TW202141532A

TW202141532A - Electroconductive paste, electronic component, and laminated ceramic capacitor

Info

Publication number: TW202141532A
Application number: TW110107776A
Authority: TW
Inventors: 納谷匡邦; 安藤徹; 角田崇明; 高野清
Original assignee: 日商住友金屬鑛山股份有限公司
Priority date: 2020-03-04
Filing date: 2021-03-04
Publication date: 2021-11-01
Also published as: JPWO2021177420A1; CN115210823A; KR20220145326A; WO2021177420A1

Abstract

Provided is an electroconductive paste having a reduced number of projections present in a dry film. Provided is an electroconductive paste that contains an electroconductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein in the electroconductive paste, for the dispersant, contained are an amino acid dispersant represented by general formula (1) in an amount of 0.01-4 parts by mass (inclusive) with respect to 100 parts by mass of the electroconductive powder, and an amine dispersant represented by general formula (2) in an amount of 0.01-4 parts by mass (inclusive) with respect to 100 parts by mass of the electroconductive powder.

Description

導電性漿料、電子零件以及積層陶瓷電容器Conductive paste, electronic parts, and multilayer ceramic capacitors

本發明係關於一種導電性漿料、電子零件以及積層陶瓷電容器。The present invention relates to a conductive paste, electronic parts, and multilayer ceramic capacitors.

伴隨行動電話、數位設備等電子設備的小型化以及高性能化，對於包括積層陶瓷電容器等的電子零件也期望小型化以及高容量化。積層陶瓷電容器具有將多個電介質層和多個內部電極層交替積層而成的結構，藉由使上述電介質層以及內部電極層薄膜化而能夠實現小型化以及高容量化。With the miniaturization and higher performance of electronic devices such as mobile phones and digital devices, miniaturization and higher capacity are also desired for electronic components including multilayer ceramic capacitors. 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 above-mentioned dielectric layers and internal electrode layers, miniaturization and high capacity can be achieved.

例如，可以藉由如下方式來製造積層陶瓷電容器。首先，在含有鈦酸鋇（BaTiO₃ ）等電介質粉末以及黏合劑樹脂的電介質生片的表面上，以規定的電極圖案印刷（塗布）內部電極用的導電性漿料，並進行乾燥而形成乾燥膜。接著，將乾燥膜與電介質生片以交替地重疊的方式進行積層，並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惰性氣體環境中進行脫有機黏合劑處理之後進行燒製，得到燒製晶片。接著，在燒製晶片的兩端部塗布外部電極用漿料，在燒製後，在外部電極表面實施鍍鎳等，從而得到積層陶瓷電容器。For example, a multilayer ceramic capacitor can be manufactured in the following manner. First, a conductive paste for internal electrodes is printed (coated) with a predetermined electrode pattern on the surface of a dielectric green sheet containing dielectric powder such as barium titanate (BaTiO _{3) and a binder resin, and dried to form a dry} membrane. Next, the dry film and the dielectric green sheet are laminated so as to be alternately stacked, and they are heated and pressure-bonded to be integrated to form a pressure-bonded body. The pressure-bonded body is cut, and the organic binder is removed in an oxidizing gas atmosphere or an inert gas atmosphere, and then fired to obtain a fired wafer. Next, the external electrode slurry is applied to both ends of the fired wafer, and after firing, nickel plating or the like is applied to the surface of the external electrode to obtain a multilayer ceramic capacitor.

一般而言，用於形成內部電極層的導電性漿料含有導電性粉末、陶瓷粉末、黏合劑樹脂以及有機溶劑。另外，為了提高導電性粉末等的分散性，導電性漿料有時含有分散劑。伴隨近年來的內部電極層的薄膜化，導電性粉末也存在小粒徑化的傾向。在導電性粉末的粒徑較小的情況下，其顆粒表面的比表面積變大，因此導電性粉末（金屬粉末）的表面活性變高，分散性降低，粉末彼此容易凝集，從而形成凝集物。若在導電性漿料內存在凝集物，則在內部電極層形成起因於凝集物的凸部，該凸部有時會貫通生片而引起短路不良。Generally, the conductive paste for forming the internal electrode layer contains conductive powder, ceramic powder, binder resin, and organic solvent. In addition, in order to improve the dispersibility of conductive powder and the like, the conductive paste may contain a dispersant. With the thinning of the internal electrode layer in recent years, the conductive powder also tends to have a smaller particle size. When the particle size of the conductive powder is small, the specific surface area of the particle surface becomes larger. Therefore, the surface activity of the conductive powder (metal powder) becomes higher, the dispersibility is lowered, and the powders tend to agglomerate with each other to form agglomerates. If agglomerates are present in the conductive paste, protrusions due to the agglomerates are formed in the internal electrode layer, and the protrusions may penetrate the green sheet and cause short-circuit failure.

例如，在專利文獻1中記載了為了抑制短路不良而使用平均粒徑為0.2μm以下的鎳粉末。因此，即使產生凝集物，也不易形成內部導電體層的凸部，因此能夠減少貫通生片的短路不良。另外，在專利文獻1中記載了如下內容：藉由利用網目為5μm以下的過濾器對導電性漿料進行過濾，能夠去除鎳粉的凝集顆粒，從而得到所印刷的內部導電體層的平滑性，能夠減少貫通的短路不良。［先前技術文獻］［專利文獻］For example, Patent Document 1 describes the use of nickel powder with an average particle size of 0.2 μm or less in order to suppress short-circuit defects. Therefore, even if agglomerates are generated, it is difficult to form the convex portion of the internal conductor layer, so it is possible to reduce the short-circuit failure through the green sheet. In addition, Patent Document 1 describes that by filtering the conductive slurry with a filter with a mesh size of 5 μm or less, it is possible to remove aggregated particles of nickel powder, thereby obtaining the smoothness of the printed internal conductive layer. It is possible to reduce the short-circuit failure through penetration. [Prior technical literature] [Patent Literature]

［專利文獻1］日本特開2005-197019號公報[Patent Document 1] Japanese Patent Application Publication No. 2005-197019

［發明所欲解決之技術問題］[The technical problem that the invention intends to solve]

但是，在使用了以往的導電性漿料的積層陶瓷電容器中，伴隨著電極圖案的薄膜化，有時積層陶瓷電容器的短路不良增加，產生可靠性降低的問題。However, in multilayer ceramic capacitors using conventional conductive pastes, along with thinning of electrode patterns, the multilayer ceramic capacitors may have increased short-circuit defects and lower reliability.

根據本發明的發明人的研究可知，例如，如上述專利文獻1所記載：在導電性漿料的製造步驟中，即使將所使用的鎳粉末的平均粒徑設為2μm以下、或者利用過濾器對導電性漿料進行過濾，有時也無法充分地抑制積層陶瓷電容器的短路不良。According to research conducted by the inventors of the present invention, as described in Patent Document 1, for example, in the conductive paste production step, even if the average particle size of the nickel powder used is set to 2 μm or less, or a filter is used Filtering the conductive slurry may not sufficiently suppress the short-circuit failure of the multilayer ceramic capacitor.

因此，本發明的發明人進一步進行了研究的結果是新發現作為伴隨著電極圖案的薄膜化而產生上述問題的主要原因之一，可列舉為在印刷導電性漿料後的乾燥膜上產生的微小的突起。Therefore, the inventors of the present invention have further studied as a result of the newly discovered as one of the main causes of the above-mentioned problems associated with the thinning of the electrode pattern, which can be exemplified as the occurrence on the dried film after printing the conductive paste. Tiny protrusions.

即，當在乾燥膜上存在相當數量的突起的情況下，在積層陶瓷電容器的製造中，再將乾燥膜及電介質生片交替地積層時、在積層後膜厚減小時，由於該微小的突起而產生向相鄰的層的穿透，有時會產生積層陶瓷電容器的短路不良等的可靠性的降低。That is, when there are a considerable number of protrusions on the dry film, in the manufacture of a multilayer ceramic capacitor, when the dry film and the dielectric green sheet are alternately laminated, and the film thickness decreases after the lamination, the minute protrusions In addition, penetration to adjacent layers may occur, which may cause a decrease in reliability such as short-circuit failure of the multilayer ceramic capacitor.

另外，根據本發明的發明人的研究可知，上述微小突起的產生在通常的乾燥膜的粗糙度評價中難以檢測。In addition, according to research conducted by the inventors of the present invention, it has been found that the occurrence of the above-mentioned minute protrusions is difficult to detect in the roughness evaluation of a normal dry film.

本發明基於上述見解，其目的在於提供一種使存在於乾燥膜上的突起數減少的導電性漿料。［技術手段］The present invention is based on the above findings, and its object is to provide a conductive paste that reduces the number of protrusions present on a dry film. [Technical means]

在本發明的第一態樣中，提供一種導電性漿料，其含有導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂以及有機溶劑，其中，分散劑含有相對於導電性粉末100質量份為0.01質量份以上4質量份以下的下述通式（1）所示的胺基酸系分散劑、以及相對於導電性粉末100質量份為0.01質量份以上4質量份以下的下述通式（2）所示的胺系分散劑。In a first aspect of the present invention, there is provided a conductive paste containing conductive powder, ceramic powder, dispersant, binder resin, and organic solvent, wherein the dispersant contains 100 parts by mass of the conductive powder 0.01 to 4 parts by mass of the amino acid-based dispersant represented by the following general formula (1), and the following general formula ( 2) The amine-based dispersant shown.

［化1］

[化1]

（其中，在通式（1）中，R₁ 表示碳原子數為10~20的鏈狀烴基。）(In general formula (1), R ₁ represents a chain hydrocarbon group having 10 to 20 carbon atoms.)

［化2］

[化2]

（其中，在通式（2）中，R₂ 表示碳原子數為12~22的鏈狀烴基。）(In general formula (2), R ₂ represents a chain hydrocarbon group having 12 to 22 carbon atoms.)

另外，理想地，分散劑進一步含有相對於導電性粉末100質量份為0.01質量份以上4質量份以下的下述通式（3）所示的胺系分散劑，並且導電性漿料含有相對於導電性漿料整體為40質量%以上60質量%以下的導電性粉末。In addition, desirably, the dispersant further contains an amine-based dispersant represented by the following general formula (3) in an amount of 0.01 parts by mass to 4 parts by mass relative to 100 parts by mass of the conductive powder, and the conductive paste contains The conductive paste as a whole is 40% by mass or more and 60% by mass or less of conductive powder.

［化3］

[化3]

（其中，在通式（3）中，R₃ 表示碳原子數為8~16的烷基、烯基或炔基，R₄ 表示氧化乙烯基、氧化丙烯基或亞甲基，R₅ 表示氧化乙烯基或氧化丙烯基，R₄ 及R₅ 可以相同，或者也可以不同。另外，式（3）中的N原子與R₄ 及R₅ 中的O原子不直接鍵合，且Y為0~2的數，Z為1~2的數。）(Among them, in the general formula (3), R ₃ represents an alkyl, alkenyl or alkynyl group with 8 to 16 carbon atoms, R ₄ represents an oxyethylene group, an oxypropylene group or a methylene group, and R ₅ represents an oxidized group. Ethyl group or oxypropylene group, R ₄ and R ₅ may be the same or different. In addition, the N atom in formula (3) and the O atom in R ₄ and R ₅ are not directly bonded, and Y is 0~ The number of 2, Z is the number of 1~2.)

