TW202412017A - Conductive paste, electrode, electronic component, and electronic instrument - Google Patents
Conductive paste, electrode, electronic component, and electronic instrument Download PDFInfo
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- TW202412017A TW202412017A TW112124932A TW112124932A TW202412017A TW 202412017 A TW202412017 A TW 202412017A TW 112124932 A TW112124932 A TW 112124932A TW 112124932 A TW112124932 A TW 112124932A TW 202412017 A TW202412017 A TW 202412017A
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- conductive paste
- electrode
- conductive
- particles
- metal particles
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Abstract
Description
本發明係有關一種導電膏，其係可使用於例如電子零件之電極的形成者。又，本發明係有關一種使用該導電膏所形成之電極、及具有該電極之晶片電阻器(chip resistor)等電子零件。 The present invention relates to a conductive paste that can be used, for example, to form an electrode of an electronic component. Furthermore, the present invention relates to an electrode formed using the conductive paste, and an electronic component such as a chip resistor having the electrode.
屬於電子零件之一的晶片電阻器，其電極之形成係可使用包含銀粉(銀粒子)之導電膏。在圖1中，表示晶片電阻器100之剖面構造的一例。晶片電阻器100係具有矩形之氧化鋁基板102，且在氧化鋁基板102之上面形成電阻體104、用以從電阻體104汲取電力之取出電極106。又，在氧化鋁基板102之下面係形成用以將晶片電阻器100裝設至基板之下面電極108。再者，在氧化鋁基板102之端面係形成用以連接取出電極106與下面電極108之連接電極110。取出電極106及下面電極108係藉由氧化鋁基板102之上面及下面以印刷塗佈導電膏之後進行燒製而分別形成。在取出電極106、下面電極108、及連接電極110之上，一般係形成鎳鍍覆膜112及錫鍍覆膜114。 A chip resistor, which is one of the electronic components, can use a conductive paste containing silver powder (silver particles) to form its electrodes. FIG1 shows an example of a cross-sectional structure of a chip resistor 100. The chip resistor 100 has a rectangular alumina substrate 102, and a resistor 104 and an extraction electrode 106 for extracting power from the resistor 104 are formed on the upper surface of the alumina substrate 102. In addition, a lower electrode 108 for mounting the chip resistor 100 on the substrate is formed on the lower surface of the alumina substrate 102. Furthermore, a connecting electrode 110 for connecting the extraction electrode 106 and the lower electrode 108 is formed on the end surface of the alumina substrate 102. The extraction electrode 106 and the lower electrode 108 are formed by printing and coating the conductive paste on the upper and lower surfaces of the alumina substrate 102 and then firing them. A nickel-plated film 112 and a tin-plated film 114 are generally formed on the extraction electrode 106, the lower electrode 108, and the connecting electrode 110.
作為被使用於電極之形成的導電膏，在專利文獻1已揭示一種晶片電阻器上面電極用膏，其係將導電性粉末、玻璃料(glass frit)、無機黏合劑分散於有機載體(vehicle)中而成者。 As a conductive paste used for forming electrodes, Patent Document 1 discloses a paste for electrodes on chip resistors, which is prepared by dispersing conductive powder, glass frit, and inorganic adhesive in an organic carrier (vehicle).
又，在專利文獻2已揭示一種導電膏，其係含有：(A)包含Ag及Sn之表面處理金屬粒子、(C)玻璃料、及(B)黏結劑樹脂(binder resin)，其中，(A)在導電性粒子中之Sn的重量比例為未達10重量%。 Furthermore, Patent Document 2 discloses a conductive paste comprising: (A) surface-treated metal particles containing Ag and Sn, (C) glass frit, and (B) binder resin, wherein the weight ratio of Sn in the conductive particles (A) is less than 10 weight %.
近年來，隨著電子器材或電子零件的高效能化等，係進一步針對電極或配線等要求低電阻化。作為降低比電阻的方法之一，係將導電性粒子進行高填充。例如，在專利文獻3揭示一種導電膏，其係以85重量份以上之較高的比例調配銀粉末而成者。另一方面，成為電極或配線等之導體圖案係隨著電子器材或電子零件之高效能化等而有高精密化/複雜化之傾向。因此，對導電膏要求：用以固定至基盤之接著性、和能夠可形成微細的圖案之優異的印刷特性(例如，在塗佈時用以形成平滑的塗膜之調平性、為了於塗佈後再進行鍍覆處理等之塗膜的平滑性)等。在專利文獻3中，係揭示相對於銀粉末與黏結劑樹脂之合計100重量份，若銀粉末超過95重量份，對印刷性或接著性會造成影響。 In recent years, with the improvement of the efficiency of electronic equipment and electronic parts, the requirements for lower resistance of electrodes and wirings have been further increased. One method of reducing the specific resistance is to fill conductive particles with a high content. For example, Patent Document 3 discloses a conductive paste that is prepared by mixing silver powder at a high ratio of more than 85 parts by weight. On the other hand, the conductive patterns that become electrodes and wirings tend to be more precise and complex as electronic equipment and electronic parts become more efficient. Therefore, the conductive paste is required to have the following characteristics: adhesion to the substrate, and excellent printing properties that can form fine patterns (for example, leveling to form a smooth coating during coating, and smoothness of the coating for coating treatment after coating). Patent document 3 discloses that if the silver powder exceeds 95 parts by weight relative to a total of 100 parts by weight of the silver powder and the binder resin, the printing or adhesion will be affected.
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開平7-335402號公報 [Patent Document 1] Japanese Patent Publication No. 7-335402
[專利文獻2]國際公開第2021/145269號 [Patent Document 2] International Publication No. 2021/145269
[專利文獻3]日本特開2005-294254號公報 [Patent Document 3] Japanese Patent Publication No. 2005-294254
導電膏之低電阻化及高的印刷性、接著性皆為伴隨電子器材之進步所要求的特性，但也有成為需加以權衡的關係之情形，而存在對於任一性能皆優異的導電膏之需求。又，對於高精密化的電子器材，除了要求低電阻、高印刷性、高接著性之外，還存在其他特性上的要求。 The low resistance, high printability and high adhesion of conductive paste are all required characteristics accompanying the advancement of electronic devices, but there are also situations where a trade-off is required, and there is a demand for conductive paste with excellent performance in any one of them. In addition, for high-precision electronic devices, in addition to low resistance, high printability and high adhesion, there are also requirements for other characteristics.
在汽油車及火力發電所等之中，係燃燒化石燃料而大量地排出硫氧化物至大氣中。又，在污水處理場及垃圾處理場等之中，硫也會被厭氧性細菌(anaerobic bacteria)還原而產生硫化氫。因此，在大氣中存在著硫氧化物及硫化氫等含硫之成分。 In gasoline vehicles and thermal power plants, fossil fuels are burned and a large amount of sulfur oxides are discharged into the atmosphere. Also, in sewage treatment plants and garbage disposal sites, sulfur is reduced by anaerobic bacteria to produce hydrogen sulfide. Therefore, sulfur-containing components such as sulfur oxides and hydrogen sulfide exist in the atmosphere.
若大氣中之含硫的成分到達銀等金屬之表面，硫成分會附著於銀等金屬之表面，並與銀等金屬進行反應而成為硫化銀等金屬硫化物。由於即使例如在晶片電阻器之電極等以銀為主材料之電極中，亦會產生同樣的反應，故會有電極內部的銀等金屬變成硫化銀等金屬硫化物之情形。若在電極內部產生硫化銀等金屬硫化物，則有在電極產生斷線之情形。因此，就具有以銀等金屬為材料之電極的晶片電阻器等元件而言，係有發生運作不良之情形。如此之現象被稱為硫化所致的斷線。硫化所致的斷線除了發生在銀以外，在銅、銦及鋁、以及包含此等中之至少一者的合金之電極亦有可能發生。 If the sulfur-containing components in the atmosphere reach the surface of metals such as silver, the sulfur components will adhere to the surface of metals such as silver and react with the metals such as silver to form metal sulfides such as silver sulfide. Since the same reaction occurs even in electrodes made of silver as the main material, for example, such as electrodes of chip resistors, there are cases where the silver and other metals inside the electrode become metal sulfides such as silver sulfide. If metal sulfides such as silver sulfide are generated inside the electrode, there is a possibility that the electrode will be broken. Therefore, for components such as chip resistors with electrodes made of silver and other metals, there is a possibility of malfunction. Such a phenomenon is called a broken wire due to sulfidation. In addition to silver, wire breakage due to sulfidation may also occur in electrodes of copper, indium, aluminum, and alloys containing at least one of these.
由於若將金屬粒子高填充化，引起硫化反應之程度亦會隨之提高，故要求即使將導電膏低電阻化也可以抑制硫化所致的斷線。為了抑 制硫化所致的斷線，在晶片電阻器等之元件所使用的以銀等金屬為主材料之電極必須為抗硫化性高的電極。 Since the degree of sulfidation reaction will increase if the metal particles are highly filled, it is required to suppress the disconnection caused by sulfidation even if the conductive paste has low resistance. In order to suppress the disconnection caused by sulfidation, the electrode mainly made of silver or other metals used in components such as chip resistors must have high sulfidation resistance.
已有提案係添加預定量(例如，約20重量%)之鈀單體、或者鈀來作為用以形成抗硫化性高的電極之導電膏的導電性粒子。然而，因為鈀之價格高昂，故會由於添加鈀單體或鈀而有「導電膏之成本上昇，電極之成本變高」之問題。 There has been a proposal to add a predetermined amount (e.g., about 20% by weight) of palladium monomer or palladium as conductive particles for forming a conductive paste for an electrode with high anti-sulfurization properties. However, since palladium is expensive, the addition of palladium monomer or palladium will cause the cost of the conductive paste to increase, and the cost of the electrode to increase.
因此，本發明之目的在於提供一種導電膏，其係具有高的抗硫化性，且即使更增加導電性粒子之含量，亦可實現優異的印刷特性者。 Therefore, the purpose of the present invention is to provide a conductive paste which has high anti-sulfurization properties and can achieve excellent printing properties even if the content of conductive particles is increased.
為了解決上述課題，本發明係具有以下之構成。 In order to solve the above problems, the present invention has the following structure.
(構成1) (Constitution 1)
構成1為一種導電膏，其係包含： Composition 1 is a conductive paste, which includes:
(A)導電性粒子、及 (A) Conductive particles, and
(B)黏結劑樹脂；其中， (B) Adhesive resin; wherein,
前述(A)導電性粒子具有金屬粒子、及配置於金屬粒子之表面的至少一部分之包含鈀化合物的表面處理層； The aforementioned (A) conductive particles have metal particles and a surface treatment layer containing a palladium compound disposed on at least a portion of the surface of the metal particles;
相對於導電膏100重量份，係以80重量份以上之量含有前述(A)導電性粒子。 The conductive particles (A) mentioned above are contained in an amount of 80 parts by weight or more relative to 100 parts by weight of the conductive paste.
(構成2) (Constitution 2)
構成2係如構成1所述之導電膏，其中，以HB型黏度計在25℃ 10rpm之條件下測定出的黏度為50至700Pa‧s之範圍。 Composition 2 is a conductive paste as described in Composition 1, wherein the viscosity measured by an HB type viscometer at 25°C and 10rpm is in the range of 50 to 700 Pa‧s.
(構成3) (Constitution 3)
構成3係如構成1或2所述之導電膏，其中，以HB型黏度計在25℃之條件下測定出的轉速1rpm之黏度與轉速10rpm之黏度的比之搖變指數值(TI)為2.5以下。 Composition 3 is a conductive paste as described in Composition 1 or 2, wherein the slew index value (TI) of the ratio of the viscosity at a rotation speed of 1 rpm to the viscosity at a rotation speed of 10 rpm measured at 25°C by an HB type viscometer is less than 2.5.
(構成4) (Constitution 4)
構成4係如構成1至3中任一項所述之導電膏，其中，前述(A)導電性粒子之平均粒徑(D50)為0.1至10μm。 Configuration 4 is a conductive paste as described in any one of Configurations 1 to 3, wherein the average particle size (D50) of the conductive particles (A) is 0.1 to 10 μm.
(構成5) (Constitution 5)
構成5係如構成1至4中任一項所述之導電膏，其中，前述金屬粒子包含50重量%以上之銀。 Configuration 5 is a conductive paste as described in any one of Configurations 1 to 4, wherein the metal particles contain more than 50% by weight of silver.
(構成6) (Constitution 6)
構成6係如構成1至5中任一項所述之導電膏，其中，相對於前述導電性粒子100重量份，在前述表面處理層所包含的鈀化合物之含量為0.01至1.0重量份。 Composition 6 is a conductive paste as described in any one of Compositions 1 to 5, wherein the content of the palladium compound contained in the surface treatment layer is 0.01 to 1.0 parts by weight relative to 100 parts by weight of the conductive particles.
(構成7) (Constitution 7)
構成7係如構成6所述之導電膏，其中，相對於前述導電性粒子100重量份，在前述表面處理層所包含的鈀化合物之含量為0.2至0.4重量份。 Composition 7 is a conductive paste as described in Composition 6, wherein the content of the palladium compound contained in the surface treatment layer is 0.2 to 0.4 parts by weight relative to 100 parts by weight of the conductive particles.
(構成8) (Constitution 8)
構成8係如構成1至7中任一項所述之導電膏，其中，前述表面處理層更包含有機物。 Configuration 8 is a conductive paste as described in any one of Configurations 1 to 7, wherein the surface treatment layer further comprises an organic substance.
(構成9) (Construction 9)
構成9係一種電極，其係將構成1至8中任一項所述之導電膏進行燒製或熱處理而得到者。 Composition 9 is an electrode obtained by sintering or heat treating the conductive paste described in any one of Compositions 1 to 8.
(構成10) (Constitute 10)
構成10係如構成9所述之電極，其中，將電極表面依據JIS B 0601(1994)測定出的算術平均粗度(Ra)為0.5μm以下。 Configuration 10 is an electrode as described in Configuration 9, wherein the arithmetic mean roughness (Ra) of the electrode surface measured in accordance with JIS B 0601 (1994) is less than 0.5 μm.
(構成11) (Constitution 11)
構成11係一種電子零件或電子器材，其係包含構成9或10所述之電極。 Component 11 is an electronic component or electronic device, which includes the electrode described in component 9 or 10.
依據本發明，可提供一種導電膏，其係具有高的抗硫化性，且即使更增加導電性粒子之含量，亦可實現優異的印刷特性。 According to the present invention, a conductive paste can be provided, which has high anti-sulfurization properties and can achieve excellent printing properties even if the content of conductive particles is increased.
50:抗硫化性試驗之試驗片 50: Test piece for anti-sulfurization test
52:抗硫化性試驗用氧化鋁基板 52: Alumina substrate for anti-sulfurization test
54:抗硫化性試驗用印刷圖案 54: Printed pattern for anti-sulfurization test
54a,54b:抗硫化性試驗用印刷圖案之端部 54a, 54b: End of the printed pattern for anti-sulfurization test
60:抗遷移試驗之試驗片 60: Test piece for anti-migration test
62:抗遷移試驗用氧化鋁基板 62: Alumina substrate for anti-migration test
64a,64b:抗遷移試驗用印刷圖案 64a, 64b: Printing pattern for anti-migration test
66a:第1電極 66a: 1st electrode
66b:第2電極 66b: Second electrode
100:晶片電阻器 100:Chip resistor
102:氧化鋁基板 102: Alumina substrate
104:電阻體 104: Resistor
106:取出電極 106: Remove the electrode
108:下面電極 108: Lower electrode
110:連接電極 110: Connect the electrodes
112:鎳鍍覆膜 112: Nickel plating coating
114:錫鍍覆膜 114: Tin coating
L:印刷寬度 L: Printing width
S:間隙 S: Gap
圖1係表示晶片電阻器之剖面構造的一例之示意圖。 Figure 1 is a schematic diagram showing an example of the cross-sectional structure of a chip resistor.
圖2係表示實施例及比較例之抗硫化性試驗用之試驗片的形狀之示意圖。 Figure 2 is a schematic diagram showing the shape of the test piece used for the anti-sulfurization test of the embodiment and the comparative example.
圖3係表示實施例及比較例之抗遷移(anti-migration)試驗用之試驗片的試驗用印刷圖案之形狀的光學顯微鏡照片。 FIG3 is an optical microscope photograph showing the shape of the test printed pattern of the test piece used for the anti-migration test of the embodiment and the comparative example.
圖4係將圖3所示的抗遷移試驗用之試驗片的試驗用印刷圖案之光學顯微鏡照片之中央附近放大後的光學顯微鏡照片。 FIG4 is an optical microscope photograph of the center of the test printed pattern of the test piece for the anti-migration test shown in FIG3 after enlargement.
圖5係將以與實施例3相同的條件所製作之試驗片在含硫的氣體環境中保管150小時而使其硫化之後的導電膏的燒製體表面之掃描型電子顯微鏡(SEM)照片(倍率5000倍)。 Figure 5 is a scanning electron microscope (SEM) photograph (magnification 5000 times) of the surface of the sintered conductive paste after the test piece made under the same conditions as Example 3 was stored in a sulfur-containing gas environment for 150 hours to be vulcanized.
圖6係將以與比較例1相同的條件所製作之試驗片在含硫的氣體環境中保管150小時而使其硫化之後的導電膏的燒製體表面之掃描型電子顯微鏡(SEM)照片(倍率5000倍)。 Figure 6 is a scanning electron microscope (SEM) photograph (magnification 5000 times) of the surface of the sintered conductive paste after the test piece made under the same conditions as Comparative Example 1 was stored in a sulfur-containing gas environment for 150 hours to be vulcanized.
圖7係表示進行抗遷移試驗時之實施例1、實施例3及比較例1之絕緣電阻值的經時變化之圖。 FIG7 is a graph showing the time-dependent changes in the insulation resistance values of Example 1, Example 3, and Comparative Example 1 during the anti-migration test.
