TW201606007A - Conductive paste - Google Patents
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本發明係關於積層陶瓷裝置用之導電性糊，更詳言之，係關於不會產生薄片侵蝕(sheet attack)或生胚片(green sheet)剝離不良，且隨時間經過所造成的黏度變化少的導電性糊。 The present invention relates to a conductive paste for a laminated ceramic device, and more particularly, to a sheet attack or a green sheet peeling failure, and a small change in viscosity due to passage of time. Conductive paste.
隨著行動電話和數位機器等電子機器的輕薄短小化，屬於晶片零件之積層陶瓷電容(Multilayered Ceramic Capacitor，以下稱為MLCC)等積層陶瓷裝置也期望可小型化、高容量化及高性能化。為了實現該等之最有效的手段係將內部電極層與介電質層予以薄化而謀求多層化。 In the case of a thinner and thinner electronic device such as a mobile phone and a digital device, a multilayer ceramic device such as a multilayered ceramic capacitor (hereinafter referred to as MLCC) which is a wafer component is also desired to be downsized, high in capacity, and high in performance. In order to achieve the most effective means, the internal electrode layer and the dielectric layer are thinned to achieve multilayering.
MLCC一般係可依如下方式來製造。首先，為了形成介電質層，係形成包括鈦酸鋇(BaTiO3)等介電質陶瓷粉末及聚乙烯基丁醛等有機黏合劑之介電質生胚片。又，為了形成內部電極層，係製作使導電性金屬粉末分散於包含樹脂黏合劑之有機載體的導電性糊。在依既定圖案將該導電性糊印刷至介電質生胚片表面上之後，施行用以去除有機溶劑之乾燥，形成成為內部電極之 乾燥膜。接著，依將乾燥膜與介電質生胚片予以多層重疊的狀態進行加熱壓接而予以一體化，形成壓接體。將此壓接體切斷，於氧化性環境或惰性環境中、500℃下進行去除有機黏合劑處理，之後，以內部電極不會氧化之方式，在還原環境中、1300℃左右下進行加熱燒成，得到燒成晶片。接下來，將外部電極用糊塗布於燒成晶片上，予以燒成後，針對外部電極上施以鍍鎳等，則MLCC完成。 MLCCs are generally manufactured in the following manner. First, in order to form a dielectric layer, a dielectric green sheet including a dielectric ceramic powder such as barium titanate (BaTiO 3 ) and an organic binder such as polyvinyl butyral is formed. Further, in order to form the internal electrode layer, a conductive paste in which the conductive metal powder is dispersed in an organic carrier containing a resin binder is prepared. After the conductive paste is printed on the surface of the dielectric green sheet in a predetermined pattern, drying to remove the organic solvent is performed to form a dried film which becomes an internal electrode. Then, the dried film and the dielectric green sheet are superposed on each other in a plurality of layers, and are joined by heating and pressure bonding to form a pressure-bonded body. The pressure-bonding body is cut, and the organic binder is removed in an oxidizing atmosphere or an inert environment at 500 ° C. Thereafter, the internal electrode is not oxidized, and is heated in a reducing atmosphere at about 1300 ° C. Into, a fired wafer is obtained. Next, the external electrode paste is applied onto the fired wafer and fired, and then nickel plating or the like is applied to the external electrode to complete the MLCC.
然而，在上述燒成步驟中，介電質陶瓷粉末開始燒結的溫度為1200℃左右，其與鎳等導電性金屬粉末之燒結/收縮開始的溫度會產生頗大的偏差，故容易發生脫層(層間剝離)或龜裂等結構缺陷。尤其是隨著小型化/高容量化，積層數越增加或者是介電質層之厚度越薄，則結構缺陷的發生變得越顯著。 However, in the above calcination step, the temperature at which the dielectric ceramic powder starts to be sintered is about 1200 ° C, and the temperature at which the sintering/shrinkage of the conductive metal powder such as nickel starts is greatly deviated, so delamination is liable to occur. Structural defects such as (interlayer peeling) or cracking. In particular, as the number of layers increases or the thickness of the dielectric layer becomes thinner with miniaturization/higher capacity, the occurrence of structural defects becomes more remarkable.
通常，內部電極層所使用之導電性糊係為了要抑制介電質層之早期燒結/收縮，而添加與介電質層之組成類似的鈦酸鋇系或鋯酸鍶系等鈣鈦礦型氧化物為主成分之陶瓷粉末。藉此，可控制導電性金屬粉末的燒結動作，控制內部電極層與介電質層之燒結收縮動作的偏差。又，還可以控制介電質層之主成分的構成元素與電極糊中所含介電質粉末之構成元素大不相同所引起之結構缺陷所造成的介電損失之增大等電特性降低的產生。 Usually, the conductive paste used in the internal electrode layer is a perovskite type such as barium titanate or yttrium zirconate which is similar to the composition of the dielectric layer in order to suppress early sintering/shrinkage of the dielectric layer. A ceramic powder containing an oxide as a main component. Thereby, the sintering operation of the conductive metal powder can be controlled, and the variation in the sintering shrinkage operation of the internal electrode layer and the dielectric layer can be controlled. Further, it is also possible to control the decrease in dielectric properties due to structural defects caused by structural defects caused by constituent elements of the main component of the dielectric layer and the constituent elements of the dielectric powder contained in the electrode paste, and the like. produce.
內部電極層所使用之導電性糊係使導電性金屬粉末分散在包含黏合劑樹脂之有機載體中，可藉由有機溶劑調整其黏度。在構成該有機載體之黏合劑樹脂中 ，一般係使用乙基纖維素等，在有機溶劑中，一般係使用萜品醇等。 The conductive paste used in the internal electrode layer disperses the conductive metal powder in an organic vehicle containing a binder resin, and the viscosity can be adjusted by an organic solvent. In the binder resin constituting the organic vehicle In general, ethyl cellulose or the like is used, and in an organic solvent, terpineol or the like is generally used.
然而，當將在有機溶劑中使用萜品醇之導電性糊與將諸如丁醛樹脂使用在黏合劑樹脂之陶瓷生胚片組合使用時，會有萜品醇在印刷乾燥步驟途中殘存於塗膜中的情形，此時，會有在陶瓷生胚片上引起將作為黏合劑樹脂而多數情況下所使用丁醛樹脂予以溶解之作用的情形。此類內部電極糊所造成之陶瓷生胚片中之對於有機黏合劑的溶解作用係稱為「薄片侵蝕」。 However, when a conductive paste using terpineol in an organic solvent is used in combination with a ceramic green sheet such as a butyral resin used in a binder resin, the terpineol remains in the coating film on the way of the printing and drying step. In the case of this, in the case of the ceramic green sheet, the butadiene resin used in many cases as a binder resin is dissolved. The dissolution of the organic binder in the ceramic green sheets caused by such internal electrode paste is called "flake erosion".
在積層陶瓷電容中，就陶瓷生胚片之厚度為10~20μm之較厚的片厚度而言，「薄片侵蝕」在實際使用上不會有問題。然而，在陶瓷生胚片厚度薄至5μm左右的情形中，當該薄片侵蝕產生時，陶瓷生胚片中的丁醛樹脂溶解，使陶瓷生胚片膨潤/溶解，從而在介電質生胚片積層時會發生於導電性糊印刷部分產生孔洞，或在燒成時介電質層與內部電極層會層間剝離(脫層)的不良情形。 In the multilayer ceramic capacitor, the "sheet erosion" is not problematic in practical use in terms of the thickness of the ceramic green sheet having a thickness of 10 to 20 μm. However, in the case where the thickness of the ceramic green sheet is as thin as about 5 μm, when the sheet is eroded, the butyral resin in the ceramic green sheet dissolves, and the ceramic green sheet is swollen/dissolved, thereby forming a dielectric green embryo. When the laminated layer is formed, a hole is formed in the printed portion of the conductive paste, or a problem occurs in which the dielectric layer and the internal electrode layer are peeled off (delaminated) during firing.
