TWI801445B - Conductive paste, electronic parts, and laminated ceramic capacitors - Google Patents
Conductive paste, electronic parts, and laminated ceramic capacitors Download PDFInfo
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- H—ELECTRICITY
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Abstract
本發明係提供一種具有適於凹版印刷的黏度、且漿料的分散性優異的導電性漿料。本發明之導電性漿料含有導電性粉末、分散劑、黏合劑樹脂以及有機溶劑、且分散劑含有分子量為5000以下的胺基酸系分散劑，黏合劑樹脂含有縮醛系樹脂，有機溶劑含有二醇醚系溶劑的導電性漿料等。 The present invention provides a conductive paste having a viscosity suitable for gravure printing and having excellent dispersibility of the paste. The conductive paste of the present invention contains conductive powder, a dispersant, a binder resin, and an organic solvent, and the dispersant contains an amino acid-based dispersant with a molecular weight of 5,000 or less, the binder resin contains an acetal resin, and the organic solvent contains Conductive paste of glycol ether solvent, etc.
Description
本發明關於一種導電性漿料、電子零件以及層積陶瓷電容器。 The present invention relates to a conductive paste, an electronic component, and a laminated ceramic capacitor.
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，對於包含層積陶瓷電容器等的電子零件亦期望小型化以及高容量化。層積陶瓷電容器具有將多個介電質層和多個內部電極層交替層積而成的結構，藉由使上述介電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。 Along with the miniaturization and high performance of electronic equipment such as mobile phones and digital devices, miniaturization and high capacity are also desired for electronic components including laminated ceramic capacitors and the like. A laminated 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 internal electrode layers, miniaturization and high capacity can be achieved.
例如，可以藉由下述方式來製造層積陶瓷電容器。首先，在含有鈦酸鋇(BaTiO3)等介電質粉末以及黏合劑樹脂的介電質生片的表面上，以規定的電極圖案印刷含有導電性粉末、黏合劑樹脂以及有機溶劑等的內部電極用漿料(導電性漿料)，將該印刷有內部電極用漿料的介電質生片層疊成多層，據此得到將內部電極和介電質生片層疊成多層的層積體。接著，對該層積體進行加熱壓接而使其一體化而形成壓接體。將該壓接體切斷，在氧化性氣體或惰性氣體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，從而得到層積陶瓷電容器。 For example, a laminated ceramic capacitor can be manufactured in the following manner. First, on the surface of a dielectric green sheet containing a dielectric powder such as barium titanate (BaTiO 3 ) and a binder resin, an internal layer containing conductive powder, a binder resin, and an organic solvent is printed in a predetermined electrode pattern. Paste for electrodes (conductive paste) The dielectric green sheets printed with the paste for internal electrodes are laminated in multiple layers, thereby obtaining a laminate in which internal electrodes and dielectric green sheets are laminated in multiple layers. Next, this laminated body is heat-compressed and integrated to form a pressure-bonded body. The press-bonded body is cut, subjected to an organic binder removal treatment in an oxidizing gas or an inert gas, and then fired to obtain a fired wafer. Next, a paste for external electrodes is applied to both ends of the fired wafer, and after firing, nickel plating or the like is performed on the surface of the external electrodes to obtain a laminated ceramic capacitor.
作為將導電性漿料印刷在介電質生片時使用的印刷方法，傳統一般使用網版印刷法，但是從電子設備的小型化、薄膜化、生產性的提高的要求出發，要求以較高的生產性來印刷更微細的電極圖案。 As a printing method for printing conductive paste on dielectric green sheets, traditionally, screen printing is generally used. Print finer electrode patterns with higher productivity.
作為導電性漿料的印刷法之一，提出作為在製版上設置的凹部中填充導電性漿料並將該製版按壓於被印刷面而從該製版轉印導電性漿料的連續印刷法的凹版印刷法。凹版印刷法的印刷速度快、生產性優異。在使用凹版印刷法的情況下，需要適當地選擇導電性漿料中的黏合劑樹脂、分散劑、溶劑等，並將黏度等的特性調整至適於凹版印刷的範圍。 As one of the printing methods of conductive paste, gravure plate is proposed as a continuous printing method in which conductive paste is transferred from the plate by filling the recesses provided on the plate with conductive paste and pressing the plate to the surface to be printed. printing method. The gravure printing method has high printing speed and excellent productivity. When using the gravure printing method, it is necessary to appropriately select a binder resin, a dispersant, a solvent, and the like in the conductive paste, and to adjust characteristics such as viscosity to a range suitable for gravure printing.
例如，在專利文獻1中記載一種導電性漿料，其是用於藉由凹版印刷來形成內部導體膜的導電性漿料，該內部導體膜具備多個陶瓷層以及沿上述陶瓷層之間的特定的界面延伸的內部導體膜的層積陶瓷電子零件中的內部導體膜，該導電性漿料包含30~70重量%的含有金屬粉末的固體成分、1~10重量%的乙氧基含有率為49.6%以上的乙基纖維素樹脂成分、0.05~5重量%的分散劑以及作為餘量的溶劑成分，是剪切速率為0.1(s-1)時的黏度η0.1為1Pa．s以上、且剪切速率為0.02(s-1)時的黏度η0.02滿足以特定的式表示的條件的觸變性流體。 For example, Patent Document 1 describes an electroconductive paste for forming an inner conductor film comprising a plurality of ceramic layers and a gap between the ceramic layers by gravure printing. An internal conductor film in a laminated ceramic electronic part with an internal conductor film extending at a specific interface, the conductive paste containing 30 to 70% by weight of solid content containing metal powder and an ethoxy group content of 1 to 10% by weight It is more than 49.6% of ethyl cellulose resin component, 0.05~5% by weight of dispersant and solvent component as the balance, and the viscosity η0.1 at the shear rate of 0.1 (s -1 ) is 1Pa. A thixotropic fluid whose viscosity η0.02 at a shear rate of 0.02 (s −1 ) satisfies the conditions expressed by the specific formula s or more.
又，在專利文獻2中記載一種導電性漿料，與上述專利文獻1同樣地亦是用於藉由凹版印刷來形成內部導體膜的導電性漿料，其包含30~70重量%的含有金屬粉末的固體成分、1~10重量%的樹脂成分、0.05~5重量%的分散劑以及作為餘量的溶劑成分、且為剪切速率為0.1(s-1)時的黏度為1Pa．s以上的觸變性流體，在以剪切速率為0.1(s-1)時的黏度作為基準時，剪切速率為10(s-1)時的黏度變化率為50%以上。 Also, Patent Document 2 describes a conductive paste that is used for forming an internal conductor film by gravure printing similarly to the above-mentioned Patent Document 1, and contains 30 to 70% by weight of a metal-containing paste. The solid content of the powder, 1-10% by weight of the resin component, 0.05-5% by weight of the dispersant, and the balance of the solvent component, and the viscosity at a shear rate of 0.1 (s -1 ) is 1Pa. For a thixotropic fluid with a shear rate of 0.1 (s -1 ) as a reference, the rate of change in viscosity at a shear rate of 10 (s -1 ) is 50% or more.
根據上述專利文獻1、2，上述導電性漿料是剪切速率為0.1(s-1)時的黏度為1Pa．s以上的觸變性流體，在凹版印刷中可獲得高速下的穩定的連續印刷性，能夠以良好的生產效率製造層積陶瓷電容器如此的層積陶瓷電子零件。 According to the above-mentioned patent documents 1 and 2, the above-mentioned conductive paste has a viscosity of 1 Pa when the shear rate is 0.1 (s -1 ). The thixotropic fluid of s or more can obtain stable continuous printability at high speed in gravure printing, and can manufacture laminated ceramic electronic parts such as laminated ceramic capacitors with good productivity.
又，在專利文獻3記載一種凹版印刷用導電性漿料，其是含有導電性粉末(A)、有機樹脂(B)、有機溶劑(C)、添加劑(D)以及介電質粉末(E)的層積陶瓷電容器內部電極用導電性漿料，有機樹脂(B)由聚合度為10000以上50000以下的聚乙烯醇縮丁醛和重均分子量為10000以上100000以下的乙基纖維素構成，有機溶劑(C)由丙二醇單丁醚、或丙二醇單丁醚與丙二醇甲醚乙酸酯的混合溶劑、或丙二醇單丁醚與礦油精的混合溶劑的任一種構成，添加劑(D)由分離抑制劑和分散劑構成，作為該分離抑制劑由含有聚羧酸聚合物或聚羧酸鹽的組成物構成。根據專利文獻3，該導電性漿料具有適於凹版印刷的黏度，可提高漿料的均勻性、穩定性，且乾燥性良好。 In addition, Patent Document 3 describes a conductive paste for gravure printing, which contains conductive powder (A), organic resin (B), organic solvent (C), additive (D) and dielectric powder (E). The conductive paste for internal electrodes of laminated ceramic capacitors, the organic resin (B) is composed of polyvinyl butyral with a degree of polymerization of 10,000 to 50,000 and ethyl cellulose with a weight average molecular weight of 10,000 to 100,000, organic The solvent (C) is composed of any one of propylene glycol monobutyl ether, or a mixed solvent of propylene glycol monobutyl ether and propylene glycol methyl ether acetate, or a mixed solvent of propylene glycol monobutyl ether and mineral spirits, and the additive (D) consists of a separation inhibitor agent and a dispersant, and the separation inhibitor is composed of a composition containing a polycarboxylate polymer or a polycarboxylate. According to Patent Document 3, the conductive paste has a viscosity suitable for gravure printing, improves the uniformity and stability of the paste, and has good drying properties.
