TW202410071A - Conductive paste, electronic components, and laminated ceramic capacitors - Google Patents

Abstract

本發明提供一種能夠進一步提高與基材的緊貼性的導電性漿料。該導電性漿料含有導電性粉末、添加劑、黏合劑樹脂以及有機溶劑，作為前述添加劑，含有具有下述式（1）所示的結構部分的化合物。 （其中，R ¹表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，脂肪族烴基可以為直鏈狀或支鏈狀，脂肪族烴基的一個以上的亞甲基（-CH2-）可以被氧（-O-）取代，R ²表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，脂肪族烴基可以為直鏈狀或支鏈狀，脂肪族烴基的一個以上的亞甲基（-CH2-）可以被氧（-O-）取代。） The present invention provides a conductive slurry that can further improve the adhesion to a base material. This conductive slurry contains conductive powder, additives, a binder resin, and an organic solvent. As the additives, the conductive slurry contains a compound having a structural moiety represented by the following formula (1). (Wherein, R ¹ represents a saturated or unsaturated aliphatic hydrocarbon group with 8 to 25 carbon atoms. The aliphatic hydrocarbon group can be linear or branched. The aliphatic hydrocarbon group has more than one methylene group (-CH2- ) can be substituted by oxygen (-O-), R ² represents hydrogen, saturated or unsaturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, the aliphatic hydrocarbon group can be linear or branched, the aliphatic hydrocarbon group More than one methylene group (-CH2-) can be replaced by oxygen (-O-).)

Description

導電性漿料、電子零件、及積層陶瓷電容器Conductive paste, electronic components, and laminated ceramic capacitors

本發明係關於導電性漿料、電子零件以及積層陶瓷電容器。The present invention relates to a conductive slurry, an electronic component and a multilayer ceramic capacitor.

伴隨著行動電話、數位設備等電子設備的小型化以及高性能化，對於含有積層陶瓷電容器等的電子零件亦期望小型化以及高容量化。積層陶瓷電容器具有複數個電介質層及複數個內部電極層交替層積而成的結構，藉由使上述電介質層以及內部電極層薄膜化，能夠實現小型化以及高容量化。As electronic devices such as mobile phones and digital devices become smaller and have higher performance, electronic components including laminated ceramic capacitors and the like are also expected to be smaller and have higher capacities. Multilayer ceramic capacitors have a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated. By thinning the dielectric layers and internal electrode layers, miniaturization and high capacity can be achieved.

積層陶瓷電容器例如以如下方式製造。首先，在含有鈦酸鋇（BaTiO ₃）等電介質粉末以及黏合劑樹脂的生片的表面上，以預定的電極圖案印刷內部電極用的導電性漿料，進行乾燥，形成乾燥膜（導電膜）。接著，將乾燥膜及生片以交替重疊的方式進行層積，得到積層體。接著，對該積層體進行加熱壓接而一體化，形成壓接體。將該壓接體切斷，在氧化性氣體環境或非活性氣體環境中進行脫有機黏合劑處理後，進行燒製，得到燒製晶片。接著，在燒製晶片的兩端部塗佈外部電極用漿料，燒製後，對外部電極表面實施鍍鎳等，得到積層陶瓷電容器。 A multilayer ceramic capacitor is manufactured, for example, in the following manner. First, a conductive slurry for the internal electrode is printed in a predetermined electrode pattern on the surface of a green sheet containing a dielectric powder such as barium titanium oxide (BaTiO ₃ ) and a binder resin, and dried to form a dry film (conductive film). Then, the dry film and the green sheet are stacked in an alternating manner to obtain a laminate. Then, the laminate is heated and pressed to form a press-bonded body. The press-bonded body is cut, and after being subjected to a treatment to remove the organic binder in an oxidizing gas environment or an inert gas environment, it is fired to obtain a fired chip. Next, external electrode slurry is applied to both ends of the fired wafer, and after firing, the surface of the external electrode is plated with nickel or the like to obtain a multilayer ceramic capacitor.

在對將乾燥膜及生片層積而形成的積層體進行加熱壓接以及切斷的步驟中，在乾燥膜與生片（基材）的緊貼性不充分的情況下，有時乾燥膜（導電膜）從生片（基材）剝離、或層結構偏移，所得到的積層陶瓷電容器不具有所期望的電特性。In the step of heating, pressing and cutting the laminate formed by stacking the dry film and the green sheet, if the adhesion between the dry film and the green sheet (substrate) is insufficient, the dry film (conductive film) may be peeled off from the green sheet (substrate) or the layer structure may be shifted, and the resulting laminated ceramic capacitor may not have the desired electrical characteristics.

例如，在專利文獻1中揭示一種導電性漿料，其目的在於提高含有（甲基）丙烯酸樹脂作為黏合劑樹脂的導電性漿料對陶瓷生片的緊貼性，該導電性漿料含有作為黏合劑樹脂的（甲基）丙烯酸樹脂、有機溶劑以及金屬粉末，其中，（甲基）丙烯酸樹脂的玻璃轉化溫度Tg在-60℃~120℃的範圍，分子中的羥基在0.01質量%~5質量%的範圍，酸值在1mgKOH/g~50mgKOH/g的範圍，重均分子量在10000Mv~350000Mv的範圍。For example, Patent Document 1 discloses a conductive slurry, the purpose of which is to improve the adhesion of the conductive slurry containing a (meth)acrylic resin as a binder resin to a ceramic green sheet. The conductive slurry contains a (meth)acrylic resin as a binder resin, an organic solvent, and a metal powder, wherein the glass transition temperature Tg of the (meth)acrylic resin is in the range of -60°C to 120°C, the hydroxyl group in the molecule is in the range of 0.01 mass% to 5 mass%, the acid value is in the range of 1 mgKOH/g to 50 mgKOH/g, and the weight average molecular weight is in the range of 10000Mv to 350000Mv.

又，在專利文獻2中揭示一種導電性漿料，其目的在於提供一種能夠形成與基材的緊貼性優異的導電膜的導電性漿料，該導電性漿料用於在基材上形成電極層，該導電性漿料含有導電性粉末、樹脂黏合劑、有機添加劑及有機溶劑，上述有機添加劑含有在一個分子中具有兩個以上（甲基）丙烯醯基且數均分子量為1000以下的（甲基）丙烯酸酯化合物。Furthermore, Patent Document 2 discloses a conductive slurry, the purpose of which is to provide a conductive slurry capable of forming a conductive film having excellent adhesion to a substrate. The conductive slurry is used to form an electrode layer on a substrate. The conductive slurry contains a conductive powder, a resin binder, an organic additive, and an organic solvent. The organic additive contains a (meth)acrylate compound having two or more (meth)acrylic groups in one molecule and a number average molecular weight of 1000 or less.

又，在專利文獻3中，以提供一種能夠形成與電介質層的緊貼性優異且形狀在熱處理的前後不會大幅變化的內部電極的內部電極用乾燥膜為目的，揭示一種積層陶瓷電容器的內部電極用乾燥膜，其係由含有導電性粉末及有機黏合劑樹脂的組成物形成的積層陶瓷電容器的內部電極用乾燥膜，其特徵在於，該內部電極用乾燥膜的維氏硬度為47Hv以上且51Hv以下。 ［先前技術文獻］ Furthermore, Patent Document 3 discloses the inside of a laminated ceramic capacitor for the purpose of providing a dry film for internal electrodes that can form an internal electrode that has excellent adhesion to a dielectric layer and whose shape does not change significantly before and after heat treatment. A dry film for electrodes, which is a dry film for internal electrodes of a multilayer ceramic capacitor formed from a composition containing conductive powder and an organic binder resin, characterized in that the Vickers hardness of the dry film for internal electrodes is 47 Hv or more and Below 51Hv. [Prior technical literature]

［專利文獻1］國際公開第2013/187183號 ［專利文獻2］日本特開2018-055933號公報 ［專利文獻3］日本特開2019-121744號公報 [Patent Document 1] International Publication No. 2013/187183 [Patent Document 2] Japanese Patent Publication No. 2018-055933 [Patent Document 3] Japanese Patent Publication No. 2019-121744

［發明所欲解決之技術問題］[Technical problem to be solved by the invention]

近年來，從提高生產性、削減成本的觀點而言，在積層陶瓷電容器的製造步驟中，在對將乾燥膜及陶瓷生片交替層積而得到的積層體進行加熱壓接時，有時縮短壓接時的衝壓時間、降低壓力。In recent years, from the viewpoint of improving productivity and reducing costs, in the manufacturing process of laminated ceramic capacitors, when a laminated body obtained by alternately laminating dry films and ceramic green sheets is heat-pressed and bonded, the length of the laminated ceramic capacitor may be shortened in some cases. Pressing time and reducing pressure during crimping.

然而，在縮短壓接時的衝壓時間、降低壓力的情況下，以往的導電性漿料有時在乾燥膜與基材之間無法得到充分的緊貼性，產生乾燥膜的位置偏移，導致收率的降低。因此，要求在形成乾燥膜時能夠進一步提高與基材的緊貼性的導電性漿料。However, when the pressing time and pressure during pressure bonding are shortened, the conventional conductive paste sometimes cannot obtain sufficient adhesion between the dry film and the base material, causing positional deviation of the dry film, resulting in Reduction in yield. Therefore, there is a demand for a conductive slurry that can further improve the adhesion to the base material when forming a dry film.

本發明鑑於如此的狀況，其目的在於提供一種能夠進一步提高與基材的緊貼性的導電性漿料。 ［技術手段］ In view of such a situation, the present invention aims to provide a conductive slurry that can further improve the adhesion with the substrate. [Technical means]

在本發明的第一態樣中，提供一種導電性漿料，其中，前述導電性漿料含有導電性粉末、添加劑、黏合劑樹脂以及有機溶劑，作為添加劑，含有具有下述式（1）所示的結構部分的化合物。In a first aspect of the present invention, there is provided a conductive slurry, wherein the conductive slurry contains conductive powder, an additive, a binder resin, and an organic solvent, and as the additive, a conductive slurry having the following formula (1) is provided. A compound with the structural part shown.

［化1］ [Chemicalization 1]

其中，在上述式（1）中，R ¹表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ²表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。 Among them, in the above formula (1), R ¹ represents a saturated or unsaturated aliphatic hydrocarbon group with 8 to 25 carbon atoms. The aforementioned aliphatic hydrocarbon group can be linear or branched. One of the aforementioned aliphatic hydrocarbon groups The above methylene group (-CH ₂ -) can be replaced by oxygen (-O-), R ² represents hydrogen, a saturated or unsaturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, and the aforementioned aliphatic hydrocarbon group can be straight Chain or branched, one or more methylene groups (-CH ₂ -) of the aforementioned aliphatic hydrocarbon group may be substituted by oxygen (-O-).

又，理想地，前述化合物具有下述式（2）或下述式（3）所示的結構。Furthermore, preferably, the compound has a structure represented by the following formula (2) or the following formula (3).

［化2］ [Chemicalization 2]

［化3］ [Chemistry 3]

其中，在上述式（2）、（3）中，R ¹、R ⁵分別獨立地表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ²、R ³、R ⁴分別獨立地表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ⁶表示飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。 In the above formulae (2) and (3), R ¹ and R ⁵ each independently represent a saturated or unsaturated aliphatic hydrocarbon group having 8 to 25 carbon atoms, the aliphatic hydrocarbon group may be in a linear or branched form, and one or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-), R ² , R ³ and R ⁴ each independently represent hydrogen, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, the aliphatic hydrocarbon group may be in a linear or branched form, and one or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-), R ⁶ represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. One or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-).