藉由此類薄片侵蝕的影響，MLCC之耐電壓性、絕緣性降低，或無法獲得視為目標之靜電容量，或負荷壽命特性惡化。因此，從以前至今，為了迴避此類薄片侵蝕，係進行針對導電性糊所使用之有機溶劑的檢討。 Due to the influence of such sheet erosion, the withstand voltage and insulation of the MLCC are lowered, or the electrostatic capacitance as the target or the load life characteristics are not deteriorated. Therefore, from the past, in order to avoid such sheet erosion, a review of the organic solvent used for the conductive paste was carried out.
例如，就使用在於內部電極中所使用之導電性糊的有機溶劑而言，有提議使用與丁醛樹脂之相溶性較低的溶劑(例如，參照專利文獻1)。具體來說，專利文獻1中 有提議使用乙酸二氫萜品酯的導電性糊。 For example, in the case of using an organic solvent which is a conductive paste used in an internal electrode, it is proposed to use a solvent having low compatibility with a butyral resin (for example, refer to Patent Document 1). Specifically, Patent Document 1 It is proposed to use a conductive paste of dihydrofurfuryl acetate.
然而，此類乙酸酯系溶劑雖在薄片侵蝕迴避性方面被認定是有效的，但相較於作為導電性糊之有機溶劑之一般所使用的萜品醇，由於SP值(Solubility Parameter；溶解度參數)低，與黏合劑樹脂之相溶性低，所以導電性糊之流變性質受到影響。 However, such an acetate solvent is considered to be effective in terms of sheet erosion avoidance, but compared to terpineol which is generally used as an organic solvent of a conductive paste, due to SP value (Solubility Parameter; solubility) The parameter) is low and the compatibility with the binder resin is low, so the rheological properties of the conductive paste are affected.
一般來說，黏合劑樹脂與有機溶劑之SP值的差異越大，則導電性糊會高黏度化，或者是黏合劑樹脂不會溶解於有機溶劑中。又，乙酸酯系有機溶劑係一般當作黏合劑樹脂所使用之乙基纖維素的溶解性低於萜品醇，使用此有機溶劑之導電性糊會有容易產生隨著時間經過所造成的黏度變化問題。於是，當導電性糊的黏度如此變化時，由於會產生印刷性之變動，所以會在印刷時無法獲得適當的膜厚和形狀，或者是變得無法製造品質穩定的電極等。 In general, the greater the difference in the SP value of the binder resin and the organic solvent, the higher the viscosity of the conductive paste, or the binder resin is not dissolved in the organic solvent. Further, in the acetate-based organic solvent, the solubility of ethyl cellulose which is generally used as a binder resin is lower than that of terpineol, and the conductive paste using the organic solvent tends to be generated over time. Viscosity change problem. Then, when the viscosity of the conductive paste changes in this manner, variations in printability occur, so that an appropriate film thickness and shape cannot be obtained at the time of printing, or an electrode having stable quality cannot be manufactured.
又，在專利文獻2中，有提議抑制導電性糊之黏度變化的方法，例如可使用乙酸萜品酯作為有機溶劑，藉以抑制黏度變化。然而，就專利文獻2之實施例中所載導電性糊而言，導電性金屬粉末之分散性低，而變得無法控制導電性糊之隨時間經過所造成的黏度變化，或黏度變化之控制不夠，因而不適合電極膜的薄層化。 Further, in Patent Document 2, there is a proposal to suppress a change in viscosity of the conductive paste. For example, a phthalic acid ester can be used as an organic solvent to suppress a change in viscosity. However, in the conductive paste contained in the example of Patent Document 2, the dispersibility of the conductive metal powder is low, and it becomes impossible to control the viscosity change caused by the passage of the conductive paste over time, or the control of the viscosity change. Not enough, so it is not suitable for thin layering of the electrode film.
此外，作為導電性糊，有提議：於黏合劑樹脂使用乙基羥基乙基纖維素，使導電性金屬粉末分散在於有機溶劑使用脂肪族醇與礦物油的有機載體上，厚度薄且均勻，而且難以引起薄片侵蝕的導電性糊(例如，參 照專利文獻3)。然而，專利文獻3中所揭示之導電性糊係雖難以引起薄片侵蝕，但黏度之隨時間變化大，會有不易獲得長期穩定之導電膜的困難。 Further, as the conductive paste, it is proposed to use ethyl hydroxyethyl cellulose as the binder resin to disperse the conductive metal powder in an organic solvent using an organic vehicle of an aliphatic alcohol and a mineral oil, and the thickness is thin and uniform, and Conductive paste that is difficult to cause sheet erosion (for example, According to patent document 3). However, the conductive paste disclosed in Patent Document 3 is less likely to cause sheet erosion, but the viscosity changes greatly with time, and it is difficult to obtain a long-term stable conductive film.
又，在專利文獻4中，有提議一種導電性糊，其係藉由組合包含作為黏合劑樹脂之疏水性乙基羥基乙基纖維素衍生物的有機載體與特定有機溶劑，而不會產生薄片侵蝕，隨時間的變化小。然而，專利文獻4中所揭示之導電性糊雖然可以改善黏度隨時間的變化，但是在生胚片變薄時，會有無法充分防止薄片侵蝕的情形。近年來，MLCC的小型化、高積體化變得更顯著，生胚片厚度亦被要求在3μm以下的薄度，即便是以習知由於片厚而不會被視為是問題的材料構成，也會發生薄片侵蝕的問題。 Further, in Patent Document 4, there is proposed a conductive paste which does not produce a sheet by combining an organic vehicle containing a hydrophobic ethylhydroxyethylcellulose derivative as a binder resin with a specific organic solvent. Erosion, small changes over time. However, although the conductive paste disclosed in Patent Document 4 can improve the change in viscosity with time, when the green sheet is thinned, there is a case where the sheet cannot be sufficiently prevented from being eroded. In recent years, the miniaturization and high integration of the MLCC have become more remarkable, and the thickness of the green sheet has been required to be thinner than 3 μm, even if it is a material that is not considered to be a problem due to the thickness of the sheet. The problem of thin sheet erosion also occurs.
又，為了提高導電性金屬粉末的分散性，亦有對導電性糊添加硬脂酸等酸系分散劑的情形(例如，參照專利文獻5)，當過度添加時，在印刷後之乾燥步驟中，會無法充分去除酸系分散劑，於積層步驟中，在將生胚片從PET薄膜剝離時，印刷乾燥後所殘留之酸系分散劑浸透至生胚片，藉由賦予可塑性，而在生胚片剝離時，會有剝離力變得過大，引起片破損等的情形。另外，透過使乾燥膜變柔軟，會有引起切斷性惡化的情形。 In addition, in order to improve the dispersibility of the conductive metal powder, an acid-based dispersant such as stearic acid may be added to the conductive paste (for example, refer to Patent Document 5), and when excessively added, in the drying step after printing In the step of laminating, when the green sheet is peeled off from the PET film, the acid-based dispersant remaining after printing and drying is impregnated into the green sheet, and the plasticity is imparted. When the green sheet is peeled off, the peeling force may become excessively large, causing the sheet to be damaged or the like. Further, when the dried film is softened, the cutability may be deteriorated.
[專利文獻1]日本專利第2976268號 [Patent Document 1] Japanese Patent No. 2976268
[專利文獻2]日本特開2006-12690號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-12690
[專利文獻3]日本特開平7-326534號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 7-326534
[專利文獻4]日本特開2011-159393號公報 [Patent Document 4] Japanese Laid-Open Patent Publication No. 2011-159393
[專利文獻5]日本特開2012-77372號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2012-77372
本發明係有鑑於如此狀況而以提供導電性糊為其課題，該導電性糊係積層陶磁裝置上所使用之導電性糊，可抑制薄片侵蝕或生胚片剝離不良，且隨時間經過所造成的黏度變化少。 The present invention has been made in view of the above circumstances, and it is a problem that the conductive paste used in the conductive paste-based ceramic device can suppress sheet erosion or poor peeling of the green sheets, and is caused by the passage of time. The viscosity changes little.
