TW201926365A - Conductive paste, electronic component, and laminate ceramic capacitor - Google Patents
Conductive paste, electronic component, and laminate ceramic capacitor Download PDFInfo
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- 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
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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
Abstract
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。 With the miniaturization and high performance of electronic devices such as mobile phones and digital devices, it is also desired to reduce the size and capacity of electronic components including laminated ceramic capacitors. The laminated ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated, and the dielectric layer and the internal electrode layer are formed into a thin film, thereby achieving downsizing and high capacity.
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)，並進行乾燥而形成乾燥膜。接著，以使乾燥膜和介電質生片交替地重疊的方式層疊為多層之後，進行加熱壓接而使其一體化，從而形成壓接體。將該壓接體切斷，在氧化氣體環境或惰性氣體環境中進行脫有機黏合劑處理之後進行燒製，得到燒製晶片。接著，在燒製晶片的兩端部塗佈外部電極用漿料，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 fabricated by the following method. 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 powder, a binder resin, an organic solvent, or the like is printed on a predetermined electrode pattern. The slurry for an electrode (conductive paste) is dried to form a dried film. Next, the dry film and the dielectric green sheets are stacked in a plurality of layers so as to be alternately stacked, and then pressure-bonded by heating and pressure bonding to form a pressure-bonded body. The crimped body was cut, and subjected to de-organic binder treatment in an oxidizing gas atmosphere or an inert gas atmosphere, followed by firing to obtain a fired wafer. Next, the slurry for external electrodes is applied to both ends of the fired wafer, and after firing, nickel plating or the like is applied to the surface of the external electrode to obtain a 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，但是基於電子設備的小型化、薄膜化、生產性的提高的要求，要求以較高的生產性來印刷更微細的電極圖案。 As a printing method used for printing a conductive paste on a dielectric green sheet, a screen printing method is generally used in the past, but it is required to be high in terms of miniaturization, thinning, and productivity improvement of an electronic device. Produce to print finer electrode patterns.
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 the conductive paste, a gravure printing method in which a conductive paste is filled in a concave portion provided in a plate making and the plate is pressed against a surface to be printed to transfer a conductive paste from the plate is proposed. Printing method. The gravure printing method has a high printing speed and excellent productivity. When the gravure printing method is used, it is necessary to appropriately select the binder resin, the dispersant, the solvent, and the like in the conductive paste, and adjust the 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介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 a conductive paste which is a conductive paste for forming an internal conductor film by gravure printing, the internal conductor film having a plurality of ceramic layers and being interposed between the ceramic layers The internal conductor film in the ceramic electronic component in which the internal conductor film of the specific interface is extended, the conductive paste contains 30 to 70% by weight of the solid content containing the metal powder, and the ethoxy group content of 1 to 10% by weight 49.6% or more of the ethyl cellulose resin component, 0.05 to 5% by weight of the dispersant, and the solvent component as the balance, the viscosity η 0.1 when the shear rate is 0.1 (s -1 ) is 1 Pa. The viscosity η 0.02 when s is above and the shear rate is 0.02 (s -1 ) satisfies the thixotropic fluid of the condition expressed by the specific formula.
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。 Further, Patent Document 2 describes a conductive paste, and similarly to the above-described Patent Document 1, a conductive paste for forming an internal conductor film by gravure printing, which contains 30 to 70% by weight of a metal containing material. The solid content of the powder, 1 to 10% by weight of the resin component, 0.05 to 5% by weight of the dispersant, and the solvent component as the balance, and the viscosity at a shear rate of 0.1 (s -1 ) is 1 Pa. The thixotropy fluid of s or more has a viscosity change rate of 50% or more at a shear rate of 10 (s -1 ) when the viscosity at a shear rate of 0.1 (s -1 ) is used as a reference.
根據上述專利文獻1、2，上述導電性漿料剪切速率為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如層積陶瓷電容器的層積陶瓷電子零件。 According to the above Patent Documents 1 and 2, the viscosity of the above-mentioned conductive paste when the shear rate is 0.1 (s -1 ) is 1 Pa. The thixotropic fluid above s can obtain stable continuous printing at high speed in gravure printing, and can manufacture laminated ceramic electronic parts such as laminated ceramic capacitors with good production efficiency.
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。 Further, Patent Document 3 describes a conductive paste for gravure printing containing conductive powder (A), organic resin (B), organic solvent (C), additive (D), and dielectric powder (E). The conductive paste for the internal electrode of the laminated ceramic capacitor, the organic resin (B) is composed of polyvinyl butyral having a polymerization degree of 10,000 or more and 50,000 or less, and ethyl cellulose having a weight average molecular weight of 10,000 or more and 100,000 or less, and organic The solvent (C) is composed of propylene glycol monobutyl ether, 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) is inhibited by separation. The agent and the dispersant are composed of a composition containing a polycarboxylic acid polymer or a polycarboxylate as the separation inhibitor. According to Patent Document 3, the conductive paste has a viscosity suitable for gravure printing, improves the uniformity and stability of the slurry, 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 Publication No. 2003-187638
【專利文獻2】日本特開2003-242835號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-242835
【專利文獻3】日本特開2012-174797號公報 [Patent Document 3] Japanese Patent Laid-Open Publication 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。 With the recent thinning of the internal electrode layer, the conductive powder tends to have a small particle size. When the particle size of the conductive powder is small, the specific surface area of the surface of the particles is increased. Therefore, the surface activity of the conductive powder (metal powder) is increased, and the dispersibility of the conductive paste is lowered. A conductive paste having a 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。 Further, when the conductive paste is printed by the gravure printing method, the slurry viscosity is lower than that of the screen printing method. Therefore, it is considered that the conductive powder having a large specific gravity settles and the slurry is dispersed. Reduced sex. Further, in the conductive pastes described in the above-mentioned Patent Documents 1 and 2, the slurry in the conductive paste is removed by using a filter to improve the dispersibility of the slurry, but the step of removing the bulk is required. Therefore, the manufacturing process is easily 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 the above circumstances, an object of the present invention is to provide a conductive paste which has a slurry viscosity suitable for gravure printing and which is excellent in dispersibility and productivity of a slurry.
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，分散劑含有第一酸系分散劑以及第二酸系分散劑，第一酸系分散劑是磷酸烷基酯化合物，第二酸系分散劑是上述第一酸系分散劑以外的具有羧基的酸系分散劑，黏合劑樹脂含有縮醛系樹脂，有機溶劑含有二醇醚系溶劑。 A first aspect of the present invention provides a conductive paste comprising a conductive powder, a dispersant, a binder resin, and an organic solvent, the dispersant comprising a first acid dispersant and a second acid dispersant, the first acid system The dispersant is an alkyl phosphate compound, and the second acid dispersant is an acid dispersant having a carboxyl group other than the first acid dispersant, the binder resin contains an acetal resin, and the organic solvent contains a glycol ether solvent. .