又，理想地，相對於導電性漿料整體含有0.01質量%以上且2.0質量%以下的前述化合物。又，理想地，前述化合物在熱重量分析中的重量減少速度達到最大的溫度為200℃以上。又，理想地，前述化合物的分子量為250以上且3000以下。理想地，導電性漿料進一步含有酸系分散劑及/或鹼系分散劑。又，理想地，導電性粉末含有選自Ni、Pd、Pt、Au、Ag、Cu以及其等的合金中的至少一種金屬粉末。又，理想地，導電性粉末的平均粒徑為0.05μm以上且1.0μm以下。又，理想地，黏合劑樹脂含有縮丁醛系樹脂。又，理想地，導電性漿料進一步含有陶瓷粉末。又，理想地，陶瓷粉末含有鈦酸鋇。又，理想地，陶瓷粉末的平均粒徑為0.01μm以上且0.5μm以下。又，理想地，相對於導電性漿料整體含有1質量%以上且20質量%以下的陶瓷粉末。又，理想地，導電性漿料用於積層陶瓷零件的內部電極。Moreover, it is desirable to contain 0.01 mass % or more and 2.0 mass % or less of the said compound with respect to the whole conductive paste. Furthermore, ideally, the temperature at which the weight loss rate of the compound described above reaches the maximum in thermogravimetric analysis is 200°C or higher. Moreover, the molecular weight of the said compound is desirably 250 or more and 3000 or less. Desirably, the conductive slurry further contains an acid dispersant and/or an alkali dispersant. Furthermore, the conductive powder preferably contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu and alloys thereof. Furthermore, the average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less. Furthermore, preferably, the binder resin contains a butyral resin. Moreover, it is desirable that the electrically conductive slurry further contains ceramic powder. Furthermore, preferably, the ceramic powder contains barium titanate. Furthermore, the average particle diameter of the ceramic powder is preferably 0.01 μm or more and 0.5 μm or less. Moreover, it is desirable to contain 1 mass % or more and 20 mass % or less of ceramic powder with respect to the whole conductive slurry. Furthermore, the conductive slurry is ideally used for laminating internal electrodes of ceramic parts.

在本發明的第二態樣中，提供一種電子零件，其中，前述電子零件使用前述導電性漿料而形成。In a second aspect of the present invention, an electronic component is provided, wherein the electronic component is formed using the conductive slurry.

在本發明的第三態樣中，提供一種積層陶瓷電容器，其中，前述積層陶瓷電容器至少具有將電介質層及內部電極層層積而成的積層體，內部電極層使用前述導電性漿料而形成。 ［發明之效果］ In a third aspect of the present invention, a multilayer ceramic capacitor is provided, wherein the multilayer ceramic capacitor has at least a laminated body formed by stacking dielectric layers and internal electrode layers, and the internal electrode layer is formed using the conductive slurry. [Effect of the invention]

本發明的導電性漿料能夠進一步提高與基材的緊貼性。又，在積層陶瓷電容器的製造步驟中，使用本發明的導電性漿料而形成的乾燥膜（內部電極層）具有與生片（電介質層）的高緊貼性。The conductive paste of the present invention can further improve the adhesion to the base material. Furthermore, in the manufacturing process of the laminated ceramic capacitor, the dry film (internal electrode layer) formed using the conductive slurry of the present invention has high adhesion to the green sheet (dielectric layer).

［導電性漿料］ 本實施型態的導電性漿料含有導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂以及有機溶劑。以下，對各成分進行詳細說明。 [Conductive slurry] The conductive slurry of this embodiment contains conductive powder, ceramic powder, dispersant, binder resin and organic solvent. The following is a detailed description of each component.

（導電性粉末） 作為導電性粉末，沒有特別限定，可以使用金屬粉末，例如可以使用選自Ni、Pd、Pt、Au、Ag、Cu以及其等的合金中的一種以上的粉末。其中，從導電性、耐腐蝕性以及成本的觀點而言，理想為Ni或其合金的粉末（以下，有時稱為「Ni粉末」）。作為Ni合金，例如可以使用選自由Mn、Cr、Co、Al、Fe、Cu、Zn、Ag、Au、Pt以及Pd組成的群組中的至少一種以上的元素與Ni的合金。Ni合金中的Ni的含量例如為50質量%以上，理想為80質量%以上。又，Ni粉末為抑制在脫黏合劑處理時由黏合劑樹脂的部分的熱分解引起的急劇的氣體產生，可以含有數百ppm左右的元素S。 (Conductive powder) The conductive powder is not particularly limited, and metal powder can be used. For example, one or more powders selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof can be used. Among them, from the viewpoint of electrical conductivity, corrosion resistance, and cost, powder of Ni or its alloy (hereinafter, sometimes referred to as "Ni powder") is preferable. As the Ni alloy, for example, an alloy of at least one element selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt, and Pd and Ni can be used. The Ni content in the Ni alloy is, for example, 50 mass% or more, and ideally is 80 mass% or more. In addition, the Ni powder may contain approximately several hundred ppm of element S in order to suppress rapid gas generation caused by partial thermal decomposition of the binder resin during the binder removal process.

導電性粉末的平均粒徑理想為0.05μm以上且1.0μm以下，更理想為0.1μm以上且0.5μm以下。在導電性粉末的平均粒徑為上述範圍的情況下，能夠適合用作薄膜化的積層陶瓷電容器（積層陶瓷零件）的內部電極用漿料。平均粒徑係由利用掃描型電子顯微鏡（SEM）的觀察而求出的值，係從利用SEM以10,000倍的倍率進行觀察而得到的圖像中，對複數個顆粒的每一個的粒徑進行測定而得到的平均值（SEM平均粒徑）。The average particle diameter of the conductive powder is preferably from 0.05 μm to 1.0 μm, and more preferably from 0.1 μm to 0.5 μm. When the average particle diameter of the conductive powder is within the above range, it can be suitably used as a slurry for internal electrodes of thinned multilayer ceramic capacitors (laminated ceramic components). The average particle diameter is a value determined by observation using a scanning electron microscope (SEM). The average particle diameter is measured for each particle diameter of a plurality of particles from an image obtained by observation with a SEM at a magnification of 10,000 times. The average value obtained by measurement (SEM average particle size).

導電性粉末的含量相對於導電性漿料整體理想為30質量%以上且小於70質量%，更理想為40質量%以上且60質量%以下。在導電性粉末的含量為上述範圍的情況下，導電性以及分散性優異。The content of the conductive powder is preferably 30 mass % or more and less than 70 mass % with respect to the entire conductive slurry, and more preferably 40 mass % or more and 60 mass % or less. When the content of the conductive powder is within the above range, conductivity and dispersibility are excellent.

（陶瓷粉末） 作為陶瓷粉末，沒有特別限定，例如，在為積層陶瓷電容器的內部電極用漿料的情況下，根據所應用的積層陶瓷電容器的種類而適當選擇習知的陶瓷粉末。作為陶瓷粉末，例如可以使用含有Ba以及Ti的鈣鈦礦型氧化物，理想含有鈦酸鋇（BaTiO ₃）。 (Ceramic Powder) The ceramic powder is not particularly limited. For example, in the case of a slurry for internal electrodes of a multilayer ceramic capacitor, a conventional ceramic powder is appropriately selected depending on the type of multilayer ceramic capacitor to be used. As the ceramic powder, for example, a perovskite-type oxide containing Ba and Ti can be used, preferably barium titanate (BaTiO ₃ ).

作為陶瓷粉末，亦可以使用含有鈦酸鋇作為主成分、含有氧化物作為副成分的陶瓷粉末。作為氧化物，可列舉為Mn、Cr、Si、Ca、Ba、Mg、V、W、Ta、Nb以及一種以上的稀土元素的氧化物。又，作為陶瓷粉末，例如亦可以使用鈦酸鋇（BaTiO ₃）的Ba原子、Ti原子被其他原子例如Sn、Pb、Zr等取代的鈣鈦礦型氧化物強電介質的陶瓷粉末。 As the ceramic powder, a ceramic powder containing barium titanate as a main component and oxides as a subcomponent may be used. Examples of the oxides include oxides of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and one or more rare earth elements. In addition, as the ceramic powder, for example, a calcite-titanic oxide ferroelectric ceramic powder in which the Ba atoms and Ti atoms of barium titanate (BaTiO ₃ ) are replaced by other atoms such as Sn, Pb, Zr, etc. may be used.

在作為內部電極用的導電性漿料使用的情況下，陶瓷粉末亦可以使用與構成積層陶瓷電容器（電子零件）的生片的電介質陶瓷粉末相同組成的粉末。據此，可抑制燒結步驟中的電介質層與內部電極層的界面處的收縮的失配所導致的裂紋的產生。作為如此之陶瓷粉末，除上述以外，例如可列舉為ZnO、鐵氧體、PZT、BaO、Al ₂O ₃、Bi ₂O ₃、R（稀土元素） ₂O ₃、TiO ₂、Nd ₂O ₃等氧化物。此外，陶瓷粉末可以使用一種，亦可以使用兩種以上。 When used as a conductive slurry for an internal electrode, the ceramic powder may have the same composition as the dielectric ceramic powder constituting the green sheet of the multilayer ceramic capacitor (electronic component). This can suppress the generation of cracks caused by the mismatch of shrinkage at the interface between the dielectric layer and the internal electrode layer in the sintering step. Examples of such ceramic powders include oxides such as ZnO, _ferrite , PZT, BaO, _Al2O3 , _Bi2O3 , R (rare _earth element) _2O3 , _TiO2 , and _{Nd2O3 ,} in addition to the above. In addition, the ceramic powder may be one kind or two or more _kinds .

陶瓷粉末的平均粒徑例如為0.01μm以上且0.5μm以下，理想為0.01μm以上且0.3μm以下的範圍。藉由使陶瓷粉末的平均粒徑為上述範圍，在用作內部電極用漿料的情況下，能夠形成足夠細且薄的均勻的內部電極。平均粒徑係由利用掃描型電子顯微鏡（SEM）的觀察而求出的值，係從利用SEM以50,000倍的倍率進行觀察而得到的影像中，對複數個顆粒的每一個的粒徑進行測定而得到的平均值（SEM平均粒徑）。The average particle diameter of the ceramic powder is, for example, 0.01 μm or more and 0.5 μm or less, and preferably is in the range of 0.01 μm or more and 0.3 μm or less. By setting the average particle diameter of the ceramic powder within the above range, when used as a slurry for internal electrodes, sufficiently fine and thin uniform internal electrodes can be formed. The average particle diameter is a value determined by observation with a scanning electron microscope (SEM). The average particle diameter is measured from an image obtained by observation with a SEM at a magnification of 50,000 times. The particle diameter of each of the plurality of particles is measured. And the average value obtained (SEM average particle size).

陶瓷粉末的含量相對於導電性漿料整體理想為1質量%以上且20質量%以下，更理想為3質量%以上且15質量%以下。在陶瓷粉末的含量為上述範圍的情況下，分散性以及燒結性優異。The content of the ceramic powder is preferably 1 mass % or more and 20 mass % or less, and more preferably 3 mass % or more and 15 mass % or less, relative to the entire conductive slurry. When the content of the ceramic powder is within the above range, the dispersibility and sinterability are excellent.

又，陶瓷粉末的含量相對於導電性粉末100質量份理想為1質量份以上且30質量份以下，更理想為3質量份以上且30質量份以下。The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 3 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the conductive powder.

