TWI397084B - Production method of inorganic powder paste - Google Patents
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Description
本發明係關於一種無機粉末糊劑之製造方法，尤其係關於一種能有利地用作為用於形成積層陶瓷電子零件中之內部導體之導電性糊劑製造方法的無機粉末糊劑之製造方法。The present invention relates to a method for producing an inorganic powder paste, and more particularly to a method for producing an inorganic powder paste which can be advantageously used as a method for producing a conductive paste for forming an internal conductor in a laminated ceramic electronic component.
在獲得使微小無機粉末分散於溶劑中之無機粉末糊劑時，重要的是使無機粉末均勻分散於糊劑中。作為用於使無機粉末均勻分散於糊劑中之方法，有以下方法：例如使無機粉末吸附作為用於提高無機粉末之分散穩定性之分散劑之有機化合物。該方法中，如何使有機化合物以最佳狀態附著於無機粉末上成為關鍵。When an inorganic powder paste in which a fine inorganic powder is dispersed in a solvent is obtained, it is important to uniformly disperse the inorganic powder in the paste. As a method for uniformly dispersing the inorganic powder in the paste, there is a method in which, for example, the inorganic powder is adsorbed as an organic compound as a dispersing agent for improving the dispersion stability of the inorganic powder. In this method, how to attach an organic compound to an inorganic powder in an optimum state is critical.
無機粉末糊劑通常黏度較高，故而難以使無機粉末均勻分散。因此，例如在日本專利特開2001-67951號公報(專利文獻1)中記載有一種方法，其係在分散時添加低沸點之稀釋用溶劑，使無機粉末均勻分散之後，僅揮發去除稀釋用溶劑。如專利文獻1所述，在分散時使用稀釋用溶劑而實現低黏度化，藉此可使無機粉末之表面充分吸附有機化合物。Inorganic powder pastes generally have a high viscosity, so that it is difficult to uniformly disperse the inorganic powder. For example, JP-A-2001-67951 (Patent Document 1) discloses a method in which a solvent having a low boiling point is added during dispersion to uniformly disperse the inorganic powder, and then only the solvent for dilution is evaporated. . As described in Patent Document 1, the solvent for dilution is used for dispersion to achieve low viscosity, whereby the surface of the inorganic powder can sufficiently adsorb the organic compound.
然而，無機粉末之進一步微粒化會導致僅以上述方法而無法使無機粉末之表面附著有足夠之有機化合物。因此，為解決上述課題，本案發明者發現，對有機化合物賦予剪切力以解散作為高分子之有機化合物，藉此可製作出能有效附著於無機粉末之狀態。具體而言，利用對糊劑施加壓力而噴射之濕式高壓處理裝置或剪切式攪拌機等來賦予剪切力。However, further atomization of the inorganic powder may result in insufficient adhesion of sufficient organic compounds to the surface of the inorganic powder by the above method. Therefore, in order to solve the above problems, the inventors of the present invention have found that a shearing force is applied to an organic compound to dissolve an organic compound as a polymer, whereby a state in which the inorganic powder can be effectively adhered can be produced. Specifically, the shearing force is imparted by a wet high-pressure treatment device or a shear mixer which is sprayed by applying pressure to the paste.
然而，已知於含有無機粉末之狀態下，即便如上所述賦予剪切力，亦會遭遇無法獲得所期望之分散效果之新的問題。該問題為，當存在無機粉末時，為了獲得與不含有無機粉末之情形同等之解散的狀態，須要非常大的剪切力，實質上難以由現存之設備而獲得如此大的剪切力。However, it is known that in the state containing an inorganic powder, even if the shearing force is imparted as described above, there is a new problem that the desired dispersion effect cannot be obtained. The problem is that when an inorganic powder is present, in order to obtain a state of dissolution similar to the case where the inorganic powder is not contained, a very large shear force is required, and it is substantially difficult to obtain such a large shear force from the existing equipment.
[專利文獻1]日本專利特開2001-67951號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-67951
因此，本發明欲提供一種能解決上述問題之無機粉末糊劑之製造方法。Accordingly, the present invention is intended to provide a method for producing an inorganic powder paste which can solve the above problems.
為了解決上述技術問題，本發明提供一種用於製造無機粉末糊劑之方法，其特徵在於，其係用以製造在溶劑中含有無機粉末成分及一有機化合物所成的無機粉末糊劑者，該有機化合物具有藉由吸附於上述無機粉末成分而提高該無機粉末成分之分散性之作用，該方法包括以下步驟：獲得至少含有無機粉末成分之第1被混合體；獲得至少含有溶劑與有機化合物、但不含有無機粉末成分之第2被混合體；對第2被混合體作用剪切力；及隨後混合第1被混合體及第2被混合體。In order to solve the above problems, the present invention provides a method for producing an inorganic powder paste, which is characterized in that it is used for producing an inorganic powder paste containing an inorganic powder component and an organic compound in a solvent, which is The organic compound has an effect of improving the dispersibility of the inorganic powder component by being adsorbed to the inorganic powder component, and the method includes the steps of: obtaining a first to-be-mixed body containing at least an inorganic powder component; obtaining at least a solvent and an organic compound, However, the second to-be-mixed body does not contain an inorganic powder component; the shearing force is applied to the second to-be-mixed body; and the first to-be-mixed body and the second to-be-mixed body are subsequently mixed.