又，第一酸系分散劑理想為磷酸烷基聚氧亞烷基酯化合 物。 Further, the first acid-based dispersant is preferably an alkyl polyoxyalkylene phosphate compound.
理想地，第二酸系分散劑的分子量為5000以下，且含有碳原子數為10以上且20以下的烷基或碳原子數為10以上20以下的烯基。又，分散劑理想為進一步含有鹼系分散劑。 The second acid-based dispersant preferably has a molecular weight of 5,000 or less and an alkyl group having 10 or more and 20 or less carbon atoms or an alkenyl group having 10 or more and 20 or less carbon atoms. Further, the dispersant preferably further contains an alkali dispersant.
又，以導電性粉末為100質量份計，理想為含有0.2質量份以上1質量份以下的第一酸系分散劑，以上述導電性粉末為100質量份計，理想為含有0.01質量份以上1質量份以下的第二酸系分散劑。又，分散劑亦可以進一步含有鹼系分散劑。又，以導電性粉末為100質量份計，理想為含有0.02質量份以上2質量份以下的鹼系分散劑。 In addition, the first acid-based dispersant is contained in an amount of 0.2 part by mass or more and 1 part by mass or less, and the conductive powder is preferably contained in an amount of 0.01 part by mass or more based on 100 parts by mass of the conductive powder. A second acid-based dispersant of a part by mass or less. Further, the dispersing agent may further contain an alkali dispersing agent. In addition, the amount of the conductive powder is preferably 0.02 parts by mass or more and 2 parts by mass or less based on 100 parts by mass of the conductive powder.
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0.19Pa．S以下。 The conductive powder is preferably a metal powder containing at least one selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and the like. Further, the conductive paste preferably contains ceramic powder. Further, the ceramic powder desirably contains a perovskite type oxide. Further, the average particle diameter of the ceramic powder is preferably 0.01 μm or more and 0.5 μm or less. Further, the average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less. Further, the conductive paste is desirably used as an internal electrode for laminating ceramic parts. Further, desirably, the conductive paste has a viscosity of 0.8 Pa at a shear rate of 100 sec -1 . Below S, the viscosity at a shear rate of 10000 sec -1 is 0.19 Pa. S below.
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 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，上述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 a dielectric layer and an internal electrode are laminated, and the internal electrode is formed using the conductive paste.
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 of a slurry and productivity. In addition, the electrode pattern of the electronic component such as the laminated ceramic capacitor formed by using the conductive paste of the present invention is excellent in printability of the conductive paste and has a uniform thickness when the thinned electrode is formed.
1‧‧‧層積陶瓷電容器 1‧‧‧Layered Ceramic Capacitors
10‧‧‧陶瓷層積體 10‧‧‧Ceramic laminate
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 electrode
21‧‧‧外部電極層 21‧‧‧External electrode layer
22‧‧‧電鍍層 22‧‧‧Electroplating
【圖1】表示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 showing 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 a conductive powder, a dispersant, a binder resin, and an organic solvent. Hereinafter, each component will be described in detail.
(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，基於導電性、耐腐蝕性以及成本的觀點，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，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 the like may be used. Among them, a powder of Ni or an alloy thereof is preferable from the viewpoints of 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 may be used. The content of Ni in the Ni alloy is, for example, 50% by mass or more, and preferably 80% by mass or more. Further, in order to suppress the debonding treatment, a severe gas generation is caused by thermal decomposition of a portion of the binder resin, and the Ni powder may contain S in an amount of several hundred ppm.
導電性粉末的平均粒徑理想為0.05μm以上1.0μm以下，更理想為為0.1μm以上0.5μm以下。在導電性粉末的平均粒徑為上述範圍內的情況下，能夠適宜用作薄膜化的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。在本說明書中，只要沒有特別說明，導電性粉末的平均粒徑是指根據基於BET法得到的比表面積計算出的粒徑。例如，鎳粉末的平均粒徑的計算式如下所示。 The average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.1 μm or more and 0.5 μm or less. When the average particle diameter of the conductive powder is within the above range, it can be suitably used as a slurry for internal electrodes of a thinned laminated ceramic capacitor, and for example, the smoothness of the dried film and the density of the dried film can be improved. In the present specification, the average particle diameter of the conductive powder means a particle diameter calculated from the specific surface area obtained by the BET method unless otherwise specified. For example, the calculation formula of the average particle diameter of the nickel powder is as follows.
平均粒徑=6/S.A×ρ...(式) Average particle size = 6 / S. A × ρ ... (formula)
(ρ=8.9(鎳的真密度)，S.A=鎳粉末的BET比表面積) (ρ=8.9 (true density of nickel), S.A=BET specific surface area of nickel powder)
導電性粉末的含量相對於導電性漿料整體理想為30質量%以上70質量%以下，更理想為為40質量%以上65質量%以下。在導電性粉末的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the conductive powder is preferably 30% by mass or more and 70% by mass or less based on the total amount of the conductive paste, and more preferably 40% by mass or more and 65% by mass or less. When the content of the conductive powder is within the above range, conductivity and dispersibility are excellent.
(陶瓷粉末) (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 a ceramic powder. The ceramic powder is not particularly limited. For example, in the case of a slurry for internal electrodes in which a ceramic capacitor is laminated, a conventional ceramic powder can be appropriately selected depending on the type of the laminated ceramic capacitor to be applied. The ceramic powder is, for example, a perovskite-type oxide containing Ba and Ti, and is preferably barium titanate (BaTiO 3 ). Further, 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. The oxide may be one or more oxides selected from the group consisting of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and a rare earth element.
又，作為陶瓷粉末，例如亦可以列舉為將鈦酸鋇(BaTiO3)的Ba原子、Ti原子以例如Sn、Pb、Zr等其他原子取代後的鈣鈦礦型氧化物強介電質的陶瓷粉末。 Further, examples of the ceramic powder include a perovskite-type oxide ferroelectric ceramic in which Ba atoms of barium titanate (BaTiO 3 ) and Ti atoms are substituted with other atoms such as Sn, Pb, and Zr. 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介電質生片的介電質陶瓷粉末相同組成的粉末。據此，可抑制由於燒結工序中的介電質層與內部電極層之間的介面處的收縮失配而導致的裂紋的產生。作為如此的陶瓷粉末，除了上述含有Ba以及Ti的鈣鈦礦型氧化物以外，例如，亦可列舉為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, a powder having the same composition as that of the dielectric ceramic powder constituting the dielectric green sheet of the laminated ceramic capacitor can be used. According to this, 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. As such a ceramic powder, in addition to the above-described perovskite-type oxide containing Ba and Ti, for example, ZnO, ferrite, PZT, BaO, Al 2 O 3 , Bi 2 O 3 , R (rare earth) may also be mentioned. An elemental oxide such as 2 O 3 , TiO 2 or Nd 2 O 3 .
