TW202239980A - Nickel nanoparticles, paste materials, and laminated ceramic capacitors wherein the nickel nanoparticles have an average particle diameter of 5 nm to 100 nm and contain 99.5 parts by weight or more of a nickel component in 100 parts by weight of a metal component - Google Patents
Nickel nanoparticles, paste materials, and laminated ceramic capacitors wherein the nickel nanoparticles have an average particle diameter of 5 nm to 100 nm and contain 99.5 parts by weight or more of a nickel component in 100 parts by weight of a metal component Download PDFInfo
- Publication number
- TW202239980A TW202239980A TW111112004A TW111112004A TW202239980A TW 202239980 A TW202239980 A TW 202239980A TW 111112004 A TW111112004 A TW 111112004A TW 111112004 A TW111112004 A TW 111112004A TW 202239980 A TW202239980 A TW 202239980A
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- Prior art keywords
- nickel
- particles
- weight
- particle diameter
- parts
- Prior art date
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 350
- 239000002245 particle Substances 0.000 title claims abstract description 201
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 179
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims description 17
- 239000003985 ceramic capacitor Substances 0.000 title claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 230000001133 acceleration Effects 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 abstract description 13
- 238000011049 filling Methods 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 53
- 150000002902 organometallic compounds Chemical class 0.000 description 39
- 239000000243 solution Substances 0.000 description 36
- 238000010668 complexation reaction Methods 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
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- -1 nickel carboxylate Chemical class 0.000 description 22
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- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
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- 239000002002 slurry Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000002815 nickel Chemical class 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
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- 239000003981 vehicle Substances 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000011354 acetal resin Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
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- 239000011258 core-shell material Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004034 viscosity adjusting agent Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000009918 complex formation Effects 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 3
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- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 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 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 229920001249 ethyl cellulose Polymers 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
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- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
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- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
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- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
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- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
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Abstract
Description
本發明是有關於一種鎳奈米粒子、膏材料及層疊陶瓷電容器。The invention relates to a nickel nano particle, a paste material and a stacked ceramic capacitor.
多層陶瓷電容器（Multilayer Ceramic Condenser，MLCC）包含將陶瓷電介質層與內部電極層交替層疊並一體化而成的電容器，以小型化與高容量化為目的正推進薄膜多層化。隨著薄膜化，電介質或電極中所使用的粒子也推進微粒子化，由此粒子凝聚的問題變得明顯，要求高度的分散技術或粒子形狀控制技術。Multilayer ceramic capacitors (Multilayer Ceramic Condenser, MLCC) include capacitors in which ceramic dielectric layers and internal electrode layers are alternately stacked and integrated, and multilayer thin films are being promoted for the purpose of miniaturization and high capacity. Particles used in dielectrics and electrodes are also reduced to finer particles as thinner films are made. As a result, the problem of particle agglomeration becomes apparent, and advanced dispersion technology and particle shape control technology are required.
就粒子形狀而言，在將膏延展來形成薄膜時，若存在粒度分佈廣、且大的粒子，則會以大的粒子為起點發生斷液等，產生無法以均等的厚度進行塗布的問題。為了使均勻的張力作用於膏整體，需要均勻、且以一定量平衡良好地配置大的粒子的粒子徑。In terms of particle shape, when the paste is stretched to form a thin film, if there are large particles with a wide particle size distribution, liquid breakage will occur starting from the large particles, and there will be a problem that it cannot be coated with a uniform thickness. In order to apply a uniform tension to the entire paste, it is necessary to arrange the particle diameters of the large particles uniformly and well-balanced at a certain amount.
另外，在形成電磁波遮罩體或觸控式螢幕等的配線的用途中，為了防止配線的滲出或擴散，正研究向奈米壓印後的基板的槽中填充金屬粒子。已知，即便在狹窄的槽中進行高填充，粒子的粒整齊的情況也可保持膏整體的張力的均勻性，容易高填充化。In addition, in the application of forming wirings such as electromagnetic wave shields and touch screens, in order to prevent bleeding or diffusion of wirings, filling metal particles into grooves of substrates after nanoimprinting has been studied. It is known that even when high filling is performed in a narrow groove, the uniformity of the tension of the entire paste can be maintained when the particles are uniform, and high filling is easy.
作為製造均勻的粒子的方法，可列舉：利用肼對使鎳鹽與鹼金屬氫氧化物在水中進行反應而得的氫氧化鎳粒子還原而得的鎳粒子的製造方法（專利文獻1）。利用所述製造方法製造的粒子為具有狹窄的粒度分佈、且平均粒子徑為0.44 μm～0.51 μm的鎳粒子，所述粒度分佈中，具有通過掃描電子顯微鏡（scanning electron microscope，SEM）觀察而得的平均粒子徑的1.2倍以上的粒子徑的粒子個數為總粒子個數的5%以下，具有所述平均粒子徑的0.8倍以下的粒子徑的粒子個數為總粒子個數的5%以下。另外，專利文獻1的製造方法由於是在水溶液中進行反應，因此無法完全去除氫氧化物，且當應用於粒徑100 nm以下時、當應用於所述用途中所適宜地使用的非極性溶媒中的情況等下，無法獲得充分的分散性。因此，存在引起粒子彼此的凝聚的問題。另外，可列舉如下點：難以合成粒徑100 nm以下且粒度整齊的粒子。As a method for producing uniform particles, a method for producing nickel particles obtained by reducing nickel hydroxide particles obtained by reacting a nickel salt and an alkali metal hydroxide in water with hydrazine is mentioned (Patent Document 1). The particles produced by the production method are nickel particles having a narrow particle size distribution and an average particle diameter of 0.44 μm to 0.51 μm. The number of particles with a particle diameter of 1.2 times or more of the average particle diameter is less than 5% of the total number of particles, and the number of particles with a particle diameter of 0.8 times or less of the average particle diameter is 5% of the total number of particles the following. In addition, since the production method of Patent Document 1 reacts in an aqueous solution, the hydroxide cannot be completely removed, and when applied to a non-polar solvent that is preferably used in the application with a particle size of 100 nm or less, In the case of medium, etc., sufficient dispersibility cannot be obtained. Therefore, there is a problem of causing aggregation of particles. In addition, the point that it is difficult to synthesize particles having a particle diameter of 100 nm or less and a uniform particle size can be cited.
