TW201013707A - Method for manufacturing inorganic powder paste - Google Patents
Method for manufacturing inorganic powder paste Download PDFInfo
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- TW201013707A TW201013707A TW098127294A TW98127294A TW201013707A TW 201013707 A TW201013707 A TW 201013707A TW 098127294 A TW098127294 A TW 098127294A TW 98127294 A TW98127294 A TW 98127294A TW 201013707 A TW201013707 A TW 201013707A
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- inorganic powder
- mixture
- organic compound
- paste
- solvent
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- 239000000843 powder Substances 0.000 title claims abstract description 149
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title description 14
- 239000002904 solvent Substances 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 65
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims description 20
- 238000010008 shearing Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 8
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 28
- 239000011347 resin Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 25
- 239000002270 dispersing agent Substances 0.000 description 22
- 239000000654 additive Substances 0.000 description 19
- 230000000996 additive effect Effects 0.000 description 17
- 239000002253 acid Substances 0.000 description 11
- 238000007865 diluting Methods 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- -1 sulfonium organic compound Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229940116411 terpineol Drugs 0.000 description 6
- 230000036760 body temperature Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000009931 pascalization Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JSRLCNHTWASAJT-UHFFFAOYSA-N helium;molecular nitrogen Chemical compound [He].N#N JSRLCNHTWASAJT-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
201013707 六、發明說明： 【發明所屬之技術領域】 本發月係關;^ #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竞電子零件中之内 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0 【先前技術】 在獲得使微小無機粉末分散於溶劑中之無機粉末糊劑 θ I f要的疋使無機粉末均勾分散於糊劑中。作為用於使 無機粉末均勻分散於糊劑中之方法，有卩下方法：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。 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2〇〇167951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/谷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。 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 141780.doc 201013707 力而=無機粉ί之狀態。具體而言’利用對糊劑施加壓 切力 t濕式商壓處理裝置或煎切式授拌機等來賦予剪 :而’已知於含有無機粉末之狀態下，即便如上所述賦 1切力’亦會遭遇無法獲得所期望之分散效果之新的問 題。送問題為，當存在無機粉末時，為了獲得與不含有益 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。 [專利文獻1]曰本專利特開2001 _6795丨號公報 【發明内容】 [發明所欲解決之問題] 因此’本發明欲提供-種能解決上述問題之無機粉末糊 劑之製造方法。 [解決問題之技術手段] 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丨被混合體；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"皮混合體 及第2被混合體。 如上所述，本發明之特徵在於，在沒有無機粉末成分之 141780.doc 201013707 狀態下實施㈣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m混合體、及含有有機化人物 之第2被混合體’最後加以混合，或者亦可最初進：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。201013707 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for producing an inorganic powder paste, and more particularly to an inner conductor which can be advantageously used as an intermediate conductor for forming a laminated ceramic component Method for Producing Inorganic Powder Paste for Manufacturing Method of Conductive Paste 0 [Prior Art] In order to obtain an inorganic powder paste θ I f which disperses a fine inorganic powder in a solvent, the inorganic powder is uniformly dispersed in the paste. in. As a method for uniformly dispersing the inorganic powder in the paste, there is a method of raking the inorganic powder, for example, by adsorbing the inorganic powder 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. Inorganic powder pastes generally have a high viscosity, so that it is difficult to uniformly disperse the inorganic powder. For example, JP-A No. 2,167,951 (Patent Document 1) discloses a method in which a low-boiling dilution/grain is added to uniformly disperse an inorganic powder during dispersion, and only a volatile removal and dilution is performed. A solvent is used. As described in Patent Document 1, a low-viscosity is achieved by using a solvent for dilution at the time of dispersion, whereby the surface of the inorganic powder can sufficiently adsorb the organic compound. However, the further atomization of the inorganic powder causes only the above method. However, in order to solve the above problems, the inventors of the present invention have found that by applying a shearing force to an organic compound to dissolve an organic compound as a polymer, it is possible to produce 141,780. .doc 201013707 Force and = state of inorganic powder. Specifically, 'using a