另外，理想地，在通式（1）中，R₁ 表示碳原子數為10~20的直鏈狀烴基。另外，相對於導電性漿料整體，理想為含有0.01質量%以上4質量%以下的分散劑。另外，理想地，導電性粉末含有選自Ni、Pd、Pt、Au、Ag、Cu以及其等之合金中之至少一種的金屬粉末。另外，理想地，導電性粉末的平均粒徑為0.05μm以上1.0μm以下。另外，理想地，陶瓷粉末含有鈣鈦礦型氧化物。另外，理想地，陶瓷粉末的平均粒徑為0.01μm以上0.5μm以下。另外，理想地，黏合劑樹脂含有纖維素系樹脂、丙烯酸系樹脂以及縮丁醛系樹脂中的至少一種。另外，理想地，上述導電性漿料用於積層陶瓷零件的內部電極。In addition, ideally, in the general formula (1), R ₁ represents a linear hydrocarbon group having 10 to 20 carbon atoms. In addition, it is desirable to contain a dispersant in an amount of 0.01% by mass or more and 4% by mass or less with respect to the entire conductive paste. In addition, desirably, the conductive powder contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof. In addition, desirably, the average particle size of the conductive powder is 0.05 μm or more and 1.0 μm or less. In addition, ideally, the ceramic powder contains a perovskite-type oxide. In addition, ideally, the average particle diameter of the ceramic powder is 0.01 μm or more and 0.5 μm or less. In addition, desirably, the binder resin contains at least one of a cellulose resin, an acrylic resin, and a butyral resin. In addition, ideally, the above-mentioned conductive paste is used for internal electrodes of laminated ceramic parts.

在本發明的第二態樣中，提供一種使用上述導電性漿料而形成的電子零件。In a second aspect of the present invention, there is provided an electronic component formed using the above-mentioned conductive paste.

在本發明的第三態樣中，提供一種積層陶瓷電容器，其至少具有將電介質層及內部電極進行積層而成的積層體，內部電極使用上述導電性漿料而形成。［發明之效果］In a third aspect of the present invention, there is provided a laminated ceramic capacitor having at least a laminated body in which a dielectric layer and an internal electrode are laminated, and the internal electrode is formed using the above-mentioned conductive paste. [Effects of Invention]

本發明所涉及的導電性漿料在印刷後的乾燥膜上產生的微小的突起的數量較少。因此，本發明所涉及的導電性漿料例如能夠適宜地使用於薄膜化的電極。The conductive paste according to the present invention generates a small number of minute protrusions on the dried film after printing. Therefore, the conductive paste according to the present invention can be suitably used for thin-film electrodes, for example.

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。The conductive paste of this embodiment contains conductive powder, ceramic powder, dispersant, binder resin, and organic solvent. Hereinafter, each component will be described in detail.

（導電性粉末）對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。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所成群中的至少一種以上的元素與Ni的合金（Ni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。另外，為了抑制脫黏合劑處理時的、由黏合劑樹脂的部分的熱分解而導致的劇烈的氣體產生，Ni粉末可以含有幾百ppm程度的S。(Conductive powder) The conductive powder is not particularly limited, and metal powder can be used. For example, one or more powders selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof can be used. Among them, from the viewpoints of electrical conductivity, corrosion resistance, and cost, powders of Ni or its alloys are desirable. As the Ni alloy, for example, an alloy (Ni 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 content of Ni in the Ni alloy is, for example, 50% by mass or more, and desirably 80% by mass or more. In addition, in order to suppress the generation of violent gas caused by the thermal decomposition of the part of the binder resin during the debinding process, the Ni powder may contain about several hundred ppm of S.

導電性粉末的平均粒徑理想為0.05μm以上1.0μm以下，更理想為0.1μm以上0.5μm以下。在導電性粉末的平均粒徑為上述範圍內的情況下，能夠適宜用作薄膜化的積層陶瓷電容器的內部電極用漿料，例如，可提高乾燥膜的平滑性以及乾燥膜密度。平均粒徑是根據基於掃描型電子顯微鏡（SEM）的觀察而求出的值，是從藉由SEM以10,000倍的倍率進行觀察而得到的圖像中逐個測定多個顆粒的粒徑而得到的平均值。The average particle diameter of the conductive powder is desirably 0.05 μm or more and 1.0 μm or less, and more desirably 0.1 μm or more and 0.5 μm or less. When the average particle size of the conductive powder is within the above range, it can be suitably used as a slurry for internal electrodes of a multilayer ceramic capacitor formed into a thin film. For example, the smoothness and density of the dry film can be improved. The average particle size is a value obtained based on observations with a scanning electron microscope (SEM), and is obtained by measuring the particle sizes of multiple particles one by one from an image obtained by SEM observation at a magnification of 10,000 times average value.

導電性粉末的含量相對於導電性漿料總量理想為30質量%以上且小於70質量%，更理想為40質量%以上60質量%以下。在導電性粉末的含量為上述範圍內的情況下，導電性以及分散性優異。The content of the conductive powder is preferably 30% by mass or more and less than 70% by mass relative to the total amount of the conductive paste, and more preferably 40% by mass or more and 60% by 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，可根據所應用的積層陶瓷電容器的種類而適當地選擇習知的陶瓷粉末。作為陶瓷粉末，例如可列舉為含有Ba以及Ti的鈣鈦礦型氧化物，理想為鈦酸鋇（BaTiO₃ ）。(Ceramic powder) The ceramic powder is not particularly limited. For example, in the case of a slurry for the internal electrode of a multilayer ceramic capacitor, a conventional ceramic powder can be appropriately selected according to the type of multilayer ceramic capacitor to be applied. Examples of ceramic powders include perovskite-type oxides containing Ba and Ti, and barium titanate (BaTiO ₃ ) is desirable.

作為陶瓷粉末，可以使用含有鈦酸鋇作為主成分、且含有氧化物作為副成分的陶瓷粉末。作為氧化物，可列舉為由選自Mn、Cr、Si、Ca、Ba、Mg、V、W、Ta、Nb以及稀土類元素中的一種以上構成的氧化物。另外，作為陶瓷粉末，例如還可以列舉為將鈦酸鋇（BaTiO₃ ）的Ba原子、Ti原子以例如Sn、Pb、Zr等其他原子取代後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 secondary component can be used. Examples of oxides include oxides composed of one or more selected from Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and rare earth elements. In addition, as ceramic powder, for example, a perovskite-type oxide ferroelectric ceramic powder obtained by substituting Ba atoms and Ti atoms of _{barium titanate (BaTiO 3) with other atoms such as Sn, Pb, Zr and the like can also be cited.}

作為內部電極用漿料中的陶瓷粉末，可以使用與構成積層陶瓷電容器的電介質生片的電介質陶瓷粉末相同組成的粉末。由此，可抑制由於燒結步驟中的電介質層與內部電極層之間的界面處的收縮失配而導致的裂紋的產生。作為如此的陶瓷粉末，除了上述含有Ba以及Ti的鈣鈦礦型氧化物以外，例如，還可列舉為ZnO、鐵氧體、PZT、BaO、Al₂ O₃ 、Bi₂ O₃ 、R（稀土類元素）₂ O₃ 、TiO₂ 、Nd₂ O₃ 等氧化物。此外，陶瓷粉末可以使用一種，也可以使用兩種以上。As the ceramic powder in the slurry for internal electrodes, powder having the same composition as the dielectric ceramic powder constituting the dielectric green sheet of the multilayer ceramic capacitor can be used. Thereby, it is possible to suppress the occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering step. As such ceramic powder, in addition to the above-mentioned perovskite-type oxide containing Ba and Ti, for example, ZnO, ferrite, PZT, BaO, Al ₂ O ₃ , Bi ₂ O ₃ , R (rare earth Class elements) ₂ O ₃ , TiO ₂ , Nd ₂ O ₃ and other oxides. In addition, one type of ceramic powder may be used, or two or more types may be used.

陶瓷粉末的平均粒徑例如為0.01μm以上0.5μm以下，理想為0.01μm以上0.3μm以下的範圍。藉由使陶瓷粉末的平均粒徑在上述範圍內，在作為內部電極用漿料來使用的情況下，能夠形成足夠細薄且均勻的內部電極。平均粒徑是根據基於掃描型電子顯微鏡（SEM）的觀察而求出的值，是從藉由SEM以50,000倍的倍率進行觀察而得到的影像中逐個測定多個顆粒的粒徑而得到的平均值。The average particle diameter of the ceramic powder is, for example, 0.01 μm or more and 0.5 μm or less, and desirably is in the range of 0.01 μm or more and 0.3 μm or less. By setting the average particle size of the ceramic powder within the above range, when used as a slurry for internal electrodes, a sufficiently thin and uniform internal electrode can be formed. The average particle size is a value obtained by observation with a scanning electron microscope (SEM). It is an average value obtained by measuring the particle size of a plurality of particles one by one from an image obtained by SEM observation at a magnification of 50,000 times value.

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30質量份以下，更理想為3質量份以上30質量份以下。The content of the ceramic powder relative to 100 parts by mass of the conductive powder is desirably 1 part by mass or more and 30 parts by mass or less, and more desirably 3 parts by mass or more and 30 parts by mass or less.

陶瓷粉末的含量相對於導電性漿料總量理想為1質量%以上20質量%以下，更理想為5質量%以上20質量%以下。當陶瓷粉末的含量為上述範圍內的情況下，導電性以及分散性優異。The content of the ceramic powder is desirably 1% by mass or more and 20% by mass or less, and more desirably 5% by mass or more and 20% by mass or less with respect to the total amount of the conductive paste. When the content of the ceramic powder is within the above range, conductivity and dispersibility are excellent.

（黏合劑樹脂）作為黏合劑樹脂，沒有特別限定，可以使用習知的樹脂。作為黏合劑樹脂，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、聚乙烯醇縮丁醛等縮丁醛系樹脂等。其中，從在溶劑中的溶解性、燃燒分解性的觀點等而言，理想含有乙基纖維素。另外，在作為內部電極用漿料來使用的情況下，從提高與電介質生片的黏接強度的觀點而言，可以含有縮丁醛系樹脂，或者單獨使用縮丁醛系樹脂。黏合劑樹脂可以使用一種，或者也可以使用兩種以上。(Binder resin) The binder resin is not particularly limited, and conventional resins can be used. Examples of the binder resin include cellulose resins such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, acrylic resins, and butyral resins such as polyvinyl butyral. Aldehyde resin, etc. Among them, it is desirable to contain ethyl cellulose from the viewpoints of solubility in a solvent and combustion decomposability. In addition, when used as a slurry for internal electrodes, from the viewpoint of improving the adhesive strength with the dielectric green sheet, a butyral resin may be contained, or a butyral resin may be used alone. One type of binder resin may be used, or two or more types may be used.

