TWI421882B - Barium titanate powder, nickel paste, preparation method and laminated ceramic capacitors - Google Patents
Barium titanate powder, nickel paste, preparation method and laminated ceramic capacitors Download PDFInfo
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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
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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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
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
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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
Description
本發明係關於一種形成積層陶瓷電容器所使用的鈦酸鋇粉末、含有此粉末之鎳糊及其製造方法、以及積層陶瓷電容器。The present invention relates to a barium titanate powder used for forming a laminated ceramic capacitor, a nickel paste containing the powder, a method for producing the same, and a multilayer ceramic capacitor.
以往積層陶瓷電容器(以下亦稱為MLCC)的內部電極係使用Pd粉末。近年來，為了降低成本，在上述電極中使用了鎳粉末。於專利文獻1中揭示有一種用於MLCC內部電極之形成材料的鎳粉末。使用鎳粉末的MLCC內部電極之一般製造方法，如以下所示。In the conventional internal electrodes of laminated ceramic capacitors (hereinafter also referred to as MLCC), Pd powder is used. In recent years, in order to reduce costs, nickel powder has been used in the above electrodes. Patent Document 1 discloses a nickel powder for forming a material of an internal electrode of an MLCC. A general manufacturing method of an MLCC internal electrode using nickel powder is as follows.
將鎳粉末、黏合劑與溶劑加以混合，將媒液中分散有鎳粉與電介質陶瓷粉末的鎳糊作為內部電極材料，藉由網板印刷等塗布於電介質陶瓷的陶瓷生片(green sheet)。接著，藉由積層壓著步驟，對陶瓷生片的多層積層體進行多層化，進行加熱壓著使其一體化。並且，在氧化性環境氣氛或惰性環境氣氛中以500℃以下進行脫黏合劑處理，裁切成既定的大小後，於還原環境氣氛中進行燒成，製造出MLCC。The nickel powder, the binder, and the solvent are mixed, and a nickel paste in which the nickel powder and the dielectric ceramic powder are dispersed in the vehicle liquid is used as an internal electrode material, and is applied to a ceramic green sheet of dielectric ceramic by screen printing or the like. Next, the multilayered layered body of the ceramic green sheets is multilayered by a lamination step, and is heated and pressed to be integrated. Then, the binder is treated at 500 ° C or lower in an oxidizing atmosphere or an inert atmosphere, cut into a predetermined size, and then fired in a reducing atmosphere to produce MLCC.
在促進MLCC的小型化、多層化以及大容量化上，內部電極的薄層化成為重要的技術。因此，當使用鎳糊製造小型、大容量的MLCC時，較佳為使用以極少塗布量燒成時裂痕或剝離不易發生、為低電阻之電極材料的鎳粉末。In order to promote miniaturization, multilayering, and large capacity of MLCC, thinning of internal electrodes has become an important technology. Therefore, when a small-sized and large-capacity MLCC is produced using a nickel paste, it is preferable to use a nickel powder which is a low-resistance electrode material when cracking or peeling occurs at a very small coating amount.
MLCC電極的薄膜化，如專利文獻1所揭示，用於形成內部電極之鎳粉末粒子的大小與其粒子形狀為球狀是重要的。在MLCC的製造步驟中，球狀微粒子會提高電極糊塗膜內的填充密度，可使薄膜電極的形成變得容易，達到不會產生裂痕或剝離的效果。尤其在專利文獻1中記載有關於鎳微粒子呈球狀，會受到糊中含有之硫的含有率影響。Thin film formation of the MLCC electrode, as disclosed in Patent Document 1, is important in that the size of the nickel powder particles for forming the internal electrode and the particle shape thereof are spherical. In the manufacturing step of the MLCC, the spherical fine particles increase the packing density in the electrode paste film, and the formation of the thin film electrode can be facilitated, and the effect of not causing cracks or peeling can be achieved. In particular, Patent Document 1 discloses that nickel fine particles are spherical and are affected by the content ratio of sulfur contained in the paste.
通常鎳粉末中只含有極微量之硫(雜質)。藉由使用一般的鎳粉末之鎳糊來形成內部電極時，於脫黏合劑步驟中，黏合劑的熱分解會因鎳粒子表面的觸媒作用被誘發，而產生黏合劑成分氣體。此時，黏合劑的熱分解會集中在鎳粒子的表面附近，因為其他的黏合劑幾乎沒分解，因此此部分分解所產生的氣體會被關在內部，使得陶瓷電介質層與鎳內部電極層之間發生擴張，造成結構缺陷。Usually, the nickel powder contains only a very small amount of sulfur (impurities). When the internal electrode is formed by using a nickel paste of a general nickel powder, in the debonding step, the thermal decomposition of the binder is induced by the catalytic action on the surface of the nickel particles to generate a binder component gas. At this time, the thermal decomposition of the binder is concentrated near the surface of the nickel particles, because the other binders are hardly decomposed, so that the gas generated by this partial decomposition is shut inside, so that the ceramic dielectric layer and the nickel internal electrode layer are The expansion occurred, causing structural defects.
另一方面，在專利文獻2、3以及4中揭示有，含有硫成分的鎳糊在MLCC製造步驟中可達到燒結延遲的效果，有助於抑制上述結構缺陷的發生。On the other hand, Patent Documents 2, 3, and 4 disclose that the nickel paste containing a sulfur component can achieve the effect of sintering retardation in the MLCC manufacturing step, and contributes to suppressing the occurrence of the above structural defects.
專利文獻1：日本特開平11-80817號公報Patent Document 1: Japanese Laid-Open Patent Publication No. 11-80817
專利文獻2：日本特開2006-24539號公報Patent Document 2: Japanese Laid-Open Patent Publication No. 2006-24539
專利文獻3：日本特開2004-244654號公報Patent Document 3: Japanese Laid-Open Patent Publication No. 2004-244654
專利文獻4：日本特開2008-223068號公報Patent Document 4: Japanese Laid-Open Patent Publication No. 2008-223068
以下驗證專利文獻2～4所揭示之添加有硫的鎳糊。The sulfur-added nickel paste disclosed in Patent Documents 2 to 4 is verified below.
首先，在專利文獻2中，於媒液(將黏合劑溶解於溶劑而成)中，分散有鎳粉，且混入有三嗪硫醇系或含有硫酸根之化合物的含硫有機化合物。例如，含有硫酸根之化合物，係含有硫酸根SO3 之脂肪族或芳香族之碳氫化合物或其鹽，具體而言為月桂硫酸鈉CH3 (CH2 )11 SO3 Na、月桂苯磺酸鈉C12 H25 C6 H4 SO3 Na等。因此，即使硫含有量只有微量，於鎳糊中混入多餘的有機成分，特別是苯等為環境負荷物質，對人體的健康或環境的影響大，即使藉由燒成使其分解，燒成後亦會以殘留碳的形態存在，此外，亦有Na以雜質的形態而對MLCC之電特性造成不良影響之虞。First, in Patent Document 2, a nickel powder is dispersed in a vehicle liquid (a binder is dissolved in a solvent), and a sulfur-containing organic compound containing a triazine thiol-based compound or a sulfate-containing compound is mixed. For example, a sulfate-containing compound is an aliphatic or aromatic hydrocarbon containing sulfate SO 3 or a salt thereof, specifically sodium lauryl sulfate CH 3 (CH 2 ) 11 SO 3 Na, laurylbenzenesulfonic acid Sodium C 12 H 25 C 6 H 4 SO 3 Na, and the like. Therefore, even if the sulfur content is only a small amount, excessive organic components are mixed into the nickel paste, and in particular, benzene or the like is an environmentally-charged substance, which has a great influence on human health or the environment, and even if it is decomposed by firing, after firing, It also exists in the form of residual carbon. In addition, Na also has an adverse effect on the electrical properties of MLCC in the form of impurities.
