TW202234427A - Conductive paste and multilayer ceramic capacitor - Google Patents

Conductive paste and multilayer ceramic capacitor Download PDF

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TW202234427A
TW202234427A TW110144243A TW110144243A TW202234427A TW 202234427 A TW202234427 A TW 202234427A TW 110144243 A TW110144243 A TW 110144243A TW 110144243 A TW110144243 A TW 110144243A TW 202234427 A TW202234427 A TW 202234427A
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conductive paste
powder
conductive
mass
dispersant
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鈴木伸壽
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日商住友金屬鑛山股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/012—Form of non-self-supporting electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt

Abstract

The present invention provides a conductive paste which has high dispersibility, while exhibiting excellent long-term viscosity stability. A conductive paste which contains a conductive powder, a ceramic powder, a binder resin, an organic solvent and a dispersant, wherein: the conductive powder has an H2O adsorption per unit area of from 0.30 mg/m2 to 0.70 mg/m2 at a relative pressure P/P0 of 0.5; and the dispersant has a relative dielectric constant of 10 or more, while containing at least one compound that is selected from the group consisting of (1) compounds having an acid group and (2) compounds having an amine group.

Description

導電性漿料以及積層陶瓷電容器Conductive paste and multilayer ceramic capacitors

本發明係關於導電性漿料以及積層陶瓷電容器。The present invention relates to a conductive paste 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，對於包含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，能夠實現小型化以及高容量化。Along with the miniaturization and higher performance of electronic devices such as mobile phones and digital devices, miniaturization and higher capacitance are also desired for electronic components including multilayer ceramic capacitors and the like. The multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated. By reducing the thickness of the dielectric layers and the internal electrode layers, miniaturization and high capacitance 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電介質生片的表面上，以規定的電極圖案印刷（塗佈）內部電極用的導電性漿料，進行乾燥，形成乾燥膜。接著，將乾燥膜及生片以交替重疊的方式積層，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惰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。 The multilayer ceramic capacitor is produced, for example, as follows. First, on the surface of a dielectric green sheet containing a dielectric powder such as barium titanate (BaTiO 3 ) and a binder resin, a conductive paste for internal electrodes is printed (coated) in a predetermined electrode pattern, and dried to form a dry membrane. Next, the dry film and the green sheet are laminated alternately to obtain a laminated body. Next, this laminated body is thermocompression-bonded and integrated to form a compression-bonded body. This press-bonded body is cut and subjected to deorganization binder treatment in an oxidizing gas atmosphere or an inert gas atmosphere, and then fired to obtain a fired wafer. Next, the slurry for external electrodes is applied to both end portions of the fired wafer, and after firing, nickel plating or the like is performed on the surfaces of the external electrodes to obtain a multilayer ceramic capacitor.

用於形成內部電極層的導電性漿料例如含有導電性粉末、陶瓷粉末、黏合劑樹脂以及有機溶劑。此外，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。The conductive paste for forming the internal electrode layer contains, for example, conductive powder, ceramic powder, binder resin, and organic solvent. In addition, in order to improve the dispersibility of the conductive powder or the like, the conductive paste may contain a dispersant.

隨著近年來的內部電極層的薄膜化，導電性漿料中所含的導電性粉末亦有小粒徑化（微粉化）的傾向。若導電性粉末的粒徑變小，則每單位體積的表面積增大，因此顆粒表面的性質成為支配性的性質。尤其係構成導電性粉末的顆粒達到亞微米級時，顆粒彼此因分子間力、靜電力等力而附著，容易形成粗大的凝集體。若如此的凝集體存在於導電性粉末內，則在積層陶瓷電容器製造時其等在內部電極層表面形成凸狀部，因應情況，存在刺破陶瓷電介質層而在內部電極層間引起短路的隱患。With the thinning of the internal electrode layer in recent years, the conductive powder contained in the conductive paste also tends to have a small particle size (micronization). When the particle size of the conductive powder becomes smaller, the surface area per unit volume increases, and thus the properties of the particle surfaces become dominant properties. In particular, when the particles constituting the conductive powder reach the submicron level, the particles adhere to each other by forces such as intermolecular force and electrostatic force, and coarse aggregates are likely to be formed. If such agglomerates are present in the conductive powder, they may form convex portions on the surface of the internal electrode layers during the manufacture of multilayer ceramic capacitors, which may pierce the ceramic dielectric layers and cause short circuits between the internal electrode layers in some cases.

導電性漿料例如藉由在使黏合劑樹脂溶解於有機溶劑而成的有機載體中含有導電性粉末等其他材料並進行混煉以及分散來製作。作為傳統的導電性漿料的製造步驟中的混煉方法，例如使用如下方法：使用高速剪切混合機、雙螺杆以上的行星式混合機等裝置，在有機載體中混合（混煉）導電性粉末以及陶瓷粉末等無機粉末、分散劑、有機溶劑等。The conductive paste is produced, for example, by mixing and dispersing other materials such as conductive powders in an organic vehicle obtained by dissolving a binder resin in an organic solvent. As a conventional kneading method in the production step of the conductive paste, for example, a method of mixing (kneading) the electrical conductivity in an organic vehicle using a device such as a high-speed shear mixer, a planetary mixer with a twin-screw or more, and the like is used. Inorganic powders such as powders and ceramic powders, dispersants, organic solvents, etc.

然而，在傳統的混煉方法中，隨著導電性粉末的小粒徑化，可能形成有機載體未充分混合、或者導電性粉末及陶瓷粉末的表面未充分潤濕等狀態。進一步地，即使在混煉後利用三輥磨機等進行分散處理的情況下，亦會產生導電性粉末（金屬微粉）的分散不良、薄片等問題。However, in the conventional kneading method, as the particle size of the conductive powder is reduced, the organic vehicle may not be sufficiently mixed, or the surfaces of the conductive powder and the ceramic powder may not be sufficiently wetted. Furthermore, even when dispersion treatment is performed by a three-roll mill or the like after kneading, problems such as poor dispersion and flakes of the conductive powder (fine metal powder) occur.

此外，藉由作為一般的金屬微粉的製造方法之一的濕式製造法生成的導電性粉末，在該濕式製造法所具有的乾燥步驟的階段容易促進導電性粉末的凝集，在將導電性粉末混煉於有機載體的時間點就已經形成大量的凝集體（二次顆粒），容易產生上述問題。In addition, the conductive powder produced by the wet production method, which is one of the general production methods of metal fine powder, tends to promote the aggregation of the conductive powder at the stage of the drying step included in the wet production method. When the powder is kneaded with the organic vehicle, a large amount of agglomerates (secondary particles) are formed, and the above-mentioned problems are likely to occur.

在含有分散劑的導電性漿料的製造步驟中，在著眼於導電性粉末以及陶瓷粉末（以下，亦將兩者統稱為「無機粉末」）的分散過程的情況下，構成無機粉末的顆粒在漿料中分散的過程例如分為下述的步驟。In the production process of the conductive paste containing a dispersant, when attention is paid to the dispersion process of the conductive powder and the ceramic powder (hereinafter, both are also collectively referred to as "inorganic powder"), the particles constituting the inorganic powder are The process of dispersing in the slurry is divided into the following steps, for example.

（1）使構成無機粉末的顆粒（包含二次顆粒）的表面「潤濕」的步驟 （2）將二次顆粒粉碎，並使粉碎後的顆粒分散在漿料中的步驟 （3）抑制粉碎後的顆粒的「再凝集」的步驟 (1) Step of "wetting" the surface of particles (including secondary particles) constituting the inorganic powder (2) The step of pulverizing the secondary particles and dispersing the pulverized particles in the slurry (3) Step of suppressing "re-agglomeration" of the pulverized particles

上述（1）的潤濕過程係在構成導電性粉末以及陶瓷粉末的顆粒的表面附著有機載體/有機溶劑的步驟，在含有分散劑的導電性漿料中，在該步驟中，在分散劑吸附於二次顆粒（凝集體）表面的同時，存在於二次顆粒內部的空隙的空氣被含有分散劑的有機溶劑取代，分散劑吸附於該二次顆粒的內壁。The wetting process of the above (1) is a step of attaching an organic vehicle/organic solvent to the surfaces of the particles constituting the conductive powder and the ceramic powder. In the conductive paste containing a dispersant, in this step, the dispersant adsorbs Simultaneously with the surface of the secondary particles (agglomerates), the air existing in the voids inside the secondary particles is replaced by an organic solvent containing a dispersant, and the dispersant is adsorbed on the inner walls of the secondary particles.

此外，具體而言，（1）的潤濕步驟例如係使用上述混合機等裝置進行混煉攪拌的步驟，亦稱為前處理步驟。導電性粉末以及陶瓷粉末的「潤濕」的程度會影響接下來的分散步驟中的處理時間。Moreover, specifically, the wetting step of (1) is a step of kneading and stirring using an apparatus such as the above-mentioned mixer, and is also referred to as a pretreatment step. The degree of "wetting" of the conductive powder as well as the ceramic powder affects the processing time in the subsequent dispersion step.

上述（2）的分散步驟係對導電性漿料中的導電性粉末以及陶瓷粉末（無機粉末）的分散性產生較大影響的步驟，具體而言，例如係利用三輥磨等分散機將無機粉末的二次顆粒（凝集體）粉碎並使粉碎後的顆粒（例：單獨的一次顆粒或少數的一次顆粒凝集而成的二次顆粒）分散於有機載體中的步驟。在（2）的分散步驟後的顆粒的分散性較差的情況下，導電性漿料的各種特性的偏差變大，或者因粉碎不充分的二次顆粒引起的粗大顆粒而導致乾燥膜的表面的平滑性變差。The dispersing step (2) above is a step that greatly affects the dispersibility of the conductive powder and the ceramic powder (inorganic powder) in the conductive paste. A step of pulverizing the secondary particles (aggregates) of the powder and dispersing the pulverized particles (eg, secondary particles formed by agglomeration of a single primary particle or a small number of primary particles) in an organic vehicle. When the dispersibility of the particles after the dispersing step of (2) is poor, the variation in the various properties of the conductive paste becomes large, or the surface of the dried film is dried due to coarse particles caused by insufficiently pulverized secondary particles. Smoothness deteriorates.