黏合劑樹脂例如可以使用纖維素系樹脂及縮丁醛系樹脂。在導電性漿料中含有纖維素系樹脂和縮丁醛系樹脂的情況下，存在乾燥膜上的突起數減少的傾向。纖維素系樹脂與縮丁醛系樹脂的含有比例沒有特別限定，例如，纖維素系樹脂：縮丁醛系樹脂＝10~90：90~10（重量比，纖維素系樹脂與縮丁醛系樹脂的合計為100），理想為30~70：70~30。As the binder resin, for example, cellulose resin and butyral resin can be used. When the conductive paste contains cellulose resin and butyral resin, the number of protrusions on the dried film tends to decrease. The content ratio of cellulose resin and butyral resin is not particularly limited. For example, cellulose resin: butyral resin=10~90:90~10 (weight ratio, cellulose resin and butyral resin) The total amount of resin is 100), ideally 30~70:70~30.

另外，縮丁醛系樹脂的重均分子量Mw沒有特別限定，例如為2萬以上20萬以下，理想為3萬以上15萬以下。在重均分子量Mw為上述範圍的情況下，在用於導電性漿料時，導電性粉末等的分散性優異，能夠形成適宜的漿料黏度並且減少乾燥膜上的突起數。In addition, the weight average molecular weight Mw of the butyral resin is not particularly limited, and it is, for example, 20,000 or more and 200,000 or less, and desirably 30,000 or more and 150,000 or less. When the weight average molecular weight Mw is in the above range, when used in a conductive slurry, the dispersibility of conductive powder and the like is excellent, a suitable slurry viscosity can be formed, and the number of protrusions on the dry film can be reduced.

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10質量份以下，更理想為1質量份以上8質量份以下。The content of the binder resin relative to 100 parts by mass of the conductive powder is desirably 1 part by mass or more and 10 parts by mass or less, and more desirably 1 part by mass or more and 8 parts by mass or less.

黏合劑樹脂的含量相對於導電性漿料總量理想為0.5質量%以上10質量%以下，更理想為1質量%以上6質量%以下。在黏合劑樹脂的含量為上述範圍內的情況下，導電性以及分散性優異。The content of the binder resin relative to the total amount of the conductive paste is desirably 0.5% by mass or more and 10% by mass or less, and more desirably 1% by mass or more and 6% by mass or less. When the content of the binder resin is within the above range, conductivity and dispersibility are excellent.

（有機溶劑）作為有機溶劑，沒有特別限定，可以使用能夠溶解上述黏合劑樹脂之習知的有機溶劑。作為有機溶劑，例如可列舉：二氫萜品醇乙酸酯、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、乙二醇單丁基醚乙酸酯、二丙二醇甲醚乙酸酯等乙酸酯系溶劑、萜品醇、二氫萜品醇等萜系溶劑、十三烷、壬烷、環己烷等烴系溶劑等。此外，有機溶劑可以使用一種，也可以使用兩種以上。(Organic solvents) The organic solvent is not particularly limited, and a conventional organic solvent capable of dissolving the above-mentioned binder resin can be used. Examples of organic solvents include dihydroterpineol acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, and ethylene glycol monobutyl ether acetic acid. Acetate-based solvents such as esters, dipropylene glycol methyl ether acetate, terpene-based solvents such as terpineol and dihydroterpineol, and hydrocarbon-based solvents such as tridecane, nonane, and cyclohexane. In addition, one type of organic solvent may be used, or two or more types may be used.

有機溶劑的含量相對於導電性粉末100質量份理想為40質量份以上100質量份以下，更理想為65質量份以上95質量份以下。在有機溶劑的含量為上述範圍內的情況下，導電性以及分散性優異。The content of the organic solvent relative to 100 parts by mass of the conductive powder is desirably 40 parts by mass or more and 100 parts by mass or less, and more desirably 65 parts by mass or more and 95 parts by mass or less. When the content of the organic solvent is within the above range, conductivity and dispersibility are excellent.

有機溶劑的含量相對於導電性漿料總量理想為20質量%以上60質量%以下，更理想為35質量%以上55質量%以下。在有機溶劑的含量為上述範圍內的情況下，導電性以及分散性優異。The content of the organic solvent is desirably 20% by mass or more and 60% by mass or less with respect to the total amount of the conductive paste, and more desirably 35% by mass or more and 55% by mass or less. When the content of the organic solvent is within the above range, conductivity and dispersibility are excellent.

（分散劑）本實施型態所涉及的導電性漿料含有分散劑。另外，分散劑含有下述通式（1）所示的胺基酸系分散劑（胺基酸系界面活性劑）以及下述通式（2）所示的胺系分散劑（胺系界面活性劑）。通式（2）所示的胺系分散劑為一級胺。(Dispersant) The conductive paste according to this embodiment contains a dispersant. In addition, the dispersant contains an amino acid-based dispersant represented by the following general formula (1) (amino acid-based surfactant) and an amine-based dispersant represented by the following general formula (2) (amine-based surfactant). Agent). The amine-based dispersant represented by the general formula (2) is a primary amine.

［化4］

[化4]

其中，在上述通式（1）中，R₁ 表示碳原子數為10~20的鏈狀烴基。另外，R₁ 理想表示碳原子數為10~20的直鏈狀烴基。Among them, in the above general formula (1), R ₁ represents a chain hydrocarbon group having 10 to 20 carbon atoms. In addition, R ₁ desirably represents a linear hydrocarbon group having 10 to 20 carbon atoms.

［化5］

[化5]

其中，在上述通式（2）中，R₂ 表示碳原子數為12~22的鏈狀烴基。另外，R₂ 可以表示碳原子數為12~22的直鏈狀烴基，可以為直鏈烯基，也可以具有雙鍵。Among them, in the above general formula (2), R ₂ represents a chain hydrocarbon group having 12 to 22 carbon atoms. In addition, R ₂ may represent a linear hydrocarbon group having 12 to 22 carbon atoms, may be a linear alkenyl group, or may have a double bond.

如上所述，本發明的發明人新發現了作為伴隨著電極圖案的薄膜化而產生上述問題的主要原因之一，可列舉為在印刷導電性漿料後的乾燥膜上產生的突起。而且，本發明的發明人基於該見解，對導電性漿料中使用的分散劑進行了各種分散劑的研究的結果進一步發現：特別係在含有上述通式（1）所示之胺基酸系分散劑的導電性漿料中存在容易在乾燥膜上形成突起的傾向、以及藉由組合上述分散劑，在印刷導電性漿料後的乾燥膜中，能夠減少存在於該膜上的突起的數量。As described above, the inventors of the present invention newly discovered that as one of the main causes of the above-mentioned problems accompanying the thinning of the electrode pattern, the protrusions generated on the dried film after printing the conductive paste can be cited. Furthermore, based on this knowledge, the inventors of the present invention conducted various dispersant studies on the dispersant used in the conductive paste, and further found that: in particular, the system contains the amino acid represented by the above general formula (1) The conductive paste of the dispersant has a tendency to easily form protrusions on the dried film, and by combining the above dispersants, the number of protrusions present on the film can be reduced in the dried film after the conductive paste is printed .

在此，乾燥膜上的突起是指形成於乾燥膜上的凸部（突起），具體而言，是指對利用過濾器對得到的導電性漿料進行過濾之後進行塗布、使其乾燥而得到的乾燥膜從上表面進行觀察時，長軸方向（最長徑）的大小為5μm以上的突起。Here, the protrusions on the dry film refer to the protrusions (protrusions) formed on the dry film, specifically, the conductive slurry obtained by filtering with a filter and then coating and drying it. When observed from the upper surface of the dry film, the size of the long axis direction (longest diameter) is a protrusion with a size of 5 μm or more.

進一步地，本發明的發明人對突起（凸部）的內部的成分進行了分析的結果是可知存在有機物。例如，在上述專利文獻1中，記載了藉由利用過濾器對導電性漿料進行過濾來去除凝集物。然而，在導電性漿料中，尤其是存在起因於有機物的突起（凝集物）的情況下，如專利文獻1所記載：即使利用過濾器進行過濾，但由於凝集物具有柔軟性，因此比過濾器的網目大的凝集物也會通過，從而難以減少乾燥膜上的突起數。在乾燥膜上產生在內部含有有機物的突起的機理的詳細情況尚不明確，但例如可考慮以下的機理。Furthermore, the inventors of the present invention analyzed the internal components of the protrusions (convex portions), as a result, it was found that organic matter was present. For example, in Patent Document 1 described above, it is described that the conductive slurry is filtered with a filter to remove agglomerates. However, in the conductive slurry, especially when there are protrusions (agglomerates) caused by organic matter, as described in Patent Document 1, even if the filter is used for filtering, the agglomerates are more flexible than the filtration. Agglomerates with large meshes of the filter can also pass through, making it difficult to reduce the number of protrusions on the dry film. The details of the mechanism by which protrusions containing organic substances are generated in the dry film are not yet clear, but the following mechanism can be considered, for example.

例如，據認為在分散劑含有通式（1）所示的胺基酸系分散劑的情況下，該胺基酸系分散劑與導電性漿料中的其他成分相互反應，生成不溶於導電性漿料的化合物，其結果是，在對導電性漿料進行印刷、乾燥後的乾燥膜上產生突起。For example, it is considered that when the dispersant contains the amino acid dispersant represented by the general formula (1), the amino acid dispersant reacts with other components in the conductive paste to produce insoluble conductive As a result, the compound of the paste produces protrusions on the dried film after printing and drying the conductive paste.

另外，如後所述，在含有通式（1）所示的胺基酸系分散劑及通式（3）所示的胺系分散劑的情況下，胺基酸系分散劑與胺系分散劑反應，也有可能生成不溶於導電性漿料的化合物。例如，在導電性漿料僅含有通式（1）所示的胺基酸系分散以及通式（3）所示的胺系分散劑作為分散劑的情況下，存在通式（3）所示的胺系分散劑的含量越增加，乾燥膜上的突起數也越增加的傾向（參照後述的比較例1、比較例2的導電性漿料）。In addition, as described later, when the amino acid dispersant represented by the general formula (1) and the amine dispersant represented by the general formula (3) are contained, the amino acid dispersant and the amine dispersant It is also possible to generate compounds that are insoluble in the conductive paste due to the reaction of the agent. For example, when the conductive paste contains only the amino acid dispersant represented by the general formula (1) and the amine dispersant represented by the general formula (3) as the dispersant, there is a dispersant represented by the general formula (3) As the content of the amine-based dispersant increases, the number of protrusions on the dried film also tends to increase (refer to the conductive paste of Comparative Example 1 and Comparative Example 2 described later).