pressure-cutting force t-wet commercial pressure treatment device or a frying-type mixer to impart shear to the paste: and 'is known to contain inorganic In the state of the powder, even if the shear force is given as described above, there is a new problem that the desired dispersion effect cannot be obtained. When an inorganic powder is present, in order to obtain a state of dissolution similar to the case where the powder of the machine 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. [Patent Document 1] SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] Therefore, the present invention is intended to provide a method for producing an inorganic powder paste which can solve the above problems. [Technical means for solving the problem] 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 comprises the steps of: obtaining a second entangled mixture containing at least an inorganic powder component; obtaining at least a solvent and an organic compound, But the second object mixture that does not contain the inorganic powder component; the shear force acting on the second object mixture; After mixing the "skin mixture and the second mixture. As described above, the present invention is characterized in that the step of performing the (four) shearing force in the state of 141780.doc 201013707 without the inorganic powder component, in this case, Alternatively, the m-th mixture containing the inorganic powder component and the second mixture containing the organic character may be prepared and finally mixed, or may be initially mixed: and then the organic compound is separated from the mixture and sheared. Force, then mix 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丨及 自混合物至少分離出有機化合物。並且，第丨被混合體中 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。 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。 較好的是，無機粉末成分含有平均粒徑為1〇〜3〇〇 之 導電性金屬粉末。 較好的是，有機化合物之重量平均分子量為1〇〇〜 500〇〇，其酸鹼量為 100-2000 μιηοΐ/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 之噴射口喷射，施加於第2被混合體之壓力較好的是被選 為 50〜3〇〇 MPa。 [發明之效果] 根據本發明，在欲獲得之無機粉末糊劑中所含之成分 141780.doc 201013707 中至夕對已去除無機粉末之狀態之第2被混合體作用剪 切力而形成各易將有機化合物吸附於無機粉末之狀態後， 將第2被&合體混合於含有無機粉末成分之第^被混合體， 故而谷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 I·生從而可獲得具有良好分散性之無機粉末糊劑。 因此’若上述無機粉末成分含有平均粒徑為10〜300 nm 之導電性金屬粉纟’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1〇〜3〇〇 ηιη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内部導體，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。 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。 141780.doc 201013707 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。 若有機化合物之重量平均分子量為100〜5〇〇〇〇 ,酸鹼量 為100〜2000 μιηοΐ/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。 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被混合體自特定之喷射口喷射，此 時，若將施加於第2被混合體之壓力選為5〇〜300 MPa，則 可使剪切力確實作用於第2被混合體。 【實施方式】 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。 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。 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。 第1被混合體1中除無機粉末成分以外，通常含有溶劑， 141780.doc 201013707 較好的是形成為使無機粉末成分分散於溶劑中％ =被混合體2係以其中必須含有有機化合物作二 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。 以下，對於無機粉末糊劑5為導電性糊劑之情形進 明。 ° 在欲製造作為無機粉末糊劑5之導電性糊劑時，第㈠皮混 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£電子科中之㈣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 之陶变之锻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。 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重量於該範圍内調整固形成 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 10〜300 nm之範圍内時，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，&而在平均粒徑為1〇〜3⑼ nm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i〇 nm，則導電 性糊劑會增黏過度而導致操作性降低，因此不佳。 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 141780.doc 201013707 為無機粉末成分之-部分。作為氧化物固形成分’可使用 例如 Ba、Ti、Zr、Dy、Me、ς; 枯知 λ y Mg si、γ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属粉末之锻燒性而在卜4〇重量％ 之範圍内進行適虽調整，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。 作為第2被混合體2中所含之溶劑’較好的是含有：在所 €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。 ^促進有機化合物之吸附，主溶劑之溶解度度參數較好的 疋8.0〜10.5，稀釋溶劑之溶解度參數較好的是8。 具體而言’作為主溶劑’可使用醋類、祐稀類、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％。 _ 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❶有機化合物，尤其是分散劑，較好的是其 重量平均分子量為1〇〇〜50000、酸鹼量為1〇〇〜2〇〇〇 Kmol/g 之陰離子性分散劑’可使用例如叛酸類化合物、續酸類化 合物、璘酸類化合物等。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％。 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 141780.doc 201013707 比率較好的是相對於導電性糊劑而選為丨〜丨〇重量％。 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。&加劑之添加量較好的 承相對於粉末成分為0.1〜10重量％。 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5〇〜3〇〇 Μρ&。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❹ 剪切式攪拌機。 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Q體2與第1被混合體丨碰撞。如此，使第丨被混合體工 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，杈好的是將第2被混合體2之溫度調整為25°c以上且未 滿溶劑之沸點。 