上述（3）的抑制再凝集的步驟係藉由使分散劑吸附於藉由粉碎而新出現的顆粒表面的新生面，從而抑制粉碎後的顆粒的「再凝集」的步驟。在上述（2）的分散步驟中，若不對分散處理設置適當的處理時間，則在粉碎後的顆粒表面的新生面可能存在未吸附分散劑的部分，而在（3）的再凝集的抑制步驟中，存在粉碎後的顆粒會再凝集，導電性漿料的分散穩定性降低的情況。又，上述（2）的分散步驟及（3）的再凝集的抑制步驟可以同時進行。The step of suppressing re-agglomeration in the above (3) is a step of suppressing "re-aggregation" of the pulverized particles by adsorbing the dispersant to the newly formed surfaces of the particle surfaces newly formed by pulverization. In the above-mentioned dispersing step (2), if an appropriate treatment time is not set for the dispersing treatment, there is a possibility that a portion where the dispersant is not adsorbed may exist on the new surface of the pulverized particle surface, and in the re-agglomeration suppressing step (3) , the pulverized particles may re-aggregate and the dispersion stability of the conductive paste may decrease. In addition, the dispersing step of (2) and the re-aggregation suppression step of (3) may be performed simultaneously.

作為提高導電性漿料的分散穩定性的方法，例如，在專利文獻1中，揭示一種使特定的金屬微粒分散於介電常數在4~24的範圍內的有機溶劑中作為分散穩定性優異的導電性漿料的技術。 ［先前技術文獻］ ［專利文獻］ As a method of improving the dispersion stability of the conductive paste, for example, in Patent Document 1, it is disclosed that specific metal fine particles are dispersed in an organic solvent having a dielectric constant in the range of 4 to 24 as a material having excellent dispersion stability. The technology of conductive paste. [Prior Art Literature] [Patent Literature]

［專利文獻1］日本特開2007-095510號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2007-095510

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

然而，在上述專利文獻1所記載的技術中，雖然分散穩定性能夠在一定程度上提高，但在上述（2）的分散步驟中，提高所形成的二次顆粒的粉碎性的效果不充分，有時會內含因粉碎不充分的二次顆粒引起的粗粒，難以適合用於薄膜化不斷發展的小型製品用。However, in the technique described in the above-mentioned Patent Document 1, although the dispersion stability can be improved to a certain extent, the effect of improving the pulverization of the secondary particles formed in the dispersion step (2) above is insufficient. In some cases, coarse particles caused by insufficiently pulverized secondary particles are contained, and it is difficult to use them for small products that are increasingly thinned.

鑑於上述問題點，本發明的發明人反復進行深入研究的結果係，本發明的發明人發現：藉由改善針對構成無機粉末的顆粒表面的「潤濕性」，在上述（2）的分散步驟中，能夠容易地進行二次顆粒的粉碎，並且能夠得到較高分散性；以及在上述（3）的抑制再凝集的步驟中，分散劑容易吸附於粉碎後的顆粒表面的新生面，能夠防止顆粒的「再凝集」，因此即使長期保存亦能夠維持導電性漿料的分散穩定性，黏度穩定性亦很優異。In view of the above-mentioned problems, the inventors of the present invention have repeatedly conducted intensive studies. As a result, the inventors of the present invention have found that in the dispersing step (2) above, by improving the "wettability" with respect to the surfaces of the particles constituting the inorganic powder , the secondary particles can be easily pulverized, and high dispersibility can be obtained; and in the step of suppressing re-agglomeration in the above (3), the dispersant is easily adsorbed on the new surface of the pulverized particle surface, which can prevent particles Therefore, the dispersion stability of the conductive paste can be maintained even after long-term storage, and the viscosity stability is also excellent.

本發明鑑於如此的狀況，目的在於提供一種導電性漿料，其使用為了積層陶瓷電子零件的小型化、薄型化而進行微細化的導電性粉末、陶瓷粉末，該導電性漿料具有較高的分散性，並且黏度穩定性優異。 ［技術手段］ In view of such a situation, the present invention aims to provide a conductive paste using conductive powders and ceramic powders that have been refined for miniaturization and thinning of laminated ceramic electronic components, the conductive paste having high Dispersibility and excellent viscosity stability. [Technical means]

根據本發明的第一態樣，提供一種導電性漿料，其含有導電性粉末、陶瓷粉末、黏合劑樹脂、有機溶劑以及分散劑，其中，導電性粉末在相對壓力P/P 0＝0.5時的每單位面積的H 2O吸附量為0.30mg/m 2以上且0.70mg/m 2以下，分散劑具有10以上的相對介電常數，並且含有選自由（1）具有酸基的化合物以及（2）具有胺基的化合物所成群中之至少一種化合物。 According to a first aspect of the present invention, there is provided a conductive paste containing conductive powder, ceramic powder, binder resin, organic solvent and dispersant, wherein the conductive powder is at a relative pressure of P/P 0 =0.5 The H 2 O adsorption amount per unit area is 0.30 mg/m 2 or more and 0.70 mg/m 2 or less, the dispersant has a relative permittivity of 10 or more, and contains a compound selected from (1) a compound having an acid group and ( 2) At least one compound in the group of compounds having an amine group.

此外，理想地，（1）具有酸基的化合物為含有羧基以及磷酸基中之至少一者的化合物。此外，理想地，黏合劑樹脂含有選自由纖維素系樹脂以及縮丁醛系樹脂所成群中之一種以上。此外，理想地，黏合劑樹脂的含量相對於導電性漿料100質量%為0.5質量%以上且10質量%以下。此外，理想地，導電性粉末含有選自由Ni、Cu、Ag、Pd、Au、Pt粉末及其等的合金粉末所成群中之一種以上的金屬粉末。此外，理想地，導電性粉末為鎳粉末。此外，理想地，在鎳粉末的表面組成中，NiO為20莫耳%以上且90莫耳%以下。此外，理想地，導電性粉末的含量相對於導電性漿料100質量%為30質量%以上且70質量%以下。此外，理想地，陶瓷粉末為選自由鈦酸鋇系以及鋯酸鍶系所成群中之至少一種。此外，理想地，導電性漿料在製造後在25℃下靜置30天，利用布氏黏度計在25℃、10rpm的條件下測定時的導電性漿料的黏度的變化率相對於製造8小時後的導電性漿料的黏度為±10%以下。Furthermore, (1) the compound having an acid group is desirably a compound containing at least one of a carboxyl group and a phosphoric acid group. Furthermore, it is desirable that the binder resin contains at least one selected from the group consisting of cellulose-based resins and butyral-based resins. Moreover, it is desirable that content of a binder resin is 0.5 mass % or more and 10 mass % or less with respect to 100 mass % of conductive pastes. Further, the conductive powder desirably contains one or more metal powders selected from the group consisting of Ni, Cu, Ag, Pd, Au, Pt powders, and alloy powders thereof. Furthermore, the conductive powder is desirably nickel powder. Moreover, it is desirable that NiO is 20 mol % or more and 90 mol % or less in the surface composition of the nickel powder. Furthermore, it is desirable that the content of the conductive powder is 30% by mass or more and 70% by mass or less with respect to 100% by mass of the conductive paste. Furthermore, it is desirable that the ceramic powder is at least one selected from the group consisting of barium titanate and strontium zirconate. In addition, ideally, the rate of change of the viscosity of the conductive paste when the conductive paste is allowed to stand at 25° C. for 30 days after production and is measured with a Brookfield viscometer at 25° C. and 10 rpm is relative to the production rate of 8 The viscosity of the conductive paste after one hour is ±10% or less.

根據本發明的第二態樣，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層進行積層而成的積層體，內部電極層使用上述的導電性漿料而形成。 ［發明之效果］ According to a second aspect of the present invention, there is provided a multilayer ceramic capacitor having at least a laminate in which a dielectric layer and an internal electrode layer are laminated, and the internal electrode layer is formed using the above-described conductive paste. [Effect of invention]

本發明的導電性漿料具有較高的分散性，且隨時間的黏度穩定性優異。因此，本發明的導電性漿料例如能夠適合用於薄膜化不斷發展的電極等，尤其係能夠適合用於不斷朝小型化發展的積層陶瓷電子部件的電極用。The conductive paste of the present invention has high dispersibility and is excellent in viscosity stability over time. Therefore, the conductive paste of the present invention can be suitably used, for example, for electrodes whose thinning is progressing, and in particular, it can be suitably used for electrodes of laminated ceramic electronic components whose miniaturization is progressing.

1、導電性漿料 本發明所關於的導電性漿料含有導電性粉末、陶瓷粉末、黏合劑樹脂、有機溶劑以及分散劑。以下，對本發明所關於的導電性漿料中所含的各成分以及導電性漿料的特性等進行詳細說明。 1. Conductive paste The conductive paste according to the present invention contains conductive powder, ceramic powder, binder resin, organic solvent, and dispersant. Hereinafter, each component contained in the electroconductive paste concerning this invention, the characteristic of an electroconductive paste, etc. are demonstrated in detail.

（1）導電性粉末 導電性粉末的材質沒有特別限定，可以由所要求的特性適當選擇使用習知的金屬粉末等。此外，此等導電性粉末可以單獨使用或混合使用。 (1) Conductive powder The material of the conductive powder is not particularly limited, and a known metal powder or the like can be appropriately selected and used according to the required properties. In addition, these conductive powders may be used alone or in combination.

作為導電性粉末，例如可以使用選自由鎳（Ni）、銅（Cu）、銀（Ag）、鈀（Pd）、金（Au）、鉑（Pt）以及其等的合金所成群中之一種以上的金屬粉末，其中，若從導電性、耐腐蝕性、價格等觀點綜合判斷，則理想為Ni、Cu以及其等的合金中的一種以上的金屬粉末，其中，更理想為Ni的金屬粉末（鎳粉末）。此外，為了在脫黏合劑處理時抑制由黏合劑樹脂的部分的熱分解引起的急劇的氣體產生，鎳粉末可以含有幾百ppm左右的硫（S）。As the conductive powder, for example, one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), palladium (Pd), gold (Au), platinum (Pt) and alloys thereof can be used Among the above metal powders, when comprehensively judged from the viewpoints of electrical conductivity, corrosion resistance, price, etc., one or more kinds of metal powders of Ni, Cu, and alloys thereof are preferable, and among them, metal powders of Ni are more preferable. (nickel powder). In addition, in order to suppress rapid gas generation caused by partial thermal decomposition of the binder resin during the debinder treatment, the nickel powder may contain about several hundred ppm of sulfur (S).