專利文獻3中，使用有一種硫被覆鎳粒子，該硫被覆鎳粒子，係對鎳粉末與含有特定量硫的氣體作接觸處理等，以硫或硫酸基被覆鎳粉末的表面。鎳粉末本身，雖然一般是藉由化學氣相反應法或濕式法製造，但是根據專利文獻3的硫被覆鎳粒子製法，在鎳粉末製造步驟中需要進行額外的硫被覆處理。因此，於專利文獻3的情況中，會有下述問題：為了進行硫被覆處理，故變更鎳粉末製造步驟，而使得製造裝置複雜化，難以在量產規模上生產低成本的Ni粉，且，若考慮硫被覆處理步驟中因使用硫化氫而對人體健康所造成的影響，則在裝置的作業性或安全性等會有問題。並且，在硫被覆處理步驟，使鎳粒子彼此結合、再凝集製成鎳糊，會有對薄膜之電極形成造成不良影響之虞。Patent Document 3 uses a sulfur-coated nickel particle which is a surface of a nickel powder coated with sulfur or a sulfuric acid group by contacting a nickel powder with a gas containing a specific amount of sulfur. Although the nickel powder itself is generally produced by a chemical vapor phase reaction method or a wet method, according to the sulfur-coated nickel particle method of Patent Document 3, an additional sulfur coating treatment is required in the nickel powder production step. Therefore, in the case of Patent Document 3, there is a problem in that, in order to perform the sulfur coating treatment, the nickel powder production step is changed, the manufacturing apparatus is complicated, and it is difficult to produce a low-cost Ni powder on a mass production scale, and In consideration of the effect on the human health caused by the use of hydrogen sulfide in the sulfur coating treatment step, there is a problem in the workability and safety of the device. Further, in the sulfur coating treatment step, the nickel particles are bonded to each other and then agglomerated to form a nickel paste, which may adversely affect the electrode formation of the film.
專利文獻4中的製法，是在生成鎳粉時，將硫化氫氣體導入反應裝置內來製造含有硫之含硫鎳粉。而且，為了防止所含有的硫原子氧化而脫離，例如進行有下述之表面氧化處理：藉由在使鎳粒子於氣相中、高溫下與氧化性氣體接觸後急速冷卻，以使表面瞬間氧化。然而，於專利文獻4中，若考慮使用硫化氫作為反應氣體對人體健康所造成的影響，則除了裝置的作業性或安全性會有問題外，且鎳粒子的表面氧化處理方法，由於在透過反應管的出口側接續的冷卻管使鎳粉冷卻時，藉由送入大量的空氣一口氣使表面氧化，因此難以控制鎳粒子的氧化程度，會有內部在進行氧化，而對電極形成後的MLCC之電特性造成不良影響之虞。In the method of Patent Document 4, when nickel powder is produced, hydrogen sulfide gas is introduced into a reaction apparatus to produce sulfur-containing sulfur-containing nickel powder. Further, in order to prevent the sulfur atom contained therein from being oxidized and desorbed, for example, a surface oxidation treatment is carried out in which the surface is instantly oxidized by rapidly cooling the nickel particles in contact with an oxidizing gas at a high temperature in a gas phase. . However, in Patent Document 4, in consideration of the influence of the use of hydrogen sulfide as a reaction gas on human health, in addition to problems in the workability or safety of the device, the surface oxidation treatment method of nickel particles is transmitted through When the cooling tube is connected to the outlet side of the reaction tube to cool the nickel powder, the surface is oxidized by feeding a large amount of air. Therefore, it is difficult to control the degree of oxidation of the nickel particles, and the inside is oxidized, and the counter electrode is formed. The electrical characteristics of the MLCC cause adverse effects.
本發明的目的之一，係鑑於上述課題，提供一種積層陶瓷電容器生成用鎳糊所使用的含硫之鈦酸鋇，該含硫之鈦酸鋇可抑制積層陶瓷電容器的製造階段中燒成時裂痕等的發生、提升電容器製造的產率。又，本發明之另一目的，係提供一種可抑制積層陶瓷電容器的製造階段中燒成時裂痕等的發生，高品質地形成內部電極之含有上述含硫之鈦酸鋇的鎳糊及其製造方法，並且本發明的目的，係提供一種使用含有含硫之鈦酸鋇的鎳糊所形成，具有無裂痕等缺陷之內部電極的積層陶瓷電容器。In view of the above problems, it is an object of the present invention to provide a sulfur-containing barium titanate for use in a nickel paste for forming a multilayer ceramic capacitor, which can suppress sintering in a production stage of a multilayer ceramic capacitor. The occurrence of cracks, etc., improves the yield of capacitor manufacturing. Moreover, another object of the present invention is to provide a nickel paste containing the sulfur-containing barium titanate which can form an internal electrode with high quality while suppressing the occurrence of cracks or the like during firing in the production stage of the multilayer ceramic capacitor, and the manufacture thereof. The method, and an object of the present invention, is to provide a laminated ceramic capacitor formed using a nickel paste containing sulfur-containing barium titanate and having internal electrodes free from cracks and the like.
本發明的第1形態，為一種積層陶瓷電容器的內部電極所使用之鎳糊，其含有鎳粉、黏合劑、溶劑、與鈦酸鋇粉中混有硫的含硫之鈦酸鋇。A first aspect of the present invention is a nickel paste used for an internal electrode of a multilayer ceramic capacitor, comprising nickel powder, a binder, a solvent, and sulfur-containing barium titanate mixed with sulfur in a barium titanate powder.
本發明的第2形態，為一種鎳糊，係於第1形態中，上述鈦酸鋇粉相對於上述鎳粉含有1～30重量%，且上述硫相對於上述鈦酸鋇粉含有0.01～1重量%。According to a second aspect of the present invention, in the first aspect, the barium titanate powder contains 1 to 30% by weight based on the nickel powder, and the sulfur contains 0.01 to 1 with respect to the barium titanate powder. weight%.
本發明的第3形態，為一種鎳糊，係於第1或第2形態中，上述含硫之鈦酸鋇粉之晶格常數比(c軸與a軸之比：c/a比)在1.0040～1.0100的範圍。According to a third aspect of the present invention, in the first or second aspect, the lattice constant ratio (r/axis ratio: c/a ratio) of the sulfur-containing barium titanate powder is The range of 1.0040 to 1.0100.
本發明的第4形態，為一種鎳糊，係於第1、第2或第3形態中，上述含硫之鈦酸鋇粉之鋇(Ba)與鈦(Ti)的組成比(Ba/Ti)為0.99～1.01。According to a fourth aspect of the present invention, in the first, second or third aspect, the composition ratio of Ba (Ti) to Ti (Ti) of the sulfur-containing barium titanate powder (Ba/Ti) ) is 0.99 to 1.01.
本發明的第5形態，為一種鎳糊，係於第1至4之任一形態中，上述含硫之鈦酸鋇粉具有10～100nm以下的平均粒徑，且為正方晶，含有具備高結晶性球狀的含硫之鈦酸鋇粉。According to a fifth aspect of the invention, the sulphur-containing barium titanate powder has an average particle diameter of 10 to 100 nm or less and is tetragonal or higher. Crystalline spherical sulfur-containing barium titanate powder.
本發明的第6形態，為一種添加於第1至5之任一形態之鎳糊的含硫之鈦酸鋇粉，其含有硫，具有10～100nm以下的平均粒徑，且為正方晶，具備高結晶性球狀。A sulphur-containing barium titanate powder which is added to the nickel paste of any one of the first to fifth aspects, which contains sulfur, has an average particle diameter of 10 to 100 nm or less, and is tetragonal, It has a highly crystalline spherical shape.
本發明的第7形態，為一種鎳糊之製造方法，係於溶解有黏合劑及溶劑的媒液，混入鎳粉、與鈦酸鋇粉中混合有硫的含硫之鈦酸鋇，來製造積層陶瓷電容器的內部電極形成用鎳糊。According to a seventh aspect of the present invention, in a method for producing a nickel paste, a medium containing a binder and a solvent is mixed with nickel powder and sulphur-containing barium titanate mixed with sulfur barium titanate powder to produce A nickel paste is formed for the internal electrodes of the multilayer ceramic capacitor.
本發明的第8形態，為一種積層陶瓷電容器，係將第1至5之任一形態之鎳糊塗布於陶瓷基材加以燒成，形成以鎳作為導電性元素的內部電極。According to an eighth aspect of the present invention, in the multilayer ceramic capacitor, the nickel paste of any one of the first to fifth embodiments is applied to a ceramic substrate and fired to form an internal electrode using nickel as a conductive element.