圖8係使用實施例22之導電膏的薄膜之立體顯微鏡的照片。 Figure 8 is a stereomicroscope photograph of a thin film using the conductive paste of Example 22.
圖9係使用比較例6之導電膏的薄膜之立體顯微鏡的照片。 Figure 9 is a stereomicroscope photograph of a film using the conductive paste of Comparative Example 6.
以下，具體說明本發明之實施型態。又，下列之實施型態係將本發明具體化之際的形態，並非將本發明限定於該範圍內者。 The following is a detailed description of the implementation of the present invention. In addition, the following implementation is a form of the present invention at the time of embodiment, and does not limit the present invention to the scope.
本實施型態之導電膏係包含(A)導電性粒子、及(B)黏結劑樹脂。本實施型態之導電膏較佳係可使用於用以形成晶片電阻器等電子零件的電極。(A)導電性粒子係具有金屬粒子、及包含鈀化合物的表面處理層，該表面處理層係配置於金屬粒子之表面之至少一部分；相對於導電膏100重量份，係以80重量份以上之量含有(A)導電性粒子。 The conductive paste of this embodiment includes (A) conductive particles and (B) binder resin. The conductive paste of this embodiment is preferably used to form electrodes for electronic components such as chip resistors. The (A) conductive particles have metal particles and a surface treatment layer containing a palladium compound, and the surface treatment layer is disposed on at least a portion of the surface of the metal particles; relative to 100 parts by weight of the conductive paste, the conductive particles (A) are contained in an amount of 80 parts by weight or more.
首先，說明本實施型態之導電膏所含有的成分。 First, the ingredients contained in the conductive paste of this embodiment are described.
<(A)導電性粒子> <(A) Conductive particles>
本實施型態之導電膏係包含(A)導電性粒子。(A)導電性粒子係包含金屬粒子、及配置於金屬粒子之表面的至少一部分之表面處理層。表面處理層為包含鈀化合物之薄膜。表面處理層係藉由將金屬粒子以前述鈀化合物進行表面處理而形成。藉由(A)導電性粒子包含具有預定之表面處理層的表 面處理金屬粒子，可抑制在導電性粒子所包含的金屬之硫化。因此，藉由使用本實施型態之導電膏，可形成具有高的抗硫化性之電極。 The conductive paste of this embodiment includes (A) conductive particles. (A) The conductive particles include metal particles and a surface treatment layer disposed on at least a portion of the surface of the metal particles. The surface treatment layer is a thin film including a palladium compound. The surface treatment layer is formed by surface treating the metal particles with the aforementioned palladium compound. By having (A) the conductive particles include surface treated metal particles having a predetermined surface treatment layer, the sulfidation of the metal contained in the conductive particles can be suppressed. Therefore, by using the conductive paste of this embodiment, an electrode having high anti-sulfidation properties can be formed.
又，本發明之發明人等發現，本實施型態之導電膏的(A)導電性粒子藉由包含預定之表面處理層而附帶的效果為所得到的電極之抗遷移性亦提昇。所謂抗遷移性，係意指可抑制遷移之性質。所謂遷移，係在對於一對之電極(正電極及負電極)施加電壓時，若在電極附近存在水及/或水蒸氣，則電極及配線部所包含的金屬會離子化，從正電極朝負電極進行移動並產生金屬之樹枝狀晶體(dendrite)，且配線部間之絕緣性降低。又，即使於如100℃以上或於真空中等般在無水分所造成的影響之環境下，亦有產生遷移之情形。此時，即使一對電極處於接近短路之狀態，在配線部間也沒有在水分存在下產生遷移時必定會看到之樹枝狀晶體的產生，而且也看不到極性(亦即，無論正電極與負電極之極性為何，都會產生)。所謂抗遷移性係意指可抑制如此之從以往便廣為人知的遷移之性質。由於金屬之遷移，一對之電極有可能會短路。藉由提升抗遷移性，可抑制電極之短路。又，發現：本實施型態之導電膏不僅是在為以較高溫(例如，500至900℃)進行燒製之類型的導電膏之情形下所得到的電極之抗遷移性提升，為藉由以較低溫(例如，100至200℃)之熱處理來熱硬化的熱硬化型導電膏之情形下，所得到的電極之抗遷移性亦會提升。惟，咸認所謂抗遷移性提升的優點並未必為本實施型態之導電膏所必須的效果，而為一個優點。 Furthermore, the inventors of the present invention have discovered that the conductive particles (A) of the conductive paste of the present embodiment, by including a predetermined surface treatment layer, have the effect that the anti-migration property of the obtained electrode is also improved. The so-called anti-migration property refers to the property of being able to suppress migration. The so-called migration means that when a voltage is applied to a pair of electrodes (positive electrode and negative electrode), if there is water and/or water vapor near the electrodes, the metal contained in the electrode and the wiring part will be ionized, move from the positive electrode to the negative electrode and generate metal dendrites, and the insulation between the wiring parts will be reduced. Furthermore, even in an environment without the influence of moisture, such as above 100°C or in a vacuum, migration can occur. At this time, even if a pair of electrodes is in a state close to short-circuiting, there is no dendrite formation between the wiring parts, which is bound to be seen when migration occurs in the presence of moisture, and no polarity is seen (that is, it occurs regardless of the polarity of the positive electrode and the negative electrode). The so-called anti-migration property means the property of suppressing such migration, which has been widely known since ancient times. Due to the migration of metal, a pair of electrodes may short-circuit. By improving the anti-migration property, the short circuit of the electrodes can be suppressed. Furthermore, it was found that the conductive paste of the present embodiment not only improves the anti-migration property of the electrode obtained in the case of a conductive paste fired at a relatively high temperature (e.g., 500 to 900°C), but also improves the anti-migration property of the electrode obtained in the case of a thermosetting conductive paste that is heat-cured by heat treatment at a relatively low temperature (e.g., 100 to 200°C). However, it is generally recognized that the so-called advantage of improved anti-migration property is not necessarily a necessary effect of the conductive paste of the present embodiment, but is an advantage.
(A)導電性粒子係可包含表面處理金屬粒子以外之金屬。惟，為了確實地獲得為低電阻且具有高的抗硫化性之電極，(A)導電性粒子較佳係包含50重量%以上之表面處理金屬粒子，更佳係包含80重量%以上之 表面處理金屬粒子，再更佳係包含90重量%以上之表面處理金屬粒子，特佳係僅由表面處理金屬粒子所構成。又，在本說明書中所謂之「(A)導電性粒子係僅由表面處理金屬粒子所構成」，係意指刻意地不調配表面處理金屬粒子以外之金屬來作為(A)導電性粒子，而非連含有無可避免地混入之表面處理金屬粒子以外之導電性粒子的情形都予以排除者。 (A) The conductive particles may contain metals other than surface-treated metal particles. However, in order to obtain an electrode with low resistance and high anti-sulfurization properties, (A) conductive particles preferably contain more than 50% by weight of surface-treated metal particles, more preferably more than 80% by weight of surface-treated metal particles, and even more preferably more than 90% by weight of surface-treated metal particles. It is particularly preferred that the conductive particles consist only of surface-treated metal particles. In addition, the phrase "(A) conductive particles consist only of surface-treated metal particles" in this specification means that metals other than surface-treated metal particles are deliberately not mixed as (A) conductive particles, and it does not exclude the case where conductive particles other than surface-treated metal particles that are inevitably mixed are included.
在無損本實施型態之效果的範圍，(A)導電性粒子係可包含Zn、In、Al及/或Si等材料之金屬粒子作為表面處理金屬粒子以外之金屬粒子。在表面處理金屬粒子所包含的金屬粒子及表面處理金屬粒子以外之金屬粒子係可為合金之金屬粒子。又，表面處理金屬粒子所包含的金屬粒子及表面處理金屬粒子以外之金屬粒子係可包含不同種類的複數種金屬或合金之金屬粒子。 In the scope of the effect of the implementation form without loss of cost, (A) conductive particles may include metal particles of materials such as Zn, In, Al and/or Si as metal particles other than the surface-treated metal particles. The metal particles included in the surface-treated metal particles and the metal particles other than the surface-treated metal particles may be alloy metal particles. In addition, the metal particles included in the surface-treated metal particles and the metal particles other than the surface-treated metal particles may include metal particles of multiple metals or alloys of different types.
表面處理金屬粒子係包含金屬粒子、及配置在金屬粒子之表面的至少一部分之表面處理層。表面處理層係形成於金屬粒子之表面之至少一部分的薄膜。藉由將金屬粒子以鈀化合物進行表面處理，可在金屬粒子之表面的至少一部分形成表面處理層。因此，表面處理金屬粒子係可為經鈀化合物進行表面處理後之金屬粒子。 The surface-treated metal particles include metal particles and a surface treatment layer disposed on at least a portion of the surface of the metal particles. The surface treatment layer is a thin film formed on at least a portion of the surface of the metal particles. By surface-treating the metal particles with a palladium compound, the surface treatment layer can be formed on at least a portion of the surface of the metal particles. Therefore, the surface-treated metal particles can be metal particles that have been surface-treated with a palladium compound.
經鈀化合物進行表面處理之金屬粒子的材料係可使用Ag、Cu、In、Al、或此等之合金等。因導電率比較高之故，金屬粒子之材料係以Ag及/或Cu為較佳，以Ag為更佳。 The material of the metal particles treated with palladium compounds can be Ag, Cu, In, Al, or alloys thereof. Due to their higher conductivity, Ag and/or Cu are preferred, and Ag is more preferred.
本實施型態之導電膏較佳係金屬粒子包含50重量%以上之銀(Ag)，更佳係包含80重量%以上之銀(Ag)，再更佳係包含90重量%以上之銀(Ag)，特佳係包含95重量%以上之銀(Ag)。最佳之實施型態係本實施 型態之導電膏所包含的表面處理金屬粒子之金屬粒子僅由銀(Ag)粒子所構成。這是因為，相較於其它金屬，銀之導電率較高之故。又，在本說明書中，所謂「表面處理金屬粒子之金屬粒子僅由銀(Ag)粒子所構成」係意指刻意地不使用銀(Ag)粒子以外之金屬粒子作為金屬粒子，而非連含有無可避免地混入之銀(Ag)粒子以外之金屬粒子的情形都予以排除者。對於其它相同的記載亦同理，並非排除無可避免地混入物質的情形者。 The conductive paste of this embodiment preferably contains more than 50% by weight of silver (Ag) in the metal particles, more preferably more than 80% by weight of silver (Ag), still more preferably more than 90% by weight of silver (Ag), and particularly preferably more than 95% by weight of silver (Ag). The best embodiment is that the metal particles of the surface-treated metal particles contained in the conductive paste of this embodiment are composed only of silver (Ag) particles. This is because, compared with other metals, the conductivity of silver is higher. In addition, in this specification, the so-called "the metal particles of the surface-treated metal particles are composed only of silver (Ag) particles" means that metal particles other than silver (Ag) particles are intentionally not used as metal particles, and it does not exclude the case where metal particles other than silver (Ag) particles are inevitably mixed. The same applies to other similar descriptions, and it does not exclude the case where substances are inevitably mixed.
相對於導電膏100重量份，本實施型態之導電膏較佳係包含50重量份以上之表面處理金屬粒子，更佳係包含70重量份以上，又更佳係包含80重量份以上。 Relative to 100 parts by weight of the conductive paste, the conductive paste of this embodiment preferably contains more than 50 parts by weight of surface-treated metal particles, more preferably more than 70 parts by weight, and even more preferably more than 80 parts by weight.
又，相對於導電膏100重量份，本實施型態之導電膏較佳係包含50至99重量份之表面處理金屬粒子，更佳係包含70至97重量份以上，又更佳係包含80至95重量份。藉由為上述範圍，可形成具有高的抗硫化性且較低成本之電極。 Furthermore, relative to 100 parts by weight of the conductive paste, the conductive paste of this embodiment preferably contains 50 to 99 parts by weight of surface-treated metal particles, more preferably 70 to 97 parts by weight or more, and even more preferably 80 to 95 parts by weight. By being within the above range, an electrode with high anti-sulfurization properties and relatively low cost can be formed.
金屬粒子之製造方法並無特別限定，例如可藉由還原法、粉碎法、電解法、霧化法(atomization method)、熱處理法、或其等之組合來進行製造。片狀(flaky)之金屬粒子係例如，可藉由將球狀或粒狀之金屬粒子以球磨機等予以壓碎來製造。 The method for producing metal particles is not particularly limited, and can be produced, for example, by reduction method, pulverization method, electrolysis method, atomization method, heat treatment method, or a combination thereof. Flaky metal particles can be produced, for example, by crushing spherical or granular metal particles with a ball mill.
表面處理金屬粒子係包含配置在金屬粒子表面之至少一部分的表面處理層。表面處理層係藉由將金屬粒子以包含鈀化合物之表面處理劑進行表面處理，而形成在金屬粒子表面之至少一部分的薄膜。 The surface-treated metal particles include a surface treatment layer disposed on at least a portion of the surface of the metal particles. The surface treatment layer is formed as a thin film on at least a portion of the surface of the metal particles by treating the metal particles with a surface treatment agent containing a palladium compound.
就成為用以將金屬粒子進行表面處理之原料的鈀化合物而言，係可使用選自由氯化鈀(II)、氧化鈀(II)、有機鈀化合物、氟化鈀、鈀 碳、正-烯丙基鈀錯合物、環戊二烯基烯丙基鈀、二氯雙(三苯基膦)鈀(II)、溴化鈀、及如油酸鈀之鈀的脂肪酸錯合物等鈀錯合物中的至少一者。就成為用以將金屬粒子進行表面處理之原料的鈀化合物而言，係以使用氯化鈀為較佳。 As the palladium compound used as the raw material for surface treatment of metal particles, at least one of palladium complexes selected from palladium chloride (II), palladium oxide (II), organic palladium compounds, palladium fluoride, palladium carbon, n-allyl palladium complex, cyclopentadienylallyl palladium, dichlorobis(triphenylphosphine)palladium (II), palladium bromide, and fatty acid complexes of palladium such as palladium oleate can be used. As the palladium compound used as the raw material for surface treatment of metal particles, it is preferred to use palladium chloride.
表面處理層係可藉由使用鈀化合物並以公知之方法進行表面處理來形成。具體而言，表面處理層係使包含鈀或鈀離子、用以使此等分散之有機物及溶劑之鈀皂溶劑(表面處理劑)附著於金屬粒子之表面，並藉由乾燥步驟去除溶劑後所形成者。藉此，可在金屬粒子之表面形成包含鈀化合物之表面處理層。又，雖然亦存在藉由還原處理而使金屬粒子之表面被覆其它金屬粒子、形成核殼構造之技術，惟在嘗試使用該技術來形成表面處理層時，為了在核粒子(例如銀粒子)表面析出殼(例如鈀金屬粒子)，在殼之鈀金屬粒子的存在量變多。亦即，鈀之使用量變多。另一方面，在本發明中係以鈀化合物附著於金屬粒子之表面的狀態來形成表面處理層，故有著鈀的使用量可為少量之效果。鈀由於其稀缺性、非普遍性而為昂貴的金屬，就即使為少量亦具有優異的抗硫化性和印刷特性一事而言，從成本方面來看是極為重要的效果。 The surface treatment layer can be formed by using a palladium compound and performing surface treatment by a known method. Specifically, the surface treatment layer is formed by attaching a palladium soap solvent (surface treatment agent) containing palladium or palladium ions to the surface of metal particles for dispersing organic substances and solvents, and removing the solvent by a drying step. In this way, a surface treatment layer containing a palladium compound can be formed on the surface of the metal particles. In addition, although there is also a technology for coating the surface of metal particles with other metal particles to form a core-shell structure by reduction treatment, when attempting to use this technology to form a surface treatment layer, in order to precipitate a shell (e.g., palladium metal particles) on the surface of the core particles (e.g., silver particles), the amount of palladium metal particles in the shell increases. That is, the amount of palladium used increases. On the other hand, in the present invention, the surface treatment layer is formed in a state where the palladium compound is attached to the surface of the metal particles, so there is an effect that the amount of palladium used can be small. Palladium is an expensive metal due to its scarcity and non-universality. The fact that it has excellent anti-sulfurization and printing properties even in a small amount is an extremely important effect from the perspective of cost.
就用以使鈀或鈀離子分散之有機物而言，較佳係選自脂肪酸及***化合物之至少一者。使用脂肪酸作為溶劑時，就脂肪酸而言，係可使用選自丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉豆蔻酸、十五酸、棕櫚酸、棕櫚油酸、十七酸(margaric acid)、硬脂酸、油酸、異油酸、亞麻油酸、次亞麻油酸、花生酸、二十碳二烯酸、二十碳三烯酸、二十碳四烯酸、花生油酸(arachidonic acid)、二十二酸、二十四酸 (lignoceric acid)、二十四烯酸(nervonic acid)、蠟酸、二十八酸及蜜蠟酸(melissic acid)等之至少一者。在此等之脂肪酸之中，較佳係使用選自棕櫚酸、硬脂酸及油酸之至少一者。作為表面處理劑所包含的有機物(脂肪酸)，更佳係使用油酸。當使用***化合物作為用以分散鈀或鈀離子之有機物時，係可使用苯并***作為***化合物。 As for the organic substance used to disperse palladium or palladium ions, it is preferred to select at least one of fatty acids and triazole compounds. When using fatty acids as solvents, as for fatty acids, at least one selected from butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, isoleic acid, linolenic acid, linolenic acid, arachidic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, wax acid, octacosanoic acid and melissic acid can be used. Among these fatty acids, it is preferred to use at least one selected from palmitic acid, stearic acid and oleic acid. As the organic substance (fatty acid) contained in the surface treatment agent, oleic acid is preferably used. When a triazole compound is used as the organic substance for dispersing palladium or palladium ions, benzotriazole can be used as the triazole compound.