導電性粉末的製造方法沒有特別限定，例如可以應用使氯化物蒸氣在氫氣中從氣相直接析出的方法、來自熔融金屬的霧化法、使用水溶液的噴霧熱分解法、將原料的金屬鹽在水溶液中進行還原處理的濕式法等。The production method of the conductive powder is not particularly limited, and for example, a method of directly precipitating chloride vapor from a gas phase in hydrogen gas, an atomization method from a molten metal, a spray thermal decomposition method using an aqueous solution, and a metal salt of a raw material can be applied. Wet method of reduction treatment in aqueous solution, etc.

導電性粉末的平均粒徑沒有特別限定，可根據使用對象的電子零件的尺寸等選定。導電性粉末的平均粒徑例如作為薄膜化不斷發展的積層陶瓷電容器用，理想為5μm以下，更理想為3μm以下。在平均粒徑超過5μm的情況下，內部電極表面的凹凸變得顯著，會使電容器的電特性劣化，故而不理想。此外，導電性粉末的平均粒徑的下限沒有特別限定，例如為0.05μm以上。在平均粒徑小於0.05μm的情況下，操作變得極其困難，容易產生自燃等危險性。The average particle size of the conductive powder is not particularly limited, and can be selected according to the size and the like of the electronic component to be used. The average particle diameter of the conductive powder is desirably 5 μm or less, and more desirably 3 μm or less, for example, for multilayer ceramic capacitors in which thinning is progressing. When the average particle size exceeds 5 μm, the unevenness on the surface of the internal electrode becomes conspicuous, and the electrical characteristics of the capacitor are degraded, which is not preferable. In addition, the lower limit of the average particle diameter of the conductive powder is not particularly limited, but is, for example, 0.05 μm or more. When the average particle diameter is less than 0.05 μm, handling becomes extremely difficult, and dangers such as spontaneous combustion are likely to occur.

必須說明的是，在本說明書中，只要沒有特別說明，導電性粉末的平均粒徑係使用基於BET法的比表面積計算出的粒徑。例如，求出鎳粉末的平均粒徑的計算式如下述的式（1）所示。In addition, in this specification, unless otherwise specified, the average particle diameter of a conductive powder uses the particle diameter calculated by the specific surface area of a BET method. For example, the calculation formula for obtaining the average particle diameter of the nickel powder is shown in the following formula (1).

粒徑＝6/(S.A×ρ)　･･･（1） ρ＝8.9（g/cm 3）：鎳粉末的真密度 S.A：鎳粉末的比表面積 Particle size=6/(SA×ρ)･･･(1) ρ=8.9 (g/cm 3 ): true density of nickel powder SA: specific surface area of nickel powder

此外，根據所使用的導電性粉末表面的親水性、疏水性的強度，與溶劑、載體的潤濕性會發生變化，尤其係對微細化不斷發展的微粉的凝集體的粉碎、分散性會產生較大影響。導電性粉末表面的親水性、疏水性的強度可以藉由H 2O吸附量來進行評價。 In addition, depending on the strength of the hydrophilicity and hydrophobicity of the surface of the conductive powder used, the wettability with the solvent and the carrier changes, and especially the pulverization and dispersibility of the aggregates of the micropowders that are progressing in micronization will occur. greater impact. The strength of hydrophilicity and hydrophobicity on the surface of the conductive powder can be evaluated by the amount of H 2 O adsorption.

在本實施型態所關於的導電性漿料中，所使用的導電性粉末在相對壓力P/P 0＝0.5時的每單位面積的H 2O吸附量為0.30mg/m 2以上且0.70mg/m 2以下，亦可以為0.30mg/m 2以上且0.60mg/m 2以下。H 2O吸附量小於0.30mg/m 2時，疏水性過強，黏度穩定性會變差。據認為，此係因相對介電常數較高（親水性較高）的分散劑不吸附於導電性粉末而產生的。此外，在H 2O吸附量超過0.70mg/m 2的情況下，親水性變得過強，黏度穩定性會變差。據認為，此係因導電性粉末的相對介電常數變得過高，因此吸附於導電性粉末的分散劑的疏水基不延伸，因此難以與溶劑相融而產生的。 In the conductive paste according to the present embodiment, the amount of H 2 O adsorption per unit area of the conductive powder used is 0.30 mg/m 2 or more and 0.70 mg when the relative pressure P/P 0 =0.5 /m 2 or less, and may be 0.30 mg/m 2 or more and 0.60 mg/m 2 or less. When the adsorption amount of H 2 O is less than 0.30 mg/m 2 , the hydrophobicity is too strong, and the viscosity stability will be deteriorated. It is considered that this is caused by the fact that a dispersant having a high relative permittivity (higher hydrophilicity) does not adsorb to the conductive powder. In addition, when the amount of H 2 O adsorption exceeds 0.70 mg/m 2 , the hydrophilicity becomes too strong, and the viscosity stability deteriorates. This is considered to be caused by the fact that the relative permittivity of the conductive powder becomes too high, and thus the hydrophobic group of the dispersant adsorbed on the conductive powder does not extend, so that it is difficult to melt with the solvent.

此外，在使用鎳粉末作為導電性粉末的情況下，在其表面組成中，NiO的比例理想為20莫耳%以上且90莫耳%以下。在NiO的比例為上述範圍外的情況下，可能會有分散劑在導電性粉末的表面的吸附狀態變得不適當，或者導電性粉末與黏合劑樹脂發生反應之情況。在分散劑未充分吸附於導電性粉末表面的情況下，與有機溶劑、有機載體的潤濕性變差，導電性粉末的凝集體（二次顆粒）的粉碎、粉碎後的顆粒（一次顆粒等）的再凝集的抑制變得不充分（即，導電性粉末的分散不充分），可能會使導電性漿料的黏度穩定性降低、或者乾燥膜的表面平滑性變差。In addition, in the case of using nickel powder as the conductive powder, the ratio of NiO in the surface composition is desirably 20 mol % or more and 90 mol % or less. When the ratio of NiO is outside the above range, the adsorption state of the dispersant on the surface of the conductive powder may become inappropriate, or the conductive powder may react with the binder resin. When the dispersant is not sufficiently adsorbed on the surface of the conductive powder, the wettability with organic solvents and organic vehicles is deteriorated, and the agglomerates (secondary particles) of the conductive powder are pulverized, and the pulverized particles (primary particles, etc. ) of reaggregation becomes insufficient (that is, the dispersion of the conductive powder is insufficient), and the viscosity stability of the conductive paste may be lowered, or the surface smoothness of the dry film may be deteriorated.

此外，從進一步提高導電性漿料的黏度穩定性、乾燥膜的表面平滑性的觀點而言，鎳粉末的表面組成中的NiO的比例在上述範圍內可以為50莫耳%以上，亦可以為60莫耳%以上，亦可以為70莫耳%以上，亦可以為80莫耳%以上。NiO的比例在上述範圍內越多，則即使後述的分散劑為少量，亦越能夠得到具有較高的分散性的導電性漿料。In addition, from the viewpoint of further improving the viscosity stability of the conductive paste and the surface smoothness of the dry film, the ratio of NiO in the surface composition of the nickel powder may be 50 mol % or more within the above range, or may be 60 mol% or more, 70 mol% or more, or 80 mol% or more. The more the ratio of NiO is in the above-mentioned range, the more conductive paste having higher dispersibility can be obtained even if the dispersant described later is small.

此外，鎳粉的表面組成中的NiO的比例可以使用X射線光電子能譜法（XPS）進行測定。例如，使用XPS對鎳粉末表面的Ni2p能譜進行分析，在檢測到Ni峰、Ni(OH) 2峰以及NiO峰的情況下，可以由NiO峰相對於這三種成分的峰面積總量的面積比，對NiO的比例（莫耳%）進行測定。 In addition, the ratio of NiO in the surface composition of nickel powder can be measured using X-ray photoelectron spectroscopy (XPS). For example, using XPS to analyze the Ni2p energy spectrum on the surface of nickel powder, when Ni peak, Ni(OH) 2 peak and NiO peak are detected, the area of NiO peak relative to the total peak area of these three components can be determined The ratio of NiO (mol %) was measured.

此外，導電性粉末的含有比例相對於導電性漿料總質量，理想為30質量%以上且70質量%以下。若導電性粉末的比例低於30質量%，則有燒製後的電極厚度顯著變薄而電阻值上升，或者電極膜的形成不充分而失去導電性，無法得到作為目的之靜電容量之情況，因此不理想。若超過70質量%，則電極膜的薄層化變得困難，因此不理想。導電性粉末相對於漿料整體的比例更理想為40質量%以上且60質量%以下。In addition, the content ratio of the conductive powder is preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the conductive paste. If the ratio of the conductive powder is less than 30% by mass, the thickness of the electrode after firing is remarkably thin and the resistance value increases, or the formation of the electrode film is insufficient and the conductivity is lost, and the intended electrostatic capacitance may not be obtained. So not ideal. If it exceeds 70 mass %, it becomes difficult to reduce the thickness of the electrode film, which is not preferable. The ratio of the conductive powder to the entire slurry is more preferably 40 mass % or more and 60 mass % or less.

（2）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，可以根據所應用的積層陶瓷電容器的種類適當地選擇習知的陶瓷粉末。陶瓷粉末例如理想為含有選自由鈦酸鋇系以及鋯酸鍶系所成群中之至少一種氧化物粉末，其中，理想為含有鈦酸鋇（BaTiO 3，下述有時稱為「BT」）的粉末。 (2) 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 can be appropriately selected according to the type of the multilayer ceramic capacitor to be applied. The ceramic powder preferably contains at least one oxide powder selected from the group consisting of barium titanate and strontium zirconate, for example, and preferably contains barium titanate (BaTiO 3 , hereinafter sometimes referred to as "BT") of powder.