本發明人，在生成MLCC之內部電極所使用的鎳糊時，有鑒於如專利文獻3及4般直接將硫載持於鎳粉的硫添加方法會產生諸多不良情形，而得到下述見解：著眼於具有電極糊之燒結抑制效果的鈦酸鋇材料，藉由將含硫之鈦酸鋇混入於媒液，而能更進一步發揮燒結延遲效果。本發明係基於該見解而完成者，若根據本發明第1形態，由於含有鎳粉、黏合劑、溶劑、與鈦酸鋇粉中混有硫的含硫之鈦酸鋇，故可達成優異的燒結延遲效果，可充分抑制積層陶瓷電容器的製造階段中燒成時裂痕等的發生。亦即，藉由以含有硫進一步提升燒結延遲效果的含硫之鈦酸鋇的燒結延遲效果，使在MLCC的製造步驟中，糊中之鎳粒子表面的黏合劑成分熱分解與所伴隨之氣體極激烈地發生受到抑制，故可防止在燒成階段的裂痕或層剝離等結構缺陷的發生。因此，使用本形態之鎳糊，可提升積層陶瓷電容器的製造產率，可得到具有高品質之內部電極的MLCC。In the case of the nickel paste used for the internal electrodes of the MLCC, the inventors of the present invention have many problems in the sulfur addition method in which sulfur is directly supported on the nickel powder as in Patent Documents 3 and 4, and the following findings are obtained: The barium titanate material having the effect of suppressing the sintering of the electrode paste can further exhibit the sintering delay effect by mixing the sulfur-containing barium titanate into the vehicle. According to the first aspect of the present invention, the present invention is excellent in that it contains nickel powder, a binder, a solvent, and sulfur-containing sulfur-containing barium titanate mixed with barium titanate powder. The sintering delay effect can sufficiently suppress the occurrence of cracks or the like during firing in the production stage of the multilayer ceramic capacitor. That is, by the sintering delay effect of the sulfur-containing barium titanate which further enhances the sintering delay effect by containing sulfur, the binder component on the surface of the nickel particles in the paste is thermally decomposed and the accompanying gas in the manufacturing step of the MLCC. Since it is extremely intensely suppressed, it is possible to prevent occurrence of structural defects such as cracks or layer peeling during the firing stage. Therefore, by using the nickel paste of the present embodiment, the manufacturing yield of the laminated ceramic capacitor can be improved, and the MLCC having a high quality internal electrode can be obtained.
另外，根據本發明人所進行之不同鎳含有率之兩種鎳糊的介電特性驗證實驗(參照後述之實施例2及3)，使用含硫之鈦酸鋇粉的鎳糊的情況，與沒含硫的情況相比，其靜電容量值較高，可知使用含硫之鈦酸鋇粉的鎳糊可實現MLCC的高容量化。因此，使用含硫之鈦酸鋇粉的鎳糊，因達到靜電容量增大的效果，故在實現界限的靜電容量時，削減鎳的含有量成為可能，可有助於MLCC之薄膜化及低價化。Further, according to the dielectric property verification test of the two kinds of nickel pastes having different nickel contents by the present inventors (see Examples 2 and 3 described later), the case of using a nickel paste containing sulfur-containing barium titanate powder, Compared with the case where no sulfur is contained, the electrostatic capacitance value is high, and it is known that the nickel paste using the sulfur-containing barium titanate powder can increase the capacity of the MLCC. Therefore, since the nickel paste using the sulfur-containing barium titanate powder has an effect of increasing the electrostatic capacitance, it is possible to reduce the nickel content when the capacitance is limited, which contributes to the thinning and low MLCC. Price.
特別在本形態中，由於不是將硫直接載持於鎳粉，而是另外使用鈦酸鋇粉中混有硫的含硫之鈦酸鋇，因此相較於專利文獻3的情形，在鎳粉製造階段時並不會使用硫化氫氣體作為反應氣體，對人體的健康不會造成影響，可確保良好的作業性或安全性，又，相較於專利文獻4的情形，亦不會誘發鎳粒子表面氧化處理所伴隨之鎳粒子的氧化，可形成高品質的內部電極。硫的載持形態，並無特定限制，除了在鈦酸鋇粉中混合硫粉外，亦可以硫酸根的形態含有，或使其包覆於鋇粉粒子。特別是以硫酸根的形態含有時，較佳為如專利文獻2的情況，不使用如月桂硫酸鈉或月桂苯磺酸鈉等含硫酸根之化合物，而是以不會殘留苯等有機成分或Na等雜質元素的方式，在鈦酸鋇上進行硫酸根的合成。In particular, in the present embodiment, since sulfur is not directly supported on the nickel powder, but sulfur-containing sulfur-containing barium titanate is additionally used in the barium titanate powder, the nickel powder is used in comparison with the case of Patent Document 3. At the manufacturing stage, hydrogen sulfide gas is not used as the reaction gas, which does not affect the health of the human body, ensures good workability or safety, and does not induce nickel particles as compared with the case of Patent Document 4. The oxidation of the nickel particles accompanying the surface oxidation treatment can form a high quality internal electrode. The sulfur supporting form is not particularly limited, and may be contained in the form of sulfate or may be coated on the tantalum powder particles in addition to the sulfur powder mixed in the barium titanate powder. In particular, when it is contained in the form of a sulfate group, it is preferably in the case of Patent Document 2, and a sulfate-containing compound such as sodium lauryl sulfate or sodium laurylbenzenesulfonate is not used, but an organic component such as benzene or the like is not left. In the form of an impurity element such as Na, the synthesis of sulfate is carried out on barium titanate.
本發明之鎳粉，可藉由對氫氧化鎳粉(係以CVD(化學氣相成長)法、PVD(物理氣相成長)法、噴霧熱分解法及濕式化學還原法、或濕式化學法所合成)在還原環境氣氛下進行熱處理得到鎳粉之製造方法或霧化法等加以製造。鎳粉的粉形態，較佳為平均粒徑10nm～1μm者，又，不限於粒子形態，亦可使用薄片粉。並且，鎳粉除藉由上述各種製造方法得到之鎳單體粉以外，例如，亦包含添加有用以賦予鎳耐氧化性之鉻、磷、鋅、貴金屬、稀土金屬等的鎳合金材料。The nickel powder of the present invention can be obtained by using nickel hydride powder (by CVD (Chemical Vapor Growth) method, PVD (Physical Vapor Growth) method, spray pyrolysis method and wet chemical reduction method, or wet chemistry It is produced by a heat treatment in a reducing atmosphere to obtain a method for producing nickel powder, an atomization method, or the like. The powder form of the nickel powder is preferably an average particle diameter of 10 nm to 1 μm, and is not limited to the particle form, and a flake powder may also be used. In addition to the nickel monomer powder obtained by the above various production methods, the nickel powder includes, for example, a nickel alloy material to which chromium, phosphorus, zinc, a noble metal, a rare earth metal or the like which imparts oxidation resistance to nickel is added.
另外，與其說鎳粉中亦可含有製造階段所產生之雜質硫，不如說若含有微量程度，則可達成抑制樹脂成分劇烈燃燒的效果。Further, the nickel powder may not contain the impurity sulfur generated in the production stage, and if it is contained in a small amount, the effect of suppressing the intense combustion of the resin component can be achieved.
本發明之溶劑，例如可使用醇、丙酮、丙醇、乙酸乙酯、乙酸丁酯、醚、石油醚、礦油精、其他石蠟系碳氫溶劑、或丁基卡必醇、萜品醇或二氫萜品醇、丁基卡必醇醋酸酯(butyl carbitol acetate)、二氫萜品醇醋酸酯(dihydroterpineol acetate)、二酸二氫香芹酯(dihydrocarvyl acetate)、二酸香芹酯、乙酸松香酯(terpinyl acetate)、乙酸沉香酯等醋酸酯系或、丙酸二氫松香酯、丙酸二氫香芹酯、丙酸異莰酯等丙酸系溶劑、乙賽璐蘇(ethyl cellosolve)或丁賽璐蘇(butyl cellosolve)等賽璐蘇類、芳香族類、鄰苯二甲酸二乙酯、其他電極糊中可使用之溶劑皆可使用。The solvent of the present invention may, for example, be an alcohol, acetone, propanol, ethyl acetate, butyl acetate, ether, petroleum ether, mineral spirits, other paraffinic hydrocarbon solvent, or butyl carbitol, terpineol or Dihydroterpineol, butyl carbitol acetate, dihydroterpineol acetate, dihydrocarvyl acetate, celery acetate, acetic acid Acetate or other esters such as terpinyl acetate or benzoic acid ester, propionic acid solvent such as dihydrogen rosinate propionate, dihydrocarvyl propionate or isodecyl propionate, ethyl cellosolve Or solvents such as butyl cellosolve, such as sulphide, aromatics, diethyl phthalate, and other electrode pastes can be used.
