TW201527458A - Agcu-based conductive filler powder - Google Patents

Agcu-based conductive filler powder Download PDF

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TW201527458A
TW201527458A TW103135060A TW103135060A TW201527458A TW 201527458 A TW201527458 A TW 201527458A TW 103135060 A TW103135060 A TW 103135060A TW 103135060 A TW103135060 A TW 103135060A TW 201527458 A TW201527458 A TW 201527458A
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powder
agcu
conductive filler
atomized
based conductive
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Tetsuji KUSE
Tetsuro Kariya
Takahisa Yamamoto
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Sanyo Special Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)

Abstract

Provided is an AgCu-based conductive filler powder which is used for a conductive adhesive. This AgCu-based conductive filler powder is an atomized alloy powder which is formed of a Cu-Ag alloy having an Ag content of 1-30% by mass. This atomized alloy powder remains in the atomized state and has an AgCu phase having a mass ratio X of Ag to Cu (MAg/MCu) of 1.2 or more in the atomized powder outermost layer. This powder outermost layer is a layer from the powder outermost surface to 20 nm deep of the atomized alloy powder. According to the present invention, there is provided an AgCu-based conductive filler powder which has electrical conductivity equivalent to that of pure Ag and remains in the atomized alloy powder state without having necessity for Ag coating.

Description

AgCu系導電性填料粉末 AgCu conductive filler powder

本發明為關於一種導電性與放熱性優異，且製造成本低，並使用在醫療用測感器或電子機器等之AgCu系導電填料粉末。 The present invention relates to an AgCu-based conductive filler powder which is excellent in conductivity and heat dissipation and which is low in production cost and which is used in a medical sensor or an electronic device.

以往，被用來作為導電性接著劑之Ag導電填料粉末中，作為被摻混之導電性填料，有廣泛利用銀粒子。銀本身為導熱性及導電性優異之金屬，且具備銀粒子的表面上所形成之氧化被膜層的伸長不容易增加之優點。另外，由於銀係延性及展性優異，且銀粒子互相接觸而凝集後，其銀粒子互相接觸部分面積的擴大容易增加，故能夠形成顯示良好導電性之導電性接著層。 Conventionally, in the Ag conductive filler powder used as a conductive adhesive, silver particles have been widely used as a conductive filler to be blended. Silver itself is a metal excellent in thermal conductivity and electrical conductivity, and has an advantage that the elongation of the oxide film layer formed on the surface of the silver particles is not easily increased. Further, since the silver ductility and the ductility are excellent, and the silver particles are in contact with each other and aggregated, the enlargement of the area in which the silver particles contact each other is likely to increase, so that a conductive adhesive layer exhibiting good conductivity can be formed.

如此之Ag導電填料粉末係藉由使用純Ag，或對為母材之Cu塗布Ag所得。然而，純Ag在原料價格方面為高成本，另一方面，Ag塗布在製程方面亦為高成本。同時解決此等問題，且以急速冷卻使Ag在粉末表面上稠化之導電填料用粉末的詳細探討例並不存在。 Such an Ag conductive filler powder is obtained by using pure Ag or by coating Ag with Cu as a base material. However, pure Ag is a high cost in terms of raw material prices, and on the other hand, Ag coating is also costly in terms of process. At the same time, a detailed investigation of the powder for a conductive filler which satisfies such problems by rapidly cooling the Ag on the surface of the powder does not exist.

目前，已知有一種Ag導電填料粉末，其特徵 為係將銅與銀之總重量設為100時，銅之重量比率為50以下(例如參照，專利文獻1(特開2007-99851號公報))。 At present, an Ag conductive filler powder is known, which is characterized In the case where the total weight of the copper and the silver is 100, the weight ratio of the copper is 50 or less (see, for example, Patent Document 1 (JP-A-2007-99851)).