作為鈦酸鋇系的氧化物粉末，例如可以使用含有鈦酸鋇（BT）作為主成分、且含有其他氧化物作為副成分的粉末。作為副成分的其他氧化物，例如，可列舉為選自錳（Mn）、鉻（Cr）、矽（Si）、鈣（Ca）、鋇（Ba）、鎂（Mg）、釩（V）、鎢（W）、鉭（Ta）、鈮（Nb）以及稀土類元素中的一種以上的氧化物。此外，作為鈦酸鋇系的氧化物粉末，亦可以使用鈦酸鋇（BaTiO 3）的Ba原子及/或Ti原子被錫（Sn）、鉛（Pb）、鋯（Zr）等其他原子取代後的鈣鈦礦型氧化物強電介質的粉末。 As the barium titanate-based oxide powder, for example, a powder containing barium titanate (BT) as a main component and other oxides as an auxiliary component can be used. As other oxides of auxiliary components, for example, one selected from the group consisting of manganese (Mn), chromium (Cr), silicon (Si), calcium (Ca), barium (Ba), magnesium (Mg), vanadium (V), Oxides of one or more of tungsten (W), tantalum (Ta), niobium (Nb) and rare earth elements. In addition, as the barium titanate-based oxide powder, it is also possible to use barium titanate (BaTiO 3 ) in which Ba atoms and/or Ti atoms are substituted with other atoms such as tin (Sn), lead (Pb), and zirconium (Zr). Perovskite oxide ferroelectric powder.

作為陶瓷粉末，亦可以含有鈦酸鋇系以及鋯酸鍶系的氧化物粉末以外的其他粉末，例如，亦可以含有作為形成積層陶瓷器件的生片的陶瓷粉末的氧化鋅（ZnO）、鐵氧體、鈦鋯酸鉛（PZT）、氧化鋇（BaO）、氧化鋁（Al 2O 3）、氧化鉍（Bi 2O 3）、稀土類氧化物、氧化鈦（TiO 2）、氧化釹（Nd 2O 3）等陶瓷粉末。 The ceramic powder may contain powders other than barium titanate-based and strontium zirconate-based oxide powders, for example, zinc oxide (ZnO), ferrite, which are ceramic powders for forming green sheets of multilayer ceramic devices. body, lead zirconate titanate (PZT), barium oxide (BaO), aluminum oxide (Al 2 O 3 ), bismuth oxide (Bi 2 O 3 ), rare earth oxides, titanium oxide (TiO 2 ), neodymium oxide (Nd 2 O 3 ) and other ceramic powders.

陶瓷粉末的平均粒徑可根據使用對象的電子零件的尺寸等來選定，例如，作為薄膜化不斷發展的積層電子零件用，理想為0.01μm以上且0.5μm以下的範圍。若超過0.5μm，則塗佈以及乾燥後的膜表面的凹凸變得顯著，此外，若小於0.01μm，則操作變得極其困難，亦容易產生自燃等危險性，因此不理想。又，陶瓷粉末的平均粒徑與上述導電性粉末的平均粒徑的測定方法相同，係使用基於BET法的比表面積計算出的粒徑（例如，在鈦酸鋇的情況下，使用ρ＝6.1（g/cm 3），由上述式（1）計算出平均粒徑）。 The average particle size of the ceramic powder can be selected according to the size of the electronic component to be used, etc. For example, it is desirably in the range of 0.01 μm or more and 0.5 μm or less, for example, for laminated electronic components which are becoming thinner. If it exceeds 0.5 μm, the unevenness of the film surface after coating and drying becomes remarkable, and if it is less than 0.01 μm, handling becomes extremely difficult and risks such as spontaneous combustion are likely to occur, which is not preferable. In addition, the average particle diameter of the ceramic powder is the same as the method for measuring the average particle diameter of the conductive powder described above, and the particle diameter calculated from the specific surface area by the BET method is used (for example, in the case of barium titanate, ρ=6.1 (g/cm 3 ), the average particle diameter is calculated from the above formula (1).

陶瓷粉末的含量相對於導電性漿料總質量例如為1質量%以上且20質量%以下，更理想為5質量%以上且20質量%以下。The content of the ceramic powder is, for example, 1 mass % or more and 20 mass % or less with respect to the total mass of the conductive paste, and more preferably 5 mass % or more and 20 mass % or less.

（3）黏合劑樹脂 在印刷導電性漿料時，黏合劑樹脂除了發揮適度的黏度及黏合性、提高印刷性以外，亦具有提高乾燥特性等的效果。 (3) Binder resin When printing the conductive paste, the binder resin has the effect of improving the drying characteristics, etc., in addition to exhibiting a moderate viscosity and adhesiveness and improving the printability.

作為黏合劑樹脂，沒有特別限定，可以根據所要求的特性使用習知的材料，例如，理想為含有選自由纖維素系樹脂、縮丁醛系樹脂以及丙烯酸樹脂所成群中的一種以上，更理想為含有選自由纖維素系樹脂以及縮丁醛系樹脂所成群中的一種以上。The binder resin is not particularly limited, and known materials can be used according to the required properties. It is desirable to contain at least one selected from the group consisting of cellulose-based resins and butyral-based resins.

作為纖維素系樹脂，可列舉為乙醯纖維素、甲基纖維素、乙基纖維素、丁基纖維素、以及硝基纖維素、部分醚化纖維素類等。此外，作為縮丁醛系樹脂，可列舉為聚乙烯醇縮丁醛等。Examples of the cellulose-based resin include acetyl cellulose, methyl cellulose, ethyl cellulose, butyl cellulose, nitrocellulose, partially etherified cellulose, and the like. Moreover, polyvinyl butyral etc. are mentioned as a butyral-type resin.

其中，從在溶劑中的溶解性、燃燒分解性的觀點等而言，理想為含有乙基纖維素。此外，在用於積層電子零件用的情況下，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，或者亦可單獨使用縮丁醛系樹脂。黏合劑樹脂可以使用一種，或者亦可以使用兩種以上。Among them, it is desirable to contain ethyl cellulose from the viewpoints of solubility in a solvent, combustion decomposability, and the like. Moreover, when using for laminated electronic components, from a viewpoint of improving the adhesive strength with a green sheet, a butyral-type resin may be contained, or a butyral-type resin may be used independently. One type of binder resin may be used, or two or more types may be used.

從膜強度、脫黏合劑性、印刷性、黏度的觀點而言，黏合劑樹脂的含量相對於導電性漿料總質量理想為0.5質量%以上且10質量%以下，更理想為1質量%以上且5質量%以下。From the viewpoint of film strength, debinding property, printability, and viscosity, the content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more, based on the total mass of the conductive paste and 5 mass % or less.

在黏合劑樹脂的含量小於上述範圍的情況下，可能會有乾燥膜的強度降低、或者積層時導電性漿料的電極圖案部與電介質片材的密著性變差而變得容易剝離之情況。另一方面，在黏合劑樹脂的含量超過上述範圍的情況下，黏合劑樹脂的含量變得過多，因此脫黏合劑性變差，可能會有黏合劑樹脂的一部分殘留之情況。When the content of the binder resin is less than the above-mentioned range, the strength of the dry film may be lowered, or the adhesion between the electrode pattern portion of the conductive paste and the dielectric sheet may be deteriorated during lamination, and may be easily peeled off. . On the other hand, when the content of the binder resin exceeds the above-mentioned range, the content of the binder resin becomes too large, so that the debindering property is deteriorated, and a part of the binder resin may remain.

（4）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、使導電性粉末分散、能夠對作為導電性漿料的黏度進行調整、能夠賦予適當的流動性、印刷性、乾燥特性等的習知的有機溶劑。作為有機溶劑，例如可以使用沸點為150℃至250℃左右的有機溶劑、萜烯系溶劑、脂肪族烴系溶劑、醇類等各種習知的有機溶劑（非水溶性溶劑）。 (4) Organic solvent The organic solvent is not particularly limited, and conventional ones capable of dissolving the above-mentioned binder resin, dispersing the conductive powder, adjusting the viscosity of the conductive paste, and imparting appropriate fluidity, printability, drying properties, and the like can be used. known organic solvents. As the organic solvent, for example, various conventional organic solvents (water-insoluble solvents) such as organic solvents having a boiling point of about 150° C. to 250° C., terpene-based solvents, aliphatic hydrocarbon-based solvents, and alcohols can be used.

作為萜烯系溶劑，例如可列舉為萜品醇、二氫萜品醇、二氫萜品醇乙酸酯。作為脂肪族烴系溶劑，例如可列舉為癸烷、十三烷等。作為醇類，例如可列舉為癸醇、十三烷醇等。作為上述以外的沸點為150℃至250℃左右的有機溶劑，例如可列舉為乙酸異冰片酯、丁基卡必醇乙酸酯、二乙二醇丁基甲基醚、三丙二醇二甲基醚等。As a terpene type solvent, terpineol, dihydroterpineol, and dihydroterpineol acetate are mentioned, for example. Examples of the aliphatic hydrocarbon-based solvent include decane, tridecane, and the like. As alcohols, decyl alcohol, tridecyl alcohol, etc. are mentioned, for example. As an organic solvent with a boiling point of about 150 to 250 degreeC other than the above, isobornyl acetate, butyl carbitol acetate, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, etc. are mentioned, for example.

從蒸發量、黏性、與黏合劑樹脂的相容性、印刷性的觀點而言，有機溶劑的含量相對於導電性漿料總質量理想為30質量%以上且70質量%以下，更理想為40質量%以上且60質量%以下。From the viewpoints of evaporation amount, viscosity, compatibility with binder resin, and printability, the content of the organic solvent is preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the conductive paste, and more preferably 40 mass % or more and 60 mass % or less.

在導電性漿料的製造步驟中，混合各材料的順序沒有特別限定，理想為預先在有機溶劑的一部分中溶解上述黏合劑樹脂而製作有機載體後，將該有機載體與其他材料及剩餘的有機溶劑（黏度調整用）混合。有機載體中含有的黏合劑樹脂的配製量沒有特別限定，從使用於不斷朝小型化發展的電子零件用的導電性漿料形成為適當的黏度的觀點而言，相對於有機載體總質量，理想為1質量%以上且30質量%以下，更理想為5質量%以上且20質量%以下。In the production step of the conductive paste, the order of mixing the materials is not particularly limited, but it is desirable to dissolve the above-mentioned binder resin in a part of the organic solvent in advance to prepare the organic carrier, and then the organic carrier, other materials and the remaining organic carrier are preferably prepared. Solvent (for viscosity adjustment) mixing. The preparation amount of the binder resin contained in the organic vehicle is not particularly limited, but is ideal relative to the total mass of the organic vehicle from the viewpoint of forming an appropriate viscosity for the conductive paste for use in electronic parts that are being miniaturized. It is 1 mass % or more and 30 mass % or less, More preferably, it is 5 mass % or more and 20 mass % or less.