本發明之黏合劑，較佳為樹脂結合劑，例如乙基纖維素、聚乙烯縮醛、丙烯酸樹脂、醇酸樹脂等，其他電極塗料所使用的樹脂皆包含在內。The binder of the present invention is preferably a resin binder such as ethyl cellulose, polyvinyl acetal, acrylic resin, alkyd resin or the like, and resins used for other electrode coatings are included.
根據本發明的第2形態，前述鈦酸鋇粉相對於前述鎳粉含有1～30重量%，且前述硫相對於前述鈦酸鋇粉含有0.01～1重量%，因此可充分發揮電極糊的燒結延遲效果，以極少的電極塗布量可實現具備高品質之內部電極的小型、大容量之MLCC。According to a second aspect of the present invention, the barium titanate powder is contained in an amount of 1 to 30% by weight based on the nickel powder, and the sulfur is contained in an amount of 0.01 to 1% by weight based on the barium titanate powder. Therefore, the electrode paste can be sufficiently sintered. The retardation effect enables a small, large-capacity MLCC with high-quality internal electrodes with a very small amount of electrode coating.
本發明之鎳糊中所含有的含硫之鈦酸鋇粉，可使用具備通常之結晶性的鈦酸鋇材料，施加上硫便可使用，特別是較佳為使用具備高結晶性之鈦酸鋇材料。亦即，根據本發明第3形態，由於添加晶格常數比(c軸與a軸之比：c/a比)在1.0040～1.0100範圍之高結晶性的含硫之鈦酸鋇粉，因此可實現充分發揮電極糊的燒結延遲效果之鎳糊。The sulfur-containing barium titanate powder contained in the nickel paste of the present invention can be used by using a barium titanate material having a usual crystallinity, and sulfur can be used. Particularly, it is preferable to use a titanic acid having high crystallinity.钡 material. In other words, according to the third aspect of the present invention, since the crystallized sulphur-containing barium titanate powder having a lattice constant ratio (r/axis ratio: c/a ratio) of 1.040 to 1.0100 is added, it is possible to A nickel paste that fully exerts the sintering delay effect of the electrode paste.
根據本發明的第4形態，由於添加鋇(Ba)與鈦(Ti)之組成比(Ba/Ti)為0.99～1.01的前述含硫之鈦酸鋇粉，因此可實現充分發揮電極糊的燒結延遲效果之鎳糊。According to the fourth aspect of the present invention, since the sulfur-containing barium titanate powder having a composition ratio (Ba/Ti) of cerium (Ba) to titanium (Ti) of 0.99 to 1.01 is added, sintering of the electrode paste can be sufficiently exhibited. Delayed effect of nickel paste.
根據本發明的第5形態，由於添加具有10～100nm以下之平均粒徑且為正方晶、具備高結晶性球狀的前述含硫之鈦酸鋇粉，因此可實現充分發揮電極糊的燒結延遲效果之鎳糊。According to the fifth aspect of the present invention, since the sulfur-containing barium titanate powder having an average particle diameter of 10 to 100 nm or less and having a tetragonal crystal and having a high crystal spherical shape is added, the sintering delay of the electrode paste can be sufficiently exhibited. The effect of nickel paste.
根據本發明的第6形態，可提供一種含有硫、具有10～100nm以下之平均粒徑且為正方晶、具備高結晶性球狀、適用於形成高品質MLCC內部電極的含硫之鈦酸鋇粉。According to the sixth aspect of the present invention, it is possible to provide a sulfur-containing barium titanate which contains sulfur, has an average particle diameter of 10 to 100 nm or less, is tetragonal, has a highly crystalline spherical shape, and is suitable for forming a high-quality MLCC internal electrode. powder.
根據本發明的第7形態，由於在上述媒液中混入鎳粉與含硫之鈦酸鋇，製造MLCC之內部電極形成用鎳糊，因此可藉由前述含硫之鈦酸鋇優異的燒結延遲效果，使燒成時不會發生裂痕等缺陷，提升MLCC的製造產率，可簡單且低價格地製造具有高品質內部電極之小型、大容量的MLCC。According to the seventh aspect of the present invention, since nickel powder and sulfur-containing barium titanate are mixed in the vehicle liquid to produce a nickel paste for internal electrode formation of MLCC, the sintering delay of the sulfur-containing barium titanate can be excellent. The effect is that defects such as cracks do not occur at the time of firing, and the manufacturing yield of the MLCC is improved, and a small-sized and large-capacity MLCC having a high-quality internal electrode can be manufactured simply and at low cost.
將第1～第6形態中任一形態之鎳糊塗布於陶瓷基材，加以燒成，以形成內部電極，因此可實現不含有燒成時之裂痕等缺陷的積層陶瓷電容器。The nickel paste of any one of the first to sixth aspects is applied to a ceramic substrate and fired to form an internal electrode. Therefore, a multilayer ceramic capacitor which does not contain defects such as cracks during firing can be realized.
以下說明本發明之實施形態的含硫之鈦酸鋇。Hereinafter, the sulfur-containing barium titanate of the embodiment of the present invention will be described.
測量鈦酸鋇(BaTiO3 )中添加有硫的含硫之鈦酸鋇粉及添加有該含硫之鈦酸鋇的鈦酸鋇糊的各種物性，檢驗糊材料之有效性(耐熱性與收縮抑制性)。製作使用100nm尺寸的鈦酸鋇粉、硫相對鈦酸鋇粉含有0.1重量%者(BT2)作為含硫之鈦酸鋇試樣。為了比較，製作相同粒徑100nm尺寸的不含硫之鈦酸鋇試樣(BT1)。Measuring the various physical properties of sulphur-containing strontium titanate powder added with barium titanate (BaTiO 3 ) and titanate paste added with the sulphur-containing barium titanate, and testing the effectiveness of the paste material (heat resistance and shrinkage) Inhibitory). A sulphur-containing barium titanate sample containing 0.1% by weight of sulphur relative to barium titanate powder (BT2) was prepared using 100 nm-sized barium titanate powder. For comparison, a sulfur-free barium titanate sample (BT1) having the same particle diameter of 100 nm was produced.
圖1係顯示BT1之SEM(掃描型電子顯微鏡)照片。圖1之(1A)顯示放大10/3倍的同圖(1B)。圖2係顯示BT2之SEM照片。圖2之(2A)顯示放大10/3倍的同圖(2B)。不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的比表面積各為13.9m2 /g，1次粒徑相同，不會因粒子大小的不同而有不同的燒結延遲效果。Fig. 1 is a SEM (Scanning Electron Microscope) photograph showing BT1. (1A) of Fig. 1 shows the same figure (1B) magnified 10/3 times. Figure 2 shows an SEM photograph of BT2. (2A) of Fig. 2 shows the same figure (2B) magnified 10/3 times. The sulfur-free barium titanate BT1 and the sulfur-containing barium titanate BT2 each have a specific surface area of 13.9 m 2 /g, and the primary particle diameter is the same, and there is no difference in sintering delay effect depending on the particle size.
圖3係不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的粒度分布圖，同圖(3A)、(3B)分別顯示BT1、BT2的粒度分布。橫軸、縱軸分別顯示粒徑(μm)、體積頻率(%)。圖4分別表示不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的個數分布、體積分布資料。粒度分布係使用市售之粒度分布測量機。個數分布資料之中，ave.係表示平均粒徑(μm)，CV值係以下式表示。3 is a particle size distribution diagram of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2, and the particle size distributions of BT1 and BT2 are shown in the same figures (3A) and (3B), respectively. The horizontal axis and the vertical axis show the particle diameter (μm) and the volume frequency (%), respectively. Fig. 4 shows the number distribution and volume distribution data of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2, respectively. The particle size distribution uses a commercially available particle size distribution measuring machine. Among the number distribution data, ave. indicates the average particle diameter (μm), and the CV value is expressed by the following formula.
CV值=((標準差σ)/(算術徑))×100CV value = ((standard deviation σ) / (arithmetic diameter)) × 100
又，使用基於體積基準分布算出粒徑分布的軟體，求出下述體積分布值(SPAN)。Further, a soft body having a particle size distribution calculated based on the volume reference distribution was used, and the following volume distribution value (SPAN) was obtained.