且，已知在芯材之銅系金屬的表面有配置銀粒子之芯殼型構造之Ag導電填料粉末，其構成芯材之金屬與Ag粒子之間有存在Ag被覆層(參照例如，專利文獻2(特開2011-249257號公報))。 Further, it is known that an Ag conductive filler powder having a core-shell structure in which silver particles are disposed on a surface of a copper-based metal of a core material is provided with an Ag coating layer between the metal constituting the core material and the Ag particles (refer to, for example, Patent Literature) 2 (JP-A-2011-249257)).

另一方面，有記載在粉末最表層有Ag稠化之合金粉末(參照例如專利文獻3(特開平10-21742號公報))。然而，粉末表層中之Ag與Cu的比率或AgCu相之存在率並不明確。 On the other hand, there is an alloy powder in which Ag is thickened in the outermost layer of the powder (see, for example, Patent Document 3 (JP-A-10-27742)). However, the ratio of Ag to Cu in the surface layer of the powder or the existence ratio of the AgCu phase is not clear.

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]特開2007-99851號公報 [Patent Document 1] JP-A-2007-99851

[專利文獻2]特開2011-249257號公報 [Patent Document 2] JP-A-2011-249257

[專利文獻3]特開平10-21742號公報 [Patent Document 3] Japanese Patent Publication No. 10-21742

另外，以往之以銀粒子被覆銅系金屬所成之芯材的表面之導電性填料中，藉由將銅系金屬作為芯材，來將電子零件之電極所使用之Sn(錫)電極與填料之間的電位差縮小，並來防止電流腐蝕。 In addition, in the conductive filler on the surface of the core material in which the silver particles are coated with the copper-based metal, the Sn (tin) electrode and the filler used for the electrode of the electronic component are used by using the copper-based metal as the core material. The potential difference between them is reduced and to prevent current corrosion.

然而，由於此物為在芯材的表面配置銀粒子 者，故存在於製造銅系粉末之後，在所得之銅系粉末上塗布銀之製法 However, since this material is a silver particle disposed on the surface of the core material Therefore, there is a method of coating silver on the obtained copper-based powder after manufacturing a copper-based powder.

如上述般在銅系粉末上塗布銀之製法由於在製造出霧化的粉末，並回收後，要以實施塗布之裝置來處理，故在成本或時間方面上較不利。且，為了避免塗布處理，使用銀粉末來取代銅系粉末之點，在成本方面上更為不利。 The method of coating silver on a copper-based powder as described above is disadvantageous in terms of cost or time because the atomized powder is produced and recovered after being processed by a coating apparatus. Further, in order to avoid the coating treatment, the use of silver powder instead of the copper-based powder is more disadvantageous in terms of cost.

本發明者們，如今得到以下之認識：藉由使在Ag含有率為1~30質量%之Cu-Ag合金所成之霧化合金粉末的最表層，存在10%以上之相對於Cu之Ag的質量比X=MAg/MCu)為1.2以上之AgCu相，即不需要塗布處理，僅以霧化製法，就能夠提供一種具有與純Ag相同程度之優異傳導率之AgCu系導電填料粉末。 The inventors of the present invention have now realized that 10% or more of Ag is present relative to Cu by the outermost layer of the atomized alloy powder formed of a Cu-Ag alloy having an Ag content of 1 to 30% by mass. The AgCu phase having a mass ratio of X=M Ag /M Cu ) of 1.2 or more, that is, an AgCu-based conductive filler powder having an excellent conductivity similar to that of pure Ag, can be provided by an atomization method only without requiring a coating treatment. .

因此，本發明之目的為提供一種AgCu系導電填料粉末，其係不需要塗布處理，僅以霧化製法，就能夠顯示與純Ag相同程度之傳導率。 Accordingly, an object of the present invention is to provide an AgCu-based conductive filler powder which does not require a coating treatment and which exhibits the same degree of conductivity as pure Ag by the atomization method alone.