如上所述，本發明之特徵在於，在沒有無機粉末成分之狀態下實施作用剪切力之步驟，於該情形時，亦可分別調製含有無機粉末成分之第1被混合體、及含有有機化合物之第2被混合體，最後加以混合，或者亦可最初進行混合，然後自混合物分離出有機化合物，並作用剪切力，之後再次混合。As described above, the present invention is characterized in that the step of applying a shearing force is carried out in the absence of the inorganic powder component, and in this case, the first mixed body containing the inorganic powder component and the organic compound-containing compound may be separately prepared. The second mixed body is finally mixed, or may be initially mixed, and then the organic compound is separated from the mixture, and shearing force is applied, followed by mixing again.
對於後者之實施態樣之情形，進而包括如下步驟：準備至少含有無機粉末成分、溶劑及有機化合物之混合物；及自混合物至少分離出有機化合物。並且，第1被混合體中所含之無機粉末成分係藉由實施自混合物分離出有機化合物之步驟而自混合物中去除有機化合物之後所殘留者，第2被混合體中所含之有機化合物係藉由實施自混合物分離出有機化合物之步驟而自混合物中取出者。In the case of the latter embodiment, the method further comprises the steps of: preparing a mixture containing at least an inorganic powder component, a solvent and an organic compound; and separating at least the organic compound from the mixture. Further, the inorganic powder component contained in the first to-be-mixed body is an organic compound contained in the second mixed body after the organic compound is removed from the mixture by the step of separating the organic compound from the mixture. The one taken out of the mixture by carrying out the step of separating the organic compound from the mixture.
較好的是，第1被混合體中所含之無機粉末成分為分散於溶劑中之狀態。It is preferred that the inorganic powder component contained in the first to-be-mixed body is in a state of being dispersed in a solvent.
較好的是，無機粉末成分含有平均粒徑為10~300nm之導電性金屬粉末。Preferably, the inorganic powder component contains a conductive metal powder having an average particle diameter of 10 to 300 nm.
較好的是，有機化合物之重量平均分子量為100~50000，其酸鹼量為100~2000μmol/g。Preferably, the organic compound has a weight average molecular weight of from 100 to 50,000 and an acid to base amount of from 100 to 2000 μmol/g.
對第2被混合體作用剪切力之步驟包括以下步驟，即，一邊對第2被混合體施加壓力，一邊使第2被混合體自特定之噴射口噴射，施加於第2被混合體之壓力較好的是被選為50~300MPa。The step of applying a shearing force to the second object to be mixed includes a step of applying a pressure to the second object to be mixed, and ejecting the second object to be mixed from the specific injection port, and applying it to the second object to be mixed. The better pressure is chosen to be 50~300MPa.
根據本發明，在欲獲得之無機粉末糊劑中所含之成分中，至少對已去除無機粉末之狀態之第2被混合體作用剪切力而形成容易將有機化合物吸附於無機粉末之狀態後，將第2被混合體混合於含有無機粉末成分之第1被混合體，故而容易對有機化合物充分賦予剪切力而易吸附於無機粉末。因此即便使用微小之無機粉末，亦可發揮優異之分散性，從而可獲得具有良好分散性之無機粉末糊劑。According to the present invention, at least the component to be contained in the inorganic powder paste to be obtained is subjected to a shearing force to the second to-be-mixed body in a state in which the inorganic powder has been removed, and the organic compound is easily adsorbed to the inorganic powder. Since the second to-be-mixed body is mixed with the first to-be-mixed body containing the inorganic powder component, it is easy to sufficiently impart a shearing force to the organic compound and is easily adsorbed to the inorganic powder. Therefore, even if a fine inorganic powder is used, excellent dispersibility can be exhibited, and an inorganic powder paste having good dispersibility can be obtained.
因此，若上述無機粉末成分含有平均粒徑為10~300nm之導電性金屬粉末，則本發明之分散性提高之意義會變得顯著。即，即便在含有平均粒徑為10~300nm如此微小之導電性金屬粉末之情形時，根據本發明，亦能獲得分散性良好之導電性糊劑。因此，若將根據本發明所製造之導電性糊劑用於形成積層陶瓷電子零件中之內部導體，則導電性糊劑之塗膜之表面平滑性會提高，從而可使由此引起之短路不良難以產生。Therefore, when the inorganic powder component contains a conductive metal powder having an average particle diameter of 10 to 300 nm, the significance of the improvement of the dispersibility of the present invention becomes remarkable. In other words, even when a conductive metal powder having an average particle diameter of 10 to 300 nm is contained, according to the present invention, a conductive paste having good dispersibility can be obtained. Therefore, when the conductive paste produced according to the present invention is used to form an internal conductor in a laminated ceramic electronic component, the surface smoothness of the coating film of the conductive paste is improved, and the resulting short-circuit defect can be caused. Hard to produce.
本發明之無機粉末糊劑之製造方法進而包括以下步驟：準備至少含有無機粉末成分、溶劑及有機化合物之混合物；及自該混合物至少分離出有機化合物；於上述第1被混合體中所含之無機粉末成分係自混合物中去除有機化合物之後所殘留者，且上述第2被混合體中所含之有機化合物係自混合物中取出者之情形時，若使用由本發明之製造方法所製造之無機粉末糊劑作為混合物，則可重複進行對第2被混合體作用剪切力之步驟及其後的混合第1被混合體與第2被混合體之步驟，從而可獲得分散性更優異之無機粉末糊劑。The method for producing an inorganic powder paste of the present invention further comprises the steps of: preparing a mixture containing at least an inorganic powder component, a solvent, and an organic compound; and separating at least an organic compound from the mixture; and comprising the first mixed body When the inorganic powder component remains after the organic compound is removed from the mixture, and the organic compound contained in the second mixture is taken out from the mixture, the inorganic powder produced by the production method of the present invention is used. When the paste is used as a mixture, the step of applying a shearing force to the second object mixture and the subsequent mixing of the first object mixture and the second object mixture can be repeated, whereby an inorganic powder having more excellent dispersibility can be obtained. Paste.