（黏合劑樹脂） 作為黏合劑樹脂，理想含有縮丁醛系樹脂。又，在作為內部電極用漿料使用的情況下，從提高與生片的黏接強度的觀點而言，可以含有縮丁醛系樹脂，或者亦可以單獨使用縮丁醛系樹脂。作為縮丁醛系樹脂，可列舉為聚乙烯醇縮丁醛（PVB）。在導電性漿料含有縮丁醛系樹脂的情況下，能夠進一步提高與生片的黏接強度。 (Binder resin) As a binder resin, it is desirable to contain a butyral resin. When used as a slurry for an internal electrode, a butyral resin may be contained from the viewpoint of improving the bonding strength with the green sheet, or a butyral resin may be used alone. As a butyral resin, polyvinyl butyral (PVB) can be cited. When the conductive slurry contains a butyral resin, the bonding strength with the green sheet can be further improved.

縮丁醛系樹脂的含量例如相對於黏合劑樹脂整體可以為20質量%以上，亦可以為40質量%以上，亦可以為60質量%以上。在縮丁醛系樹脂的含量為上述範圍的情況下，黏接性進一步提高，乾燥膜與生片（基材）的黏接強度提高。The content of the butyraldehyde resin can be, for example, 20% by mass or more, 40% by mass or more, or 60% by mass or more relative to the entire adhesive resin. When the content of the butyraldehyde resin is within the above range, the adhesiveness is further improved, and the bonding strength between the dried film and the green sheet (substrate) is improved.

又，縮丁醛系樹脂的含量的上限沒有特別限定，例如，相對於黏合劑樹脂整體，可以為90質量%以下，亦可以為80質量%以下。在縮丁醛系樹脂的含量為上述範圍的情況下，因導電性漿料具有適度的硬度，因此不易發生印刷膜不從支撐膜剝離、熱壓接時電極破碎等不良情況。In addition, the upper limit of the content of the butyraldehyde resin is not particularly limited, and for example, it can be 90% by mass or less, or 80% by mass or less relative to the entire adhesive resin. When the content of the butyraldehyde resin is within the above range, since the conductive slurry has a moderate hardness, it is not easy to cause undesirable conditions such as the printed film not being peeled off from the support film and the electrode being broken during hot pressing.

又，縮丁醛系樹脂的重均分子量（Mw）可以為3萬以上且30萬以下，亦可以為5萬以上且20萬以下，亦可以為10萬以上且15萬以下。又，縮丁醛樹脂的玻璃轉化溫度Tg可以為50℃以上且90℃以下，亦可以為60℃以上且80℃以下。藉由與具有上述特性的縮丁醛系樹脂一起含有後述的添加劑，能夠得到緊貼性進一步提高的導電性漿料。此外，縮丁醛系樹脂可以單獨使用一種，亦可以組合使用兩種以上。In addition, the weight average molecular weight (Mw) of the butyral-based resin may be 30,000 or more and 300,000 or less, may be 50,000 or more and 200,000 or less, or may be 100,000 or more and 150,000 or less. Moreover, the glass transition temperature Tg of the butyral resin may be 50°C or more and 90°C or less, or may be 60°C or more and 80°C or less. By containing an additive described below together with the butyral-based resin having the above characteristics, a conductive slurry with further improved adhesion can be obtained. In addition, one type of butyral-based resin may be used alone, or two or more types may be used in combination.

又，亦可以含有縮丁醛系樹脂以外的樹脂作為黏合劑樹脂。作為上述以外的黏合劑樹脂，沒有特別限定，可以使用習知的樹脂，例如可列舉為甲基纖維素、乙基纖維素、乙基羥乙基纖維素、硝基纖維素等纖維素系樹脂、丙烯酸系樹脂等。其中，從在溶劑中的溶解性、燃燒分解性的觀點等而言，理想含有纖維素系樹脂，更理想含有乙基纖維素。Moreover, resins other than butyral resin may be contained as a binder resin. The binder resin other than the above is not particularly limited, and conventional resins can be used. Examples include cellulose-based resins such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose. , acrylic resin, etc. Among them, from the viewpoint of solubility in a solvent, combustion decomposability, etc., it is preferable to contain a cellulose-based resin, and more preferably, it contains ethyl cellulose.

例如，在含有纖維素系樹脂作為黏合劑樹脂的情況下，重均分子量（Mw）可以為1萬以上且30萬以下，亦可以為3萬以上且25萬以下，亦可以為5萬以上且20萬以下。又，纖維素系樹脂的羥值沒有特別限定，理想為0.1mgKOH/g以上且15mgKOH/g以下，更理想為0.5mgKOH/g以上且7mgKOH/g以下，進一步理想為1.5mgKOH/g以上且3mgKOH/g以下。此外，纖維素系樹脂可以單獨含有一種，亦可以含有兩種以上。For example, when a cellulose-based resin is contained as a binder resin, the weight average molecular weight (Mw) may be 10,000 to 300,000, may be 30,000 to 250,000, or may be 50,000 to 250,000. Below 200,000. In addition, the hydroxyl value of the cellulose-based resin is not particularly limited, but is preferably 0.1 mgKOH/g or more and 15 mgKOH/g or less, more preferably 0.5 mgKOH/g or more and 7 mgKOH/g or less, further preferably 1.5 mgKOH/g or more and 3 mgKOH/g. /g or less. In addition, the cellulose-based resin may be contained individually by one type, or two or more types may be contained.

又，在黏合劑樹脂含有纖維素系樹脂以及縮丁醛系樹脂的情況下，從提高緊貼性的觀點而言，相對於纖維素系樹脂以及縮丁醛系樹脂的合計含量（100質量%），可以含有20質量%以上的縮丁醛系樹脂，亦可以含有40質量%以上，亦可以含有超過50質量%，亦可以含有60質量%以上。在兩樹脂的含量為上述範圍的情況下，有時黏接性進一步提高，乾燥膜與生片（基材）的黏接強度提高。又，縮丁醛系樹脂的含量的上限沒有特別限定，可以小於100質量%，亦可以為90質量%以下，亦可以為80質量%以下。在兩樹脂的含量為上述範圍的情況下，導電性漿料能夠具有適度的硬度，不易發生印刷膜不從支撐膜剝離、熱壓接時電極破碎等不良情況。In addition, when the binder resin contains a cellulose-based resin and a butyral-based resin, from the viewpoint of improving the adhesion, relative to the total content of the cellulose-based resin and the butyral-based resin (100 mass % ), may contain 20 mass% or more of butyral-based resin, may contain 40 mass% or more, may contain more than 50 mass%, may contain 60 mass% or more. When the contents of both resins are within the above ranges, the adhesiveness may be further improved, and the adhesive strength between the dry film and the green sheet (base material) may be improved. In addition, the upper limit of the butyral-based resin content is not particularly limited, and may be less than 100% by mass, 90% by mass or less, or 80% by mass or less. When the contents of both resins are within the above ranges, the conductive paste can have moderate hardness, and problems such as the printed film not peeling off from the support film and the electrodes being broken during thermocompression bonding are less likely to occur.

黏合劑樹脂的含量相對於導電性漿料整體理想為0.5質量%以上且10質量%以下，更理想為1質量%以上且7質量%以下。在黏合劑樹脂的含量為上述範圍的情況下，導電性以及分散性優異。The content of the binder resin is preferably 0.5 mass % or more and 10 mass % or less, and more preferably 1 mass % or more and 7 mass % or less, relative to the entire conductive slurry. When the content of the binder resin is within the above range, the conductivity and dispersibility are excellent.

黏合劑樹脂的含量相對於導電性粉末100質量份理想為1質量份以上且20質量份以下，更理想為1質量份以上且14質量份以下。The content of the binder resin is preferably not less than 1 part by mass and not more than 20 parts by mass, and more preferably not less than 1 part by mass and not more than 14 parts by mass based on 100 parts by mass of the conductive powder.

（有機溶劑） 作為有機溶劑，沒有特別限定，可以使用能夠溶解黏合劑樹脂的習知的有機溶劑。作為有機溶劑，例如可列舉為萜烯系溶劑、乙酸酯系溶劑、醚系溶劑、酮系溶劑等。 (organic solvent) The organic solvent is not particularly limited, and a conventional organic solvent capable of dissolving the binder resin can be used. Examples of the organic solvent include terpene-based solvents, acetate-based solvents, ether-based solvents, and ketone-based solvents.

作為萜烯系溶劑，可列舉為萜品醇、二氫萜品醇、二氫萜品醇乙酸酯等。Examples of the terpene solvent include terpineol, dihydroterpineol, dihydroterpineol acetate, and the like.

作為乙酸酯系溶劑，可列舉為乙酸異冰片酯、丙酸異冰片酯、丁酸異冰片酯以及異丁酸異冰片酯等、乙二醇單丁醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇單***乙酸酯、二丙二醇甲醚乙酸酯、3-甲氧基-3-甲基丁基乙酸酯、1-甲氧基丙基-2-乙酸酯等二醇醚乙酸酯類、丙二醇二乙酸酯、1,4-丁二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯等二醇二乙酸酯類、環己醇乙酸酯等。Examples of acetate-based solvents include isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, etc., ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, etc. Butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 1-methoxypropyl-2- Glycol ether acetates such as acetate, propylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diethyl Acid esters such as glycol diacetates, cyclohexanol acetate, etc.

作為醚系溶劑，可列舉為丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚等丙二醇單烷基醚類、二乙二醇單-2-乙基己醚、乙二醇單-2-乙基己醚、二乙二醇單己醚、乙二醇單己醚等乙二醇醚類、二丙二醇甲基-正丙醚、二丙二醇甲基-正丁醚、二丙二醇二甲醚等。Examples of ether solvents include propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, diethylene glycol mono-2-ethylhexyl ether, and ethylene glycol. Glycol ethers such as mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, ethylene glycol monohexyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol Dimethyl ether etc.

作為酮系溶劑，可列舉為甲基異丁基酮、二異丁基酮等。在含有酮系溶劑的情況下，能夠在不損害分散性的情況下進行黏度的調整，並且能夠提高乾燥性。Examples of ketone solvents include methyl isobutyl ketone, diisobutyl ketone, and the like. When a ketone solvent is contained, the viscosity can be adjusted without impairing the dispersibility, and the drying property can be improved.

作為有機溶劑，理想含有選自由萜品醇、二氫萜品醇、二氫萜品醇乙酸酯、丙二醇單丁醚、二乙二醇單丁醚乙酸酯組成的群組中的至少一種。藉由含有上述有機溶劑，使得與黏合劑樹脂的相容性優異，此外，填料的分散性優異。The organic solvent preferably contains at least one selected from the group consisting of terpineol, dihydroterpineol, dihydroterpineol acetate, propylene glycol monobutyl ether, and diethylene glycol monobutyl ether acetate. . By containing the above-mentioned organic solvent, the compatibility with the binder resin is excellent, and the dispersibility of the filler is also excellent.

有機溶劑（整體）的含量相對於導電性漿料總量理想為20質量%以上且60質量%以下，更理想為25質量%以上且45質量%以下。在有機溶劑的含量為上述範圍的情況下，導電性以及分散性優異。The content of the organic solvent (as a whole) is preferably 20 mass % or more and 60 mass % or less, and more preferably 25 mass % or more and 45 mass % or less, relative to the total amount of the conductive slurry. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.

有機溶劑的含量相對於導電性粉末100質量份理想為50質量份以上且130質量份以下，更理想為60質量份以上且90質量份以下。在有機溶劑的含量為上述範圍的情況下，導電性以及分散性優異。The content of the organic solvent is preferably 50 parts by mass or more and 130 parts by mass or less, and more preferably 60 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the conductive powder. When the content of the organic solvent is within the above range, conductivity and dispersibility are excellent.