（5）分散劑 分散劑的作用係吸附於無機粉末（導電性粉末以及陶瓷粉末）的表面而抑制無機粉末彼此的凝集，或者提高與有機載體的潤濕性而使其分散於導電性漿料內。分散劑（界面活性劑）一般被分類為陽離子系分散劑、陰離子系分散劑、非離子系分散劑以及兩性分散劑。 (5) Dispersant The function of the dispersant is to adsorb on the surface of the inorganic powder (conductive powder and ceramic powder) to suppress the aggregation of the inorganic powders, or to improve the wettability with the organic vehicle and to disperse it in the conductive paste. Dispersants (surfactants) are generally classified into cationic dispersants, anionic dispersants, nonionic dispersants, and amphoteric dispersants.

作為用於使無機粉末分散的分散劑，理想為使用陰離子系分散劑（例如，羧酸系分散劑、磷酸系分散劑、磷酸鹽系分散劑等酸系分散劑）。然而，隨著無機粉末的小粒徑化，即使使用陰離子系分散劑，亦存在無機粉末無法充分分散的情況。As a dispersant for dispersing the inorganic powder, it is desirable to use an anionic dispersant (for example, an acid-based dispersant such as a carboxylic acid-based dispersant, a phosphoric acid-based dispersant, and a phosphate-based dispersant). However, as the particle size of the inorganic powder becomes smaller, even if an anionic dispersant is used, the inorganic powder may not be sufficiently dispersed.

因此，本發明的發明人進行深入研究開發的結果係，發現藉由組合使用具有上述特定範圍的H 2O吸附量的導電性粉末與含有相對介電常數為10以上且具有酸基及/或胺基的化合物的分散劑，能夠提高分散性。據認為，如此的分散劑對無機粉末表面的吸附力較大，無機粉末與有機載體的潤濕性提高（前述（1）的「潤濕」步驟），因此藉由其表面改性作用促進無機粉末的粉碎（前述（2的）分散步驟），並且藉由抑制再凝集（前述（3）的抑制「再凝集」的步驟），有助於提高分散性。 Therefore, the inventors of the present invention, as a result of intensive research and development, found that by using a conductive powder having a H 2 O adsorption amount within the above-mentioned specific range in combination with an acid group having a relative permittivity of 10 or more and having an acid group and/or A dispersant of an amine-based compound can improve dispersibility. It is considered that such a dispersant has a large adsorption force on the surface of the inorganic powder, and the wettability of the inorganic powder and the organic carrier is improved (the "wetting" step of the aforementioned (1)), thus promoting the inorganic powder through its surface modification. The pulverization of the powder (the dispersing step of (2) above) and the suppression of re-aggregation (the step of suppressing "re-aggregation" of the above (3)) contribute to the improvement of dispersibility.

分散劑的相對介電常數可以為10以上，亦可以為11以上，亦可以為12以上。藉由使用相對介電常數滿足上述範圍的分散劑，能夠提高塗膜（乾燥膜）的平滑性、乾燥膜密度。必須說明的是，在本說明書中使用的分散劑的相對介電常數表示20℃下的相對介電常數。此外，相對介電常數可以藉由在液體樣品用的電極單元中加入評價用樣品（所使用的分散劑）來進行測定。又，分散劑的相對介電常數的上限沒有特別限定，例如為15以下左右。The relative permittivity of the dispersant may be 10 or more, 11 or more, or 12 or more. By using a dispersant whose relative permittivity satisfies the above-mentioned range, the smoothness of the coating film (dry film) and the dry film density can be improved. It should be noted that the relative permittivity of the dispersant used in this specification means the relative permittivity at 20°C. In addition, the relative permittivity can be measured by adding the sample for evaluation (dispersant used) to the electrode unit for liquid samples. In addition, the upper limit of the relative permittivity of the dispersant is not particularly limited, but is, for example, about 15 or less.

此外，分散劑含有選自由（1）具有酸基的化合物以及（2）具有胺基的化合物所成群中之至少一種化合物。此外，分散劑可以係相當於上述（1）具有酸基的化合物以及（2）具有胺基的化合物此兩者的化合物，即，可以係（3）在同一分子內具有酸基及胺基的化合物，亦可以係含有（1）具有酸基的化合物及（2）具有胺基的化合物此兩者的化合物的混合物。Further, the dispersant contains at least one compound selected from the group consisting of (1) a compound having an acid group and (2) a compound having an amine group. In addition, the dispersing agent may be a compound corresponding to both (1) a compound having an acid group and (2) a compound having an amine group, that is, (3) a compound having an acid group and an amine group in the same molecule. The compound may be a mixture of compounds containing both (1) a compound having an acid group and (2) a compound having an amine group.

作為具有酸基的化合物，理想為含有羧基以及磷酸基中的至少一者的化合物。此外，具有胺基的化合物係指包含伯胺、仲胺以及叔胺。The compound having an acid group is preferably a compound containing at least one of a carboxyl group and a phosphoric acid group. Moreover, the compound which has an amine group means that a primary amine, a secondary amine, and a tertiary amine are contained.

此外，分散劑更理想為含有胺值為100以上的分散劑。在使用胺值為100以上的分散劑的情況下，導電性漿料的分散性進一步提高，能夠進一步提高塗佈後的乾燥膜表面的平滑性。Moreover, it is more preferable that a dispersing agent contains the dispersing agent with an amine value of 100 or more. When a dispersant having an amine value of 100 or more is used, the dispersibility of the conductive paste is further improved, and the smoothness of the surface of the dried film after coating can be further improved.

此外，在分散劑含具有酸基的化合物的情況下，具有酸基的分散劑的酸值可以為30以上且300以下，亦可以為30以上且200以下。Moreover, when a dispersing agent contains the compound which has an acid group, the acid value of the dispersing agent which has an acid group may be 30 or more and 300 or less, and may be 30 or more and 200 or less.

分散劑的含量相對於導電性漿料總質量理想為0.1質量%以上且2.0質量%以下，更理想為0.3質量%以上且1.0質量%以下。若分散劑的含量小於0.1質量%，則分散劑的含量過少，可能會無法得到粉碎、再凝集抑制的效果。另一方面，若分散劑的含量超過2.0質量%，則印刷性等漿料特性會大幅地變化，故不理想。The content of the dispersant is preferably 0.1% by mass or more and 2.0% by mass or less, more preferably 0.3% by mass or more and 1.0% by mass or less, based on the total mass of the conductive paste. If the content of the dispersing agent is less than 0.1 mass %, the content of the dispersing agent is too small, and the effects of pulverization and re-agglomeration inhibition may not be obtained. On the other hand, when content of a dispersing agent exceeds 2.0 mass %, since paste characteristics, such as printability, will change largely, it is not preferable.

（6）其他添加成分 在本發明的導電性漿料中，可以在不脫離本發明的主旨的範圍內因應需求添加消泡劑、增塑劑、增稠劑、螯合劑、上述分散劑以外的分散劑、觸變劑等習知的添加物中的一種以上。 (6) Other additives In the conductive paste of the present invention, a defoaming agent, a plasticizer, a thickener, a chelating agent, a dispersant other than the above-mentioned dispersant, and a thixotropic agent may be added according to needs within the scope of not departing from the gist of the present invention. One or more of conventional additives.

（7）導電性漿料的製造方法以及特性 （製造方法） 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，可以使用習知的方法來製造。例如，導電性漿料藉由利用混合機、球磨機、捏合機、輥磨機等裝置對上述各材料進行混煉以及分散進行漿料化而製造。 (7) Manufacturing method and characteristics of conductive paste (Manufacturing method) The manufacturing method of the electroconductive paste which concerns on this embodiment is not specifically limited, It can manufacture using a well-known method. For example, the conductive paste is produced by kneading and dispersing each of the above-mentioned materials in a slurry using an apparatus such as a mixer, a ball mill, a kneader, and a roll mill.

（黏度變化率） 本實施型態所涉及的導電性漿料在製造後在25℃下靜置30天，利用布氏黏度計在25℃、10rpm的條件下測定時的黏度（η 30）的變化率相對於製造8小時後的黏度（η 0）理想為±10%以下。在導電性漿料的黏度的變化率為上述範圍內的情況下，導電性漿料的分散性優異。 (Rate of Viscosity Change) The viscosity (η 30 ) when the conductive paste according to the present embodiment is allowed to stand at 25° C. for 30 days after manufacture, and is measured with a Brookfield viscometer at 25° C. and 10 rpm. The rate of change is preferably ±10% or less with respect to the viscosity (η 0 ) after 8 hours of production. When the rate of change of the viscosity of the conductive paste is within the above range, the dispersibility of the conductive paste is excellent.

又，靜置30天後的導電性漿料的黏度變化率可以藉由下述的式（2）求出。In addition, the viscosity change rate of the conductive paste after standing for 30 days can be calculated|required by following formula (2).

黏度變化率（%）＝(η 30-η 0)/η 0×100･･･（2） η 30：30天後的10rpm黏度 η 0：製造8小時後的10rpm黏度（初始黏度） Viscosity change rate (%) = (η 30 -η 0 )/η 0 ×100･･･(2) η 30 : Viscosity at 10 rpm after 30 days η 0 : Viscosity at 10 rpm after 8 hours of production (initial viscosity)

（光澤度） 本實施型態所涉及的導電性漿料的乾燥膜的光澤度理想為10以上，更理想為15以上，進一步理想為20以上。乾燥膜的光澤度越高，表示乾燥膜的表面整體的漫反射越少，越能夠得到更平滑的表面。 (Gloss) The glossiness of the dry film of the conductive paste according to the present embodiment is desirably 10 or more, more desirably 15 or more, and further desirably 20 or more. The higher the glossiness of the dry film, the less diffuse reflection on the entire surface of the dry film, and the smoother the surface can be obtained.