若第1被混合體中所含之無機粉末成分為分散於溶劑中之狀態，則可使含有無機粉末成分之第1被混合體之操作性提高。When the inorganic powder component contained in the first to-be-mixed body is in a state of being dispersed in a solvent, the workability of the first to-be-mixed body containing the inorganic powder component can be improved.
若有機化合物之重量平均分子量為100~50000，酸鹼量為100~2000μmol/g，則可形成更適合使有機化合物吸附於無機粉末而提高分散性者。When the weight average molecular weight of the organic compound is 100 to 50,000 and the amount of acid and alkali is 100 to 2000 μmol/g, it is possible to form an organic compound which is more suitable for adsorption to an inorganic powder to improve dispersibility.
在對第2被混合體作用剪切力時，可一邊對第2被混合體施加壓力，一邊使第2被混合體自特定之噴射口噴射，此時，若將施加於第2被混合體之壓力選為50~300MPa，則可使剪切力確實作用於第2被混合體。When the shear force is applied to the second object to be mixed, the second object to be mixed can be ejected from the specific injection port while applying pressure to the second object to be mixed. In this case, the second object to be mixed is applied to the second object to be mixed. When the pressure is selected to be 50 to 300 MPa, the shear force can be surely applied to the second to-be-mixed body.
圖1係表示本發明第1實施形態之無機粉末糊劑之製造方法之步驟圖。欲獲得之無機粉末糊劑係在溶劑中含有無機粉末成分，及具有藉由吸附於該無機粉末成分而提高無機粉末成分之分散性之作用的有機化合物而成者。Fig. 1 is a flow chart showing a method of producing an inorganic powder paste according to a first embodiment of the present invention. The inorganic powder paste to be obtained contains an inorganic powder component in a solvent and an organic compound having an action of increasing the dispersibility of the inorganic powder component by being adsorbed to the inorganic powder component.
為了製造此種無機粉末成分而實施以下步驟，即，獲得至少含有無機粉末成分之第1被混合體1；及獲得至少含有溶劑與有機化合物、但不含有無機粉末成分之第2被混合體2。In order to produce such an inorganic powder component, a first mixture 1 containing at least an inorganic powder component is obtained, and a second mixture 2 containing at least a solvent and an organic compound but not containing an inorganic powder component is obtained. .
其次，實施對第2被混合體2作用剪切力之剪切作用施加步驟3，然後，實施混合第1被混合體1與第2被混合體2之混合步驟4，藉此獲得無機粉末糊劑5。為了獲得無機粉末糊劑5，根據需要有時會進而添加樹脂。Next, the shearing action applying step 3 for applying the shearing force to the second mixed body 2 is carried out, and then the mixing step 4 of mixing the first mixed body 1 and the second mixed body 2 is carried out, thereby obtaining an inorganic powder paste. Agent 5. In order to obtain the inorganic powder paste 5, a resin may be further added as needed.
第1被混合體1中除無機粉末成分以外，通常含有溶劑，較好的是形成為使無機粉末成分分散於溶劑中之狀態。又，第2被混合體2係以其中必須含有有機化合物作為條件。另外，第1被混合體1亦可含有該第2被混合體2中所含之有機化合物。The first mixed body 1 usually contains a solvent in addition to the inorganic powder component, and is preferably in a state in which the inorganic powder component is dispersed in a solvent. Further, the second mixture 2 is required to contain an organic compound therein. Further, the first mixed body 1 may contain the organic compound contained in the second mixed body 2 .
以下，對於無機粉末糊劑5為導電性糊劑之情形進行說明。Hereinafter, a case where the inorganic powder paste 5 is a conductive paste will be described.
在欲製造作為無機粉末糊劑5之導電性糊劑時，第1被混合體1含有導電性金屬粉末作為無機粉末成分。在將導電性糊劑用於形成積層陶瓷電子零件中之內部導體時，作為構成導電性金屬粉末之金屬成分，只要係能耐受同時煅燒之陶瓷之煅燒溫度及環境者即可，可使用例如Ni、Pd、Ag、Au、Pt或Cu、或者該等之混合物或合金。When the conductive paste as the inorganic powder paste 5 is to be produced, the first mixture 1 contains a conductive metal powder as an inorganic powder component. When the conductive paste is used for forming the inner conductor in the laminated ceramic electronic component, the metal component constituting the conductive metal powder may be used as long as it can withstand the calcination temperature and environment of the ceramic which is simultaneously calcined. Ni, Pd, Ag, Au, Pt or Cu, or a mixture or alloy thereof.