又，有機溶劑可以使用一種，亦可以使用兩種以上。例如，作為有機溶劑，在含有兩種以上的情況下，可以含有選自由萜品醇、二氫萜品醇、二氫萜品醇乙酸酯、丙二醇單丁醚、二乙二醇單丁醚乙酸酯組成的群組中的至少一種、及烴系溶劑。又，亦可以與上述有機溶劑一起含有選自甲基異丁基酮及二異丁基酮中的至少一種。In addition, one type of organic solvent may be used, or two or more types of organic solvents may be used. For example, when two or more types of organic solvents are contained, they may be selected from the group consisting of terpineol, dihydroterpineol, dihydroterpineol acetate, propylene glycol monobutyl ether, and diethylene glycol monobutyl ether. At least one member from the group consisting of acetate esters, and a hydrocarbon solvent. Moreover, you may contain at least one selected from methyl isobutyl ketone and diisobutyl ketone together with the said organic solvent.

作為烴系溶劑，例如可列舉為含有十三烷、壬烷、環己烷等的溶劑、礦油精、環烷烴系溶劑等。其中，理想含有礦油精。烴系溶劑的含量相對於有機溶劑整體可以為10質量%以上且50質量%以下，亦可以為20質量%以上且40質量%以下。Examples of hydrocarbon-based solvents include solvents containing tridecane, nonane, cyclohexane, etc., mineral spirits, naphthenic solvents, and the like. Among them, it is desirable to contain mineral spirits. The content of the hydrocarbon-based solvent may be 10% by mass or more and 50% by mass or less, or may be 20% by mass or more and 40% by mass or less based on the entire organic solvent.

（添加劑） （a）醯胺化合物 在本實施型態所關於之導電性漿料中，作為添加劑，含有具有下述的式（1）所示的結構部分的化合物（以下，亦稱為「醯胺化合物」）。 (Additives) (a) Amide compound The conductive slurry according to the present embodiment contains, as an additive, a compound having a structural portion represented by the following formula (1) (hereinafter also referred to as an "amide compound").

［化4］ [Chemical 4]

在上述式（1）中，R ¹表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ²表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。此外，醯胺化合物可以不含酸性基團（例如羧基）。在含有酸性基團的情況下，有時乾燥膜的軟化效果會降低。 In the above formula (1), ^R1 represents a saturated or unsaturated aliphatic hydrocarbon group having 8 to 25 carbon atoms, the aliphatic hydrocarbon group may be linear or branched, and one or more methylene groups ( _-CH2- ) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-), and ^R2 represents hydrogen, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, the aliphatic hydrocarbon group may be linear or branched, and one or more methylene groups ( _-CH2- ) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-). In addition, the amide compound may not contain an acidic group (e.g., a carboxyl group). In the case of containing an acidic group, the softening effect of the dried film may be reduced.

又，理想地，醯胺化合物具有下述結構式（2）或下述結構式（3）所示的結構。Furthermore, the amide compound preferably has a structure represented by the following structural formula (2) or the following structural formula (3).

［化5］ [Chemistry 5]

［化6］ [Chemical 6]

在上述式（2）、（3）中，R ¹、R ⁵分別獨立地表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ²、R ³、R ⁴分別獨立地表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ⁶表示飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。此外，R ¹~R ⁶的碳原子數包含被氧（-O-）取代的亞甲基（-CH ₂-）的碳的數量。 In the above formulas (2) and (3), R ¹ and R ⁵ each independently represent a saturated or unsaturated aliphatic hydrocarbon group with 8 to 25 carbon atoms. The aforementioned aliphatic hydrocarbon group can be linear or branched. state, one or more methylene groups (-CH ₂ -) of the aforementioned aliphatic hydrocarbon group may be replaced by oxygen (-O-), and R ² , R ³ , and R ⁴ independently represent hydrogen, saturated or unsaturated carbon atoms. An aliphatic hydrocarbon group with a number of 1 to 6, the aforementioned aliphatic hydrocarbon group may be linear or branched, and one or more methylene groups (-CH ₂ -) of the aforementioned aliphatic hydrocarbon group may be substituted by oxygen (-O-) , R ⁶ represents a saturated or unsaturated aliphatic hydrocarbon group with 1 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group can be linear or branched, and the aforementioned aliphatic hydrocarbon group has more than one methylene group (-CH ₂ -) can be replaced by oxygen (-O-). In addition, the number of carbon atoms of R ¹ to R ⁶ includes the number of carbon atoms of methylene (-CH ₂ -) substituted with oxygen (-O-).

在導電性漿料含有上述醯胺化合物的情況下，能夠提高乾燥膜的緊貼性。其詳細理由尚不明確，但可以認為，例如，因上述醯胺化合物阻礙樹脂彼此的相互作用而使乾燥膜適度軟化，藉由因軟化而容易變形的乾燥膜、未產生相互作用的樹脂等，容易產生黏接界面處的纏結，因此乾燥膜與陶瓷生片（電介質層）的緊貼性提高。When the conductive slurry contains the above-mentioned amide compound, the adhesion of the dry film can be improved. The detailed reason for this is not clear yet, but it is considered that, for example, the above-mentioned amide compound inhibits the interaction between resins and softens the dry film moderately. The dry film is easily deformed due to softening, resins that do not interact, etc. Since entanglement at the bonding interface easily occurs, the adhesion between the dry film and the ceramic green sheet (dielectric layer) is improved.

在上述式（1）~（3）中，R ¹以及R ⁵的碳原子數的下限分別獨立地可以為8以上，亦可以為12以上，亦可以為15以上。又，R ¹及R ⁵的碳原子數亦可以相同。 In the above formulae (1) to (3), the lower limits of the number of carbon atoms of ^R1 and ^R5 may be independently 8 or more, 12 or more, or 15 or more. Furthermore, the number of carbon atoms of ^R1 and ^R5 may be the same.

又，R ¹以及R ⁵可以係一個以上的亞甲基（-CH ₂-）被氧（-O-）取代的脂肪族烴基，亦可以係未取代的脂肪族烴基。又，R ¹及R ⁵可以具有同樣的結構。 Moreover, R ¹ and R ⁵ may be an aliphatic hydrocarbon group in which one or more methylene groups (-CH ₂ -) are substituted by oxygen (-O-), or they may be an unsubstituted aliphatic hydrocarbon group. In addition, R ¹ and R ⁵ may have the same structure.

在上述式（1）~（3）中，R ²、R ³、R ⁴的碳原子數的上限可以為5以下，亦可以為3以下。又，R ²、R ³、R ⁴可以為未取代的脂肪族烴基，亦可以係，例如，一個以上的亞甲基（-CH ₂-）被氧（-O-）取代的脂肪族烴基，亦可以為氫。 In the above formulae (1) to (3), the upper limit of the number of carbon atoms of R ² , R ³ , and R ⁴ may be 5 or less, or 3 or less. R ² , R ³ , and R ⁴ may be unsubstituted aliphatic alkyl groups, or may be aliphatic alkyl groups in which, for example, one or more methylene groups (—CH ₂ —) are substituted with oxygen (—O—), or may be hydrogen.

在上述式（3）中，R ⁶的碳原子數的上限可以為5以下，亦可以為3以下，亦可以為2以下。又，R ⁶可以係一個以上的亞甲基（-CH ₂-）被氧（-O-）取代的飽和烴基，亦可以係未取代的飽和烴基。 In the above formula (3), the upper limit of the number of carbon atoms of R ⁶ may be 5 or less, 3 or less, or 2 or less. In addition, R ⁶ may be a saturated hydrocarbon group in which one or more methylene groups (-CH ₂ -) are substituted by oxygen (-O-), or may be an unsubstituted saturated hydrocarbon group.

使上述醯胺化合物在熱重量分析中的重量減少速度達到最大的溫度（最大熱分解溫度）例如可以為200℃以上，亦可以為220℃以上，理想為250℃以上。在沸點或熱分解溫度為上述範圍的情況下，可抑制積層體的脫層、裂紋。又，沸點或熱分解溫度的上限沒有特別限定，例如可以為450℃以下，亦可以為400℃以下，亦可以為350℃以下。The temperature (maximum thermal decomposition temperature) at which the weight reduction rate of the amide compound in thermogravimetric analysis reaches the maximum can be, for example, 200° C. or higher, or 220° C. or higher, and preferably 250° C. or higher. When the boiling point or thermal decomposition temperature is within the above range, delamination and cracking of the laminate can be suppressed. The upper limit of the boiling point or thermal decomposition temperature is not particularly limited, and can be, for example, 450° C. or lower, 400° C. or lower, or 350° C. or lower.

此外，最大熱分解溫度係指利用以下的方法藉由熱重量測定（TG）法求出的值。即，使用熱分解重量測定裝置（NETZSCH製造，STA25000REGULUS），在氮氣氣體環境下，以5℃/分鐘的升溫速度從20℃升溫至550℃，對此時的重量減量進行測定時，將微分加熱減量達到最大的溫度作為最大熱分解溫度。In addition, the maximum thermal decomposition temperature refers to a value determined by the thermogravimetry (TG) method using the following method. That is, a thermal decomposition weight measuring device (manufactured by NETZSCH, STA25000REGULUS) is used to increase the temperature from 20°C to 550°C at a temperature increase rate of 5°C/min in a nitrogen gas environment. When measuring the weight loss at this time, differential heating is performed. The temperature at which the reduction reaches the maximum is taken as the maximum thermal decomposition temperature.

上述醯胺化合物的分子量理想為250以上且3000以下，更理想為250以上且1000以下，進一步理想為250以上且500以下。在上述醯胺化合物的分子量為上述範圍的情況下，與陶瓷生片（電介質層）的緊貼性進一步提高。The molecular weight of the above-mentioned amide compound is preferably 250 or more and 3000 or less, more preferably 250 or more and 1000 or less, and further preferably 250 or more and 500 or less. When the molecular weight of the amide compound is within the above range, the adhesion to the ceramic green sheet (dielectric layer) is further improved.

又，上述醯胺化合物的含量相對於導電性漿料整體理想為0.01質量%以上且1.0質量%以下。在上述醯胺化合物的含量為上述範圍的情況下，乾燥膜與陶瓷生片（電介質層）的緊貼性提高。又，從進一步提高緊貼性的觀點而言，醯胺化合物的含量的下限相對於導電性漿料整體可以為0.05質量%以上，亦可以為0.1質量%以上。又，醯胺化合物的含量的上限可以為0.7質量%以下，亦可以為0.4質量%以下。Moreover, the content of the said amide compound is preferably 0.01 mass % or more and 1.0 mass % or less with respect to the whole conductive paste. When the content of the amide compound is within the above range, the adhesion between the dry film and the ceramic green sheet (dielectric layer) is improved. Moreover, from the viewpoint of further improving the adhesion, the lower limit of the content of the amide compound may be 0.05% by mass or more or 0.1% by mass or more based on the entire conductive slurry. Moreover, the upper limit of the content of the amide compound may be 0.7% by mass or less, or may be 0.4% by mass or less.

醯胺化合物的含量的上限可以為2質量%以下，亦可以為1.8質量%以下，亦可以為1.5質量%以下，亦可以為1.0質量%以下，亦可以小於1.0質量%。在醯胺化合物的含量超過1.0質量%的情況下，雖然緊貼性提高，但在對乾燥膜與陶瓷生片的積層體的壓接體進行脫黏合劑處理時，有時發生熱分解而產生氣體。醯胺化合物的含量可以在上述範圍內根據使用環境等適當調整。The upper limit of the content of the amide compound may be 2 mass % or less, 1.8 mass % or less, 1.5 mass % or less, 1.0 mass % or less, or less than 1.0 mass %. When the content of the amide compound exceeds 1.0 mass %, although the adhesion is improved, when the laminated body of the dry film and the ceramic green sheet is subjected to a debonding agent treatment, thermal decomposition may occur to generate gas. The content of the amide compound can be appropriately adjusted within the above range according to the use environment, etc.