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。陶瓷粉末的平均粒徑是與上述導電性粉末同樣地根據基於BET法得到的比表面積計算出的粒徑。 The average particle diameter of the ceramic powder is, for example, 0.01 μm or more and 0.5 μm or less, and preferably 0.01 μm or more and 0.3 μm or less. When the average particle diameter of the ceramic powder is within the above range, when it is used as a slurry for internal electrodes, it is possible to form a sufficiently thin and uniform internal electrode. The average particle diameter of the ceramic powder is a particle diameter calculated from the specific surface area obtained by the BET method in the same manner as the above conductive powder.
以導電性粉末為100質量份計，陶瓷粉末的含量理想為1質量份以上30質量份以下，更理想為3質量份以上30質量份以下。 The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the conductive powder.
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 1% by mass or more and 20% by mass or less, and more preferably 3% by mass or more and 20% by mass or less based on the total amount of the conductive paste.
(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 resin. The acetal resin is preferably a butyral resin such as polyvinyl butyral. When the binder resin contains an acetal resin, it can be adjusted to a viscosity suitable for gravure printing, and the adhesion strength to the green sheet can be further improved. The binder resin may contain, for example, 20% by mass or more of the acetal resin as a whole of the binder resin, and may be contained in an amount of 30% by mass or more, or may be contained in an amount of 60% by mass or more, or may be composed only of an acetal resin.
以導電性粉末為100質量份計，縮醛系樹脂的含量理想為1質量份以上10質量份以下，更理想為1質量份以上8質量份以下。 The content of the acetal resin is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the conductive powder.
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，基於相對於溶劑的溶解性、燃燒分解性的觀點等，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。 Further, the binder resin may contain a resin other than the acetal resin. The other resin is not particularly limited, and a conventional resin can be used. Examples of the other resin include a cellulose resin such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, and an acrylic resin, which is based on solubility in a solvent. The viewpoint of combustion decomposition property, etc. is ideally ethyl cellulose. Further, 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，黏合劑樹脂的含量理想為1質量份以上10質量份以下，更理想為1質量份以上8質量份以下。 The content of the binder resin is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the conductive powder.
黏合劑樹脂的含量相對於導電性漿料整體理想為0.5質量%以上10質量%以下，更理想為0.5質量%以上6質量%以下。在黏合劑樹脂的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 6% by mass or less based on the total amount of the conductive paste. When the content of the binder resin is within the above range, conductivity 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 solvent and an acetate solvent, and preferably contains a glycol ether 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，理想為丙二醇單烷基醚類，更理想為丙二醇單丁基醚。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 the glycol ether-based solvent include diethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, and ethylene glycol monohexyl ether. (2) glycol ethers, propylene glycol monomethyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether (PNB), and the like. 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。 For example, the organic solvent may contain 25% by mass or more of the glycol ether solvent, or may be contained in an amount of 50% by mass or more, or may be composed only of a glycol ether solvent. Further, the glycol ether-based solvent may be used singly or in combination of two or more.
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 the acetate-based solvent include dihydroterpineol acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, and ethylene glycol monobutylate. Glycol ether acetates such as ethyl 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，更理想為乙酸異冰片酯。相對於除了二醇醚系溶劑以外的有機溶劑整體，理想為含有90質量%以上100質量%以下的乙酸酯系溶劑，更理想為含有100質量%。 In the case where the organic solvent contains an acetate-based solvent, for example, it may contain a selected from the group consisting of dihydroterpineol acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate. An acetate-based solvent (A) of at least one of the ester groups. Among them, more preferably isobornyl acetate. It is preferable to contain 90% by mass or more and 100% by mass or less of the acetate-based solvent, and more preferably 100% by mass, based on the entire organic solvent other than the glycol ether-based solvent.
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)。在使用如此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。 Further, when the organic solvent contains an acetate-based solvent, for example, the above-mentioned acetate-based solvent (A) and ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate may be contained. At least one acetate solvent (B). When such a mixed solvent is used, the viscosity of the conductive paste can be easily adjusted, and the drying speed of the conductive paste can be increased.
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，相對於乙酸酯系溶劑整體，理想為含有50質量%以上90質量%以下的乙酸酯系溶劑(A)，更理想為含有60質量%以上80質量%以下。在為上述混合液的情況下，以乙酸酯系溶劑整體為100質量%計，理想為含有10質量%以上50質量%以下的乙酸酯系溶劑(B)，更理想為含有20質量%以上40質量%以下。 In the case of a mixed liquid containing the acetate-based solvent (A) and the acetate-based solvent (B), it is preferable to contain 50% by mass or more and 90% by mass or less of acetic acid based on the entire acetate-based solvent. The ester solvent (A) is more preferably contained in an amount of 60% by mass or more and 80% by mass or less. In the case of the above-mentioned mixed liquid, the acetate-based solvent (B) is preferably contained in an amount of 10% by mass or more and 50% by mass or less, and more preferably 20% by mass, based on 100% by mass of the total amount of the acetate-based solvent. The above 40% by mass or less.
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、環己烷等脂肪族系烴溶劑等。其中，理想為脂肪族系烴溶劑，在脂肪族系烴溶劑之中更理想為礦油精。此外，其他有機溶劑可以使用一種，亦可以使用兩種以上。 Further, the organic solvent may contain an organic solvent other than the glycol ether solvent and the acetate solvent. The other organic solvent is not particularly limited, and a conventional organic solvent capable of dissolving the above binder resin can be used. Examples of the other organic solvent include an acetate solvent such as ethyl acetate, propyl acetate, isobutyl acetate or butyl acetate; a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; An anthraquinone solvent such as terpineol or dihydroterpineol, or an aliphatic hydrocarbon solvent such as tridecane, decane or cyclohexane. Among them, an aliphatic hydrocarbon solvent is preferred, and mineral oil concentrate is more preferred among the aliphatic hydrocarbon solvents. Further, other organic solvents may be used alone or in combination of two or more.
有機溶劑例如可以含有二醇醚系溶劑作為主溶劑、且含有脂肪族系烴溶劑作為副溶劑。在這種情況下，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，更理想為含有40質量份以上50質量份以下，以導電性粉末為100質量份計，例如含有15質量份以上80質量份以下的脂肪族系烴溶劑，理想為含有20質量份以上80質量份以下，更理想為含有20質量份以上40質量份以下。 The organic solvent may contain, for example, a glycol ether solvent as a main solvent and an aliphatic hydrocarbon solvent as a sub solvent. In this case, it is preferable to contain 30 parts by mass or more and 50 parts by mass or less of the glycol ether solvent, more preferably 40 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the conductive powder. The amount of the powder is, for example, 15 parts by mass or more and 80 parts by mass or less of the aliphatic hydrocarbon solvent, and preferably 20 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 40 parts by mass or less.