作為導電性糊劑中之固形成分之導電性金屬粉末之含有比例較好的是選為20~70重量%。於該範圍內調整固形成分之含有比例，藉此可穩定地獲得作為目標之印刷塗膜厚度。又，對於導電性金屬粉末之粒徑，當平均粒徑在10~300nm之範圍內時，通常凝集效果變得顯著，但根據本發明，由於分散性得以提高，故而在平均粒徑為10~300nm之情形時，可謂尤其是本發明之分散性提高之效果會變得顯著。另外，從是否能發揮本發明之效果之觀點而言，平均粒徑不存在下限，但若平均粒徑未滿10nm，則導電性糊劑會增黏過度而導致操作性降低，因此不佳。The content ratio of the conductive metal powder which is a solid component in the conductive paste is preferably from 20 to 70% by weight. The content ratio of the solid component is adjusted within this range, whereby the target printing film thickness can be stably obtained. Further, when the average particle diameter of the conductive metal powder is in the range of 10 to 300 nm, the aggregation effect is remarkable. However, according to the present invention, since the dispersibility is improved, the average particle diameter is 10~. In the case of 300 nm, it is particularly effective that the effect of improving the dispersibility of the present invention becomes remarkable. In addition, the average particle diameter does not have a lower limit from the viewpoint of whether or not the effect of the present invention can be exhibited. However, when the average particle diameter is less than 10 nm, the conductive paste is excessively thickened and the workability is lowered, which is not preferable.
於第1被混合體1中，除導電性金屬粉末以外，以延緩導電性金屬粉末之煅燒為目的，亦可添加氧化物固形成分作為無機粉末成分之一部分。作為氧化物固形成分，可使用例如Ba、Ti、Zr、Dy、Mg、Si、Y等各種氧化物或者將該等氧化物混合而成者。導電性糊劑中之氧化物固形成分之含有比例可根據導電性金屬粉末之煅燒性而在1~40重量%之範圍內進行適當調整，但特別好的是相對於導電性金屬粉末而為5~20重量%之添加量。In addition to the conductive metal powder, in addition to the conductive metal powder, in order to delay the firing of the conductive metal powder, an oxide solid component may be added as a part of the inorganic powder component. As the oxide solid component, for example, various oxides such as Ba, Ti, Zr, Dy, Mg, Si, and Y or a mixture of these oxides can be used. The content ratio of the solid content of the oxide in the conductive paste can be appropriately adjusted within the range of 1 to 40% by weight based on the calcinability of the conductive metal powder, but it is particularly preferably 5 with respect to the conductive metal powder. ~20% by weight of added amount.
作為第2被混合體2中所含之溶劑，較好的是含有：在所獲得之導電性糊劑中殘留之主溶劑；以及在導電性糊劑中未殘留、僅在製造導電性糊劑之過程中使用之稀釋溶劑。為促進有機化合物之吸附，主溶劑之溶解度度參數較好的是8.0~10.5，稀釋溶劑之溶解度參數較好的是7.4~13.8。具體而言，作為主溶劑，可使用酯類、萜烯類、酮類、醚類、醇類等溶劑，作為稀釋溶劑，可使用酮類、醇類、烴類等溶劑。所獲得之導電性糊劑中之主溶劑之含有比例較好的是10~70重量%。The solvent contained in the second mixture 2 preferably contains a main solvent remaining in the obtained conductive paste; and does not remain in the conductive paste, and only the conductive paste is produced. The dilution solvent used in the process. In order to promote the adsorption of organic compounds, the solubility parameter of the main solvent is preferably 8.0 to 10.5, and the solubility parameter of the dilution solvent is preferably 7.4 to 13.8. Specifically, as the main solvent, a solvent such as an ester, a terpene, a ketone, an ether or an alcohol can be used, and as the diluent solvent, a solvent such as a ketone, an alcohol or a hydrocarbon can be used. The content of the main solvent in the obtained conductive paste is preferably from 10 to 70% by weight.
作為第2被混合體2中所含之有機化合物，有分散劑、樹脂、添加劑等。有機化合物，尤其是分散劑，較好的是其重量平均分子量為100~50000、酸鹼量為100~2000μmol/g之陰離子性分散劑，可使用例如羧酸類化合物、磺酸類化合物、磷酸類化合物等。分散劑之添加量較好的是相對於粉末成分(包含導電性金屬粉末及氧化物固形成分)而選為0.1~10重量%。The organic compound contained in the second mixture 2 includes a dispersant, a resin, an additive, and the like. The organic compound, particularly the dispersing agent, is preferably an anionic dispersing agent having a weight average molecular weight of 100 to 50,000 and an acid-base amount of 100 to 2000 μmol/g, and for example, a carboxylic acid compound, a sulfonic acid compound, or a phosphoric acid compound can be used. Wait. The amount of the dispersant added is preferably from 0.1 to 10% by weight based on the powder component (including the conductive metal powder and the oxide solid component).
作為樹脂，特別好的是使用乙基纖維素樹脂，但此外亦可使用丙烯樹脂、聚氨酯樹脂、苯酚樹脂等。樹脂之含有比率較好的是相對於導電性糊劑而選為1~10重量%。As the resin, an ethyl cellulose resin is particularly preferably used, but an acrylic resin, a urethane resin, a phenol resin or the like can also be used. The content ratio of the resin is preferably from 1 to 10% by weight based on the conductive paste.
添加劑係用以進行導電性糊劑之黏度調整根據需要而添加，較好的是使用例如胺類樹脂。添加劑之添加量較好的是相對於粉末成分為0.1~10重量%。The additive is used to adjust the viscosity of the conductive paste as needed, and it is preferred to use, for example, an amine resin. The amount of the additive added is preferably from 0.1 to 10% by weight based on the powder component.
在對第2被混合體2所實施之剪切作用施加步驟3中，使用例如濕式高壓處理裝置，一邊對第2被混合體2施加壓力，一邊使第2被混合體2自特定之噴射口噴射。此時，施加於第2被混合體2之壓力較好的是選為50~300MPa。在剪切作用施加步驟3中，亦可取代濕式高壓處理裝置而使用剪切式攪拌機。In the shearing action applying step 3 performed on the second to-be-mixed body 2, the second mixed body 2 is sprayed from the specific one while applying pressure to the second to-be-mixed body 2 using, for example, a wet high-pressure processing apparatus. Mouth jet. At this time, the pressure applied to the second mixture 2 is preferably 50 to 300 MPa. In the shearing action applying step 3, a shearing agitator may be used instead of the wet high pressure processing apparatus.