又，醯胺化合物的含量可以根據上述黏合劑樹脂的種類以及含量而適當設定。例如，醯胺化合物的含量可以根據縮丁醛系樹脂的含量來設定。例如，相對於縮丁醛系樹脂100質量份，可以含有10質量份以上且90質量份以下的醯胺化合物，亦可以為10質量份以上且60質量份以下，亦可以為10質量份以上且50質量份以下。Furthermore, the content of the amide compound can be appropriately set according to the type and content of the above-mentioned adhesive resin. For example, the content of the amide compound can be set according to the content of the butyral resin. For example, relative to 100 parts by mass of the butyral resin, the amide compound can be contained in an amount of 10 parts by mass or more and 90 parts by mass or less, or in an amount of 10 parts by mass or more and 60 parts by mass or less, or in an amount of 10 parts by mass or more and 50 parts by mass or less.

（b）分散劑 在導電性漿料含有分散劑的情況下，能夠提高導電性粉末以及陶瓷粉末的分散性。作為分散劑，例如可以含有酸系分散劑、鹼系分散劑、非離子系分散劑、兩性分散劑等，理想含有酸系分散劑以及鹼系分散劑中的至少一者，更理想含有酸系分散劑。此外，上述分散劑可以使用一種或組合使用兩種以上。 (b) Dispersant When the conductive slurry contains a dispersant, the dispersibility of the conductive powder and the ceramic powder can be improved. The dispersant may contain, for example, an acidic dispersant, an alkaline dispersant, a nonionic dispersant, an amphoteric dispersant, etc. It is desirable to contain at least one of an acidic dispersant and an alkaline dispersant, and it is more desirable to contain an acidic dispersant. In addition, the above-mentioned dispersants may be used alone or in combination of two or more.

作為酸系分散劑，可以含有高級脂肪酸等羧酸系分散劑、聚羧酸系分散劑、磷酸系分散劑、高分子表面活性劑等具有酸性基團的酸系分散劑等，理想含有聚羧酸系分散劑以及磷酸系分散劑中的至少一者。又，聚羧酸系分散劑亦可以係具有梳型結構的梳型羧酸。The acid-based dispersant may include carboxylic acid-based dispersants such as higher fatty acids, polycarboxylic acid-based dispersants, phosphoric acid-based dispersants, acid-based dispersants such as polymer surfactants, etc., and preferably contains polycarboxylic acid-based dispersants. At least one of an acid dispersant and a phosphoric acid dispersant. In addition, the polycarboxylic acid-based dispersant may be a comb-type carboxylic acid having a comb-type structure.

作為高級脂肪酸，可以係不飽和羧酸，亦可以係飽和羧酸，沒有特別限定，可列舉為硬脂酸、油酸、肉豆蔻酸、棕櫚酸、亞油酸、月桂酸、亞麻酸等碳原子數為11以上的高級脂肪酸。其中，理想為油酸或硬脂酸。The higher fatty acid may be an unsaturated carboxylic acid or a saturated carboxylic acid, and is not particularly limited. Examples thereof include stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, linolenic acid, and the like, which have 11 or more carbon atoms. Among them, oleic acid or stearic acid is preferred.

又，作為酸系分散劑，例如可以為作為甘胺酸與油酸的化合物的油醯基肌胺酸、作為代替油酸而使用硬脂酸或月桂酸等高級脂肪酸的醯胺化合物的烷基單胺鹽型。Examples of the acid-based dispersant include oleylsarcosine, which is a compound of glycine and oleic acid, and an alkyl group of an amide compound using a higher fatty acid such as stearic acid or lauric acid instead of oleic acid. Monoamine salt type.

又，從進一步提高導電性粉末與陶瓷粉末的分離抑制效果的觀點而言，亦可以含有二羧酸。二羧酸為具有兩個羧基（COO-基）的羧酸。又，二羧酸的平均分子量沒有特別限定，例如可以為200以上且1000以下。Moreover, from the viewpoint of further improving the separation-inhibiting effect of the conductive powder and the ceramic powder, a dicarboxylic acid may be contained. Dicarboxylic acids are carboxylic acids with two carboxyl groups (COO-groups). In addition, the average molecular weight of the dicarboxylic acid is not particularly limited, and may be, for example, 200 or more and 1,000 or less.

作為鹼系分散劑，例如，可列舉為月桂胺、松香胺、鯨蠟胺、肉豆蔻胺、硬脂胺等脂肪族胺等。在導電性漿料含有上述酸系分散劑及鹼系分散劑的情況下，有時分散性更優異，經時的黏度穩定性亦很優異。Examples of alkaline dispersants include aliphatic amines such as lauryl amine, rosin amine, cetyl amine, myristic amine, and stearyl amine. When the conductive slurry contains the above acidic dispersant and alkaline dispersant, the dispersibility is sometimes better and the viscosity stability over time is also excellent.

相對於導電性漿料整體，例如含有0.01質量%以上且3質量%以下的分散劑。分散劑的含量的含有上限的範圍可以為2質量%以下，亦可以為1質量%以下，亦可以為0.5質量%以下。在分散劑的含量為上述範圍的情況下，能夠提高導電性漿料的分散性，或者抑制片材侵蝕、生片的剝離不良。For example, the conductive slurry contains 0.01 mass % or more and 3 mass % or less of the dispersant relative to the entire conductive slurry. The upper limit of the content of the dispersant may be 2 mass % or less, 1 mass % or less, or 0.5 mass % or less. When the content of the dispersant is within the above range, the dispersibility of the conductive slurry can be improved, or sheet erosion and poor peeling of the green sheet can be suppressed.

（c）其他添加劑 本實施型態的導電性漿料可以根據需要含有上述成分以外的其他添加劑。作為其他添加劑，例如可以使用消泡劑、增塑劑、界面活性劑、增稠劑等以往習知的添加物。 (c) Other additives The conductive slurry of this embodiment may contain other additives other than the above-mentioned components as needed. As other additives, for example, conventionally known additives such as defoamers, plasticizers, surfactants, and thickeners may be used.

（導電性漿料） 本實施型態所關於之導電性漿料的製造方法沒有特別限定，可以使用以往習知的方法。導電性漿料例如可以藉由將上述各成分用三輥磨、球磨機、混合機等進行攪拌、混煉來製造。 (Conductive slurry) The method for producing the conductive slurry according to the present embodiment is not particularly limited, and a conventionally known method can be used. The conductive slurry can be produced, for example, by stirring and kneading the above-mentioned components using a three-roll mill, a ball mill, a mixer, etc.

本實施型態所關於之導電性漿料藉由含有上述醯胺化合物，能夠提高乾燥膜與生片的緊貼性，作為該緊貼性提高的一個原因，如上所述，認為醯胺化合物阻礙樹脂彼此的相互作用，從而使乾燥膜適度軟化（降低玻璃轉化溫度Tg），變得容易變形。The conductive slurry according to the present embodiment can improve the adhesion between the dry film and the green sheet by containing the above-mentioned amide compound. As one of the reasons for the improvement of the adhesion, as mentioned above, it is believed that the amide compound hinders the interaction between the resins, thereby making the dry film moderately softened (lowering the glass transition temperature Tg) and becoming easier to deform.

例如，在將導電性漿料中的除導電性粉末以及陶瓷粉末以外的成分在120℃下乾燥40分鐘而準備去除有機溶劑的乾燥體（評價用樣品）的情況下，該乾燥體的玻璃轉化溫度Tg理想與除不含上述醯胺化合物以外在同樣的條件下形成的乾燥體的玻璃轉化溫度Tg’相比降低。上述醯胺化合物可以係使Tg與Tg’相比降低10℃以上、14℃以上、20℃以上、25℃以上或30℃以上的醯胺化合物。例如，乾燥體的玻璃轉化溫度Tg可以為60℃以下，亦可以為55℃以下，亦可以為50℃以下。此外，玻璃轉化溫度Tg的下限例如為30℃以上。For example, when the components other than the conductive powder and the ceramic powder in the conductive slurry are dried at 120°C for 40 minutes to prepare a dried body (evaluation sample) from which the organic solvent is removed, the glass transition temperature Tg of the dried body is preferably lower than the glass transition temperature Tg' of a dried body formed under the same conditions except that the amide compound is not contained. The amide compound may be an amide compound that reduces Tg by 10°C or more, 14°C or more, 20°C or more, 25°C or more, or 30°C or more compared to Tg'. For example, the glass transition temperature Tg of the dried body may be 60°C or less, 55°C or less, or 50°C or less. In addition, the lower limit of the glass transition temperature Tg is, for example, 30°C or more.

此外，在導電性漿料含有兩種以上的樹脂作為黏合劑樹脂的情況下，根據所含有的樹脂，有時對複數個玻璃轉化溫度Tg進行測定，但本說明書中的評價用樣品的玻璃轉化溫度Tg表示最低溫區域中的玻璃轉化溫度Tg。又，上述乾燥體（評價用樣品）的玻璃轉化溫度Tg可以藉由實施例中記載的方法進行測定。In addition, when the conductive paste contains two or more resins as binder resins, a plurality of glass transition temperatures Tg may be measured depending on the resins contained. However, the glass transition temperature of the evaluation sample in this specification Temperature Tg represents the glass transition temperature Tg in the lowest temperature region. In addition, the glass transition temperature Tg of the above-mentioned dried body (sample for evaluation) can be measured by the method described in the Examples.

又，在將導電性漿料塗佈於基材的表面，並在75℃下乾燥20分鐘而形成乾燥膜的情況下，室溫下的乾燥膜表面的維氏硬度理想為10以下，更理想為9以下，進一步理想為8以下。此外，維氏硬度（室溫）的下限例如為3.5以上。Furthermore, when the conductive slurry is applied to the surface of the substrate and dried at 75°C for 20 minutes to form a dry film, the Vickers hardness of the dry film surface at room temperature is preferably 10 or less, more preferably 9 or less, and further preferably 8 or less. The lower limit of the Vickers hardness (room temperature) is, for example, 3.5 or more.

又，60℃下的乾燥膜表面的維氏硬度理想為8以下，更理想為7以下，進一步理想為6以下。此外，維氏硬度（60℃）的下限例如為3以上。此外，乾燥膜在維氏硬度（60℃）的測定時，理想預先將所測定的乾燥膜在60℃下放置3分鐘來進行狀態調節。Furthermore, the Vickers hardness of the dried film surface at 60°C is preferably 8 or less, more preferably 7 or less, and further preferably 6 or less. The lower limit of the Vickers hardness (60°C) is, for example, 3 or more. When measuring the Vickers hardness (60°C) of the dried film, it is desirable to condition the dried film by leaving it at 60°C for 3 minutes in advance.

導電性漿料能夠適合用於積層陶瓷電容器等電子零件，尤其係能夠適合用作積層陶瓷電容器的內部電極用的漿料。在將導電性漿料用作內部電極用的漿料的情況下，導電性漿料的黏度在剪切速度100（s ^-1）下例如可以設為0.2 Pa·S以上且30Pa·S以下左右的黏度。 The conductive paste can be suitably used for electronic components such as multilayer ceramic capacitors, and is particularly suitably used as a paste for internal electrodes of multilayer ceramic capacitors. When a conductive slurry is used as a slurry for internal electrodes, the viscosity of the conductive slurry can be, for example, about 0.2 Pa·S or more and 30 Pa·S or less at a shear rate of 100 (s ^-1 ). viscosity.