以導電性粉末為100質量份計，有機溶劑的含量理想為50質量份以上130質量份以下，更理想為60質量份以上90質量份以下。在有機溶劑的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the organic solvent is preferably 50 parts by mass or more and 130 parts by mass or less, more preferably 60 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the conductive powder. When the content of the organic solvent is within the above range, conductivity and dispersibility are excellent.
有機溶劑的含量相對於導電性漿料整體理想為20質量%以上50質量%以下，更理想為25質量%以上45質量%以下。在有機溶劑的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the organic solvent is preferably 20% by mass or more and 50% by mass or less, more preferably 25% by mass or more and 45% by mass or less based on the total amount of the conductive paste. When the content of the organic solvent is within the above range, conductivity and dispersibility are excellent.
(分散劑) (Dispersant)
本實施型態的導電性漿料，作為酸系分散劑而理想為含有具有磷的酸系分散劑，其中理想為含有由磷酸烷基酯化合物構成的第一酸系分散劑。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，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第一酸系分散劑，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 the present embodiment preferably contains an acid-based dispersant having phosphorus as the acid-based dispersant, and preferably contains a first acid-based dispersant composed of an alkyl phosphate compound. The inventors of the present invention have studied the various dispersants for the dispersant used in the conductive paste. Although the reason is not clear, it has been found that the first acid system is contained together with the above binder resin and the organic solvent. The dispersant can greatly suppress the generation of agglomerates when the internal electrodes are formed, thereby improving the dispersibility of the slurry.
又，第一酸系分散劑是具有烷基的磷酸酯。又，磷酸烷基酯化合物理想具有聚氧亞烷基結構，理想為磷酸烷基聚氧亞烷基酯化合物。 Further, the first acid-based dispersant is a phosphate ester having an alkyl group. Further, the alkyl phosphate compound preferably has a polyoxyalkylene structure, and is preferably an alkyl polyoxyalkylene phosphate compound.
又，第一酸系分散劑可以是直鏈結構的分散劑，亦可以為具有複雜的支鏈結構(例如，支鏈為兩個以上)的酸系分散劑，理想為直鏈結構。 Further, the first acid-based dispersant may be a dispersant having a linear structure, or may be an acid-based dispersant having a complicated branched structure (for example, two or more branches), and is preferably a linear structure.
第一酸系分散劑理想為含有例如下述化學式(1)所示的化合物。 The first acid-based dispersant preferably contains, for example, a compound represented by the following chemical formula (1).
在上述化學式(1)中，X表示碳原子數為1~18的直鏈的烷基，Y表示-(OCH2CH2)n-，n為1~18。 In the above chemical formula (1), X represents a linear alkyl group having 1 to 18 carbon atoms, Y represents -(OCH 2 CH 2 )n-, and n is 1 to 18.
雖然其細節尚不明確，但推測藉由使用磷酸烷基酯化合物作為第一酸系分散劑，磷酸部位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，並且除了磷酸部位以外的部位含有烷基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進一步提高漿料黏度的穩定性。又，第一酸系分散劑理想為不是與其他磷酸系分散劑的混合物，而由單一的分散劑構成。 Although the details are not clear, it is presumed that by using an alkyl phosphate compound as the first acid-based dispersant, the phosphoric acid site is adsorbed on the surface of the conductive powder or the like to neutralize the surface potential or to inactivate the hydrogen bond site, and The specific three-dimensional structure including an alkyl group in a portion other than the phosphoric acid site can effectively suppress aggregation of the conductive powder or the like, thereby further improving the stability of the slurry viscosity. Further, the first acid-based dispersant is preferably composed of a single dispersant, not a mixture with another phosphate-based dispersant.
此外，本實施型態的導電性漿料可以含有除了第一酸系分散劑以外的含有磷的酸系分散劑(磷酸系分散劑)，但作為導電性漿料中的含有磷的酸系分散劑，理想為僅含有磷酸烷基酯化合物，更理想為僅含有磷酸烷基聚氧亞烷基酯化合物。又，第一酸系分散劑可以是混合物，但理想為單一的化合物。 Further, the conductive paste of the present embodiment may contain an acid-based dispersant (phosphoric acid dispersant) containing phosphorus in addition to the first acid-based dispersant, but is an acid-based dispersion containing phosphorus in the conductive paste. The agent preferably contains only an alkyl phosphate compound, and more preferably contains only an alkyl polyoxyalkylene phosphate compound. Further, the first acid-based dispersant may be a mixture, but is desirably a single compound.
以導電性粉末為100質量份計，例如可以含有0.2質量份以上2質量份以下的第一酸系分散劑，亦可以含有0.2質量份以上1質量份以下，理想為含有0.2質量份以上不足1質量份。當上述酸系分散劑的含量在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。 For example, the first acid-based dispersant may be contained in an amount of 0.2 part by mass or more and 2 parts by mass or less, or may be contained in an amount of 0.2 part by mass or more and 1 part by mass or less, and preferably 0.2 part by mass or more and less than 1 part by mass. Parts by mass. When the content of the acid-based dispersant is within the above range, the conductive powder in the conductive paste is excellent in dispersibility.
相對於導電性漿料整體，例如含有3質量%以下的第一酸系分散劑。上述酸系分散劑的含量的上限理想為2質量%以下，更理想為1.5質量%以下，進一步理想為1質量%以下。對上述酸系分散劑的含量的下限沒有特別限定，例如為0.1質量%以上。 The first acid-based dispersant is contained in an amount of, for example, 3% by mass or less based on the entire conductive paste. The upper limit of the content of the acid-based dispersant is preferably 2% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1% by mass or less. The lower limit of the content of the acid-based dispersant is not particularly limited, and is, for example, 0.1% by mass or more.
第一酸系分散劑，例如可以從市售的產品中選擇滿足上述 特性的產品來使用。又，上述分散劑，亦可以使用傳統習知的製造方法來製造以滿足上述特性。 The first acid-based dispersant can be used, for example, from a commercially available product to satisfy a product satisfying the above characteristics. Further, the above dispersing agent can also be produced by a conventionally known manufacturing method to satisfy the above characteristics.