而且，在本實施型態所涉及的導電性漿料中，藉由含有通式（2）所示的胺系分散劑，能夠減少乾燥膜上的突起數。其理由的詳細情況尚不明確，但認為例如通式（2）所示的胺系分散劑抑制通式（1）所示的胺基酸系分散劑與其他成分的反應，且抑制不溶的化合物的生成，或者與通式（1）所示的胺基酸系分散劑、其他成分反應，使生成物的溶解性提高，生成物不以塊的形式存在，由此減少乾燥膜上的突起。Furthermore, in the conductive paste according to this embodiment, by containing the amine-based dispersant represented by the general formula (2), the number of protrusions on the dry film can be reduced. The details of the reason are not clear, but it is thought that, for example, the amine-based dispersant represented by the general formula (2) inhibits the reaction of the amino acid-based dispersant represented by the general formula (1) with other components, and suppresses insoluble compounds The formation of or the reaction with the amino acid-based dispersant represented by the general formula (1) and other components improves the solubility of the product, and the product does not exist in the form of agglomerates, thereby reducing the protrusions on the dried film.

在導電性漿料中，相對於導電性粉末100質量份，含有0.01質量份以上4質量份以下、理想為0.02質量份以上3質量份以下、更理想為0.03質量份以上2質量份以下的通式（1）所示的胺基酸系分散劑。另外，可以含有0.03質量份以上0.6質量份以下的上述式（1）所示的胺基酸系分散劑，也可以含有0.1質量份以上0.6質量份以下。In the conductive paste, relative to 100 parts by mass of the conductive powder, it contains 0.01 parts by mass or more and 4 parts by mass or less, preferably 0.02 parts by mass or more and 3 parts by mass or less, more preferably 0.03 parts by mass or more and 2 parts by mass or less. The amino acid-based dispersant represented by formula (1). In addition, the amino acid-based dispersant represented by the above formula (1) may be contained in an amount of 0.03 parts by mass or more and 0.6 parts by mass or less, or may be contained in an amount of 0.1 parts by mass or more and 0.6 parts by mass or less.

在以上述範圍含有通式（1）所示的胺基酸系分散劑的情況下，能夠提高乾燥膜密度。另外，當在上述範圍內增加胺基酸系分散劑的情況下，例如，相對於導電性粉末100質量份，含有0.1質量份以上2質量份以下、理想為0.1質量份以上1.5質量份以下的胺基酸系分散劑的情況下，可以提高乾燥膜密度、表面粗糙度。When the amino acid-based dispersant represented by the general formula (1) is contained in the above range, the dry film density can be increased. In addition, when the amino acid-based dispersant is added within the above range, for example, relative to 100 parts by mass of the conductive powder, it contains 0.1 parts by mass or more and 2 parts by mass or less, preferably 0.1 parts by mass or more and 1.5 parts by mass or less. In the case of an amino acid-based dispersant, the dry film density and surface roughness can be increased.

此外，相對於導電性粉末100質量份，在通式（1）所示的胺基酸系分散劑的含量超過2質量份的情況下，乾燥性變差，因此在將導電性漿料印刷於電介質生片並乾燥後，成為未乾燥的乾燥膜，在積層時成為內部電極層的破壞等的原因，有時會使晶片形狀變差、使乾燥膜上的突起增加。In addition, when the content of the amino acid-based dispersant represented by the general formula (1) exceeds 2 parts by mass relative to 100 parts by mass of the conductive powder, the drying property becomes poor. Therefore, when the conductive paste is printed on After the dielectric green sheet is dried, it becomes an undried dry film, which may cause damage to the internal electrode layer during lamination, which may deteriorate the shape of the wafer and increase the protrusions on the dry film.

通式（1）所示的胺基酸系分散劑例如可以從市售的產品中選擇滿足上述特性的胺基酸系分散劑來使用。另外，上述胺基酸系分散劑可以使用以往習知的製造方法以滿足上述特性的方式進行製造。The amino acid dispersant represented by the general formula (1) can be used, for example, by selecting an amino acid dispersing agent that satisfies the above-mentioned characteristics from commercially available products. In addition, the above-mentioned amino acid-based dispersant can be manufactured using a conventionally known manufacturing method to satisfy the above-mentioned characteristics.

在導電性漿料中，相對於導電性粉末100質量份，含有0.01質量份以上4質量份以下的通式（2）所示的胺系分散劑，理想為含有0.02質量份以上3質量份以下，更理想為含有0.04質量份以上2質量份以下，也可以含有0.1質量份以上1質量份以下。在通式（2）所示的胺系分散劑的含量為上述範圍的情況下，能夠提高分散性，並且能夠有效地抑制乾燥膜的突起。在通式（2）所示的胺系分散劑的含量比上述範圍多的情況下，由於乾燥性變差，因此在將導電性漿料印刷於電介質生片並乾燥後，成為未乾燥的乾燥膜，在積層時成為內部電極層的破壞等的原因，有時會使晶片形狀變差、使乾燥膜上的突起增加。The conductive paste contains 0.01 to 4 parts by mass of the amine-based dispersant represented by the general formula (2) relative to 100 parts by mass of the conductive powder, preferably 0.02 to 3 parts by mass , It is more desirable to contain 0.04 part by mass or more and 2 parts by mass or less, and it may be contained in 0.1 part by mass or more and 1 part by mass or less. When the content of the amine-based dispersant represented by the general formula (2) is in the above-mentioned range, the dispersibility can be improved, and the protrusion of the dried film can be effectively suppressed. When the content of the amine-based dispersant represented by the general formula (2) is more than the above range, the drying property becomes poor. Therefore, after the conductive paste is printed on the dielectric green sheet and dried, it becomes undried dry The film becomes a cause of destruction of the internal electrode layer when it is laminated, and may deteriorate the shape of the wafer and increase the protrusions on the dry film.

另外，在導電性漿料含有通式（1）所示的胺基酸系分散劑及通式（2）所示的胺系分散劑之兩者的情況下，通式（2）所示的胺系分散劑的含量相對於通式（1）所示的胺基酸系分散劑的含量，以質量比計可以為0.1倍以上3倍以下，也可以為0.5倍以上2.5倍以下，還可以為0.8倍以上1.5倍以下。In addition, when the conductive paste contains both the amino acid-based dispersant represented by the general formula (1) and the amine-based dispersant represented by the general formula (2), the The content of the amine-based dispersant relative to the content of the amino-acid-based dispersant represented by the general formula (1) may be 0.1 times or more and 3 times or less, or 0.5 times or more and 2.5 times or less in terms of mass ratio. It is 0.8 times or more and 1.5 times or less.

另外，如後所述，在導電性漿料含有通式（1）所示的胺基酸系分散劑、通式（2）所示的胺系分散劑以及通式（3）所示的胺系分散劑的情況下，通式（2）所示的胺系分散劑的含量相對於通式（1）所示的胺基酸系分散劑與通式（3）所示的胺系分散劑的合計含量，以質量比計可以為0.1倍以上3倍以下，也可以為0.2倍以上2倍以下，還可以為0.3倍以上1.5倍以下。In addition, as described later, the conductive paste contains an amino acid-based dispersant represented by the general formula (1), an amine-based dispersant represented by the general formula (2), and an amine represented by the general formula (3). In the case of a dispersant, the content of the amine-based dispersant represented by the general formula (2) is relative to the amino acid-based dispersant represented by the general formula (1) and the amine-based dispersant represented by the general formula (3) The total content of, in terms of mass ratio, may be 0.1 times or more and 3 times or less, or 0.2 times or more and 2 times or less, or 0.3 times or more and 1.5 times or less.

又，分散劑可以由通式（1）所示的胺基酸系分散劑以及通式（2）所示的胺系分散劑構成，也可以含有此等以外的分散劑。In addition, the dispersant may be composed of an amino acid-based dispersant represented by the general formula (1) and an amine-based dispersant represented by the general formula (2), or may contain dispersants other than these.

例如，在僅含有通式（1）所示的胺基酸系分散劑以及通式（2）所示的胺系分散劑作為分散劑的情況下，R₂ 理想碳原子數為15~22。另外，在該情況下，相對於通式（1）所示的胺基酸系分散劑的含量，通式（2）所示的胺系分散劑的含量以質量比計可以為0.8倍以上1.5倍以下。For example, when only the amino acid-based dispersant represented by the general formula (1) and the amine-based dispersant represented by the general formula (2) are contained as the dispersant, the ideal number of carbon atoms of _{R 2 is 15-22.} In addition, in this case, the content of the amine-based dispersant represented by the general formula (2) may be 0.8 times or more by mass ratio relative to the content of the amino acid-based dispersant represented by the general formula (1). Less than times.

本實施型態所涉及的導電性漿料可以進一步含有下述通式（3）所示的胺系分散劑作為分散劑。The conductive paste according to this embodiment may further contain an amine-based dispersant represented by the following general formula (3) as a dispersant.

［化6］

[化6]

在上述通式（3）中，R₃ 表示碳原子數為8~16的烷基、烯基或炔基，R₄ 表示氧化乙烯基、氧化丙烯基或亞甲基，R₅ 表示氧化乙烯基或氧化丙烯基。此外，R₄ 及R₅ 可以相同，或者也可以不同。另外，通式（3）中的N原子與R₄ 及R₅ 中的O原子不直接鍵合，且Y為0~2的數，Z為1~2的數。In the above general formula (3), R ₃ represents an alkyl, alkenyl or alkynyl group with 8 to 16 carbon atoms, R ₄ represents an oxyethylene group, an oxypropylene group or a methylene group, and R ₅ represents an oxyethylene group Or oxypropylene group. In addition, R ₄ and R ₅ may be the same or different. In addition, the N atom in the general formula (3) and the O atom in R ₄ and R ₅ are not directly bonded, Y is the number of 0-2, and Z is the number of 1-2.

通式（3）所示的胺系分散劑為三級胺或二級胺，具有胺基與一個或兩個氧化烯基鍵合而成的結構。The amine-based dispersant represented by the general formula (3) is a tertiary amine or a secondary amine, and has a structure in which an amine group is bonded to one or two oxyalkylene groups.

在與通式（1）所示的胺基酸系分散劑、通式（2）所示的胺系分散劑一起含有通式（3）所示的胺系分散劑的情況下，所得到的導電性漿料在形成薄膜化的電極時印刷性也很優異，使用該導電性漿料形成的積層陶瓷電容器等電子零件的電極圖案精度良好且能夠具有均勻的寬度以及厚度。When the amine-based dispersant represented by the general formula (3) is contained together with the amino acid-based dispersant represented by the general formula (1) and the amine-based dispersant represented by the general formula (2), the resulting The conductive paste is also excellent in printability when forming thin-film electrodes, and the electrode pattern of electronic components such as multilayer ceramic capacitors formed using the conductive paste is highly accurate and can have a uniform width and thickness.

在通式（3）中，R₃ 表示碳原子數為8~16的烷基、烯基或炔基。在R₃ 的碳原子數為上述範圍的情況下，導電性漿料中的粉末具有充分的分散性，在溶劑中的溶解度優異。此外，R₃ 理想為直鏈狀烴基。In the general formula (3), R ₃ represents an alkyl group, alkenyl group, or alkynyl group having 8 to 16 carbon atoms. When the _{number of carbon atoms of R 3} is in the above range, the powder in the conductive paste has sufficient dispersibility and excellent solubility in the solvent. In addition, R _{3 is} desirably a linear hydrocarbon group.