又，評價用的乾燥膜例如可以如下得到：將導電性漿料在PET薄膜上以5×10cm的面積以膜厚達到30μm的方式進行印刷後，在120℃下在空氣中乾燥40分鐘而得到。In addition, the dry film for evaluation can be obtained, for example, by printing the conductive paste on a PET film in an area of 5×10 cm so that the film thickness may be 30 μm, and then drying it in air at 120° C. for 40 minutes. .

2、積層陶瓷電容器 以下，參照圖式對本發明所關於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。此外，適當地參照圖1等所示的XYZ正交坐標系對部件的位置、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方向為鉛直方向（上下方向）。 2. Multilayer ceramic capacitors Hereinafter, embodiments of the multilayer ceramic capacitor according to the present invention will be described with reference to the drawings. In the drawings, it may be shown in a schematic manner or shown by changing the scale as appropriate. In addition, the position, direction, etc. of a member are demonstrated with reference to the XYZ orthogonal coordinate system shown in FIG. 1 etc. suitably. In this XYZ orthogonal coordinate system, the X direction and the Y direction are the horizontal directions, and the Z direction is the vertical direction (up-down direction).

圖1中的A以及圖1中的B係表示作為實施型態所關於的電子零件的一例的積層陶瓷電容器1的圖。積層陶瓷電容器1具備電介質層12以及內部電極層11交替地積層而成的陶瓷積層體10及外部電極20。A in FIG. 1 and B in FIG. 1 are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component according to the embodiment. The multilayer ceramic capacitor 1 includes a ceramic multilayer body 10 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated, and an external electrode 20 .

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，在陶瓷生片上印刷導電性漿料並進行乾燥而形成乾燥膜。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積層而得到積層體之後，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交替積層而成的陶瓷積層體10。之後，藉由在陶瓷積層體10的兩端部形成一對外部電極而製造積層陶瓷電容器1。以下，進行更詳細的說明。Hereinafter, the manufacturing method of the multilayer ceramic capacitor using the said conductive paste is demonstrated. First, a conductive paste 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 laminated by crimping to obtain a laminated body, the laminated body is fired and integrated, whereby the internal electrode layers 11 and the dielectric layers 12 are alternately produced. The laminated ceramic layered body 10 . After that, the multilayer ceramic capacitor 1 is manufactured by forming a pair of external electrodes on both ends of the ceramic multilayer body 10 . Hereinafter, a more detailed description will be given.

首先，準備作為未燒製的陶瓷片的陶瓷生片。作為該陶瓷生片，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薄膜等的支撐薄膜上塗佈成片材狀並使其乾燥去除溶劑而形成的陶瓷生片等。又，對由陶瓷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, ceramic green sheets which are unfired ceramic sheets are prepared. Examples of the ceramic green sheet include a slurry for a dielectric layer obtained 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 ceramic green sheet or the like formed by coating a support film such as a PET film in a sheet shape and drying it to remove the solvent. In addition, the thickness of the dielectric layer composed of the ceramic green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less from the viewpoint of the requirement for miniaturization of the multilayer ceramic capacitor.

接著，準備複數片藉由在該陶瓷生片的一個面上使用凹版印刷法印刷塗佈上述導電性漿料並進行乾燥而在陶瓷生片的一個面上形成有乾燥膜的片材。又，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 a dry film is formed on one surface of the ceramic green sheet by printing and applying the above-mentioned conductive paste on one surface of the ceramic green sheet using a gravure printing method and drying it. In addition, from the viewpoint of the requirement to reduce the thickness of the internal electrode layer 11 , the thickness of the dry film formed from the conductive paste is desirably 1 μm or less after drying.

接著，從支撐薄膜上將陶瓷生片剝離，並且以陶瓷生片與形成於該陶瓷生片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。又，亦可以設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的構成。Next, the ceramic green sheets are peeled off from the support film, and the ceramic green sheets and the dry films formed on one surface of the ceramic green sheets are alternately arranged and laminated, and then heated and pressurized to obtain laminated layers. body. Moreover, you may set it as the structure which arrange|positions further the ceramic green sheet for protection which is not apply|coated with the electroconductive paste on both surfaces of a laminated body.

接著，將積層體切斷為規定尺寸而形成生晶片之後，對生晶片實施脫黏合劑處理，並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）。又，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，進行脫黏合劑處理時的上述溫度的保持時間理想為0.5小時以上且24小時以下。又，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，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, after cutting the laminated body into a predetermined size to form a green wafer, the green wafer is subjected to a debinder treatment and fired in a reducing gas atmosphere to produce a laminated ceramic fired body (ceramic laminated body 10 ). In addition, the gas atmosphere in the debinder treatment is preferably the atmosphere or the N 2 gas atmosphere. The temperature at the time of performing the binder removal treatment is, for example, 200°C or higher and 400°C or lower. Moreover, it is preferable that the holding time of the said temperature at the time of performing a binder removal process is 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, the firing is performed in a reducing gas atmosphere, and the temperature at the time of firing the laminated body is, for example, 1000° C. or higher and 1350° C. or lower. The temperature 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，並且對陶瓷的原料粉末進行燒製而形成陶瓷製的電介質層12。又，去除乾燥膜中的有機載體，並且使以鎳粉末或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與內部電極層11複數片交替地積層而成的積層陶瓷燒製體。又，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，亦可以對燒製後的積層陶瓷燒製體實施退火處理。By firing the green wafer, the organic binder in the ceramic green sheet is completely removed, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12 . In addition, the organic carrier in the dried film is removed, and nickel powder or an alloy powder containing nickel as a main component is sintered or melted to be integrated to form internal electrode layers 11 , and a plurality of dielectric layers 12 and internal electrode layers 11 are alternately formed. Laminated ceramic fired body formed by depositing layers. Furthermore, from the viewpoint of improving reliability by introducing oxygen into the interior of the dielectric layer and suppressing reoxidation of the internal electrodes, an annealing treatment may be performed on the fired laminated ceramic body after firing.

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，來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。又，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。又，電子零件亦可以使用除了積層陶瓷電容器以外的電子零件。 ［實施例］ Next, the multilayer ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 to the manufactured multilayer ceramic fired body. 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 an alloy thereof can be preferably used. In addition, electronic components other than the multilayer ceramic capacitor can also be used as electronic components. [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.

［評價項目及其方法］ （1）導電性漿料的隨時間的黏度變化率 導電性漿料的隨時間的黏度變化率如下式（2）所示，首先，對製造8小時後的導電性漿料的黏度進行測定作為初始黏度（η 0），接著，分別測定在常溫（25℃）下靜置1天、10天以及30天後的導電性漿料的黏度（η x），接著以靜置各個天數後的黏度的變化量除以初始黏度（η 0）而得到的百分率（%）來進行表示。不僅對30天後的黏度變化率進行測定，亦對1天後、10天後的黏度變化率進行測定，據此亦確認黏度變化的傾向。 [Evaluation Item and Method] (1) Time-dependent viscosity change rate of conductive paste The time-dependent viscosity change rate of the conductive paste is represented by the following formula (2). The viscosity of the paste was measured as the initial viscosity (η 0 ). Next, the viscosity (η x ) of the conductive paste after being left to stand at room temperature (25° C.) for 1 day, 10 days, and 30 days was measured. The amount of change in viscosity after standing for each number of days was expressed as a percentage (%) obtained by dividing the initial viscosity (η 0 ). By measuring not only the viscosity change rate after 30 days, but also the viscosity change rate after 1 day and 10 days, the tendency of viscosity change was also confirmed.

黏度變化率（%）＝(η x-η 0)/η 0×100 ･･･（2） η x：X天後的10rpm黏度 η 0：製造8小時後的10rpm黏度（初始黏度） Viscosity change rate (%) = (η x -η 0 )/η 0 ×100 ･･･(2) η x : Viscosity at 10 rpm after X days η 0 : Viscosity at 10 rpm after 8 hours of production (initial viscosity)

必須說明的是，各導電性漿料的黏度使用Brookfield公司製造的B型黏度計在25℃、10rpm（剪切速率＝4sec -1）的條件下進行測定。導電性漿料的隨時間的黏度變化率越小越理想。 In addition, the viscosity of each electroconductive paste was measured on the conditions of 25 degreeC and 10 rpm (shear rate=4sec -1 ) using the B-type viscometer manufactured by Brookfield. The smaller the time-dependent viscosity change rate of the conductive paste, the better.

（2）乾燥膜表面的平滑性（光澤度） 作為乾燥膜表面的平滑性的指標，對藉由下述的方法所測定的值（光澤度）進行評價。 (2) Smoothness (gloss) of dry film surface As an index of the smoothness of the dry film surface, the value (glossiness) measured by the following method was evaluated.

首先，在PET薄膜上以5×10cm的面積以膜厚達到30μm的方式印刷導電性漿料後，在120℃下在空氣中乾燥40分鐘，得到乾燥膜（乾燥後的導電性漿料）。針對所得到的乾燥膜的表面，使用光澤度計（堀場製作所製造的光澤檢測器；IG-320）對入射角為60°時的光澤度進行測定。光澤度越高，表示漫反射越少，得到更平滑的表面。First, a conductive paste was printed on a PET film in an area of 5 × 10 cm so that the film thickness would be 30 μm, and then dried in air at 120° C. for 40 minutes to obtain a dry film (dried conductive paste). About the surface of the obtained dry film, the glossiness at the incident angle of 60 degrees was measured using the gloss meter (Gloss detector by Horiba Corporation; IG-320). A higher gloss level means less diffuse reflection, resulting in a smoother surface.