SPAN=(D90-D10)/D50SPAN=(D90-D10)/D50
其中，粒徑分布，D10指此值以下之粒子的比率為10%之粒徑(μm)，D50指粒子的50%比此值大、50%比此值小之粒徑(μm)，D90指此值以下之粒子的比率為90%之粒徑(μm)。從粒度分布的結果，無法確認含有硫是否會影響鈦酸鋇粉的凝集，當含有硫時，即使與不含硫之鈦酸鋇相比較，亦為分散性(具有無粗大粒子之均一的粒度分布)非常優異的鈦酸鋇粉。Wherein, the particle size distribution, D10 means that the ratio of the particles below this value is 10% of the particle diameter (μm), D50 means that 50% of the particles are larger than this value, and 50% is smaller than this value (μm), D90 The ratio of the particles below this value is 90% of the particle diameter (μm). From the results of the particle size distribution, it was not confirmed whether the sulfur content affected the aggregation of the barium titanate powder, and when it contained sulfur, it was dispersible even when compared with the barium titanate containing no sulfur (having a uniform particle size without coarse particles). Distribution) Very excellent barium titanate powder.
圖5係顯示不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的TMA(熱機械測量裝置)測量結果。TMA測量係於含有2%H2 之氮氣中進行。圖5的橫軸、縱軸分別表示溫度(℃)、長度變化率(%)。由TMA測量結果可知，若比較不含硫之鈦酸鋇BT1與含硫之鈦酸鋇BT2，則含硫之鈦酸鋇BT2比不含硫的BT1在燒結延遲效果上較為優異。Fig. 5 shows the results of TMA (thermomechanical measuring device) measurement of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2. The TMA measurement was carried out in nitrogen containing 2% H 2 . The horizontal axis and the vertical axis of Fig. 5 indicate temperature (°C) and length change rate (%), respectively. From the measurement results of TMA, it is understood that if sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2 are compared, sulfur-containing barium titanate BT2 is superior in sintering delay effect to sulfur-free BT1.
圖6係顯示不含硫之鈦酸鋇BT1與含硫之鈦酸鋇BT2的X光繞射結果。同圖(6A)、(6B)，分別顯示試樣BT1、BT2的X光繞射圖案、波峰。Fig. 6 is a graph showing X-ray diffraction results of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2. The X-ray diffraction patterns and peaks of the samples BT1 and BT2 are shown in the same figures (6A) and (6B), respectively.
圖7係顯示以MLCC模型印刷試樣BT1、BT2(係將不含硫之鈦酸鋇BT1與含硫之鈦酸鋇BT2糊化時的試樣)並使其乾燥時的表面粗糙度測量結果(Ra、Rmax)。糊化，係將試樣BT1、BT2投入混合有乙基纖維素粉末、電極糊用分散劑、萜品醇之媒液，藉由珠磨機(bead mill)進行分散處理。BT1的情形，Ra為0.019μm，Rmax為0.445μm。BT2的情形，Ra為0.015μm，Rmax為0.333μm。經糊化之試樣的表面粗度非常平滑，分散性上亦無明顯差異而相當優異，適合使用於薄膜電極上。7 is a graph showing surface roughness measurement results when the samples BT1 and BT2 (the samples obtained by gelatinizing the sulfur-free barium titanate BT1 and the sulfur-containing barium titanate BT2) are dried and dried by the MLCC model. (Ra, Rmax). In the gelatinization, the samples BT1 and BT2 were mixed with an ethyl cellulose powder, a dispersing agent for an electrode paste, and a vehicle liquid of terpineol, and subjected to dispersion treatment by a bead mill. In the case of BT1, Ra was 0.019 μm and Rmax was 0.445 μm. In the case of BT2, Ra was 0.015 μm and Rmax was 0.333 μm. The surface of the gelatinized sample is very smooth and has excellent dispersibility and is excellent, and is suitable for use on a thin film electrode.
由圖5之TMA測量結果可知，含硫之鈦酸鋇的耐熱性，亦即收縮抑制效果優異，可作為有助於MLCC之良好容量特性的鎳糊材料來使用。As is clear from the measurement results of TMA of FIG. 5, the sulfur-containing barium titanate has excellent heat resistance, that is, a shrinkage suppressing effect, and can be used as a nickel paste material which contributes to good capacity characteristics of MLCC.
以下表示含有含硫之鈦酸鋇的鎳糊及使用此鎳糊之MLCC的實施例。The following shows an example of a nickel paste containing sulfur-containing barium titanate and an MLCC using the nickel paste.
＜實施例1＞<Example 1>
鎳糊組成，係由以下成分所構成：平均粒徑0.2μm之鎳粉30重量%，平均粒徑100nm之含硫的高結晶鈦酸鋇粉或僅由不含硫之鈦酸鋇陶瓷所構成的高結晶鈦酸鋇粉6.0重量%(相對鎳粉為20重量%)，樹脂固體成分(乙基纖維素粉末)7.0重量%，電極糊用分散劑0.5重量%，溶劑(萜品醇系溶劑)56.5重量%。以3支陶瓷輥對此等成分進行分散處理混合，製作出2種(不含硫之M11、含硫之M12)鎳糊。並且，將鎳糊M11、M12以電極圖案的樣子印刷於鈦酸鋇陶瓷片(厚度：約4.0μm)，積層20層，製得MLCC試樣。對於高結晶鈦酸鋇粉，較佳為使用晶格常數比(c軸與a軸之比：c/a比)為1.0040～1.0100範圍之鈦酸鋇材料。又，對於鈦酸鋇粉，較佳為使用鋇(Ba)與鈦(Ti)之組成比(Ba/Ti)為0.99～1.01的鈦酸鋇材料。The nickel paste composition is composed of the following components: 30% by weight of nickel powder having an average particle diameter of 0.2 μm, a sulfur-containing high-crystalline barium titanate powder having an average particle diameter of 100 nm, or only composed of a sulfur-free barium titanate ceramic. High crystalline barium titanate powder 6.0% by weight (20% by weight relative to nickel powder), resin solid content (ethyl cellulose powder) 7.0% by weight, electrode paste dispersant 0.5% by weight, solvent (terpineol solvent) ) 56.5 wt%. These components were dispersed and mixed by three ceramic rolls to prepare two kinds of (M11, sulfur-free M12) nickel paste. Further, the nickel pastes M11 and M12 were printed on a barium titanate ceramic sheet (thickness: about 4.0 μm) in the form of an electrode pattern, and 20 layers were laminated to obtain an MLCC sample. For the high-crystalline barium titanate powder, a barium titanate material having a lattice constant ratio (r-axis to a-axis ratio: c/a ratio) of 1.040 to 1.0100 is preferably used. Further, as the barium titanate powder, a barium titanate material having a composition ratio (Ba/Ti) of barium (Ba) to titanium (Ti) of 0.99 to 1.01 is preferably used.
另，鎳糊M11、M12各別的無機含有率為36.0%、35.9%，又各鎳含有率為30.0%、29.9%。Further, the inorganic content of each of the nickel pastes M11 and M12 was 36.0% and 35.9%, and the respective nickel contents were 30.0% and 29.9%.
圖8係顯示使用鎳糊M11、M12製作之MLCC試樣的截面結構照片。圖8之(8A)、(8B)係顯示使用鎳糊M11製作之MLCC試樣的截面結構照片，(8A)顯示放大2倍的(8B)。圖8之(8C)、(8D)係顯示使用鎳糊M12製作之MLCC試樣的截面結構照片，(8C)顯示放大2倍的(8D)。MLCC試樣的燒成條件，係於含有3%H2 之氮氣環境氣氛中以1230℃進行2小時的再氧化處理，然後於氮氣環境氣氛下以1000℃進行3小時的再氧化處理。Fig. 8 is a photograph showing a cross-sectional structure of an MLCC sample produced using nickel pastes M11 and M12. (8A) and (8B) of Fig. 8 show a photograph of the cross-sectional structure of the MLCC sample produced using the nickel paste M11, and (8A) shows (8B) which is magnified twice. (8C) and (8D) of Fig. 8 show a photograph of the cross-sectional structure of the MLCC sample prepared using the nickel paste M12, and (8C) shows a magnification of (8D) twice. The firing conditions of the MLCC sample were reoxidized at 1230 ° C for 2 hours in a nitrogen atmosphere containing 3% H 2 , and then reoxidized at 1000 ° C for 3 hours in a nitrogen atmosphere.
圖9及圖10，係顯示使用鎳糊M11、M12製作之MLCC試樣的各電特性測量結果。圖9之(9A)、(9B)分別顯示靜電容量、絕緣電阻值，圖10之(10A)、(10B)分別顯示損失係數、直流破壞電壓值。Fig. 9 and Fig. 10 show measurement results of electrical characteristics of MLCC samples prepared using nickel pastes M11 and M12. (9A) and (9B) of Fig. 9 show the electrostatic capacitance and the insulation resistance value, respectively, and (10A) and (10B) of Fig. 10 respectively show the loss coefficient and the DC breakdown voltage value.