由本發明之一型態，提供一種AgCu系導電填料粉末，其係導電性接著劑所使用之AgCu系導電填料粉末，且前述AgCu系導電填料粉末係Ag含有率為1~30質量%之Cu-Ag合金所成之霧化合金粉末，前述霧化合金粉末為保持被霧化之狀態，且在霧化粉末最表層具有相對於Cu之Ag的質量比X=(MAg/MCu)為1.2以上之AgCu相，該粉末最表層為從前述霧化合金粉 末的粉末最表面至內部20nm為止之層。 According to one aspect of the present invention, there is provided an AgCu-based conductive filler powder which is an AgCu-based conductive filler powder used for a conductive adhesive, and the AgCu-based conductive filler powder has a Ag content of 1 to 30% by mass of Cu- The atomized alloy powder formed by the Ag alloy, the atomized alloy powder is kept in a state of being atomized, and the mass ratio of the surface layer of the atomized powder to the Ag of Cu is X=(M Ag /M Cu ) is 1.2. In the above AgCu phase, the outermost layer of the powder is a layer from the outermost surface of the powder of the atomized alloy powder to the inner side of 20 nm.

由本發明之較佳型態，前述霧化合金粉末中，前述比X為1.2以上之AgCu相存在粉末最表層的10%以上。 According to a preferred embodiment of the present invention, in the atomized alloy powder, the AgCu phase having a ratio X of 1.2 or more is present in 10% or more of the outermost layer of the powder.

霧化合金粉末能夠為氣體霧化合金粉末、圓盤霧化合金粉末等，但不限於此。 The atomized alloy powder can be a gas atomized alloy powder, a disk atomized alloy powder, or the like, but is not limited thereto.

Ag與Cu在微細共晶組織的形成上為有效，藉由Ag較多且Cu較少之AgCu相佔有於粉末表層中，能使接觸阻力較純Cu低，並將導電度提高。尤其是最表層之AgCu相中，相對於Cu之Ag的質量比X為1.2以上時，能夠得到不遜色於純Ag之優異導電度。這是因為，當比X為1.2以上時，氧化物變得較難形成，且即使有形成氧化物時，也會抑制比阻力較高之Cu系的氧化物形成，而形成比阻力較低之Ag系的氧化物。 Ag and Cu are effective in the formation of a fine eutectic structure, and an AgCu phase having a large amount of Ag and a small amount of Cu is present in the surface layer of the powder, so that the contact resistance is lower than that of pure Cu, and the conductivity is improved. In particular, in the AgCu phase of the outermost layer, when the mass ratio X of Cu to Cu is 1.2 or more, excellent conductivity which is not inferior to pure Ag can be obtained. This is because when the ratio X is 1.2 or more, the oxide becomes difficult to form, and even when an oxide is formed, formation of a Cu-based oxide having a higher specific resistance is suppressed, and formation of a lower specific resistance is formed. Ag-based oxide.

且，藉由相對於Cu之Ag的質量比為1.2以上之AgCu相佔有粉末表層之面積比率的10%以上，能夠極力地防止Cu露出於大氣中，該Cu為存在於Ag較少且Cu較多之CuAg相的粉末內層。其結果，Ag彼此之金屬接合能良好地進行，並能確保接合的信賴性。 Further, since the AgCu phase having a mass ratio of Ag of 1.2 or more with respect to Cu accounts for 10% or more of the area ratio of the surface layer of the powder, Cu can be prevented from being exposed to the atmosphere as much as possible. More powder inner layer of CuAg phase. As a result, the metal bonding of Ag can be performed satisfactorily, and the reliability of bonding can be ensured.

如以上所述，本發明為達成能夠提供一種具有不遜色於純Ag之導電度，且為保持被霧化之狀態(as atomized)的合金粉末，並不需要Ag塗布之AgCu系導電填料粉末之極為優異之效果。 As described above, the present invention provides an alloy powder having an electrical conductivity which is not inferior to pure Ag and which is maintained as an atomized state, and does not require Ag-coated AgCu-based conductive filler powder. Extremely excellent results.

1‧‧‧霧化合金粉末 1‧‧‧Atomized alloy powder

2‧‧‧粉末最表層 2‧‧‧The top layer of powder

3‧‧‧AgCu相 3‧‧‧AgCu phase

[圖1]本發明相關之Ag與Cu之共晶合金的霧化合金粉末之剖面模式圖。 Fig. 1 is a schematic cross-sectional view showing an atomized alloy powder of a eutectic alloy of Ag and Cu according to the present invention.