［積層陶瓷電容器］ 以下，參照圖式對本發明的積層陶瓷電容器的實施型態進行說明。在圖式中，有時會適當地以示意性的方式來進行表示、變更比例尺來進行表示。又，適當地參照圖1等所示的XYZ正交坐標系對零件的位置、方向等進行說明。在該XYZ正交坐標系中，X方向以及Y方向為水平方向，Z方向為垂直方向（上下方向）。 [Multilayer Ceramic Capacitors] Hereinafter, embodiments of the multilayer ceramic capacitor of the present invention will be described with reference to the drawings. In the drawings, the figures may be represented in a schematic manner or the scale may be changed as appropriate. Moreover, the position, direction, etc. of a component are demonstrated suitably with reference to the XYZ orthogonal coordinate system shown in FIG. 1 etc. In this XYZ orthogonal coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is the vertical direction (up and down direction).

圖1中的A以及圖1中的B係表示積層陶瓷電容器1的圖。積層陶瓷電容器1具備交替地層積電介質層12以及內部電極層11而成的陶瓷積層體10及外部電極20。A in FIG. 1 and B in FIG. 1 are diagrams showing the multilayer ceramic capacitor 1 . The multilayer ceramic capacitor 1 includes a ceramic multilayer body 10 and external electrodes 20 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated.

以下，對使用上述導電性漿料作為內部電極用的漿料的積層陶瓷電容器的製造方法進行說明。首先，在陶瓷生片上印刷導電性漿料，進行乾燥，形成乾燥膜。藉由壓接對在上表面具有該乾燥膜的複數個陶瓷生片進行層積而得到積層體之後，對積層體進行燒製而使其一體化，據此製作內部電極層11及電介質層12交替地層積而成的陶瓷積層體10。之後，藉由在陶瓷積層體10的兩端部形成一對外部電極20而製造積層陶瓷電容器1。以下，更詳細地進行說明。The following is a description of a method for manufacturing a multilayer ceramic capacitor using the above-mentioned conductive slurry as a slurry for an internal electrode. First, a conductive slurry is printed on a ceramic green sheet and dried to form a dry film. After a plurality of ceramic green sheets having the dry film on the upper surface are stacked by compression to obtain a laminate, the laminate is fired to be integrated, thereby manufacturing a ceramic laminate 10 in which internal electrode layers 11 and dielectric layers 12 are alternately stacked. Thereafter, a pair of external electrodes 20 are formed at both ends of the ceramic laminate 10 to manufacture a multilayer ceramic capacitor 1. The following is a more detailed description.

首先，準備作為未燒製的陶瓷片的生片。作為該生片，例如，可列舉為將在鈦酸鋇等預定的陶瓷的原料粉末中加入聚乙烯醇縮丁醛等黏合劑樹脂及萜品醇等溶劑而得到的電介質層用漿料在PET膜等支撐膜上塗佈成片狀並使其乾燥去除溶劑而得到的生片。此外，對由生片構成的電介質層的厚度沒有特別限定，但從積層陶瓷電容器的小型化的要求的觀點而言，理想為0.05μm以上且3μm以下。First, a green sheet which is an unfired ceramic sheet is prepared. Examples of the green sheet include a slurry for a dielectric layer obtained by adding a binder resin such as polyvinyl butyral and a solvent such as terpineol to a raw material powder of a predetermined ceramic such as barium titanate and adding it to PET. A green sheet obtained by coating a supporting film such as a film into a sheet shape and drying it to remove the solvent. In addition, the thickness of the dielectric layer composed of the green sheet is not particularly limited, but from the viewpoint of the requirement for miniaturization of the multilayer ceramic capacitor, it is preferably 0.05 μm or more and 3 μm or less.

接著，準備複數片在生片的一個面上印刷塗佈上述導電性漿料並進行乾燥而在生片的一個面上形成有乾燥膜的片材。此外，從內部電極層11的薄層化的要求的觀點而言，由導電性漿料形成的乾燥膜的厚度理想為乾燥後為1μm以下。Next, a plurality of sheets are prepared, in which the conductive paste is printed and applied on one side of the green sheet and dried to form a dry film on one side of the green sheet. In addition, from the viewpoint of the requirement of thinning the internal electrode layer 11, the thickness of the dry film formed of the conductive slurry is preferably 1 μm or less after drying.

接著，從支撐膜上將生片剝離，並且以生片及形成於該生片的一個面上的乾燥膜交替地配置的方式進行層積之後，藉由加熱、加壓處理而得到積層體。此外，亦可以構成為在積層體的兩面進一步配置未塗佈導電性漿料的保護用的陶瓷生片。Next, the green sheet is peeled off from the support film, laminated so that the green sheet and the dry film formed on one surface of the green sheet are alternately arranged, and then heated and pressurized to obtain a laminated body. Furthermore, it may be configured so that protective ceramic green sheets to which conductive slurry is not applied are further disposed on both sides of the laminate.

接著，將積層體切斷成預定尺寸而形成生晶片後，對生晶片實施脫黏合劑處理，在還原氣體環境下進行燒製，據此製造積層陶瓷燒製體（陶瓷積層體10）。此外，脫黏合劑處理中的氣體環境理想為大氣或N ₂氣體氣體環境。進行脫黏合劑處理時的溫度例如為200℃以上且400℃以下。又，理想將進行脫黏合劑處理時的上述溫度的保持時間設為0.5小時以上且24小時以下。又，為抑制內部電極層中使用的金屬的氧化而在還原氣體環境下進行燒製，又，進行積層體的燒製時的溫度例如為1000℃以上且1350℃以下，進行燒製時的溫度的保持時間例如為0.5小時以上且8小時以下。 Next, the laminated body is cut into a predetermined size to form a green wafer, and then the green wafer is subjected to a binder removal process and fired in a reducing gas environment to produce a laminated ceramic fired body (ceramic laminated body 10 ). In addition, the gas environment in the binder removal treatment is ideally an atmosphere or an N ₂ gas atmosphere. The temperature when performing the binder removal process is, for example, 200°C or more and 400°C or less. Moreover, it is desirable to set the holding time at the above temperature during the binder removal process to 0.5 hours or more and 24 hours or less. In addition, in order to suppress oxidation of the metal used in the internal electrode layer, the firing is performed in a reducing gas environment, and the temperature during firing of the laminated body is, for example, 1000°C or more and 1350°C or less. The holding time is, for example, 0.5 hours or more and 8 hours or less.

藉由進行生晶片的燒製，將陶瓷生片中的有機黏合劑完全去除，並且陶瓷的原料粉末得到燒製而形成陶瓷制的電介質層12。又，去除乾燥膜中的有機載體，並且使鎳粉末或以鎳作為主成分的合金粉末燒結或熔融而一體化，從而形成內部電極層11，進而形成電介質層12及內部電極層11複數片交替地層積而成的積層陶瓷燒製體。此外，從將氧帶入電介質層的內部而提高可靠性、並且抑制內部電極的再氧化的觀點而言，可以對燒製後的積層陶瓷燒製體實施退火處理。By firing the green sheet, the organic binder in the ceramic green sheet is completely removed, and the raw material powder of the ceramic is fired to form a ceramic dielectric layer 12. In addition, the organic carrier in the dried film is removed, and the nickel powder or the alloy powder containing nickel as the main component is sintered or melted to form an internal electrode layer 11, and a laminated ceramic fired body is formed in which a plurality of dielectric layers 12 and internal electrode layers 11 are alternately stacked. In addition, from the viewpoint of bringing oxygen into the interior of the dielectric layer to improve reliability and suppressing reoxidation of the internal electrode, the laminated ceramic fired body after firing can be annealed.

接著，藉由對所製作的積層陶瓷燒製體設置一對外部電極20，據此製造積層陶瓷電容器1。例如，外部電極20具備外部電極層21以及電鍍層22。外部電極層21與內部電極層11電連接。此外，作為外部電極20的材料，例如可以理想地使用銅、鎳或其等的合金。此外，作為電子零件，進一步可以使用積層陶瓷電容器以外的電子零件。 ［實施例］ Next, a pair of external electrodes 20 are provided on the manufactured multilayer ceramic sintered body, thereby manufacturing a multilayer ceramic capacitor 1. For example, the external electrode 20 has an external electrode layer 21 and a plated layer 22. The external electrode layer 21 is electrically connected to the internal electrode layer 11. In addition, as a material of the external electrode 20, for example, copper, nickel or an alloy thereof can be preferably used. In addition, as an electronic component, electronic components other than multilayer ceramic capacitors can be further used. [Example]

以下，基於實施例及比較例對本發明進行詳細說明，但本發明不受實施例的任何限定。Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited to the Examples at all.

［評價方法］ （緊貼性評價） 在預先製作的含有鈦酸鋇以及聚乙烯醇縮丁醛的生片的表面塗佈導電性漿料（試樣），形成濕膜厚為35μm的導電性漿料膜。將所得到的生片以及在其表面形成的由內部電極用的導電性漿料膜構成的片材在75℃下乾燥處理20分鐘，在生片上形成乾燥膜。將乾燥後的片材（乾燥膜-生片）與其他生片以塗佈有導電性漿料的面被生片夾持的形式進行重疊之後，在溫度40℃、壓力20MPa下進行20秒的衝壓，據此製作積層體（評價用）。 [Evaluation method] (Evaluation of tightness) Conductive slurry (sample) was applied to the surface of a previously prepared green sheet containing barium titanate and polyvinyl butyral to form a conductive slurry film with a wet film thickness of 35 μm. The obtained green sheet and the sheet composed of the conductive slurry film for internal electrodes formed on the surface were dried at 75° C. for 20 minutes to form a dry film on the green sheet. The dried sheet (dried film-green sheet) was overlapped with another green sheet so that the surfaces coated with the conductive slurry were sandwiched between the green sheets, and then the drying process was performed for 20 seconds at a temperature of 40°C and a pressure of 20 MPa. Press and produce a laminated body (for evaluation).

將所得到的積層體以1cm見方切斷後，使用膠帶將積層體的兩面分別設置於拉伸試驗機（島津製作所股份有限公司製造，AGS-50NX）的夾具後，進行拉伸試驗。以20mm/min的試驗速度，記錄斷裂時的力（從生片上將乾燥膜剝離時的力）。將比較例1的斷裂時的力設為100%，以%對各自的斷裂時的力進行評價。The obtained laminate was cut into 1 cm squares, and both sides of the laminate were placed in the clamps of a tensile tester (AGS-50NX, manufactured by Shimadzu Corporation) using adhesive tape, and then a tensile test was performed. The force at break (the force when the dried film is peeled off from the green sheet) was recorded at a test speed of 20 mm/min. The force at break of Comparative Example 1 was set to 100%, and the force at break of each was evaluated in %.

（硬度測定） 使用顯微維氏硬度計（島津製作所股份有限公司製造，HMV-G21DT），在試驗力98mN的條件下，以n＝5點，對形成有在與緊貼性評價同樣的條件下製作的導電性漿料膜（乾燥膜）的生片的表面（乾燥膜側），對表面的維氏硬度進行測量，求出其等的平均值。硬度測定係將樣品貼附於玻璃基板，放置於作為硬度計的試樣台的加熱工作臺上，在未加熱的室溫（25℃）以及加熱至60℃的狀態下分別進行。此外，在測定維氏硬度（60℃）時，將預先測定的乾燥膜在60℃下放置3分鐘進行狀態調節後，在保持以60℃進行加熱後的狀態不變的狀態下進行測定。 (hardness measurement) Using a micro-Vickers hardness tester (manufactured by Shimadzu Corporation, HMV-G21DT), under the condition of a test force of 98 mN, at n = 5 points, the conductive film formed under the same conditions as the adhesion evaluation was evaluated. The surface of the green sheet (dry film side) of the slurry film (dry film) is measured, and the Vickers hardness of the surface is measured, and the average value is calculated. The hardness measurement is performed by attaching the sample to a glass substrate, placing it on a heated workbench as the sample stage of the hardness tester, and conducting it at unheated room temperature (25°C) and heated to 60°C. In addition, when measuring the Vickers hardness (60°C), the dry film measured in advance was left at 60°C for 3 minutes to adjust the state, and then the measurement was performed while maintaining the state after heating at 60°C.