導電性漿料含有除了第一酸系分散劑以外的第二酸系分散劑。第二酸系分散劑是具有羧基的酸系分散劑，理想為磷酸系分散劑以外的酸系分散劑。雖然其細節尚不明確，但本實施型態的導電性漿料藉由與第一酸系分散劑一起並用第二酸系分散劑，漿料的分散性、黏度穩定性變得良好。 The conductive paste contains a second acid-based dispersant other than the first acid-based dispersant. The second acid-based dispersant is an acid-based dispersant having a carboxyl group, and is preferably an acid-based dispersant other than a phosphate-based dispersant. Although the details are not clear, the conductive paste of the present embodiment is excellent in dispersibility and viscosity stability of the slurry by using the second acid-based dispersant together with the first acid-based dispersant.
第二酸系分散劑理想為分子量為5000以下，更理想為分子量為1000以下，進一步理想為分子量為500以下。第二酸系分散劑例如是具有烴基的酸系分散劑。作為烴基，理想為含有碳原子數為10以上且20以下的烷基或碳原子數為10以上且20以下的烯基。又，第二酸系分散劑具有羧基。在第二酸系分散劑與第一酸系分散劑同樣地具有上述那樣的結構的情況下，能夠在維持藉由添加第一酸系分散劑而帶來的效果的同時，進一步提高漿料的分散性。 The second acid-based dispersant preferably has a molecular weight of 5,000 or less, more preferably has a molecular weight of 1,000 or less, and further preferably has a molecular weight of 500 or less. The second acid-based dispersant is, for example, an acid-based dispersant having a hydrocarbon group. The hydrocarbon group preferably contains an alkyl group having 10 or more and 20 or less carbon atoms or an alkenyl group having 10 or more and 20 or less carbon atoms. Further, the second acid-based dispersant has a carboxyl group. When the second acid-based dispersant has the above-described configuration in the same manner as the first acid-based dispersant, the slurry can be further improved while maintaining the effect of adding the first acid-based dispersant. Dispersibility.
作為第二酸系分散劑，例如可列舉為高級脂肪酸、胺基酸等酸系分散劑等。此外，第二分散劑可以使用一種或者兩種以上組合使用。 The second acid-based dispersant may, for example, be an acid-based dispersant such as a higher fatty acid or an amino acid. Further, the second dispersant may 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, and examples thereof include stearic acid, oleic acid, behenic acid, myristic acid, palmitic acid, linoleic acid, and lauric acid. A higher fatty acid having 11 or more carbon atoms such as linolenic acid. Among them, oleic acid or stearic acid is desirable.
作為除高級脂肪酸以外的第二酸系分散劑，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)1,3-二胺基丙烷為代表的二胺的氧乙烯加成型，其中，理想為烷基單胺鹽型。 The second acid-based dispersing agent other than the higher fatty acid is not particularly limited, and examples thereof include surfactants selected from the following surfactants: alkyl monoamine salts represented by monoalkylamine salts, and N - an alkyl diamine salt type represented by an alkyl group (C14-C18) propylene diamine dioleate, an alkyl trimethyl ammonium salt type represented by an alkyl trimethyl ammonium chloride, a palm alkyl group a dimethyl benzyl ammonium salt type represented by dimethyl benzyl ammonium chloride, a quaternary ammonium salt type represented by an alkyl group / dimer oxyethylene methyl ammonium chloride, an alkyl pyridinium salt type, a tertiary amine type represented by dimethyl stearylamine, a polyoxyethylene alkylamine type represented by polyoxypropylene/polyoxyethylene alkylamine, and N, N', N'-tris (2-hydroxyethyl) The oxyethylene addition molding of a diamine represented by a group of -N-alkyl (C14-18) 1,3-diaminopropane, and preferably an alkylmonoamine salt type.
作為烷基單胺鹽型，理想為油醯肌胺酸、月桂醯肌胺酸、硬脂酸醯胺等。 The alkyl monoamine salt type is preferably oleoresin, lauric creatinine, decylamine or the like.
以導電性粉末為100質量份計，例如含有0.01質量份以上2質量份以下的第二酸系分散劑，理想為含有0.01質量份以上1質量份以下，更理想為含有0.01質量份以上不足1質量份，進一步理想為含有0.05質量份以上0.5質量份以下。與第一酸系分散劑一併地在上述範圍內含有第二酸系分散劑的情況下，在導電性漿料中，特別是導電性粉末的分散性更加優異。 The second acid-based dispersant is contained in an amount of 0.01 parts by mass or more and 2 parts by mass or less, and preferably contains 0.01 parts by mass or more and 1 part by mass or less, more preferably 0.01 parts by mass or more and less than 1 part by mass of the conductive powder. The mass part is further preferably contained in an amount of 0.05 parts by mass or more and 0.5 parts by mass or less. When the second acid-based dispersant is contained in the above range together with the first acid-based dispersant, the conductive paste is particularly excellent in dispersibility of the conductive powder.
又，以第一酸系分散劑為100質量份計，例如含有50質量份以上200質量份以下的第二酸系分散劑，理想為含有50質量份以上150質量份以下。 In addition, the second acid-based dispersant is contained in an amount of 50 parts by mass or more and 200 parts by mass or less, and preferably 50 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the first acid-based dispersing agent.
導電性漿料可以含有除了第一酸系分散劑和第二酸系分散劑以外的其他分散劑。作為其他分散劑，可列舉為鹼系分散劑、非離子系分散劑、兩性分散劑等。其他分散劑可以使用一種或者兩種以上組合使 用。 The conductive paste may contain a dispersant other than the first acid dispersant and the second acid dispersant. Examples of the other dispersant include an alkali dispersant, a nonionic dispersant, and an amphoteric dispersant. Other dispersing agents may 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、硬脂胺等脂肪族胺等。當在導電性漿料中與具有羧基的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隨時間的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, rosin amine, hexadecylamine, myristylamine, and stearylamine. When an alkali-based dispersant is also contained in the conductive paste together with the acid-based dispersant having a carboxyl group, the viscosity stability and the slurry dispersibility over time can be achieved 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0.01質量份以上1質量份以下，更理想為含有0.02質量份以上且不足1質量份。又，例如，以上述第一酸系分散劑為100質量份計，可以含有10質量份以上300質量份以下的鹼系分散劑，理想為含有50質量份以上150質量份以下。在上述範圍內含有鹼系分散劑的情況下，漿料的隨時間的黏度穩定性更加優異。 For example, the amount of the conductive dispersant may be 0.01 parts by mass or more and less than 2 parts by mass, and preferably 0.01 parts by mass or more and 1 part by mass or less, more preferably 0.02 parts by mass or more. Less than 1 part by mass. In addition, the alkali-based dispersing agent may be contained in an amount of 10 parts by mass or more and 300 parts by mass or less, and preferably 50 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the first acid-based dispersing agent. When the alkali-based dispersing agent is contained in the above range, the viscosity stability of the slurry over time is further improved.