圖2是表不本發明第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，對與圖丨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。 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n通過過濾器而分離出有機化 合物及溶劑。而且，第〖被混合體1中所含之無機粉末成分 141780.doc .10- 201013707 係藉由實施分離步驟12而自混合漿料U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。 第2實施形態中準備之混合漿料11可作為由上述第丨實施 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$之 ® 分散性。 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 ❿ Μ先評估所獲得之無機粉末糊劑5，ϋ對無機粉末糊劑5 之每一種類而設定重複次數。 . 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内部導體之 形成，可製造出例如積層陶瓷電容器、積層陶瓷電感器、 積層陶竟LC零件、多層陶究基板等積層陶曼電子零件。 接下來，為確認本發明之效果而對已實施之實驗例進行 說明〇 本實驗例中’於以下表卜表7中所示之組成及處理條件 141780.doc 201013707 下製作試樣1〜7之導電性糊劑。 (1)試樣1 表1The case of the latter embodiment further includes the steps of preparing at least an inorganic powder component, a mixture of a solvent and an organic compound, and at least separating the organic compound from the mixture. Further, the inorganic powder component contained in the second mixed body is the organic compound contained in the second mixed body after the organic compound is removed from the mixture by performing 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. 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. Preferably, the inorganic powder component contains a conductive metal powder having an average particle diameter of 1 Å to 3 Å. Preferably, the organic compound has a weight average molecular weight of from 1 Å to 500 Å and an acid-base amount of from 100 to 2,000 μm η ΐ / g. 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 pressure is preferably selected to be 50 to 3 MPa. [Effects of the Invention] According to the present invention, in the 141780.doc 201013707 contained in the inorganic powder paste to be obtained, the shearing force is applied to the second mixed body in a state in which the inorganic powder has been removed, thereby forming each easy After the organic compound is adsorbed to the inorganic powder, the second mixture is mixed with the second mixture containing the inorganic powder component. Therefore, the organic compound sufficiently imparts a shearing force to the organic compound and is easily adsorbed to the inorganic powder. By using a fine inorganic powder, it is also possible to exert an excellent dispersion I·sheng to obtain an inorganic powder paste having good dispersibility. Therefore, if 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. That is, even if the average particle diameter is 1 〇 3 In the case of 微小ηιη such a small conductive metal powder, 'the conductive paste having good dispersibility can also be obtained according to the present invention. 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. 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 is obtained by removing the organic compound 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. 141780.doc 201013707 When the inorganic powder component contained in the first mixture is dispersed in a solvent, the workability of the first mixture containing the inorganic powder component can be improved. When the weight average molecular weight of the organic compound is 100 to 5 Å and the amount of acid and alkali is 100 to 2000 μm ΐ ΐ / g, it is possible to form an organic compound which is more suitable for adsorption to an inorganic powder to improve dispersibility. When a shearing force is applied to the second to-be-mixed body, the second object to be mixed can be ejected from the specific injection port while applying pressure to the second to-be-mixed body. In this case, the second to-be-mixed body is applied to the second to-be-mixed body. When the pressure is selected from 5 〇 to 300 MPa, the shear force can be surely applied to the second mixed body. [Embodiment] 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 is obtained by containing an inorganic powder component in a solvent and an organic compound having an action of increasing the dispersibility of the inorganic powder component by adsorbing the inorganic powder component. 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. . Next, 'the shearing action applying step 3 to the second mixed body 2 is applied. 