（玻璃轉化溫度Tg的測定） 以與導電性漿料中所含的量相同的方式稱量導電性漿料中所含的成分中的除導電性粉末以及陶瓷粉末以外的成分、即乙基纖維素樹脂、聚乙烯醇縮丁醛樹脂、添加劑以及有機溶劑，使用自轉公轉混合機（THINKY製造，ARE-310），以2000rpm混合4分鐘後，使用敷抹器以濕膜厚為254μm將所得的液體（混合物）塗佈於PET膜上，在120℃下乾燥40分鐘，得到評價用的樣品。此外，混合物中的有機溶劑在乾燥時被去除。 (Measurement of glass transition temperature Tg) Among the components contained in the conductive slurry, components other than conductive powder and ceramic powder, namely, ethyl cellulose resin and polyvinyl butylidene, were weighed in the same amount as those contained in the conductive slurry. The aldehyde resin, additives, and organic solvent were mixed using a rotation-revolution mixer (ARE-310 manufactured by THINKY) at 2000 rpm for 4 minutes, and then the resulting liquid (mixture) was applied to PET with a wet film thickness of 254 μm using an applicator. The film was dried at 120° C. for 40 minutes to obtain a sample for evaluation. Furthermore, organic solvents in the mixture are removed during drying.

使用差示掃描量熱計（NETZSCH Japan股份有限公司，DSC3100），將乾燥後的評價用的樣品10mg放入鋁製的盤中，在100mL/分鐘的氮氣氣流下，以10℃/分鐘的升溫速度從0℃升溫至140℃，由所得到的吸熱曲線的峰求出低溫區域側的玻璃轉化溫度Tg。Using a differential scanning calorimeter (NETZSCH Japan Co., Ltd., DSC3100), 10 mg of the dried sample for evaluation was placed in an aluminum pan, and the temperature was increased at 10°C/min under a nitrogen gas flow of 100 mL/min. The temperature was increased from 0° C. to 140° C., and the glass transition temperature Tg on the low-temperature region side was calculated from the peak of the obtained endothermic curve.

（熱分解溫度測定） 導電性漿料中使用的添加劑的熱分解溫度使用熱分解重量測定裝置（NETZSCH製造，STA25000REGULUS）進行測定。測定溫度氣體環境為氮氣下，作為測定溫度範圍，以5℃/分鐘的升溫速度從20℃升溫至550℃。將微分加熱減量達到最大的溫度、即熱重量分析中的重量減少速度達到最大的溫度作為熱分解溫度（最大熱分解溫度）。 (Thermal decomposition temperature measurement) The thermal decomposition temperature of the additive used in the conductive slurry was measured using a thermal decomposition weight measuring device (NETZSCH, STA25000REGULUS). The temperature was measured in a nitrogen atmosphere, and the temperature was increased from 20°C to 550°C at a rate of 5°C/min. The temperature at which the differential heating loss reached the maximum, that is, the temperature at which the weight loss rate in thermogravimetric analysis reached the maximum, was taken as the thermal decomposition temperature (maximum thermal decomposition temperature).

［使用材料］ （導電性粉末） 作為導電性粉末，使用Ni粉末（SEM平均粒徑為0.2μm）。 [Material used] (Conductive powder) As the conductive powder, Ni powder (SEM average particle size: 0.2μm) was used.

（陶瓷粉末） 作為陶瓷粉末，使用鈦酸鋇（BaTiO ₃，SEM平均粒徑為0.10μm）。 (Ceramic Powder) As the ceramic powder, barium titanate (BaTiO ₃ , SEM average particle diameter: 0.10 μm) was used.

（黏合劑樹脂） 作為黏合劑樹脂，使用聚乙烯醇縮丁醛樹脂（PVB）、乙基纖維素樹脂（EC）。 (Adhesive resin) As the adhesive resin, polyvinyl butyral resin (PVB) and ethyl cellulose resin (EC) are used.

（分散劑） 在實施例以及比較例中，作為共同含有的分散劑（添加劑），使用作為酸系分散劑的聚羧酸系分散劑。 (dispersant) In the Examples and Comparative Examples, a polycarboxylic acid-based dispersant that is an acid-based dispersant was used as a commonly contained dispersant (additive).

（添加劑） 作為醯胺化合物，使用以下的化合物（4）（上述結構式（2）的化合物）、（5）（上述結構式（3）的化合物）。 (Additives) As amide compounds, the following compounds (4) (compound of the above structural formula (2)) and (5) (compound of the above structural formula (3)) were used.

［化7］ [Chemistry 7]

［化8］ [Chemical 8]

作為比較例，使用以下的添加劑。 ·添加劑a：具有聚氧化烯作為接枝鏈的聚羧酸 ·添加劑b：氧乙烯月桂胺（聚醚胺） ·添加劑c：二羧酸 As a comparative example, the following additives were used. ·Additive a: polycarboxylic acid with polyoxyalkylene as graft chain ·Additive b: oxyethylene laurylamine (polyetheramine) ·Additive c: dicarboxylic acid

（有機溶劑） 作為有機溶劑，使用二氫萜品醇（DHT）以及礦油精（MSA）。 (organic solvent) As organic solvents, dihydroterpineol (DHT) and mineral spirits (MSA) are used.

［實施例1］ 添加導電性粉末49質量%、陶瓷粉末12質量%、酸系分散劑0.15質量%、式（4）的添加劑0.3質量%、黏合劑樹脂2.5質量%（PVB:EC＝7:3（質量比））、以及作為餘量的有機溶劑（DHT:MSA＝60:40（質量比）），以整體為100質量%的方式進行配合，將此等材料混合而製作導電性漿料。將導電性漿料的各材料的含量以及評價結果示於表1。 [Example 1] 49 mass% of conductive powder, 12 mass% of ceramic powder, 0.15 mass% of acid dispersant, 0.3 mass% of additive of formula (4), 2.5 mass% of binder resin (PVB:EC=7:3 (mass ratio)), and the rest of organic solvent (DHT:MSA=60:40 (mass ratio)) were added to make a total of 100 mass% and mixed to prepare conductive slurry. The content of each material in the conductive slurry and the evaluation results are shown in Table 1.

［實施例2~5、比較例1~4］ 如表1所示如此變更添加劑的種類以及含量，除此以外，與實施例1同樣地製作導電性漿料，並進行評價。將導電性漿料的各材料的含量以及評價結果示於表1。 [Examples 2 to 5, Comparative Examples 1 to 4] Except for changing the type and content of additives as shown in Table 1, conductive slurries were prepared and evaluated in the same manner as in Example 1. The content of each material in the conductive slurry and the evaluation results are shown in Table 1.

〔表1〕 〔Table 1〕

（評價結果） 實施例1~5的導電性漿料與不含有式（1）或（2）所示的醯胺化合物的比較例1~4的導電性漿料相比，低溫區域的玻璃轉化溫度（Tg）降低，維氏硬度降低，緊貼性提高。 ［產業利用性］ (Evaluation results) Compared with the conductive slurries of Comparative Examples 1 to 4 which do not contain the amide compound represented by formula (1) or (2), the conductive slurries of Examples 1 to 5 have lower glass transition temperatures (Tg) in the low temperature region, lower Vickers hardness, and improved adhesion. [Industrial Applicability]

在將本發明的導電性漿料用於積層陶瓷電容器的內部電極的形成的情況下，能夠以高生產性得到可靠性高的積層陶瓷電容器。因此，本發明的導電性漿料特別適合用作行動電話、數位設備等的小型化發展的電子設備的晶片零件即積層陶瓷電容器的內部電極用。When the conductive slurry of the present invention is used for the formation of internal electrodes of a multilayer ceramic capacitor, a highly reliable multilayer ceramic capacitor can be obtained with high productivity. Therefore, the conductive slurry of the present invention is particularly suitable for use as an internal electrode of a laminated ceramic capacitor, which is a chip component of electronic equipment such as mobile phones and digital devices that are being miniaturized.

此外，本發明的技術範圍並不限定於在上述的實施型態等中說明的方式。有時省略在上述的實施型態等中說明的要件的一個以上。又，在上述的實施型態等中說明的要件能夠適當組合。又，只要法令允許，援引在上述的實施型態等中引用的全部的文獻的揭示而作為本說明書的記載的一部分。又，只要法令允許，援引作為日本專利申請的日本特願2022-052666的內容作為本說明書的記載的一部分。In addition, the technical scope of the present invention is not limited to the methods described in the above-mentioned embodiments, etc. Sometimes one or more of the requirements described in the above-mentioned embodiments, etc. are omitted. Furthermore, the requirements described in the above-mentioned embodiments, etc. can be appropriately combined. Furthermore, as long as the law permits, the disclosure of all the documents cited in the above-mentioned embodiments, etc. shall be cited as part of the description of this specification. Furthermore, as long as the law permits, the contents of Japanese Patent Application No. 2022-052666, which is a Japanese patent application, shall be cited as part of the description of this specification.

本發明的實施型態可以含有以下的構成。The embodiments of the present invention may include the following configurations.

［1］一種導電性漿料，其特徵係，前述導電性漿料含有導電性粉末、添加劑、黏合劑樹脂以及有機溶劑， 作為前述添加劑，含有具有下述式（1）所示的結構部分的化合物， ［化9］ 其中，R ¹表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ²表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。 [1] A conductive slurry, characterized in that the conductive slurry contains a conductive powder, an additive, a binder resin, and an organic solvent, and as the additive, it contains a component having a structural part represented by the following formula (1) Compound, [Chemistry 9] Among them, R ¹ represents a saturated or unsaturated aliphatic hydrocarbon group with 8 to 25 carbon atoms. The aforementioned aliphatic hydrocarbon group can be linear or branched, and the aforementioned aliphatic hydrocarbon group has more than one methylene group (-CH ₂ -) can be substituted by oxygen (-O-), R ² represents hydrogen, saturated or unsaturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, the aforementioned aliphatic hydrocarbon group can be linear or branched, the aforementioned One or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-).

〔2〕如〔1〕所述之導電性漿料，其中，前述化合物具有下述式（2）或下述式（3）所示的結構， ［化10］ ［化11］ 其中，R ¹、R ⁵分別獨立地表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代， R ²、R ³、R ⁴分別獨立地表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代， R ⁶表示飽和或不飽和的碳原子數為1~6的脂肪族烴基，前述脂肪族烴基可以為直鏈狀或支鏈狀，前述脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。 [2] The conductive paste according to [1], wherein the compound has a structure represented by the following formula (2) or the following formula (3), [Chemical 10] [Chemical 11] Among them, R ¹ and R ⁵ each independently represent a saturated or unsaturated aliphatic hydrocarbon group with 8 to 25 carbon atoms. The aforementioned aliphatic hydrocarbon group can be linear or branched. More than one of the aforementioned aliphatic hydrocarbon groups Methylene (-CH ₂ -) can be substituted by oxygen (-O-), R ² , R ³ , and R ⁴ each independently represent hydrogen, a saturated or unsaturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, The aforementioned aliphatic hydrocarbon group may be linear or branched, and one or more methylene groups (-CH ₂ -) of the aforementioned aliphatic hydrocarbon group may be substituted by oxygen (-O-). R ⁶ represents a saturated or unsaturated carbon An aliphatic hydrocarbon group with 1 to 6 atoms. The aliphatic hydrocarbon group may be linear or branched. One or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be oxygenated (-O-). replace.