又，用以形成表面處理層之表面處理劑所包含的溶劑，若為能夠用來使鈀或鈀離子分散，並使鈀化合物良好地附著於金屬粒子者即可。作為溶劑，例如可列舉：甲醇、乙醇、及異丙醇(IPA)等醇類、乙酸乙烯酯等有機酸類、甲苯及二甲苯等芳香族烴類、N-甲基-2-吡咯啶酮(NMP)等N-烷基吡咯啶酮類、N,N-二甲基甲醯胺(DMF)等醯胺類、甲基乙基酮(MEK)等酮類、萜品醇(TEL)、及二乙二醇單丁基醚(丁基卡必醇、BC)等環狀碳酸酯類、雙[2-(2-丁氧基乙氧基)乙基]己二酸酯、2,2,4-三甲基戊烷-1,3-二醇單異丁酸酯(Texanol)以及水等。 Furthermore, the solvent contained in the surface treatment agent for forming the surface treatment layer may be any solvent as long as it can be used to disperse palladium or palladium ions and allow the palladium compound to be well attached to the metal particles. Examples of solvents include alcohols such as methanol, ethanol, and isopropyl alcohol (IPA), organic acids such as vinyl acetate, aromatic hydrocarbons such as toluene and xylene, N-alkylpyrrolidones such as N-methyl-2-pyrrolidone (NMP), amides such as N,N-dimethylformamide (DMF), ketones such as methyl ethyl ketone (MEK), terpineol (TEL), cyclic carbonates such as diethylene glycol monobutyl ether (butyl carbitol, BC), bis[2-(2-butoxyethoxy)ethyl] adipate, 2,2,4-trimethylpentane-1,3-diol monoisobutyrate (Texanol), and water.
使包含分散有上述之鈀化合物的溶劑之表面處理劑附著於金屬粒子之表面，並藉由乾燥而去除溶劑，藉此可在金屬粒子之表面形成表面處理層。以如此方式，可獲得表面處理金屬粒子。 A surface treatment agent containing a solvent in which the above-mentioned palladium compound is dispersed is attached to the surface of the metal particles, and the solvent is removed by drying, thereby forming a surface treatment layer on the surface of the metal particles. In this way, surface-treated metal particles can be obtained.
又，表面處理金屬粒子之表面處理層係可以如下列方式進行製造。亦即，首先使金屬粒子分散於水。在分散有金屬粒子之水中，添加分散有上述之鈀化合物之溶劑作為被覆劑，而獲得包含被覆有含鈀之被覆劑的金屬粒子之水漿液後，藉由傾析法使被覆有被覆劑之金屬粒子沉澱。然後，去除上清液，並將所得到的濕潤狀態之被覆有被覆劑的金屬粒子與丙烯酸系分散劑一起添加於沸點為150至300℃之極性溶劑。然後，藉由 在氮氣環境中，以室溫至100℃之溫度(較佳係在80℃以下之溫度)乾燥12小時以上而去除水分，藉此可製造表面處理金屬粒子。又，若乾燥溫度過高，則會導致表面處理金屬粒子燒結，故為不佳。 Furthermore, the surface treatment layer of the surface-treated metal particles can be manufactured in the following manner. That is, first, the metal particles are dispersed in water. A solvent in which the above-mentioned palladium compound is dispersed is added as a coating agent to the water in which the metal particles are dispersed, and after obtaining a slurry containing metal particles coated with the palladium-containing coating agent, the metal particles coated with the coating agent are precipitated by decanting. Then, the supernatant is removed, and the obtained wet metal particles coated with the coating agent are added together with an acrylic dispersant to a polar solvent having a boiling point of 150 to 300°C. Then, by drying for more than 12 hours in a nitrogen environment at a temperature ranging from room temperature to 100°C (preferably below 80°C) to remove moisture, surface-treated metal particles can be produced. In addition, if the drying temperature is too high, the surface-treated metal particles will be sintered, which is not good.
本實施型態之在導電膏所包含的表面處理金屬粒子之表面處理層，係以包含有機物為更佳。例如，使用上述之鈀化合物而形成表面處理層時，表面處理層係包含有機物。表面處理金屬粒子藉由具有包含有機物之表面處理層，即使鈀化合物量為少量，所得到的電極亦可具有高的抗硫化性。又，有機物係可為液狀之有機脂肪酸，亦可為固體之脂肪酸。作為液狀之脂肪酸的例子係可列舉：丁酸、戊酸、己酸、庚酸、辛酸及壬酸等飽和脂肪酸，以及肉豆蔻油酸、棕櫚油酸、蓖麻油酸、油酸、亞麻油酸及次亞麻油酸等不飽和脂肪酸。此等脂肪酸係可單獨使用1種，亦可併用2種以上。此等之中係以使用油酸、亞麻油酸或此等之混合物為較佳。作為固體之脂肪酸的例子係可列舉：辛酸、棕櫚酸及硬脂酸等碳原子數10以上的飽和脂肪酸；以及巴豆酸及山梨酸等不飽和脂肪酸。 In the present embodiment, the surface treatment layer of the surface-treated metal particles contained in the conductive paste preferably contains an organic substance. For example, when the surface treatment layer is formed using the above-mentioned palladium compound, the surface treatment layer contains an organic substance. Since the surface-treated metal particles have a surface treatment layer containing an organic substance, the obtained electrode can have high resistance to sulfidation even if the amount of the palladium compound is small. In addition, the organic substance can be a liquid organic fatty acid or a solid fatty acid. Examples of liquid fatty acids include saturated fatty acids such as butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid and nonanoic acid, and unsaturated fatty acids such as myristic acid, palmitic acid, ricinoleic acid, oleic acid, linoleic acid and linolenic acid. These fatty acids can be used alone or in combination of two or more. Among these, oleic acid, linoleic acid or a mixture thereof is preferred. Examples of solid fatty acids include saturated fatty acids with more than 10 carbon atoms such as caprylic acid, palmitic acid and stearic acid; and unsaturated fatty acids such as crotonic acid and sorbic acid.
使用於本實施型態之表面處理金屬粒子的表面處理層，係鈀化合物之薄膜。就本實施型態而言，表面處理金屬粒子之表面處理層並非以鈀金屬或鈀合金所構成之薄膜。當表面處理層為以鈀金屬或鈀合金所構成之薄膜時，會因為鈀之調配量過多而有產生所得到的電極之電阻增加等不良影響之情形。又，在燒製後，由於在金屬粒子之表面存在大量的鈀金屬或鈀合金，焊料對銀粒子等金屬粒子的潤濕性變差，阻礙焊接的可能性變高。又，若鈀之使用量變多，則成本高。 The surface treatment layer of the surface treated metal particles used in this embodiment is a thin film of a palladium compound. In this embodiment, the surface treatment layer of the surface treated metal particles is not a thin film composed of palladium metal or a palladium alloy. When the surface treatment layer is a thin film composed of palladium metal or a palladium alloy, there will be adverse effects such as an increase in the resistance of the obtained electrode due to excessive palladium blending. In addition, after sintering, due to the presence of a large amount of palladium metal or a palladium alloy on the surface of the metal particles, the wettability of the solder to metal particles such as silver particles becomes poor, and the possibility of hindering welding becomes higher. In addition, if the amount of palladium used increases, the cost is high.
表面處理層係形成於金屬粒子之表面的至少一部分之薄膜。表面處理層較佳係覆蓋金屬粒子表面之50%以上的薄膜，更佳係覆蓋金屬粒子表面之80%以上的薄膜，又更佳係覆蓋金屬粒子表面之90%以上的薄膜，特佳係覆蓋金屬粒子表面之95%以上的薄膜。表面處理層係以覆蓋金屬粒子之表面整體的薄膜為最佳。 The surface treatment layer is a thin film formed on at least a portion of the surface of the metal particle. The surface treatment layer is preferably a thin film covering more than 50% of the surface of the metal particle, more preferably a thin film covering more than 80% of the surface of the metal particle, more preferably a thin film covering more than 90% of the surface of the metal particle, and particularly preferably a thin film covering more than 95% of the surface of the metal particle. The surface treatment layer is best when it covers the entire surface of the metal particle.
表面處理金屬粒子之表面處理層的膜厚雖然並非必需要為均勻，但為了更有效地抑制金屬粒子之硫化，係以均勻為較佳。又，就表面處理層之膜厚的控制而言，係例如可藉由調控鈀化合物被分散於溶劑中之鈀皂溶劑(表面處理劑)之黏度、及鈀皂溶劑(表面處理劑)中之鈀化合物的濃度來進行控制。又，藉由控制表面處理層之膜厚，可控制表面處理層所包含的鈀之量。又，表面處理層之膜厚係以1至100nm以下為較佳，以1至70nm以下為更佳，以1至50nm以下為特佳。表面處理層之厚度係例如可以X射線光電子光譜法測定。藉由將表面處理層之膜厚設為該範圍，雖然鈀化合物量為少量，但可形成抗硫化性高的電極。 Although the film thickness of the surface treatment layer of the surface-treated metal particles does not necessarily need to be uniform, it is preferred to be uniform in order to more effectively suppress the sulfidation of the metal particles. In addition, as for the control of the film thickness of the surface treatment layer, it can be controlled by, for example, adjusting the viscosity of the palladium soap solvent (surface treatment agent) in which the palladium compound is dispersed in the solvent, and the concentration of the palladium compound in the palladium soap solvent (surface treatment agent). In addition, by controlling the film thickness of the surface treatment layer, the amount of palladium contained in the surface treatment layer can be controlled. In addition, the film thickness of the surface treatment layer is preferably 1 to 100 nm or less, more preferably 1 to 70 nm or less, and particularly preferably 1 to 50 nm or less. The thickness of the surface treatment layer can be measured, for example, by X-ray photoelectron spectroscopy. By setting the film thickness of the surface treatment layer to this range, an electrode with high sulfidation resistance can be formed even though the amount of palladium compound is small.
本實施型態之導電膏係包含經鈀化合物進行表面處理後之表面處理金屬粒子作為(A)導電性粒子，藉此可以不多量地使用昂貴的鈀而形成具有高的抗硫化性之電極。因此，藉由使用本實施型態之導電膏，係可形成具有高的抗硫化性，且成本比較低之電極。尤其，使用銀粒子作為金屬粒子時，銀容易被硫化。藉由使用本實施型態之導電膏，可以低成本且有效地抑制「以銀作為主材料之電極被硫化而斷線」之情事。 The conductive paste of this embodiment includes surface-treated metal particles treated with a palladium compound as (A) conductive particles, thereby forming an electrode with high anti-sulfurization properties without using a small amount of expensive palladium. Therefore, by using the conductive paste of this embodiment, an electrode with high anti-sulfurization properties and relatively low cost can be formed. In particular, when silver particles are used as metal particles, silver is easily sulfided. By using the conductive paste of this embodiment, the situation of "the electrode with silver as the main material being sulfided and broken" can be effectively suppressed at low cost.
例如，使用銀粒子作為金屬粒子時，藉由使用經鈀化合物進行表面處理後之表面處理金屬粒子(表面處理銀粒子)，可以抑制銀粒子之 硫化的理由係可推論如下。亦即，可推斷作為表面處理成分之鈀與金屬粒子係藉由燒結而形成均勻的合金層，並藉此成為經提高抗硫化性者。當為以較高的溫度(例如，500至900℃)進行燒製之類型的導電膏之情形下，鈀化合物中之鈀係藉由燒製而作為金屬粒子與鈀金屬合金層(金屬粒子為銀粒子時，係鈀-銀合金層)存在。咸認該鈀金屬合金層會賦予金屬粒子高的抗硫化性。又，咸認當為藉由較低溫(例如，100至200℃)之熱處理而使其熱硬化的熱硬化型之導電膏時，鈀化合物係在銀粒子等金屬粒子之表面形成為薄膜，並藉此可獲得抗硫化性。又，在表面處理層所包含的鈀之含量並不太多。因此，相較於另外添加鈀粒子的情形，係以較少的鈀之使用量即完成，故可以較低成本獲得高的抗硫化性。如此方式所得到的電極係具有高的抗硫化性，且對基板之密著性優異。對於銀粒子以外之其它的金屬粒子亦可同樣地推論。惟，本發明並非拘於該項推論者。 For example, when silver particles are used as metal particles, the reason why the sulfidation of the silver particles can be suppressed by using surface-treated metal particles (surface-treated silver particles) that have been surface-treated with a palladium compound can be inferred as follows. That is, it can be inferred that the palladium as the surface treatment component and the metal particles form a uniform alloy layer by sintering, thereby becoming a conductive paste with improved sulfidation resistance. In the case of a conductive paste of a type that is sintered at a relatively high temperature (for example, 500 to 900°C), the palladium in the palladium compound exists as metal particles and a palladium metal alloy layer (a palladium-silver alloy layer when the metal particles are silver particles) by sintering. It is believed that the palladium metal alloy layer will give the metal particles high sulfidation resistance. In addition, it is believed that when the conductive paste is heat-cured by heat treatment at a relatively low temperature (for example, 100 to 200°C), the palladium compound forms a thin film on the surface of metal particles such as silver particles, thereby obtaining anti-sulfurization properties. In addition, the content of palladium contained in the surface treatment layer is not too much. Therefore, compared with the case of adding palladium particles separately, it is completed with a smaller amount of palladium, so high anti-sulfurization properties can be obtained at a lower cost. The electrode obtained in this way has high anti-sulfurization properties and excellent adhesion to the substrate. The same inference can be made for other metal particles other than silver particles. However, the present invention is not limited to this inference.
本實施型態之導電膏的(A)導電性粒子藉由包含預定之表面處理金屬粒子，附帶的效果為所得到的電極之抗遷移性亦可提昇。就藉由使用經鈀化合物進行表面處理後的表面處理金屬粒子(表面處理銀粒子)亦可提高抗遷移性之理由而言，係因為藉由使用經鈀化合物進行表面處理後之表面處理金屬粒子，不但具有鈀之抗遷移的效果，還會提高電極之緻密性。藉此，推測為抗遷移性提高者。惟，本發明並非拘於該項推論者。 The conductive particles (A) of the conductive paste of this embodiment contain predetermined surface-treated metal particles, which has the additional effect that the anti-migration property of the obtained electrode can also be improved. The reason why the anti-migration property can be improved by using surface-treated metal particles (surface-treated silver particles) after surface treatment with a palladium compound is because the surface-treated metal particles after surface treatment with a palladium compound not only have the anti-migration effect of palladium, but also improve the compactness of the electrode. Therefore, it is inferred that the anti-migration property is improved. However, the present invention is not limited to this inference.
相對於金屬粒子100重量份，本實施型態之導電膏係以表面處理金屬粒子所包含的鈀之含量是0.01重量份以上為較佳，以0.05重量份以上為更佳，以0.08重量份以上為特佳，以0.2重量份以上為最佳。又，相對於金屬粒子100重量份，鈀之含量係以1.0重量份以下為較佳，以0.8 重量份以下為更佳，以0.6重量份以下為再更佳，以0.4重量份以下為特佳，以0.3重量份以下為最佳。藉由表面處理金屬粒子所包含的鈀之含量為上述範圍，可以在鈀之使用量少、成本低的情況下，可減少因電極之硫化所造成的電極之電阻值的變化。再者，在經膏化之情形下可提升導電性粒子之流動性，並可更提升印刷時之調平性。又，在表面處理金屬粒子所包含的鈀之含量係可以ICP發光分光分析法(高頻感應耦合電漿光學發射光譜分析法，Inductively Coupled Plasma-Optical Emission Spectrometry)進行測定。 In the conductive paste of the present embodiment, the content of palladium contained in the surface-treated metal particles is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, particularly preferably 0.08 parts by weight or more, and most preferably 0.2 parts by weight or more, relative to 100 parts by weight of the metal particles. Furthermore, the content of palladium is preferably 1.0 parts by weight or less, more preferably 0.8 parts by weight or less, even more preferably 0.6 parts by weight or less, particularly preferably 0.4 parts by weight or less, and most preferably 0.3 parts by weight or less, relative to 100 parts by weight of the metal particles. By setting the content of palladium contained in the surface-treated metal particles to the above range, the change in the resistance value of the electrode caused by the sulfidation of the electrode can be reduced while using less palladium and at a low cost. Furthermore, the fluidity of the conductive particles can be improved after being pasted, and the leveling during printing can be further improved. In addition, the content of palladium contained in the surface-treated metal particles can be measured by ICP spectroscopy (Inductively Coupled Plasma-Optical Emission Spectrometry).
(A)導電性粒子之形狀並無特別限定，例如可使用：球狀、粒狀、片狀及/或鱗片狀之表面處理金屬粒子。 (A) The shape of the conductive particles is not particularly limited. For example, spherical, granular, flake and/or scale-shaped surface-treated metal particles can be used.
(A)導電性粒子之平均粒徑係以0.1μm至10μm為較佳，更佳係0.2μm至8μm，再更佳係0.3μm至7μm，特佳係0.4至6μm。在此所謂之平均粒徑，係意指藉由雷射繞射散射式粒度分布測定法所得到的體積基準中值徑(D50)。當(A)導電性粒子之平均粒徑(D50)大於10μm時，燒結性差，無法獲得緻密的膜。又，當(A)導電性粒子之平均粒徑(D50)未達0.1μm時，係有分散性變差之傾向，而有在印刷導電膏時難以獲得均勻的薄膜之情形。 The average particle size of the (A) conductive particles is preferably 0.1μm to 10μm, more preferably 0.2μm to 8μm, still more preferably 0.3μm to 7μm, and particularly preferably 0.4 to 6μm. The average particle size here refers to the volume-based median diameter (D50) obtained by the laser diffraction scattering particle size distribution measurement method. When the average particle size (D50) of the (A) conductive particles is greater than 10μm, the sintering property is poor and a dense film cannot be obtained. In addition, when the average particle size (D50) of the (A) conductive particles is less than 0.1μm, the dispersion tends to deteriorate, and it is difficult to obtain a uniform film when printing the conductive paste.