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 an inorganic powder paste 5', a resin may be further added as needed. The first mixed body 1 usually contains a solvent in addition to the inorganic powder component, and 141780.doc 201013707 is preferably formed so that the inorganic powder component is dispersed in the solvent. % = the mixed body 2 is required to contain the organic compound as the second The 1 to be mixed body 1 may also contain the organic compound contained in the second mixture 2 . Hereinafter, the case where the inorganic powder paste 5 is a conductive paste will be described. ° When the conductive paste as the inorganic powder paste 5 is to be produced, the (1)th skin mixture 1 contains a conductive metal powder as an inorganic powder component. When the conductive paste is used to form the (four) conductor in the laminated ceramics, the metal component constituting the conductive metal powder may be one that can withstand the calcination temperature and environment of the ceramic which is simultaneously calcined. For example, Ni, pd, Ag, Au, Pt or Cu, or a mixture or alloy thereof may be used. The content ratio of the conductive metal powder which is a solid component in the conductive paste is preferably 20 to 70 by weight, and the content ratio of the solid component is adjusted within the range, whereby the target printing film can be stably obtained. thickness. Further, with respect to the particle diameter of the conductive metal powder, when the average particle diameter is in the range of 10 to 300 nm, the aggregation effect generally becomes remarkable, but according to the present invention, the dispersibility is improved, and the average particle diameter is In the case of 1 〇 to 3 (9) nm, it is particularly effective that the effect of improving the dispersibility of the present invention becomes remarkable. Further, from the viewpoint of whether or not the effect of the present invention can be exerted, the average particle diameter does not have a lower limit. However, if the average particle diameter is less than i 〇 nm, the conductive paste is excessively viscous and the workability is lowered, so good. In the first mixed body 1, in addition to the conductive metal powder, for the purpose of delaying the firing of the conductive metal powder, the oxide solid content may be added as a portion of the inorganic powder component. As the oxide solid component, for example, Ba, Ti, Zr, Dy, Me, or yttrium; various oxides such as λ y Mg si and γ 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 adjusted in accordance with the calcinability of the conductive metal powder within the range of 5% by weight, but particularly preferably with respect to the conductive metal powder. It is 5~20 weight. /. The amount added. The solvent contained in the second mixture 2 preferably contains a main solvent remaining in the conductive paste obtained; and does not remain in the conductive paste, and only the conductive paste is produced. The diluent solvent used in the process of the agent. ^ Promote the adsorption of organic compounds, the solubility parameter of the main solvent is better 疋 8.0~10.5, and the solubility parameter of the dilution solvent is preferably 8. Specifically, as the main solvent, a solvent such as vinegar, a thinner, 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. _ As the organic compound contained in the second to-be-mixed body 2, there are a sulfonium organic compound such as a dispersant, a resin or an additive, and particularly a dispersant, preferably having a weight average molecular weight of from 1 〇〇 to 50,000, and an amount of acid and alkali. For example, an anionic dispersing agent of 1 〇〇 to 2 〇〇〇 Kmol/g can be used, for example, a oxo acid compound, a reductive acid compound, a phthalic acid compound or the like. The amount of the dispersant to be added is preferably 0.1 to 10% by weight based on the powder component (including the conductive metal powder and the oxide solid component). As the resin, it is particularly preferable to use an ethyl cellulose resin, but an acrylic resin, a urethane resin, a phenol resin or the like can also be used. Resin content 141780.doc 201013707 The ratio is preferably 丨~丨〇% by weight relative to the conductive paste. 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 addition amount of the & additive is preferably from 0.1 to 10% by weight based on the powder component. In the shearing action applying step 3 performed on the second to-be-mixed body 2, for example, the wetted high-pressure processing apparatus ' is used to apply pressure to the second to-be-mixed body 2, and the second to-be-mixed body 2 is self-specifically injected. injection. At this time, the pressure applied to the second mixture 2 is preferably selected from 5 〇 to 3 〇〇 & ρ & In the shearing action applying step 3, a wet shearing apparatus can also be used instead of the wet high pressure processing apparatus. In the mixing step 4, the second mixed Q body 2 in which the shearing action applying step 3 has been completed collides with the first mixed body 丨. In this manner, the second mixed body 2 is caused to collide with the second mixed body 2 after the shearing action, whereby the organic compound having the dispersing action contained in the second mixed body 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, the temperature of the second mixture 2 is adjusted to be 25 ° C or more and less than the boiling point of the solvent. Fig. 2 is a flow chart showing a method of producing the inorganic powder paste according to the second embodiment of the present invention. In FIG. 2, elements that are the same as those shown in the drawings are denoted by the same reference numerals, and the description thereof will not be repeated. 