作為製造100 nm以下且均勻的粒子的方法，報告有：通過使用在包含羧酸鎳的鹽中加入甲酸銅並利用胺進行還原而得的10 nm～50 nm的種粒子，可獲得變異係數（coefficient of variation）CV為0.2以下的均勻的粒子（專利文獻2），但種粒子中使用銅。另外，在專利文獻2的其他實施例中，雖不使用甲酸銅，但使用硝酸銀、乙酸鈀、氯鉑酸六水合物或氯金酸四水合物，均並用鎳以外的異種金屬。就電性、成本的觀點而言，要求鎳純度盡可能高的鎳粒子。 [現有技術文獻] [專利文獻] As a method of producing uniform particles of 100 nm or less, it is reported that by using seed particles of 10 nm to 50 nm obtained by adding copper formate to a salt containing nickel carboxylate and reducing it with an amine, the coefficient of variation ( Coefficient of variation) CV is uniform particles of 0.2 or less (Patent Document 2), but copper is used for the seed particles. In addition, in other examples of Patent Document 2, although copper formate is not used, silver nitrate, palladium acetate, chloroplatinic acid hexahydrate, or chloroauric acid tetrahydrate are used, and dissimilar metals other than nickel are used in combination. From the viewpoint of electrical properties and cost, nickel particles having as high a purity of nickel as possible are required. [Prior art literature] [Patent Document]
[專利文獻1]日本專利第3280372號 [專利文獻2] WO2016/052067 [Patent Document 1] Japanese Patent No. 3280372 [Patent Document 2] WO2016/052067
[發明所欲解決之課題][Problem to be Solved by the Invention]
本發明的目的在於提供一種薄膜形成性或向極窄間隙的填充性優異、且高純度的5 nm～100 nm的鎳奈米粒子。 [解決課題之手段] An object of the present invention is to provide high-purity nickel nanoparticles of 5 nm to 100 nm, which are excellent in thin film formability and filling property into extremely narrow gaps. [Means to solve the problem]
本發明者等人反復進行了努力研究，結果發現，通過在鎳奈米粒子的合成時，進行攪拌動力及產生的氣體成分的控制，可製造即便在利用高解析度SEM進行觀察的情況下，粒度也整齊的鎳奈米粒子，從而完成了本發明。The inventors of the present invention have repeatedly conducted diligent research and found that by controlling the stirring power and the gas components generated during the synthesis of nickel nanoparticles, it is possible to manufacture Nickel nanoparticles with uniform particle size have been obtained, thus completing the present invention.
即，本發明是關於一種鎳奈米粒子，平均粒子徑為5 nm～100 nm，且金屬成分100重量份中所含的鎳成分包含99.5重量份以上，所述鎳奈米粒子的特徵在於：在利用加速電壓為15 kV時二次電子解析度為1.0 nm以下的掃描式電子顯微鏡（SEM）所拍攝的全部400個鎳奈米粒子中，相對於這些的平均粒子徑，粒子徑為1/2以下的粒子與粒子徑為3/2以上的粒子的合計數量所占的比例為5%以下。That is, the present invention relates to a nickel nanoparticle having an average particle diameter of 5 nm to 100 nm, and the nickel component contained in 100 parts by weight of the metal component contains 99.5 parts by weight or more, and the nickel nanoparticle is characterized in that: Among all 400 nickel nanoparticles photographed by a scanning electron microscope (SEM) with a secondary electron resolution of 1.0 nm or less at an accelerating voltage of 15 kV, the average particle diameter of these particles is 1/ The ratio of the total number of particles having a particle size of 2 or less and particles having a particle diameter of 3/2 or more is 5% or less.
本發明的鎳奈米粒子優選為包含0.00003重量份～0.5重量份的鋰。The nickel nanoparticles of the present invention preferably contain 0.00003 parts by weight to 0.5 parts by weight of lithium.
本發明的膏材料的特徵在於：是將所述鎳奈米粒子與樹脂混合而成。The paste material of the present invention is characterized in that it is obtained by mixing the nickel nanoparticles and resin.