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，理想為含有0質量%以上1.5質量%以下，更理想為含有0質量%以上1.0質量%以下，進一步理想為含有0.1質量%以上1.0質量%以下，更進一步理想為含有0.1質量%以上0.8質量%以下。在以上述範圍含有鹼系分散劑的情況下，漿料的隨時間的黏度穩定性更加優異。 For example, the alkali-based dispersant containing 0% by mass or more and 2.5% by mass or less, based on the entire conductive paste, is preferably contained in an amount of 0% by mass or more and 1.5% by mass or less, more preferably 0% by mass or more and 1.0% by mass or less. Further, it is preferably contained in an amount of 0.1% by mass or more and 1.0% by mass or less, and more preferably 0.1% by mass or more and 0.8% by mass or less. When the alkali-based dispersant is contained in the above range, the viscosity stability of the slurry over time is further improved.
在導電性漿料中，含有第一酸系分散劑以及第二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0.21質量份以上2質量份以下。在分散劑(整體)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 dispersing agent (overall) containing the first acid dispersing agent and the second acid dispersing agent is, for example, 0.11 part by mass or more, based on 100 parts by mass of the conductive powder. The following. When the content of the dispersant (overall) exceeds the above range, the drying property of the conductive paste may be deteriorated, sheet corrosion may occur, and the green sheet may not be peeled off from the PET film of the liner.
(其他成分) (other ingredients)
本實施型態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 conductive paste of the present embodiment may contain other components than the above components as needed. As other components, for example, conventionally known additives such as an antifoaming agent, a plasticizer, a surfactant, and a thickener can be used.
(導電性漿料) (conductive paste)
對本實施型態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佈分散劑，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 method for producing the conductive paste of the present embodiment is not particularly limited, and a conventionally known method can be used. For example, the conductive paste can be produced by stirring and kneading each of the above components by a three-roll mill, a ball mill, a mixer, or the like. At this time, when the dispersing agent is applied to the surface of the conductive powder in advance, the conductive powder does not aggregate, and can be sufficiently dispersed, and the dispersing agent is spread over the surface thereof to easily obtain a uniform conductive paste. In addition, the binder resin may be dissolved in a part of the organic solvent in advance, and after the organic vehicle is prepared, the conductive powder, the ceramic powder, the dispersant, and the organic vehicle are added to the organic solvent for slurry adjustment, followed by stirring. The mixture was kneaded 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 viscosity of the conductive paste at a shear rate of 100 sec -1 is desirably 0.8 Pa. S below. When the viscosity at a shear rate of 100 sec -1 is within the above range, it can be suitably used as a conductive paste for gravure printing. If it exceeds the above range, the viscosity is too high and it is not suitable for gravure printing. The lower limit of the viscosity at a shear rate of 100 sec -1 is not particularly limited, and is, for example, 0.2 Pa. S or above.
又，導電性漿料在剪切速率為10000sec-1時的黏度理想為0.19Pa．S以下，更理想為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。 Moreover, the viscosity of the conductive paste at a shear rate of 10000 sec -1 is preferably 0.19 Pa. Below S, more preferably 0.18Pa. S below. When the viscosity at a shear rate of 10000 sec -1 is within the above range, it can be suitably used as a conductive paste for gravure printing. When it exceeds the above range, there is a case where the viscosity is too high and it is not suitable as a gravure printing. The lower limit of the viscosity at a shear rate of 10000 sec -1 is not particularly limited, and is, for example, 0.05 Pa. S or 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 in electronic parts such as laminated ceramic capacitors. The 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、介電質生片的剝離不良。 In the laminated ceramic capacitor, the dielectric ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste are desirably powders having the same composition. In the laminated ceramic device prepared by using the conductive paste of the present embodiment, even when the thickness of the dielectric green sheet is, for example, 3 μm or less, it is possible to suppress sheet corrosion and peeling failure of the dielectric green sheet.
[電子零件] [electronic parts]
以下，參照圖式對本發明的電子零件等的實施型態進行說明。在圖式中，有時會適當地以示意性的方式來進行表示、變更比例尺來進行表示。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 the electronic component and the like of the present invention will be described with reference to the drawings. In the drawings, the scale may be expressed and changed in a schematic manner as appropriate. The position, direction, and the like of the component will be described with reference to the XYZ orthogonal coordinate system shown in FIG. 1 and the like as appropriate. In the XYZ orthogonal coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is a vertical direction (up and down direction).
圖1中的A以及圖1中的B是作為實施型態的電子零件的一個例子，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交替地層疊而成的陶瓷層積體10和外部電極20。 A in FIG. 1 and B in FIG. 1 are diagrams showing the laminated ceramic capacitor 1 as an example of an electronic component of an embodiment. The laminated ceramic capacitor 1 has a ceramic laminate 10 in which a dielectric layer 12 and an internal electrode layer 11 are alternately laminated, and an external electrode 20.
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，在介電質生片上藉由印刷法形成導電性漿料，並形成乾燥膜。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(陶瓷層積體10)。之後，藉由在陶瓷層積體10的兩端部形成一對外部電極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 conductive paste will be described. First, a conductive paste is formed on a dielectric green sheet by a printing method to form a dried film. A plurality of dielectric green sheets having the dried film on the upper surface are laminated by pressure bonding, and then fired and integrated, thereby preparing a laminated ceramic fired body (ceramic layer) which becomes a ceramic capacitor main body. Integral 10). Thereafter, the laminated ceramic capacitor 1 is produced by forming a pair of external electrodes at both end portions of the ceramic laminate 10. Hereinafter, a more detailed description will be given.
首先，準備作為未燒製的陶瓷片的介電質生片。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佈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，但基於層積陶瓷電容器的小型化的要求的觀點，理想為0.05μm以上3μm以下。 First, a dielectric green sheet as an unfired ceramic sheet is prepared. The dielectric green sheet is, for example, a slurry for a dielectric layer obtained by adding a solvent such as an organic binder such as polyvinyl butyral or a solvent such as terpineol to a predetermined ceramic powder such as barium titanate. A dielectric green sheet formed by applying a sheet to a support film such as a PET film and drying it to remove the solvent. In addition, the thickness of the dielectric layer composed of the dielectric green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less from the viewpoint of miniaturization of the laminated ceramic capacitor.
接下來，準備多個藉由在該介電質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而形成有由導電性漿料構成的內部電極層11的片材。此外，對於由導電性漿料構成的內部電極層11的厚度而言，基於該內部電極層11的薄層化的要求的觀點，理想為乾燥後為1μm以下。 Next, a plurality of sheets in which the internal electrode layer 11 made of a conductive paste is formed by printing and coating the conductive paste on one surface of the dielectric green sheet by a gravure printing method are prepared. In addition, the thickness of the internal electrode layer 11 made of a conductive paste is preferably 1 μm or less from the viewpoint of the requirement for thinning of the internal electrode layer 11 .