在通式（3）中，R₄ 表示氧化乙烯基、氧化丙烯基或亞甲基，R₅ 表示氧化乙烯基或氧化丙烯基，R₄ 及R₅ 可以相同，或者也可以不同。另外，式（2）中的N原子與R₄ 及R₅ 中的O原子不直接鍵合，Y為0以上2以下的數，Z為1以上2以下的數。In the general formula (3), R ₄ represents an oxyethylene group, an oxypropylene group or a methylene group, R ₅ represents an oxyethylene group or an oxypropylene group, and R ₄ and R ₅ may be the same or different. In addition, the N atom in the formula (2) and the O atom in R ₄ and R ₅ are not directly bonded, Y is a number of 0 or more and 2 or less, and Z is a number of 1 or more and 2 or less.

例如，在通式（3）中，在R₄ 為-AO-所示的氧化烯基、且Y為1~2的情況下，最端部的氧化烯基中的O原子與和（R₄ ）_Y 相鄰的H原子鍵合。另外，在R₄ 為亞甲基的情況下，（R₄ ）_Y 由-（CH₂ ）_Y -表示，在Y為1~2的情況下，與相鄰的H元素鍵合而形成甲基（-CH₃ ）或乙基（-CH₂ -CH₃ ）。另外，在R₅ 為-AO-所示的氧化烯基的情況下，最端部的氧化烯基中的O原子與和（R₅ ）_Z 相鄰的H原子鍵合。For example, in the general formula (3), when R ₄ is an oxyalkylene group represented by -AO- and Y is 1 to 2, the O atom in the oxyalkylene group at the end and the sum (R ₄ ) The adjacent H atoms of _{Y are bonded.} In addition, when R ₄ is a methylene group, (R ₄ ) _{Y is} represented by -(CH ₂ ) _Y -, and when Y is 1 to 2, it bonds with adjacent H elements to form a methyl group. (-CH ₃ ) or ethyl (-CH ₂ -CH ₃ ). In addition, when R ₅ is an oxyalkylene group represented by -AO-, the O atom in the oxyalkylene group at the end is bonded to the H atom adjacent to _{(R 5} ) _Z.

在通式（3）中，在Y為0的情況下，上述胺系分散劑為具有-R₃ 、一個氫基及-（R₅ ）_Z H的二級胺。例如，在Y為0、Z為2的情況下，上述胺系分散劑為由碳原子數為8~16的烷基、烯基或炔基、一個氫基、二氧化乙烯基以及二氧化丙烯基中的任一個與H元素鍵合而成的-（AO）₂ H構成的二級胺。In the general formula (3), in the case where Y is 0, said dispersant having amine -R & lt _3, a hydrogen group, and - secondary amines (R ₅₎ _Z H a. For example, when Y is 0 and Z is 2, the above-mentioned amine dispersant is composed of an alkyl, alkenyl, or alkynyl group with 8 to 16 carbon atoms, a hydrogen group, vinyl dioxide, and propylene dioxide. A secondary amine _{composed of -(AO) 2} H formed by bonding any one of the groups with the H element.

另外，在通式（3）中，在Y為1的情況下，上述胺系分散劑為具有-R₃ 、-R₄ H及-（R₅ ）_Z H的三級胺。而且，在Y為2的情況下，上述胺系分散劑為具有-R₃ 、作為-（R₄ ）₂ H的二氧化乙烯基、二氧化丙烯基、或乙烯基與H元素鍵合而成的-（AO）₂ H或-C₂ H₅ 、和-（R₅ ）_Z H的三級胺。In addition, in the general formula (3), when Y is 1, the amine-based dispersant is a tertiary amine _{having -R 3} , -R ₄ H, and -(R ₅ ) _{Z H.} Moreover, when Y is 2, the above-mentioned amine-based dispersant is a _{vinyl dioxide group having -R 3} as -(R ₄ ) ₂ H, a propylene dioxide group, or a combination of a vinyl group and H element The -(AO) ₂ H or -C ₂ H ₅ , and -(R ₅ ) _Z H tertiary amine.

在導電性漿料中，相對於導電性粉末100質量份，可以含有0.01質量份以上4質量份以下的通式（3）所示的胺系分散劑，理想為0.02質量份以上2.5質量份以下，更理想為0.03質量份以上2質量份以下，也可以含有0.05質量份以上0.6質量份以下。在以上述範圍含有通式（3）所示的胺系分散劑的情況下，能夠抑制隨時間的黏度變化，從而提高黏度穩定性。In the conductive paste, with respect to 100 parts by mass of the conductive powder, the amine dispersant represented by the general formula (3) may be contained in an amount of 0.01 parts by mass or more and 4 parts by mass or less, preferably 0.02 parts by mass or more and 2.5 parts by mass or less , More preferably 0.03 parts by mass or more and 2 parts by mass or less, and may also contain 0.05 parts by mass or more and 0.6 parts by mass or less. When the amine-based dispersant represented by the general formula (3) is contained in the above-mentioned range, the viscosity change with time can be suppressed, and the viscosity stability can be improved.

此外，在導電性漿料不含有通式（2）所示的胺系分散劑，僅含有通式（1）所示的胺基酸系分散劑和通式（3）所示的胺系分散劑的情況下，存在通式（3）所示的胺系分散劑的含量越增加越能夠提高黏度穩定性及分散性但乾燥膜上的突起數也增加的傾向。然而，在本實施型態所涉及的導電性漿料中，藉由含有通式（2）所示的胺系分散劑，即使在較多地含有通式（3）所示的胺系分散劑的情況下（例如，相對於導電性粉末100質量份，含有0.5質量份以上、或0.6質量份以上的情況下），也能夠提高黏度穩定性及分散性，並且抑制乾燥膜的突起的產生。In addition, the conductive paste does not contain the amine-based dispersant represented by the general formula (2), but only contains the amino-acid-based dispersant represented by the general formula (1) and the amine-based dispersant represented by the general formula (3) In the case of an agent, the more the content of the amine-based dispersant represented by the general formula (3) increases, the more the viscosity stability and dispersibility can be improved, but the number of protrusions on the dry film tends to increase. However, in the conductive paste according to this embodiment, by containing the amine-based dispersant represented by the general formula (2), even if the amine-based dispersant represented by the general formula (3) is contained more In the case of (for example, 0.5 parts by mass or more, or 0.6 parts by mass or more relative to 100 parts by mass of the conductive powder), the viscosity stability and dispersibility can also be improved, and the generation of protrusions in the dry film can be suppressed.

此外，在通式（3）所示的胺系分散劑的含量超過2質量份的情況下，由於乾燥性變差，因此在將導電性漿料印刷於電介質生片並乾燥後，成為未乾燥的乾燥膜，在積層時成為內部電極層的破壞等的原因，有時會使晶片形狀變差、使乾燥膜上的突起增加。In addition, when the content of the amine-based dispersant represented by the general formula (3) exceeds 2 parts by mass, the drying property is deteriorated, so after the conductive paste is printed on the dielectric green sheet and dried, it becomes undried The dry film of the film may cause the destruction of the internal electrode layer during the stacking, and may deteriorate the shape of the wafer and increase the protrusions on the dry film.

通式（3）所示的胺系分散劑例如可以從市售的產品中選擇滿足上述特性的胺系分散劑來使用。另外，上述胺系分散劑可以使用以往習知的製造方法以滿足上述特性的方式進行製造。The amine-based dispersant represented by the general formula (3) can be used, for example, by selecting an amine-based dispersing agent that satisfies the above-mentioned characteristics from commercially available products. In addition, the above-mentioned amine-based dispersant can be manufactured using a conventionally known manufacturing method so as to satisfy the above-mentioned characteristics.

在導電性漿料中，相對於導電性粉末100質量份，分散劑整體的含量理想為0.01質量份以上5質量份以下，更理想為0.04質量份以上3質量份以下，也可以為0.2質量份以上2質量份以下。在分散劑的含量為上述範圍的情況下，能夠將導電性漿料的黏度調整至適當的範圍，並且能夠抑制片材侵蝕、電介質生片的剝離不良。In the conductive paste, relative to 100 parts by mass of the conductive powder, the content of the dispersant as a whole is desirably 0.01 part by mass or more and 5 parts by mass or less, more preferably 0.04 part by mass or more and 3 parts by mass or less, or 0.2 parts by mass The above 2 parts by mass or less. When the content of the dispersant is within the above range, the viscosity of the conductive paste can be adjusted to an appropriate range, and sheet erosion and poor peeling of the dielectric green sheet can be suppressed.

另外，分散劑整體的含量相對於導電性漿料總量理想為含有4質量%以下。分散劑的含量的上限理想為3質量%以下，更理想為2質量%以下，也可以為1質量%以下。分散劑的含量的下限沒有特別限定，例如為0.01質量%以上，理想為0.05質量%以上，也可以為0.1質量%以上。在分散劑的含量為上述範圍的情況下，能夠將導電性漿料的黏度調整至適當的範圍，並且能夠抑制片材侵蝕、電介質生片的剝離不良。In addition, the content of the entire dispersant is desirably 4% by mass or less with respect to the total amount of the conductive paste. The upper limit of the content of the dispersant is desirably 3% by mass or less, more desirably 2% by mass or less, and may be 1% by mass or less. The lower limit of the content of the dispersant is not particularly limited. For example, it is 0.01% by mass or more, desirably 0.05% by mass or more, and may be 0.1% by mass or more. When the content of the dispersant is within the above range, the viscosity of the conductive paste can be adjusted to an appropriate range, and sheet erosion and poor peeling of the dielectric green sheet can be suppressed.

此外，導電性漿料可以在不阻礙本發明的效果的範圍內含有除上述胺基酸系分散劑以及胺系分散劑以外的分散劑。作為上述以外的分散劑，例如可以含有包含高級脂肪酸、高分子界面活性劑等的酸系分散劑、酸系分散劑以外的陽離子系分散劑、非離子系分散劑、兩性界面活性劑以及高分子系分散劑等。另外，此等分散劑可以使用一種或組合使用兩種以上。In addition, the conductive paste may contain a dispersant other than the above-mentioned amino acid-based dispersant and amine-based dispersant within a range that does not inhibit the effects of the present invention. As dispersants other than the above, for example, acid-based dispersants including higher fatty acids, polymer surfactants, etc., cationic dispersants other than acid-based dispersants, nonionic dispersants, amphoteric surfactants, and polymers may be contained. Department of dispersant and so on. In addition, these dispersing agents can be used singly or in combination of two or more.