當將導電膏設為100重量份時，(A)導電性粒子之含量為80重量份以上之量，以含有83重量份以上為較佳，以含有85重量份以上為更佳。導電性粒子之含量的上限並無特別限制，但從導電膏具備充分的印刷特性之觀點來看，相對於導電膏100重量份，係以99.9重量份以下為較 佳，以99.5重量份以下為更佳，以99重量份以下為再更佳，以95重量份以下為特佳。 When the conductive paste is set to 100 parts by weight, the content of (A) conductive particles is 80 parts by weight or more, preferably 83 parts by weight or more, and more preferably 85 parts by weight or more. There is no particular upper limit on the content of conductive particles, but from the perspective of the conductive paste having sufficient printing properties, it is preferably 99.9 parts by weight or less, more preferably 99.5 parts by weight or less, even more preferably 99 parts by weight or less, and particularly preferably 95 parts by weight or less, relative to 100 parts by weight of the conductive paste.
<(B)黏結劑樹脂> <(B) Adhesive resin>
本實施型態之導電膏係包含(B)黏結劑樹脂。 The conductive paste of this embodiment includes (B) binder resin.
(B)黏結劑樹脂係在導電膏中將(A)導電性粒子彼此互相連結者。又，本實施型態之導電膏係可包含後述之(C)玻璃料，亦可不包含後述之(C)玻璃料。在本實施型態之導電膏包含(C)玻璃料之情形下、及本實施型態之導電膏不包含(C)玻璃料之情形下，本實施型態之導電膏所包含的(B)黏結劑樹脂之功能係有所不同。 (B) Binder resin is used to connect (A) conductive particles to each other in the conductive paste. In addition, the conductive paste of this embodiment may contain (C) glass frit described later, or may not contain (C) glass frit described later. When the conductive paste of this embodiment contains (C) glass frit, and when the conductive paste of this embodiment does not contain (C) glass frit, the function of the (B) binder resin contained in the conductive paste of this embodiment is different.
當本實施型態之導電膏包含(C)玻璃料時，係可藉由將本實施型態之導電膏以成為預定之電極圖案之方式塗佈於預定的基材，並以較高的溫度(例如，500至900℃)進行燒製而形成電極。此時，(B)黏結劑樹脂會在燒製之際被燒除。因此，在此情況下之(B)黏結劑樹脂的功能，是在將本實施型態之導電膏以成為預定之電極圖案之方式塗佈於預定的基材時，使(A)導電性粒子彼此互相連結。 When the conductive paste of the present embodiment includes (C) glass frit, the conductive paste of the present embodiment can be applied to a predetermined substrate in a manner to form a predetermined electrode pattern and fired at a relatively high temperature (e.g., 500 to 900°C) to form an electrode. At this time, the (B) binder resin will be fired during the firing. Therefore, the function of the (B) binder resin in this case is to connect the (A) conductive particles to each other when the conductive paste of the present embodiment is applied to a predetermined substrate in a manner to form a predetermined electrode pattern.
當本實施型態之導電膏不包含(C)玻璃料時，可藉由將本實施型態之導電膏以成為預定之電極圖案之方式塗佈於預定的基材，並以較低的溫度(例如，100至200℃)進行熱處理而形成電極。此時，(B)黏結劑樹脂不會在熱處理之際被燒除。就在此情況下之(B)黏結劑樹脂的功能而言，除了有著在將本實施型態之導電膏以成為預定之電極圖案之方式塗佈於預定的基材時使(A)導電性粒子彼此互相連結的功能之外，還有在熱處理之後使(A)導電性粒子彼此互相連結，藉此保持熱處理後之電極的形狀的功能。 When the conductive paste of the present embodiment does not contain (C) glass frit, the conductive paste of the present embodiment can be applied to a predetermined substrate in a manner to form a predetermined electrode pattern and heat-treated at a relatively low temperature (e.g., 100 to 200°C) to form an electrode. At this time, the (B) binder resin will not be burned off during the heat treatment. In this case, the function of the (B) binder resin is not only to connect the (A) conductive particles to each other when the conductive paste of the present embodiment is applied to a predetermined substrate in a manner to form a predetermined electrode pattern, but also to connect the (A) conductive particles to each other after the heat treatment, thereby maintaining the shape of the electrode after the heat treatment.
作為(B)黏結劑樹脂，係例如可使用：乙基纖維素樹脂、硝基纖維素樹脂等纖維素系樹脂、丙烯酸樹脂、醇酸樹脂(alkyd resin)、飽和聚酯樹脂、丁醛樹脂、聚乙烯醇及羥基丙基纖維素等熱塑性樹脂。此等之樹脂係可單獨使用，亦可混合兩種以上而使用。 As the binder resin (B), for example, cellulose resins such as ethyl cellulose resin and nitrocellulose resin, and thermoplastic resins such as acrylic resin, alkyd resin, saturated polyester resin, butyraldehyde resin, polyvinyl alcohol and hydroxypropyl cellulose can be used. These resins can be used alone or in combination of two or more.
作為(B)黏結劑樹脂，較佳係使用選自乙基纖維素樹脂、硝基纖維素樹脂等纖維素系樹脂、及醇酸樹脂中之至少一種。 As the binder resin (B), it is preferred to use at least one selected from cellulose resins such as ethyl cellulose resin, nitrocellulose resin, and alkyd resin.
當本實施型態之導電膏不包含(C)玻璃料時，本實施型態之導電膏係可為了提昇表面處理金屬粒子彼此間之接著性而包含環氧樹脂作為(B)黏結劑樹脂。環氧樹脂之種類並無特別限制，可使用公知之環氧樹脂。環氧樹脂例如可列舉：雙酚A型、雙酚F型、聯苯基型、四甲基聯苯基型、甲酚酚醛清漆型、酚酚醛清漆型、雙酚A酚醛清漆型、二環戊二烯酚縮合型、酚芳烷基縮合型及縮水甘油基胺型等環氧樹脂、溴化環氧樹脂、脂環式環氧樹脂、以及脂肪族環氧樹脂等。此等環氧樹脂係可單獨使用一種或混合兩種以上而使用。又，亦可以提昇表面處理金屬粒子彼此間之接著性為目的而使用環氧樹脂以外之熱硬化性樹脂。再者，亦可使用聚胺酯樹脂(polyurethane resin)及/或聚碳酸酯樹脂等熱塑性樹脂。 When the conductive paste of the present embodiment does not contain (C) glass frit, the conductive paste of the present embodiment may contain epoxy resin as (B) binder resin in order to improve the adhesion between the surface-treated metal particles. The type of epoxy resin is not particularly limited, and known epoxy resins can be used. Examples of epoxy resins include: bisphenol A type, bisphenol F type, biphenyl type, tetramethylbiphenyl type, cresol novolac type, phenol novolac type, bisphenol A novolac type, dicyclopentadienol condensation type, phenol aralkyl condensation type and glycerylamine type epoxy resins, brominated epoxy resins, aliphatic epoxy resins, and the like. These epoxy resins can be used alone or in combination of two or more. In addition, thermosetting resins other than epoxy resins can be used for the purpose of improving the adhesion between surface-treated metal particles. Furthermore, thermoplastic resins such as polyurethane resins and/or polycarbonate resins can also be used.
相對於(A)導電性粒子100重量份，(B)黏結劑樹脂之含量較佳係25重量份以下，更佳係18重量份以下，再更佳係11重量份以下，特佳係9重量份以下。又，(B)黏結劑樹脂之含量的下限係以0.1重量份為較佳，以0.5重量份為更佳，以1重量份為再更佳，以1.5重量份為特佳。導電膏中之(B)黏結劑樹脂的含量為上述之範圍內時，導電膏對基板(基材)之塗佈性、及/或膏調平性會提高，可獲得優異的印刷形狀。另一方面， 若(B)黏結劑樹脂之含量超過上述之範圍，則所塗佈的導電膏中所包含的(B)黏結劑樹脂之量過多。因此，可能有無法高精度地形成電極等之情形。 The content of the binder resin (B) is preferably 25 parts by weight or less, more preferably 18 parts by weight or less, even more preferably 11 parts by weight or less, and particularly preferably 9 parts by weight or less relative to 100 parts by weight of the conductive particles (A). The lower limit of the content of the binder resin (B) is preferably 0.1 parts by weight, more preferably 0.5 parts by weight, even more preferably 1 part by weight, and particularly preferably 1.5 parts by weight. When the content of the binder resin (B) in the conductive paste is within the above range, the coating property of the conductive paste on the substrate (base material) and/or the leveling property of the paste are improved, and an excellent printed shape can be obtained. On the other hand, if the content of the binder resin (B) exceeds the above range, the amount of the binder resin (B) contained in the applied conductive paste is excessive. Therefore, there may be a situation where electrodes cannot be formed with high precision.
<(C)玻璃料> <(C) Glass frit>
本實施型態之導電膏係可更包含(C)玻璃料。 The conductive paste of this embodiment may further include (C) glass frit.
當本實施型態之導電膏包含(C)玻璃料時，可藉由將本實施型態之導電膏以成為預定之電極圖案之方式塗佈於預定的基材，並以較高的溫度(例如，500至900℃)進行燒製，而形成電極。此時，上述之(B)黏結劑樹脂在燒製之際會被燒除。藉由導電膏所包含的(C)玻璃料使(A)導電性粒子彼此互相連結，可保持燒製後之電極的形狀。 When the conductive paste of this embodiment includes (C) glass frit, the conductive paste of this embodiment can be applied to a predetermined substrate in a predetermined electrode pattern and fired at a relatively high temperature (e.g., 500 to 900°C) to form an electrode. At this time, the above-mentioned (B) binder resin will be burned off during the firing. The (C) glass frit contained in the conductive paste connects the (A) conductive particles to each other, and the shape of the electrode after firing can be maintained.
玻璃料並無特別限定，惟可使用較佳係軟化點300℃以上之玻璃料，更佳係軟化點400至900℃之玻璃料，再更佳係軟化點500至800℃之玻璃料。玻璃料之軟化點係可使用熱重量測定裝置(例如，BRUKER AXS公司製、TG-DTA2000SA)來進行測定。 The glass frit is not particularly limited, but preferably the glass frit with a softening point of 300°C or above, more preferably the glass frit with a softening point of 400 to 900°C, and even more preferably the glass frit with a softening point of 500 to 800°C can be used. The softening point of the glass frit can be measured using a thermogravimetric measuring device (e.g., TG-DTA2000SA manufactured by BRUKER AXS).
作為(C)玻璃料之例子，可列舉硼矽酸系及硼矽酸鋇系等之玻璃料。又，作為玻璃料之例子，係可列舉：硼矽酸鉍系、硼矽酸鹼金屬系、硼矽酸鹼土金屬系、硼矽酸鋅系、硼矽酸鉛系、硼酸鉛系、矽酸鉛系、硼酸鉍系及硼酸鋅系等之玻璃料。此等玻璃料亦可混合兩種以上而使用。考量對環境的影響之點而言，玻璃料係以無鉛為較佳。 Examples of (C) glass frits include borosilicate and barium borosilicate glass frits. Examples of glass frits include bismuth borosilicate, alkali metal borosilicate, alkali earth metal borosilicate, zinc borosilicate, lead borosilicate, lead borate, lead silicate, bismuth borate, and zinc borate. Two or more of these glass frits may be mixed and used. Considering the impact on the environment, lead-free glass frits are preferred.
玻璃料較佳係包含選自由ZnO、Bi2O3、BaO、Na2O、CaO及Al2O3所組成群組中之至少一種。玻璃料更佳係包含選自由ZnO及Bi2O3所組成群組中之至少一種。 The glass frit preferably includes at least one selected from the group consisting of ZnO, Bi2O3 , BaO, Na2O , CaO, and Al2O3 . The glass frit more preferably includes at least one selected from the group consisting of ZnO and Bi2O3 .
當本實施型態之導電膏包含(C)玻璃料時，玻璃料係以包含ZnO為更佳。使用包含ZnO之玻璃料(鋅系玻璃料)作為玻璃料時，可獲得抗硫化性更高的電極。 When the conductive paste of this embodiment includes (C) glass frit, it is more preferable that the glass frit includes ZnO. When glass frit (zinc-based glass frit) including ZnO is used as the glass frit, an electrode with higher sulfidation resistance can be obtained.
當本實施型態之導電膏包含(C)玻璃料時，玻璃料係以包含Bi2O3為更佳。使用包含Bi2O3之玻璃料(鉍系玻璃料)作為玻璃料時，可提高電極之緻密性。 When the conductive paste of the present embodiment includes (C) glass frit, the glass frit preferably includes Bi 2 O 3. When glass frit including Bi 2 O 3 (bismuth-based glass frit) is used as the glass frit, the compactness of the electrode can be improved.
玻璃料之平均粒徑較佳係0.1至20μm，更佳係0.2至10μm，特佳係0.5至5μm。在此所謂之平均粒徑，係意指藉由雷射繞射散射式粒度分布測定法所得到的體積基準中值徑(D50)。 The average particle size of the glass material is preferably 0.1 to 20 μm, more preferably 0.2 to 10 μm, and particularly preferably 0.5 to 5 μm. The average particle size here refers to the volume standard median diameter (D50) obtained by the laser diffraction scattering particle size distribution measurement method.
當本實施型態之導電膏包含(C)玻璃料時，相對於(A)導電性粒子100重量份，(C)玻璃料之含量係以0.05至10重量份為較佳，以0.5至8重量份為更佳，以1至6重量份為更佳，以2至4重量份為特佳。玻璃料之含量少於該範圍時，燒製導電膏所得到的電極對基板(基材)之密著性會降低。玻璃料之含量多於該範圍時，因燒製導電膏所得到的電極之電阻值高，且燒製體之表面被玻璃成分覆蓋，故鍍覆性會變差。又，玻璃料之含量比較少時，可獲得低電阻之電極。又，玻璃料之含量比較多時，可獲得耐藥品性優異的電極。因為在電極之表面形成鍍覆膜時，必須進行鍍覆前處理，故耐藥品性為所要求的特性。進行鍍覆前處理目的在於：從電極之表面去除污染物質，使電極之表面進行活性化，形成適合鍍覆之潔淨的狀態。就應予去除之汚染物質而言，可大致區分為有機系與無機系。前處理步驟並非以單一步驟來去除全部之汚染物質的步驟。例如，有機系物 質係在使用鹼系洗淨劑之步驟進行去除。無機系物質係在使用酸系洗淨劑之步驟進行去除。因此，對於電極係要求高的耐藥品性。 When the conductive paste of this embodiment contains (C) glass frit, the content of (C) glass frit is preferably 0.05 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, more preferably 1 to 6 parts by weight, and particularly preferably 2 to 4 parts by weight relative to 100 parts by weight of (A) conductive particles. When the content of the glass frit is less than the range, the adhesion of the electrode obtained by firing the conductive paste to the substrate (base material) will be reduced. When the content of the glass frit is more than the range, the coating property will be deteriorated because the resistance value of the electrode obtained by firing the conductive paste is high and the surface of the fired body is covered with glass components. In addition, when the content of the glass frit is relatively small, a low-resistance electrode can be obtained. In addition, when the content of the glass frit is relatively high, an electrode with excellent chemical resistance can be obtained. Because pre-plating treatment is necessary when forming a coating on the surface of the electrode, chemical resistance is a required characteristic. The purpose of pre-plating treatment is to remove pollutants from the surface of the electrode, activate the surface of the electrode, and form a clean state suitable for plating. In terms of the pollutants to be removed, they can be roughly divided into organic and inorganic. The pre-treatment step is not a step to remove all pollutants in a single step. For example, organic substances are removed in the step of using alkaline detergents. Inorganic substances are removed in the step of using acidic detergents. Therefore, high chemical resistance is required for the electrode.
當本實施型態之導電膏包含(C)玻璃料時，玻璃料會隨溫度之上昇而軟化，並進行(A)導電性粒子之燒結(燒製)。玻璃料含量多時，會有玻璃成分被擠出至燒製體之表面的情形。在該情形下，燒製體之表面會有被玻璃成分覆蓋的狀況。(C)玻璃料包含氧化鋅時，由於在結晶化溫度下玻璃料中之Zn成分會成為ZnO而析出，故與表面處理金屬粒子中之鈀同樣可對於燒製後之(A)導電性粒子的抗硫化性有所助益。 When the conductive paste of this embodiment includes (C) glass frit, the glass frit softens as the temperature rises, and the (A) conductive particles are sintered (fired). When the glass frit content is high, the glass component may be extruded to the surface of the sintered body. In this case, the surface of the sintered body may be covered with the glass component. When the (C) glass frit includes zinc oxide, the Zn component in the glass frit will precipitate as ZnO at the crystallization temperature, so it can help the anti-sulfurization property of the (A) conductive particles after sintering, just like the palladium in the surface-treated metal particles.
<(D)添加劑> <(D) Additives>
本實施型態之導電膏係可包含分散劑作為(D)添加劑。藉由本實施型態之導電膏包含分散劑，可提高導電膏中之(A)導電性粒子的分散性，並可防止(A)導電性粒子凝集。 The conductive paste of this embodiment may contain a dispersant as the (D) additive. By containing a dispersant in the conductive paste of this embodiment, the dispersibility of the (A) conductive particles in the conductive paste can be improved, and the aggregation of the (A) conductive particles can be prevented.
作為分散劑係可使用公知之分散劑。作為分散劑，例如可使用脂肪酸醯胺、酸型之低分子分散劑、或氧化鉍(Bi2O3)。 As the dispersant, a known dispersant can be used. For example, fatty acid amide, an acid-type low molecular weight dispersant, or bismuth oxide (Bi 2 O 3 ) can be used.