本發明者經過仔細研究開發的結果，發現到單單只是一直以來所關注的有機溶劑與黏合劑樹脂之組合，並不會是影響到薄片侵蝕或生胚片剝離不良的因子，導電性糊中之分散劑的增量才是引導至已薄膜化生胚片之薄片侵蝕或生胚片剝離不良的因子，從而完成本發明。 As a result of careful research and development, the inventors have found that the combination of the organic solvent and the binder resin which has been only concerned for a long time is not a factor that affects the erosion of the sheet or the peeling of the green sheet, and is in the conductive paste. The increase in dispersant is a factor that leads to the erosion of the thinned green sheets or the poor peeling of the green sheets, thereby completing the present invention.
亦即，本發明之一實施形態的導電性糊係包含導電性金屬粉末、陶瓷粉末、黏合劑樹脂、分散劑及有機溶劑之積層陶瓷裝置用的導電性糊，其中，該有機溶劑係包括由乙酸二氫萜品酯、乙酸異莰酯、丙酸異莰酯、丁酸異莰酯及異丁酸異莰酯所選出之至少1種，該分散劑係相對於導電性糊總量而含有超過0質量%且0.4質量%以下之酸系分散劑。 In other words, the conductive paste according to the embodiment of the present invention includes a conductive paste for a multilayer ceramic device of a conductive metal powder, a ceramic powder, a binder resin, a dispersant, and an organic solvent, wherein the organic solvent includes At least one selected from the group consisting of dihydrofurfuryl acetate, isodecyl acetate, isodecyl propionate, isodecyl butyrate, and isodecyl isobutyrate, the dispersant being contained with respect to the total amount of the conductive paste An acid-based dispersant exceeding 0% by mass and 0.4% by mass or less.
又，本發明之一實施形態的導電性糊係包含 導電性金屬粉末、陶瓷粉末、黏合劑樹脂、分散劑及有機溶劑之積層陶瓷裝置用的導電性糊，其中，該有機溶劑係包括混合溶劑，該混合溶劑係將(A)由乙酸二氫萜品酯、乙酸異莰酯、丙酸異莰酯、丁酸異莰酯及異丁酸異莰酯所選出之至少1種與(B)由乙二醇單丁基醚乙酸酯及二丙二醇甲基醚乙酸酯所選出之至少1種予以混合而成，該分散劑係相對於導電性糊總量而含有超過0質量%且0.4質量%以下之酸系分散劑。 Moreover, the conductive paste according to an embodiment of the present invention includes A conductive paste for a laminated ceramic device of a conductive metal powder, a ceramic powder, a binder resin, a dispersant, and an organic solvent, wherein the organic solvent includes a mixed solvent of (A) from indoline acetate At least one selected from ester, isodecyl acetate, isodecyl propionate, isodecyl butyrate and isodecyl isobutyrate and (B) ethylene glycol monobutyl ether acetate and dipropylene glycol At least one selected from the group consisting of methyl ether acetate is used, and the dispersant contains an acid-based dispersant in an amount of more than 0% by mass and not more than 0.4% by mass based on the total amount of the conductive paste.
又，該導電性金屬粉末係由Ni、Pd、Pt、Au、Ag、Cu及該等之合金所選出之1種金屬粉末為佳。 Further, the conductive metal powder is preferably one metal powder selected from Ni, Pd, Pt, Au, Ag, Cu, and the like.
又，該陶瓷粉末係以屬於鈣鈦礦型氧化物之鈦酸鋇(BaTiO3)為佳。 Further, the ceramic powder is preferably barium titanate (BaTiO 3 ) which is a perovskite-type oxide.
又，該陶瓷粉末係以鈣鈦礦型氧化物強介電質為佳。 Further, the ceramic powder is preferably a perovskite-type oxide ferroelectric.
又，較佳的是該積層陶瓷裝置係具有使用介電質生胚片所形成之介電質層及使用該導電性糊所形成之內部電極層，該介電質生胚片係與該陶瓷粉末為同一種。 Further, it is preferable that the laminated ceramic device has a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using the conductive paste, the dielectric green sheet system and the ceramic The powder is the same type.
又，該酸系分散劑係由具有醯胺鍵之胺基酸、碳數11以上之高級脂肪酸及該等之衍生物所選出之1種以上為佳。 Moreover, it is preferable that the acid-based dispersing agent is one or more selected from the group consisting of amino acid having a guanamine bond, a higher fatty acid having a carbon number of 11 or more, and the like.
又，該分散劑係以含有由酸系分散劑以外之陽離子系分散劑、非離子系分散劑、兩性界面活性劑及高分子系分散劑所選出之1種以上為佳。 In addition, the dispersant is preferably one or more selected from the group consisting of a cationic dispersant other than the acid dispersant, a nonionic dispersant, an amphoteric surfactant, and a polymer dispersant.
又，較佳的是該積層陶瓷裝置係具有使用介電質生胚片所形成之介電質層及使用該導電性糊所形成之內部 電極層，該介電質生胚片之厚度為3μm以下。 Further, it is preferable that the laminated ceramic device has a dielectric layer formed using a dielectric green sheet and an inner portion formed using the conductive paste. In the electrode layer, the dielectric green plate has a thickness of 3 μm or less.
本發明之導電性糊係即便是在使用於諸如由3μm以下之薄膜生胚片所構成之積層陶瓷裝置時，也可以達成抑制薄片侵蝕和生胚片之剝離不良等問題，且隨時間所造成之黏度變化少的優異效果。 When the conductive paste of the present invention is used in a laminated ceramic device composed of a thin film green sheet of 3 μm or less, problems such as suppression of sheet erosion and peeling of the green sheet can be achieved, and it is caused by time. Excellent effect with less change in viscosity.
本實施形態之導電性糊包含導電性金屬粉末、陶瓷粉末、黏合劑樹脂、分散劑及有機溶劑，為使用分散劑來使導電性金屬粉末及陶瓷粉末分散在有機溶劑中而經黏度調整過的導電性糊，可適當使用於積層陶瓷電容器等積層陶瓷裝置。另外，在本說明書中，有機溶劑係指包含於有機載體上所含有之載體用有機溶劑與調整導電性糊之黏度用的糊用有機溶劑。 The conductive paste of the present embodiment contains a conductive metal powder, a ceramic powder, a binder resin, a dispersant, and an organic solvent, and is a viscosity-adjusted product in which a conductive metal powder and a ceramic powder are dispersed in an organic solvent using a dispersant. The conductive paste can be suitably used in a laminated ceramic device such as a multilayer ceramic capacitor. In the present specification, the organic solvent refers to an organic solvent for paste containing an organic solvent for a carrier contained in an organic carrier and a viscosity for adjusting the conductive paste.
本實施形態之導電性糊係藉由對特定有機溶劑選擇適當量的酸系分散劑，而可解決薄片侵蝕或生胚片剝離不良的問題，且黏度之隨時間的變化少之容易使用的導電性糊。 In the conductive paste of the present embodiment, by selecting an appropriate amount of an acid-based dispersant for a specific organic solvent, it is possible to solve the problem of sheet erosion or poor peeling of the green sheets, and it is easy to use conductive with little change in viscosity with time. Sex paste.
本實施形態之導電性糊係含有導電性金屬粉末、陶瓷粉末、黏合劑樹脂、分散劑及有機溶劑等，(1)有機溶劑含有由乙酸二氫萜品酯、乙酸異莰酯、丙酸異莰酯、丁酸異莰酯及異丁酸異莰酯所選出之至少1種， (2)分散劑係相對於導電性糊總量而含有超過0質量%且0.4質量%以下之酸系分散劑。 The conductive paste of the present embodiment contains a conductive metal powder, a ceramic powder, a binder resin, a dispersant, an organic solvent, and the like. (1) The organic solvent contains indoline acetate, isodecyl acetate, and propionic acid. At least one selected from the group consisting of decyl ester, isodecyl butyrate and isodecyl isobutyrate, (2) The dispersant contains an acid-based dispersant in an amount of more than 0% by mass and not more than 0.4% by mass based on the total amount of the conductive paste.
以下，針對各構成要素進行詳細說明。 Hereinafter, each component will be described in detail.