[圖2]圖1(霧化合金粉末之剖面模式圖)中，以圓所包圍之粉末最表層部分A的擴大圖。 Fig. 2 is an enlarged view of the outermost layer portion A of the powder surrounded by a circle in Fig. 1 (a cross-sectional schematic view of the atomized alloy powder).

[實施發明之形態] [Formation of the Invention]

本發明之粉末為導電性接著劑所使用之AgCu系導電填料粉末。此AgCu系導電填料粉末係Ag含有率為1~30質量%之Cu-Ag合金所成之霧化合金粉末。此霧化合金粉末為保持在被霧化(as atomized)之狀態，且在霧化粉末最表層上具有相對於Cu之Ag的質量比X=(MAg/MCu)為1.2以上之AgCu相。於此，粉末最表層為從霧化合金粉末之粉末最表面至內部20nm為止之層。 The powder of the present invention is an AgCu-based conductive filler powder used for a conductive adhesive. The AgCu-based conductive filler powder is an atomized alloy powder of a Cu-Ag alloy having an Ag content of 1 to 30% by mass. The atomized alloy powder is in an atomized state, and has an AgCu phase having a mass ratio of X=(M Ag /M Cu ) of 1.2 or more with respect to Ag on the outermost layer of the atomized powder. . Here, the outermost layer of the powder is a layer from the outermost surface of the powder of the atomized alloy powder to the inner side of 20 nm.

本發明之導電填料粉末中，採用Ag之理由如以下所述。亦即，導電填料粉末之導電度是以電子的移動量來決定。並要求電子會大量移動，且為不存在阻礙移動者之狀態。於此，雖然在導電填料材料使用純Au、純Ag或純Cu即可，但純Au與純Ag在成本方面、以及純Cu容易被氧化方面有問題。於此，進行能夠有更多電子移動之合金的研究後，得知此等合金中亦使Ag存在於Cu系合金表面上之合金較有希望。於此，如以上所述而採用 Ag。 Among the conductive filler powders of the present invention, the reason for using Ag is as follows. That is, the conductivity of the conductive filler powder is determined by the amount of movement of electrons. It also requires that the electrons move a lot, and there is no state that hinders the mover. Here, although pure Au, pure Ag, or pure Cu may be used as the conductive filler material, pure Au and pure Ag are problematic in terms of cost and the fact that pure Cu is easily oxidized. Here, after conducting an investigation of an alloy capable of more electron mobility, it has been found that alloys in which Ag is present on the surface of a Cu-based alloy are also promising. Here, as described above Ag.

且，本發明之特徵為：在粉末最表層使AgCu相存在，該AgCu相為將相對於Cu之Ag的質量比X控制在1.2以上。相對於Cu之Ag的質量比X之較佳範圍為1.2以上，更佳為1.5以上，再更佳為1.7以上。且，霧化合金粉末中，上述比X為1.2以上之AgCu相存在粉末最表層的10%以上較佳，更佳為20%以上，再更佳為30%以上。 Further, the present invention is characterized in that an AgCu phase is present in the outermost layer of the powder, and the AgCu phase is controlled to have a mass ratio X of 1.2 or more with respect to Cu. The preferred range of the mass ratio X with respect to Cu of Cu is 1.2 or more, more preferably 1.5 or more, still more preferably 1.7 or more. Further, in the atomized alloy powder, the AgCu phase having a ratio X of 1.2 or more is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of the outermost layer of the powder.

且，溶融金屬在被冷卻時，由於Cu較多且Ag較少之CuAg為高融點，故會先開始凝固，並以低融點之Ag較多且Cu較少之AgCu覆蓋於凝固後的CuAg周圍之形態來凝固。 Moreover, when the molten metal is cooled, CuAg is a high melting point due to the large amount of Cu, so the solidification starts first, and the AgCu with a low melting point and a small amount of Cu is covered with the AgCu. The shape around CuAg is solidified.