在混合步驟4中，使上述剪切作用施加步驟3已結束之第2被混合體2與第1被混合體1碰撞。如此，使第1被混合體1碰撞到賦予剪切作用後之第2被混合體2，藉此可使第2被混合體中含有之具有分散作用之有機化合物高效地附著於第1被混合體1中含有之無機粉末之表面。於該混合步驟4中，較好的是將第2被混合體2之溫度調整為25℃以上且未滿溶劑之沸點。In the mixing step 4, the second to-be-mixed body 2 having the above-described shearing action applying step 3 is caused to collide with the first to-be-mixed body 1. In this manner, the first object mixture 1 is caused to collide with the second object mixture 2 after the shearing action, whereby the organic compound having the dispersing action contained in the second object mixture can be efficiently adhered to the first mixed body. The surface of the inorganic powder contained in the body 1. In the mixing step 4, it is preferred to adjust the temperature of the second mixture 2 to 25 ° C or higher and less than the boiling point of the solvent.
圖2是表示本發明第2實施形態之無機粉末糊劑之製造方法之步驟圖。在圖2中，對與圖1所示之要素相當之要素附以相同之參照符號，省略重複之說明。Fig. 2 is a flow chart showing a method of producing an inorganic powder paste according to a second embodiment of the present invention. In FIG. 2, elements that are the same as those in FIG. 1 are denoted by the same reference numerals, and the description thereof will not be repeated.
第2實施形態之特徵在於包括分離步驟12，即，準備至少含有無機粉末成分、溶劑及有機化合物之混合物即混合漿料11，並自該混合物漿料11通過過濾器而分離出有機化合物及溶劑。而且，第1被混合體1中所含之無機粉末成分係藉由實施分離步驟12而自混合漿料11中去除有機化合物之後所殘留者，第2被混合體2中所含之有機化合物係藉由實施分離步驟12而自混合漿料11中取出者。其後之步驟與第1實施形態之情形相同。The second embodiment is characterized in that it includes a separation step 12 of preparing a mixed slurry 11 containing at least an inorganic powder component, a solvent and an organic compound, and separating the organic compound and the solvent from the mixture slurry 11 through a filter. . In addition, the inorganic powder component contained in the first to-be-mixed body 1 is the organic compound contained in the second to-be-mixed body 2 after the removal of the organic compound from the mixed slurry 11 by performing the separation step 12 The person who has taken out from the mixed slurry 11 by performing the separation step 12 is carried out. The subsequent steps are the same as those in the first embodiment.
第2實施形態中準備之混合漿料11可作為由上述第1實施形態而獲得之無機粉末糊劑5，進而，亦可作為由第2實施形態而獲得之無機粉末糊劑5。藉此，重複實施剪切作用施加步驟3，從而可進一步提高所獲得之無機粉末糊劑5之分散性。The mixed slurry 11 prepared in the second embodiment can be used as the inorganic powder paste 5 obtained in the first embodiment, and further as the inorganic powder paste 5 obtained in the second embodiment. Thereby, the shearing action applying step 3 is repeatedly performed, whereby the dispersibility of the obtained inorganic powder paste 5 can be further improved.
即，在使第1被混合體1與第2被混合體2碰撞而混合之步驟僅實施1次之情況下，無機粉末成分會仍以凝集狀態而殘留，但如上所述重複實施剪切作用施加步驟3，且其重複次數越增加，則越可進一步提高分散性。另外，剪切作用施加步驟3之較佳的重複次數根據欲獲得之無機粉末糊劑5之組成或無機粉末之粒徑而有所不同，因此，較好的是預先評估所獲得之無機粉末糊劑5，並對無機粉末糊劑5之每一種類而設定重複次數。In other words, when the first mixed body 1 and the second mixed body 2 collide and are mixed only once, the inorganic powder component remains in a coagulated state, but the shearing action is repeated as described above. When step 3 is applied and the number of repetitions is increased, the more the dispersibility is further improved. Further, the preferred number of repetitions of the shearing action applying step 3 differs depending on the composition of the inorganic powder paste 5 to be obtained or the particle diameter of the inorganic powder, and therefore, it is preferred to pre-evaluate the obtained inorganic powder paste. Agent 5, and the number of repetitions is set for each type of inorganic powder paste 5.
作為根據本發明之製造方法所製造之無機粉末糊劑，代表性地有導電性糊劑，將此種導電性糊劑用於內部導體之形成，可製造出例如積層陶瓷電容器、積層陶瓷電感器、積層陶瓷LC零件、多層陶瓷基板等積層陶瓷電子零件。As the inorganic powder paste produced by the production method of the present invention, a conductive paste is typically used, and such a conductive paste is used for the formation of an internal conductor, and for example, a laminated ceramic capacitor or a laminated ceramic inductor can be manufactured. Multilayer ceramic electronic components such as laminated ceramic LC parts and multilayer ceramic substrates.
接下來，為確認本發明之效果而對已實施之實驗例進行說明。Next, an experimental example that has been implemented will be described in order to confirm the effects of the present invention.
本實驗例中，於以下表1~表7中所示之組成及處理條件下製作試樣1~7之導電性糊劑。In this experimental example, the conductive pastes of the samples 1 to 7 were produced under the compositions and processing conditions shown in the following Tables 1 to 7.