1.導電性金屬粉末 Conductive metal powder
導電性金屬粉末係無特別限定，可適當選擇由Ni、Pd、Pt、Au、Ag、Cu及該等之合金所選出之1種以上的金屬粉末。其中，當考慮到導電性、耐蝕性、價格等時，鎳(Ni)粉末最佳。另外，在使用Ni粉末的情形下，為了抑制脫黏合劑處理時之黏合劑樹脂的局部熱分解所造成之激烈的氣體發生，可使用含數百ppm左右之S(硫)的Ni粉末。 The conductive metal powder is not particularly limited, and one or more metal powders selected from Ni, Pd, Pt, Au, Ag, Cu, and the like may be appropriately selected. Among them, nickel (Ni) powder is the best when considering conductivity, corrosion resistance, price, and the like. Further, in the case of using Ni powder, in order to suppress the intense gas generation caused by the local thermal decomposition of the binder resin during the debonding treatment, Ni powder containing about several ppm of S (sulfur) can be used.
隨著MLCC的小型化，為了形成更細薄之內部電極層，就提升乾燥膜之平滑性及乾燥膜密度的觀點而言，金屬粉末之粒徑係以0.05~1.0μm為佳，更佳為0.1~0.5μm。當金屬粉末之粒徑小於0.05μm時，粒子之比表面積變得過大，金屬粉末之表面活性變得過高，不僅僅是對乾燥、脫黏合劑特性有不良影響，獲得適當黏度特性也變得困難，會有在導電性糊之長期保存中產生變質之虞。又，當粒徑大於1.0μm時，將糊之塗布膜予以薄層化時之成膜性惡化，而無法獲得既定的靜電容量，或乾燥膜上平滑性不足，且金屬粉末的填充變得不夠而無法確保所期望之乾燥膜密度，所以會變得難以形成夠細薄且均勻的內部電極，故而不佳。 With the miniaturization of the MLCC, in order to form a thinner internal electrode layer, the particle diameter of the metal powder is preferably 0.05 to 1.0 μm, more preferably from the viewpoint of improving the smoothness of the dried film and the density of the dried film. 0.1~0.5μm. When the particle diameter of the metal powder is less than 0.05 μm, the specific surface area of the particles becomes excessively large, and the surface activity of the metal powder becomes too high, which not only adversely affects the characteristics of the drying and debonding agents, but also obtains appropriate viscosity characteristics. Difficulties, there will be deterioration in the long-term preservation of the conductive paste. In addition, when the particle diameter is more than 1.0 μm, the film forming property when the coating film of the paste is thinned is deteriorated, and a predetermined electrostatic capacity cannot be obtained, or the smoothness on the dried film is insufficient, and the filling of the metal powder is insufficient. However, the desired dry film density cannot be ensured, so that it becomes difficult to form a thin and uniform internal electrode, which is not preferable.
導電性糊之導電性金屬粉末的含量係以40~60質量%為佳，更佳為45~55質量%。當含量小於40質量 %，則無法獲得充分的導電性，當含量超過60質量%時，會有分散性降低的情形。 The content of the conductive metal powder of the conductive paste is preferably 40 to 60% by mass, more preferably 45 to 55% by mass. When the content is less than 40 mass When % is sufficient, sufficient conductivity cannot be obtained, and when the content exceeds 60% by mass, the dispersibility may be lowered.
2.陶瓷粉末 2. Ceramic powder
導電性糊之陶瓷粉末係無特別限定，可因應所應用之積層陶瓷裝置之種類而適當選擇。其中，較佳為使用強介電質之鈣鈦礦型氧化物，特佳為使用鈦酸鋇(BaTiO3，以下稱為BT)。 The ceramic powder of the conductive paste is not particularly limited and may be appropriately selected depending on the type of the laminated ceramic device to be applied. Among them, a perovskite-type oxide of a ferroelectric material is preferably used, and barium titanate (BaTiO 3 , hereinafter referred to as BT) is particularly preferably used.
又，導電性糊之陶瓷粉末係可使用以鈦酸鋇為主成分，以氧化物(例如，Mn、Cr、Si、Ca、Ba、Mg、V、W、Ta、Nb及一種以上的稀土類元素之氧化物)為副成分而含有之陶瓷粉末，亦可使用將鈦酸鋇(BaTiO3)之Ba原子和Ti原子以其他原子、Sn、Pb、Zr等予以取代之鈣鈦礦型氧化物強介電質之陶瓷粉。此外，導電性糊之陶瓷粉末係可使用與構成積層陶瓷裝置之生胚片的介電質陶瓷粉末相同的組成之粉末。介電質陶瓷粉末係例如可選擇ZnO、肥粒鐵、PZT、BaO、Al2O3、Bi2O3、R(稀土類元素)2O3、TiO2、Nd2O3等氧化物。 Further, as the ceramic powder of the conductive paste, barium titanate as a main component and oxides (for example, Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and one or more kinds of rare earths) can be used. The ceramic powder contained in the oxide of the element is a subcomponent, and a perovskite-type oxide in which Ba atoms and Ti atoms of barium titanate (BaTiO 3 ) are substituted with other atoms, Sn, Pb, Zr or the like can also be used. Strong dielectric ceramic powder. Further, as the ceramic powder of the conductive paste, a powder having the same composition as that of the dielectric ceramic powder constituting the green sheet of the laminated ceramic device can be used. The dielectric ceramic powder may be selected from oxides such as ZnO, ferrite iron, PZT, BaO, Al 2 O 3 , Bi 2 O 3 , R (rare earth element) 2 O 3 , TiO 2 , and Nd 2 O 3 .
陶瓷粉末之粒徑係以0.01~0.5μm之範圍為佳，更佳為0.01~0.3μm之範圍。藉由陶瓷粉末之粒徑在上述範圍，可形成夠細薄且均勻之內部電極。當陶瓷粉末之粒徑小於0.01μm時，由於粒子之比表面積變得過大，陶瓷粉末之表面活性變得過高，不僅僅是對乾燥、脫黏合劑特性有不良影響，獲得適當黏度特性也變得困難，會有在導電性糊之長期保存中產生變質之虞。另一方面，當粒徑超過0.5μm時，將導電性糊之塗布膜予以薄層化時之 成膜性惡化，而無法獲得既定的靜電容量，或乾燥膜上平滑性不足。又，陶瓷粉末的填充變得不夠而無法確保所期望之乾燥膜密度。 The particle diameter of the ceramic powder is preferably in the range of 0.01 to 0.5 μm, more preferably in the range of 0.01 to 0.3 μm. By the particle diameter of the ceramic powder being in the above range, an internal electrode which is thin and uniform can be formed. When the particle diameter of the ceramic powder is less than 0.01 μm, since the specific surface area of the particles becomes excessively large, the surface activity of the ceramic powder becomes too high, not only adversely affecting the characteristics of the drying and debonding agents, but also obtaining appropriate viscosity characteristics. If it is difficult, there will be deterioration in the long-term preservation of the conductive paste. On the other hand, when the particle diameter exceeds 0.5 μm, when the coating film of the conductive paste is thinned, The film forming property is deteriorated, and a predetermined electrostatic capacity cannot be obtained, or the smoothness on the dried film is insufficient. Moreover, the filling of the ceramic powder becomes insufficient to ensure the desired dry film density.
3.黏合劑樹脂 3. Binder resin
黏合劑樹脂係無特別限定，例如可使用將甲基纖維素、乙基纖維素、乙基羥基乙基纖維素、硝基纖維素等纖維素系樹脂、丙烯酸系樹脂、丁醛系樹脂等溶解於有機溶劑中者。其中，較佳為乙基纖維素。又，黏合劑樹脂之分子量係以20000~200000左右為佳。 The binder resin is not particularly limited, and for example, a cellulose resin such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose or nitrocellulose, an acrylic resin, a butyral resin, or the like can be used. In organic solvents. Among them, ethyl cellulose is preferred. Further, the molecular weight of the binder resin is preferably from about 20,000 to 200,000.