本發明的層疊陶瓷電容器的特徵在於：使用所述鎳奈米粒子作為電極用材料。 [發明的效果] The multilayer ceramic capacitor of the present invention is characterized in that the nickel nanoparticles are used as a material for electrodes. [Effect of the invention]
本發明的鎳奈米粒子由於即便在利用加速電壓為15 kV時二次電子解析度為1.0 nm以下的高解析度SEM進行觀察的情況下，平均粒子徑的1/2以下的粒子與平均粒子徑的3/2以上的粒子的合計數量在整體粒子中所占的比例也為5%以下，因此在形成薄膜時作用於膏內部的張力變得均勻。因此，容易形成均勻的超薄膜，例如，可適宜地用於MLCC（Multilayer Ceramic Condenser）等需要多層薄膜層疊的用途中。 另外，使用本發明的鎳奈米粒子的膏材料也可以防止配線的滲出或擴散為目的作為向印刷形成的槽中填充膏的材料，而廣泛利用於製造電磁波遮罩體或觸控式螢幕等的用途中。 The nickel nanoparticles of the present invention are observed by a high-resolution SEM with a secondary electron resolution of 1.0 nm or less at an accelerating voltage of 15 kV, and particles with an average particle diameter of 1/2 or less are different from the average particle diameter. The ratio of the total number of particles with a diameter of 3/2 or more to the total particles is also 5% or less, so the tension acting on the inside of the paste becomes uniform when forming a thin film. Therefore, it is easy to form a uniform ultra-thin film, for example, it can be suitably used in applications requiring multi-layer thin film lamination, such as MLCC (Multilayer Ceramic Condenser). In addition, the paste material using the nickel nanoparticles of the present invention can also be used as a material for filling paste into grooves formed by printing for the purpose of preventing bleeding or diffusion of wiring, and is widely used in the manufacture of electromagnetic wave shields, touch screens, etc. in use.
以下對本發明的實施形態進行說明。 本發明的鎳奈米粒子為平均粒子徑為5 nm～100 nm、且金屬成分100重量份中所含的鎳成分包含99.5重量份以上的鎳奈米粒子，並且在利用加速電壓為15 kV時二次電子解析度為1.0 nm以下的SEM所拍攝的全部400個鎳奈米粒子中，相對於這些的平均粒子徑，粒子徑為1/2以下的粒子（以下，有時稱為“相對小粒子”）與粒子徑為3/2以上的粒子（以下，有時稱為“相對大粒子”）的合計數量所占的比例為5%以下。如此，通過相對小粒子與相對大粒子的合計數量在整體粒子數中所占的比例為5%以下，從而在粒度分佈中大幅偏離平均粒子徑的粒子的存在比率少，粒度分佈尖銳，因此薄膜形成性或向極窄間隙的填充性優異。 Embodiments of the present invention will be described below. The nickel nanoparticles of the present invention have an average particle diameter of 5 nm to 100 nm, and the nickel component contained in 100 parts by weight of the metal component contains 99.5 parts by weight or more of nickel nanoparticles, and when the acceleration voltage is 15 kV Among all 400 nickel nanoparticles captured by an SEM with a secondary electron resolution of 1.0 nm or less, those whose average particle diameter was 1/2 or less (hereinafter sometimes referred to as “relatively small Particles") and the total number of particles with a particle diameter of 3/2 or more (hereinafter, sometimes referred to as "relatively large particles") shall be 5% or less. In this way, when the ratio of the total number of relatively small particles and relatively large particles to the total number of particles is 5% or less, the ratio of particles greatly deviating from the average particle diameter in the particle size distribution is small, and the particle size distribution is sharp. Therefore, the thin film Excellent formability and fillability into extremely narrow gaps.
現有技術的鎳奈米粒子存在大量包含相對小粒子的問題。在MLCC等為了防止燒結時的收縮而添加陶瓷填料的用途中，由於為了填充到鎳奈米粒子的間隙中而使用微粒子，因此若相對小粒子的比率大，則最優的粒度平衡崩壞，且黏度特性也發生變化，因此對薄膜形成或燒結性產生障礙。另外，若存在比平均粒子徑的2倍大的粒子，則在形成若干層電極等薄膜的情況下，有可能產生穿透絕緣層而導通等問題，因此優選為相對大粒子的比率小。因此，相對小粒子與相對大粒子在粒子整體中所占的比例分別優選為3%以下，將相對小粒子與相對大粒子加以合計的比例為5%以下。Nickel nanoparticles of the prior art suffer from the problem of containing a large number of relatively small particles. In applications such as MLCC where ceramic fillers are added to prevent shrinkage during sintering, since fine particles are used to fill the gaps of nickel nanoparticles, if the ratio of relatively small particles is large, the optimal particle size balance will collapse. In addition, the viscosity characteristics also change, which hinders film formation and sinterability. In addition, if there are particles larger than twice the average particle diameter, when several layers of thin films such as electrodes are formed, problems such as penetration through insulating layers and conduction may occur, so the ratio of relatively large particles is preferably small. Therefore, the proportions of relatively small particles and relatively large particles in the entire particle are preferably 3% or less, and the total ratio of relatively small particles and relatively large particles is 5% or less.
本發明的鎳奈米粒子優選為以利用加速電壓為15 kV時二次電子解析度為1.0 nm以下的SEM所拍攝的400個鎳奈米粒子的粒子徑的標準差除以平均粒子徑而得的值（CV值）為0.25以下，更優選為0.20以下。The nickel nanoparticles of the present invention are preferably obtained by dividing the standard deviation of particle diameters of 400 nickel nanoparticles photographed by an SEM with a secondary electron resolution of 1.0 nm or less at an accelerating voltage of 15 kV by the average particle diameter The value (CV value) of is 0.25 or less, more preferably 0.20 or less.