（導電性漿料）本實施型態所涉及的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。例如，本實施型態的導電性漿料可以藉由準備上述各成分，並利用三輥磨、球磨機、混合機等對各成分進行攪拌、混煉來製造。此時，若在導電性粉末表面預先塗布分散劑，則導電性粉末不會凝集，可充分地散開，其表面遍佈有分散劑，易於得到均勻的導電性漿料。另外，也可以是，在將黏合劑樹脂溶解於載體用的有機溶劑中而製作有機載體後，向漿料用的有機溶劑中添加導電性粉末、陶瓷粉末、有機載體以及分散劑，進行攪拌、混煉，從而製作導電性漿料。(Conductive paste) The manufacturing method of the conductive paste concerning this embodiment is not specifically limited, A conventionally well-known method can be used. For example, the conductive paste of this embodiment can be produced by preparing the above-mentioned components, and stirring and kneading the components using a three-roll mill, a ball mill, a mixer, or the like. At this time, if a dispersant is applied to the surface of the conductive powder in advance, the conductive powder will not aggregate and can be sufficiently dispersed, the dispersant is spread all over the surface, and it is easy to obtain a uniform conductive paste. Alternatively, after the binder resin is dissolved in the organic solvent for the carrier to prepare the organic vehicle, conductive powder, ceramic powder, organic vehicle, and dispersant may be added to the organic solvent for the slurry, followed by stirring, Kneaded to produce a conductive paste.

另外，在有機溶劑中，作為載體用的有機溶劑，為了改善有機載體的親和性，理想為使用與調整導電性漿料的黏度的漿料用的有機溶劑相同的有機溶劑。相對於導電性粉末100質量份，載體用的有機溶劑的含量例如為5質量份以上80質量份以下。另外，載體用的有機溶劑的含量相對於導電性漿料整體量理想為10質量%以上40質量%以下。In addition, among the organic solvents, as the organic solvent for the vehicle, in order to improve the affinity of the organic vehicle, it is desirable to use the same organic solvent as the organic solvent for the slurry for adjusting the viscosity of the conductive paste. The content of the organic solvent for the carrier is, for example, 5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the conductive powder. In addition, the content of the organic solvent for the carrier is desirably 10% by mass or more and 40% by mass or less with respect to the entire amount of the conductive paste.

以下，對本實施型態所涉及的導電性漿料的理想特性進行說明。Hereinafter, the ideal characteristics of the conductive paste according to this embodiment will be described.

［乾燥膜密度：DFD］印刷導電性漿料後進行乾燥而得到的乾燥膜的密度（DFD）理想為超過4.8g/cm³ ，更理想為5.0g/cm³ 以上，進一步理想為5.2g/cm³ 以上，特別理想為5.4g/cm³ 以上。[Dry Film Density: DFD] The density (DFD) of the dry film obtained by drying the conductive paste after printing is desirably more than 4.8 g/cm ³ , more desirably 5.0 g/cm ³ or more, and still more desirably 5.2 g/ cm ³ or more, particularly preferably 5.4 g/cm ³ or more.

［乾燥膜的表面粗糙度］對導電性漿料進行網版印刷，在大氣中以120℃乾燥1小時，由此製作20mm見方、膜厚為1~3μm的乾燥膜時的表面粗糙度Ra（算術平均粗糙度）理想為0.10μm以下，可以為0.07μm以下，也可以為0.06μm以下。此外，表面粗糙度Ra（算術平均粗糙度）的下限理想為表面平坦，沒有特別限定，但理想為超過0的值且越小的值越好。[Surface roughness of dry film] The surface roughness Ra (arithmetic mean roughness) when a dry film with a thickness of 1 to 3 μm and a thickness of 1 to 3 μm is produced by screen printing the conductive paste in the air for 1 hour in the air is ideally 0.10 μm or less, may be 0.07 μm or less, or may be 0.06 μm or less. In addition, the lower limit of the surface roughness Ra (arithmetic mean roughness) is desirably a flat surface and is not particularly limited, but it is desirably a value exceeding 0 and a smaller value is better.

［乾燥膜的突起數］使用導電性漿料在下述條件下製作的乾燥膜上的突起的數量理想為100個以下，更理想為50個以下，進一步理想為20個以下。在乾燥膜的突起的數量為上述範圍的情況下，能夠抑制使用導電性漿料而形成的積層陶瓷電容器等電子零件的短路不良。[Number of protrusions of dry film] The number of protrusions on the dry film produced using the conductive paste under the following conditions is desirably 100 or less, more desirably 50 or less, and still more desirably 20 or less. When the number of protrusions of the dry film is within the above-mentioned range, it is possible to suppress short-circuit defects of electronic components such as multilayer ceramic capacitors formed using conductive paste.

［乾燥膜的製造條件］在2英吋見方、厚度為1mm的玻璃基板上，以35μm的厚度使用敷抹器（applicator）塗布利用寬度為1.5cm、長度為4cm、網目為6μm的過濾器進行過濾後的導電性漿料，在120℃下乾燥10分鐘，得到乾燥膜。另外，使用光學顯微鏡，利用×10的透鏡對塗布膜的整個面（寬度1.5cm×長度4cm）進行觀察，計數俯視（平面視）時5μm以上的尺寸的突起的數量，並計算出乾燥膜上的突起的個數。[Manufacturing conditions of dry film] On a 2 inch square glass substrate with a thickness of 1 mm, the conductive slurry is applied with a thickness of 35 μm using an applicator, which is filtered with a filter with a width of 1.5 cm, a length of 4 cm, and a mesh of 6 μm , Dried at 120°C for 10 minutes to obtain a dry film. In addition, an optical microscope was used to observe the entire surface of the coating film (width 1.5 cm × length 4 cm) with a ×10 lens, and count the number of protrusions with a size of 5 μm or more in a plan view (plan view), and calculate the number of protrusions on the dry film The number of protrusions.

導電性漿料能夠適宜地使用在積層陶瓷電容器等電子零件中。積層陶瓷電容器具有使用電介質生片而形成的電介質層以及使用導電性漿料而形成的內部電極層。The conductive paste can be suitably used for electronic parts such as multilayer ceramic capacitors. The multilayer ceramic capacitor has a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.

對於積層陶瓷電容器而言，電介質生片中含有的電介質陶瓷粉末及導電性漿料中含有的陶瓷粉末理想為同一組成的粉末。使用本實施型態的導電性漿料製造的積層陶瓷電容器，即使在生片的厚度例如為3μm以下的情況下，也能夠抑制片材侵蝕、生片的剝離不良。For multilayer ceramic capacitors, the dielectric ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste are preferably powders of the same composition. The multilayer ceramic capacitor manufactured using the conductive paste of this embodiment can suppress sheet erosion and peeling failure of the green sheet even when the thickness of the green sheet is 3 μm or less, for example.

［電子零件］以下，參照圖式對本發明的電子零件等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。另外，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方向為鉛垂方向（上下方向）。[Electronic Parts] Hereinafter, embodiments of electronic components and the like of the present invention will be described with reference to the drawings. In the drawings, it may be indicated in a schematic manner as appropriate, and the scale may be changed. In addition, the position, direction, etc. of the parts will be described with reference to the XYZ orthogonal coordinate system shown in FIG. 1 etc. as appropriate. 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是表示作為實施型態所涉及的電子零件的一個例子的、積層陶瓷電容器1的圖。積層陶瓷電容器1具有電介質層12以及內部電極層11交替地積層而成的積層體10與外部電極20。A in FIG. 1 and B in FIG. 1 are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component according to the embodiment. The multilayer ceramic capacitor 1 has a 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的積層陶瓷電容器的製造方法進行說明。首先，在由電介質生片構成的電介質層上印刷導電性漿料並進行乾燥而形成乾燥膜。藉由對在上表面具有該乾燥膜的多個電介質層藉由壓接而進行積層之後，進行燒製而使其一體化，由此製備內部電極層11與電介質層12交替地積層而成的陶瓷積層體10（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，進行更詳細的說明。Hereinafter, a method of manufacturing a multilayer ceramic capacitor using the above-mentioned conductive paste will be described. First, a conductive paste is printed on a dielectric layer composed of a dielectric green sheet and dried to form a dry film. A plurality of dielectric layers having the dry film on the upper surface are laminated by pressure bonding, and then fired to be integrated, thereby preparing an internal electrode layer 11 and a dielectric layer 12 alternately laminated Ceramic laminated body 10 (laminated body 10). After that, by forming a pair of external electrodes 20 on both ends of the ceramic laminate 10, the multilayer ceramic capacitor 1 is manufactured. Hereinafter, a more detailed description will be given.

首先，準備作為未燒製的陶瓷片材的生片。作為該生片，例如，可列舉為將在鈦酸鋇等規定的陶瓷原料粉末中加入聚乙烯醇縮丁醛等有機黏合劑及萜品醇等溶劑而得到的電介質層用漿料在PET薄膜等支撐薄膜上塗布成片材狀並進行乾燥去除溶劑而形成的生片等。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3μm以下。First, a green sheet as an unfired ceramic sheet is prepared. As the green sheet, for example, a PET film is prepared by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate. A green sheet formed by coating a support film in a sheet shape and drying 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 miniaturization of multilayer ceramic capacitors, it is desirably 0.05 μm or more and 3 μm or less.

接下來，準備多個藉由在該生片的一個面上根據網版印刷法等習知的方法印刷（塗布）上述導電性漿料並進行乾燥而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，印刷後的導電性漿料（乾燥膜）的厚度理想為乾燥後為1μm以下。Next, a plurality of sheets in which a dry film is formed by printing (coating) the above-mentioned conductive paste on one surface of the green sheet according to a known method such as a screen printing method and drying it is prepared. In addition, from the viewpoint of the requirement for thinning of the internal electrode layer 11, the thickness of the conductive paste (dry film) after printing is desirably 1 μm or less after drying.

接下來，從支撐薄膜上將生片剝離，並且以由生片構成的電介質層與形成於該電介質層的一個面上的乾燥膜交替地配置的方式進行積層之後，藉由加熱、加壓處理而得到積層體（壓接體）。此外，亦可以設為在積層體（壓接體）的兩面進一步配置未塗布導電性漿料的保護用的生片的構成。Next, the green sheet is peeled from the support film, and the dielectric layer composed of the green sheet and the dry film formed on one surface of the dielectric layer are laminated alternately, and then heated and pressurized. The laminated body (crimped body) is obtained. Moreover, it can also be set as the structure which arrange|positions the green sheet for protection which does not apply a conductive paste further on both surfaces of a laminated body (press-bonded body).

接下來，將積層體（壓接體）切斷為規定尺寸而形成生晶片之後，對該生晶片實施脫黏合劑處理，並在還原氣體環境下進行燒製，由此製造陶瓷積層體10。此外，脫黏合劑處理中的氣體環境理想為大氣或N₂ 氣體氣體環境。進行脫黏合劑處理時的溫度例如為200℃以上400℃以下。另外，進行脫黏合劑處理時的上述溫度的保持時間理想為0.5小時以上24小時以下。另外，為了抑制在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，另外，進行積層體（壓接體）的燒製時的溫度例如為1000℃以上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8小時以下。Next, after cutting the laminated body (crimped body) into a predetermined size to form a green wafer, the green wafer is subjected to a debonding agent treatment and fired in a reducing gas atmosphere, thereby manufacturing the ceramic laminated body 10. In addition, the gas environment in the debinding agent treatment is ideally atmospheric or N ₂ gas environment. The temperature at the time of the debinding agent treatment is, for example, 200°C or more and 400°C or less. In addition, the retention time of the above-mentioned temperature at the time of the debinding agent treatment is desirably 0.5 hour or more and 24 hours or less. In addition, in order to suppress oxidation of the metal used in the internal electrode layer, firing is performed in a reducing gas atmosphere. In addition, the temperature at which the laminate (compression-bonded body) is fired is, for example, 1000° C. or more and 1350° C. or less. The holding time of the temperature at the time of firing is, for example, 0.5 hour or more and 8 hours or less.