【專利文獻1】日本特開2003-187638號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2003-187638
【專利文獻2】日本特開2003-242835號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2003-242835
【專利文獻3】日本特開2012-174797號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2012-174797
伴隨近年來的內部電極層的薄膜化，導電性粉末亦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，存在導電性漿料的分散性降低的情況，從而要求具有更高分散性的導電性漿料。 Along with the reduction in the thickness of the internal electrode layer in recent years, the particle size of the conductive powder also tends to be reduced. When the particle size of the conductive powder is small, the specific surface area of the particle surface increases, so the surface activity of the conductive powder (metal powder) becomes high, and the dispersibility of the conductive paste may decrease, so it is required Conductive paste with higher dispersibility.
又，在使用凹版印刷法對導電性漿料進行印刷的情況下，要求比網版印刷法更低的漿料黏度，因此可考慮到比重較大的導電性粉末會沉降而使漿料的分散性降低。此外，在上述專利文獻1、2所記載的導電性漿料中，雖然藉由使用過濾器去除導電性漿料中的塊狀物而改善漿料的分散性，但是需要去除塊狀物的工序，因此製造工序容易變得複雜。 In addition, when the gravure printing method is used to print the conductive paste, the viscosity of the paste is required to be lower than that of the screen printing method, so the dispersion of the paste can be considered due to the sedimentation of the conductive powder with a large specific gravity. reduced sex. In addition, in the conductive pastes described in the aforementioned Patent Documents 1 and 2, although the dispersibility of the slurry is improved by removing lumps in the conductive paste using a filter, a step of removing lumps is required. , so the manufacturing process tends to become complicated.
鑑於此狀況，本發明之目的在於提供一種具有適於凹版印刷的漿料黏度、且漿料的分散性以及生產性優異的導電性漿料。 In view of this situation, the object of this invention is to provide the electroconductive paste which has the paste viscosity suitable for gravure printing, and is excellent in the dispersibility of a paste, and productivity.
本發明的第一態樣提供一種導電性漿料，含有導電性粉末、分散劑、黏合劑樹脂以及有機溶劑，分散劑含有分子量為5000以下的胺基酸系分散劑，黏合劑樹脂含有縮醛系樹脂，有機溶劑含有二醇醚系溶劑。 The first aspect of the present invention provides a conductive paste containing conductive powder, a dispersant, a binder resin, and an organic solvent, the dispersant contains an amino acid-based dispersant with a molecular weight of 5,000 or less, and the binder resin contains acetal It is a resin, and the organic solvent contains a glycol ether-based solvent.
胺基酸系分散劑理想為下述化學式(1)所示的胺基酸系分散劑。 The amino acid-based dispersant is preferably an amino acid-based dispersant represented by the following chemical formula (1).
【化1】
(其中，在化學式(1)中，R1表示碳原子數為10以上且20以下的直鏈烷基或碳原子數為10以上且20以下的直鏈烯基。) (wherein, in the chemical formula (1), R 1 represents a straight-chain alkyl group having 10 or more and 20 or less carbon atoms or a straight-chain alkenyl group having 10 or more and 20 or less carbon atoms.)
又，以導電性粉末為100質量份計，理想為含有0.01質量份以上2質量份以下的胺基酸系分散劑。又，以導電性粉末為100質量份計，理想為含有30質量份以上50質量份以下的二醇醚系溶劑。又，分散劑亦可含有鹼系分散劑。又，以導電性粉末為100質量份計，理想為含有0.01質量份以上2質量份以下的分散劑。 Moreover, it is desirable to contain 0.01 mass part or more and 2 mass parts or less of an amino acid type dispersant based on 100 mass parts of electroconductive powders. Moreover, it is preferable to contain 30 mass parts or more and 50 mass parts or less glycol ether type solvents based on 100 mass parts of electroconductive powders. In addition, the dispersant may contain an alkali-based dispersant. Moreover, it is desirable to contain 0.01 mass part or more of 2 mass parts or less of a dispersing agent based on 100 mass parts of electroconductive powders.
導電性粉末理想為含有選自Ni、Pd、Pt、Au、Ag、Cu以及其等合金所成群中的至少一種的金屬粉末。又，導電性漿料理想為含有陶瓷粉末。又，陶瓷粉末理想為含有鈣鈦礦型氧化物。又，陶瓷粉末的平均粒徑理想為0.01μm以上0.5μm以下。又，導電性粉末的平均粒徑理想為0.05μm以上1.0μm以下。又，導電性漿料理想為用於層積陶瓷零件的內部電極。又，理想地，導電性漿料在剪切速率為100sec-1時的黏度為0.8Pa．S以下，在剪切速率為10000sec-1時的黏度為0.18Pa．S以下。 The conductive powder is preferably a metal powder containing at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof. Moreover, it is desirable that an electroconductive paste contains ceramic powder. Also, the ceramic powder preferably contains a perovskite-type oxide. In addition, the average particle diameter of the ceramic powder is preferably not less than 0.01 μm and not more than 0.5 μm. In addition, the average particle diameter of the conductive powder is preferably not less than 0.05 μm and not more than 1.0 μm. Also, the conductive paste is ideally used for internal electrodes of laminated ceramic parts. Also, ideally, the viscosity of the conductive paste at a shear rate of 100sec -1 is 0.8Pa. Below S, the viscosity is 0.18Pa when the shear rate is 10000sec -1 . Below S.
本發明的第二態樣提供一種使用上述導電性漿料而形成的電子零件。 A second aspect of the present invention provides an electronic component formed using the above-mentioned conductive paste.
本發明的第三態樣提供一種層積陶瓷電容器，其至少具有將介電質層和內部電極進行層疊而成的層積體，內部電極使用上述導電性漿 料而形成。 A third aspect of the present invention provides a laminated ceramic capacitor comprising at least a laminate in which dielectric layers and internal electrodes are laminated, and the internal electrodes use the above-mentioned conductive paste. material formed.
本發明的導電性漿料具有適於凹版印刷的黏度、且漿料的分散性以及生產性優異。又，使用本發明的導電性漿料而形成的層積陶瓷電容器等電子零件的電極圖案，在形成薄膜化的電極時導電性漿料的印刷性亦很優異、且具有均勻的厚度。 The conductive paste of the present invention has a viscosity suitable for gravure printing, and is excellent in dispersibility and productivity of the paste. In addition, electrode patterns of electronic components such as laminated ceramic capacitors formed using the conductive paste of the present invention are excellent in printability of the conductive paste and have a uniform thickness when thinned electrodes are formed.
1‧‧‧層積陶瓷電容器 1‧‧‧Laminated Ceramic Capacitors
10‧‧‧層積體 10‧‧‧laminated body
11‧‧‧內部電極層 11‧‧‧internal electrode layer
12‧‧‧介電質層 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
【圖1】為本發明之實施型態之層積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 of a laminated ceramic capacitor according to an embodiment of the present invention.
[導電性漿料] [Conductive Paste]
本實施型態的導電性漿料含有導電性粉末、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, a dispersant, a binder resin, and an organic solvent. Each component will be described in detail below.
(導電性粉末) (conductive powder)
對導電性粉末沒有特別限定，例如，可以使用選自Ni、Pd、Pt、Au、Ag、Cu以及其等合金所成群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出發，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合金中的Ni的含量例如為50質量%以上，理想為80質量%以上。此外，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劇烈的氣體產生，Ni粉末可以含有幾百ppm程度的S。 The conductive powder is not particularly limited, and for example, one or more powders selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof can be used. Among them, powder of Ni or its alloy is preferable from the viewpoint of electrical conductivity, corrosion resistance, and cost. As the Ni alloy, for example, an alloy of at least one element selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt, and Pd and Ni can be used. The content of Ni in the Ni alloy is, for example, 50% by mass or more, preferably 80% by mass or more. In addition, in order to suppress the debinding process during the The Ni powder may contain S on the order of hundreds of ppm due to violent gas generation due to partial thermal decomposition of the binder resin.
導電性粉末的平均粒徑0.05μm以上1.0μm以下為佳，0.1μm以上0.5μm以下更佳。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層積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，是指根據SEM觀察而求出的個數平均值(以各個顆粒測定的粒徑的總和/觀察的顆粒的個數)。 The average particle diameter of the conductive powder is preferably from 0.05 μm to 1.0 μm, more preferably from 0.1 μm to 0.5 μm. When the average particle size of the conductive powder is within the above range, it can be suitably used as a slurry for an internal electrode of a thinned multilayer ceramic capacitor, and for example, the smoothness and dry film density of a dry film can be improved. The average particle diameter is a value obtained by observation based on a scanning electron microscope (SEM), and refers to an average value of the number (sum of particle diameters measured by individual particles/number of observed particles) obtained by SEM observation. number).