（3）H 2O吸附量 對評價用樣品（導電性粉末）在25℃下真空脫氣8小時後，使用高精度蒸氣吸附量測定裝置BELSORP-aqua3（MicrotracBEL股份有限公司）對H 2O吸附等溫線進行測定，求出相對壓力P/P 0＝0.5時的H 2O吸附量。此外，使用基於氮吸附法的BET法，求出評價用樣品的比表面積值。所得到的H 2O吸附量除以比表面積值，據此計算出每單位面積的H 2O吸附量。 (3) H 2 O adsorption amount to the evaluation sample (conductive powder) after vacuum degassing at 25°C for 8 hours, and then using a high-precision vapor adsorption amount measuring device BELSORP-aqua3 (MicrotracBEL Co., Ltd.) to adsorb H 2 O The isotherm was measured, and the H 2 O adsorption amount when the relative pressure P/P 0 =0.5 was obtained. Moreover, the specific surface area value of the sample for evaluation was calculated|required using the BET method based on the nitrogen adsorption method. The obtained H 2 O adsorption amount was divided by the specific surface area value, and the H 2 O adsorption amount per unit area was calculated accordingly.

（4）鎳粉末表面的NiO的比例 藉由X射線光電子能譜法（XPS）對作為導電性粉末而使用的鎳粉末的表面進行測定，檢測出歸屬於氫氧化鎳（Ni(OH) 2）、氧化鎳（NiO）的鎳以及金屬鎳的峰，由各自的存在比例計算出NiO的比例（莫耳%）。 (4) The ratio of NiO on the surface of the nickel powder The surface of the nickel powder used as the conductive powder was measured by X-ray photoelectron spectroscopy (XPS), and it was detected that it was attributed to nickel hydroxide (Ni(OH) 2 ). , the peaks of nickel of nickel oxide (NiO), and metallic nickel, and the ratio (mol%) of NiO was calculated from the respective existing ratios.

（5）分散劑的相對介電常數 將所使用的分散劑放入液體樣品用的電極單元中，在頻率：1MHz、電壓：1V的條件下使用LCR計（HP-4278A）求出相對介電常數。 (5) Relative dielectric constant of dispersant The used dispersant was put into the electrode unit for liquid samples, and the relative permittivity was determined using an LCR meter (HP-4278A) under the conditions of frequency: 1 MHz and voltage: 1 V.

［實施例1］ 配製47質量%的作為導電性粉末的鎳粉末（H 2O吸附量為0.31mg/m 2，NiO的表面存在比例為34莫耳%，粒徑為0.4μm）、4.7質量%的作為陶瓷粉末的鈦酸鋇（粒徑為0.05μm）、26.67質量%的有機載體、0.4質量%的分散劑、21.23質量%的作為餘量的有機溶劑。 [Example 1] 47% by mass of nickel powder (H 2 O adsorption amount: 0.31 mg/m 2 , surface presence ratio of NiO: 34 mol %, particle size: 0.4 μm) as conductive powder, 4.7 mass % was prepared. % of barium titanate (particle size: 0.05 μm) as ceramic powder, 26.67 mass % of organic vehicle, 0.4 mass % of dispersant, and 21.23 mass % of organic solvent as balance.

作為有機載體，使用配製有13質量%的作為黏合劑樹脂的乙基纖維素、87質量%的作為有機溶劑的萜品醇並在60℃下加熱混合而製作的有機載體。As the organic vehicle, an organic vehicle prepared by mixing 13% by mass of ethyl cellulose as a binder resin and 87% by mass of terpineol as an organic solvent and heated and mixed at 60°C was used.

分散劑使用相對介電常數為12.5、酸值為58、胺值為110的胺系分散劑（具有酸基的化合物與具有胺基的化合物的混合物）。As the dispersant, an amine-based dispersant (a mixture of a compound having an acid group and a compound having an amine group) having a relative dielectric constant of 12.5, an acid value of 58, and an amine value of 110 was used.

作為有機溶劑，使用萜品醇。As the organic solvent, terpineol was used.

將此等材料在25℃、相對濕度55%的環境下利用三輥磨機進行混煉以及分散，製作導電性漿料。對所製作的導電性漿料的初始黏度以及經過預定時間後的黏度進行測定，計算出經過各個時間後的黏度變化率。此外，對使用所製作的導電性漿料製作的乾燥膜的光澤度進行測定。These materials were kneaded and dispersed with a three-roll mill in an environment of 25° C. and a relative humidity of 55% to prepare conductive paste. The initial viscosity of the produced conductive paste and the viscosity after a predetermined time elapsed were measured, and the viscosity change rate after each time elapsed was calculated. Moreover, the glossiness of the dry film produced using the produced conductive paste was measured.

將所使用的各材料的種類、含量等示於表1，將測定結果以及計算結果示於表2。Table 1 shows the type, content, and the like of each material used, and Table 2 shows the measurement results and calculation results.

［實施例2］ 作為導電性粉末，使用H 2O吸附量為0.53mg/m 2、NiO的表面存在比例為26莫耳%、粒徑為0.2μm的鎳粉末；將分散劑的含量設為0.6質量%，將有機溶劑設為二氫萜品醇乙酸酯並將餘量含量設為21.03質量%；除此以外，按照與實施例1同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［實施例3］ 作為導電性粉末，使用H 2O吸附量為0.42mg/m 2、NiO的表面存在比例為45莫耳%、粒徑為0.08μm的鎳粉末；作為陶瓷粉末，使用粒徑為0.02μm的BT，將分散劑的含量設為1.5質量%，將有機溶劑的餘量含量設為20.13質量%；除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［實施例4］ 使用相對介電常數為11.4、酸值為129的具有羧基的酸系分散劑作為分散劑，除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［實施例5］ 作為導電性粉末，使用H 2O吸附量為0.42mg/m 2、NiO的表面存在比例為45莫耳%、粒徑為0.08μm的鎳粉末；作為陶瓷粉末，使用粒徑為0.02μm的BT，將分散劑的含量設為1.5質量%，將有機溶劑的餘量含量設為20.13質量%；除此以外，按照與實施例4同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［實施例6］ 將分散劑的含量設為1.5質量%，將有機溶劑的餘量含量設為20.13質量%，除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［實施例7］ 作為導電性粉末，使用H 2O吸附量為0.34mg/m 2、NiO的表面存在比例為79莫耳%、粒徑為0.2μm的鎳粉末，除此以外，按照與實施例6同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［實施例8］ 作為導電性粉末，使用H 2O吸附量為0.38mg/m 2、NiO的表面存在比例為89莫耳%、粒徑為0.2μm的鎳粉末，除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 [Example 2] As the conductive powder, a nickel powder having a H 2 O adsorption amount of 0.53 mg/m 2 , a surface presence ratio of NiO of 26 mol %, and a particle size of 0.2 μm was used; the content of the dispersant was set to A conductive paste was produced in the same manner as in Example 1, except that the organic solvent was 0.6% by mass, the organic solvent was dihydroterpineol acetate, and the remaining content was 21.03% by mass. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Example 3] As the conductive powder, a nickel powder with a H 2 O adsorption amount of 0.42 mg/m 2 , a surface presence ratio of NiO of 45 mol %, and a particle size of 0.08 μm was used; as the ceramic powder, the particle size was used. A conductive paste was produced in the same manner as in Example 2, except that the BT was 0.02 μm, the content of the dispersant was 1.5 mass %, and the remaining content of the organic solvent was 20.13 mass %. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Example 4] A conductive paste was produced in the same manner as in Example 2, except that an acid-based dispersant having a carboxyl group having a relative permittivity of 11.4 and an acid value of 129 was used as a dispersant. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Example 5] As the conductive powder, a nickel powder having a H 2 O adsorption amount of 0.42 mg/m 2 , a surface presence ratio of NiO of 45 mol %, and a particle diameter of 0.08 μm was used; as the ceramic powder, a particle diameter of 0.08 μm was used A conductive paste was produced in the same manner as in Example 4, except that the BT was 0.02 μm, the content of the dispersant was 1.5 mass %, and the remaining content of the organic solvent was 20.13 mass %. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Example 6] A conductive paste was produced in the same manner as in Example 2, except that the content of the dispersant was 1.5% by mass and the remaining content of the organic solvent was 20.13% by mass. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Example 7] As the conductive powder, a nickel powder having a H 2 O adsorption amount of 0.34 mg/m 2 , a surface presence ratio of NiO of 79 mol %, and a particle size of 0.2 μm was used, and the same A conductive paste was produced in the same manner as in Example 6. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Example 8] As the conductive powder, a nickel powder having a H 2 O adsorption amount of 0.38 mg/m 2 , a surface presence ratio of NiO of 89 mol %, and a particle size of 0.2 μm was used, and the same A conductive paste was produced in the same manner as in Example 2. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2.

［比較例1］ 使用相對介電常數為3.0、酸值為53、胺值為48的具有胺基的分散劑（具有酸基的化合物與具有胺基的化合物的混合物）作為分散劑，除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［比較例2］ 使用相對介電常數為8.5、酸值為60、胺值為60的具有胺基的分散劑（具有酸基的化合物與具有胺基的化合物的混合物）作為分散劑，除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［比較例3］ 作為導電性粉末，使用H 2O吸附量為0.29mg/m 2、NiO的表面存在比例為49莫耳%、粒徑為0.2μm的鎳粉末，除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。此外又，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［比較例4］ 作為導電性粉末，使用H 2O吸附量為0.29mg/m 2、NiO的表面存在比例為49莫耳%、粒徑為0.2μm的鎳粉末，除此以外，按照與實施例6同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 ［比較例5］ 作為導電性粉末，使用H 2O吸附量為0.71mg/m 2、NiO的表面存在比例為42莫耳%、粒徑為0.2μm的鎳粉末，除此以外，按照與實施例2同樣的方式製作導電性漿料。將所使用的各材料的種類、含量等示於表1。又，關於所得到的導電性漿料，按照與實施例1同樣的方式求出黏度變化率以及光澤度。將其結果示於表2。 [Comparative Example 1] A dispersant having an amine group (a mixture of a compound having an acid group and a compound having an amine group) having a relative permittivity of 3.0, an acid value of 53, and an amine value of 48 was used as a dispersant, except that Except for this, conductive paste was produced in the same manner as in Example 2. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Comparative Example 2] A dispersant having an amine group (a mixture of a compound having an acid group and a compound having an amine group) having a relative permittivity of 8.5, an acid value of 60, and an amine value of 60 was used as the dispersant, except that Except for this, conductive paste was produced in the same manner as in Example 2. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2. [Comparative Example 3] As the conductive powder, a nickel powder having a H 2 O adsorption amount of 0.29 mg/m 2 , a surface presence ratio of NiO of 49 mol %, and a particle size of 0.2 μm was used, and the same procedures were used. A conductive paste was produced in the same manner as in Example 2. Table 1 shows the type, content, and the like of each material used. In addition, the viscosity change rate and glossiness were calculated|required in the same manner as Example 1 about the obtained electroconductive paste. The results are shown in Table 2. [Comparative Example 4] As the conductive powder, a nickel powder having a H 2 O adsorption amount of 0.29 mg/m 2 , a surface presence ratio of NiO of 49 mol %, and a particle size of 0.2 μm was used, and the same A conductive paste was produced in the same manner as in Example 6. Table 1 shows the type, content, and the like of each material used. , about the obtained conductive paste, the viscosity change rate and glossiness were calculated|required in the same manner as Example 1. The results are shown in Table 2. [Comparative Example 5] As the conductive powder, a nickel powder having a H 2 O adsorption amount of 0.71 mg/m 2 , a surface presence ratio of NiO of 42 mol %, and a particle diameter of 0.2 μm was used, and the same A conductive paste was produced in the same manner as in Example 2. Table 1 shows the type, content, and the like of each material used. Moreover, about the obtained electrically conductive paste, it carried out similarly to Example 1, and calculated|required the viscosity change rate and glossiness. The results are shown in Table 2.