本實施型態之導電膏係可包含有機添加劑及無機添加劑等來作為分散劑以外之(D)添加劑。作為(D)添加劑，例如可使用：二氧化矽填充劑(silica filler)、搖變調節劑(rheology control agent)及/或顏料等。 The conductive paste of this embodiment may contain organic additives and inorganic additives as (D) additives other than dispersants. As (D) additives, for example, silica fillers, rheology control agents and/or pigments may be used.
藉由在導電膏添加有機添加劑而作為(D)添加劑，可提昇導電膏之印刷性。藉由在導電膏添加分散劑作為(D)添加劑，可提昇(A)導電性粒子等之分散性。藉由在導電膏添加無機添加劑作為(D)添加劑，可提昇導電膏在燒製後之密著性。 By adding an organic additive to the conductive paste as the (D) additive, the printability of the conductive paste can be improved. By adding a dispersant to the conductive paste as the (D) additive, the dispersibility of the (A) conductive particles can be improved. By adding an inorganic additive to the conductive paste as the (D) additive, the adhesion of the conductive paste after firing can be improved.
<(E)溶劑> <(E)Solvent>
本實施型態之導電膏可包含(E)溶劑。作為溶劑，係例如可列舉：甲醇、乙醇及異丙醇(IPA)等醇類、乙酸乙烯酯等有機酸類、甲苯及二甲苯等芳香族烴類、N-甲基-2-吡咯啶酮(NMP)等N-烷基吡咯啶酮類、N,N-二甲基甲醯胺(DMF)等醯胺類、甲基乙基酮(MEK)等酮類、萜品醇(TEL)、及二乙二醇單丁基醚(丁基卡必醇、BC)等環狀碳酸酯類、雙[2-(2-丁氧基乙氧基)乙基]己二酸酯、2,2,4-三甲基戊烷-1,3-二醇單異丁酸酯(Texanol)以及水等。 The conductive paste of this embodiment may include (E) a solvent. Examples of the solvent include: alcohols such as methanol, ethanol and isopropyl alcohol (IPA), organic acids such as vinyl acetate, aromatic hydrocarbons such as toluene and xylene, N-alkylpyrrolidones such as N-methyl-2-pyrrolidone (NMP), amides such as N,N-dimethylformamide (DMF), ketones such as methyl ethyl ketone (MEK), terpineol (TEL), cyclic carbonates such as diethylene glycol monobutyl ether (butyl carbitol, BC), bis[2-(2-butoxyethoxy)ethyl] adipate, 2,2,4-trimethylpentane-1,3-diol monoisobutyrate (Texanol), and water.
本實施型態之導電膏中的溶劑之含量並無特別限定。就溶劑之含量而言，例如相對於(A)導電性粒子100重量份，較佳係1至100重量份，更佳係5至60重量份，再更佳係8至35重量份。 The content of the solvent in the conductive paste of this embodiment is not particularly limited. For example, the content of the solvent is preferably 1 to 100 parts by weight, more preferably 5 to 60 parts by weight, and even more preferably 8 to 35 parts by weight relative to 100 parts by weight of (A) conductive particles.
本實施型態之導電膏的黏度係依黏度測定之條件而改變，使用HB型黏度計(BROOKFIELD公司製)(SC4-14 Spindle)，於溫度25℃之條件下，在1rpm之轉速(剪切速度0.4sec-1)之條件時，較佳係100至1000Pa‧s，更佳係200至800Pa‧s。本實施型態之導電膏的黏度係可藉由適當地控制溶劑之含量而進行調整。藉由導電膏之黏度被調整至該範圍，導電膏對基板(基材)之塗佈性及/或處理性會變良好，而能夠將導電膏以均勻之厚度塗佈於基板。 The viscosity of the conductive paste of this embodiment changes according to the conditions of viscosity measurement. Using an HB type viscometer (manufactured by Brookfield) (SC4-14 Spindle), at a temperature of 25°C and a rotation speed of 1 rpm (shear rate 0.4 sec -1 ), it is preferably 100 to 1000 Pa‧s, and more preferably 200 to 800 Pa‧s. The viscosity of the conductive paste of this embodiment can be adjusted by appropriately controlling the content of the solvent. By adjusting the viscosity of the conductive paste to this range, the coating and/or handling properties of the conductive paste on the substrate (base material) will become good, and the conductive paste can be coated on the substrate with a uniform thickness.
本實施型態之導電膏的黏度，亦可以與上述條件不同的條件之值來表示，在使用HB型黏度計(Brookfield公司製)(SC4-14 Spindal)，於溫度25℃之條件下，為10rpm之轉速(剪切速度4.0sec-1)之條件時，較佳係50至700Pa‧s，更佳係100至300Pa‧s。本實施型態之導電膏的黏度係可藉由適當控制溶劑之含量而進行調整。藉由導電膏之黏度被調整成 該範圍，導電膏對基板(基材)之塗佈性及/或處理性會變好，而能夠將導電膏以均勻的厚度塗佈於基板。 The viscosity of the conductive paste of this embodiment can also be expressed as a value under conditions different from the above conditions. When using an HB type viscometer (manufactured by Brookfield) (SC4-14 Spindal) at a temperature of 25°C and a rotation speed of 10 rpm (shear rate 4.0 sec -1 ), it is preferably 50 to 700 Pa‧s, and more preferably 100 to 300 Pa‧s. The viscosity of the conductive paste of this embodiment can be adjusted by appropriately controlling the content of the solvent. By adjusting the viscosity of the conductive paste to this range, the coating and/or handling properties of the conductive paste on the substrate (base material) will be improved, and the conductive paste can be coated on the substrate with a uniform thickness.
本實施型態之導電膏較佳係以HB型黏度計在25℃之條件下測定出之屬於轉速1rpm之黏度與轉速10rpm之黏度的比之搖變指數值(TI)為2.5以下，以2.4以下為更佳。搖變指數值係黏度計之轉速在成為比率1：10之測定條件間的黏度之比，且為流動性之指標的值。若TI為2.5以下，因為適度的流動性而容易獲得良好的調平性，故為較佳。TI之下限並無特別限制，惟從防止印刷擴散等並保持尺寸穩定性之觀點來看，係以1.3以上為較佳。 The conductive paste of this embodiment preferably has a swing index value (TI) of 2.5 or less, and preferably 2.4 or less, as the ratio of the viscosity at a rotation speed of 1 rpm to the viscosity at a rotation speed of 10 rpm measured by an HB type viscometer at 25°C. The swing index value is the ratio of the viscosity between the measurement conditions where the rotation speed of the viscometer becomes a ratio of 1:10, and is an indicator of fluidity. If the TI is 2.5 or less, it is better because it is easy to obtain good leveling due to moderate fluidity. There is no special limit on the lower limit of TI, but from the perspective of preventing printing diffusion and maintaining dimensional stability, it is better to be 1.3 or more.
<(F)硬化劑> <(F) Hardener>
本實施型態之導電膏較佳係更包含(F)硬化劑。本實施型態之導電膏包含環氧樹脂作為(B)黏結劑樹脂時，係可藉由包含(F)硬化劑而適當地控制環氧樹脂之硬化。 The conductive paste of this embodiment preferably further includes (F) a hardener. When the conductive paste of this embodiment includes epoxy resin as (B) a binder resin, the hardening of the epoxy resin can be appropriately controlled by including (F) a hardener.
(F)硬化劑係可使用公知之硬化劑。作為(F)硬化劑，較佳係包含選自酚系硬化劑、陽離子聚合起始劑、咪唑系硬化劑及三氟化硼化合物中之至少一種。作為三氟化硼化合物係可列舉三氟化硼單乙基胺、三氟化硼哌啶及三氟化硼二乙基醚等。作為(F)硬化劑，較佳係可使用三氟化硼單乙基胺。 (F) The hardener may be a known hardener. As the (F) hardener, it is preferred to include at least one selected from phenolic hardeners, cationic polymerization initiators, imidazole hardeners, and boron trifluoride compounds. Examples of the boron trifluoride compounds include boron trifluoride monoethylamine, boron trifluoride piperidine, and boron trifluoride diethyl ether. As the (F) hardener, it is preferred to use boron trifluoride monoethylamine.
就本實施型態之導電膏而言，將(A)導電性粒子及屬於(C)黏結劑樹脂之環氧樹脂的合計重量設為100重量份時，導電膏較佳係包含(F)硬化劑0.1至5重量份，以包含0.15至2重量份為更佳，以包含0.2至1重量份為再更佳，以包含0.3至0.6重量份為特佳。藉由將(F)硬化劑之重 量比例設為預定之範圍，可適當地進行屬於(B)黏結劑樹脂成分之環氧樹脂的硬化，並可獲得所希望之形狀的電極。 In the conductive paste of this embodiment, when the total weight of (A) conductive particles and the epoxy resin belonging to the binder resin (C) is set to 100 parts by weight, the conductive paste preferably contains 0.1 to 5 parts by weight of the (F) hardener, more preferably 0.15 to 2 parts by weight, even more preferably 0.2 to 1 parts by weight, and particularly preferably 0.3 to 0.6 parts by weight. By setting the weight ratio of the (F) hardener to a predetermined range, the epoxy resin belonging to the binder resin component (B) can be properly hardened, and an electrode of a desired shape can be obtained.
本實施型態之導電膏，係例如可使用擂潰機、罐式研磨機(potmill)、三輥研磨機、旋轉式混合機及/或二軸混合機等來混合上述之各成分而製造。 The conductive paste of this embodiment can be produced by mixing the above-mentioned ingredients using a pestle, pot mill, three-roller mill, rotary mixer and/or two-shaft mixer, etc.
<電極> <Electrode>
本實施型態係將上述之本實施型態的導電膏進行燒製或熱處理而得到的電極。 This embodiment is an electrode obtained by sintering or heat treating the conductive paste of the above-mentioned embodiment.
當本實施型態之導電膏包含(C)玻璃料時，係可藉由將本實施型態之導電膏以成為預定之電極圖案之方式塗佈於預定的基材案，並以較高的溫度(例如，500至900℃)在空氣環境中進行燒製，而形成電極。因此，本實施型態之導電膏包含(C)玻璃料時之電極係可含有包含表面處理金屬粒子之(A’)導電性粒子及以(C)玻璃料作為材料之(C’)玻璃成分。燒製後，(A’)導電性粒子係成為被燒結的狀態。又，將本實施型態之導電膏以較高的溫度(例如，500至900℃)進行燒製時，導電膏所包含的(B)黏結劑樹脂及(E)溶劑係於燒製之際氣化或燃燒。因此，電極係實質上不含(B)黏結劑樹脂及(E)溶劑。 When the conductive paste of this embodiment includes (C) glass frit, the conductive paste of this embodiment can be applied to a predetermined substrate in a predetermined electrode pattern and fired at a relatively high temperature (e.g., 500 to 900°C) in an air environment to form an electrode. Therefore, when the conductive paste of this embodiment includes (C) glass frit, the electrode can contain (A') conductive particles including surface-treated metal particles and (C') glass components made of (C) glass frit. After firing, the (A') conductive particles are in a sintered state. Furthermore, when the conductive paste of this embodiment is fired at a relatively high temperature (e.g., 500 to 900°C), the (B) binder resin and (E) solvent contained in the conductive paste are vaporized or burned during the firing. Therefore, the electrode is substantially free of (B) binder resin and (E) solvent.
當本實施型態之導電膏為不包含(C)玻璃料時，係可藉由將本實施型態之導電膏以成為預定之電極圖案之方式塗佈於預定的基材，並以較低的溫度(例如，100至200℃)進行燒製，而形成電極。因此，本實施型態之導電膏為不包含(C)玻璃料時之本實施型態的電極係可含有包含表面 處理金屬粒子之(A’)導電性粒子及以(B)黏結劑樹脂作為材料之(B’)黏結劑成分。(A’)導電性粒子係成為經由(B’)黏結劑成分而互相連結之狀態。 When the conductive paste of this embodiment does not contain (C) glass frit, the conductive paste of this embodiment can be applied to a predetermined substrate in a predetermined electrode pattern and fired at a relatively low temperature (e.g., 100 to 200°C) to form an electrode. Therefore, when the conductive paste of this embodiment does not contain (C) glass frit, the electrode of this embodiment can contain (A') conductive particles containing surface-treated metal particles and (B') binder components made of (B) binder resin. The (A') conductive particles are connected to each other via the (B') binder component.
本實施型態之導電膏所包含的表面處理金屬粒子因為是藉由鈀化合物來進行表面處理，故本實施型態之電極為包含鈀。本實施型態之電極係以包含0.01至10重量%之鈀為較佳，以包含0.05至5重量%之鈀為更佳，以包含0.07至1重量%之鈀為再更佳，以包含0.08至0.5重量%之鈀為特佳。又，本實施型態之導電膏包含(C)玻璃料時，本實施型態之電極係可包含源於(C)玻璃料之鈀。本實施型態之電極係包含預定量之鈀，藉此，本實施型態之電極可具有高的抗硫化性。又，電極中之鈀的含量係可以藉由EDS(能量分散型X射線分光法、Energy Dispersive X-ray Spectroscopy)進行的元素分析來進行測定。 Since the surface-treated metal particles contained in the conductive paste of this embodiment are surface-treated by a palladium compound, the electrode of this embodiment contains palladium. The electrode of this embodiment preferably contains 0.01 to 10% by weight of palladium, more preferably 0.05 to 5% by weight of palladium, even more preferably 0.07 to 1% by weight of palladium, and particularly preferably 0.08 to 0.5% by weight of palladium. Furthermore, when the conductive paste of this embodiment contains (C) glass frit, the electrode of this embodiment may contain palladium derived from the (C) glass frit. The electrode of this embodiment contains a predetermined amount of palladium, thereby the electrode of this embodiment can have high resistance to sulfidation. In addition, the palladium content in the electrode can be measured by elemental analysis using EDS (Energy Dispersive X-ray Spectroscopy).
當本實施型態之導電膏包含(C)玻璃料時，本實施型態之電極係可包含源於(C)玻璃料之鋅(氧化鋅)。本實施型態之電極藉由除了包含鈀之外還包含鋅，可獲得高的抗硫化性。 When the conductive paste of this embodiment includes (C) glass frit, the electrode of this embodiment may include zinc (zinc oxide) derived from the (C) glass frit. The electrode of this embodiment may obtain high anti-sulfurization properties by including zinc in addition to palladium.
成為本實施型態之電極的薄膜之薄片電阻(sheet resistance)係因膜厚而異，惟，大致可設為10mΩ/□(10mΩ/sguare)左右或10mΩ/□以下。因此，較佳係可使用於要求為低電阻之電極的形成。 The sheet resistance of the thin film that becomes the electrode of this embodiment varies depending on the film thickness, but can be set to about 10mΩ/□ (10mΩ/sguare) or less. Therefore, it is preferably used in the formation of electrodes that require low resistance.
其次，說明有關使用本實施型態之導電膏而在基板(基材)上形成電極之方法。首先，將導電膏塗佈於基板上。導電膏之塗佈方法為任意，例如可使用薄塗機、噴塗機、孔版印刷、網版印刷、針式轉印、或打印(stamping)等公知之方法來進行塗佈。 Next, the method of forming an electrode on a substrate (base material) using the conductive paste of this embodiment is described. First, the conductive paste is applied on the substrate. The conductive paste can be applied by any method, for example, a thin film coater, a spray coater, stencil printing, screen printing, needle transfer, or stamping, etc., which are known methods.
當本實施型態之導電膏包含(C)玻璃料時，係在基板上塗佈導電膏之後，視需要而使其乾燥，並將基板投入於燒製爐等。接著，將已塗佈在基板上之導電膏以500至900℃、更佳係600至880℃、再更佳係700至870℃來進行燒製。燒製溫度之具體例為850℃。藉此，導電膏所包含的溶劑成分係在300℃以下蒸發，樹脂成分係在400℃至600℃下被燒除，而形成導電膏之燒製體(電極)。又，在表面處理金屬粒子所包含的有機成分係因在空氣環境中之燒製而消失，鈀化合物中之鈀則係作為鈀金屬合金層(金屬粒子為銀粒子時係鈀-銀合金層)而存在於金屬粒子之表面。咸認金屬粒子表面之鈀金屬合金層會賦予金屬粒子高的抗硫化性。因此，藉由金屬粒子所包含的表面處理層為包含鈀化合物之薄膜，係可獲得高的抗硫化性。又，在表面處理層所包含的鈀之含量並不太多。因此，相較於另行添加鈀粒子之情形，係以較少的鈀之使用量即完成，故可以較低成本獲得高的抗硫化性。以如此方式所得到的電極係具有高的抗硫化性，對基板之密著性優異。 When the conductive paste of this embodiment includes (C) glass material, after the conductive paste is applied on the substrate, it is dried as needed and the substrate is placed in a firing furnace or the like. Then, the conductive paste applied on the substrate is fired at 500 to 900°C, preferably 600 to 880°C, and more preferably 700 to 870°C. A specific example of the firing temperature is 850°C. Thus, the solvent component contained in the conductive paste evaporates at below 300°C, and the resin component is fired at 400°C to 600°C, thereby forming a fired body (electrode) of the conductive paste. Furthermore, the organic components contained in the surface-treated metal particles disappear due to sintering in an air environment, and the palladium in the palladium compound exists on the surface of the metal particles as a palladium metal alloy layer (a palladium-silver alloy layer when the metal particles are silver particles). It is generally recognized that the palladium metal alloy layer on the surface of the metal particles will give the metal particles high resistance to sulfidation. Therefore, by making the surface treatment layer contained in the metal particles a thin film containing a palladium compound, high resistance to sulfidation can be obtained. Furthermore, the content of palladium contained in the surface treatment layer is not too much. Therefore, compared with the case of adding palladium particles separately, it is completed with a smaller amount of palladium, so high resistance to sulfidation can be obtained at a lower cost. The electrode obtained in this way has high resistance to sulfurization and excellent adhesion to the substrate.