上述之Ag與Cu之共晶組織之外，藉由控制Ag的比率，可進一步預測AgCu系導電填料粉末之改善。若Ag含有率過少，則在粉末表層上難以出現Ag較多且Cu較少之AgCu相。且，若Ag含有率過多，雖然在粉末表層上容易出現含有較多Ag之AgCu相，但在成本方面有問題。因此，粉末全體之Ag含有率為1~30質量%，較佳為1~25質量%，再較佳為1~20質量%。 In addition to the above-described eutectic structure of Ag and Cu, the improvement of the AgCu-based conductive filler powder can be further predicted by controlling the ratio of Ag. If the Ag content is too small, it is difficult to form an AgCu phase having a large amount of Ag and a small amount of Cu on the surface layer of the powder. Further, when the Ag content is too large, an AgCu phase containing a large amount of Ag tends to occur on the surface layer of the powder, but there is a problem in terms of cost. Therefore, the Ag content of the entire powder is 1 to 30% by mass, preferably 1 to 25% by mass, and more preferably 1 to 20% by mass.

針對Ag與Cu之共晶組織的控制，除了上述所規定之成分控制之外，能夠藉由原料金屬溶解後之凝固時的冷卻速度之控制。作為製造方法，有氣體霧化法、圓盤霧化法、水霧化法等，但不限於此。 The control of the eutectic structure of Ag and Cu can be controlled by the cooling rate at the time of solidification after the raw material metal is dissolved, in addition to the above-described composition control. Examples of the production method include a gas atomization method, a disk atomization method, and a water atomization method, but are not limited thereto.

氣體霧化法藉由在溶融金屬出鋼時，調整噴 霧氣體之壓力，能夠使溶融金屬之凝固速度產生變化。例如，藉由降低噴霧氣體之壓力或策劃其他製造條件之最適化，溶融金屬之凝固冷卻速度會變慢，且在AgCu粉末之表層上容易偏向析出Ag較多且Cu較少之AgCu相。 Gas atomization method by adjusting the spray when molten metal is tapped The pressure of the mist gas can change the solidification rate of the molten metal. For example, by reducing the pressure of the spray gas or planning the optimization of other manufacturing conditions, the solidification cooling rate of the molten metal is slowed, and the AgCu phase having a large amount of Ag and a small amount of Cu tends to be precipitated on the surface layer of the AgCu powder.

圓盤霧化法由於在溶融金屬出鋼時沒有使用噴霧氣體，故相較於氣體霧化法，能將冷卻速度控制地較慢。藉此，搭配其他製造條件的最適化，在AgCu粉末之表層上容易偏向析出Ag較多且Cu較少之AgCu相。 Since the disk atomization method does not use a spray gas when the molten metal is tapped, the cooling rate can be controlled to be slower than the gas atomization method. Thereby, in accordance with the optimization of other production conditions, it is easy to precipitate an AgCu phase having a large amount of Ag and a small amount of Cu on the surface layer of the AgCu powder.

藉由使用控制Ag之比率所製作出的AgCu系導電填料粉末，能夠得到一種保持在霧化所得之狀態的合金粉末，不需要Ag塗布，且顯示不遜色於純Ag之優異導電度之粉末。 By using the AgCu-based conductive filler powder produced by controlling the ratio of Ag, it is possible to obtain an alloy powder which is maintained in an atomized state, which does not require Ag coating and which exhibits an excellent conductivity which is inferior to that of pure Ag.

除了Cu與Ag之外，亦可添加顯示低融點之金屬或與Cu、Ag液相分離之Zn、In、Ga、Sn、Bi、Pb等。 In addition to Cu and Ag, a metal exhibiting a low melting point or Zn, In, Ga, Sn, Bi, Pb, or the like separated from a liquid phase of Cu or Ag may be added.

[實施例] [Examples]

以下，針對本發明，以實施例具體說明。 Hereinafter, the present invention will be specifically described by way of examples.