［表1］

Figure 02_image001
[Table 1]
Figure 02_image001

［表2］

Figure 02_image003
[Table 2]
Figure 02_image003

（評價結果） 可知含有相對介電常數為10以上的分散劑的實施例的導電性漿料與相對介電常數小於10的比較例的導電性漿料相比，乾燥膜表面的光澤度較高，平滑性優異。此外，可知由於黏度變化率亦較小，因此可長時間維持由分散劑的吸附帶來的分散性的提高的效果。 (Evaluation results) It was found that the conductive pastes of Examples containing a dispersant having a relative permittivity of 10 or more had higher gloss on the dry film surface and excellent smoothness than the conductive pastes of Comparative Examples having a relative permittivity of less than 10. . Moreover, since the viscosity change rate is also small, it turns out that the effect of improving the dispersibility by the adsorption|suction of a dispersing agent can be maintained for a long time.

使用不具有胺值（胺基）而僅具有酸值（酸基）的分散劑的實施例4及實施例5與其他實施例相比，光澤度稍低，但與比較例相比，顯示出足夠高的光澤度及較小的黏度變化率。因此可知，從提高乾燥膜表面整體的平滑性的觀點而言，理想為使用胺值為100以上的分散劑。In Examples 4 and 5 using a dispersant that does not have an amine value (amine group) but only has an acid value (acid group), the glossiness is slightly lower than that of the other examples, but compared with the comparative example, the Sufficient high gloss and small viscosity change rate. Therefore, from the viewpoint of improving the smoothness of the entire dry film surface, it was found that it is desirable to use a dispersant having an amine value of 100 or more.

另一方面，可知含有相對介電常數小於10的分散劑的比較例1、比較例2的導電性漿料的乾燥膜表面的光澤度非常低，平滑性較差。據認為，此係因分散劑不滿足預定的特性，因此相對於顆粒表面的潤濕性較差，分散劑無法充分地吸附於顆粒表面，故而無法充分地實現顆粒的粉碎、再凝集的抑制，因此導電性漿料的分散性較差，產生材料的偏差，乾燥膜表面的平滑性較差。此外，據認為，因分散劑的吸附性較差，分散穩定性較差，各材料的凝集等隨著時間而增加，因此黏度變化率隨著時間而變大。On the other hand, it turned out that the glossiness of the dry film surface of the conductive paste of the comparative example 1 and the comparative example 2 containing the dispersing agent with a relative dielectric constant of less than 10 was very low, and smoothness was inferior. This is considered to be because the dispersing agent does not satisfy the predetermined characteristics, and thus the wettability with respect to the particle surface is poor, and the dispersing agent cannot be sufficiently adsorbed on the particle surface, so that the pulverization of the particles and the suppression of re-agglomeration cannot be sufficiently achieved. The dispersibility of the conductive paste is poor, resulting in material variation, and the smoothness of the dry film surface is poor. In addition, it is considered that the viscosity change rate increases with time because the dispersing agent has poor adsorption properties and poor dispersion stability, and the aggregation of each material increases with time.

此外，關於每單位面積的H 2O吸附量在本發明的範圍外的比較例3~5，據認為，平滑性在一定程度上較低，導電性粉末的表面狀態均不適當，因此漿料化時的分散穩定性較差，導電性粉末彼此的凝集等隨著時間而增加，黏度變化率亦隨著時間而變大。 In addition, in Comparative Examples 3 to 5 in which the amount of H 2 O adsorption per unit area is outside the scope of the present invention, it is considered that the smoothness is low to a certain extent, and the surface state of the conductive powder is not appropriate, so the slurry is considered The dispersion stability at the time of conversion is poor, the agglomeration of the conductive powders increases with time, and the viscosity change rate also increases with time.

又，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。有時將在上述實施型態等中說明的一個以上的要件省略。此外，在上述實施型態等中說明的要件可以適當組合。此外，只要在法律所允許的範圍內，則援引在日本特願2020-196256、以及在上述的實施型態等中引用的全部的文獻的揭示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 modes described in the above-described embodiments and the like. One or more requirements described in the above-described embodiments and the like may be omitted. In addition, the requirements described in the above-described embodiments and the like can be appropriately combined. In addition, the disclosure contents of all the documents cited in Japanese Patent Application No. 2020-196256 and the above-mentioned embodiments and the like are incorporated as a part of the description of the present specification to the extent permitted by law.

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: MLCC 10: Ceramic laminate 11: Internal electrode layer 12: Dielectric layer 20: External electrodes 21: External electrode layer 22: Electroplating layer

〔圖1〕係表示實施型態所關於的積層陶瓷電容器的斜視圖以及剖視圖。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: MLCC

10:陶瓷積層體 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 electrodes

21:外部電極層 21: External electrode layer

22:電鍍層 22: Electroplating layer

Claims (11)

一種導電性漿料，其係含有導電性粉末、陶瓷粉末、黏合劑樹脂、有機溶劑及分散劑，其特徵係， 該導電性粉末在相對壓力P／P 0＝0.5時的每單位面積的H 2O吸附量為0.30mg／m 2以上且0.70mg／m 2以下； 該分散劑具有10以上的相對介電常數，並且含有選自由（1）具有酸基的化合物以及（2）具有胺基的化合物所成群中之至少一種化合物。 A conductive paste, which contains conductive powder, ceramic powder, binder resin, organic solvent and dispersant, characterized in that the conductive powder has H per unit area when relative pressure P/P 0 =0.5 The 2 O adsorption amount is 0.30 mg/m 2 or more and 0.70 mg/m 2 or less; the dispersant has a relative permittivity of 10 or more, and contains a compound selected from (1) a compound having an acid group and (2) a compound having an amino group at least one compound in the group of compounds. 如請求項1所述之導電性漿料，其中，該（1）具有酸基的化合物為含有羧基以及磷酸基中之至少一者的化合物。The conductive paste according to claim 1, wherein the (1) compound having an acid group is a compound containing at least one of a carboxyl group and a phosphoric acid group. 如請求項1或2所述之導電性漿料，其中，該黏合劑樹脂含有選自由纖維素系樹脂以及縮丁醛系樹脂所成群中之一種以上。The conductive paste according to claim 1 or 2, wherein the binder resin contains at least one selected from the group consisting of cellulose-based resins and butyral-based resins. 如請求項1至3中任一項所述之導電性漿料，其中，該黏合劑樹脂的含量相對於導電性漿料100質量%為0.5質量%以上且10質量%以下。The conductive paste according to any one of claims 1 to 3, wherein the content of the binder resin is 0.5 mass % or more and 10 mass % or less with respect to 100 mass % of the 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由Ni、Cu、Ag、Pd、Au、Pt粉末及其等的合金粉末所成群中之一種以上的金屬粉末。The conductive paste according to any one of claims 1 to 4, wherein the conductive powder contains a powder selected from the group consisting of Ni, Cu, Ag, Pd, Au, Pt powders and alloy powders thereof. More than one metal powder. 如請求項1至5中任一項所述之導電性漿料，其中，該導電性粉末為鎳粉末。The conductive paste according to any one of claims 1 to 5, wherein the conductive powder is nickel powder. 如請求項6所述之導電性漿料，其中，在該鎳粉末的表面組成中，NiO為20莫耳%以上且90莫耳%以下。The conductive paste according to claim 6, wherein in the surface composition of the nickel powder, NiO is 20 mol % or more and 90 mol % or less. 如請求項1至7中任一項所述之導電性漿料，其中，該導電性粉末的含量相對於導電性漿料100質量%為30質量%以上且70質量%以下。The conductive paste according to any one of claims 1 to 7, wherein the content of the conductive powder is 30% by mass or more and 70% by mass or less with respect to 100% by mass of the conductive paste. 如請求項1至8中任一項所述之導電性漿料，其中，該陶瓷粉末為選自由鈦酸鋇系以及鋯酸鍶系所成群中之至少一種。The conductive paste according to any one of claims 1 to 8, wherein the ceramic powder is at least one selected from the group consisting of barium titanate and strontium zirconate. 如請求項1至9中任一項所述之導電性漿料，其中，該導電性漿料在製造後在25℃下靜置30天，利用布氏黏度計在25℃、10rpm的條件下測定時的導電性漿料的黏度的變化率相對於製造8小時後的導電性漿料的黏度為±10%以下。The conductive paste according to any one of claims 1 to 9, wherein the conductive paste is allowed to stand at 25° C. for 30 days after manufacture, and the conductive paste is kept at 25° C. and 10 rpm using a Brookfield viscometer. The rate of change of the viscosity of the conductive paste at the time of measurement is ±10% or less with respect to the viscosity of the conductive paste 8 hours after production. 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層進行積層而成的積層體； 該內部電極層使用如請求項1至10中任一項所述之導電性漿料而形成。 A multilayer ceramic capacitor is characterized in that it has at least a multilayer body formed by laminating a dielectric layer and an internal electrode layer; The internal electrode layer is formed using the conductive paste described in any one of claims 1 to 10.
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