藉由進行生晶片的燒製，將生片中的有機黏合劑完全去除，並且陶瓷原料粉末得到燒製而形成陶瓷製的電介質層12。另外，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，進而形成電介體層12與內部電極層11多層交替地積層而成的陶瓷積層體10。此外，從將氧帶入電介質層的內部而提高可靠性、且抑制內部電極的再氧化的觀點而言，可以對燒製後的陶瓷積層體10實施退火處理。By firing the green wafer, the organic binder in the green wafer is completely removed, and the ceramic raw material powder is fired to form the dielectric layer 12 made of ceramic. In addition, the organic carrier in the dried film is removed, and nickel powder or alloy powder with nickel as the main component is sintered or melted to form an internal electrode, and then a dielectric layer 12 and an internal electrode layer 11 are alternately laminated in multiple layers The ceramic laminate 10 made. In addition, from the viewpoint of bringing oxygen into the dielectric layer to improve reliability and suppress reoxidation of the internal electrodes, the ceramic laminate 10 after firing may be annealed.

然後，藉由對所製備的陶瓷積層體10設置一對外部電極20，由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，例如可以適宜地使用銅、鎳或其等的合金。此外，電子零件不限於積層陶瓷電容器，還可以是除積層陶瓷電容器以外的電子零件。［實施例］Then, by providing a pair of external electrodes 20 to the prepared ceramic laminate 10, the multilayer ceramic capacitor 1 is manufactured. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. The external electrode layer 21 is electrically connected to the internal electrode layer 11. In addition, as the material of the external electrode 20, for example, copper, nickel, or alloys thereof can be suitably used. In addition, the electronic component is not limited to the multilayer ceramic capacitor, and may be an electronic component other than the multilayer ceramic capacitor. [Example]

以下，基於實施例及比較例對本發明進行詳細說明，但本發明並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 by the examples at all.

［評價方法］（導電性漿料的突起數）製作導電性漿料，利用網目為6μm的過濾器進行過濾之後，在2英吋見方、厚度為1mm的玻璃基板上，使用敷抹器將過濾後的導電性漿料塗布成厚度為35μm、寬度為1.5cm、長度為4cm，在120℃下乾燥10分鐘，製作試樣（乾燥膜）。之後，使用奧林巴斯製造的光學顯微鏡，利用×10的透鏡從上面觀察所得到的乾燥膜的整個面（1.5cm×4cm），計數突起的大小（最長軸方向的長度）為5μm以上的尺寸的突起的數量。此外，突起數越少越理想。[Evaluation method] (Number of protrusions of conductive paste) Prepare the conductive slurry and filter it with a 6μm mesh filter. Use an applicator to apply the filtered conductive slurry to a thickness of 35μm and a width of 1mm on a glass substrate of 2 inches square. It is 1.5 cm in length and 4 cm in length, and dried at 120°C for 10 minutes to prepare a sample (dry film). After that, using an optical microscope manufactured by Olympus, the entire surface (1.5cm×4cm) of the obtained dry film was observed from above with a ×10 lens, and the size of the protrusions (length in the longest axis direction) of 5μm or more were counted. The number of protrusions of the size. In addition, the smaller the number of protrusions, the better.

（乾燥膜密度DFD）將所製作的導電性漿料載置於PET薄膜上，利用寬度為50mm、間隙為125μm的敷抹器延伸至長度約為100mm。將得到的PET薄膜在120℃下乾燥40分鐘而形成乾燥體後，將該乾燥體以2.54cm（1英吋）見方切斷為四片，在將PET薄膜剝離的基礎上，測定各四片的乾燥膜的厚度、重量，並計算出乾燥膜密度（平均值）。(Dry film density DFD) The prepared conductive paste was placed on a PET film and extended to a length of approximately 100 mm with an applicator with a width of 50 mm and a gap of 125 μm. After drying the obtained PET film at 120°C for 40 minutes to form a dried body, the dried body was cut into four pieces in a square of 2.54 cm (1 inch). After the PET film was peeled off, the four pieces were measured. Calculate the thickness and weight of the dry film, and calculate the dry film density (average value).

（表面粗糙度）在2.54cm（1英吋）見方的耐熱強化玻璃上網版印刷所製作的導電漿料，在大氣中以120℃乾燥1小時，由此製作20mm見方、膜厚為1~3μm的乾燥膜。基於JIS B0601-2001的標準，對所製作的乾燥膜的表面粗糙度Ra（算術平均粗糙度）進行測定。(Surface roughness) The conductive paste produced by the on-screen printing of heat-resistant tempered glass of 2.54 cm (1 inch) square is dried in the air at 120°C for 1 hour to produce a dried film of 20 mm square with a film thickness of 1 to 3 μm. Based on the standard of JIS B0601-2001, the surface roughness Ra (arithmetic mean roughness) of the produced dry film was measured.

（綜合評價）作為乾燥膜的綜合評價，將突起的數量為20個以下、且表面粗糙度Ra為0.1μm以下的情況評價為「〇」，將突起的數量超過20且為99個以下、且表面粗糙度Ra為0.1μm以下的情況評價為「△」，將突起的數量超過100個的情況及/或表面粗糙度Ra超過0.1μm的情況評價為「×」。(Overview) As a comprehensive evaluation of the dry film, the case where the number of protrusions is 20 or less and the surface roughness Ra is 0.1 μm or less is evaluated as "〇", and the number of protrusions exceeds 20 and is 99 or less, and the surface roughness Ra The case where the thickness is 0.1 μm or less is evaluated as "△", and the case where the number of protrusions exceeds 100 and/or the case where the surface roughness Ra exceeds 0.1 μm is evaluated as "×".

［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）。[Use materials] (Conductive powder) As the conductive powder, Ni powder (SEM average particle size 0.2 μm) was used.

（陶瓷粉末）作為陶瓷粉末，使用鈦酸鋇（BaTiO₃ ；SEM平均粒徑為0.10μm）。(Ceramic Powder) As the ceramic powder, barium titanate (BaTiO ₃ ; SEM average particle size is 0.10 μm) is used.

（黏合劑樹脂）作為黏合劑樹脂，使用乙基纖維素樹脂（EC樹脂）及/或聚乙烯醇縮丁醛樹脂（PVB樹脂）。此外，黏合劑樹脂使用作為溶解於乙酸異冰片酯（有機溶劑）的載體而準備的黏合劑樹脂。(Binder resin) As the binder resin, ethyl cellulose resin (EC resin) and/or polyvinyl butyral resin (PVB resin) are used. In addition, as the binder resin, a binder resin prepared as a carrier dissolved in isobornyl acetate (organic solvent) was used.

（分散劑）使用以下的分散劑。（1）作為分散劑a，使用上述通式（1）中R₁ ＝C₁₇ H₃₃ （直鏈狀烴基）所示的胺基酸系分散劑。（2）作為分散劑b，使用上述通式（2）中R₂ ＝C₁₈ H₃₅ （直鏈狀烴基）所示的胺系分散劑。（3）作為分散劑b2，使用上述通式（2）中R₂ ＝C₁₂ H₂₅ （直鏈狀烴基）所示的胺系分散劑。（4）作為分散劑c，使用上述通式（3）中R₃ ＝C₁₂ H₂₅ 、R₄ ＝C₂ H₄ O、R₅ ＝C₂ H₄ O、Y＝1、Z＝1所示的胺系分散劑。(Dispersant) The following dispersants are used. (1) As the dispersant a, an amino acid-based dispersant represented by _{R 1} =C ₁₇ H _{33 (linear hydrocarbon group) in the general formula (1) above is used.} (2) As the dispersant b, an amine-based dispersant represented by _{R 2} =C ₁₈ H _{35 (linear hydrocarbon group) in the general formula (2) above is used.} (3) As the dispersant b2, an amine-based dispersant represented by _{R 2} =C ₁₂ H _{25 (linear hydrocarbon group) in the general formula (2) above is used.} (4) As the dispersant c, use the formula (3) where R ₃ ＝C ₁₂ H ₂₅ , R ₄ ＝C ₂ H ₄ O, R ₅ ＝C ₂ H ₄ O, Y=1, Z=1 The amine-based dispersant shown.

（有機溶劑）作為有機溶劑，使用乙酸異冰片酯（IBA）或萜品醇（TPO）。(Organic solvents) As the organic solvent, isobornyl acetate (IBA) or terpineol (TPO) is used.

［實施例1］以整體為100質量%的方式配合下述材料：導電性粉末為50質量%、陶瓷粉末為10質量%、由乙基纖維素樹脂以及聚乙烯醇縮丁醛樹脂構成的載體中的黏合劑樹脂合計為3質量%（乙基纖維素樹脂：聚乙烯醇縮丁醛樹脂＝60：40（重量比））、以表1所示的比例配合的分散劑合計為0.62質量%、以及有機溶劑，將此等材料混合而製作導電性漿料。藉由上述方法對所製作的導電性漿料的乾燥膜的表面粗糙度以及突起數等進行評價。將評價結果示於表1。[Example 1] The following materials are blended at 100% by mass as a whole: conductive powder is 50% by mass, ceramic powder is 10% by mass, and binder resin in a carrier composed of ethyl cellulose resin and polyvinyl butyral resin The total is 3% by mass (ethyl cellulose resin: polyvinyl butyral resin=60:40 (weight ratio)), the total dispersant blended in the ratio shown in Table 1 is 0.62% by mass, and the organic solvent, These materials are mixed to prepare a conductive paste. The surface roughness, the number of protrusions, and the like of the dried film of the produced conductive paste were evaluated by the above-mentioned method. The evaluation results are shown in Table 1.

［實施例2~12、比較例1~3］除了將分散劑的含量變更為表1所示的量以外，在與實施例1同樣的條件下製作導電性漿料。使用所製作的導電性漿料，藉由上述方法對表面粗糙度以及突起數等進行評價。將評價結果示於表1。[Examples 2 to 12, Comparative Examples 1 to 3] Except for changing the content of the dispersant to the amount shown in Table 1, a conductive paste was produced under the same conditions as in Example 1. Using the produced conductive paste, the surface roughness, the number of protrusions, and the like were evaluated by the above-mentioned method. The evaluation results are shown in Table 1.

此外，在表中，表示各分散劑的含有率的「質量份」是相對於導電性粉末100質量份的比例。另外，在表中，表示各分散劑的含有率的「質量%」是相對於導電性漿料100質量%的比例。In addition, in the table, the "parts by mass" indicating the content of each dispersant is a ratio with respect to 100 parts by mass of the conductive powder. In addition, in the table, the "mass %" indicating the content rate of each dispersant is a ratio with respect to 100% by mass of the conductive paste.