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 n through the filter. . Further, the inorganic powder component 141780.doc .10 - 201013707 contained in the mixture 1 is left after the organic compound is removed from the mixed slurry U by performing the separation step 12, and the second mixture 2 is The organic compound contained in the organic compound is taken out from the mixed slurry 11 by performing the separation step 12. The subsequent steps are the same as those in the first embodiment. The mixed slurry 11 prepared in the second embodiment can be used as the inorganic powder paste 5 obtained in the above-described second embodiment, and further as the inorganic powder paste 5 obtained in the second embodiment. Thereby, the shearing action application step 3 is repeatedly carried out, whereby the dispersibility of the obtained inorganic powder paste can be further improved. 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, the preferred inorganic powder is evaluated first. The paste 5, ϋ sets the number of repetitions for each type of the inorganic powder paste 5. 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, for example, a laminated ceramic capacitor or a laminated ceramic inductor can be manufactured. Multi-layered Tauman electronic parts such as LC, laminated ceramics, and multi-layer ceramic substrates. Next, the experimental examples which have been carried out will be described in order to confirm the effects of the present invention. In the present experimental example, samples 1 to 7 were prepared under the composition and processing conditions shown in Table 7 below. Conductive paste. (1) Sample 1 Table 1
添加比率 備註 第1被混合體 粉末成分 Cu 30重量％/糊劑 粒徑：200 nm 主溶劑 松油醇 25重量％/糊劑 溶解度參數：10.4 沸點：219°C 稀釋溶劑 - - 分散劑 導 樹脂 - - 添加劑 - - 第2被混合體 主溶劑 松油醇 25重量％/糊劑 溶解度參數：10.4 沸點：219°C 稀釋溶劑 - - 分散劑 馬來酸酐-聚苯乙烯 共聚物 1重量％/粉末 酸驗量：1000 μπιοΐ/g 重量平均分子量：20000 陰離子性 樹脂 - * 添加劑 * 處理條件 處理次數 1次 處理壓力 200 MPa 被混合體溫度 45〇C (2)試樣2 表2Addition ratio Remarks 1st mixed body powder component Cu 30% by weight / paste particle size: 200 nm Main solvent terpineol 25% by weight / paste Solubility parameter: 10.4 Boiling point: 219 ° C Dilution solvent - - Dispersant conductive resin - - Additive - - 2nd mixed solvent main solvent terpineol 25% by weight / paste Solubility parameter: 10.4 Boiling point: 219 ° C Dilution solvent - - Dispersant Maleic anhydride - Polystyrene copolymer 1% by weight / powder Acid test: 1000 μπιοΐ/g Weight average molecular weight: 20000 Anionic resin - * Additive * Treatment conditions Treatment times 1 treatment pressure 200 MPa Mixture temperature 45 〇 C (2) Sample 2 Table 2
添加比率 備註 第1被混合體 粉末成 分 Ni 35重量％/糊劑 粒徑：200 nm BaTi03 3重量％/糊劑 粒徑：30 nm 主溶劑 松油醇 15重量％/糊劑 溶解度參數：10.4 沸點：219°C 稀釋溶 劑 丙嗣 20重量％/糊劑 溶解度參數：9.1 沸點：56°C 分散劑 - - 樹脂 - - 添加劑 - 第2被混合體 主溶劑 松油醇 15重量％/糊劑 溶解度參數：10.4 沸點：219°C 稀釋溶 劑 丙嗣 20重量％/糊劑 溶解度參數：9.1 沸點：56°C 141780.doc -12- 201013707Addition ratio Remarks 1st mixed body powder component Ni 35 wt% / paste particle size: 200 nm BaTi03 3 wt% / paste particle size: 30 nm Main solvent terpineol 15 wt% / paste solubility parameter: 10.4 boiling point :219°C Diluting solvent Propylene 20% by weight/paste Solubility Parameter: 9.1 Boiling point: 56°C Dispersant - - Resin - - Additive - 2nd mixed solvent main solvent terpineol 15% by weight / paste solubility parameter : 10.4 Boiling point: 219 ° C Diluting solvent Propionate 20% by weight / paste Solubility Parameter: 9.1 Boiling point: 56 ° C 141780.doc -12- 201013707
分散劑 馬來酸 酐- 聚苯乙烯 共聚物 0.3重量％/粉末 酸驗量：1000 μιηοΐ/g 重量平均分子量：20000 陰離子性 樹脂 - 添加劑 - - 處理條件 處理次數 5次 處理壓力 175 MPa 被混合體溫度 40°C (3)試樣3 表3Dispersant maleic anhydride - polystyrene copolymer 0.3% by weight / powder acid test: 1000 μιηοΐ / g Weight average molecular weight: 20000 Anionic resin - Additive - - Treatment conditions Treatment times 5 times Treatment pressure 175 MPa Mixed body temperature 40°C (3) Sample 3 Table 3