4.有機溶劑 4. Organic solvents
有機溶劑係作為有機載體之構成成分，可溶解黏合劑樹脂。又，有機溶劑係使導電性金屬粉末、陶瓷粉末及有機載體分散，調整導電性糊整體之黏度，使可依既定圖案印刷導電性糊。 The organic solvent is a constituent component of an organic vehicle, and the binder resin can be dissolved. Further, in the organic solvent, the conductive metal powder, the ceramic powder, and the organic vehicle are dispersed, and the viscosity of the entire conductive paste is adjusted so that the conductive paste can be printed in a predetermined pattern.
又，有機溶劑係可包括由乙酸二氫萜品酯、乙酸異莰酯、丙酸異莰酯、丁酸異莰酯及異丁酸異莰酯所選出之至少1種的乙酸酯系溶劑(A)。其中，較佳為乙酸異莰酯。此時，乙酸酯系溶劑(A)係相對於有機溶劑100重量份而可含有例如90~100重量份，較佳為100重量份。 Further, the organic solvent may include at least one acetate solvent selected from indanyl acetate, isodecyl acetate, isodecyl propionate, isodecyl butyrate, and isodecyl isobutyrate. (A). Among them, isodecyl acetate is preferred. In this case, the acetate-based solvent (A) may be, for example, 90 to 100 parts by weight, preferably 100 parts by weight, per 100 parts by weight of the organic solvent.
又，有機溶劑係可由混合溶劑所形成，該混合溶劑係將由乙酸二氫萜品酯、乙酸異莰酯、丙酸異莰酯、丁酸異莰酯及異丁酸異莰酯所選出之至少1種的乙酸酯系溶劑(A)與由乙二醇單丁基醚乙酸酯及二丙二醇甲基醚乙酸酯所選出之至少1種的乙酸酯系溶劑(B)予以混合而成。在使用此類混合溶劑時，導電性糊之黏度特性 的調整變得更容易，可加速導電性糊之乾燥速率。 Further, the organic solvent may be formed by a mixed solvent selected from at least diterpene acetate, isodecyl acetate, isodecyl propionate, isodecyl butyrate, and isodecyl isobutyrate. One type of acetate solvent (A) is mixed with at least one type of acetate solvent (B) selected from ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate. to make. Viscosity characteristics of conductive paste when using such a mixed solvent The adjustment becomes easier and accelerates the drying rate of the conductive paste.
乙酸酯系溶劑(A)係相對於有機溶劑100重量份而以含有50~90重量份為佳，更佳為60~80重量份。又，乙酸酯系溶劑(B)係相對於有機溶劑100重量份而以含有10~50重量份為佳，更佳為20~40重量份。 The acetate-based solvent (A) is preferably contained in an amount of 50 to 90 parts by weight, more preferably 60 to 80 parts by weight, per 100 parts by weight of the organic solvent. Further, the acetate-based solvent (B) is preferably contained in an amount of 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, per 100 parts by weight of the organic solvent.
又，有機溶劑中，作為載體用之有機溶劑，為了使有機載體的混合優化，較佳的是使用與調整導電性糊黏度之糊用的有機溶劑相同者。有機載體用之有機溶劑含量係相對於導電性金屬粉末100質量份而例如可含有5~30重量份。又，導電性糊用之有機溶劑含量係相對於導電性糊總量而較佳可為10~40質量%左右。 Further, in the organic solvent, as the organic solvent for the carrier, in order to optimize the mixing of the organic vehicle, it is preferred to use the same organic solvent as the paste for adjusting the conductivity of the conductive paste. The organic solvent content of the organic vehicle may be, for example, 5 to 30 parts by weight based on 100 parts by mass of the conductive metal powder. Further, the content of the organic solvent for the conductive paste is preferably about 10 to 40% by mass based on the total amount of the conductive paste.
5.分散劑 5. Dispersant
分散劑係可抑制導電性金屬粉末彼此之凝集或黏合劑樹脂與導電性金屬粉末之分離。本實施形態之導電性糊係以酸系分散劑為必要成分而含有。此處所謂的酸系分散劑係指於溶解至有機溶劑時，顯示酸性之分散劑。作為酸系分散劑，例如可列舉出高級脂肪酸或高分子界面活性劑等酸系分散劑。其中，亦以含有由具有醯胺鍵之胺基酸、碳數11以上之高級脂肪酸或該等之衍生物所選出之1種以上的酸系分散劑為佳。 The dispersant suppresses the aggregation of the conductive metal powders or the separation of the binder resin and the conductive metal powder. The conductive paste of the present embodiment is contained as an essential component of the acid-based dispersant. The acid-based dispersant herein refers to a dispersant which exhibits acidity when dissolved in an organic solvent. The acid-based dispersant may, for example, be an acid-based dispersant such as a higher fatty acid or a polymer surfactant. Among them, one or more acid-based dispersing agents selected from the group consisting of amino acids having a guanamine bond, higher fatty acids having a carbon number of 11 or more, or derivatives thereof are also preferred.
作為高級脂肪酸，可為不飽和羧酸亦可為飽和羧酸，並無特別限定，可列舉出硬脂酸、油酸、肉豆蔻酸、棕櫚酸、亞麻油酸、月桂酸、次亞麻油酸等碳數11以上者。特佳為油酸或硬脂酸。 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, myristic acid, palmitic acid, linoleic acid, lauric acid, and linoleic acid. Those with a carbon number of 11 or higher. Particularly preferred is oleic acid or stearic acid.
作為高分子界面活性劑，並無特別限定，可 列舉出由單烷基胺鹽所代表之烷基單胺鹽型、N-烷基(C14~C18)伸丙基二胺二油酸鹽所代表之烷基二胺鹽、烷基三甲基銨氯化物所代表之烷基三甲基銨鹽型、椰子烷基二甲基苄基銨氯化物所代表之烷基二甲基苄基銨鹽型、烷基/二聚氧伸乙基甲基銨氯化物所代表之4級銨鹽型、烷基吡啶鎓鹽型、二甲基硬脂基胺所代表之3級胺型、聚氧丙烯/聚氧伸乙基烷基胺所代表之聚氧伸乙基烷基胺型、N,N',N'-三(2-羥基乙基)-N-烷基(C14~C18)1,3-二胺丙烷所代表之二胺的氧乙烯加成型所選擇之陽離子系界面活性劑，其中，較佳為烷基單胺鹽型。 The polymer surfactant is not particularly limited and can be used. The alkyl diamine salt represented by the monoalkylamine salt, the alkyl diamine salt represented by the N-alkyl (C14-C18) propyl diamine dioleate, and the alkyl trimethyl group are listed. Alkyltrimethylammonium salt type represented by ammonium chloride, alkyldimethylbenzylammonium salt type represented by coconut alkyldimethylbenzylammonium chloride, alkyl/dimerized oxygen ethyl group The quaternary ammonium salt type represented by the quaternary ammonium chloride, the alkyl pyridinium salt type, the tertiary amine type represented by dimethyl stearylamine, and the polyoxypropylene/polyoxyethylidene amine Oxygen of a diamine represented by polyoxyethylene ethylaminoamine type, N, N', N'-tris(2-hydroxyethyl)-N-alkyl (C14-C18) 1,3-diamine propane The cationic surfactant selected for ethylene addition molding is preferably an alkyl monoamine salt type.
作為烷基單胺鹽型，較佳的是例如可為使用甘胺酸與油酸之化合物的油醯肌胺酸或取代油酸而使用硬脂酸或月桂酸等高級脂肪酸的醯胺化合物。 The alkyl monoamine salt type is preferably, for example, an oleoresin compound which uses a fatty acid mentenoic acid of a compound of glycine and oleic acid or a substituted fatty acid and uses a higher fatty acid such as stearic acid or lauric acid.
本實施形態所使用之有機溶劑中，於與黏合劑樹脂組合而使用時，雖會產生薄片侵蝕或生胚片剝離不良，但依以特定量含有上述酸系分散劑，則可抑制該等問題。 In the organic solvent used in the present embodiment, when used in combination with a binder resin, sheet erosion or green sheet peeling failure occurs. However, if the acid-based dispersant is contained in a specific amount, the problems can be suppressed. .