本發明的鎳奈米粒子的平均粒子徑為5 nm～100 nm，但就添加的親核試劑昂貴的方面、與現有技術的鎳奈米粒子（小粒徑鎳奈米粒子的含量多）的不同點變明確的理由而言，所述平均粒子徑的下限優選為10 nm以上，更優選為15 nm以上。另一方面，就粒子徑越大，成核劑的添加量越微量，粒子徑的精度越降低的理由而言，所述平均粒子徑的上限優選為90 nm以下，更優選為80 nm以下。The average particle size of the nickel nanoparticles of the present invention is 5 nm to 100 nm, but in terms of the expensive nucleophile added, it is different from the nickel nanoparticles of the prior art (the content of the nickel nanoparticles with small particle size is large). To clarify the difference, the lower limit of the average particle diameter is preferably 10 nm or more, more preferably 15 nm or more. On the other hand, the larger the particle size, the smaller the amount of nucleating agent added and the lower the precision of the particle size, the upper limit of the average particle size is preferably 90 nm or less, more preferably 80 nm or less.
本發明的鎳奈米粒子的金屬成分100重量份中所含的鎳成分包含99.5重量份以上，但就顯現出導電性或遷移等良好的電特性的理由而言，優選為99.8重量份以上，更優選為99.95重量份以上。The nickel component contained in 100 parts by weight of the metal component of the nickel nanoparticles of the present invention contains 99.5 parts by weight or more, but it is preferably 99.8 parts by weight or more for the reason of exhibiting good electrical properties such as conductivity or migration, More preferably, it is 99.95 parts by weight or more.
就容易控制粒子徑的理由而言，本發明的鎳奈米粒子優選為包含0.00003重量份～0.5重量份的鋰。更優選的下限為0.00005重量份。另一方面，更優選的上限為0.2重量份。The nickel nanoparticles of the present invention preferably contain 0.00003 parts by weight to 0.5 parts by weight of lithium for the reason of easy particle size control. A more preferable lower limit is 0.00005 parts by weight. On the other hand, a more preferable upper limit is 0.2 parts by weight.
再者，本發明的鎳奈米粒子也可成為以所述鎳奈米粒子為核、以其他金屬為殼的核-殼型粒子。所述情況下，本發明的鎳奈米粒子相當於核-殼型粒子的核部分。即，在本說明書中，規定了鋰的重量份或通過電感耦合等離子體（Inductively Coupled Plasma，ICP）品質分析法獲得的鹼金屬或鹼土金屬的含量，但這些是對核-殼型粒子的核部分進行規定。Furthermore, the nickel nanoparticles of the present invention may also be core-shell particles with the nickel nanoparticles as the core and other metals as the shell. In said case, the nickel nanoparticles of the present invention correspond to the core part of the core-shell type particle. That is, in this specification, the weight part of lithium or the content of alkali metal or alkaline earth metal obtained by the inductively coupled plasma (Inductively Coupled Plasma, ICP) quality analysis method is specified, but these are for the core of the core-shell type particle. Partially stipulated.
另外，所述其他金屬優選為鐵、鈷、銅、鈀、鉑、金或鎢。另外，核-殼型粒子的平均粒子徑優選為10 nm～105 nm。In addition, the other metal is preferably iron, cobalt, copper, palladium, platinum, gold or tungsten. In addition, the average particle diameter of the core-shell particles is preferably 10 nm to 105 nm.
接下來，對本發明的鎳奈米粒子的製造方法進行例示。 本實施形態的鎳奈米粒子的製造方法包括下述步驟A及步驟B： A）將鎳鹽及還原劑混合而獲得鎳錯合化反應液的步驟； B）對鎳錯合化反應液進行加熱，使所述鎳錯合化反應液中的鎳離子還原，獲得鎳奈米粒子的漿料的步驟。 而且，關於本實施形態的鎳奈米粒子的製造方法，在步驟B中，一邊對鎳錯合化反應液100 g吹入0.1 L/分鐘～5 L/分鐘的氮，一邊將攪拌裝置的動力調整為0.025 kW～0.1 kW的範圍內後，加溫到190℃～240℃，生成鎳奈米粒子。另外，也可於從步驟A至在步驟B中對金屬錯合化反應液進行加熱為止的期間的任一時間點添加有機金屬化合物。 Next, a method for producing nickel nanoparticles of the present invention will be exemplified. The manufacturing method of the nickel nanoparticles of the present embodiment includes the following steps A and B: A) the step of mixing nickel salt and reducing agent to obtain nickel complexation reaction solution; B) The step of heating the nickel complexation reaction solution to reduce the nickel ions in the nickel complexation reaction solution to obtain a slurry of nickel nanoparticles. Moreover, in the method for producing nickel nanoparticles of the present embodiment, in step B, while blowing 0.1 L/min to 5 L/min of nitrogen into 100 g of the nickel complexation reaction solution, the power of the stirring device is turned to After adjusting to the range of 0.025 kW to 0.1 kW, it is heated to 190°C to 240°C to generate nickel nanoparticles. In addition, the organometallic compound may be added at any point in the period from step A to heating the metal complexation reaction solution in step B.
[步驟A] 步驟A是將鎳鹽及還原劑混合而獲得鎳錯合化反應液的步驟。 [Step A] Step A is a step of mixing a nickel salt and a reducing agent to obtain a nickel complexation reaction solution.