將表1所示之組成的AgCu系導電填料粉末以氣體霧化法或圓盤霧化法來製作。 The AgCu-based conductive filler powder having the composition shown in Table 1 was produced by a gas atomization method or a disk atomization method.

關於氣體霧化法，將特定組成之原料置入在底部設置有細孔的石英坩堝內，並在Ar氣體環境中以高頻感應溶解爐加熱溶融後，在Ar氣體環境中，以氣體噴射使其出鋼，並藉由急冷凝固，得到氣體霧化微粉末。 Regarding the gas atomization method, a raw material of a specific composition is placed in a quartz crucible provided with pores at the bottom, and is heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then gas-jetted in an Ar gas atmosphere. The steel is tapped and solidified by quenching to obtain a gas atomized fine powder.

藉由調整氣體噴射壓，能夠使急冷凝固之速度產生變化。若降低氣體噴射壓，則氣體所造成之溶融金屬的冷卻會變小，故急冷凝固之速度會變慢。相對於此，若提高氣體噴射壓，則氣體所造成之溶融金屬的冷卻會變大，故急冷凝固之速度會變快。 By adjusting the gas injection pressure, the speed of rapid solidification can be changed. If the gas injection pressure is lowered, the cooling of the molten metal by the gas becomes small, so the speed of rapid solidification becomes slow. On the other hand, when the gas injection pressure is increased, the cooling of the molten metal by the gas is increased, so that the speed of rapid solidification is increased.

關於圓盤霧化法，將特定組成之原料置入在底部設置有細孔的石英坩堝內，在Ar氣體環境中以高頻感應溶解爐加熱溶融後，在Ar氣體環境中，使其於40000~60000r.p.m.之旋轉盤上出鋼，並藉由使其急冷凝固，得到圓盤霧化微粉末。 Regarding the disk atomization method, a material having a specific composition is placed in a quartz crucible provided with pores at the bottom, heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then subjected to an Ar gas atmosphere at 40,000. The steel disk of ~60000r.pm is tapped and solidified by quenching to obtain a disk atomized fine powder.

為了評估以氣體霧化法、圓盤霧化法等所製作的霧化合金粉末，使用TOYO Corporation製之粉體阻抗測定用4末端試樣夾，測定霧化合金粉末之導電度。 In order to evaluate the atomized alloy powder produced by a gas atomization method, a disk atomization method, or the like, the conductivity of the atomized alloy powder was measured using a 4-terminal sample holder for powder impedance measurement by TOYO Corporation.

導電度測定所使用之霧化合金粉末使用篩子統一成45μm以下的粒度之後，填充於直徑25mm、高度10mm之圓柱狀的試樣夾後，從高度方向的上下給予4牛頓米之荷重。 The atomized alloy powder used for the measurement of the conductivity was uniformly formed into a particle size of 45 μm or less using a sieve, and then filled in a cylindrical sample holder having a diameter of 25 mm and a height of 10 mm, and then a load of 4 Newton meters was applied from the upper and lower sides in the height direction.

導電度測定為使用下述之四末端法，其係在荷重方向上裝上電流I之正型末端與電壓V之正型末端，並在荷重方向下裝上電流I之負型末端與電壓V之負型末端，通電流之後測定電壓。 The conductivity is measured by using the four-terminal method described below, in which the positive terminal of the current I and the positive terminal of the voltage V are mounted in the direction of the load, and the negative terminal of the current I and the voltage V are mounted in the direction of the load. At the negative end, the voltage is measured after the current is passed.