(1)試樣1(1) Sample 1
(2)試樣2(2) Sample 2
(3)試樣3(3) Sample 3
(4)試樣4(4) Sample 4
(5)試樣5(5) Sample 5
(6)試樣6(6) Sample 6
(7)試樣7(7) Sample 7
在表1~表7中，「添加比率」欄中所示之「重量%/糊劑」係表示在所獲得導電性糊劑中之重量%，「重量%/粉末」係表示相對於添加之粉末成分之重量%。In Tables 1 to 7, the "% by weight/paste" shown in the column of "addition ratio" indicates the weight % in the obtained conductive paste, and "% by weight/powder" means relative to the addition. % by weight of the powder component.
此外，「溶解度參數」係根據Fedors法而計算者。「酸鹼量」係藉由中和滴定而測定者。「重量平均分子量」係於四氫呋喃(THF)中溶解，並利用高速液相層析法來進行所獲得之溶液之分子量分布評估而求出者。In addition, the "solubility parameter" is calculated according to the Fedors method. The "acid amount" is determined by neutralization titration. The "weight average molecular weight" is obtained by dissolving in tetrahydrofuran (THF) and evaluating the molecular weight distribution of the obtained solution by high performance liquid chromatography.
試樣1~7各自之導電性糊劑之製備順序如下所述。The order of preparation of each of the conductive pastes of Samples 1 to 7 is as follows.
為了獲得第1被混合體1，如表1~表7之「第1被混合體」欄所示，於粉末成分中添加主溶劑，並根據試樣而進一步添加稀釋溶劑、分散劑、樹脂及/或添加劑，將該等用剪切式攪拌機進行混合攪拌。In order to obtain the first to-be-mixed body 1, as shown in the column of "the first to-be-mixed body" of Tables 1 to 7, the main solvent is added to the powder component, and a diluent solvent, a dispersing agent, a resin, and the like are further added depending on the sample. / or additives, which are mixed and stirred with a shear mixer.
另一方面，為了獲得第2被混合體，如表1~表7之「第2被混合體」欄所示，於主溶劑中添加分散劑，並根據試樣而進一步添加稀釋溶劑、分散劑、樹脂及/或添加劑，將該等用剪切式攪拌機進行混合攪拌。On the other hand, in order to obtain the second to-be-mixed body, a dispersing agent is added to the main solvent as shown in the column of "second mixed body" in Tables 1 to 7, and a diluent solvent and a dispersing agent are further added depending on the sample. And a resin and/or an additive, which are mixed and stirred by a shear mixer.
然後，為了使剪切力作用於以上述方式所獲得之第2被混合體，使用濕式高壓處理裝置，以表1~表7之「處理條件」中之「處理壓力」欄所示之壓力而加壓噴射第2被混合體。Then, in order to apply a shearing force to the second to-be-mixed body obtained as described above, the pressure shown in the "treatment pressure" column in the "processing conditions" of Tables 1 to 7 is used using the wet high-pressure processing apparatus. On the other hand, the second mixture is pressurized.
接著，在加壓噴射後，一邊利用加熱器或冷凝水將第2被混合體控制為表1~表7之「處理條件」中之「被混合體溫度」欄所示之溫度，一邊使其與第1被混合體碰撞，藉此獲得導電性糊劑。Then, after the pressure injection, the second object to be mixed is controlled by the heater or the condensed water to the temperature shown in the column of "mixture temperature" in the "processing conditions" of Tables 1 to 7. The first mixed body collides with each other to obtain a conductive paste.
對於表1~表7之「處理條件」中之「處理次數」為複數次之試樣，僅以「處理次數」中所示之次數重複進行如下處理：過濾以上述方式所獲得導電性糊劑，藉此分離出含有無機粉末成分之漿料、以及含有溶劑及有機化合物成分但不含有無機粉末成分之有機化合物溶液，對於有機化合物溶液，在與上述情形相同之條件下施加剪切作用，並使剪切作用後之有機化合物溶液碰撞到上述含有無機粉末成分之漿料。另外，處理次數係以處理時間來管理。例如，在欲進行X次處理時，進行與由下式計算出的處理時間相當的處理：處理時間=(導電性糊劑量)/(導電性糊劑處理速度)×X。For the samples in which the "number of times of processing" in the "processing conditions" in Tables 1 to 7 are plural times, the following processing is repeated only for the number of times shown in "number of times of processing": the conductive paste obtained by the above method is filtered. Thereby, the slurry containing the inorganic powder component and the organic compound solution containing the solvent and the organic compound component but not containing the inorganic powder component are separated, and the organic compound solution is subjected to shearing under the same conditions as described above, and The organic compound solution after the shearing action is caused to collide with the above slurry containing the inorganic powder component. In addition, the number of processes is managed by the processing time. For example, when X times of processing is to be performed, a process corresponding to the processing time calculated by the following formula is performed: processing time = (conductive paste amount) / (conductive paste processing speed) × X.
又，在表7所示之試樣7中，不進行上述之處理，僅混合第1被混合體與第2被混合體，然後，用剪切式攪拌機進行混合攪拌，獲得導電性糊劑。Further, in the sample 7 shown in Table 7, the first mixture and the second mixture were mixed without performing the above-described treatment, and then the mixture was mixed and stirred by a shear mixer to obtain a conductive paste.