酸系分散劑係相對於導電性糊總量而含有超過0質量%且0.4質量%以下，較佳為0.1~0.4質量%，更佳為0.2~0.4質量%。藉由酸系分散劑含量為上述範圍，則可獲得充分的分散性。另一方面，當分散劑超過0.4質量%時，除了難以抑制薄片侵蝕之外，就成本面而言也不佳。 The acid-based dispersant is contained in an amount of more than 0% by mass and 0.4% by mass or less, preferably 0.1% to 0.4% by mass, more preferably 0.2% to 0.4% by mass, based on the total amount of the conductive paste. When the acid dispersant content is in the above range, sufficient dispersibility can be obtained. On the other hand, when the dispersant exceeds 0.4% by mass, it is not preferable in terms of cost in addition to the difficulty in suppressing the erosion of the sheet.
又，酸系分散劑係相對於導電性金屬粉末100質量份，較佳為含有0.2~1.0質量份，更佳為0.4~1.0質量份， 再更佳為0.5~1.0質量份。 Further, the acid-based dispersant is preferably contained in an amount of 0.2 to 1.0 part by mass, more preferably 0.4 to 1.0 part by mass, per 100 parts by mass of the conductive metal powder. More preferably, it is 0.5 to 1.0 part by mass.
分散劑係可含有由酸系分散劑以外之陽離子系分散劑、非離子系分散劑及兩性界面活性劑及高分子系分散劑所選出之1種以上。藉由含有該等分散劑，則可以導電性金屬粉末或陶瓷粉末經細微化之狀態下而使穩定分散在黏合劑樹脂和有機溶劑中。作為酸系分散劑以外之陽離子系分散劑，可使用胺鹼系分散劑，例如，可含有月桂胺、松香胺等脂肪族胺。該等分散劑係可使用1種或者是組合2種以上來使用。 The dispersing agent may contain one or more selected from the group consisting of a cationic dispersing agent other than the acid dispersing agent, a nonionic dispersing agent, an amphoteric surfactant, and a polymer dispersing agent. By containing such a dispersing agent, the conductive metal powder or the ceramic powder can be stably dispersed in the binder resin and the organic solvent in a state of being finely pulverized. As the cationic dispersant other than the acid dispersant, an amine base dispersant can be used, and for example, an aliphatic amine such as laurylamine or rosin amine can be contained. These dispersing agents can be used alone or in combination of two or more.
上述酸系分散劑以外的分散劑係相對於導電性糊整體，可為0~1.0質量%，較佳為0.1~1.0質量%，更佳為0.1~0.8質量%。當酸系分散劑以外的分散劑超過1.0重量%時，不僅是導電性糊的乾燥性惡化，就成本面而言也不佳。 The dispersing agent other than the acid-based dispersing agent may be 0 to 1.0% by mass, preferably 0.1 to 1.0% by mass, and more preferably 0.1 to 0.8% by mass based on the entire conductive paste. When the dispersing agent other than the acid-based dispersing agent exceeds 1.0% by weight, not only the drying property of the conductive paste is deteriorated, but also the cost is not preferable.
又，酸系分散劑以外的分散劑係相對於導電性金屬粉末100質量份，例如可含有0.2~2.5質量份。又，酸系分散劑以外的分散劑係相對於酸系分散劑100質量份，可含有50~300質量份左右。 In addition, the dispersing agent other than the acid-based dispersing agent may be contained in an amount of, for example, 0.2 to 2.5 parts by mass based on 100 parts by mass of the conductive metal powder. In addition, the dispersing agent other than the acid-based dispersing agent may be contained in an amount of about 50 to 300 parts by mass based on 100 parts by mass of the acid-based dispersing agent.
6.導電性糊之製造 6. Manufacture of conductive paste
本實施形態之導電性糊係可藉由準備上述各成分並以混合機加以攪拌/混練而製造出。此時，當預先將分散劑塗布在導電性金屬粉末表面時，導電性金屬粉末不會凝集而充分散開，分散劑遍及其表面，容易獲得均勻導電性糊。又，亦可使黏合劑樹脂溶解在載體用之有機溶劑中，而製作有機載體，對糊用之有機溶劑添加導電性 金屬粉末、陶瓷粉末、有機載體及分散劑，以混合機加以攪拌/混練，而製作導電性糊。 The conductive paste of the present embodiment can be produced by preparing the above components and stirring and kneading them in a mixer. At this time, when the dispersant is applied to the surface of the conductive metal powder in advance, the conductive metal powder does not aggregate and is sufficiently dispersed, and the dispersant is spread over the surface thereof, and a uniform conductive paste is easily obtained. Further, the binder resin may be dissolved in an organic solvent for the carrier to prepare an organic vehicle, and conductivity may be added to the organic solvent for the paste. The metal powder, the ceramic powder, the organic vehicle, and the dispersing agent are stirred and kneaded by a mixer to prepare a conductive paste.
本實施形態之導電性糊係可適當使用於MLCC等積層陶瓷裝置。積層陶瓷裝置係具有使用介電質生胚片所形成之介電質層及使用導電性糊所形成之內部電極層。 The conductive paste of the present embodiment can be suitably used in a laminated ceramic device such as MLCC. The laminated ceramic device has a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.
使用本實施形態之導電性糊所製造之積層陶瓷裝置較佳的是介電質生胚片中所含介電質陶瓷粉末與導電性糊中所含陶瓷粉末為相同組成之粉末。使用本實施形態之導電性糊所製造之積層陶瓷裝置係即便介電質生胚片厚度為3μm以下，亦可抑制薄片侵蝕和生胚片剝離不良。 The laminated ceramic device produced by using the conductive paste of the present embodiment is preferably a powder having the same composition as the ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste. In the multilayer ceramic device produced by using the conductive paste of the present embodiment, even if the thickness of the dielectric green sheet is 3 μm or less, sheet erosion and green sheet peeling failure can be suppressed.
以下，根據實施例與比較例來詳細說明本發明，但本發明並非限定於實施例。 Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to the examples.
[導電性糊之特性] [Characteristics of Conductive Paste]
(1)導電性糊之隨時間經過的黏度變化率 (1) Rate of change of viscosity of conductive paste over time
導電性糊之隨時間經過的黏度變化率係依下述方法在導電性糊製造後馬上測量樣本黏度及測量常溫(25℃)下靜置1天、10天、30天後之各別樣本黏度，將製造後立即測量的黏度設為基準(0%)時之各靜置後的樣本黏度之變化量依百分率(%)表示之值([(靜置1、10或30天後之黏度測量值-製造後立即測量之值)/製造後立即測量之值]×100)。另外，導電性糊之隨時間經過的黏度變化率越少越好。 The change rate of the viscosity of the conductive paste over time is measured by the following method immediately after the conductive paste is manufactured, and the viscosity of each sample after standing at room temperature (25 ° C) for 1 day, 10 days, and 30 days is measured. The viscosity of the sample after each measurement is set as the reference (0%), and the change in the viscosity of the sample after standing is expressed as a percentage (%) ([(Standard measurement after 1, 1, 10 or 30 days) Value - value measured immediately after manufacture) / value measured immediately after manufacture] × 100). In addition, the less the change rate of the viscosity of the conductive paste over time, the better.
導電性糊之黏度：使用Brookfield公司製B型黏度計 ，在10rpm(剪切速度=4sec-1)的條件下進行測量。 Viscosity of the conductive paste: Measurement was carried out under the conditions of 10 rpm (shear speed = 4 sec -1 ) using a Brookfield B-type viscometer.
(2)薄片侵蝕性 (2) thin sheet erosion
將糊印刷至2μm生胚片(鈦酸鋇(BT)，含聚乙烯基丁醛)上，(80℃，3分鐘乾燥後，其後馬上)以利用顯微鏡之背面觀察，當未確認到薄片侵蝕特有之膨潤現象時為○，如有確認到則為×。 The paste was printed on a 2 μm green sheet (barium titanate (BT), containing polyvinyl butyral) (80 ° C, dried for 3 minutes, immediately thereafter) to observe the back side of the microscope, when no sheet erosion was confirmed. The characteristic swelling phenomenon is ○, and if it is confirmed, it is ×.