當本實施型態之導電膏不包含(C)玻璃料時，係在基板上塗佈導電膏之後，將基板投入於熱處理爐等。接著，將被塗佈於基板上之導電膏以100至200℃、更佳係150至200℃進行熱處理。熱處理時間係以20至90分鐘為較佳，以30至60分鐘為更佳。熱處理條件之具體例係在150℃下進行60分鐘。藉此，使導電膏所包含的溶劑成分乾燥，並使導電膏熱硬化，藉此而可形成導電膏之硬化體(電極)。如此方式所得到的電極係具有高的抗硫化性，且對基板之密著性優異。 When the conductive paste of this embodiment does not contain (C) glass material, after the conductive paste is applied to the substrate, the substrate is placed in a heat treatment furnace. Then, the conductive paste applied to the substrate is heat treated at 100 to 200°C, preferably 150 to 200°C. The heat treatment time is preferably 20 to 90 minutes, and more preferably 30 to 60 minutes. A specific example of the heat treatment condition is 60 minutes at 150°C. In this way, the solvent components contained in the conductive paste are dried, and the conductive paste is thermally cured, thereby forming a hardened body (electrode) of the conductive paste. The electrode obtained in this way has high anti-sulfurization properties and excellent adhesion to the substrate.
當本實施型態之導電膏不含(C)玻璃料時，在本實施型態之電極中所包含的鈀之特佳的含量之例子為0.2至0.5重量%。 When the conductive paste of the present embodiment does not contain (C) glass material, an example of a particularly preferred content of palladium contained in the electrode of the present embodiment is 0.2 to 0.5 weight %.
本實施型態之導電膏作為塗膜之印刷特性優異，藉由如上所述之方法設為電極時，具有高的塗膜平滑性。若平滑性高，則塗膜之表面積會變小，受到大氣中之硫的影響之部分變少，故就抗硫化性而言為有利。又，若塗膜為平滑，則在對電極更施予鎳鍍覆等之情形下鍍覆之精度會提升。因此，塗膜之平滑性係有助於精密的電極之形成。在本說明書中，塗膜之平滑性係藉由表面粗度Ra來評估。所謂表面粗度Ra係中線平均粗度(算術平均粗度)，意指依據JIS B 0601(1994)，使用表面粗度/形狀測定機而測定出的值。電極表面之算術平均粗度(Ra)係以0.5μm以下為較佳，以0.46μm以下為更佳，以0.43μm以下為特佳。 The conductive paste of this embodiment has excellent printing properties as a coating, and when it is set as an electrode by the method described above, it has high coating smoothness. If the smoothness is high, the surface area of the coating will become smaller, and the part affected by the sulfur in the atmosphere will be reduced, so it is advantageous in terms of anti-sulfurization. In addition, if the coating is smooth, the accuracy of the coating will be improved when the electrode is further nickel-plated. Therefore, the smoothness of the coating is helpful in the formation of precise electrodes. In this specification, the smoothness of the coating is evaluated by the surface roughness Ra. The so-called surface roughness Ra is the center line average roughness (arithmetic mean roughness), which means the value measured using a surface roughness/shape measuring machine in accordance with JIS B 0601 (1994). The arithmetic mean roughness (Ra) of the electrode surface is preferably below 0.5μm, more preferably below 0.46μm, and particularly preferably below 0.43μm.
又，使用本實施型態之導電膏而以如上所述之方式得到的電極，係可具有所謂抗遷移性提昇之附帶的優點。在導電膏係包含(C)玻璃料的情形及不包含(C)玻璃料的情形這兩種情形下，可獲得該附帶的優點。惟，咸認該優點並未必為本實施型態之導電膏所必須之效果，而為一個優點。 Furthermore, the electrode obtained by using the conductive paste of this embodiment in the manner described above can have the incidental advantage of improved anti-migration properties. This incidental advantage can be obtained in both the case where the conductive paste contains (C) glass frit and the case where it does not contain (C) glass frit. However, it is generally recognized that this advantage is not necessarily a necessary effect of the conductive paste of this embodiment, but is an advantage.
<電子零件或電子器材> <Electronic parts or electronic equipment>
本實施型態係具有上述電極的電子零件或電子器材。在本說明書中，所謂的電子零件係意指晶片電阻器及基板電路等被使用於電子器材等之零件。在本說明書中，所謂電子零件係意指電性驅動之零件，具體而言，係可為以48V以下之直流電運作之零件。在本說明書中，所謂電子器材係意指包含具有本實施型態之電極的電子零件之器材。 This embodiment is an electronic component or electronic equipment having the above-mentioned electrode. In this specification, the so-called electronic component means a chip resistor and a substrate circuit and other components used in electronic equipment. In this specification, the so-called electronic component means an electrically driven component, specifically, a component that can be operated with a direct current of less than 48V. In this specification, the so-called electronic equipment means equipment including an electronic component having an electrode of this embodiment.
本實施型態之導電膏係能夠使用於電子零件或電子器材之電路的形成、電極之形成及電子零件等元件(例如，半導體晶片)對基板(基材)之接合等。 The conductive paste of this embodiment can be used for forming circuits of electronic parts or electronic devices, forming electrodes, and bonding electronic parts and other components (for example, semiconductor chips) to substrates (base materials).
本實施型態之導電膏較佳係可使用於晶片電阻器之電極的形成。在圖1，係表示本實施型態之晶片電阻器100的剖面構造之一個例子。晶片電阻器100係可具有矩形之氧化鋁基板102、及配置於氧化鋁基板102之表面的電阻體104及取出電極106。取出電極106係用以從電阻體104汲取電力之電極。又，在氧化鋁基板102之下面係可配置用以將晶片電阻器100裝設至基板之下面電極108。再者，可將用以連接取出電極106與下面電極108之連接電極110配置於氧化鋁基板102之端面。使用本實施型態之導電膏，可形成取出電極106、下面電極108及連接電極110之至少一者。尤其，取出電極106較佳係使用本實施型態之導電膏而形成。又，可在取出電極106、下面電極108及連接電極110之上面(與氧化鋁基板102為相反側之表面)，配置鎳鍍覆膜112及錫鍍覆膜114。 The conductive paste of this embodiment can be preferably used for forming electrodes of a chip resistor. FIG1 shows an example of a cross-sectional structure of a chip resistor 100 of this embodiment. The chip resistor 100 may have a rectangular alumina substrate 102, and a resistor 104 and an extraction electrode 106 arranged on the surface of the alumina substrate 102. The extraction electrode 106 is an electrode for drawing power from the resistor 104. In addition, a lower electrode 108 for mounting the chip resistor 100 on the substrate may be arranged under the alumina substrate 102. Furthermore, a connecting electrode 110 for connecting the extraction electrode 106 and the lower electrode 108 may be arranged on the end surface of the alumina substrate 102. Using the conductive paste of this embodiment, at least one of the extraction electrode 106, the lower electrode 108, and the connecting electrode 110 can be formed. In particular, the extraction electrode 106 is preferably formed using the conductive paste of this embodiment. In addition, a nickel-plated film 112 and a tin-plated film 114 can be arranged on the upper surface (the surface opposite to the alumina substrate 102) of the extraction electrode 106, the lower electrode 108, and the connecting electrode 110.
本實施型態之電極並不侷限於晶片電阻器之電極。使用本實施型態之導電膏所形成的電極係可使用來作為各種種類之電子零件的電極。作為電子零件係可列舉被動零件(例如，晶片電阻器、電容器、電阻器及電感器(inductor)等)、電路基板[例如，在氧化鋁基板、氮化鋁基板及玻璃基板等之基板之上形成預定之電路(電極或配線)者]、太陽電池單元及電磁波屏蔽等。使用本實施型態之導電膏，可形成此等電子零件之電極及/或配線。本實施型態之包含具有電極的電子零件之電子器材係可列舉半導 體裝置、太陽光電模組(Solar Photovoltaic Module)及包含電路基板之電子器材。 The electrodes of this embodiment are not limited to the electrodes of chip resistors. The electrodes formed using the conductive paste of this embodiment can be used as electrodes of various types of electronic components. Examples of electronic components include passive components (e.g., chip resistors, capacitors, resistors, and inductors), circuit substrates [e.g., those with predetermined circuits (electrodes or wiring) formed on substrates such as alumina substrates, aluminum nitride substrates, and glass substrates], solar cell units, and electromagnetic wave shielding, etc. The conductive paste of this embodiment can be used to form electrodes and/or wiring of these electronic components. The electronic equipment including the electronic parts with electrodes in this embodiment can be exemplified by semiconductor devices, solar photovoltaic modules, and electronic equipment including circuit substrates.
本實施型態之導電膏係可使用來作為在半導體裝置中用以安裝半導體晶片之黏晶(die attach)材。當半導體裝置為功率半導體(power semiconductor)裝置時，本實施型態之導電膏係可使用來作為用以安裝功率半導體晶片之蠟材。本實施型態之導電膏係可使用來作為太陽電池之電極。本實施型態之導電膏係可使用來作為導電性接著劑。又，本實施型態之導電膏並不侷限於形成晶片電阻器之端子電極，而例如亦可適合使用來作為MLCC、晶片電感器(chip inductor)等被動零件的端子電極用之導電膏。 The conductive paste of this embodiment can be used as a die attach material for mounting a semiconductor chip in a semiconductor device. When the semiconductor device is a power semiconductor device, the conductive paste of this embodiment can be used as a wax material for mounting a power semiconductor chip. The conductive paste of this embodiment can be used as an electrode of a solar cell. The conductive paste of this embodiment can be used as a conductive adhesive. In addition, the conductive paste of this embodiment is not limited to forming the terminal electrode of a chip resistor, but can also be used as a conductive paste for the terminal electrode of passive parts such as MLCC and chip inductors.
藉由使用本實施型態之導電膏，可形成具有高的抗硫化性，且為低電阻、較低成本之電極。因此，藉由使用本實施型態之導電膏，可以較低的成本獲得形成有高可靠性的電極之晶片電阻器等電子零件。 By using the conductive paste of this embodiment, an electrode with high anti-sulfurization, low resistance and low cost can be formed. Therefore, by using the conductive paste of this embodiment, electronic parts such as chip resistors with electrodes with high reliability can be obtained at a relatively low cost.
[實施例] [Implementation example]
以下，係藉由實施例具體地說明本發明，但本發明並非受此等所限定者。 The present invention is specifically described below through examples, but the present invention is not limited thereto.
[導電膏之調製] [Preparation of conductive paste]
使下列之(A)至(F)成分以表1至3所示的比例進行混合，而調製成導電膏。又，在表1至3所示的各成分之比例，皆係以重量份表示。在表1至3中，係將(A)導電性粒子之重量(金屬粒子及表面處理金屬粒子之合計重量)設為100重量份。又，平均粒徑係意指藉由雷射繞射散射式粒度分布測定法所得到的體積基準中值徑(D50)。 The following components (A) to (F) are mixed in the proportions shown in Tables 1 to 3 to prepare a conductive paste. In addition, the proportions of the components shown in Tables 1 to 3 are all expressed in parts by weight. In Tables 1 to 3, the weight of the conductive particles (A) (the total weight of the metal particles and the surface-treated metal particles) is set to 100 parts by weight. In addition, the average particle size refers to the volume-based median diameter (D50) obtained by the laser diffraction scattering particle size distribution measurement method.
(A)導電性粒子 (A) Conductive particles
在表4中，係表示使用來作為實施例及比較例之(A)導電性粒子((A)成分)的金屬粒子a1至a4及表面處理金屬粒子A1至A6。金屬粒子a1及a2為銀粒子，金屬粒子a4為鈀粒子。金屬粒子a1至a4係未經表面處理。表面處理金屬粒子A1至A6係對屬於金屬粒子之銀粒子進行了表面處理，該表面處理係藉由使於溶劑中分散有鈀化合物之鈀皂溶劑(表面處理劑)附著於金屬粒子之表面，並藉由乾燥步驟去除溶劑而進行。因此，表面處理金屬粒子A1至A6係具有包含鈀化合物之表面處理層。在表4之「Pd含量」的欄位中，係以重量%為單位來表示表面處理層所包含的鈀之重量相對於表面處理金屬粒子A1至A6之重量的比例。表面處理金屬粒子中之鈀的重量比例係藉由ICP發光分光分析法(高頻感應耦合電漿光學發射光譜分析法)進行測定。 Table 4 shows metal particles a1 to a4 and surface-treated metal particles A1 to A6 used as (A) conductive particles ((A) component) of examples and comparative examples. Metal particles a1 and a2 are silver particles, and metal particle a4 is a palladium particle. Metal particles a1 to a4 are not surface-treated. Surface-treated metal particles A1 to A6 are silver particles that are metal particles and are surface-treated by attaching a palladium soap solvent (surface treatment agent) in which a palladium compound is dispersed in a solvent to the surface of the metal particles and removing the solvent by a drying step. Therefore, surface-treated metal particles A1 to A6 have a surface treatment layer containing a palladium compound. In the "Pd content" column of Table 4, the weight of palladium contained in the surface treatment layer relative to the weight of the surface treated metal particles A1 to A6 is expressed in weight %. The weight ratio of palladium in the surface treated metal particles is measured by ICP emission spectrometry (high frequency inductively coupled plasma optical emission spectroscopy).
鈀化合物對銀粒子之表面處理係以如下方式進行。亦即，鈀化合物對銀粒子之表面處理係使用鈀皂溶劑(表面處理劑)來進行，該鈀皂溶劑包含：鈀化合物、用以使此等分散之有機物、及溶劑。表面處理係使鈀皂溶劑(表面處理劑)附著於銀粒子之表面，並藉由乾燥步驟去除溶劑而進行。鈀化合物係使用氯化鈀。再者，銀粒子之表面處理劑所包含的溶劑係使用油酸。以如上所述的方式，在表面處理金屬粒子A1至A6形成表面處理層。 The surface treatment of silver particles with palladium compounds is performed as follows. That is, the surface treatment of silver particles with palladium compounds is performed using a palladium soap solvent (surface treatment agent), which contains: a palladium compound, an organic substance for dispersing these, and a solvent. The surface treatment is performed by attaching the palladium soap solvent (surface treatment agent) to the surface of the silver particles and removing the solvent by a drying step. The palladium compound used is palladium chloride. Furthermore, the solvent contained in the surface treatment agent of the silver particles is oleic acid. In the manner described above, a surface treatment layer is formed on the surface-treated metal particles A1 to A6.
(B)黏結劑樹脂 (B) Adhesive resin
在表5中，係表示在實施例及比較例所使用之(B)黏結劑樹脂(樹脂B1至B5)。在表1至3中，表示實施例及比較例之導電膏的樹脂B1至B5之調配量。 Table 5 shows the (B) adhesive resins (resins B1 to B5) used in the embodiments and comparative examples. Tables 1 to 3 show the formulation amounts of resins B1 to B5 in the conductive pastes of the embodiments and comparative examples.
(C)玻璃料 (C) Glass frit
在表6中，表示在實施例及比較例所使用的(C)玻璃料(C1至C5)。在表1至3中，係表示實施例及比較例之導電膏的玻璃料C1至C5之調配量。 Table 6 shows the (C) glass materials (C1 to C5) used in the embodiments and comparative examples. Tables 1 to 3 show the mixing amounts of glass materials C1 to C5 in the conductive pastes of the embodiments and comparative examples.
(D)添加劑 (D) Additives
在表7中，係表示在實施例及比較例所使用的(D)添加劑(添加劑D1至D3)。在表1至3中，係表示實施例及比較例之導電膏的添加劑D1至D3之調配量。添加劑D1為有機添加劑。藉由添加添加劑D1，可提升導電膏之印刷性。添加劑D2為分散劑。藉由添加添加劑D2，可提升(A)導電性粒子等之分散性。添加劑D3為無機添加劑。藉由添加添加劑D3，可提升導電膏在燒製後之密著性。 Table 7 shows the (D) additives (additives D1 to D3) used in the embodiments and comparative examples. Tables 1 to 3 show the amounts of additives D1 to D3 in the conductive pastes of the embodiments and comparative examples. Additive D1 is an organic additive. By adding additive D1, the printability of the conductive paste can be improved. Additive D2 is a dispersant. By adding additive D2, the dispersibility of (A) conductive particles, etc. can be improved. Additive D3 is an inorganic additive. By adding additive D3, the adhesion of the conductive paste after firing can be improved.
(E)溶劑 (E)Solvent
在表8中，係表示在實施例及比較例所使用的(E)溶劑(溶劑E1至E3)。在表1至3中，係表示實施例及比較例之導電膏的溶劑E1至E3之調配量。 Table 8 shows the (E) solvents (solvents E1 to E3) used in the embodiments and comparative examples. Tables 1 to 3 show the amounts of solvents E1 to E3 in the conductive pastes of the embodiments and comparative examples.
(F)硬化劑 (F) Hardener
在實施例及比較例之導電膏，係使用三氟化硼單乙基胺(STELLA CHEMIFA股份有限公司、型號：BF3MEA)作為(F)硬化劑F1。在表1至3中，係表示實施例及比較例之導電膏的硬化劑F1之調配量。 In the conductive paste of the embodiment and the comparative example, boron trifluoride monoethylamine (STELLA CHEMIFA Co., Ltd., model: BF3MEA) is used as (F) hardener F1. Tables 1 to 3 show the formulation amount of hardener F1 of the conductive paste of the embodiment and the comparative example.
[抗硫化性試驗之試驗片50之製作] [Preparation of test piece 50 for anti-sulfurization test]
在圖2，係表示抗硫化性試驗之試驗片50的示意圖。使用包含(C)玻璃料之導電膏，依以下之程序，製作實施例1至16及比較例1至5之抗硫化性試驗的試驗片50。 FIG2 is a schematic diagram of a test piece 50 for the anti-sulfurization test. The test pieces 50 for the anti-sulfurization test of Examples 1 to 16 and Comparative Examples 1 to 5 were prepared using a conductive paste containing (C) glass frit according to the following procedure.