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(壓接體)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 off from the support film, and the dielectric green sheet is alternately arranged with the conductive paste (dry film) formed on one surface of the dielectric green sheet. After lamination, a laminate (pressure-bonding body) is obtained by heat and pressure treatment. In addition, a configuration may be adopted in which a dielectric green sheet for protection which is not coated with a conductive paste is further disposed on both surfaces of a laminate (pressure-bonding body).
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，並在還原氣體環境下進行燒製，據此製備層積陶瓷燒製體(陶瓷層積體10)。此外，脫黏合劑處理中的氣體環境理想為大氣或N2氣體環境。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，進行層積體的燒製時的溫度例如為1000℃以上1350℃以下，進行燒製時的溫度的保持時間例如為0.5小時以上8小時以下。 Next, after the laminate is cut into a predetermined size to form a green wafer, the green wafer is subjected to a debonding treatment and fired in a reducing gas atmosphere, thereby preparing a laminated ceramic fired body (ceramic layer). Integral 10). In addition, the gaseous environment in the debonder treatment is desirably an atmospheric or N 2 gas environment. The temperature at which the debonding agent treatment is performed is, for example, 200 ° C or more and 400 ° C or less. Moreover, it is preferable that the holding time of the above-mentioned temperature at the time of performing a debonding agent process is 0.5 hours or more and 24 hours or less. In addition, in order to suppress the 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 laminate is, for example, 1000 ° C or more and 1350 ° C or less, and the firing is performed. The temperature retention 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，去除內部電極層11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，進而形成介電質層12與內部電極層11多層交替地層疊而成的陶瓷層積體10。此外，基於將氧帶入介電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，可以對燒製後的陶瓷層積體10實施退火處理。 The organic binder in the green sheet is completely removed by firing the green wafer, and the ceramic raw material powder is fired to form a ceramic dielectric layer 12. Further, the organic carrier in the internal electrode layer 11 is removed, and the alloy powder containing nickel powder or nickel as a main component is sintered or melted and integrated to form an internal electrode, thereby forming a multilayer of the dielectric layer 12 and the internal electrode layer 11. The ceramic laminate 10 is alternately laminated. Further, the ceramic laminate 10 after firing can be annealed from the viewpoint of improving the reliability by introducing oxygen into the interior of the dielectric layer and suppressing reoxidation of the internal electrode.
然後，藉由對所製備的陶瓷層積體10設置一對外部電極20，藉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, a laminated ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 to the prepared ceramic laminate 10. For example, the external electrode 20 includes the external electrode layer 21 and the plating layer 22. The external electrode layer 21 is electrically connected to the internal electrode layer 11. Further, as the material of the external electrode 20, for example, copper, nickel or the like can be preferably used. In addition, electronic parts other than laminated ceramic capacitors can be used for electronic parts.
以下，基於實施例和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.
[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 at a shear rate of 100sec -1, the viscosity of the conductive paste manufactured measured under the conditions of 10000sec -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(2英寸)上，印刷樣品(所製備的導電性漿料)(GAP厚度=5μm)並進行乾燥。乾燥在帶式爐內的最大溫度為120~150℃、大氣氣體環境下進行。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(背光=從玻璃基板的背面照射光)，確認塊狀物的有無。在沒有觀察到塊狀物的情況下，將導電性漿料的分散性評價為「良好」，在觀察到一個以上的塊狀物的情況下，將導電性漿料的分散性評價為「不良」。 On the glass substrate (2 inches), a sample (prepared conductive paste) (GAP thickness = 5 μm) was printed and dried. Drying is carried out in a belt furnace at a maximum temperature of 120 to 150 ° C in an atmospheric atmosphere. The dried film (2 cm × 2 cm, thickness: 3 μm) obtained after drying was observed with an optical microscope while irradiating light (backlight) from the back surface of the glass substrate with ×100 (eyepiece, objective lens; 10 times each) (backlight = from The back surface of the glass substrate was irradiated with light, and the presence or absence of the bulk was confirmed. When no bulk was observed, the dispersibility of the conductive paste was evaluated as "good", and when one or more bulks were observed, the dispersibility of the conductive paste was evaluated as "poor" "."
[使用材料] [Use materials]
(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，縮醛系樹脂)、乙基纖維素(EC)。 As the binder resin, polyvinyl butyral resin (PVB, acetal resin) or ethyl cellulose (EC) is used.
(分散劑) (Dispersant)
(1)使用磷酸烷基聚氧亞烷基酯化合物作為第一酸系分散劑(A)。 (1) An alkyl polyoxyalkylene phosphate compound is used as the first acid-based dispersant (A).
(2)使用油醯肌胺酸(C21H39NO3)作為第二酸系分散劑(B)。 (2) Oil Creatine (C 21 H 39 NO 3 ) was used as the second acid-based dispersant (B).
(3)使用松香胺(C)、聚乙二醇月桂胺(D)、油胺(E)作為鹼系分散劑。 (3) Using rosin amine (C), polyethylene glycol laurylamine (D), and oleylamine (E) as an alkali-based dispersing agent.
(4)使用含有磷酸聚酯(具有磷酸基的聚酯)作為主要成分、餘量為磷酸的磷酸系分散劑(F)作為除了上述的酸系分散劑(A)以外的酸系分散劑(比較例用)。 (4) A phosphate-based dispersant (F) containing a phosphoric acid polyester (polyester having a phosphate group) as a main component and the balance being phosphoric acid is used as an acid-based dispersant other than the above-described acid-based dispersant (A) ( For the comparative example).