若根據實施例1，關於MLCC的靜電容量，在有含硫與不含硫的情形下具有顯著的差異。亦即，使用含硫之鈦酸鋇粉之鎳糊M12的情形，其靜電容量相較於使用不含硫之鈦酸鋇粉之鎳糊M11的情形，平均約高6%。因此，藉由使用具有含硫之鈦酸鋇粉的鎳糊，對於既定容量值，可削減陶瓷片的積層數，且可藉由減低原材料成本而提供便宜的MLCC製品。又，若使用含硫之鈦酸鋇粉，則可實現結構缺陷非常少、小型且大容量之MLCC。According to Example 1, regarding the electrostatic capacity of the MLCC, there is a significant difference in the case of having sulfur and sulfur. That is, in the case of using the nickel paste M12 of the sulfur-containing barium titanate powder, the electrostatic capacity is about 6% higher than that of the nickel paste M11 using the sulfur-free barium titanate powder. Therefore, by using a nickel paste having sulfur-containing barium titanate powder, the number of layers of the ceramic sheets can be reduced for a predetermined capacity value, and an inexpensive MLCC product can be provided by reducing the cost of raw materials. Further, when sulfur-containing barium titanate powder is used, it is possible to realize a MLCC having a small structural defect and a small size and a large capacity.
在實施例1中，使用鎳糊M11、M12之MLCC試樣，每單位面積之鎳附著量(mg/cm2 )分別為0.61、0.62。鎳附著量係基於燒成後之重量值，考慮鎳含有率而求出。因此，雖然鎳附著量在任一之鎳糊中並沒有變化，但電極的連續性，係使用含硫之鈦酸鋇粉之鎳糊的情況較優異，由此亦可知使用具有含硫之鈦酸鋇粉之鎳糊的MLCC，其容量特性較佳。In Example 1, the MLCC samples of the nickel pastes M11 and M12 were used, and the amount of nickel adhesion per unit area (mg/cm 2 ) was 0.61 and 0.62, respectively. The nickel adhesion amount is determined based on the weight value after firing and considering the nickel content. Therefore, although the nickel adhesion amount does not change in any of the nickel pastes, the continuity of the electrodes is excellent in the case of using a nickel paste containing sulfur-containing barium titanate powder, and thus it is also known to use a sulfuric acid-containing titanic acid. The MLCC of the powdered nickel paste has better capacity characteristics.
接著說明經調整鎳糊之無機含有率及鎳含有率的實施例2及3。Next, Examples 2 and 3 of the inorganic content and the nickel content of the adjusted nickel paste will be described.
＜實施例2＞<Example 2>
鎳糊組成係由以下成分所構成：平均粒徑0.2μm之鎳粉35.0重量%，平均粒徑100nm之含硫的高結晶鈦酸鋇粉或僅由不含硫之鈦酸鋇陶瓷所構成之高結晶鈦酸鋇粉7.0重量%(相對鎳粉為20重量%)，樹脂固體成分(乙基纖維素粉末)5.3重量%，電極糊用分散劑0.5重量%，溶劑(萜品醇系溶劑)52.2重量%。以3支陶瓷輥對此等成分進行分散處理混合，製作出2種(不含硫之M21，含硫之M22)鎳糊。並且，將鎳糊M21、M22以電極圖案的樣子印刷於鈦酸鋇陶瓷片(厚度：約4.0μm)，積層10層，製得MLCC試樣。對於高結晶鈦酸鋇粉，較佳為使用晶格常數比(c軸與a軸之比：c/a比)為1.0040～1.0100範圍之鈦酸鋇材料。又，對於鈦酸鋇粉，較佳為使用鋇(Ba)與鈦(Ti)之組成比(Ba/Ti)為0.99～1.01之鈦酸鋇材料。另，鎳糊M21、M22各別的無機含有率為42.12%、42.10%，又各鎳含有率為35.13%、35.08%。The nickel paste composition is composed of the following components: 35.0% by weight of nickel powder having an average particle diameter of 0.2 μm, a sulfur-containing high-crystalline barium titanate powder having an average particle diameter of 100 nm, or a ceramic containing only sulfur-free barium titanate. High crystalline barium titanate powder 7.0% by weight (20% by weight relative to nickel powder), resin solid content (ethyl cellulose powder) 5.3% by weight, electrode paste dispersant 0.5% by weight, solvent (terpineol solvent) 52.2% by weight. These components were dispersed and mixed by three ceramic rolls to prepare two kinds of (M22, sulfur-free M22) nickel paste. Further, the nickel pastes M21 and M22 were printed on a barium titanate ceramic sheet (thickness: about 4.0 μm) in the form of an electrode pattern, and 10 layers were laminated to obtain an MLCC sample. For the high-crystalline barium titanate powder, a barium titanate material having a lattice constant ratio (r-axis to a-axis ratio: c/a ratio) of 1.040 to 1.0100 is preferably used. Further, as the barium titanate powder, a barium titanate material having a composition ratio (Ba/Ti) of barium (Ba) to titanium (Ti) of 0.99 to 1.01 is preferably used. Further, the inorganic content of each of the nickel pastes M21 and M22 was 42.12% and 42.10%, and the respective nickel contents were 35.13% and 35.08%.
圖11係顯示使用鎳糊M21、M22製作之MLCC試樣的截面結構照片。圖11之(11A)、(11B)係顯示使用鎳糊M21製作之MLCC試樣的截面結構照片，(11A)顯示放大2倍的(11B)。圖11之(11C)、(11D)係顯示使用鎳糊M22製作之MLCC試樣的截面結構照片，(11C)顯示放大2倍的(11D)。使用鎳糊M21、M22之MLCC試樣的燒成條件，與鎳糊M11、M12相同。Fig. 11 is a photograph showing a cross-sectional structure of an MLCC sample produced using nickel pastes M21 and M22. (11A) and (11B) of Fig. 11 show a photograph of the cross-sectional structure of the MLCC sample produced using the nickel paste M21, and (11A) shows (11B) which is magnified twice. (11C) and (11D) of Fig. 11 show a photograph of the cross-sectional structure of the MLCC sample produced using the nickel paste M22, and (11C) shows a magnification of (11D) twice. The firing conditions of the MLCC samples using the nickel pastes M21 and M22 were the same as those of the nickel pastes M11 and M12.
圖12係顯示使用鎳糊M21、M22製作之MLCC試樣的各電特性測量結果。圖12之(12A)、(12B)、(12C)及(12D)分別表示靜電容量、絕緣電阻值、損失係數、直流破壞電壓值。Fig. 12 is a graph showing measurement results of electrical characteristics of MLCC samples prepared using nickel pastes M21 and M22. (12A), (12B), (12C), and (12D) of Fig. 12 indicate electrostatic capacitance, insulation resistance value, loss coefficient, and DC breakdown voltage value, respectively.
＜實施例3＞<Example 3>
鎳糊組成係由以下成分所構成：平均粒徑0.2μm之鎳粉37.5重量%，平均粒徑100nm之含硫的高結晶鈦酸鋇粉或僅由不含硫之鈦酸鋇陶瓷所構成之高結晶鈦酸鋇粉7.5重量%(相對鎳粉為20重量%)，樹脂固體成分(乙基纖維素粉末)4.3重量%，電極糊用分散劑0.5重量%，溶劑(萜品醇系溶劑)50.2重量%。以3支陶瓷輥對此等成分進行分散處理混合，製作出2種(不含硫之M31，含硫之M32)鎳糊。並且，將鎳糊M31、M32以電極圖案的樣子印刷於鈦酸鋇陶瓷片(厚度：約4.0μm)，積層10層，製得MLCC試樣。對於高結晶鈦酸鋇粉，較佳為使用晶格常數比(c軸與a軸之比：c/a比)為1.0040～1.0100範圍之鈦酸鋇材料。又，對於鈦酸鋇粉，較佳為使用鋇(Ba)與鈦(Ti)之組成比(Ba/Ti)為0.99～1.01之鈦酸鋇材料。另，鎳糊M31、M32各別的無機含有率為45.09%、45.00%，又各鎳含有率為37.58%、37.50%。The nickel paste composition is composed of the following components: a zinc powder having an average particle diameter of 0.2 μm, 37.5% by weight, a sulfur-containing high-crystalline barium titanate powder having an average particle diameter of 100 nm, or a ceramic containing only sulfur-free barium titanate. High crystalline barium titanate powder 7.5% by weight (20% by weight relative to nickel powder), resin solid content (ethyl cellulose powder) 4.3% by weight, electrode paste dispersant 0.5% by weight, solvent (terpineol solvent) 50.2% by weight. These components were dispersed and mixed by three ceramic rolls to prepare two kinds of (M1, sulfur-free M32) nickel paste. Further, the nickel pastes M31 and M32 were printed on a barium titanate ceramic sheet (thickness: about 4.0 μm) in the form of an electrode pattern, and 10 layers were laminated to obtain an MLCC sample. For the high-crystalline barium titanate powder, a barium titanate material having a lattice constant ratio (r-axis to a-axis ratio: c/a ratio) of 1.040 to 1.0100 is preferably used. Further, as the barium titanate powder, a barium titanate material having a composition ratio (Ba/Ti) of barium (Ba) to titanium (Ti) of 0.99 to 1.01 is preferably used. Further, the inorganic content of each of the nickel pastes M31 and M32 was 45.09% and 45.00%, and the respective nickel contents were 37.58% and 37.50%.