＜鎳鹽＞ 作為鎳鹽，可列舉公知的鎳的鹽。例如可列舉：羧酸鎳鹽等有機酸鎳鹽、或氯化鎳鹽、硫酸鎳鹽、硝酸鎳鹽、碳酸鎳鹽等無機鎳鹽。這些中，就容易控制鎳奈米粒子的粒子徑或粒子徑分佈的理由而言，優選為將COOH基去除的部分的碳數為1～12的羧酸鎳鹽。這些中，更優選為乙酸鎳。 ＜Nickel salt＞ As a nickel salt, a well-known salt of nickel is mentioned. Examples thereof include organic acid nickel salts such as carboxylate nickel salts, and inorganic nickel salts such as nickel chloride salts, nickel sulfate salts, nickel nitrate salts, and nickel carbonate salts. Among these, nickel carboxylate salts having 1 to 12 carbon atoms in the part from which the COOH group is removed are preferable because it is easy to control the particle diameter or particle diameter distribution of nickel nanoparticles. Among these, nickel acetate is more preferable.
作為本實施形態中所使用的還原劑，並無特別限制，優選為可形成與鎳的錯合物的還原劑，例如可適宜地使用一級胺。一級胺可形成與鎳的錯合物，可有效地發揮對於鎳錯合物的還原能力，因此優選。另一方面，二級胺由於立體阻礙大，因此有可能阻礙鎳錯合物的良好的形成，三級胺由於不具有鎳的還原能力，因此均無法單獨使用。其中，在使用一級胺的基礎上，在不對生成的鎳奈米粒子的形狀帶來障礙的範圍內，將這些並用的情況並無妨礙。The reducing agent used in this embodiment is not particularly limited, but is preferably a reducing agent capable of forming a complex with nickel, for example, a primary amine can be suitably used. The primary amine is preferable because it can form a complex with nickel and can effectively exhibit its reducing ability with respect to the nickel complex. On the other hand, secondary amines may hinder the good formation of nickel complexes due to their large steric hindrance, and tertiary amines cannot be used alone because they do not have the ability to reduce nickel. However, in addition to the use of primary amines, there is no problem in using them in combination as long as the shape of nickel nanoparticles to be produced is not hindered.
還原劑可使用常溫下為固體或液體的還原劑。此處，所謂常溫，是指20℃±15℃。常溫下為液體的一級胺也作為形成鎳錯合物時的有機溶媒發揮功能。再者，即便是常溫下為固體的一級胺，若為通過100℃以上的加熱而為液體、或者使用有機溶媒而溶解的一級胺，則並無特別的問題。As the reducing agent, a reducing agent that is solid or liquid at normal temperature can be used. Here, normal temperature means 20°C±15°C. The primary amine, which is liquid at normal temperature, also functions as an organic solvent when forming a nickel complex. In addition, even if it is a primary amine which is solid at normal temperature, if it becomes a liquid by heating 100 degreeC or more, or dissolve|melts using an organic solvent, there is no particular problem.
一級胺可為芳香族一級胺，但就反應液中的鎳錯合物形成的容易性的觀點而言，適宜的是脂肪族一級胺。脂肪族一級胺例如可通過對其碳鏈的長度進行調整來控制生成的鎳奈米粒子的分散性，因此在要求分散性的用途中有利。就控制鎳奈米粒子的凝聚的觀點而言，脂肪族一級胺適宜的是從其碳數為6～20左右的脂肪族一級胺中選擇使用。作為此種胺，例如可列舉：辛基胺、三辛基胺、二辛基胺、十六烷基胺、十二烷基胺、十四烷基胺、硬脂基胺、油胺、肉豆蔻基胺、月桂基胺。油胺及十二烷基胺由於在鎳奈米粒子生成過程中的溫度條件下以液體狀態存在，因此可在均勻溶液中有效率地進行反應，因此特別優選。最優選為油胺。The primary amine may be an aromatic primary amine, but an aliphatic primary amine is suitable from the viewpoint of easiness of forming a nickel complex in the reaction liquid. The aliphatic primary amine can control the dispersibility of the produced nickel nanoparticles by adjusting the length of its carbon chain, for example, so it is advantageous in applications requiring dispersibility. From the viewpoint of controlling the aggregation of nickel nanoparticles, the primary aliphatic amine is preferably selected from primary aliphatic amines having about 6 to 20 carbon atoms. Examples of such amines include: octylamine, trioctylamine, dioctylamine, hexadecylamine, dodecylamine, tetradecylamine, stearylamine, oleylamine, carotene Myristylamine, Laurylamine. Oleylamine and dodecylamine are particularly preferable because they exist in a liquid state under the temperature conditions during the formation of nickel nanoparticles, and thus react efficiently in a homogeneous solution. Most preferred is oleylamine.