導電性粉末的含量相對於導電性漿料整體30質量%以上70質量%以下為佳，40質量%以上65質量%以下更佳。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 70% by mass or less, more preferably 40% by mass or more and 65% by mass or less with respect to the entire conductive paste. When content of electroconductive powder exists in the said range, electroconductivity and dispersibility are excellent.
(陶瓷粉末) (ceramic powder)
導電性漿料可以含有陶瓷粉末。作為陶瓷粉末，沒有特別限定，例如，在為層積陶瓷電容器的內部電極用漿料的情況下，可根據所應用的層積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)。此外，陶瓷粉末可以使用一種，亦可以使用兩種以上。 The conductive paste may contain ceramic powder. The ceramic powder is not particularly limited. For example, in the case of a paste for internal electrodes of a laminated ceramic capacitor, a known ceramic powder can be appropriately selected according to the type of laminated ceramic capacitor to be used. Examples of the ceramic powder include perovskite-type oxides containing Ba and Ti, preferably barium titanate (BaTiO 3 ). In addition, one type of ceramic powder may be used, or two or more types may be used.
作為陶瓷粉末，可以使用以鈦酸鋇作為主成分、且以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以及稀土類元素所成群中的一種以上構成的氧化物。 As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent can be used. Examples of oxides include oxides composed of one or more selected from the group consisting of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and rare earth elements.
又，作為陶瓷粉末，例如亦可列舉為將鈦酸鋇(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介電質的陶瓷粉末。 In addition, as ceramic powder, for example, perovskite-type oxide ferroelectric ceramics in which Ba atoms and Ti atoms of barium titanate (BaTiO 3 ) are substituted with other atoms such as Sn, Pb, and Zr can also be mentioned. powder.
作為內部電極用漿料中的陶瓷粉末，可以使用與構成層積陶瓷電容器的生片的介電質陶瓷粉末相同組成的粉末。據此，可抑制因燒結工序中的介電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。作為這樣的陶瓷粉末，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、Al2O3、Bi2O3、R(稀土類元素)2O3、TiO2、Nd2O3等氧化物。 As the ceramic powder in the slurry for internal electrodes, powder having the same composition as the dielectric ceramic powder constituting the green sheet of the laminated ceramic capacitor can be used. Accordingly, generation of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering process can be suppressed. Such ceramic powders include, for example, ZnO, ferrite, PZT, BaO, Al 2 O 3 , Bi 2 O 3 , R (rare earth element) 2 O 3 , TiO 2 , Nd 2 O 3 and other oxides.
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。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，是指根據SEM觀察而求出的個數平均值(以各個顆粒測定的粒徑的總和/觀察的顆粒的個數)。 The average particle size of the ceramic powder is, for example, from 0.01 μm to 0.5 μm, preferably from 0.01 μm to 0.3 μm. When the average particle size of the ceramic powder is 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 diameter is a value obtained by observation based on a scanning electron microscope (SEM), and refers to an average value of the number (sum of particle diameters measured by individual particles/number of observed particles) obtained by SEM observation. number).
以導電性粉末為100質量份計，陶瓷粉末的含量1質量份以上30質量份以下為佳，3質量份以上30質量份以下更佳。 Based on 100 parts by mass of the conductive powder, the content of the ceramic powder is preferably not less than 1 part by mass and not more than 30 parts by mass, more preferably not less than 3 parts by mass and not more than 30 parts by mass.
陶瓷粉末的含量相對於導電性漿料整體理想為1質量%以上20質量%以下，更理想為3質量%以上20質量%以下。 The content of the ceramic powder is preferably from 1 mass % to 20 mass % with respect to the whole conductive paste, more preferably from 3 mass % to 20 mass %.
(黏合劑樹脂) (Binder resin)
黏合劑樹脂含有縮醛系樹脂。作為縮醛系樹脂，理想為聚乙烯醇縮丁醛等丁醛系樹脂。在黏合劑樹脂含有縮醛系樹脂的情況下，能夠調整至適於凹版印刷的黏度、且能夠進一步提高與生片的黏接強度。黏合劑樹脂， 例如相對於黏合劑樹脂整體可以含有20質量%以上的縮醛系樹脂，亦可以含有30質量%以上，亦可以含有60質量%以上，亦可以僅由縮醛系樹脂構成。 The binder resin contains an acetal-based resin. As the acetal-based resin, butyral-based resins such as polyvinyl butyral are preferable. When the binder resin contains an acetal-based resin, the viscosity can be adjusted to a viscosity suitable for gravure printing, and the adhesive strength with the green sheet can be further improved. adhesive resin, For example, the acetal-based resin may be contained in an amount of 20% by mass or more, 30% by mass or more, or 60% by mass or more of the entire binder resin, or may be composed of only the acetal-based resin.
此外，如後述狀況，在導電性漿料含有鹼系分散劑作為分散劑的情況下，即使縮醛系樹脂的含量不足40質量%，亦能夠設為較低的漿料黏度。 In addition, as described later, when the conductive paste contains an alkali-based dispersant as a dispersant, even if the content of the acetal-based resin is less than 40% by mass, the viscosity of the paste can be relatively low.
以導電性粉末為100質量份計，縮醛系樹脂的含量1質量份以上10質量份以下為佳，1質量份以上8質量份以下更佳。 Based on 100 parts by mass of the conductive powder, the content of the acetal resin is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass.
又，黏合劑樹脂可以含有除了縮醛系樹脂以外的其他樹脂。作為其他樹脂沒有特別限定，可以使用習知的樹脂。作為其他樹脂，例如可列舉為甲基纖維素、乙基纖維素、乙基羥乙基纖維素、硝基纖維素等纖維素系樹脂、丙烯酸系樹脂等，其中，從相對於溶劑的溶解性、燃燒分解性的觀點等出發，理想為乙基纖維素。又，黏合劑樹脂的分子量例如為20000~200000左右。 In addition, the binder resin may contain other resins than the acetal-based resin. Other resins are not particularly limited, and known resins can be used. Examples of other resins include cellulose-based resins such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, and acrylic resins. From the viewpoint of combustion and decomposability, etc., ethyl cellulose is ideal. In addition, the molecular weight of the binder resin is, for example, about 20,000 to 200,000.
以導電性粉末為100質量份計，黏合劑樹脂的含量1質量份以上10質量份以下為佳，1質量份以上8質量份以下更佳。 Based on 100 parts by mass of the conductive powder, the content of the binder resin is preferably not less than 1 part by mass and not more than 10 parts by mass, more preferably not less than 1 part by mass and not more than 8 parts by mass.
黏合劑樹脂的含量相對於導電性漿料整體0.5質量%以上10質量%以下為佳，0.5質量%以上6質量%以下更佳。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 is preferably not less than 0.5% by mass and not more than 10% by mass relative to the entire conductive paste, more preferably not less than 0.5% by mass and not more than 6% by mass. When content of binder resin is in the said range, electroconductivity and dispersibility are excellent.
(有機溶劑) (Organic solvents)
有機溶劑含有二醇醚系溶劑以及乙酸酯系溶劑中的至少一種，理想為含有二醇醚系溶劑。 The organic solvent contains at least one of a glycol ether-based solvent and an acetate-based solvent, and preferably contains a glycol ether-based solvent.
作為二醇醚系溶劑，例如可列舉為二乙二醇單-2-乙基己基 醚、乙二醇單-2-乙基己基醚、二乙二醇單己基醚、乙二醇單己醚等(二)乙二醇醚類、以及丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚(PNB)等丙二醇單烷基醚類等。其中，丙二醇單烷基醚類為佳，丙二醇單丁基醚更佳。在有機溶劑含有二醇醚系溶劑的情況下，與上述的黏結劑樹脂的相容性優異、且乾燥性優異。 Examples of glycol ether solvents include diethylene glycol mono-2-ethylhexyl Ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, ethylene glycol monohexyl ether, etc. (two) glycol ethers, and propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol monopropyl ether, propylene glycol monobutyl ether (PNB) and other propylene glycol monoalkyl ethers, etc. Among them, propylene glycol monoalkyl ethers are preferred, and propylene glycol monobutyl ether is more preferred. When the organic solvent contains a glycol ether-based solvent, it is excellent in compatibility with the above-mentioned binder resin and excellent in drying property.
有機溶劑，例如，相對於有機溶劑整體，可以含有25質量%以上的二醇醚系溶劑，亦可以含有50質量%以上，亦可以僅由二醇醚系溶劑構成。又，二醇醚系溶劑可以單獨使用一種，亦可以兩種以上並用。 The organic solvent may contain, for example, 25% by mass or more of a glycol ether-based solvent, or may contain 50% by mass or more of a glycol ether-based solvent based on the entire organic solvent, or may consist of only a glycol ether-based solvent. Moreover, a glycol ether solvent may be used individually by 1 type, and may use 2 or more types together.
作為乙酸酯系溶劑，例如，可列舉為二氫萜品醇乙酸酯、乙酸異冰片酯、丙酸異冰片酯、丁酸異冰片酯、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、3-甲氧基3-甲基丁基乙酸酯、1-甲氧基丙基-2-乙酸酯等二醇醚乙酸酯類等。 Examples of acetate-based solvents include dihydroterpineol acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, ethylene glycol monobutyl Glycol ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy 3-methylbutyl acetate, 1-methoxypropyl-2-acetate, etc. .