添加比率 備註 粉末成分 Ag-Pd 35重量％/糊劑 粒徑：300 run 第1被混合體 主溶劑 醋酸正 15重量％/糊劑 溶解度參數：9.0 己酯 沸點：172°C 稀釋溶劑 甲苯 20重量％/糊劑 溶解度參數：9.1 沸點：110°C 分散劑 - - 樹脂 - 添加劑 - - 第2被混合體 主溶劑 醋酸正 10重量％/糊劑 溶解度參數：9.0 沸點：172°C 己酯 稀釋溶劑 曱笨 25重量％/糊劑 溶解度參數：9.1 沸點：110°C 分散劑 馬來酸酐- 5重量％/糊劑 酸驗量：100 μιηοΐ/g 聚苯乙烯 重量平均分子量：20000 共聚物 陰離子性 樹脂 - - 添加劑 - - 處理條件 處理次數 10次 處理壓力 300 MPa 被混合體溫度 50°C (4)試樣4 141780.doc -13- 201013707 表4Addition ratio Remarks Powder composition Ag-Pd 35 wt%/paste particle size: 300 run First mixed body main solvent acetic acid positive 15% by weight/paste solubility parameter: 9.0 hexyl ester boiling point: 172 ° C Dilution solvent toluene 20 weight %/paste solubility parameter: 9.1 Boiling point: 110 ° C Dispersant - - Resin - Additive - - 2nd mixture main solvent Acetic acid positive 10% by weight / paste Solubility parameter: 9.0 Boiling point: 172 ° C Hexyl ester dilution solvent曱 25 25% by weight / paste solubility parameters: 9.1 boiling point: 110 ° C dispersant maleic anhydride - 5 wt% / paste acid test: 100 μιηοΐ / g polystyrene weight average molecular weight: 20000 copolymer anionic resin - - Additives - - Treatment conditions Processing times 10 times Treatment pressure 300 MPa Mixed body temperature 50 ° C (4) Sample 4 141780.doc -13- 201013707 Table 4
添加比率 備註 第1被混合體 粉末成分 Ni 30重量％/糊劑 粒徑：10nm BaTi03 2重量％/糊劑 粒徑：5 nm 主溶劑 二異丁基酮 25重量％/糊劑 溶解度參數：8.5 沸點：168°C 稀釋溶劑 丙酮 20重量％/糊劑 溶解度參數：9.1 沸點：56°C 分散劑 馬來酸酐-聚苯乙烯 共聚物 1重量％/粉末 酸驗量：2000 μιηοΐ/g 重量平均分子量：1000 陰離子性 樹脂 乙基纖維素 1重量％/粉末 添加劑 二胺 氧化稀加成物 1重量％/糊劑 胺類化合物 第2被混合體 主溶劑 二異丁基酮 25重量％/糊劑 溶解度參數：8.5 沸點：168°C 稀釋溶劑 丙剩 20重量％/糊劑 溶解度參數：9.1 沸點：56°C 分散劑 馬來酸酐-聚苯乙烯 共聚物 1重量％/粉末 酸驗量：2000 μπιοΐ/g 重量平均分子量：100 陰離子性 樹脂 乙基纖維素 1重量％/粉末 添加劑 二胺 氧化稀加成物 1重量％/粉末 胺類化合物 處理條件 處理次數 10次 處理壓力 300 MPa 被混合體溫度 50°C (5)試樣5 表5 添加比率 備註 第1被混合體 粉末成分 Cu 30重量％/糊劑 粒徑：200 nm 主溶劑 1-戊醇 5重量％/糊劑 溶解度參數：10.5 沸點：176°C 稀釋溶劑 曱醇 30重量％/糊劑 溶解度參數：13.8 沸點：65°C 分散劑 - - 樹脂 - - 添加劑 - - 141780.doc -14- 201013707Addition ratio Remarks 1st mixed body powder component Ni 30% by weight/paste particle diameter: 10 nm BaTi03 2% by weight/paste particle diameter: 5 nm Main solvent diisobutyl ketone 25% by weight/paste solubility parameter: 8.5 Boiling point: 168 ° C Diluting solvent Acetone 20% by weight / paste Solubility Parameter: 9.1 Boiling point: 56 ° C Dispersant Maleic anhydride - Polystyrene copolymer 1% by weight / powder acid test: 2000 μιηοΐ / g Weight average molecular weight : 1000 anionic resin ethyl cellulose 1% by weight / powder additive diamine oxide dilute adduct 1% by weight / paste amine compound second mixed body main solvent diisobutyl ketone 25% by weight / paste solubility Parameters: 8.5 Boiling point: 168 ° C Diluting solvent: Remaining 20% by weight / paste Solubility Parameter: 9.1 Boiling point: 56 ° C Dispersant Maleic anhydride-polystyrene copolymer 1% by weight / powder acid test: 2000 μπιοΐ / g Weight average molecular weight: 100 Anionic resin ethyl cellulose 1% by weight / powder additive Diamine oxide dilute adduct 1% by weight / powder amine compound treatment conditions 10 times Treatment pressure 300 MPa Mixed body temperature 50 ° C (5) Sample 5 Table 5 Addition ratio Remarks First mixed body powder component Cu 30% by weight / paste particle size: 200 nm Main solvent 1-pentanol 5 % by weight Solubility Solubility parameters: 10.5 Boiling point: 176 ° C Diluting solvent sterol 30% by weight / paste Solubility Parameters: 13.8 Boiling point: 65 ° C Dispersant - - Resin - - Additive - - 141780.doc -14- 201013707
第2被混合體 主溶劑 1-戊醇 5重量％/糊劑 溶解度參數·· 10.5 沸點：176°C 稀釋溶劑 甲醇 30重量％/糊劑 溶解度參數：12.9 沸點：65°C 分散劑 馬來酸肝-聚苯乙烯 共聚物 1重量％/粉末 酸驗量：500 μιηοΐ/g 重量平均分子量：50000 陰離子性 樹脂 - - 添加劑 - - 處理條件 處理次數 10次 處理壓力 50 MPa 被混合體溫度 25〇C (6)試樣6Second mixed body main solvent 1-pentanol 5% by weight / paste solubility parameter · · 10.5 Boiling point: 176 ° C Diluting solvent methanol 30% by weight / paste solubility parameter: 12.9 Boiling point: 65 ° C Dispersant maleic acid Liver-polystyrene copolymer 1% by weight / powder acid test: 500 μιηοΐ / g Weight average molecular weight: 50000 Anionic resin - - Additive - - Treatment conditions Treatment times 10 times Treatment pressure 50 MPa Mixed body temperature 25 〇C (6) Sample 6
表6Table 6
添加比率 備註 第1被混合體 粉末成分 Cu 30重量％/糊劑 粒徑：200 nm 主溶劑 二己基醚 25重量％/糊劑 溶解度參數：8.0 沸點：226°C 稀釋溶劑 庚炫 20重量％/糊劑 溶解度參數：7.4 沸點：98°C 分散劑 - - 樹脂 - - 添加劑 - _ 第2被混合體 主溶劑 二己基醚 25重量％/糊劑 溶解度參數：8.0 沸點：226°C 稀釋溶劑 庚炫 20重量％/糊劑 溶解度參數：7.4 沸點：98°C 分散劑 馬來酸酐-聚苯乙烯 共聚物 1重量％/粉末 酸驗量：1000 μιηοΐ/g 重量平均分子量：20000 陰離子性 樹脂 - - 添加劑 - - 處理條件 處理次數 5次 處理壓力 200 MPa 被混合體溫度 45〇C (7)試樣7 141780.doc -15- 201013707 表7 添加比率 備註 第1被混合體 粉末成分 Cu 35重量％/糊劑 粒徑：200 nm 主溶劑 松油醇 10重量％/糊劑 溶解度參數：10.4 沸點：219°C 稀釋溶劑 丙酮 25重量％/糊劑 溶解度參數：9.1 沸點：56°C 分散劑 - - 樹脂 - 添加劑 - - 第2被混合體 主溶劑 松油醇 10重量％/糊劑 溶解度參數：10.4 沸點：219°C 稀釋溶劑 丙明 25重量％/糊劑 溶解度參數：9.1 沸點：56°C 分散劑 馬來酸酐-聚苯乙烯 共聚物 1重量％/粉末 酸驗量：1000 μιηοΐ/g 重量平均分子量：20000 陰離子性 樹脂 - - 添加劑 - - 無高壓分散處理 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％。 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。 試樣1〜7各自之導電性糊劑之製備順序如下所述。 為了獲得第1被混合體1，如表1〜表7之「第1被混合體」 攔所示，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 141780.doc •16- 201013707 切式攪拌機進行混合攪拌。 