一級胺在鎳奈米粒子的生成時作為表面修飾劑發揮功能，因此即便在去除所述一級胺後也可抑制二次凝聚。另外，就在步驟B中的還原反應後，將所生成的鎳奈米粒子的固體成分與溶媒或未反應的一級胺分離的清洗步驟中的處理操作的容易性的觀點而言，一級胺優選為在室溫下為液體。進而，就對鎳錯合物進行還原而獲得鎳奈米粒子時的反應控制的容易性的觀點而言，一級胺優選為沸點比還原溫度高。一級胺的量優選為相對於鎳1 mol而以鎳的價數2×1倍mol以上的倍率使用，更優選為以價數2×1.1倍mol以上使用，進而優選為以價數2×2倍mol以上使用。若一級胺的量小於鎳的價數2×1倍mol，則難以控制所獲得的鎳奈米粒子的粒子徑，粒子徑容易產生偏差。另外，一級胺的量的上限並無特別，例如就生產性的觀點而言，優選為設為鎳價數2×10倍mol以下。Since the primary amine functions as a surface modifier during the formation of nickel nanoparticles, secondary aggregation can be suppressed even after the primary amine is removed. In addition, from the viewpoint of the ease of handling in the cleaning step of separating the solid content of the nickel nanoparticles generated from the solvent or unreacted primary amine after the reduction reaction in step B, the primary amine is preferably is a liquid at room temperature. Furthermore, the primary amine preferably has a boiling point higher than the reduction temperature from the viewpoint of easiness of reaction control when the nickel complex is reduced to obtain nickel nanoparticles. The amount of the primary amine is preferably used at a ratio of 2×1 mole or more of the valence of nickel relative to 1 mole of nickel, more preferably 2×1.1 times the mole or more of the valence, and still more preferably 2×2 mole of the valence. Use more than 1 times mol. If the amount of the primary amine is less than 2×1 mol of the valence of nickel, it will be difficult to control the particle size of the obtained nickel nanoparticles, and the particle size will easily vary. In addition, the upper limit of the quantity of primary amine is not specifically limited, For example, it is preferable to set it as 2x10 times mol or less of nickel valence from a viewpoint of productivity.
關於步驟A中的鎳錯合化反應液的形成條件、即鎳鹽及還原劑的混合條件，例舉使用羧酸鎳作為鎳鹽、使用一級胺作為還原劑的情況作為例子進行說明。所述情況下，錯合形成反應也可在室溫下進行，為了進行充分且效率更良好的錯合形成反應，優選為加熱到例如100℃～165℃的範圍內的溫度來進行反應。加熱溫度可優選為設為超過100℃的溫度，更優選為設為105℃以上的溫度。通過此種加熱溫度，與羧酸鎳配位的配位水和一級胺的配體置換反應效率良好地進行，可使作為錯合物配體的水分子解離，進而可將所述水排出到系統外，因此可效率良好地形成與胺的錯合物。加熱時間可根據加熱溫度、或各原料的含量來適宜決定。加熱時間的上限並無特別，就能量消耗及節約步驟時間的觀點而言，不必要地長時間進行熱處理是無用的。The formation conditions of the nickel complexation reaction solution in step A, that is, the mixing conditions of the nickel salt and the reducing agent, will be described using nickel carboxylate as the nickel salt and primary amine as the reducing agent. In such a case, the complex formation reaction may be performed at room temperature, but it is preferable to perform the reaction by heating at a temperature within a range of, for example, 100°C to 165°C in order to perform a sufficient and more efficient complex formation reaction. The heating temperature may preferably be set to a temperature exceeding 100°C, more preferably set to a temperature of 105°C or higher. By such a heating temperature, the ligand replacement reaction between the coordination water coordinated with the nickel carboxylate and the primary amine proceeds efficiently, and the water molecule as a complex ligand can be dissociated, and the water can be discharged to the Since it is outside the system, complexes with amines can be efficiently formed. The heating time can be appropriately determined according to the heating temperature or the content of each raw material. There is no particular upper limit to the heating time, and it is useless to heat-treat for an unnecessarily long time from the viewpoint of energy consumption and step time saving.
步驟A中的加熱方法並無特別限制，例如可為利用油等熱介質進行的加熱，也可為利用微波照射或超聲波照射進行的加熱。The heating method in step A is not particularly limited, and may be, for example, heating with a heat medium such as oil, or heating with microwave irradiation or ultrasonic irradiation.
在步驟A中，為了更有效率地進行均勻溶液中的反應，也可新添加與一級胺不同的有機溶媒。在使用有機溶媒的情況下，可將有機溶媒與羧酸鎳及一級胺同時混合，若先將羧酸鎳及一級胺混合並在錯合形成後加入有機溶媒，則一級胺有效率地與鎳原子配位，因此更優選。作為可使用的有機溶媒，只要是不阻礙羧酸鎳與一級胺的錯合形成的溶媒且不使所生成的鎳氧化的溶媒，則並無特別限定，例如可使用碳數7～30的飽和或不飽和的烴系有機溶媒等。另外，就即便在加熱條件下也能夠使用的觀點而言，使用的有機溶媒優選為選擇沸點為170℃以上的溶媒。作為此種有機溶媒的具體例，可列舉石蠟油。In step A, an organic solvent different from the primary amine may be newly added for more efficient reaction in a homogeneous solution. In the case of using an organic solvent, the organic solvent can be mixed with the nickel carboxylate and the primary amine at the same time. If the nickel carboxylate and the primary amine are mixed first and the organic solvent is added after the complex is formed, the primary amine is efficiently mixed with the nickel The atoms are coordinated and therefore more preferred. The organic solvent that can be used is not particularly limited as long as it is a solvent that does not inhibit the complex formation of nickel carboxylate and primary amine and does not oxidize the generated nickel. For example, a saturated solvent having 7 to 30 carbon atoms can be used. Or unsaturated hydrocarbon-based organic solvents, etc. In addition, the organic solvent to be used is preferably a solvent having a boiling point of 170° C. or higher from the viewpoint of being usable even under heating conditions. Specific examples of such an organic solvent include paraffin oil.