(有機溶劑) (Organic solvents)
作為有機溶劑，使用丙二醇單丁醚(PNB，乙二醇醚系溶劑)、礦油精(MA)、萜品醇(TPO)。 As the organic solvent, propylene glycol monobutyl ether (PNB, glycol ether solvent), mineral spirits (MA), terpineol (TPO) is 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0.3質量份的第一酸系分散劑(A)以及0.5質量份的第二酸系分散劑(B)、作為黏合劑樹脂的2質量份的PVB和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。 25 parts by mass of the ceramic powder, 0.3 parts by mass of the first acid-based dispersant (A) as a dispersing agent, and 0.5 parts by mass of the second acid-based dispersing agent, based on 100 parts by mass of the Ni powder as the conductive powder (B), 2 parts by mass of PVB as a binder resin, 4 parts by mass of EC, 41 parts by mass of PNB as an organic solvent, 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 slurry were evaluated by the above method. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例2] [Embodiment 2]
作為分散劑，使用0.5質量份的第一酸系分散劑(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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that 0.5 parts by mass of the first acid-based dispersant (A) was used as the dispersant. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation 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1.0質量份的第一酸系分散劑(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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that 1.0 mass part of the first acid-based dispersant (A) was used as the dispersing agent. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation 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0.2質量份的第二酸系分散劑(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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that 0.2 parts by mass of the second acid-based dispersant (B) was used as the dispersant. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation 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1.0質量份的第二酸系分散劑(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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that 1.0 mass part of the second acid-based dispersant (B) was used as the dispersing agent. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例6] [Embodiment 6]
將0.3質量份的第一酸系分散劑(A)、0.5質量份的第二酸系分散劑(B)以及0.2質量份的松香胺(C)混合作為分散劑，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。 0.3 parts by mass of the first acid dispersant (A), 0.5 parts by mass of the second acid dispersant (B), and 0.2 parts by mass of rosin amine (C) are mixed as a dispersing agent, and A conductive paste was prepared and evaluated in the same manner as in Example 1. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例7] [Embodiment 7]
將0.3質量份的第一酸系分散劑(A)、0.5質量份的第二酸系分散劑(B)以及0.2質量份的聚乙二醇月桂胺(D)混合作為分散劑，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。 0.3 parts by mass of the first acid dispersant (A), 0.5 part by mass of the second acid dispersant (B), and 0.2 parts by mass of polyethylene glycol laurylamine (D) are mixed as a dispersing agent. Further, a conductive paste was prepared and evaluated in the same manner as in Example 1. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例8] [Embodiment 8]
將0.3質量份的第一酸系分散劑(A)、0.5質量份的第二酸系分散劑(B)以及0.2質量份的油胺(E)混合作為分散劑，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。 0.3 parts by mass of the first acid dispersant (A), 0.5 parts by mass of the second acid dispersant (B), and 0.2 parts by mass of oleylamine (E) are mixed as a dispersing agent, and A conductive paste was prepared and evaluated in the same manner as in Example 1. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例9] [Embodiment 9]
作為分散劑，使用0.4質量份的油胺(E)，除此之外，按照與實施例8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。 A conductive paste was prepared and evaluated in the same manner as in Example 8 except that 0.4 parts by mass of oleylamine (E) was used as the dispersing agent. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例10] [Embodiment 10]
作為分散劑，使用0.8質量份的油胺(E)，除此之外，按照與實施例8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。 A conductive paste was prepared and evaluated in the same manner as in Example 8 except that 0.8 parts by mass of oleylamine (E) was used as the dispersing agent. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例11] [Example 11]
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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that only 6 parts by mass of PVB was used as the binder resin. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[實施例12] [Embodiment 12]
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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that 50 parts by mass of PNB and 18 parts by mass of MA were used as the organic solvent. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation 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質量份的含有磷酸聚酯作為主要成分的磷酸系分散劑(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。 In the same manner as in Example 1, except that 0.8 parts by mass of a phosphate-based dispersant (F) containing a phosphoric acid polyester as a main component and 0.2 parts by mass of an alkali-based dispersant (C) were used as the dispersing agent. A conductive paste was prepared and evaluated. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例2] [Comparative Example 2]
作為有機溶劑，僅使用萜品醇(TPO)，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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that terpineol (TPO) was used as the organic solvent. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例3] [Comparative Example 3]
作為黏合劑樹脂，僅使用EC，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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that only the EC was used as the binder resin. The content of the dispersant or the like of the conductive paste is shown in Table 1, and the results of evaluation of the viscosity and dispersibility of the conductive paste are shown in Table 2.
[比較例4] [Comparative Example 4]
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，除此以外，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。 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that EC was used as the binder resin and only terpineol was used as the organic solvent. The content of the dispersant or the like of the conductive paste is as shown in Table 1, and the results of evaluation 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0.36~0.58Pa．S，剪切速率為10000sec-1時的黏度為0.12~0.17Pa．S，是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 conductive paste of the example has a viscosity of 0.36 to 0.58 Pa at a shear rate of 100 sec -1 . S, the viscosity at a shear rate of 10000 sec -1 is 0.12 to 0.17 Pa. S, is the viscosity suitable for gravure printing. Further, the conductive paste of the present example did not show agglomerates on the surface of the dried film after printing, indicating that the dispersibility of the slurry was excellent.
另一方面，在使用除酸系分散劑(A)以外的磷酸系分散劑(F)的比較例1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，在有機溶劑在本發明的範圍之外的比較 例2、黏合劑樹脂在本發明的範圍之外的比較例3、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4的導電性漿料中，無法獲得適於凹版印刷的黏度。因此，未能得到適當的乾燥膜，未能進行分散性的評價。 On the other hand, in the conductive paste of Comparative Example 1 using the phosphate-based dispersant (F) other than the acid-based dispersant (A), agglomerates were observed on the surface of the dried film after printing, indicating that the slurry Poor dispersion. Further, Comparative Example 2 in which the organic solvent was outside the scope of the present invention, Comparative Example 3 in which the binder resin was outside the scope of the present invention, and Comparative Example 4 in which the organic solvent and the binder resin were outside the scope of the present invention In the conductive paste, the viscosity suitable for gravure printing cannot be obtained. Therefore, an appropriate dry film could not be obtained, and the evaluation of dispersibility could not be performed.
【產業利用性】[Industry Utilization]
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 dispersibility of the slurry is good. Therefore, the conductive paste of the present invention is particularly preferably used as a raw material for internal electrodes of a laminated ceramic capacitor of a wafer component of an electronic device such as a mobile phone or a digital device, and is particularly preferably used as a conductive paste for gravure printing.
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| TW202141532A (en) * | 2020-03-04 | 2021-11-01 | 日商住友金屬鑛山股份有限公司 | Electroconductive paste, electronic component, and laminated ceramic capacitor |
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| JPH1092226A (en) * | 1996-09-11 | 1998-04-10 | Murata Mfg Co Ltd | Conductive composition |
| JP4389431B2 (en) | 2001-12-13 | 2009-12-24 | 株式会社村田製作所 | Conductive paste for gravure printing, method for producing the same, and multilayer ceramic electronic component |
| 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 |
| JP4146823B2 (en) * | 2003-06-26 | 2008-09-10 | 積水化学工業株式会社 | Binder resin for conductive paste and conductive paste |
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| JP2010118470A (en) * | 2008-11-12 | 2010-05-27 | Sekisui Chem Co Ltd | Conductive paste for laminated ceramic capacitor |
| KR101198004B1 (en) * | 2010-12-10 | 2012-11-05 | 삼성전기주식회사 | A ceramic paste composition for a multilayer ceramic capacitor, a multilayer ceramic capacitor and methods of manufacturing the same |
| JP5569747B2 (en) * | 2011-02-18 | 2014-08-13 | 住友金属鉱山株式会社 | Gravure printing conductive paste used for multilayer ceramic capacitor internal electrode |
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