(3)生胚片剝離性 (3) Green sheet peeling
將糊印刷至2μm生胚片(鈦酸鋇(BT)，含聚乙烯基丁醛)150×150mm上，在80℃、3分鐘乾燥後，利用真空吸附來剝離薄片，沒失誤的話為○，而有失誤時×。 The paste was printed on a 2 μm green sheet (barium titanate (BT), containing polyvinyl butyral) at 150 × 150 mm, and dried at 80 ° C for 3 minutes, and then the sheet was peeled off by vacuum suction, and ○ was not mistaken. And when there are mistakes ×.
[使用材料] [Use materials]
(4)導電性金屬粉末 (4) Conductive metal powder
使用鎳粉末(粒徑0.3μm)於評估所使用之導電性金屬粉末。 Nickel powder (particle size: 0.3 μm) was used to evaluate the conductive metal powder used.
(5)陶瓷粉末 (5) Ceramic powder
使用鈦酸鋇(BT)於評估所使用之陶瓷粉末。 Barium titanate (BT) was used to evaluate the ceramic powder used.
(6)有機載體 (6) Organic carrier
評估所使用之有機載體1係摻配作為黏合劑樹脂成分之乙基纖維素15質量%、作為有機溶劑之乙酸異莰酯85質量%，加熱至60℃而予以製作。 The organic vehicle 1 used for the evaluation was prepared by blending 15% by mass of ethyl cellulose as a binder resin component and 85% by mass of isodecyl acetate as an organic solvent, and heating to 60 °C.
又，有機載體2係摻配作為黏合劑樹脂成分之乙基纖維素15質量%、作為有機溶劑之萜品醇85質量%，加熱至60℃而予以製作。 Further, the organic vehicle 2 was prepared by blending 15% by mass of ethyl cellulose as a binder resin component and 85% by mass of terpineol as an organic solvent, and heating to 60 °C.
(7)分散劑 (7) Dispersant
評估所使用之分散劑係依表1所示配方製作5種混合酸系分散劑、胺鹼系(以下稱為鹼系)分散劑，使用在評 估上。 The dispersant used in the evaluation was prepared according to the formulation shown in Table 1 to prepare five kinds of mixed acid dispersant and amine base system (hereinafter referred to as alkali) dispersant. Estimated.
(8)有機溶劑 (8) Organic solvent
用於評估之有機溶劑1中使用乙酸異莰酯，於有機溶劑2中使用乙酸異莰酯與二丙二醇甲基醚基乙酸酯以50：50進行摻配者，於有機溶劑3中使用萜品醇。 Isodecyl acetate was used in the organic solvent 1 for evaluation, and isopropion acetate and dipropylene glycol methyl ether acetate were blended in the organic solvent 2 at 50:50, and the organic solvent 3 was used. Alcohol.
(實施例1) (Example 1)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之鎳粉末(Ni)47.0質量%、作為陶瓷粉末之粒徑0.06μm之鈦酸鋇(BT)11.6質量%、前述有機載體1 20.0質量%及包括酸系分散劑0.2質量%與鹼系分散劑0.4質量%的分散劑1溶解在20.8質量%之有機溶劑1中，製作導電性糊。 As shown in Table 2, 47.0 mass% of nickel powder (Ni) having a particle diameter of 0.3 μm as a conductive metal powder, 11.6 mass% of barium titanate (BT) having a particle diameter of 0.06 μm as a ceramic powder, and the organic carrier 1 described above. 20.0% by mass and a dispersing agent 1 containing 0.2% by mass of an acid-based dispersing agent and 0.4% by mass of an alkali-based dispersing agent were dissolved in 20.8% by mass of the organic solvent 1 to prepare a conductive paste.
(實施例2) (Example 2)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之鎳粉末(Ni)47.0質量%、作為陶瓷粉末之粒徑0.06μm之鈦酸鋇(BT)11.6質量%、前述有機載體1 20.0質量%及包括酸系分散劑0.3質量%與鹼系分散劑0.4質量%的分散劑2溶解在20.7質量%之有機溶劑1中，製作導電性糊。 As shown in Table 2, 47.0 mass% of nickel powder (Ni) having a particle diameter of 0.3 μm as a conductive metal powder, 11.6 mass% of barium titanate (BT) having a particle diameter of 0.06 μm as a ceramic powder, and the organic carrier 1 described above. 20.0% by mass and a dispersing agent 2 containing 0.3% by mass of an acid dispersing agent and 0.4% by mass of an alkali dispersing agent were dissolved in 20.7% by mass of the organic solvent 1 to prepare a conductive paste.
(實施例3) (Example 3)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之 鎳粉末(Ni)47.0質量%、作為陶瓷粉末之粒徑0.06μm之鈦酸鋇(BT)11.6質量%、前述有機載體1 20.0質量%及包括酸系分散劑0.4質量%與鹼系分散劑0.4質量%的分散劑3溶解在20.6質量%之有機溶劑1中，製作導電性糊。 As shown in Table 2, the particle diameter of the conductive metal powder is 0.3 μm. 47.0% by mass of nickel powder (Ni), 11.6% by mass of barium titanate (BT) having a particle diameter of 0.06 μm as a ceramic powder, 10.0% by mass of the organic vehicle, 0.4% by mass of an acid-based dispersant, and 0.4 by mass of an alkali dispersant. The mass % of the dispersing agent 3 was dissolved in 20.6% by mass of the organic solvent 1 to prepare a conductive paste.
(實施例4) (Example 4)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之鎳粉末(Ni)47.0質量%、作為陶瓷粉末之粒徑0.06μm之鈦酸鋇(BT)11.6質量%、前述有機載體1 20.0質量%及包括酸系分散劑0.2質量%與鹼系分散劑0.4質量%的分散劑1溶解在20.8質量%之有機溶劑2中，製作導電性糊。 As shown in Table 2, 47.0 mass% of nickel powder (Ni) having a particle diameter of 0.3 μm as a conductive metal powder, 11.6 mass% of barium titanate (BT) having a particle diameter of 0.06 μm as a ceramic powder, and the organic carrier 1 described above. 20.0% by mass and a dispersing agent 1 containing 0.2% by mass of the acid-based dispersing agent and 0.4% by mass of the alkali-based dispersing agent were dissolved in 20.8% by mass of the organic solvent 2 to prepare a conductive paste.
(實施例5) (Example 5)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之鎳粉末(Ni)53.3質量%、作為陶瓷粉末之粒徑0.06μm之鈦酸鋇(BT)5.3質量%、前述有機載體1 20.0質量%及包括酸系分散劑0.3質量%與鹼系分散劑0.4質量%的分散劑2溶解在20.7質量%之有機溶劑1中，製作導電性糊。 As shown in Table 2, 53.3 mass% of nickel powder (Ni) having a particle diameter of 0.3 μm as a conductive metal powder, 5.3 mass% of barium titanate (BT) having a particle diameter of 0.06 μm as a ceramic powder, and the organic carrier 1 described above 20.0% by mass and a dispersing agent 2 containing 0.3% by mass of an acid dispersing agent and 0.4% by mass of an alkali dispersing agent were dissolved in 20.7% by mass of the organic solvent 1 to prepare a conductive paste.
(實施例6) (Example 6)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之鎳粉末(Ni)47.0質量%、作為陶瓷粉末之粒徑0.06μm之鈦酸鋇(BT)11.6質量%、前述有機載體1 20.0質量%及包括酸系分散劑0.3質量%與鹼系分散劑0.8質量%的分散劑5溶解在20.3質量%之有機溶劑1中，製作導電性糊。 As shown in Table 2, 47.0 mass% of nickel powder (Ni) having a particle diameter of 0.3 μm as a conductive metal powder, 11.6 mass% of barium titanate (BT) having a particle diameter of 0.06 μm as a ceramic powder, and the organic carrier 1 described above. 20.0% by mass and a dispersing agent 5 containing 0.3% by mass of an acid-based dispersing agent and 0.8% by mass of an alkali-based dispersing agent were dissolved in 20.3% by mass of the organic solvent 1 to prepare a conductive paste.