[步驟B] 在步驟B中，以規定的流量對通過錯合形成反應而得的鎳錯合化反應液吹入惰性氣體，一邊調整為與液量和所期望的粒子徑相應的動力並進行攪拌，一邊進行加熱，使錯合化反應液中的鎳離子還原，獲得鎳奈米粒子的漿料。具體而言，一邊對鎳錯合化反應液100 g吹入0.1 L/分鐘～5 L/分鐘的氮，一邊將攪拌裝置的動力調整為0.025 kW～0.1 kW的範圍內後，加溫至190℃～240℃而生成鎳奈米粒子。 [step B] In step B, an inert gas is blown into the nickel complexation reaction solution obtained by the complexation formation reaction at a predetermined flow rate, and stirring is performed while adjusting the power corresponding to the liquid volume and the desired particle diameter. heating to reduce the nickel ions in the complexation reaction solution to obtain a slurry of nickel nanoparticles. Specifically, while blowing 0.1 L/min to 5 L/min of nitrogen into 100 g of the nickel complexation reaction solution, while adjusting the power of the stirring device within the range of 0.025 kW to 0.1 kW, the temperature was raised to 190 ℃ ~ 240 ℃ to generate nickel nanoparticles.
步驟B中的加熱溫度根據所獲得的鎳奈米粒子的粒子徑、粒子徑分佈等而不同，優選為在產生伴隨吸熱的反應的溫度下進行保持。若大幅超過反應溫度充分地加熱，則因所生成的鎳的催化作用而烴被分解，在鎳奈米粒子表面析出並覆蓋碳，因此鎳表面中的鎳離子的生成受到抑制。因此，在使用鎳奈米粒子作為膏材料的情況等下，有鎳奈米粒子彼此或鎳奈米粒子與其他粒子的接合性降低的傾向。The heating temperature in step B varies depending on the particle size and particle size distribution of the obtained nickel nanoparticles, and it is preferable to keep at a temperature at which a reaction accompanied by endothermic reaction occurs. If the reaction temperature is sufficiently heated, the hydrocarbons are decomposed by the catalytic action of the generated nickel, and carbon is deposited and covered on the surface of the nickel nanoparticles, so that the generation of nickel ions on the nickel surface is suppressed. Therefore, when nickel nanoparticles are used as a paste material, etc., the bondability between nickel nanoparticles or between nickel nanoparticles and other particles tends to decrease.
此處，惰性氣體是指在步驟B中不會與鎳奈米粒子的合成反應中使用的其他物質產生反應的化學性穩定的氣體。例如可列舉氮、氬氣。就可廉價地獲取的理由而言，優選為氮。Here, the inert gas refers to a chemically stable gas that does not react with other substances used in the synthesis reaction of nickel nanoparticles in step B. Examples thereof include nitrogen and argon. Nitrogen is preferred because it can be obtained at low cost.
作為惰性氣體的一例的氮的流量優選為調整為與反應時產生的氣體相應的流量，並根據所期望的粒子徑及合成量而變化，因此可適宜選擇流量的範圍。優選為相對於鎳錯合化反應液100 g～750 g、更優選為500 g～750 g而為0.1 L/分鐘～5 L/分鐘。 更具體而言，在合成粒子徑為15 nm的粒子的情況下，相對於鎳錯合化反應液量750 g，優選為2 L/分鐘～4 L/分鐘，進而優選為2.8 L/分鐘～3.2 L/分鐘。另外，也優選為根據鎳奈米粒子的粒子徑，在190℃～215℃的溫度範圍內使氮流量變化。例如，在合成粒子徑超過30 nm的粒子、例如40 nm的粒子的情況下，優選為相對於鎳錯合化反應液量500 g～750 g，將生成成為核的粒子的小於200℃時的氮流量設為2 L/分鐘～4L/分鐘，在200℃以上時將氮流量調整為0.1 L/分鐘～3.3 L/分鐘，由此可獲得目標粒子。 The flow rate of nitrogen, which is an example of an inert gas, is preferably adjusted to a flow rate corresponding to the gas generated during the reaction, and varies depending on the desired particle size and synthesis amount, so the range of the flow rate can be appropriately selected. It is preferably 0.1 L/min to 5 L/min with respect to 100 g to 750 g of the nickel complexation reaction liquid, more preferably 500 g to 750 g. More specifically, in the case of synthesizing particles with a particle diameter of 15 nm, it is preferably 2 L/min to 4 L/min, more preferably 2.8 L/min to 750 g of the nickel complexation reaction solution. 3.2 L/min. In addition, it is also preferable to change the flow rate of nitrogen in the temperature range of 190° C. to 215° C. according to the particle diameter of the nickel nanoparticles. For example, in the case of synthesizing particles with a particle diameter exceeding 30 nm, such as 40 nm, it is preferable to produce particles that become nuclei at a temperature lower than 200° C. with respect to a nickel complexation reaction solution volume of 500 g to 750 g. The nitrogen flow rate is set to 2 L/min to 4 L/min, and the nitrogen flow rate is adjusted to 0.1 L/min to 3.3 L/min at 200° C. or higher to obtain target particles.