首先，在20mm×20mm×1mm(t)之抗硫化性試驗用氧化鋁基板52(純度96%)上，藉由網版印刷，以成為如圖2所示的曲折(zigzag)狀之抗硫化性試驗用印刷圖案54的方式塗佈導電膏。抗硫化性試驗用印刷圖案54之2個端部54a、54b之間的長度為71mm，抗硫化性試驗用印刷圖案54之寬度為1mm。為了形成導電膏之抗硫化性試驗用印刷圖案54，係使用不鏽鋼製之325網目的網版(乳劑厚度5μm)而進行網版印刷。其次，使用批次式之熱風式乾燥機，在150℃下使導電膏之抗硫化性試驗用印刷圖案54乾燥10分鐘。使導電膏之抗硫化性試驗用印刷圖案54乾燥之後，使用輸送帶式之燒製爐，燒製抗硫化性試驗用印刷圖案54。燒製溫度係在850℃下保持10分鐘。從置入於燒製爐之後起算直到取出為止之合計時間為60分鐘。以如上所述方式，製作實施例1至16及比較例1至5之試驗片50。 First, a conductive paste is applied by screen printing on an anti-sulfurization test alumina substrate 52 (purity 96%) of 20 mm × 20 mm × 1 mm (t) to form a zigzag anti-sulfurization test printed pattern 54 as shown in FIG. 2 . The length between the two ends 54a and 54b of the anti-sulfurization test printed pattern 54 is 71 mm, and the width of the anti-sulfurization test printed pattern 54 is 1 mm. In order to form the anti-sulfurization test printed pattern 54 of the conductive paste, a 325 mesh screen (emulsion thickness 5 μm) made of stainless steel is used for screen printing. Next, a batch hot air dryer is used to dry the anti-sulfurization test printed pattern 54 of the conductive paste at 150°C for 10 minutes. After drying the printed pattern 54 for the anti-sulfurization test of the conductive paste, a conveyor-type firing furnace is used to fire the printed pattern 54 for the anti-sulfurization test. The firing temperature is maintained at 850°C for 10 minutes. The total time from the time of placement in the firing furnace until removal is 60 minutes. In the manner described above, the test pieces 50 of Examples 1 to 16 and Comparative Examples 1 to 5 are prepared.
對於使用不含(C)玻璃料之導電膏的實施例17至19，係以與實施例1至16及比較例1至5相同方式，使用實施例17至19之導電膏，在20mm×20mm×1mm(t)之抗硫化性試驗用氧化鋁基板52(純度96%)上，藉由網版印刷而以成為寬度1mm及長度71mm之曲折狀抗硫化性試驗用印刷圖案54(參照圖2)之方式，塗佈導電膏。其次，使用批次式之熱風式乾燥機，在150℃下將導電膏之抗硫化性試驗用印刷圖案54進行熱處理10 分鐘，藉此使抗硫化性試驗用印刷圖案54硬化。以如上所述方式，製作出實施例17至19之試驗片50。 For Examples 17 to 19 using a conductive paste without (C) glass frit, the conductive paste of Examples 17 to 19 was applied on a 20 mm × 20 mm × 1 mm (t) anti-sulfurization test aluminum oxide substrate 52 (purity 96%) by screen printing in the same manner as Examples 1 to 16 and Comparative Examples 1 to 5 to form a zigzag anti-sulfurization test printed pattern 54 (see FIG. 2 ) with a width of 1 mm and a length of 71 mm. Next, the conductive paste anti-sulfurization test printed pattern 54 was heat-treated at 150°C for 10 minutes using a batch hot air dryer to harden the anti-sulfurization test printed pattern 54. In the above manner, the test pieces 50 of Examples 17 to 19 were produced.
[抗硫化性試驗方法] [Anti-sulfurization test method]
首先，測定實施例及比較例之試驗片的印刷圖案54的2個端部54a、54b之間的電阻(初期電阻)。然後，將以平坦地放入有硫粉10g的培養皿(高度18mm、直徑86mm)置入於玻璃製之乾燥器(desiccator)(高度420mm、直徑300mm)之底部，在中蓋之上載置實施例及比較例之試驗片。將該乾燥器在恆定於60℃之恆溫槽中保管150小時而使試驗片硫化。其次，測定硫化後之電性電阻。在表1至3之「電阻值變化比例(抗硫化性試驗)」的欄位中，係以百分比單位來表示硫化後之電阻相對於實施例及比較例之初期電阻的電阻值變化比例。電阻值變化比例係可以下述之式表示。 First, measure the resistance (initial resistance) between the two ends 54a and 54b of the printed pattern 54 of the test piece of the embodiment and comparative example. Then, place a culture dish (height 18mm, diameter 86mm) with 10g of sulfur powder flatly in the bottom of a glass desiccator (height 420mm, diameter 300mm), and place the test piece of the embodiment and comparative example on the middle cover. The desiccator is kept in a constant temperature bath at 60°C for 150 hours to vulcanize the test piece. Next, measure the electrical resistance after vulcanization. In the column "Resistance value change ratio (anti-sulfurization test)" of Tables 1 to 3, the resistance value change ratio of the resistance after vulcanization relative to the initial resistance of the embodiment and comparative example is expressed in percentage units. The resistance value change ratio can be expressed by the following formula.
電阻值變化比例=(硫化後之電阻-初期電阻)/初期電阻 Resistance value change ratio = (resistance after vulcanization - initial resistance) / initial resistance
[接著強度試驗之試驗片的製作] [Next, preparation of test pieces for strength test]
使用所調製的導電膏，依下列之程序，製作包含(C)玻璃料之實施例1至16及比較例1至5的試驗片。首先，在20mm×20mm×1mm(t)之氧化鋁基板(純度96%)上，藉由網版印刷塗佈導電膏。藉此，在氧化鋁基板上形成25個(5個×5個)之接著強度試驗用圖案，該接著強度試驗用圖案係由一邊為1.5mm之方墊形狀所構成者。為了形成導電膏之接著強度試驗用圖案，係使用不鏽鋼製之325網目的網版(乳劑厚度5μm)來進行網版印刷。 Using the prepared conductive paste, test pieces of Examples 1 to 16 and Comparative Examples 1 to 5 containing (C) glass material were prepared according to the following procedure. First, the conductive paste was applied on a 20mm×20mm×1mm(t) alumina substrate (purity 96%) by screen printing. Thus, 25 (5×5) bonding strength test patterns were formed on the alumina substrate, and the bonding strength test pattern was composed of a square pad shape with a side of 1.5mm. In order to form the bonding strength test pattern of the conductive paste, a 325 mesh screen made of stainless steel (emulsion thickness 5μm) was used for screen printing.
其次，使用批次式之熱風式乾燥機，在150℃下將導電膏乾燥10分鐘。使導電膏之接著強度試驗用圖案乾燥之後，使用輸送帶式之燒製爐來燒製導電膏之接著強度試驗用圖案。燒製溫度係在850℃下保持10 分鐘。從置入於燒製爐之後起算直到取出為止之合計時間為60分鐘。以如上所述方式，製作實施例1至16及比較例1至5之試驗片。 Next, a batch hot air dryer was used to dry the conductive paste at 150°C for 10 minutes. After the conductive paste was dried, a conveyor-type firing furnace was used to fire the conductive paste. The firing temperature was maintained at 850°C for 10 minutes. The total time from placement in the firing furnace until removal was 60 minutes. Test pieces of Examples 1 to 16 and Comparative Examples 1 to 5 were prepared as described above.
其次，在接著強度試驗用圖案進行Ni/Au鍍覆。然後，使焊料(千住金屬工業股份有限公司製M705、含Sn-Ag 3.0重量%及Cu 0.5重量%之Sn合金)在260℃下附著於接著強度試驗用圖案3秒鐘之後，使鍍Sn軟銅線(直徑0.8mm)焊接於接著強度試驗用圖案。又，鍍Sn軟銅線之焊接係藉由下述方式進行：在氧化鋁基板上之5個×5個接著強度試驗用圖案當中，對於第2列之5個接著強度試驗用圖案分別焊接1條、合計5條之鍍Sn軟銅線，對於第4列之5個接著強度試驗用圖案分別焊接各1條、合計5條之鍍Sn軟銅線。焊接合計10條之鍍Sn軟銅線，並以強度試驗機測定導線之拉伸接著強度。具體而言，以接著強度試驗用圖案成為上面之方式，將氧化鋁基板以相對於強度試驗機呈90度之角度的方式垂直地設置，並將導線往相對於氧化鋁基板呈垂直地朝上方向拉伸，藉此測定拉伸接著強度。將導線被剝離時之力(N)設為拉伸接著強度。 Next, the pattern for the strength test was Ni/Au plated. Then, solder (M705 manufactured by Senju Metal Industries, Ltd., a Sn alloy containing 3.0 wt% Sn-Ag and 0.5 wt% Cu) was attached to the pattern for the strength test at 260°C for 3 seconds, and then a Sn-plated soft copper wire (0.8 mm in diameter) was soldered to the pattern for the strength test. Furthermore, the Sn-plated soft copper wire was welded in the following manner: among the 5×5 bonding strength test patterns on the alumina substrate, one Sn-plated soft copper wire was welded to each of the 5 bonding strength test patterns in the second row, for a total of 5 wires, and one Sn-plated soft copper wire was welded to each of the 5 bonding strength test patterns in the fourth row, for a total of 5 wires. A total of 10 Sn-plated soft copper wires were welded, and the tensile bonding strength of the wire was measured using a strength tester. Specifically, the alumina substrate was vertically set at an angle of 90 degrees relative to the strength tester in a manner such that the bonding strength test pattern became the upper side, and the wire was stretched in a vertically upward direction relative to the alumina substrate to measure the tensile bonding strength. The force (N) at which the wire is peeled off is set as the tensile strength.
以與實施例1至16及比較例1至5之試驗片相同方式，使用調製作為實施例17至19的導電膏，在20mm×20mm×1mm(t)之氧化鋁基板(純度96%)上，藉由網版印刷塗佈導電膏。藉此，在氧化鋁基板上形成25個(5個×5個)接著強度試驗用圖案，該接著強度試驗用圖案係由一邊為1.5mm之方墊形狀所構成者。其次，使用熱風式乾燥機，在150℃下熱處理導電膏10分鐘，藉此使導電膏之接著強度試驗用圖案硬化。以如上所述方式，製作實施例17至19之試驗片。然後，以與實施例1至16及比較例1至5相同方式，在實施例17至19之接著強度試驗用圖案進行Ni /Au鍍覆。繼而，以與實施例1至16及比較例1至5之試驗片相同方式，將鍍Sn軟銅線(導線)焊接於接著強度試驗用圖案，並以強度試驗機測定導線之拉伸接著強度。 In the same manner as the test pieces of Examples 1 to 16 and Comparative Examples 1 to 5, the conductive paste prepared as Examples 17 to 19 was applied by screen printing on a 20 mm × 20 mm × 1 mm (t) alumina substrate (purity 96%). In this way, 25 (5 × 5) bonding strength test patterns were formed on the alumina substrate, and the bonding strength test patterns were composed of square pads with a side of 1.5 mm. Next, the conductive paste was heat-treated at 150°C for 10 minutes using a hot air dryer to harden the conductive paste bonding strength test patterns. Test pieces of Examples 17 to 19 were prepared in the manner described above. Then, Ni /Au plating was performed on the bonding strength test pattern of Examples 17 to 19 in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 5. Then, Sn-plated soft copper wire (conductor) was welded to the bonding strength test pattern in the same manner as in the test pieces of Examples 1 to 16 and Comparative Examples 1 to 5, and the tensile bonding strength of the conductor was measured by a strength tester.
藉由針對各實施例及各比較例之10個試驗片測定拉伸接著強度，獲得接著強度試驗之結果。在表1至3之「接著強度(N)」的欄位中，表示以如上述方式所測定出的各實施例及各比較例之10個試驗片的拉伸接著強度之平均值。 The results of the bonding strength test were obtained by measuring the tensile bonding strength of 10 test pieces of each embodiment and each comparative example. In the column of "bonding strength (N)" in Tables 1 to 3, the average value of the tensile bonding strength of the 10 test pieces of each embodiment and each comparative example measured in the above manner is shown.
[抗遷移試驗] [Anti-migration test]
在圖3中，係表示抗遷移試驗之試驗片60的一例之試驗用印刷圖案64a、64b之光學顯微鏡照片。使用所調製出的導電膏，依下列之程序，製作出實施例1、3及17至19及比較例1之抗遷移試驗的試驗片60。 FIG3 shows an optical microscope photograph of the test printed patterns 64a and 64b of an example of a test piece 60 for anti-migration test. The prepared conductive paste was used to produce the test piece 60 for anti-migration test of Examples 1, 3, 17 to 19 and Comparative Example 1 according to the following procedure.
實施例1、3及比較例1之抗遷移試驗之試驗片60係依下列之程序製作出。首先，在110mm×20mm×0.8mm(t)之抗遷移試驗用氧化鋁基板62(純度96%)上，藉由網版印刷，如圖3、及屬於圖3之放大照片的圖4所示般，以2個梳型抗遷移試驗用印刷圖案64a、64b呈互相錯開之方式塗佈導電膏。抗遷移試驗用印刷圖案64a係連接於第1電極66a，抗遷移試驗用印刷圖案64b係連接於第2電極66b。抗遷移試驗用印刷圖案64a、64b之印刷寬度L為200μm，抗遷移試驗用印刷圖案64a、64b之間的間隙S為200μm。為了形成導電膏之抗遷移試驗用印刷圖案64a、64b及電極66a、66b，係使用不鏽鋼製之400網目的網版(乳劑厚度10μm)來進行網版印刷。其次，使用批次式之熱風式乾燥機，在150℃下使導電膏之抗遷移試驗用印刷圖案64a、64b及電極66a、66b乾燥10分鐘。使導 電膏之抗遷移試驗用印刷圖案64a、64b及電極66a、66b乾燥之後，使用輸送帶式之燒製爐，燒製出抗遷移試驗用印刷圖案64a、64b及電極66a、66b。燒製溫度係在850℃下保持10分鐘。從置入於燒製爐之後起算直到取出為止之合計時間為60分鐘。燒製後之抗遷移試驗用印刷圖案64a、64b及電極66a、66b的厚度為10至20μm。以如上所述方式，製作實施例1至16及比較例1至5之抗遷移試驗的試驗片60。 The test piece 60 for the anti-migration test of Examples 1, 3 and Comparative Example 1 was manufactured according to the following procedure. First, on an alumina substrate 62 (purity 96%) for the anti-migration test of 110 mm×20 mm×0.8 mm (t), a conductive paste was applied by screen printing in a manner that two comb-shaped anti-migration test printed patterns 64a and 64b were staggered, as shown in FIG3 and FIG4 which is an enlarged photograph of FIG3. The anti-migration test printed pattern 64a was connected to the first electrode 66a, and the anti-migration test printed pattern 64b was connected to the second electrode 66b. The printing width L of the anti-migration test patterns 64a and 64b is 200 μm, and the gap S between the anti-migration test patterns 64a and 64b is 200 μm. In order to form the anti-migration test patterns 64a and 64b of the conductive paste and the electrodes 66a and 66b, a 400-mesh stainless steel screen (emulsion thickness 10 μm) is used for screen printing. Next, a batch hot air dryer is used to dry the anti-migration test patterns 64a and 64b of the conductive paste and the electrodes 66a and 66b at 150°C for 10 minutes. After drying the printed patterns 64a, 64b and electrodes 66a, 66b of the conductive paste for anti-migration test, a conveyor-type firing furnace is used to fire the printed patterns 64a, 64b and electrodes 66a, 66b for anti-migration test. The firing temperature is maintained at 850°C for 10 minutes. The total time from placement in the firing furnace to removal is 60 minutes. The thickness of the printed patterns 64a, 64b and electrodes 66a, 66b for anti-migration test after firing is 10 to 20 μm. In the manner described above, the test piece 60 for the anti-migration test of Examples 1 to 16 and Comparative Examples 1 to 5 is prepared.
實施例17至19之抗遷移試驗的試驗片60係依下列之程序製作。首先，以與實施例1、3及比較例1之試驗片60相同方式，在110mm×20mm×0.8mm(t)之抗遷移試驗用氧化鋁基板62(純度96%)上，藉由網版印刷，如圖3及圖4所示般，以2個梳型抗遷移試驗用印刷圖案64a、64b呈互相錯開之方式塗佈導電膏。其次，使用熱風式乾燥機，在200℃下熱處理導電膏30分鐘，藉此使導電膏之接著強度試驗用圖案硬化。以如上所述之方式，製作實施例17至19之抗遷移試驗用的試驗片。 The test pieces 60 for the anti-migration test of Examples 17 to 19 are made according to the following procedure. First, in the same manner as the test pieces 60 of Examples 1, 3 and Comparative Example 1, on an alumina substrate 62 (purity 96%) for anti-migration test of 110 mm × 20 mm × 0.8 mm (t), two comb-shaped anti-migration test printed patterns 64a, 64b are applied by screen printing in a staggered manner as shown in Figures 3 and 4. Secondly, the conductive paste is heat-treated at 200°C for 30 minutes using a hot air dryer to harden the conductive paste's bonding strength test pattern. The test pieces for the anti-migration test of Examples 17 to 19 are made in the manner described above.