接著，將作為樹脂成分之乙基纖維素樹脂與主溶劑預先混合成以重量比計為20：80所得之有機媒劑添加到各試樣之導電性糊劑中，調和成可獲得乙基纖維素樹脂之含量為2重量%之導電性糊劑，然後，用剪切式攪拌機進行混合攪拌。Next, an ethylcellulose resin as a resin component and a main solvent are preliminarily mixed to obtain an organic solvent obtained by adding 20:80 by weight to the conductive paste of each sample, and blended to obtain an ethyl fiber. The conductive paste having a content of the resin of 2% by weight was mixed and stirred by a shear mixer.
接著，將上述混合攪拌後之導電性糊劑於已加溫之狀態下調整成黏度為0.5Pa‧s以下之後，使用網眼為10μm、5μm、3μm及最終階段的導電性金屬粉末之平均1次粒徑之2倍之網眼的薄膜式過濾器，採用壓力未滿1.5kg/cm2 之加壓過濾而去除塊狀物。Next, after the above-mentioned conductive paste mixed and stirred is adjusted to have a viscosity of 0.5 Pa ‧ s or less, the average of the conductive metal powders of 10 μm, 5 μm, 3 μm, and the final stage is used. The membrane filter of the mesh which is twice the secondary particle size is subjected to pressure filtration under a pressure of less than 1.5 kg/cm 2 to remove the cake.
最後，於上述過濾處理後之導電性糊劑中含有稀釋溶劑之情況下，在2.0×10-1 氣壓之減壓下加熱至40℃而去除稀釋溶劑之後，對過濾處理後之導電性糊劑，用3μm之薄膜式過濾器，採用壓力未滿1.5kg/cm2 之加壓過濾，再次去除塊狀物，獲得作為目標之各試樣之導電性糊劑。Finally, in the case where the conductive paste containing the filtration treatment contains a diluent solvent, the conductive paste is filtered after being heated to 40 ° C under a reduced pressure of 2.0 × 10 -1 atmosphere to remove the dilution solvent. Using a 3 μm membrane filter and pressure filtration under a pressure of less than 1.5 kg/cm 2 , the cake was again removed to obtain a conductive paste of each sample as a target.
為了評估由此所得之各試樣之導電性糊劑，以下述方式製作積層陶瓷電容。In order to evaluate the conductive paste of each sample thus obtained, a laminated ceramic capacitor was produced in the following manner.
即，於厚度為2μm之電介質陶瓷生片上，以網版印刷法印刷各試樣之導電性糊劑，形成包含厚度為1μm之導電性糊劑之塗膜。此處，使用三維形狀測定裝置觀察塗膜形狀，測定塗膜表面粗糙度。其結果示於表8。Specifically, a conductive paste of each sample was printed by a screen printing method on a dielectric ceramic green sheet having a thickness of 2 μm to form a coating film containing a conductive paste having a thickness of 1 μm. Here, the shape of the coating film was observed using a three-dimensional shape measuring device, and the surface roughness of the coating film was measured. The results are shown in Table 8.
接著，使導電性糊劑乾燥後，積層、壓接電介質陶瓷生片以獲得450層之積層結構，其次，切割成3.2mm×2.5mm之平面形狀，獲得積層體晶片。接下來，以最高溫度280℃對積層體芯片進行脫脂處理後，於氫/氮混合氣體中，以1200℃之最高溫度進行煅燒，且於煅燒後，藉由塗佈及燒接而形成外部電極，在各試樣中獲得積層陶瓷電容。Next, after the conductive paste was dried, the dielectric ceramic green sheets were laminated and pressure-bonded to obtain a laminated structure of 450 layers, and secondly, cut into a planar shape of 3.2 mm × 2.5 mm to obtain a laminated body wafer. Next, the laminated body chip is degreased at a maximum temperature of 280 ° C, and then calcined at a maximum temperature of 1200 ° C in a hydrogen/nitrogen mixed gas, and after firing, an external electrode is formed by coating and baking. A laminated ceramic capacitor was obtained in each sample.
對100個所獲得之試樣之積層陶瓷電容，用LCR測量儀測定靜電容量，計算出短路不良率。其結果示於表8。關於表8所示之短路不良率，若未滿10%，則可判定為良品，若為10%以上，則可判定為不良品。The capacitance of the multilayer ceramic capacitor of the obtained samples was measured by an LCR meter, and the short-circuit defect rate was calculated. The results are shown in Table 8. When the short-circuit defect rate shown in Table 8 is less than 10%, it can be judged as a good product, and if it is 10% or more, it can be judged as a defective product.
由表8而確認，根據試樣1~6，印刷塗膜平滑性提高，其結果可將積層陶瓷電容器之短路不良率抑制為未滿10%。可推測其原因在於，有機化合物於粉末成分上之吸附狀態得以最佳化，從而導電性糊劑中之粉末成分之分散性提高。As is clear from Table 8, according to Samples 1 to 6, the smoothness of the printed coating film was improved, and as a result, the short-circuit defective ratio of the multilayer ceramic capacitor was suppressed to less than 10%. It is presumed that the reason for the adsorption state of the organic compound on the powder component is optimized, and the dispersibility of the powder component in the conductive paste is improved.
相對於此，試樣7中，與試樣1~6相比，印刷塗膜平滑性劣化，且短路不良率大幅增加。可推測其原因在於，有機化合物於粉末成分上之吸附狀態不佳，從而導電性糊劑之分散性降低。On the other hand, in the sample 7, the smoothness of the printing coating film was deteriorated compared with the samples 1 to 6, and the short-circuit defect rate was greatly increased. The reason for this is presumed to be that the adsorption state of the organic compound on the powder component is not good, and the dispersibility of the conductive paste is lowered.