圖13係顯示使用鎳糊M31、M32製作之MLCC試樣的SEM照片。圖13之(13A)、(13B)係顯示使用鎳糊M31製作之MLCC試樣的截面結構照片，(13A)顯示放大2倍的(13B)。圖13之(13C)、(13D)係顯示使用鎳糊M32製作之MLCC試樣的截面結構照片，(13C)顯示放大2倍的(13D)。使用鎳糊M31、M32之MLCC試樣的燒成條件，與鎳糊M11、M12相同。Fig. 13 is a SEM photograph showing an MLCC sample prepared using nickel pastes M31 and M32. (13A) and (13B) of Fig. 13 show a photograph of the cross-sectional structure of the MLCC sample produced using the nickel paste M31, and (13A) shows (13B) which is magnified twice. (13C) and (13D) of Fig. 13 show a photograph of the cross-sectional structure of the MLCC sample prepared using the nickel paste M32, and (13C) shows a magnification of (13D) twice. The firing conditions of the MLCC samples using the nickel pastes M31 and M32 were the same as those of the nickel pastes M11 and M12.
圖14係顯示使用鎳糊M31、M32製作之MLCC試樣的各電特性測量結果。圖14之(14A)、(14B)、(14C)及(14D)分別表示靜電容量、絕緣電阻值、損失係數、直流破壞電壓值。Fig. 14 is a graph showing measurement results of electrical characteristics of MLCC samples prepared using nickel pastes M31 and M32. (14A), (14B), (14C), and (14D) of Fig. 14 respectively indicate electrostatic capacitance, insulation resistance value, loss coefficient, and DC breakdown voltage value.
於實施例2及實施例3，使用鎳糊M21、M22、M31及M32的MLCC試樣，每單位面積之鎳附著量(mg/cm2 )分別為0.546、0.540、0.596、0.583。鎳附著量係基於印刷後的重量值，考慮鎳含有率而求得。對應於鎳粉的Ni含有量的差異(35.0重量%、37.5重量%)，Ni含有率大的鎳糊(M31、M32)，相較於鎳糊(M21、M22)，鎳附著量變得較多。因此，無論鈦酸鋇粉有無含硫，皆可藉由鎳含有率來控制鎳附著量。In Example 2 and Example 3, the MLCC samples of the nickel pastes M21, M22, M31 and M32 were used, and the nickel adhesion amount per unit area (mg/cm 2 ) was 0.546, 0.540, 0.596, and 0.583, respectively. The nickel adhesion amount is determined based on the weight value after printing and considering the nickel content. Corresponding to the difference in the Ni content of the nickel powder (35.0% by weight, 37.5% by weight), the nickel paste (M31, M32) having a large Ni content, and the nickel adhesion amount are more than those of the nickel paste (M21, M22). . Therefore, regardless of the presence or absence of sulfur in the barium titanate powder, the nickel adhesion rate can be controlled by the nickel content.
針對鎳含有率不同之2種鎳糊，若以有無含硫的觀點來看，使用含硫之鈦酸鋇粉之鎳糊的情形(M22、M32)，與不含硫的情形(M21、M31)相比，靜電容量較高，可知使用含硫之鈦酸鋇粉之鎳糊有助於MLCC的高容量化。因此，於使用含硫之鈦酸鋇粉之鎳糊的情形(M22、M32)，藉由燒結延遲效果可大幅縮減結構缺陷，且與不含硫的情形(M21、M31)相比，因靜電容量提升，故在實現界限的靜電容量時，可削減鎳含有量，於MLCC之高品質化、薄膜化及低價化之中，使用含硫之鈦酸鋇粉更加有效果。For the two kinds of nickel pastes with different nickel contents, in the case of the presence or absence of sulfur, the case of using the sulfur paste of the barium titanate powder (M22, M32), and the case of not containing sulfur (M21, M31) Compared with the high electrostatic capacity, it is known that the use of sulfur-containing nickel strontium titanate paste contributes to the increase in capacity of the MLCC. Therefore, in the case of using the nickel paste of the sulfur-containing barium titanate powder (M22, M32), the structural defects can be greatly reduced by the sintering delay effect, and the static electricity is compared with the case of the sulfur-free case (M21, M31). Since the capacity is increased, the nickel content can be reduced when the limit capacitance is achieved, and the use of sulfur-containing barium titanate powder is more effective in the high quality, thinning, and lowering of MLCC.
於實施例1～3，所使用的全部鎳糊，鎳粉的平均粒徑為0.2μm，鈦酸鋇粉的平均粒徑為100nm，如表1所示，實施例4、5中，係使用鎳粉與鈦酸鋇粉的平均粒徑較小者，製作鎳糊。再者，在表1中記載有製作各糊所使用之鈦酸鋇粉與鎳粉的混合比率(重量%)、平均粒徑(nm)。又，表中記載有鈦酸鋇粉是否含有硫。In all of the nickel pastes used in Examples 1 to 3, the average particle diameter of the nickel powder was 0.2 μm, and the average particle diameter of the barium titanate powder was 100 nm. As shown in Table 1, in Examples 4 and 5, the use was carried out. When the average particle diameter of the nickel powder and the barium titanate powder is small, a nickel paste is produced. In addition, Table 1 shows the mixing ratio (% by weight) and the average particle diameter (nm) of the barium titanate powder and the nickel powder used for producing each paste. Further, the table indicates whether or not the barium titanate powder contains sulfur.
＜實施例4＞<Example 4>
於實施例4，鎳糊係含有平均粒徑150nm之鎳粉36.5重量%、平均粒徑20nm之含硫的高結晶鈦酸鋇粉或僅由不含硫之鈦酸鋇陶瓷所構成的高結晶鈦酸鋇粉4.0重量%(相對鎳粉約為10重量%)、樹脂固體成分(乙基纖維素粉末)3.0重量%、電極糊用分散劑1.0重量%、溶劑(萜品醇系溶劑)55.5重量%。以3支陶瓷輥對此等成分進行分散處理混合，製作出2種(不含硫之M41，含硫之M42)鎳糊。In Example 4, the nickel paste contained 36.5 wt% of nickel powder having an average particle diameter of 150 nm, a sulfur-containing high-crystalline barium titanate powder having an average particle diameter of 20 nm, or a high crystal consisting only of sulfur-free barium titanate ceramics. Barium titanate powder 4.0% by weight (about 10% by weight relative to nickel powder), 3.0% by weight of resin solid content (ethylcellulose powder), 1.0% by weight of dispersant for electrode paste, and solvent (terpineol solvent) 55.5 weight%. These components were dispersed and mixed by three ceramic rolls to prepare two kinds of (M46 containing no sulfur, M42 containing sulfur) nickel paste.
並且，將鎳糊M41、M42以電極圖案的樣子印刷於鈦酸鋇陶瓷片(厚度：約4.0μm)，積層10層，製得MLCC試樣。再者，前述電極圖案印刷之Ni附著量，在使用鎳糊M41、M42的情形，分別為0.300mg/cm2 、0.307mg/cm2 。燒成條件係與實施例1之情況略同，故省略記載。於使用鎳糊M41、M42製作之MLCC試樣之電特性的測量中，可確認各自的靜電容量為平均570nF、680nF左右。即，藉由在製作MLCC試樣所使用的鎳糊中混合含硫之高結晶鈦酸鋇粉，可增大靜電容量。Further, the nickel pastes M41 and M42 were printed on a barium titanate ceramic sheet (thickness: about 4.0 μm) in the form of an electrode pattern, and 10 layers were laminated to obtain an MLCC sample. Further, Ni deposition amount of the electrode pattern is printed, using a nickel paste M41, M42 of the case, respectively, 0.300mg / cm 2, 0.307mg / cm 2. Since the firing conditions are the same as those in the first embodiment, the description is omitted. In the measurement of the electrical characteristics of the MLCC samples prepared using the nickel pastes M41 and M42, it was confirmed that the respective electrostatic capacitances were about 570 nF and about 680 nF. That is, the electrostatic capacity can be increased by mixing the sulfur-containing high crystalline barium titanate powder in the nickel paste used for the production of the MLCC sample.