［表1］

[Table 1]

［實施例13~16、比較例3、比較例4］除了將各材料的種類以及含量設為表2所示的種類以及量以外，在與實施例1同樣的條件下製作導電性漿料。使用所製作的導電性漿料，藉由上述方法對表面粗糙度以及突起數等進行評價。將評價結果示於表2。此外，表2中的比較例3與表1中的比較例3相同（為了比較而示出）。[Examples 13-16, Comparative Example 3, Comparative Example 4] Except having made the kind and content of each material into the kind and amount shown in Table 2, the conductive paste was produced under the same conditions as Example 1. Using the produced conductive paste, the surface roughness, the number of protrusions, and the like were evaluated by the above-mentioned method. The evaluation results are shown in Table 2. In addition, Comparative Example 3 in Table 2 is the same as Comparative Example 3 in Table 1 (shown for comparison).

［表2］

[Table 2]

［評價結果］如表1所示，在含有胺基酸系分散劑a、胺系分散劑b以及胺系分散劑c的實施例的導電性漿料中，乾燥膜的表面粗糙度Ra（算術平均粗糙度）為0.10μm以下，且乾燥膜的突起數少至100個以下。另外，在實施例的導電性漿料中，乾燥膜密度（DFD）為5.5g/cm³ 以上，顯示出分散性優異。[Evaluation results] As shown in Table 1, in the conductive paste of the example containing amino acid dispersant a, amine dispersant b, and amine dispersant c, the surface roughness Ra (arithmetic The average roughness) is 0.10 μm or less, and the number of protrusions of the dry film is as few as 100 or less. In addition, in the conductive paste of the example, the dry film density (DFD) is 5.5 g/cm ³ or more, showing excellent dispersibility.

另一方面，在不含有胺系分散劑b的比較例1~3的導電性漿料中，與除了不含有胺系分散劑b以外，在同樣的條件下製造的實施例1、實施例4、實施例7相比，乾燥膜的突起數增加。另外，在比較例2的導電性漿料中，由於胺系分散劑c的含量較少，因此雖然乾燥膜的突起數某種程度地減少，但乾燥膜的表面粗糙度Ra超過0.10μm。另外，在比較例3的導電性漿料中，由於分散劑整體的含量足夠多，因此雖然乾燥膜的表面粗糙度Ra為0.10μm以下，但在乾燥膜上產生了大量突起。On the other hand, in the conductive pastes of Comparative Examples 1 to 3 that did not contain the amine-based dispersant b, they were produced under the same conditions as those of Example 1 and Example 4, except that they did not contain the amine-based dispersant b. , Compared with Example 7, the number of protrusions of the dried film increased. In addition, in the conductive paste of Comparative Example 2, since the content of the amine-based dispersant c was small, although the number of protrusions of the dried film was reduced to some extent, the surface roughness Ra of the dried film exceeded 0.10 μm. In addition, in the conductive paste of Comparative Example 3, since the content of the entire dispersant is sufficiently high, although the surface roughness Ra of the dry film is 0.10 μm or less, a large number of protrusions are generated on the dry film.

另外，如表2所示，在含有胺基酸系分散劑a以及胺系分散劑b或b2的實施例13~16的導電性漿料中，也顯示出乾燥膜的表面粗糙度Ra為0.10μm以下，且乾燥膜的突起數少至100個以下。尤其是，在含有乙基纖維素樹脂（EC）以及聚乙烯醇縮丁醛樹脂（PVB）作為黏合劑樹脂的實施例16的導電性漿料中，與實施例15的導電性漿料（黏合劑樹脂：僅EC）相比，乾燥膜的突起數進一步減少。In addition, as shown in Table 2, the conductive pastes of Examples 13 to 16 containing amino acid dispersant a and amine dispersant b or b2 also showed that the surface roughness Ra of the dry film was 0.10 μm or less, and the number of protrusions in the dry film is as few as 100 or less. In particular, in the conductive paste of Example 16 containing ethyl cellulose resin (EC) and polyvinyl butyral resin (PVB) as the binder resin, the conductive paste of Example 15 (bonding Agent resin: EC only) The number of protrusions of the dry film is further reduced.

另一方面，在僅含有胺基酸系分散劑a的比較例4的導電性漿料中，乾燥膜的表面粗糙度Ra超過0.10μm，且在乾燥膜上產生了大量突起。On the other hand, in the conductive paste of Comparative Example 4 containing only the amino acid-based dispersant a, the surface roughness Ra of the dried film exceeded 0.10 μm, and a large number of protrusions were generated on the dried film.

此外，本發明的技術範圍不限於上述實施型態等中說明的型態。有時會省略上述實施型態等中說明的要件中的一個以上。另外，可以適當地對上述實施型態等中說明的要件進行組合。另外，只要法律允許，援引在上述實施型態等中引用的全部文獻的公開內容作為本說明書記載的一部分。另外，只要法律允許，援引作為日本專利申請的日本特願2020-036584的內容並作為本說明書記載的一部分。In addition, the technical scope of the present invention is not limited to the types described in the above-mentioned embodiments and the like. In some cases, one or more of the requirements described in the above-mentioned embodiments and the like may be omitted. In addition, the requirements described in the above-mentioned embodiments and the like can be appropriately combined. In addition, as long as permitted by law, the disclosures of all the documents cited in the above-mentioned implementation patterns etc. are cited as part of the description of this specification. In addition, as long as permitted by law, the content of Japanese Patent Application No. 2020-036584, which is a Japanese patent application, is cited as a part of the description of this specification.

1:積層陶瓷電容器 10:陶瓷積層體 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 laminated body 11: Internal electrode layer 12: Dielectric layer 20: External electrode 21: External electrode layer 22: Plating layer

〔圖1〕是表示實施型態所涉及的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.

Claims

一種導電性漿料，其含有導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂以及有機溶劑，其特徵係：該分散劑含有相對於該導電性粉末100質量份為0.01質量份以上4質量份以下之下述通式（1）所示之胺基酸系分散劑、以及相對於該導電性粉末100質量份為0.01質量份以上4質量份以下之下述通式（2）所示之胺系分散劑；〔化1〕

其中，在通式（1）中，R₁ 表示碳原子數為10～20的鏈狀烴基；〔化2〕

其中，在通式（2）中，R₂ 表示碳原子數為12～22的鏈狀烴基。A conductive paste containing conductive powder, ceramic powder, dispersant, binder resin, and organic solvent, characterized in that: the dispersant contains 0.01 to 4 parts by mass relative to 100 parts by mass of the conductive powder The following amino acid-based dispersant represented by the following general formula (1), and the amine represented by the following general formula (2), which is 0.01 parts by mass to 4 parts by mass relative to 100 parts by mass of the conductive powder Series dispersant; 〔化1〕

Among them, in the general formula (1), R ₁ represents a chain hydrocarbon group having 10 to 20 carbon atoms; [化2]

Among them, in the general formula (2), R ₂ represents a chain hydrocarbon group having 12 to 22 carbon atoms.

如請求項1所述之導電性漿料，其中，該分散劑進一步含有相對於該導電性粉末100質量份為0.01質量份以上4質量份以下之下述通式（3）所示之胺系分散劑，並且該導電性漿料含有相對於導電性漿料整體為40質量%以上60質量%以下之該導電性粉末；〔化3〕

其中，在通式（3）中，R₃ 表示碳原子數為8～16之烷基、烯基或炔基，R₄ 表示氧化乙烯基、氧化丙烯基或亞甲基，R₅ 表示氧化乙烯基或氧化丙烯基，R₄ 及R₅ 可以相同或者也可以不同；另外，式（3）中的N原子與R₄ 及R₅ 中的O原子不直接鍵合，且Y為0～2的數，Z為1～2的數。The conductive paste according to claim 1, wherein the dispersant further contains an amine system represented by the following general formula (3) in an amount of 0.01 parts by mass to 4 parts by mass relative to 100 parts by mass of the conductive powder A dispersant, and the conductive paste contains 40% by mass or more and 60% by mass or less of the conductive powder with respect to the entire conductive paste; [化3]

Among them, in the general formula (3), R ₃ represents an alkyl, alkenyl or alkynyl group with 8 to 16 carbon atoms, R ₄ represents an oxyethylene group, an oxypropylene group or a methylene group, and R ₅ represents an ethylene oxide group. R ₄ and R ₅ may be the same or different; in addition, the N atom in formula (3) and the O atom in R ₄ and R ₅ are not directly bonded, and Y is 0-2 Number, Z is a number from 1 to 2.

如請求項1或2所述之導電性漿料，其中，在該通式（1）中，R₁ 表示碳原子數為10～20的直鏈狀烴基。The conductive paste according to claim 1 or 2, wherein in the general formula (1), R ₁ represents a linear hydrocarbon group having 10 to 20 carbon atoms.

如請求項1至3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0.01質量%以上4質量%以下之該分散劑。The conductive paste according to any one of claims 1 to 3, wherein the dispersant is contained in an amount of 0.01% by mass or more and 4% by mass or less with respect to the entire conductive paste.

如請求項1至4中任一項所述之導電性漿料，其中，該導電性粉末含有選自Ni、Pd、Pt、Au、Ag、Cu以及其等之合金中之至少一種之金屬粉末。The conductive paste according to any one of claims 1 to 4, wherein the conductive powder contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof .

如請求項1至5中任一項所述之導電性漿料，其中，該導電性粉末之平均粒徑為0.05μm以上1.0μm以下。The conductive paste according to any one of claims 1 to 5, 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至6中任一項所述之導電性漿料，其中，該陶瓷粉末含有鈣鈦礦型氧化物。The conductive paste according to any one of claims 1 to 6, wherein the ceramic powder contains a perovskite-type oxide.

如請求項1至7中任一項所述之導電性漿料，其中，該陶瓷粉末之平均粒徑為0.01μm以上0.5μm以下。The conductive paste according to any one of claims 1 to 7, wherein the average particle size of the ceramic powder is 0.01 μm or more and 0.5 μm or less.

如請求項1至8中任一項所述之導電性漿料，其中，該黏合劑樹脂含有纖維素系樹脂、丙烯酸系樹脂以及縮丁醛系樹脂中之至少一種。The conductive paste according to any one of claims 1 to 8, wherein the binder resin contains at least one of a cellulose resin, an acrylic resin, and a butyral resin.

如請求項1至9中任一項所述之導電性漿料，其中，該導電性漿料用於積層陶瓷零件的內部電極。The conductive paste according to any one of claims 1 to 9, wherein the conductive paste is used for internal electrodes of laminated ceramic parts.

一種電子零件，其特徵係其為使用請求項1至10中任一項所述之導電性漿料而形成之電子零件。An electronic component characterized in that it is an electronic component formed using the conductive paste described in any one of claims 1 to 10.

一種積層陶瓷電容器，其特徵係其至少具有將電介質層及內部電極進行積層而成的積層體，該內部電極使用請求項10所述之導電性漿料而形成。A laminated ceramic capacitor characterized by having at least a laminated body in which a dielectric layer and an internal electrode are laminated, and the internal electrode is formed using the conductive paste described in claim 10.