在有機溶劑含有乙酸酯系溶劑的情況下，例如，可以含有選自二氫萜品醇乙酸酯、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所成群中的至少一種的乙酸酯系溶劑(A)。其中，乙酸異冰片酯更佳。相對於有機溶劑整體，含有90質量%以上100質量%以下的乙酸酯系溶劑為佳，含有100質量%更佳。 When the organic solvent contains an acetate-based solvent, for example, it may contain a solvent selected from dihydroterpineol acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate. An acetate-based solvent (A) of at least one of the ester group. Among them, isobornyl acetate is more preferable. It is preferable to contain the acetate-based solvent at 90 mass % or more and 100 mass % or less with respect to the whole organic solvent, and it is more preferable to contain 100 mass %.
又，在有機溶劑含有乙酸酯系溶劑的情況下，例如，可以含有上述乙酸酯系溶劑(A)以及選自乙二醇單丁基醚乙酸酯、二丙二醇甲醚乙酸酯中的至少一種的乙酸酯系溶劑(B)。在使用這樣的混合溶劑的情況下，能夠容易地進行導電性漿料的黏度調整，能夠加快導電性漿料的乾燥速度。 In addition, when the organic solvent contains an acetate-based solvent, for example, the above-mentioned acetate-based solvent (A) and a solvent selected from ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate may be included. at least one acetate-based solvent (B). When using such a mixed solvent, the viscosity adjustment of an electroconductive paste can be performed easily, and the drying rate of an electroconductive paste can be accelerated.
在為含有乙酸酯系溶劑(A)和乙酸酯系溶劑(B)的混合液的情況下，有機溶劑相對於有機溶劑整體含有50質量%以上90質量%以下的乙酸酯系溶劑(A)為佳，含有60質量%以上80質量%以下更佳。在為上述混合液的情況下，以有機溶劑整體為100質量%計，有機溶劑含有10質量%以上50質量%以下的乙酸酯系溶劑(B)，含有20質量%以上40質量%以下更佳。 In the case of a mixed solution containing an acetate-based solvent (A) and an acetate-based solvent (B), the organic solvent contains 50% by mass or more and 90% by mass or less of the acetate-based solvent ( A) is preferable, and it is more preferable to contain 60 mass % or more and 80 mass % or less. In the case of the above mixed solution, based on 100% by mass of the organic solvent as a whole, the organic solvent contains 10% by mass to 50% by mass of the acetate-based solvent (B), and contains 20% by mass to 40% by mass or less. good.
又，有機溶劑可以含有除了二醇醚系溶劑以及乙酸酯系溶劑以外的其他有機溶劑。作為其他有機溶劑，沒有特別的限定，可以使用能夠溶解上述黏合劑樹脂的習知的有機溶劑。作為其他有機溶劑，例如，可列舉為乙酸乙酯、乙酸丙酯、乙酸異丁酯、乙酸丁酯等乙酸酯系溶劑、甲基乙基酮、甲基異丁基酮等酮系溶劑、萜品醇、二氫萜品醇等萜系溶劑、十三烷、壬烷、環己烷等脂肪族烴系溶劑等。其中，脂肪族烴系溶劑為佳，在脂族烴系溶劑之中為礦油精更佳。此外，其他有機溶劑可以使用一種，亦可以使用兩種以上。 In addition, the organic solvent may contain other organic solvents other than the glycol ether-based solvent and the acetate-based solvent. It does not specifically limit as another organic solvent, A well-known organic solvent which can dissolve the said binder resin can be used. Examples of other organic solvents include acetate-based solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate; ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone; Terpine-based solvents such as terpineol and dihydroterpineol, aliphatic hydrocarbon-based solvents such as tridecane, nonane, and cyclohexane, etc. Among them, aliphatic hydrocarbon solvents are preferable, and among the aliphatic hydrocarbon solvents, mineral spirits are more preferable. In addition, one kind or two or more kinds of other organic solvents may be used.
有機溶劑例如可以含有二醇醚系溶劑作為主溶劑、且含有脂肪族烴系溶劑作為副溶劑。在此情況下，以導電性粉末為100質量份計，含有30質量份以上50質量份以下的二醇醚系溶劑為佳，含有40質量份以上50質量份以下更佳，以導電性粉末為100質量份計，含有20質量份以上80質量份以下的脂肪族烴系溶劑為佳，含有20質量份以上40質量份以下更佳。又，以導電性粉末為100質量份計，即使含有25質量份以上的脂肪族烴系溶劑，亦能夠使得導電性漿料的分散性優異。 The organic solvent may contain, for example, a glycol ether-based solvent as a main solvent and an aliphatic hydrocarbon-based solvent as a sub-solvent. In this case, based on 100 parts by mass of the conductive powder, it is better to contain not less than 30 parts by mass and not more than 50 parts by mass of the glycol ether solvent, more preferably to contain not less than 40 parts by mass and not more than 50 parts by mass. 100 parts by mass of the aliphatic hydrocarbon solvent is preferably contained in an amount of 20 to 80 parts by mass, more preferably in a range of 20 to 40 parts by mass. Moreover, even if it contains 25 mass parts or more of aliphatic hydrocarbon solvents based on 100 mass parts of electroconductive powders, the dispersibility of an electroconductive paste can be made excellent.
以導電性粉末為100質量份計，有機溶劑的含量50質量份 以上130質量份以下為為佳，60質量份以上90質量份以下更佳。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。 Based on 100 parts by mass of conductive powder, the content of organic solvent is 50 parts by mass More than 130 mass parts is preferable, and 60 mass parts or more and 90 mass parts or less are more preferable. When content of an organic solvent exists in the said range, electroconductivity and dispersibility are excellent.
有機溶劑的含量相對於導電性漿料整體20質量%以上50質量%以下為佳，為25質量%以上45質量%以下更佳。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 preferably not less than 20% by mass and not more than 50% by mass, more preferably not less than 25% by mass and not more than 45% by mass, based on the entire conductive paste. When content of an organic solvent exists in the said range, electroconductivity and dispersibility are excellent.
(分散劑) (Dispersant)
本實施型態的導電性漿料含有胺基酸系分散劑。本發明的發明人針對在導電性漿料中使用的分散劑對各種分散劑進行研究的結果為，雖然其原因尚不明確，但是發現藉由與上述黏合劑樹脂以及有機溶劑一起含有胺基酸系分散劑，在形成內部電極時能夠極大地抑制塊狀物的產生，從而提高漿料的分散性。 The conductive paste of this embodiment contains an amino acid type dispersant. The inventors of the present invention have studied various dispersants for dispersants used in conductive pastes. Although the reason for this has not been clarified, they found that amino acid It is a dispersant, which can greatly suppress the generation of lumps when forming internal electrodes, thereby improving the dispersibility of the slurry.
又，胺基酸系分散劑具有羧基與醯胺鍵。雖然其細節尚不明確，但推測因胺基酸系分散劑具有羧基，羧基吸附於導電性粉末等的表面而將表面電位中和或者使氫鍵部位惰性化，並且除了羧基以外的部位如上述的特定的立體結構能夠有效地抑制導電性粉末等的凝集從而亦提高漿料的分散性。 Also, the amino acid-based dispersant has a carboxyl group and an amide bond. Although the details are not clear, it is presumed that the amino acid-based dispersant has a carboxyl group, and the carboxyl group is adsorbed on the surface of conductive powder, etc. to neutralize the surface potential or inert the hydrogen bond site, and the site other than the carboxyl group is as described above. The specific three-dimensional structure can effectively inhibit the aggregation of conductive powder and the like, thereby also improving the dispersibility of the slurry.
又，胺基酸系分散劑的分子量為5000以下，分子量為1000以下為佳、分子量為500以下的顯示酸性的低分子量的分散劑更佳。另一方面，分子量的下限100以上為佳，為200以上更佳。此外，胺基酸系分散劑可以使用一種，亦可以使用兩種以上。 Also, the molecular weight of the amino acid-based dispersant is 5000 or less, preferably 1000 or less, and an acidic low molecular weight dispersant with a molecular weight of 500 or less is more preferable. On the other hand, the lower limit of the molecular weight is preferably 100 or more, more preferably 200 or more. In addition, one kind of amino acid-based dispersants may be used, or two or more kinds may be used.
作為胺基酸系分散劑，理想地可列舉為下述化學式(1)所示的胺基酸系分散劑。 As an amino acid type dispersant, the amino acid type dispersant represented by following chemical formula (1) is mentioned ideally.
在上述化學式(1)中，R1表示碳原子數為10以上且20以下的直鏈烷基或碳原子數為10以上且20以下的直鏈烯基。R1碳原子數為15以上20以下為佳，碳原子數為17更佳。又，R1可以是直鏈烷基，亦可以是具有碳雙鍵的直鏈烯基，理想為直鏈烯基。 In the above chemical formula (1), R 1 represents a linear alkyl group having 10 to 20 carbon atoms or a linear alkenyl group having 10 to 20 carbon atoms. R 1 preferably has 15 to 20 carbon atoms, more preferably 17 carbon atoms. In addition, R 1 may be a straight-chain alkyl group or a straight-chain alkenyl group having a carbon double bond, and is preferably a straight-chain alkenyl group.