＜實施例5＞<Example 5>
於實施例5，鎳糊係含有平均粒徑120nm之鎳粉36.5重量%、平均粒徑20nm之含硫的高結晶鈦酸鋇粉或僅由不含硫之鈦酸鋇陶瓷所構成之高結晶鈦酸鋇粉4.0重量%(相對鎳粉約為10重量%)、樹脂固體成分(乙基纖維素粉末)5.3重量%、電極糊用分散劑1.5重量%、溶劑(萜品醇系溶劑)52.7重量%。以3支陶瓷輥對此等成分進行分散處理混合，製作2種(不含硫之M51，含硫之M52)鎳糊。In Example 5, the nickel paste contained 36.5 wt% of nickel powder having an average particle diameter of 120 nm, a sulfur-containing high-crystalline barium titanate powder having an average particle diameter of 20 nm, or a high crystal consisting only of sulfur-free barium titanate ceramics. Barium titanate powder 4.0% by weight (about 10% by weight relative to nickel powder), resin solid content (ethylcellulose powder) 5.3% by weight, electrode paste dispersant 1.5% by weight, solvent (terpineol solvent) 52.7 weight%. These components were dispersed and mixed by three ceramic rolls to prepare two kinds of (M51 containing no sulfur, M52 containing sulfur) nickel paste.
並且，將鎳糊M51、M52以電極圖案的樣子印刷於鈦酸鋇陶瓷片(厚度：約4.0μm)，積層10層，製得MLCC試樣。再者，前述電極圖案印刷之Ni附著量，在使用鎳糊M51、M52的情形，為0.346mg/cm2 、0.343mg/cm2 。於使用鎳糊M51和M52之MLCC試樣的電特性的測量中，可確認靜電容量各別為600nF、730nF左右。亦即，與實施例4相同，藉由在鎳糊中混合含硫之高結晶鈦酸鋇粉，可提升MLCC試樣的電特性。Further, nickel pastes M51 and M52 were printed on a barium titanate ceramic sheet (thickness: about 4.0 μm) in the form of an electrode pattern, and 10 layers were laminated to obtain an MLCC sample. In addition, in the case where the nickel pastes M51 and M52 were used, the Ni adhesion amount of the electrode pattern printing was 0.346 mg/cm 2 and 0.343 mg/cm 2 . In the measurement of the electrical characteristics of the MLCC sample using the nickel pastes M51 and M52, it was confirmed that the electrostatic capacitances were about 600 nF and about 730 nF, respectively. That is, as in the case of Example 4, the electrical characteristics of the MLCC sample can be improved by mixing the sulfur-containing high crystalline barium titanate powder in the nickel paste.
再者，前述鎳粉的平均粒徑較佳在10nm～1μm的範圍，未達10nm的情形時，由於是超微粒子，在空氣中容易氧化而變得不安定，而有粉塵***等危險性，故不適於作為鎳糊的材料。又，若超過1μm，則使用鎳糊所製造之MLCC的電極難以薄層化。並且，鎳糊中含硫之高結晶鈦酸鋇粉的含有量，相對於鎳粉，較佳在1～30重量%的範圍，未達1重量%時，無法得到所欲之燒結抑制劑應有的充分效果，若超過30重量%，則由於為絕緣物，故會大幅降低鎳糊的導電性，而無法用於MLCC等電子零件。In addition, the average particle diameter of the nickel powder is preferably in the range of 10 nm to 1 μm, and when it is less than 10 nm, it is easily oxidized in the air due to ultrafine particles, and is unstable, and there is a risk of dust explosion or the like. Therefore, it is not suitable as a material for nickel paste. Moreover, when it exceeds 1 micrometer, it is difficult to thin the electrode of the MLCC manufactured using the nickel paste. Further, the content of the sulfur-containing high-crystalline barium titanate powder in the nickel paste is preferably in the range of 1 to 30% by weight based on the nickel powder, and when it is less than 1% by weight, the desired sintering inhibitor should not be obtained. If it is more than 30% by weight, it is an insulator, so that the conductivity of the nickel paste is greatly reduced, and it cannot be used for electronic parts such as MLCC.
另，本發明並不限定於上述實施形態，在不超出本發明之技術思想的範圍，各種變形例、設計變更等當然亦包含在其技術範圍內。The present invention is not limited to the above-described embodiments, and various modifications, design changes, and the like are of course included in the technical scope without departing from the scope of the invention.
產業上可利用性Industrial availability
根據本發明，藉由含有含硫之鈦酸鋇粉的鎳糊，可以非常少之鎳附著量實現MLCC之高容量化、薄膜化或小型化，而且可提供結構缺陷極少、低廉且小型之高品質MLCC。According to the present invention, by the nickel paste containing sulfur-containing barium titanate powder, the capacity of the MLCC can be increased, the film thickness or the miniaturization can be achieved with a very small amount of nickel adhesion, and the structural defects are extremely small, inexpensive, and small. Quality MLCC.
圖1，係本發明之不含硫之鈦酸鋇BT1的SEM(掃描式電子顯微鏡)照片。Figure 1 is a SEM (Scanning Electron Microscope) photograph of the sulfur-free barium titanate BT1 of the present invention.
圖2，係本發明之含硫之鈦酸鋇BT2的SEM照片。Figure 2 is a SEM photograph of the sulfur-containing barium titanate BT2 of the present invention.
圖3，不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的粒度分布圖。Fig. 3 is a particle size distribution diagram of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2.
圖4，係分別顯示不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的個數分布、體積分布資料之表。Fig. 4 is a table showing the number distribution and volume distribution data of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2, respectively.
圖5，係顯示不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的TMA(熱機械測量裝置)測量結果之圖。Fig. 5 is a graph showing the measurement results of TMA (thermomechanical measuring device) of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2.
圖6，係顯示不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2的X光繞射結果之圖。Fig. 6 is a graph showing the results of X-ray diffraction of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2.
圖7，係顯示經糊化之不含硫之鈦酸鋇BT1、含硫之鈦酸鋇BT2經MLCC模型印刷乾燥時表面粗糙度測量結果(Ra、Rmax)之圖。Fig. 7 is a graph showing surface roughness measurement results (Ra, Rmax) of gelatinized sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2 after printing and drying by MLCC model.
圖8，係使用鎳糊M11、M12製作的MLCC試樣之截面結構照片。Fig. 8 is a photograph showing the cross-sectional structure of an MLCC sample produced using nickel pastes M11 and M12.
圖9，係顯示使用鎳糊M11、M12製作的MLCC試樣之靜電容量及絕緣電阻值的測量結果之圖。Fig. 9 is a graph showing measurement results of electrostatic capacitance and insulation resistance value of an MLCC sample produced using nickel pastes M11 and M12.
圖10，係顯示使用鎳糊M11、M12製作的MLCC試樣之損失係數、直流破壞電壓值的測量結果之圖。Fig. 10 is a graph showing the measurement results of the loss coefficient and the DC breakdown voltage value of the MLCC sample produced using the nickel pastes M11 and M12.
圖11，係使用鎳糊M21、M22製作的MLCC試樣之截面結構照片。Fig. 11 is a photograph showing the cross-sectional structure of an MLCC sample produced using nickel pastes M21 and M22.
圖12，係顯示使用鎳糊M21、M22製作的MLCC試樣之各種電特性測量結果之圖。Fig. 12 is a graph showing measurement results of various electrical characteristics of MLCC samples produced using nickel pastes M21 and M22.
圖13，係使用鎳糊M31、M32製作的MLCC試樣之截面結構照片。Fig. 13 is a photograph showing the cross-sectional structure of an MLCC sample produced using nickel pastes M31 and M32.
圖14，係顯示使用鎳糊M32、M33製作的MLCC試樣之各種電特性測量結果之圖。Fig. 14 is a graph showing measurement results of various electrical characteristics of MLCC samples prepared using nickel pastes M32 and M33.
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