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」攔所示，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。 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喷射第2被混 合體。 接著’在加壓喷射後，一邊利用加熱器或冷凝水將第2 被混合體控制為表〗〜表7之「處理條件」中之「被混合體 度」搁所不之溫度，一邊使其與第1被混合體碰撞，藉 此獲得導電性糊劑。 對於表1〜表7之「處理條件」中之「處理次數」為複數 •人之試樣，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 X。 141780.doc •17· 201013707 又，在表7所示之試樣7令，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 混合授拌，獲得導電性糊劑。 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。 口 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0.5 Pa，s以下之後，使用網眼為丨〇 、5 μιη、3 μπι及最終階段的導電性金屬粉末之平均丨次粒徑之 2倍之網眼的薄膜式過濾器，採用壓力未滿丨5 kg/cm2之加 壓過濾而去除塊狀物。 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2.〇Xl〇-i氣壓之減壓下加熱至仂它而去除稀 釋溶劑之後，對過濾處理後之導電性糊劑’用3 μιη之薄膜 式過濾器，採用壓力未滿1 ·5 kg/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。 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。 即，於厚度為2 μηι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，形成包含厚度為丨pm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’測定塗膜表面粗縫度。其結果示於表8。 141780.doc -18- 201013707 接著’使導電性糊劑乾燥後’積層、壓接電介質 片以獲得450層之積層結構，其次， 吾』成 3.2 mmx2.5 mm 之平面形狀，獲得積層體晶片。 斟接藤胁# 下來’以最高溫度 280 C對積層體芯片進行脫脂處 丄 。 交於虱/氮混合氣體 中，以1200。(：之最高溫声i隹耔 敢^皿度進魏燒，且於锻燒後，藉由塗 佈及燒接㈣成外部電極，在各試樣中獲得積層陶 容。 對1 00個所獲得之試樣之積層 々J文電容，用LCR測量儀 測定靜電容量，計算出短路不良率 _ 干再結果不於表8。關 於表8所示之短路不色率，芒土 艮羊右未滿10%，則可判定為良 品，若為10%以上，則可判定為不良品。 表8Addition ratio Remarks 1st mixed body powder component Cu 30% by weight / paste particle size: 200 nm Main solvent Dihexyl ether 25% by weight / paste Solubility parameter: 8.0 Boiling point: 226 ° C Diluting solvent Geng Xuan 20% by weight / Paste solubility parameter: 7.4 Boiling point: 98 ° C Dispersant - - Resin - - Additive - _ 2nd mixed body main solvent Dihexyl ether 25% by weight / paste Solubility parameter: 8.0 Boiling point: 226 ° C Diluting solvent Geng Hyun 20% by weight/paste solubility parameter: 7.4 Boiling point: 98°C Dispersant Maleic anhydride-polystyrene copolymer 1% by weight/powder acidity: 1000 μιηοΐ/g Weight average molecular weight: 20000 Anionic resin - - Additive - - Processing condition Processing times 5 times Processing pressure 200 MPa Mixed body temperature 45 〇 C (7) Sample 7 141780.doc -15- 201013707 Table 7 Addition ratio Remarks 1st mixed body powder component Cu 35 wt% / paste Particle size: 200 nm Main solvent Terpineol 10% by weight/paste Solubility Parameter: 10.4 Boiling point: 219 °C Diluting solvent Acetone 25% by weight / Paste Solubility Parameters: 9.1 Boiling point: 5 6°C Dispersant - - Resin - Additive - - 2nd Reagent Main solvent Terpineol 10% by weight / Paste Solubility Parameter: 10.4 Boiling Point: 219 °C Diluting Solvent Bing Ming 25% by weight / Paste Solubility Parameters: 9.1 Boiling point: 56 ° C Dispersant Maleic anhydride-polystyrene copolymer 1% by weight / powder acid test: 1000 μιηοΐ / g Weight average molecular weight: 20000 Anionic resin - - Additive - - No high pressure dispersion treatment in Table 1 In Table 7, the "% by weight/paste" shown in the column of "addition ratio" indicates the weight % in the obtained conductive paste, and "% by weight/powder" indicates the relative to the added powder component. weight%. 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. The order of preparation of each of the conductive pastes of Samples 1 to 7 is as follows. In order to obtain the first to-be-mixed body 1, as shown in the "first mixed body" of Tables 1 to 7, the main solvent is added to the powder component, and a diluent solvent, a dispersing agent, and a resin are further added depending on the sample. / or additives, these are mixed with a 141780.doc •16- 201013707 cut mixer. On the other hand, in order to obtain the second to-be-mixed body, as shown in the "second to-be-mixed body" of Tables 1 to 7, a dispersing agent is added to the main solvent, 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. Then, in order to apply a shearing force to the second to-be-mixed body obtained in the above-described manner, the wet high-pressure treatment apparatus is used, and the pressures shown in the "treatment pressure" column in the "processing conditions" of Tables 1 to 7 are used. On the other hand, the second mixture is pressurized. Then, after the pressure injection, the second object to be mixed is controlled by the heater or the condensed water to the temperature of the "mixed body" in the "processing conditions" of Table 7 to Table 7 The first mixed body collides with each other to obtain a conductive paste. The "number of times of processing" in the "processing conditions" in Tables 1 to 7 is a sample of a plurality of persons, and 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. By separating 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, the organic compound solution is subjected to shearing under the same conditions as described above. 