以導電性粉末為100質量份計，含有0.01質量份以上2質量份以下的胺基酸系分散劑為佳，含有0.05質量份以上1.5質量份以下更佳，含有0.05質量份以上1.0質量份以下進一步更佳。在胺基酸系分散劑的含量為上述範圍內的情況下，導電性漿料中的導電性粉末的分散性優異。又，雖然藉由在上述範圍內增大胺基酸系分散劑的含量而據此具有使導電性漿料的黏度降低而提高印刷性的傾向，但亦存在導電性漿料的乾燥性降低而容易發生片材侵蝕、無法維持印刷形狀等的傾向。因此，在實際使用時，根據使用導電性漿料的電子零件的要求，選擇成為適當的平衡的組合的含量組成即可。 Based on 100 parts by mass of the conductive powder, the amino acid-based dispersant preferably contains 0.01 to 2 parts by mass, more preferably 0.05 to 1.5 parts by mass, and 0.05 to 1.0 parts by mass Further better. When content of an amino acid type dispersant exists in the said range, the dispersibility of the electroconductive powder in an electroconductive paste is excellent. In addition, by increasing the content of the amino acid-based dispersant within the above range, there is a tendency to reduce the viscosity of the conductive paste and improve the printability, but there is also a reduction in the dryness of the conductive paste. There is a tendency that the sheet is corroded and the printed shape cannot be maintained. Therefore, what is necessary is just to select the content composition which becomes a suitable balanced combination according to the request|requirement of the electronic component using an electroconductive paste at the time of actual use.
相對於導電性漿料整體，例如含有3質量%以下的胺基酸系分散劑。胺基酸系分散劑的含量的上限2質量%以下為佳，為1.5質量%以下更佳，為1質量%以下進一步更佳。對胺基酸系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。 The amino acid-based dispersant is contained, for example, in an amount of 3% by mass or less with respect to the whole conductive paste. The upper limit of the content of the amino acid-based dispersant is preferably at most 2% by mass, more preferably at most 1.5% by mass, still more preferably at most 1% by mass. The lower limit of the content of the amino acid-based dispersant is not particularly limited, and is, for example, 0.01% by mass or more, preferably 0.05% by mass or more.
在有機溶劑中，在與黏合劑樹脂組合使用時，有時會產生片材侵蝕、生片剝離不良，但是藉由以特定量含有胺基酸系分散劑，能夠抑制這些問題的產生。又，在黏合劑樹脂中含有縮醛系樹脂、且有機溶劑中含有二醇醚系溶劑的導電性漿料中，不使用胺基酸系分散劑而是使用作為其他酸系分散劑的磷酸系分散劑等的情況下，有時會產生塊狀物，但是在使用本實施方式的導電性漿料的情況下，能夠極大地抑制塊狀物的產生。 In organic solvents, when used in combination with a binder resin, sheet erosion and green sheet peeling failure may occur, but these problems can be suppressed by including an amino acid-based dispersant in a specific amount. In addition, in the conductive paste containing an acetal-based resin in the binder resin and a glycol ether-based solvent in the organic solvent, a phosphoric acid-based dispersant that is another acid-based dispersant is used instead of an amino acid-based dispersant. In the case of a dispersant or the like, lumps may be generated, but when the conductive paste of this embodiment is used, generation of lumps can be greatly suppressed.
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。又，胺基酸系分散劑，亦可以使用傳統習知的製造方法來製造以滿足上述特性。 As the amino acid-based dispersant, for example, an amino acid-based dispersant satisfying the above characteristics can be selected from commercially available products and used. In addition, the amino acid-based dispersant can also be produced using conventionally known production methods to satisfy the above-mentioned characteristics.
導電性漿料可以含有除了胺基酸系分散劑以外的其他酸系分散劑。作為其他酸系分散劑，例如可列舉為高級脂肪酸、高分子表面活性劑等。這些分散劑可以使用一種或者兩種以上組合使用。 The conductive paste may contain other acid-based dispersants other than the amino acid-based dispersant. Examples of other acid-based dispersants include higher fatty acids, polymer surfactants, and the like. These dispersants can be used alone or in combination of two or more.
作為高級脂肪酸，既可以是不飽和羧酸亦可以是飽和羧酸，沒有特別限定，可列舉為硬脂酸、油酸、山崳酸、肉豆蔻酸、棕櫚酸、亞油酸、月桂酸、亞麻酸等碳原子數為11以上的高級脂肪酸。其中，理想為油酸或硬脂酸。 The higher fatty acid may be an unsaturated carboxylic acid or a saturated carboxylic acid, and is not particularly limited. Examples thereof include stearic acid, oleic acid, behenic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, Higher fatty acids with 11 or more carbon atoms such as linolenic acid. Among them, oleic acid or stearic acid is preferable.
作為除此以外的酸系分散劑，沒有特別限定，可列舉為從以下表面活性劑中選擇的表面活性劑：以單烷基胺鹽為代表的烷基單胺鹽型、以N-烷基(C14~C18)丙二胺二油酸鹽為代表的烷基二胺鹽型、以烷基三甲基氯化銨為代表的烷基三甲基銨鹽型、以棕櫚烷基二甲基苄基氯化銨為代表的烷基二甲基苄基銨鹽型、以烷基/二聚氧乙烯甲基氯化銨為代表的季銨鹽型、烷基吡啶鹽型、以二甲基硬脂胺為代表的叔胺型、以聚氧丙烯/聚 氧乙烯烷基胺為代表的聚氧乙烯烷基胺型、以N,N',N'-三(2-羥乙基)-N-烷基(C14~18)1,3-二氨基丙烷為代表的二胺的氧乙烯加成型。 The other acid-based dispersants are not particularly limited, and include surfactants selected from the following surfactants: alkylmonoamine salt type represented by monoalkylamine salt, N-alkyl (C14~C18) Alkyl diamine salt type represented by propylene diamine dioleate, Alkyl trimethyl ammonium salt type represented by alkyl trimethyl ammonium chloride, Palm alkyl dimethyl Alkyl dimethyl benzyl ammonium salt type represented by benzyl ammonium chloride, quaternary ammonium salt type represented by alkyl/dipolyoxyethylene methyl ammonium chloride, alkyl pyridinium salt type, dimethyl Tertiary amine type represented by stearyl amine, polyoxypropylene/poly Polyoxyethylene alkylamine type represented by oxyethylene alkylamine, N,N',N'-tris(2-hydroxyethyl)-N-alkyl(C14~18)1,3-diaminopropane The oxyethylene addition type of the representative diamine.
又，分散劑可以含有除了酸系分散劑以外的分散劑。作為除了酸系分散劑以外的分散劑，可列舉為鹼系分散劑、非離子系分散劑、兩性分散劑等。這些分散劑可以使用一種或者兩種以上組合使用。 In addition, the dispersant may contain dispersants other than the acid-based dispersant. As a dispersant other than an acidic dispersant, an alkaline dispersant, a nonionic dispersant, an amphoteric dispersant, etc. are mentioned. These dispersants can be used alone or in combination of two or more.
作為鹼系分散劑，可列舉為月桂胺、聚乙二醇月桂胺、松香胺、十六烷基胺、十四烷基胺、硬脂胺、油胺等脂肪族胺等。當在導電性漿料中與胺基酸系分散劑一起亦含有鹼系分散劑的情況下，能夠以非常高的水準兼顧經時黏度穩定性和漿料分散性。 Examples of the alkali-based dispersant include aliphatic amines such as laurylamine, polyethylene glycol laurylamine, rosinamine, cetylamine, myristylamine, stearylamine, and oleylamine. When an alkali-based dispersant is also included in the conductive paste together with the amino-acid-based dispersant, it is possible to achieve both viscosity stability over time and paste dispersibility at a very high level.
例如，以導電性粉末為100質量份計，可以含有0.01質量份以上且不足2質量份的鹼系分散劑，理想為含有0.02質量份以上1質量份以下。又，例如，以胺基酸系分散劑為100質量份計，可以含有10質量份以上300質量份以下程度的鹼系分散劑。 For example, based on 100 parts by mass of the conductive powder, the alkali-based dispersant may be contained in an amount of not less than 0.01 parts by mass and not more than 2 parts by mass, and preferably not less than 0.02 parts by mass and not more than 1 part by mass. Moreover, for example, an alkali-based dispersant of about 10 to 300 parts by mass may be contained based on 100 parts by mass of the amino acid-based dispersant.