表1表示本發明中之實施例1~12，表2表示比較例1~24。此等之特性根據以下基準來各別評估：- 評估A：相對於填料材之Ag為1質量%以上且30質量%以下，比X為1.2以上，且表示與Ag相同程度之導電度4000AV-1m-1以上者、- 評估B：相對於填料材之Ag為1質量%以上且30質量%以下，比X為1.2以上，且導電度為3000AV-1m-1以上且未滿4000AV-1m-1者、 - 評估C：相對於填料材之Ag為1質量%以上且30質量%以下，比X為1.2以上，且導電度未滿3000AV-1m-1者、以及- 評估D：相對於填料材之Ag未滿1質量%或超過30質量%，或比X未滿1.2者。 Table 1 shows Examples 1 to 12 in the present invention, and Table 2 shows Comparative Examples 1 to 24. These characteristics are evaluated separately according to the following criteria: - Evaluation A: Ag is 1% by mass or more and 30% by mass or less with respect to the filler material, and the ratio X is 1.2 or more, and represents the same degree of conductivity as the Ag of 4000AV - 1 m -1 or more, - Evaluation B: Ag is 1% by mass or more and 30% by mass or less with respect to the filler material, the ratio X is 1.2 or more, and the conductivity is 3,000 AV -1 m -1 or more and less than 4000 AV - 1 m -1 , - Evaluation C: Ag is 1% by mass or more and 30% by mass or less with respect to the filler material, the ratio X is 1.2 or more, and the conductivity is less than 3000 AV -1 m -1 , and - Evaluation D : less than 1% by mass or more than 30% by mass with respect to Ag of the filler material, or less than 1.2 for X.

且，表1以及表2中，將導電度單純地記載為傳導度。且，表2中，比X中的底線表示比X之值未滿1.2，且，填料材之組織中的Ag之值的底線表示未滿1質量%或超過30質量%。 Further, in Tables 1 and 2, the conductivity is simply referred to as conductivity. Further, in Table 2, the bottom line in the ratio X indicates that the value of X is less than 1.2, and the bottom line of the value of Ag in the structure of the filler material indicates less than 1% by mass or more than 30% by mass.

亦即，最優良之評估為評估A，並依評估B、評估C、評估D之順序，評估而降低。 That is, the best evaluation is evaluation A, and is evaluated according to the evaluation B, the evaluation C, and the evaluation D.

例如，實施例12滿足下列條件：相對於填料材之Ag為30質量%，比X為1.2以上，存在率Y為10%以上。滿足如此本發明之條件，且導電度為4140AV-1m-1，會顯示最優良之特性。 For example, Example 12 satisfies the following conditions: 30% by mass of Ag with respect to the filler, a ratio of X of 1.2 or more, and an existence ratio of 10% or more. Satisfying the conditions of the present invention and having a conductivity of 4140 AV -1 m -1 shows the most excellent characteristics.

比較例1~24由於Ag含有率未滿1質量%，或較30質量%大，且由於比X未滿1.2，不滿足本條件。 In Comparative Examples 1 to 24, the Ag content was less than 1% by mass or more than 30% by mass, and since the ratio X was less than 1.2, the above conditions were not satisfied.

例如，比較例4中，雖然滿足Ag含有率為20%，且存在率Y為14%，但並不滿足比X為1.2以上，且導電度為2210AV-1m-1，無法顯示優良特性。 For example, in Comparative Example 4, although the Ag content was 20% and the existence ratio Y was 14%, the ratio X was not more than 1.2 and the conductivity was 2210 AV -1 m -1 , and excellent characteristics could not be exhibited.

比較例20中，比X為2.2，存在率Y為22%，導電度為4070AV-1m-1，雖然會顯示優良特性，但由於相對於填料材之Ag為90質量%，並不滿足Ag之含有率為1~30質量%之條件。 In Comparative Example 20, the ratio X was 2.2, the existence ratio Y was 22%, and the conductivity was 4070 AV -1 m -1 . Although excellent characteristics were exhibited, the Ag was 90% by mass with respect to the filler material, and Ag was not satisfied. The content is 1 to 30% by mass.

存在率Y為：將相對於Cu之Ag的質量比X為1.2以上之AgCu相在粉末1粒子之最表層(從表面至內部20nm)中的存在率，由計算任意之處20點之TEM像的分析結果來算出。 The existence ratio Y is: the existence ratio of the AgCu phase having a mass ratio X of 1.2 or more with respect to Cu to the outermost layer of the powder 1 particle (20 nm from the surface to the inside), and the TEM image of 20 points at any place is calculated. The analysis results are calculated.

