.5%.
使用Dmax/D50之值為2.5、D50為3.3μm之原料銅粉代替實施例1中所使用之原料銅粉。該原料銅粉係含有0.13%之鋁元素者。鋁元素存在於粒子中之內表面。除此以外，以與實施例2相同之方式獲得複合銅粒子。利用上述方法對無機氧化物粒子占複合銅粒子之比率進行測定，結果為0.5%。 Instead of the raw material copper powder used in Example 1, a raw material copper powder having a D max /D 50 value of 2.5 and a D 50 of 3.3 μm was used. The raw material copper powder contains 0.13% of aluminum element. Aluminum is present on the inner surface of the particle. Except for this, composite copper particles were obtained in the same manner as in Example 2. The ratio of the inorganic oxide particles to the composite copper particles was measured by the above method and found to be 0.5%.
於實施例1中，不使用氧化鋯之粉體而進行珠磨機之處理。除此以外，以與實施例1相同之方式獲得扁平狀銅粒子。 In Example 1, the treatment of the bead mill was carried out without using the powder of zirconia. Otherwise, flat copper particles were obtained in the same manner as in Example 1.
於實施例3中，不使用氧化鋁之粉體而進行珠磨機之處理。除此以外，以與實施例3相同之方式獲得扁平狀銅粒子。 In Example 3, the treatment of the bead mill was carried out without using the powder of alumina. Otherwise, flat copper particles were obtained in the same manner as in Example 3.
針對實施例及比較例中所獲得之銅粒子，進行熱機械分析(TMA)測定。使用Seiko Instruments公司製造之TMA/SS6300作為測定裝置。 環境設為氮氣環境，以升溫速度10℃/min進行測定。將其結果示於圖4。自圖4所示之結果明確如下情況：各實施例中所獲得之複合銅粒子與比較例中所獲得之銅粒子相比，熱收縮起始溫度即燒結起始溫度同等或者高於比較例中所獲得之銅粒子。 Thermomechanical analysis (TMA) measurement was performed on the copper particles obtained in the examples and the comparative examples. TMA/SS6300 manufactured by Seiko Instruments Inc. was used as the measuring device. The environment was set to a nitrogen atmosphere, and the measurement was performed at a temperature increase rate of 10 ° C / min. The result is shown in Fig. 4. The results shown in FIG. 4 are clear as follows: the composite copper particles obtained in the respective examples have the same heat-starting temperature, that is, the sintering start temperature, as compared with the copper particles obtained in the comparative example, or higher than the comparative examples. Copper particles obtained.
使用實施例及比較例中所獲得之銅粒子作為原料而製備導電性膏。關於導電性膏，銅粒子之比率為70%，松油醇之比率為25%，乙基纖維素之比率為5%。使用敷料器，將該導電性膏塗佈於氧化鋁基板之表面而形成膜厚20μm之塗膜。將該塗膜於氮氣環境下以800℃持續煅燒1小時。利用目視觀察藉由煅燒而獲得之導電膜之表面狀態，並對電極之連續性進行評價。將電極有連續性之情形評價為「○」，將無連續性之情形評價為「×」。將其結果示於以下之表1。自表1所示之結果可明確，於使用實施例中所獲得之銅粒子之情形時，未觀察到電極之鼓出等不連續性，相對於此，於使用比較例中所獲得之銅粒子之情形時，觀察到電極之鼓出。 A conductive paste was prepared using the copper particles obtained in the examples and the comparative examples as a raw material. Regarding the conductive paste, the ratio of copper particles was 70%, the ratio of terpineol was 25%, and the ratio of ethyl cellulose was 5%. The conductive paste was applied onto the surface of the alumina substrate using an applicator to form a coating film having a film thickness of 20 μm. The coating film was continuously calcined at 800 ° C for 1 hour under a nitrogen atmosphere. The surface state of the conductive film obtained by calcination was visually observed, and the continuity of the electrode was evaluated. The case where the continuity of the electrode was evaluated was "○", and the case where there was no continuity was evaluated as "x". The results are shown in Table 1 below. As is clear from the results shown in Table 1, when the copper particles obtained in the examples were used, no discontinuity such as bulging of the electrodes was observed, and in contrast, copper particles obtained in the comparative examples were used. In the case of the case, the bulging of the electrode was observed.
根據本發明，提供一種維持與先前所使用之銅粉之燒結溫度相同程度之燒結起始溫度，並且可容易地製造鼓出產生得到抑制之電極之複合銅粒子及其製造方法。 According to the present invention, there is provided a composite copper particle which maintains a sintering initiation temperature which is the same as a sintering temperature of a previously used copper powder, and which can easily produce an electrode having suppressed bulging generation and a method for producing the same.
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