又，在導電性漿料中，鹼系分散劑的含量可以少於胺基酸系分散劑的含量，以胺基酸系分散劑為100質量份計，可以為80質量份以下，亦可以為50質量份以下，亦可以為30質量份以下。與上述的黏結劑樹脂、有機溶劑以及胺基酸系分散劑一起，在上述範圍內含有鹼系分散劑的情況下，能夠亦降低導電性漿料的黏度。 Also, in the conductive paste, the content of the alkali-based dispersant may be less than that of the amino-acid-based dispersant, based on 100 parts by mass of the amino-acid-based dispersant, it may be less than 80 parts by mass, or it may be 50 mass parts or less may be 30 mass parts or less. Together with the above-mentioned binder resin, organic solvent, and amino acid-based dispersant, when the alkali-based dispersant is contained within the above-mentioned range, the viscosity of the conductive paste can also be reduced.
例如，相對於導電性漿料整體，含有0質量%以上2.5質量%以下的鹼系分散劑，含有0質量%以上1.0質量%以下為佳，含有0.1質量%以上1.0質量%以下更佳，含有0.1質量%以上0.8質量%以下進一步更佳。又，鹼系分散劑相對於導電性漿料整體可以為0.3質量%以下。在以上 述範圍含有鹼系分散劑的情況下，漿料的經時黏度穩定性更加優異。 For example, the alkali-based dispersant is preferably contained in an amount of 0% by mass to 2.5% by mass, preferably 0% by mass to 1.0% by mass, more preferably 0.1% by mass to 1.0% by mass, and more preferably 0.1% by mass to 1.0% by mass. More preferably, it is 0.1 mass % or more and 0.8 mass % or less. Moreover, the alkali-type dispersant may be 0.3 mass % or less with respect to the whole electroconductive paste. above When the alkali-based dispersant is contained within the above range, the viscosity stability of the slurry over time is more excellent.
在導電性漿料中，含有胺基酸系分散劑的分散劑(整體)的含量，例如，以導電性粉末為100質量份計，理想為0.2質量份以上2質量份以下，亦可以為1質量份以下。在分散劑(全部)的含量超過上述範圍的情況下，存在導電性漿料的乾燥性變差、產生片材侵蝕、生片無法從襯紙的PET薄膜上剝離的情況。 In the conductive paste, the content of the dispersant (whole) containing the amino acid-based dispersant is, for example, based on 100 parts by mass of the conductive powder, preferably 0.2 parts by mass or more and 2 parts by mass or less, and may be 1 part by mass. Parts by mass or less. When the content of the dispersant (total amount) exceeds the above range, the drying property of the conductive paste deteriorates, sheet erosion occurs, and the green sheet may not be peeled from the PET film of the backing paper.
(其他成分) (other ingredients)
本實施方式的導電性漿料可以根據需要含有除上述成分以外的其他成分。作為其他成分，例如，可以使用消泡劑、增塑劑、表面活性劑、增稠劑等傳統習知的添加物。 The electroconductive paste of this embodiment may contain other components other than the said components as needed. As other components, for example, conventionally known additives such as defoamers, plasticizers, surfactants, and thickeners can be used.
(導電性漿料) (conductive paste)
對本實施方式的導電性漿料的製造方法沒有特別限定，可以使用傳統習知的方法。例如，可以藉由將上述各成分藉由三輥磨、球磨機、混合機等進行攪拌、混煉來製造導電性漿料。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，可充分地分散，分散劑遍佈於在其表面，易於得到均勻的導電性漿料。此外，亦可以預先將黏合劑樹脂溶解於有機溶劑的一部分中，在製備有機載體之後，向漿料調整用的有機溶劑中添加導電性粉末、陶瓷粉末、分散劑以及有機載體之後，進行攪拌、混煉，從而製備導電性漿料。 The manufacturing method of the electroconductive paste of this embodiment is not specifically limited, A conventionally well-known method can be used. For example, the conductive paste can be produced by stirring and kneading each of the above-mentioned components with a three-roll mill, a ball mill, a mixer, or the like. At this time, if the dispersant is pre-coated on the surface of the conductive powder, the conductive powder can be sufficiently dispersed without agglomeration, and the dispersant spreads over the surface, making it easy to obtain a uniform conductive paste. In addition, it is also possible to dissolve the binder resin in a part of the organic solvent in advance, and after preparing the organic vehicle, add conductive powder, ceramic powder, dispersant, and organic vehicle to the organic solvent for slurry adjustment, and then stir, kneading to prepare a conductive paste.
導電性漿料在剪切速率為100sec-1時的黏度理想為0.8Pa．S以下。當剪切速率為100sec-1時的黏度在上述範圍內的情況下，能夠適宜作為凹版印刷用的導電性漿料來使用。如果超過上述範圍，則黏度過高而存 在不適宜作為凹版印刷用的情況。對剪切速率為100sec-1時的黏度的下限沒有特別限定，例如為0.2Pa．S以上。 The ideal viscosity of the conductive paste is 0.8Pa when the shear rate is 100sec -1 . Below S. When the viscosity at a shear rate of 100 sec -1 is within the above range, it can be suitably used as an electroconductive paste for gravure printing. If it exceeds the above range, the viscosity may be too high and may not be suitable for gravure printing. The lower limit of the viscosity when the shear rate is 100sec -1 is not particularly limited, for example, it is 0.2Pa. S and above.
又，導電性漿料在剪切速率為10000sec-1時的黏度理想為0.18Pa．S以下。當剪切速率為10000sec-1時的黏度在上述範圍內的情況下，能夠適宜作為凹版印刷用的導電性漿料來使用。在超過上述範圍的情況下，存在黏度過高而不適宜作為凹版印刷用的情況。對剪切速率為10000sec-1時的黏度的下限沒有特別限定，例如為0.05Pa．S以上。 Also, the ideal viscosity of the conductive paste is 0.18Pa when the shear rate is 10000sec -1 . Below S. When the viscosity at a shear rate of 10000 sec -1 is within the above range, it can be suitably used as an electrically conductive paste for gravure printing. When exceeding the said range, a viscosity may become too high and it may not be suitable for gravure printing. The lower limit of the viscosity when the shear rate is 10000sec -1 is not particularly limited, for example, it is 0.05Pa. S and above.
導電性漿料能夠適宜地使用在層積陶瓷電容器等電子零件中。層積陶瓷電容器具有使用介電質生片而形成的介電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 components such as laminated ceramic capacitors. A laminated ceramic capacitor has a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.
對於層積陶瓷電容器而言，介電質生片中含有的介電質陶瓷粉末和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備的層疊陶瓷器件，即使在介電質生片的厚度例如為3μm以下的情況下，亦能夠抑制片材侵蝕、生片的剝離不良。 For a laminated ceramic capacitor, it is desirable that the dielectric ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste have the same composition. The multilayer ceramic device produced using the conductive paste of this embodiment can suppress sheet erosion and green sheet peeling defects even when the thickness of the dielectric green sheet is, for example, 3 μm or less.
[電子零件] [electronic parts]
以下，參照附圖對本發明的電子零件等的實施型態進行說明。在附圖中，有時會適當地以示意性的方式來進行表示、變更比例尺來進行表示。又，零件的位置、方向等，適當地參照圖1等所示的XYZ正交坐標系來進行說明。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)。 Hereinafter, embodiments of electronic components and the like according to the present invention will be described with reference to the drawings. In the drawings, it may be shown schematically or with a changed scale in some cases as appropriate. In addition, the position, direction, etc. of a component are demonstrated referring suitably the XYZ rectangular coordinate system shown in FIG. 1 etc. FIG. In this XYZ rectangular coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is a vertical direction (vertical direction).
圖1中的A以及圖1中的B是作為實施型態所關於的電子零件的一個例子的、表示層積陶瓷電容器1的圖。層積陶瓷電容器1具有
介電質層12以及內部電極層11交替地層疊而成的層積體10和外部電極20。
A in FIG. 1 and B in FIG. 1 are diagrams showing a laminated ceramic capacitor 1 as an example of an electronic component related to the embodiment. MLCC1 has
以下，對使用上述導電性漿料的層積陶瓷電容器的製造方法進行說明。首先，在介電質生片上印刷導電性漿料，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多個介電質生片進行層疊之後，進行燒製而使其一體化，據此製備成為陶瓷電容器主體的層積陶瓷燒製體(層積體10)。之後，藉由在層積體10的兩端部形成一對外部電極20而製造層積陶瓷電容器1。以下，進行更詳細的說明。
Hereinafter, a method of manufacturing a laminated ceramic capacitor using the above-mentioned conductive paste will be described. First, a conductive paste is printed on a dielectric green sheet, dried to form a dry film, a plurality of dielectric green sheets having the dry film on the upper surface are stacked by pressure bonding, and then fired to form a These are integrated, thereby producing a laminated ceramic fired body (laminated body 10 ) that becomes a main body of a ceramic capacitor. Thereafter, the laminated ceramic capacitor 1 is produced by forming a pair of
首先，準備作為未燒製的陶瓷片的介電質生片(陶瓷生片)。作為該介電質生片，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和萜品醇等溶劑而得到的介電質層用漿料在PET薄膜等的支承薄膜上塗布成片狀並進行乾燥去除溶劑而形成的介電質生片等。此外，對由介電質生片構成的介電質層的厚度沒有特別限定，但從層積陶瓷電容器1的小型化的要求的觀點出發，理想為0.05μm以上3μm以下。 First, a dielectric green sheet (ceramic green sheet) that is an unfired ceramic sheet is prepared. Examples of such dielectric green sheets include those for dielectric layers obtained by adding organic binders such as polyvinyl butyral and solvents such as terpineol to predetermined ceramic raw material powders such as barium titanate. A dielectric green sheet or the like formed by coating a slurry on a support film such as a PET film in a sheet shape and drying to remove the solvent. In addition, the thickness of the dielectric layer made of the dielectric green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less in view of the demand for miniaturization of the laminated ceramic capacitor 1 .