如以上所述，本發明中，藉由如圖2所示，將相對於Cu之Ag的質量比X為1.2以上之AgCu相3控制在存在於如圖1所示之霧化合金粉末1的粉末最表層2中，能夠提供一種具有不遜色於純Ag之導電度，且為保持在被霧化狀態之合金粉末，並不需要Ag塗布之AgCu系導電填料粉末。 As described above, in the present invention, as shown in FIG. 2, the AgCu phase 3 having a mass ratio X of respect to Cu of 1.2 or more is controlled to be present in the atomized alloy powder 1 as shown in FIG. In the outermost layer 2 of the powder, it is possible to provide an AgCu-based conductive filler powder having an electrical conductivity which is not inferior to that of pure Ag and which is maintained in an atomized state, and which does not require Ag coating.

2‧‧‧粉末最表層 2‧‧‧The top layer of powder

3‧‧‧AgCu相 3‧‧‧AgCu phase

A‧‧‧表層部分 A‧‧‧ surface part

Claims (8)

一種AgCu系導電填料粉末，其係導電性接著劑所使用之AgCu系導電填料粉末，前述AgCu系導電填料粉末係Ag含有率為1~30質量%之Cu-Ag合金所成之霧化合金粉末，前述霧化合金粉末為保持被霧化之狀態，且在霧化粉末最表層具有相對於Cu之Ag的質量比X=(MAg/MCu)為1.2以上之AgCu相，該粉末最表層為從前述霧化合金粉末的粉末最表面至內部20nm為止之層。 An AgCu-based conductive filler powder, which is an AgCu-based conductive filler powder used for a conductive adhesive, and the AgCu-based conductive filler powder is an atomized alloy powder of a Cu-Ag alloy having an Ag content of 1 to 30% by mass. The atomized alloy powder is in an atomized state, and has an AgCu phase having a mass ratio of X=(M Ag /M Cu ) of 1.2 or more in the outermost layer of the atomized powder to the Ag of Cu , and the outermost layer of the powder It is a layer from the outermost surface of the powder of the aforementioned atomized alloy powder to the inside of 20 nm. 如請求項1之AgCu系導電填料粉末，其中，前述霧化合金粉末中，前述比X為1.2以上之AgCu相存在前述粉末最表層的10%以上。 The AgCu-based conductive filler powder according to claim 1, wherein in the atomized alloy powder, the AgCu phase having a ratio X of 1.2 or more is present in 10% or more of the outermost layer of the powder. 如請求項1之AgCu系導電填料粉末，其中，前述Cu-Ag合金之Ag含有率為1~25質量%。 The AgCu-based conductive filler powder according to claim 1, wherein the Cu-Ag alloy has an Ag content of 1 to 25% by mass. 如請求項1之AgCu系導電填料粉末，其中，前述Cu-Ag合金之Ag含有率為1~20質量%。 The AgCu-based conductive filler powder according to claim 1, wherein the Cu-Ag alloy has an Ag content of 1 to 20% by mass. 如請求項1之AgCu系導電填料粉末，其中，前述質量比X為1.5以上。 The AgCu-based conductive filler powder according to claim 1, wherein the mass ratio X is 1.5 or more. 如請求項1之AgCu系導電填料粉末，其中，前述質量比X為1.7以上。 The AgCu-based conductive filler powder according to claim 1, wherein the mass ratio X is 1.7 or more. 如請求項1之AgCu系導電填料粉末，其中，前述質量比X為1.2以上之AgCu相存在前述粉末最表層的20%以上。 The AgCu-based conductive filler powder according to claim 1, wherein the AgCu phase having a mass ratio X of 1.2 or more is present in 20% or more of the outermost layer of the powder. 如請求項1之AgCu系導電填料粉末，其中，前 述質量比X為1.2以上之AgCu相存在前述粉末最表層的30%以上。 The AgCu-based conductive filler powder of claim 1, wherein The AgCu phase having a mass ratio X of 1.2 or more is present in 30% or more of the outermost layer of the powder.
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