依下列之程序測定實施例1、3及17至19以及比較例1之試驗片60的抗遷移試驗用印刷圖案64a、64b之抗遷移性。首先，如圖3所示般，於2個抗遷移試驗用印刷圖案64a、64b之第1電極66a、與第2電極66b之間施加電壓(40V)。以保管在溫度85℃及濕度85%之環境的狀態，測定第1電極66a與第2電極66b之間的絕緣電阻值。從在第1電極66a與第2電極66b之間流動的電流之測定值及施加電壓40V算出絕緣電阻值。將經施加施加電壓40V之試驗片60保持在最長487小時、溫度85℃及濕度85%之環境下。在表9中，係表示抗遷移試驗之結果。試驗前係全部之試料的絕緣電阻值均為107Ω以上。將在10小時以內絕緣電阻值成 為106Ω以下之試驗片60判斷為不良，並在表9記載為「不良」。就即使經過80小時絕緣電阻值亦不成為106Ω以下之試驗片60而言，因抗遷移性係優異至一定程度，判斷為能夠視用途而使用，而在表9記載為「可使用」。即使經過487小時絕緣電阻值亦不成為106Ω以下之試驗片60，係判斷為抗遷移性優異，而在表9記載為「良」。 The anti-migration properties of the anti-migration test printed patterns 64a and 64b of the test piece 60 of Examples 1, 3, and 17 to 19 and Comparative Example 1 were measured according to the following procedure. First, as shown in FIG3 , a voltage (40V) was applied between the first electrode 66a and the second electrode 66b of the two anti-migration test printed patterns 64a and 64b. The insulation resistance value between the first electrode 66a and the second electrode 66b was measured in a state of being stored in an environment of a temperature of 85°C and a humidity of 85%. The insulation resistance value was calculated from the measured value of the current flowing between the first electrode 66a and the second electrode 66b and the applied voltage of 40V. The test piece 60 to which a voltage of 40V was applied was kept in an environment of 85°C and 85% humidity for a maximum of 487 hours. Table 9 shows the results of the anti-migration test. Before the test, the insulation resistance values of all the samples were above 10 7 Ω. The test piece 60 whose insulation resistance value became below 10 6 Ω within 10 hours was judged as defective and recorded as "defective" in Table 9. For the test piece 60 whose insulation resistance value did not become below 10 6 Ω even after 80 hours, because the anti-migration property was excellent to a certain extent, it was judged that it could be used according to the purpose, and it was recorded as "usable" in Table 9. Even after 487 hours, the insulation resistance of test piece 60 did not become less than 10 6 Ω, which was judged to have excellent anti-migration properties and was recorded as "good" in Table 9.
在圖7，係表示經進行抗遷移試驗時之實施例1、實施例3、及比較例1的絕緣電阻值之經時變化。被判斷為抗遷移性優異的實施例3之試驗片60(在表9中，記載為「良」)即使經過了480小時，絕緣電阻值亦不成為106Ω以下。因為抗遷移性優異至一定程度而被判斷為能夠視用途而使用之實施例1的試驗片60(在表9中，記載為「可使用」者)，其絕緣電阻值係即使經過80小時亦不成為106Ω以下者。被判斷為抗遷移性差之比較例1的試驗片60(在表9中，記載為「不良」)的絕緣電阻值係在10小時以內成為106Ω以下。 FIG7 shows the time-dependent changes in the insulation resistance values of Example 1, Example 3, and Comparative Example 1 during the anti-migration test. The insulation resistance value of the test piece 60 of Example 3, which was judged to be excellent in anti-migration (recorded as "good" in Table 9), did not become less than 10 6 Ω even after 480 hours. The insulation resistance value of the test piece 60 of Example 1, which was judged to be usable depending on the purpose because of its excellent anti-migration to a certain extent (recorded as "usable" in Table 9), did not become less than 10 6 Ω even after 80 hours. The insulation resistance value of the test piece 60 of Comparative Example 1 judged to have poor anti-migration properties (described as "bad" in Table 9) became less than 10 6 Ω within 10 hours.
[焊料耐熱性試驗] [Solder heat resistance test]
使用所調製之導電膏，依下列程序，製作出包含(C)玻璃料之實施例1至16及比較例1至5的焊料耐熱性試驗用之試驗片。 Using the prepared conductive paste, test pieces for solder heat resistance tests of Examples 1 to 16 and Comparative Examples 1 to 5 containing (C) glass frit were prepared according to the following procedure.
首先，在20mm×20mm×1mm(t)之氧化鋁基板(純度96%)上，藉由網版印刷塗佈導電膏。藉此，在氧化鋁基板上形成25個(5個×5個)接著強度試驗用圖案，該接著強度試驗用圖案係由一邊為1.5mm之方墊形狀所構成。為了形成導電膏之接著強度試驗用圖案，係使用不鏽鋼製之325網目的網版(乳劑厚度5μm)而進行網版印刷。 First, a conductive paste was applied by screen printing on an alumina substrate (purity 96%) of 20mm×20mm×1mm(t). Thus, 25 (5×5) bonding strength test patterns were formed on the alumina substrate. The bonding strength test pattern consisted of a square pad shape with a side of 1.5mm. In order to form the bonding strength test pattern of the conductive paste, a 325 mesh screen (emulsion thickness 5μm) made of stainless steel was used for screen printing.
其次，使用批次式之熱風式乾燥機，以150℃使乾燥導電膏10分鐘。使導電膏之接著強度試驗用圖案乾燥之後，使用輸送帶式之燒製爐，燒製導電膏之接著強度試驗用圖案。燒製溫度係在850℃下保持10分鐘。從置入於燒製爐之後起算直到取出為止之合計時間為60分鐘。以如上所述之方式，製作實施例1至16及比較例1至5之試驗片。 Next, a batch hot air dryer was used to dry the conductive paste at 150°C for 10 minutes. After the conductive paste bonding strength test pattern was dried, a conveyor belt type firing furnace was used to fire the conductive paste bonding strength test pattern. The firing temperature was maintained at 850°C for 10 minutes. The total time from placement in the firing furnace until removal was 60 minutes. The test pieces of Examples 1 to 16 and Comparative Examples 1 to 5 were prepared in the manner described above.
以與實施例1至16及比較例1至5之焊料耐熱性試驗用的試驗片為相同方式，使用不含(C)玻璃料之導電膏，製作出實施例17至19之焊料耐熱性試驗用之試驗片。惟，對於實施例17至19之試驗片，係使用熱風式乾燥機在150℃下將熱處理導電膏10分鐘，取代導電膏之接著強度試驗用圖案之乾燥及燒製，藉此使導電膏之接著強度試驗用圖案硬化。 In the same manner as the test pieces for the solder heat resistance test of Examples 1 to 16 and Comparative Examples 1 to 5, the test pieces for the solder heat resistance test of Examples 17 to 19 were made using a conductive paste that did not contain (C) glass frit. However, for the test pieces of Examples 17 to 19, the conductive paste was heat-treated at 150°C for 10 minutes using a hot air dryer, instead of drying and firing the conductive paste bonding strength test pattern, so that the conductive paste bonding strength test pattern was hardened.
然後，在置入有焊料(千住金屬工業股份有限公司製M705、包含Sn-Ag 3.0重量%及Cu 0.5重量%之Sn合金)之焊料槽(焊料之溫度：260℃)中，浸漬試驗片10秒鐘。 Then, the test piece was immersed in a solder bath (solder temperature: 260°C) containing solder (M705 manufactured by Senju Metal Industries Co., Ltd., a Sn alloy containing 3.0 wt% Sn-Ag and 0.5 wt% Cu) for 10 seconds.
在試驗片浸漬於焊料槽之後，取出試驗片，並將在試驗片殘留有95%以上的電極者判斷為焊料耐熱性試驗合格者。在表9之「焊料耐熱性」的欄位中，對於焊料耐熱性試驗合格的情形係記載為「良」，對於焊料耐熱性試驗不合格的情形則係記載為「不良」。 After the test piece is immersed in the solder tank, the test piece is taken out and the one with more than 95% of the electrode remaining in the test piece is judged as having passed the solder heat resistance test. In the "Solder Heat Resistance" column of Table 9, the case of passing the solder heat resistance test is recorded as "good", and the case of failing the solder heat resistance test is recorded as "bad".
[以SEM進行的表面及剖面觀察、以及以EDS分析進行的剖面觀察] [Surface and cross-sectional observations by SEM, and cross-sectional observations by EDS analysis]
在圖5中，係表示SEM照片，該SEM照片係藉由掃描型電子顯微鏡(SEM)以5000倍之倍率所拍攝出之試驗片的表面，該試驗片係以與電阻值變化比例為較小之實施例3的抗硫化性試驗之試驗片50相同的條件所製 作出者。在圖6中，係表示SEM照片，該SEM照片係藉由SEM以5000倍之倍率所拍攝出之試驗片的表面，該試驗片係以與電阻值變化比例為較大之比較例1的抗硫化性試驗之試驗片50相同的條件所製作出者。又，試驗片係與硫化性試驗之情形相同，係在硫環境(60℃)下經保管150小時之後，進行SEM觀察。 FIG5 shows an SEM photograph of the surface of the test piece photographed by a scanning electron microscope (SEM) at a magnification of 5000 times. The test piece was produced under the same conditions as the test piece 50 of the anti-sulfurization test of Example 3, in which the resistance value change ratio is smaller. FIG6 shows an SEM photograph of the surface of the test piece photographed by a SEM at a magnification of 5000 times. The test piece was produced under the same conditions as the test piece 50 of the anti-sulfurization test of Comparative Example 1, in which the resistance value change ratio is larger. In addition, the test piece was observed by SEM after being stored in a sulfur environment (60°C) for 150 hours, as in the case of the sulfidation test.
[評估] [evaluate]
從表1至3所示的結果可明瞭，將實施例1至19之導電膏進行燒製所得到的電極圖案的電阻值變化比例為65.0%(實施例11)以下，是為較低。相對於此，將比較例1至5之導電膏進行燒製所得到的電極圖案的電阻值變化比例為140%(比較例5)以上。因此，燒製實施例1至19之導電膏所得到的電極圖案係可謂為抗硫化性優異。 From the results shown in Tables 1 to 3, it is clear that the resistance value change ratio of the electrode pattern obtained by firing the conductive pastes of Examples 1 to 19 is less than 65.0% (Example 11), which is relatively low. In contrast, the resistance value change ratio of the electrode pattern obtained by firing the conductive pastes of Comparative Examples 1 to 5 is more than 140% (Comparative Example 5). Therefore, the electrode pattern obtained by firing the conductive pastes of Examples 1 to 19 can be said to have excellent anti-sulfurization properties.
從表1至3所示的結果可明瞭，將實施例1至19之導電膏進行燒製所得到的接著強度試驗用圖案之拉伸接著強度在13.2N(實施例17)至17.8N(實施例11及15)之範圍，係可獲得高的拉伸接著強度。另一方面，將比較例1至4之導電膏進行燒製所得到的電極圖案之拉伸接著強度在14.2N(比較例4)至15.2N(比較例1至3)之範圍，就拉伸接著強度而言為無問題之範圍。又，將比較例5之導電膏進行燒製所得到的電極圖案之拉伸接著強度為7.1N。相較於其它實施例及比較例，比較例5之導電膏係燒結性差，故認為拉伸接著強度為低的值。 As can be seen from the results shown in Tables 1 to 3, the tensile bonding strength of the bonding strength test pattern obtained by firing the conductive pastes of Examples 1 to 19 is in the range of 13.2N (Example 17) to 17.8N (Examples 11 and 15), which is a high tensile bonding strength. On the other hand, the tensile bonding strength of the electrode pattern obtained by firing the conductive pastes of Comparative Examples 1 to 4 is in the range of 14.2N (Comparative Example 4) to 15.2N (Comparative Examples 1 to 3), which is a range without problems in terms of tensile bonding strength. In addition, the tensile bonding strength of the electrode pattern obtained by firing the conductive paste of Comparative Example 5 is 7.1N. Compared with other embodiments and comparative examples, the conductive paste of comparative example 5 has poor sintering properties, so it is believed that the tensile strength is a low value.
從表1至3所示的結果可明瞭，將實施例1至19之導電膏進行燒製所得到的電極圖案之焊料耐熱性試驗的結果，係全部為合格(「良」)。另一方面，將比較例1至4之導電膏進行燒製所得到的電極圖 案之焊料耐熱性試驗的結果係不合格(「不良」)。又，將比較例5之導電膏進行燒製所得到的電極圖案之焊料耐熱性試驗之結果為合格(「良」)。從以上可知，將實施例1至19之導電膏進行燒製所得到的電極圖案係可謂為焊料耐熱性優異。 As can be seen from the results shown in Tables 1 to 3, the results of the solder heat resistance test of the electrode patterns obtained by firing the conductive pastes of Examples 1 to 19 are all qualified ("good"). On the other hand, the results of the solder heat resistance test of the electrode patterns obtained by firing the conductive pastes of Comparative Examples 1 to 4 are unqualified ("bad"). Moreover, the results of the solder heat resistance test of the electrode patterns obtained by firing the conductive paste of Comparative Example 5 are qualified ("good"). From the above, it can be seen that the electrode patterns obtained by firing the conductive pastes of Examples 1 to 19 can be said to have excellent solder heat resistance.
從表9所示之結果可明瞭，相較於比較例1，本實施型態之實施例1、3及17至19之電極係抗遷移性優異。 It is clear from the results shown in Table 9 that compared with Comparative Example 1, the electrodes of Examples 1, 3, and 17 to 19 of this embodiment have excellent anti-migration properties.
若將圖5所示之實施例3、與圖6所示之比較例1的SEM照片進行比較，則可理解相較於實施例3，比較例1係因硫化而形成較大的硫化銀20之結晶。在其它實施例及比較例中亦觀察到相同之傾向。因此，相較於比較例，本實施型態之實施例的電極係可謂為具有高的抗硫化性。又，藉由X射線光電子光譜法(XPS)測定出實施例3之試料的深度方向之Pd的含量，而確認到在深度80nm處存在著Pd之含量為30原子%左右之部分。此事係教示：至少在實施例3之試料中，係藉由在電極之表面形成銀-鈀合金層而提高了電極之抗硫化性。 If the SEM photographs of Example 3 shown in FIG. 5 and Comparative Example 1 shown in FIG. 6 are compared, it can be understood that, compared with Example 3, Comparative Example 1 forms larger crystals of silver sulfide 20 due to sulfidation. The same tendency is also observed in other examples and comparative examples. Therefore, compared with the comparative example, the electrode of the example of the present embodiment can be said to have high resistance to sulfidation. In addition, the Pd content in the depth direction of the sample of Example 3 was measured by X-ray photoelectron spectroscopy (XPS), and it was confirmed that there was a portion with a Pd content of about 30 atomic % at a depth of 80 nm. This indicates that, at least in the sample of Example 3, the anti-sulfurization property of the electrode is improved by forming a silver-palladium alloy layer on the surface of the electrode.
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
[表7]
[表8]
[表9]
<實施例20至32、比較例6至7：塗膜平滑性之評估> <Examples 20 to 32, Comparative Examples 6 to 7: Evaluation of coating smoothness>
以表10所示的調配，以與實施例1相同方式調製導電膏。所得到的導電膏係使用HB型黏度計(Brookfield公司製)(SC4-14 Spindal)，以溫度25℃、1rpm或10rpm之條件測定黏度，並求出TI值。然後，將各實施例/比較例之導電膏以成為寬10mm、長度50mm之圖案且厚度約0.05mm之方式塗佈於載玻璃上以，並以500℃燒製20分鐘，形成燒製後之膜厚為0.2μm的導電薄膜。對於所得到的導電薄膜，依據JIS B 0601(1994)，使用表面粗度/形狀測定機(東京精密公司製、SURFCOM 1500SD2-12)而測定出表 面粗度Ra。表面粗度Ra為未達0.4μm時係評估為特別優異之(○)，為0.4至0.5μm時係評估為實用上無問題之(△)，大於0.5μm時係評估為表面粗糙的(×)。將各實施例及比較例之調配及測定結果與抗硫化性之測定結果一併表示於表10中。又，關於抗硫化性試驗，係以與實施例1至19及比較例1至5相同之方法來實施。 A conductive paste was prepared in the same manner as in Example 1 using the formulation shown in Table 10. The viscosity of the conductive paste obtained was measured using an HB type viscometer (manufactured by Brookfield) (SC4-14 Spindal) at a temperature of 25°C and 1 rpm or 10 rpm, and the TI value was obtained. Then, the conductive paste of each example/comparative example was applied on a carrier glass in a pattern of 10 mm in width and 50 mm in length and a thickness of about 0.05 mm, and fired at 500°C for 20 minutes to form a conductive film having a film thickness of 0.2 μm after firing. The surface roughness Ra of the conductive film obtained was measured using a surface roughness/shape measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., SURFCOM 1500SD2-12) in accordance with JIS B 0601 (1994). When the surface roughness Ra is less than 0.4μm, it is evaluated as particularly excellent (○), when it is 0.4 to 0.5μm, it is evaluated as having no practical problems (△), and when it is greater than 0.5μm, it is evaluated as having a rough surface (×). The formulation and measurement results of each embodiment and comparative example are shown together with the measurement results of anti-sulfurization in Table 10. In addition, the anti-sulfurization test is carried out in the same way as in Examples 1 to 19 and Comparative Examples 1 to 5.
[表10]
[評估] [evaluate]
從表10所示的結果可明瞭，本實施型態之導電膏不僅抗硫化性優異，還因為TI值小之故而流動性大、調平性提升、印刷特性優異。又，同時係Ra值小，可形成平滑的塗膜。將實施例22與比較例6之導電薄膜的立體顯微鏡圖像表示於圖8、9中。雖然在實施例22係觀察到平坦的表面，但在比較例6確認到網目痕。由此等結果顯示:本實施型態之導電膏作為用以形成高精密的電極圖案之膏係特別優異者。 From the results shown in Table 10, it is clear that the conductive paste of this embodiment not only has excellent anti-sulfurization properties, but also has high fluidity, improved leveling properties, and excellent printing properties due to the small TI value. In addition, the Ra value is small, and a smooth coating can be formed. The stereoscopic microscope images of the conductive films of Example 22 and Comparative Example 6 are shown in Figures 8 and 9. Although a flat surface is observed in Example 22, mesh marks are confirmed in Comparative Example 6. These results show that the conductive paste of this embodiment is particularly excellent as a paste for forming high-precision electrode patterns.
Claims (11)
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| JP2022-134753 | 2022-08-26 |
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