接下來，準備多枚藉由在該介電質生片的一個面上使用凹版印刷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，對於印刷後的導電性漿料(乾燥膜)的厚度而言，從內部電極層11的薄層化的要求的觀點出發，理想為乾燥後為1μm以下。
Next, a plurality of sheets in which a dry film was formed by printing and applying the above-mentioned conductive paste on one surface of the dielectric green sheet by the gravure printing method and drying were prepared. In addition, the thickness of the conductive paste (dried film) after printing is desirably 1 μm or less after drying from the viewpoint of thinning the
接下來，從支承薄膜上將介電質生片剝離，並且以介電質生片與形成於該介電質生片的一個面上的導電性漿料(乾燥膜)交替地配置的方式進行層疊之後，藉由加熱、加壓處理而得到層積體(壓接體)。此外， 亦可以設為在層積體的兩面進一步配置未塗佈導電性漿料的保護用的介電質生片的構成。 Next, the dielectric green sheet is peeled from the support film, and the dielectric green sheet and the conductive paste (dry film) formed on one surface of the dielectric green sheet are alternately arranged. After lamination, a laminated body (press-bonded body) is obtained by heating and pressurizing. also, A configuration in which protective dielectric green sheets not coated with the conductive paste are further arranged on both surfaces of the laminate may also be adopted.
接下來，將層積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，並在還原氣體下進行燒製，據此製備層積陶瓷燒製體(層積體10)。此外，脫黏合劑處理中的氣體理想為大氣或N2氣體氣體。進行脫黏合劑處理時的溫度例如為200℃以上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24小時以下。又，為了抑制在內部電極層11中使用的金屬的氧化而在還原氣體下進行燒製，又，進行層積體10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 into a predetermined size to form a green wafer, the green wafer is subjected to a binder removal process and fired under a reducing gas, thereby preparing a laminated ceramic fired body (laminated body 10). In addition, the gas in the binder removal process is ideally the atmosphere or N 2 gas. The temperature at the time of performing binder removal process is 200 to 400 degreeC, for example. In addition, the retention time at the above-mentioned temperature when performing the binder removal treatment is preferably not less than 0.5 hours and not more than 24 hours. In addition, in order to suppress the oxidation of the metal used in the
藉由進行生晶片的燒製，將介電質生片中的有機黏合劑完全去除，並且對陶瓷原料粉末進行燒製而形成陶瓷制的介電質層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要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，進而形成介電質層12與內部電極層11多枚交替地層疊而成的層積陶瓷燒製體(層積體10)。此外，從將氧帶入介電質層12的內部而提高可靠性、且抑制內部電極層11的再氧化的觀點出發，可以對燒製後的層積陶瓷燒製體(層積體10)實施退火處理。
By firing the green wafer, the organic binder in the dielectric green sheet is completely removed, and the ceramic raw material powder is fired to form the
然後，藉由對所製備的層積陶瓷燒製體(層積體10)設置一對外部電極20，據此製造層積陶瓷電容器1。例如，外部電極20具備外部電極層21以及電鍍層22。外部電極層21與內部電極層11電連接。此外，作為外部電極20的材料，例如可以理想地使用銅、鎳或其等合金。此外，
電子零件亦可以使用除了層積陶瓷電容器以外的電子零件。
Then, the laminated ceramic capacitor 1 is manufactured by providing a pair of
實施例 Example
以下，基於實施例和對比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 at all by the examples.
[評價方法] [Evaluation method]
(導電性漿料的黏度) (Viscosity of conductive paste)
使用流變儀，在剪切速率為100sec-1、10000sec-1的條件下測定導電性漿料的製造後的黏度。 Using a rheometer, the viscosity after production of the electroconductive paste was measured under conditions of a shear rate of 100 sec -1 and 10000 sec -1 .
(導電性漿料的分散性) (Dispersibility of conductive paste)
藉由以下方法來評價導電性漿料的分散性。 The dispersibility of the conductive paste was evaluated by the following method.
在玻璃基板(2inch)上，印刷樣品(GAP厚度=5μm)並進行乾燥。乾燥在帶式爐內的最大溫度為120~150℃、大氣氣體下進行。對於乾燥後得到的乾燥膜(2cm×2cm、厚度為3μm)，使用光學顯微鏡一邊從玻璃基板的背面照射光(背光)一邊以×100(目鏡、物鏡；各10倍)進行觀察，確認塊狀物的有無。在沒有觀察到塊狀物的情況下，可以判斷為導電性漿料的分散性良好，在觀察到一個以上的塊狀物的情況下，可以判斷為導電性漿料的分散性不良。 On a glass substrate (2 inches), samples were printed (GAP thickness = 5 μm) and dried. Drying is carried out in a belt furnace at a maximum temperature of 120-150°C under atmospheric gas. The dry film (2 cm x 2 cm, thickness 3 μm) obtained after drying was observed with an optical microscope at x100 (eyepiece, objective lens; 10 magnifications each) while irradiating light (backlight) from the backside of the glass substrate, and a lump was confirmed. The presence or absence of things. When no lumps are observed, it can be judged that the dispersibility of the electroconductive paste is good, and when one or more lumps are observed, it can be judged that the dispersibility of the electroconductive paste is poor.
[使用材料] [use material]
(導電性粉末) (conductive powder)
作為導電性粉末，使用Ni粉末(平均粒徑為0.3μm)。 As the conductive powder, Ni powder (average particle diameter: 0.3 μm) was used.
(陶瓷粉末) (ceramic powder)
作為陶瓷粉末，使用鈦酸鋇(BaTiO3；平均粒徑為0.06μm)。 As the ceramic powder, barium titanate (BaTiO 3 ; average particle diameter: 0.06 μm) was used.
(黏合劑樹脂) (Binder resin)
作為黏合劑樹脂，使用聚乙烯醇縮丁醛樹脂(PVB)、乙基纖維素(EC)。 As the binder resin, polyvinyl butyral resin (PVB) and ethyl cellulose (EC) were used.
(分散劑) (Dispersant)
(1)作為分子量為5000以下的胺基酸系分散劑，在上述化學式(1)中，使用R1=C17H33所示的酸系分散劑(A)、R1=C11H23所示的酸系分散劑(B)。 (1) As an amino acid-based dispersant having a molecular weight of 5000 or less, in the above chemical formula (1), an acid-based dispersant (A) represented by R 1 =C 17 H 33 , R 1 =C 11 H 23 The acid-based dispersant (B) shown.
(2)作為鹼系分散劑，使用松香胺(C)、聚乙二醇月桂胺(D)、油胺(E)。 (2) As the alkali-based dispersant, rosinamine (C), polyethylene glycol laurylamine (D), and oleylamine (E) were used.
(3)作為磷酸系分散劑，使用磷酸聚酯(F)。 (3) Phosphoric acid polyester (F) was used as a phosphoric acid-based dispersant.
(有機溶劑) (Organic solvents)
作為有機溶劑，使用丙二醇單丁醚(PNB)、礦油精(MA)、萜品醇(TPO)。 As the organic solvent, propylene glycol monobutyl ether (PNB), mineral spirits (MA), and terpineol (TPO) were used.
[實施例1] [Example 1]
以作為導電性粉末的Ni粉末為100質量份計，將25質量份的陶瓷粉末、作為分散劑的2質量份的胺基酸系分散劑(A)、作為黏合劑樹脂的2質量份的PVB以及4質量份的EC、作為有機溶劑的41質量份的PNB以 及27質量份的MA進行混合，製備導電性漿料。藉由上述方法對所製備的導電性漿料的黏度以及漿料的分散性進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 Based on 100 parts by mass of Ni powder as conductive powder, 25 parts by mass of ceramic powder, 2 parts by mass of amino acid-based dispersant (A) as a dispersant, and 2 parts by mass of PVB as a binder resin and 4 parts by mass of EC, 41 parts by mass of PNB as an organic solvent, and and 27 parts by mass of MA were mixed to prepare a conductive paste. The viscosity of the prepared conductive paste and the dispersibility of the paste were evaluated by the above method. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例2] [Example 2]
作為分散劑，使用1.5質量份的胺基酸系分散劑(A)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, except having used 1.5 mass parts of amino acid type dispersants (A), it carried out similarly to Example 1, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例3] [Example 3]
作為分散劑，使用0.8質量份的胺基酸系分散劑(A)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, except having used 0.8 mass parts of amino acid type dispersants (A), it carried out similarly to Example 1, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例4] [Example 4]
作為分散劑，使用0.05質量份的胺基酸系分散劑(A)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, except having used 0.05 mass parts of amino acid type dispersants (A), it carried out similarly to Example 1, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例5] [Example 5]
作為分散劑，使用0.01質量份的胺基酸系分散劑(A)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2 所示。 As a dispersant, except having used 0.01 mass part of amino acid type dispersants (A), it carried out similarly to Example 1, and prepared and evaluated the electroconductive paste. The content of the dispersant of the conductive paste is shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2 shown.