〔3〕如〔1〕或〔2〕所述之導電性漿料，其中，相對於導電性漿料整體含有0.01質量%以上且2.0質量%以下的前述化合物。[3] The conductive slurry according to [1] or [2], which contains 0.01 mass % or more and 2.0 mass % or less of the aforementioned compound relative to the entire conductive slurry.

〔4〕如〔1〕~〔3〕中任一項所述之導電性漿料，其中，前述化合物在熱重量分析中的重量減少速度達到最大的溫度為200℃以上。[4] The conductive slurry according to any one of [1] to [3], wherein the temperature at which the weight loss rate of the compound reaches the maximum in thermogravimetric analysis is 200°C or higher.

〔5〕如〔1〕~〔4〕中任一項所述之導電性漿料，其中，前述化合物的分子量為250以上且3000以下。[5] The conductive slurry as described in any one of [1] to [4], wherein the molecular weight of the aforementioned compound is greater than or equal to 250 and less than or equal to 3000.

〔6〕如〔1〕~〔5〕中任一項所述之導電性漿料，其中，前述導電性漿料進一步含有酸系分散劑及/或鹼系分散劑。[6] The conductive slurry according to any one of [1] to [5], wherein the conductive slurry further contains an acidic dispersant and/or an alkali dispersant.

〔7〕如〔1〕~〔6〕中任一項所述之導電性漿料，其中，前述導電性粉末含有選自Ni、Pd、Pt、Au、Ag、Cu以及其等的合金中的至少一種金屬粉末。[7] The conductive slurry as described in any one of [1] to [6], wherein the conductive powder contains at least one metal powder selected from Ni, Pd, Pt, Au, Ag, Cu and alloys thereof.

〔8〕如〔1〕~〔7〕中任一項所述之導電性漿料，其中，前述導電性粉末的平均粒徑為0.05μm以上且1.0μm以下。[8] The conductive slurry as described in any one of [1] to [7], wherein the average particle size of the conductive powder is not less than 0.05 μm and not more than 1.0 μm.

〔9〕如〔1〕~〔8〕中任一項所述之導電性漿料，其中，前述黏合劑樹脂含有縮丁醛系樹脂。[9] The conductive slurry according to any one of [1] to [8], wherein the binder resin contains a butyral resin.

〔10〕如〔1〕~〔9〕中任一項所述之導電性漿料，其中，前述導電性漿料進一步含有陶瓷粉末。[10] The conductive slurry according to any one of [1] to [9], wherein the conductive slurry further contains ceramic powder.

〔11〕如〔10〕所述之導電性漿料，其中，前述陶瓷粉末含有鈦酸鋇。[11] The conductive slurry as described in [10], wherein the ceramic powder contains barium titanium oxide.

〔12〕如〔10〕或〔11〕所述之導電性漿料，其中，前述陶瓷粉末的平均粒徑為0.01μm以上且0.5μm以下。[12] The conductive slurry according to [10] or [11], wherein the ceramic powder has an average particle diameter of 0.01 μm or more and 0.5 μm or less.

〔13〕如〔10〕~〔12〕中任一項所述之導電性漿料，其中，相對於導電性漿料整體含有1質量%以上且20質量%以下的前述陶瓷粉末。[13] The conductive slurry according to any one of [10] to [12], which contains 1 mass % or more and 20 mass % or less of the ceramic powder with respect to the entire conductive slurry.

〔14〕如〔1〕~〔13〕中任一項所述之導電性漿料，其中，前述導電性漿料用於積層陶瓷零件的內部電極。[14] The conductive slurry as described in any one of [1] to [13], wherein the conductive slurry is used for internal electrodes of laminated ceramic parts.

〔15〕一種電子零件，其特徵係，前述電子零件使用〔1〕~〔14〕中任一項所述之導電性漿料而形成。[15] An electronic component, characterized in that the electronic component is formed using the conductive paste according to any one of [1] to [14].

〔16〕一種積層陶瓷電容器，其特徵係，前述積層陶瓷電容器至少具有將電介質層及內部電極層層積而成的積層體， 前述內部電極層使用〔14〕所述的導電性漿料而形成。 [16] A multilayer ceramic capacitor, characterized in that the multilayer ceramic capacitor has at least a laminated body formed by stacking dielectric layers and internal electrode layers, and the internal electrode layer is formed using the conductive slurry described in [14].

1:積層陶瓷電容器 10:陶瓷疊層體 11:內部電極層 12:電介質層 20:外部電極 21:外部電極層 22:電鍍層 1: Multilayer ceramic capacitor 10: Ceramic laminate 11: Internal electrode layer 12: Dielectric layer 20:External electrode 21:External electrode layer 22:Electroplating layer

〔圖1〕係表示實施型態所關於之積層陶瓷電容器的立體圖以及剖視圖。[Fig. 1] is a perspective view and a cross-sectional view showing a multilayer ceramic capacitor according to an embodiment.

1:積層陶瓷電容器 1: Multilayer ceramic capacitors

10:陶瓷疊層體 10: Ceramic laminate

11:內部電極層 11: Internal electrode layer

12:電介質層 12: Dielectric layer

20:外部電極 20: External electrode

21:外部電極層 21: External electrode layer

22:電鍍層 22: Electroplating

Claims (16)

一種導電性漿料，其特徵係，該導電性漿料含有導電性粉末、添加劑、黏合劑樹脂以及有機溶劑， 作為該添加劑，含有具有下述式（1）所示的結構部分的化合物， ［化1］ 其中，R ¹表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，該脂肪族烴基可以為直鏈狀或支鏈狀，該脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代，R ²表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，該脂肪族烴基可以為直鏈狀或支鏈狀，該脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。 A conductive slurry characterized in that the conductive slurry contains conductive powder, an additive, a binder resin and an organic solvent, and the additive contains a compound having a structural part represented by the following formula (1), [ Chemical 1] Among them, R ¹ represents a saturated or unsaturated aliphatic hydrocarbon group with 8 to 25 carbon atoms. The aliphatic hydrocarbon group can be linear or branched. The aliphatic hydrocarbon group has more than one methylene group (-CH _2- ) can be substituted by oxygen (-O-), R ² represents hydrogen, saturated or unsaturated aliphatic hydrocarbon group with 1 to 6 carbon atoms, the aliphatic hydrocarbon group can be linear or branched, the One or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-). 如請求項1所述之導電性漿料，其中，該化合物具有下述式（2）或下述式（3）所示的結構， ［化2］ ［化3］ 其中，R ¹、R ⁵分別獨立地表示飽和或不飽和的碳原子數為8~25的脂肪族烴基，該脂肪族烴基可以為直鏈狀或支鏈狀，該脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代， R ²、R ³、R ⁴分別獨立地表示氫、飽和或不飽和的碳原子數為1~6的脂肪族烴基，該脂肪族烴基可以為直鏈狀或支鏈狀，該脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代， R ⁶表示飽和或不飽和的碳原子數為1~6的脂肪族烴基，該脂肪族烴基可以為直鏈狀或支鏈狀，該脂肪族烴基的一個以上的亞甲基（-CH ₂-）可以被氧（-O-）取代。 The conductive slurry as claimed in claim 1, wherein the compound has a structure represented by the following formula (2) or the following formula (3): [Chemistry 3] wherein R ¹ and R ⁵ independently represent a saturated or unsaturated aliphatic hydrocarbon group having 8 to 25 carbon atoms, the aliphatic hydrocarbon group may be in a straight chain or branched chain, and one or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-); R ² , R ³ and R ⁴ independently represent hydrogen, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, the aliphatic hydrocarbon group may be in a straight chain or branched chain, and one or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-); R ⁶ represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be in a linear or branched chain form. One or more methylene groups (-CH ₂ -) of the aliphatic hydrocarbon group may be substituted by oxygen (-O-). 如請求項1所述之導電性漿料，其中，相對於導電性漿料整體含有0.01質量%以上且2.0質量%以下的該化合物。The conductive paste according to claim 1, which contains 0.01 mass % or more and 2.0 mass % or less of the compound relative to the entire conductive slurry. 如請求項1所述之導電性漿料，其中，該化合物在熱重量分析中的重量減少速度達到最大的溫度為200℃以上。The conductive slurry according to claim 1, wherein the temperature at which the weight loss rate of the compound reaches the maximum in thermogravimetric analysis is above 200°C. 如請求項1所述之導電性漿料，其中，該化合物的分子量為250以上且3000以下。The conductive slurry as described in claim 1, wherein the molecular weight of the compound is greater than or equal to 250 and less than or equal to 3000. 如請求項1所述之導電性漿料，其中，該導電性漿料進一步含有酸系分散劑及/或鹼系分散劑。The conductive slurry as described in claim 1, wherein the conductive slurry further contains an acidic dispersant and/or an alkaline dispersant. 如請求項1所述之導電性漿料，其中，該導電性粉末含有選自Ni、Pd、Pt、Au、Ag、Cu以及其等的合金中的至少一種金屬粉末。The conductive slurry as described in claim 1, wherein the conductive powder contains at least one metal powder selected from Ni, Pd, Pt, Au, Ag, Cu and alloys thereof. 如請求項1所述之導電性漿料，其中，該導電性粉末的平均粒徑為0.05μm以上且1.0μm以下。The conductive slurry according to claim 1, wherein the conductive powder has an average particle size of 0.05 μm or more and 1.0 μm or less. 如請求項1所述之導電性漿料，其中，該黏合劑樹脂含有縮丁醛系樹脂。The conductive slurry as described in claim 1, wherein the binder resin contains butyral resin. 如請求項1所述之導電性漿料，其中，該導電性漿料進一步含有陶瓷粉末。The conductive slurry as described in claim 1, wherein the conductive slurry further contains ceramic powder. 如請求項10所述之導電性漿料，其中，該陶瓷粉末含有鈦酸鋇。The conductive slurry according to claim 10, wherein the ceramic powder contains barium titanate. 如請求項10所述之導電性漿料，其中，該陶瓷粉末的平均粒徑為0.01μm以上且0.5μm以下。The conductive slurry as described in claim 10, wherein the average particle size of the ceramic powder is greater than 0.01 μm and less than 0.5 μm. 如請求項10所述之導電性漿料，其中，相對於導電性漿料整體含有1質量%以上且20質量%以下的該陶瓷粉末。The conductive slurry according to claim 10, which contains 1 mass % or more and 20 mass % or less of the ceramic powder with respect to the entire conductive slurry. 如請求項1所述之導電性漿料，其中，該導電性漿料用於積層陶瓷零件的內部電極。The conductive slurry according to claim 1, wherein the conductive slurry is used for laminating internal electrodes of ceramic parts. 一種電子零件，其特徵係，該電子零件使用請求項1至14中任一項所述之導電性漿料而形成。An electronic component characterized by being formed using the conductive paste according to any one of claims 1 to 14. 一種積層陶瓷電容器，其特徵係，該積層陶瓷電容器至少具有將電介質層及內部電極層層積而成的積層體， 該內部電極層使用請求項14所述之導電性漿料而形成。 A multilayer ceramic capacitor, characterized in that the multilayer ceramic capacitor has at least a laminated body formed by stacking a dielectric layer and an internal electrode layer, and the internal electrode layer is formed using the conductive slurry described in claim 14.