(比較例1) (Comparative Example 1)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之鎳粉末(Ni)47.0質量%、作為陶瓷粉末之粒徑0.06μm之鈦 酸鋇(BT)11.6質量%、前述有機載體1 20.0質量%及包括酸系分散劑0.5質量%與鹼系分散劑0.4質量%的分散劑4溶解在20.5質量%之有機溶劑1中，製作導電性糊。 As shown in Table 2, nickel powder (Ni) having a particle diameter of 0.3 μm as a conductive metal powder was 47.0% by mass, and titanium having a particle diameter of 0.06 μm as a ceramic powder was used. 11.2% by mass of the strontium carbonate (BT), 10.0% by mass of the organic vehicle, and 0.5% by mass of the acid-based dispersant and 0.4% by mass of the dispersant 4 of the alkali-based dispersant were dissolved in 20.5% by mass of the organic solvent 1 to prepare a conductive material. Sex paste.
(比較例2) (Comparative Example 2)
如表2所示，將作為導電性金屬粉末之粒徑0.3μm之鎳粉末(Ni)47.0質量%、作為陶瓷粉末之粒徑0.06μm之鈦酸鋇(BT)11.6質量%、前述有機載體2 20.0質量%及包括酸系分散劑(硬脂酸)0.3質量%與鹼系分散劑(月桂胺)0.4質量%的分散劑溶解在20.7質量%之有機溶劑3中，製作導電性糊。 As shown in Table 2, 47.0 mass% of nickel powder (Ni) having a particle diameter of 0.3 μm as a conductive metal powder, 11.6 mass% of barium titanate (BT) having a particle diameter of 0.06 μm as a ceramic powder, and the organic vehicle 2 described above 20.0% by mass and a dispersing agent containing 0.3% by mass of an acid dispersing agent (stearic acid) and 0.4% by mass of an alkali dispersing agent (laurylamine) were dissolved in 20.7% by mass of the organic solvent 3 to prepare a conductive paste.
將實施例1~6及比較例1、2之組成成分示於表2，評估結果示於表3。 The constituent components of Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 2, and the evaluation results are shown in Table 3.
由以上之表示結果的表3可清楚得知，在使用本實施形態之導電性糊的實施例1~6中，隨時間所造成之黏度變化少，且沒有發生薄片侵蝕，剝離性方面也無問題。 As is clear from Table 3 which shows the results above, in Examples 1 to 6 in which the conductive paste of the present embodiment was used, the change in viscosity with time was small, and sheet erosion did not occur, and there was no peeling property. problem.
另一方面，以一直以來所使用之水準，可知分散劑量多之比較例1係未見到薄片侵蝕，但生胚片可塑化，會引起剝離不良。又，可知使用本實施形態以外之有機溶劑之比較例2的情形係即便使用適當分散劑的量，也會產生薄片侵蝕、剝離不良。 On the other hand, in the comparative example 1 which has been used conventionally, it was found that the comparative example 1 in which the amount of dispersion was large did not show sheet erosion, but the green sheets were plasticized, which caused peeling failure. Moreover, it is understood that in the case of Comparative Example 2 using an organic solvent other than the present embodiment, even if an appropriate amount of the dispersing agent is used, sheet erosion and peeling failure occur.
據上可知，藉由使用特定溶劑，控制酸系分散劑之量，則可防止薄片侵蝕、剝離不良的發生，較習知製品大幅改善。 As described above, by controlling the amount of the acid-based dispersant by using a specific solvent, it is possible to prevent the occurrence of sheet erosion and peeling failure, and the conventional product is greatly improved.
本發明之導電性糊係可抑制薄片侵蝕和生胚片剝離性，且黏度穩定性優異，尤其是適合當作行動電話或數位機器等之電子機器的屬於晶片零件之積層陶瓷電容器之內部電極用的原料。 The conductive paste of the present invention can suppress sheet erosion and green sheet peeling property, and is excellent in viscosity stability, and is particularly suitable for use as an internal electrode of a laminated ceramic capacitor belonging to a wafer part as an electronic device such as a mobile phone or a digital device. Raw materials.
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| TWI711053B (en) * | 2016-02-29 | 2020-11-21 | 日商住友金屬鑛山股份有限公司 | Conductive paste, electronic parts and multilayer ceramic capacitors |
| TWI735846B (en) * | 2018-03-29 | 2021-08-11 | 日商東邦鈦股份有限公司 | Nickel powder and its manufacturing method |
| TWI759279B (en) * | 2017-01-26 | 2022-04-01 | 日商昭和電工材料股份有限公司 | Copper paste for pressureless bonding, bonding body, method for producing the same, and semiconductor device |
| TWI798292B (en) * | 2017-05-23 | 2023-04-11 | 日商住友金屬鑛山股份有限公司 | Conductive paste, electronic parts and laminated ceramic capacitors |
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| JP2976268B2 (en) | 1993-07-05 | 1999-11-10 | 株式会社村田製作所 | Conductive paste and method for manufacturing multilayer ceramic electronic component using the same |
| JPH07326534A (en) | 1994-05-30 | 1995-12-12 | Kyocera Corp | Organic vehicle for conductive paste, and conductive paste |
| US6989110B2 (en) * | 2003-06-13 | 2006-01-24 | Murata Manufacturing Co., Ltd. | Electroconductive paste and method of producing the same |
| 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 |
| JP4487595B2 (en) * | 2004-02-27 | 2010-06-23 | Ｔｄｋ株式会社 | Method for manufacturing multilayer unit for multilayer ceramic electronic component |
| JP4145263B2 (en) * | 2004-04-13 | 2008-09-03 | 積水化学工業株式会社 | Conductive paste |
| JP3944495B2 (en) | 2004-06-28 | 2007-07-11 | Ｔｄｋ株式会社 | Conductive paste, multilayer ceramic electronic component and manufacturing method thereof |
| KR100773534B1 (en) * | 2005-07-15 | 2007-11-05 | 삼성전기주식회사 | Mixed dispersant, paste composition and dispersion process using the same |
| JP5299904B2 (en) | 2009-02-05 | 2013-09-25 | 昭栄化学工業株式会社 | Conductive paste for internal electrode of multilayer electronic component and multilayer electronic component using the same |
| JP4930808B2 (en) * | 2010-01-29 | 2012-05-16 | 住友金属鉱山株式会社 | Conductive paste |
| JP5051553B2 (en) | 2010-04-19 | 2012-10-17 | 住友金属鉱山株式会社 | Method for producing conductive paste |
| JP5556561B2 (en) | 2010-10-06 | 2014-07-23 | 住友金属鉱山株式会社 | Silver powder and method for producing 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 |
| JP2012226865A (en) | 2011-04-15 | 2012-11-15 | Sumitomo Metal Mining Co Ltd | Conductive paste composition |
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| KR102092990B1 (en) * | 2012-11-06 | 2020-03-24 | 가부시키가이샤 노리타케 캄파니 리미티드 | Conductive paste composition |
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| TWI711053B (en) * | 2016-02-29 | 2020-11-21 | 日商住友金屬鑛山股份有限公司 | Conductive paste, electronic parts and multilayer ceramic capacitors |
| TWI759279B (en) * | 2017-01-26 | 2022-04-01 | 日商昭和電工材料股份有限公司 | Copper paste for pressureless bonding, bonding body, method for producing the same, and semiconductor device |
| TWI798292B (en) * | 2017-05-23 | 2023-04-11 | 日商住友金屬鑛山股份有限公司 | Conductive paste, electronic parts and laminated ceramic capacitors |
| TWI811320B (en) * | 2018-03-28 | 2023-08-11 | 日商住友金屬鑛山股份有限公司 | Conductive paste, electronic parts, and laminated ceramic capacitors |
| TWI735846B (en) * | 2018-03-29 | 2021-08-11 | 日商東邦鈦股份有限公司 | Nickel powder and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105321711B (en) | 2018-11-16 |
| JP6531541B2 (en) | 2019-06-19 |
| KR102410080B1 (en) | 2022-06-16 |
| TWI676658B (en) | 2019-11-11 |
| JP2016035914A (en) | 2016-03-17 |
| KR20160016612A (en) | 2016-02-15 |
| CN105321711A (en) | 2016-02-10 |
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