[實施例6] [Example 6]
作為分散劑，使用0.8質量份的胺基酸系分散劑(A)以及0.2質量份的松香胺(C)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, except that 0.8 parts by mass of an amino acid-based dispersant (A) and 0.2 parts by mass of rosin amine (C) were used, a conductive paste was prepared and evaluated in the same manner as in Example 1. . The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例7] [Example 7]
作為分散劑，使用0.8質量份的胺基酸系分散劑(A)以及0.2質量份的聚乙二醇月桂胺(D)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, a conductive paste was prepared in the same manner as in Example 1, except that 0.8 parts by mass of an amino acid-based dispersant (A) and 0.2 parts by mass of polyethylene glycol laurylamine (D) were used. materials and evaluate them. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例8] [Example 8]
作為分散劑，使用0.8質量份的胺基酸系分散劑(A)以及0.2質量份的油胺(E)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, a conductive paste was prepared and evaluated in the same manner as in Example 1, except that 0.8 parts by mass of an amino acid-based dispersant (A) and 0.2 parts by mass of oleylamine (E) were used. . The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例9] [Example 9]
作為黏合劑樹脂，僅使用6質量份的PVB，除此之外，按照與實施例3同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a binder resin, except having used only 6 mass parts of PVB, it carried out similarly to Example 3, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例10] [Example 10]
作為有機溶劑，使用50質量份的PNB以及18質量份的MA，除此之 外，按照與實施例3同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As an organic solvent, use 50 parts by mass of PNB and 18 parts by mass of MA, in addition In addition, in the same manner as in Example 3, an electroconductive paste was prepared and evaluated. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例11] [Example 11]
作為分散劑，使用0.8質量份的胺基酸系分散劑(B)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, except having used 0.8 mass parts of amino acid type dispersants (B), it carried out similarly to Example 1, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例12] [Example 12]
作為分散劑，使用0.8質量份的胺基酸系分散劑(B)以及0.2質量份的松香胺(C)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, a conductive paste was prepared and evaluated in the same manner as in Example 1, except that 0.8 parts by mass of an amino acid-based dispersant (B) and 0.2 parts by mass of rosin amine (C) were used. . The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例1] [Comparative example 1]
作為分散劑，使用0.8質量份的磷酸系分散劑(F)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, except having used the phosphoric acid type dispersant (F) of 0.8 mass parts, it carried out similarly to Example 1, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例2] [Comparative example 2]
作為分散劑，使用0.8質量份的磷酸系分散劑(F)以及0.2質量份的鹼系分散劑(C)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, a conductive paste was prepared and evaluated in the same manner as in Example 1, except that 0.8 parts by mass of a phosphoric acid-based dispersant (F) and 0.2 parts by mass of an alkali-based dispersant (C) were used. . The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例3] [Comparative example 3]
作為分散劑，僅使用0.8質量份的鹼系分散劑(C)，除此之外，按照與實施例1同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a dispersant, except having used only 0.8 mass parts of alkali-type dispersants (C), it carried out similarly to Example 1, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例4] [Comparative example 4]
作為有機溶劑，僅使用萜品醇(TPO)，除此之外，按照與實施例3同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As an organic solvent, except having used only terpineol (TPO), it carried out similarly to Example 3, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例5] [Comparative Example 5]
作為黏合劑樹脂，僅使用EC，除此之外，按照與實施例3同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 As a binder resin, except having used only EC, it carried out similarly to Example 3, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例6] [Comparative Example 6]
作為黏合劑樹脂僅使用EC、以及作為有機溶劑僅使用萜品醇(TPO)，除此以外，按照與實施例3同樣的方式製備導電性漿料並進行評價。導電性漿料的分散劑等的含量如表1所示，導電性漿料的黏度以及分散性的評價結果如表2所示。 Except having used only EC as a binder resin, and using only terpineol (TPO) as an organic solvent, it carried out similarly to Example 3, and prepared and evaluated the electroconductive paste. The contents of the dispersant and the like of the conductive paste are shown in Table 1, and the evaluation results of the viscosity and dispersibility of the conductive paste are shown in Table 2.
(評價結果) (Evaluation results)
實施例的導電性漿料在剪切速率為100sec-1時的黏度為0.44~0.79Pa．S，剪切速率為10000sec-1時的黏度為0.13~0.18Pa．S，為適於凹版印刷的黏度。又，本實施例的導電性漿料未在印刷後的乾燥膜表面觀察到塊狀物，表明漿料的分散性很優異。 The viscosity of the conductive paste of the embodiment is 0.44~0.79Pa when the shear rate is 100sec- 1 . S, the viscosity when the shear rate is 10000sec -1 is 0.13~0.18Pa. S, is the viscosity suitable for gravure printing. In addition, no lumps were observed on the surface of the dried film after printing with the conductive paste of this example, indicating that the dispersibility of the paste is excellent.
另一方面，在替代胺基酸系分散劑而含有磷酸系分散劑的比較例1以及比較例2的導電性漿料中，在印刷後的乾燥膜表面觀察到塊狀物，表明漿料的分散性不良。又，在分散劑不含有酸系分散劑而是僅有鹼 系分散劑構成的比較例3、有機溶劑在本發明的範圍之外的比較例4、黏合劑樹脂在本發明的範圍之外的比較例5、以及有機溶劑和黏合劑樹脂在本發明的範圍之外的比較例6的導電性漿料中，無法獲得適於凹版印刷的黏度。因此，印刷後的表面性狀粗糙、不足夠平滑，因此未進行塊狀物的觀察。 On the other hand, in the conductive pastes of Comparative Example 1 and Comparative Example 2 that contained a phosphoric acid-based dispersant instead of an amino acid-based dispersant, lumps were observed on the surface of the dried film after printing, indicating that the paste was not stable. Poor dispersion. Also, when the dispersant does not contain an acidic dispersant but only an alkali Comparative Example 3 in which the dispersant is used, Comparative Example 4 in which the organic solvent is outside the scope of the present invention, Comparative Example 5 in which the binder resin is outside the scope of the present invention, and the organic solvent and the binder resin are in the scope of the present invention In the conductive paste of Comparative Example 6 other than this, a viscosity suitable for gravure printing could not be obtained. Therefore, since the surface texture after printing was rough and not smooth enough, the observation of lumps was not performed.
本發明的導電性漿料具有適於凹版印刷的黏度，且漿料的分散性良好。因而，本發明的導電性漿料特別適宜用作作為行動電話、數位設備等電子設備的晶片零件的層積陶瓷電容器的內部電極用的原料，特別適宜用作凹版印刷用的導電性漿料。 The conductive paste of the present invention has a viscosity suitable for gravure printing, and the dispersion of the paste is good. Therefore, the conductive paste of the present invention is particularly suitable as a raw material for internal electrodes of laminated ceramic capacitors which are chip components of electronic equipment such as mobile phones and digital devices, and is particularly suitable as a conductive paste for gravure printing.
1‧‧‧層積陶瓷電容器 1‧‧‧MLCC
10‧‧‧層積體 10‧‧‧laminated body
11‧‧‧內部電極層 11‧‧‧internal electrode layer
12‧‧‧介電質層 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
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| JP2018035050A JP2019046781A (en) | 2017-08-30 | 2018-02-28 | Conductive paste and methods for manufacturing electronic component and multilayer ceramic capacitor |
| JP2018-035050 | 2018-02-28 |
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| JP2019046783A (en) * | 2017-08-30 | 2019-03-22 | 住友金属鉱山株式会社 | Conductive paste and methods for manufacturing electronic component and multilayer ceramic capacitor |
| CN114864132A (en) * | 2022-04-18 | 2022-08-05 | 湖南省国银新材料有限公司 | Low-temperature quick-drying mask silver paste for gravure printing and preparation method thereof |
| KR20230153615A (en) * | 2022-04-29 | 2023-11-07 | 솔브레인 주식회사 | Conductive paste composition comprising nickel complex ink composition and internal electrode including this |
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| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| JP2016031912A (en) * | 2014-07-30 | 2016-03-07 | 住友金属鉱山株式会社 | Production method of conductive paste and conductive paste obtained by the method |
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| JP2003187638A (en) | 2001-12-20 | 2003-07-04 | Murata Mfg Co Ltd | Conductive paste for gravure printing and its manufacturing method as well as laminated ceramic electronic component |
| KR20120059126A (en) * | 2010-11-30 | 2012-06-08 | 삼성전기주식회사 | Inner electrode paste composition for gravure printing, multilayer ceramic capacitor using the same and a manufacturing method thereof |
| KR101598945B1 (en) * | 2012-04-19 | 2016-03-02 | 가부시키가이샤 무라타 세이사쿠쇼 | Conductive paste, laminated ceramic electronic component and method for manufacturing laminated ceramic electronic component |
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| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| JP2016031912A (en) * | 2014-07-30 | 2016-03-07 | 住友金属鉱山株式会社 | Production method of conductive paste and conductive paste obtained by the method |
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