1．．．第1被混合體1. . . First mixed body
2．．．第2被混合體2. . . Second mixed body
3．．．剪切作用施加步驟3. . . Shear application step
4．．．混合步驟4. . . Mixing step
5．．．無機粉末糊劑5. . . Inorganic powder paste
11．．．混合漿料11. . . Mixed slurry
12．．．分離步驟12. . . Separation step
圖1係表示本發明第1實施形態之無機粉末糊劑之製造方法之步驟圖；及Fig. 1 is a flow chart showing a method of producing an inorganic powder paste according to a first embodiment of the present invention; and
圖2係表示本發明第2實施形態之無機粉末糊劑之製造方法之步驟圖。Fig. 2 is a flow chart showing a method of producing an inorganic powder paste according to a second embodiment of the present invention.
1．．．第1被混合體1. . . First mixed body
2．．．第2被混合體2. . . Second mixed body
3．．．剪切作用施加步驟3. . . Shear application step
4．．．混合步驟4. . . Mixing step
5．．．無機粉末糊劑5. . . Inorganic powder paste
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| TW098127294A TWI397084B (en) | 2008-08-20 | 2009-08-13 | Production method of inorganic powder paste |
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| JP (1) | JP5481811B2 (en) |
| KR (1) | KR101040391B1 (en) |
| CN (1) | CN101653704B (en) |
| TW (1) | TWI397084B (en) |
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| TWI527069B (en) * | 2012-02-21 | 2016-03-21 | Jx Nippon Mining & Metals Corp | And a method for producing metal powder paste |
| JP6314728B2 (en) * | 2014-07-30 | 2018-04-25 | 住友金属鉱山株式会社 | Method for producing conductive paste and conductive paste obtained thereby |
| JP6853606B2 (en) * | 2017-08-10 | 2021-03-31 | 株式会社ノリタケカンパニーリミテド | Conductive paste |
| KR102152841B1 (en) * | 2018-11-30 | 2020-09-07 | 엘에스니꼬동제련 주식회사 | Method for producing the conductive paste reducing change of elapsed time in viscosity |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6375868B1 (en) * | 1999-06-25 | 2002-04-23 | Murata Manufacturing Co., Ltd. | Method for manufacturing paste for electroconductive thick film, paste for electroconductive thick film and laminated ceramic electronic part |
| US20070114653A1 (en) * | 2001-07-12 | 2007-05-24 | Hitachi, Ltd. | Wiring glass substrate for connecting a semiconductor chip to a printed wiring substrate and a semiconductor module having the wiring glass substrate |
| TW200829610A (en) * | 2006-10-11 | 2008-07-16 | Mitsubishi Materials Corp | Electrode-forming composition and method for forming electrodes using the same |
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| JPH02284638A (en) * | 1989-04-26 | 1990-11-22 | Tadahiro Omi | Feeder of high-performance process gas |
| US6207081B1 (en) * | 1998-07-17 | 2001-03-27 | Murata Manufacturing Co., Ltd. | Method for producing conductive composition and conductive composition |
| JP3675254B2 (en) * | 1999-10-05 | 2005-07-27 | 株式会社村田製作所 | Method for manufacturing ceramic slurry, ceramic green sheet and multilayer ceramic electronic component |
| JP2001114569A (en) * | 1999-10-20 | 2001-04-24 | Murata Mfg Co Ltd | Ceramic slurry composition, ceramic green sheet and production of multilayer ceramic electronic part |
| JP2002140931A (en) * | 2000-10-31 | 2002-05-17 | Furuya Kinzoku:Kk | Silver paste and its manufacturing method |
| JP2003253301A (en) | 2002-03-01 | 2003-09-10 | Murata Mfg Co Ltd | Method for manufacturing metal powder for conductive paste, metal powder for conductive paste, conductive paste, and multilayer ceramic electronic part |
| KR100586960B1 (en) | 2004-03-31 | 2006-06-07 | 삼성전기주식회사 | A Method for Preparing Conductive Paste Having Improved Dispersibility |
| JP2006263599A (en) | 2005-03-24 | 2006-10-05 | Toray Ind Inc | Apparatus for dispersing paste and method for producing paste |
| JP2009091515A (en) | 2007-10-11 | 2009-04-30 | Ricoh Co Ltd | Method for manufacturing paste, and paste |
| CN100566803C (en) * | 2008-04-24 | 2009-12-09 | 华南理工大学 | A kind of process for dispersing of nano iron particles |
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- 2009-08-13 TW TW098127294A patent/TWI397084B/en active
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- 2009-08-20 KR KR1020090077149A patent/KR101040391B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6375868B1 (en) * | 1999-06-25 | 2002-04-23 | Murata Manufacturing Co., Ltd. | Method for manufacturing paste for electroconductive thick film, paste for electroconductive thick film and laminated ceramic electronic part |
| US20070114653A1 (en) * | 2001-07-12 | 2007-05-24 | Hitachi, Ltd. | Wiring glass substrate for connecting a semiconductor chip to a printed wiring substrate and a semiconductor module having the wiring glass substrate |
| TW200829610A (en) * | 2006-10-11 | 2008-07-16 | Mitsubishi Materials Corp | Electrode-forming composition and method for forming electrodes using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101653704B (en) | 2013-01-09 |
| JP2010049849A (en) | 2010-03-04 |
| KR101040391B1 (en) | 2011-06-09 |
| JP5481811B2 (en) | 2014-04-23 |
| KR20100022941A (en) | 2010-03-03 |
| CN101653704A (en) | 2010-02-24 |
| TW201013707A (en) | 2010-04-01 |
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