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 processing is to be performed, a processing corresponding to the processing time calculated by the following formula: processing time = (conductive paste amount) / (conductive paste processing speed) X X is performed. 141780.doc •17· 201013707 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 mixed by a shear mixer. Mix and obtain a conductive paste. 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. Then, after the above-mentioned conductive paste mixed and stirred is adjusted to have a viscosity of 0.5 Pa or less, the mesh is used as a conductive metal of 丨〇, 5 μm, 3 μm, and the final stage. The membrane filter of the mesh having twice the average particle size of the powder was subjected to pressure filtration at a pressure of less than 5 kg/cm 2 to remove the cake. Finally, in the case where the conductive paste contained in the above-mentioned filtration treatment contains a diluent solvent, the conductivity after the filtration treatment is performed after heating to a pressure of 2.〇Xl〇-i under reduced pressure to remove the dilution solvent. The paste was removed by a pressure filter having a pressure of less than 1.5 kg/cm2 using a membrane filter of 3 μm, and the block was again removed to obtain a conductive paste of each sample as a target. In order to evaluate the conductive paste of each sample thus obtained, a laminated ceramic capacitor was produced in the following manner. Namely, on each of the dielectric ceramic green sheets having a thickness of 2 μm, the conductive paste of each sample was printed by a screen printing method to form a coating film containing a conductive paste having a thickness of 丨pm. Here, the shape of the coating film was observed using a three-dimensional shape measuring device to measure the rough surface of the coating film. The results are shown in Table 8. 141780.doc -18- 201013707 Then, after drying the conductive paste, the dielectric sheets were laminated and crimped to obtain a layered structure of 450 layers, and secondly, a planar shape of 3.2 mm x 2.5 mm was obtained to obtain a laminate wafer.藤 藤藤# Go down to degrease the laminated chip at a maximum temperature of 280 C. In a helium/nitrogen mixed gas, 1200. (: The highest temperature sound i隹耔 dare to the degree of Wei Wei, and after calcination, by coating and burning (four) into an external electrode, obtained a layered ceramic capacity in each sample. The laminated layer of the sample is 々J capacitor, the electrostatic capacitance is measured by the LCR meter, and the short-circuit defect rate is calculated _ dry and the result is not in Table 8. Regarding the short-circuit colorlessness rate shown in Table 8, the mulberry is not full If it is 10%, it can be judged as a good product. If it is 10% or more, it can be judged as a defective product.
參 由表8而確認，根撼謎媒〗< 媒式樣1〜6’印刷塗膜平滑性提高，其 結果可將積層陶資^電容5|之柄& 谷器之也路不良率抑制為未滿10%。 可推測其原因在於，有播4卜人机1 口物於粉末成分上之吸附狀態 传以最佳化，從而導電性糊&丨+ 电注糊劑中之粉末成分之分散性提 南0 相對於此’試樣7中，盥斌楳,u ^ 一武樣1〜6相比，印刷塗膜平滑性 劣化，且短路不良率大掛‘ 平Χ恢增加。可推測其原因在於，有機 141780.doc -19- 201013707 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。 【圖式簡單說明】 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 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。 【主要元件符號說明】 1 第1被混合體 2 第2被混合體 3 剪切作用施加步驟 4 混合步驟 5 無機粉末糊劑 11 混合漿料 12 分離步驟 141780.doc .20.It is confirmed in Table 8 that the smoothness of the printing film is improved, and the result can suppress the defective rate of the stalk of the slabs of the slabs and the slabs of the slabs. It is less than 10%. It is presumed that the reason is that the adsorption state of the powdered component of the seeding machine is optimized, so that the dispersibility of the powder component in the conductive paste & In contrast, in the sample 7, in the case of the sample, the smoothness of the printed coating film was deteriorated, and the short-circuit defect rate was increased. It is presumed that the reason is that the organic 141780.doc -19-201013707 compound has a poor adsorption state on the powder component, and the dispersibility of the conductive paste is lowered. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method for producing an inorganic powder paste according to a first embodiment of the present invention; and FIG. 2 is a view showing a method for producing a method for producing an inorganic powder paste according to a second embodiment of the present invention. . [Description of main components] 1 1st mixed body 2 2nd mixed body 3 Shear action application step 4 Mixing step 5 Inorganic powder paste 11 Mixed slurry 12 Separation step 141780.doc .20.
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