關於氮的純度，並無特別限制，若水分多則有錯合物吸收水分而影響反應的可能性，因此使用的氮優選為使用水分含量少的純度99.9%以上的氮。另外，所謂吹入氮氣，是指對反應液直接施加一定以上的壓力來注入氮氣，而不是簡單地處於氮環境或氮流通下（所謂的“氮流”）。關於吹入氮氣的方式，可使其朝向反應液面往下流，也可利用公知的噴嘴朝向反應液面噴射。更優選為直接向反應液中注入氮氣並使其鼓泡。通過向反應液中直接“吹入”氮氣，可有效率地趕出通過反應而產生的氣體（反應生成氣體）。理想的是根據所期望的粒子徑調整吹入方式及流量、壓力等。若反應生成氣體的去除不充分，則會妨礙核生成，且通過逐步地生成核則生成具有寬廣粒子徑的粒子，因此不優選。其中，若過於有效率地去除反應生成氣體，則在核生成後的成長反應時會生成新的核，有粒子徑變寬廣的傾向。The purity of nitrogen is not particularly limited. If there is a lot of water, the complex may absorb water and affect the reaction. Therefore, the nitrogen used is preferably nitrogen with a purity of 99.9% or more with a low water content. In addition, the so-called blowing of nitrogen gas refers to injecting nitrogen gas by directly applying a certain pressure to the reaction liquid, rather than simply being in a nitrogen environment or under a nitrogen flow (so-called "nitrogen flow"). As for blowing nitrogen gas, it may flow downward toward the reaction liquid surface, or it may be sprayed toward the reaction liquid surface using a known nozzle. More preferably, nitrogen gas is injected directly into the reaction liquid and bubbled. By directly "blowing" nitrogen gas into the reaction liquid, the gas generated by the reaction (reaction generated gas) can be efficiently driven out. It is desirable to adjust the blowing method, flow rate, pressure, etc. according to the desired particle size. Insufficient removal of the reaction product gas hinders nucleation, and the gradual formation of nuclei produces particles having a wide particle diameter, which is not preferable. Among them, if the reaction-generated gas is removed too efficiently, new nuclei are generated during the growth reaction after nucleation, and the particle diameter tends to widen.
攪拌反應溶液的動力可根據攪拌葉片形狀等來適宜選擇，優選為通過與液量相應的動力來合成。為了防止因粒子彼此的締合而生成粗大粒子，相對於鎳錯合化反應液100 g，動力的優選的下限為0.025 kW以上。另外，由於由液體暴動所致的液體飛濺引起的污染的原因，有可能產生形成粗大粒子等品質方面的問題，因此相對於鎳錯合化反應液100 g，動力的上限為0.1 kW以下，優選為0.07 kW以下。另外，由於氣體的排出性發生變化，因此也成為成長反應中生成新的核等原因，因此優選為調整為適當的動力值。The power for stirring the reaction solution can be appropriately selected according to the shape of the stirring blade, etc., but it is preferably synthesized by power corresponding to the liquid volume. In order to prevent the formation of coarse particles due to the association of the particles, the lower limit of the power is preferably 0.025 kW or more with respect to 100 g of the nickel complexation reaction solution. In addition, due to the pollution caused by the liquid splash caused by the liquid riot, there may be quality problems such as the formation of coarse particles. Therefore, the upper limit of the power is 0.1 kW or less with respect to 100 g of the nickel complexation reaction solution, preferably 0.07 kW or less. In addition, since the change in gas discharge property also causes new nuclei to be generated during the growth reaction, it is preferable to adjust to an appropriate power value.
加熱時間並無特別限制，優選為進行加熱直至使用鎳濃度計（例如笠原理化工業股份有限公司製造的鎳濃度計Ni-5Z）對反應液的鎳濃度進行測定而檢測不到鎳的時間為止。若加熱時間短於所述時間，則難以獲得目標粒子徑的鎳奈米粒子，進而分散性容易降低，因此不優選。另外，關於加熱時間的上限，由於加熱時間根據粒子徑而發生變化，因此並無特別限制，但關於反應結束後的長時間的加熱，由於碳在鎳奈米粒子表面析出，因此在忌避雜質的用途、例如需要低溫燒結的用途中燒結所需的溫度會變高，因此不優選。另外，由於燒結時產生的氣體量增加，因此燒結體的形狀受損的可能性高，因此不優選。The heating time is not particularly limited, and is preferably heated until the nickel concentration of the reaction solution is measured using a nickel concentration meter (for example, Ni-5Z manufactured by Kasahara Chemical Co., Ltd.) and no nickel is detected. If the heating time is shorter than the above time, it is difficult to obtain nickel nanoparticles with the target particle size, and furthermore, the dispersibility tends to decrease, which is not preferable. In addition, the upper limit of the heating time is not particularly limited because the heating time changes according to the particle diameter, but for long-term heating after the end of the reaction, since carbon is precipitated on the surface of the nickel nanoparticles, it is important to avoid impurities. In applications, for example, in applications requiring low-temperature sintering, the temperature required for sintering becomes high, which is not preferable. In addition, since the amount of gas generated during sintering increases, the shape of the sintered body may be damaged, which is not preferable.
作為步驟B中的生產工藝，使用對不銹鋼制容器進行加熱的分批方式或連續反應機，作為加熱方法，可列舉使用油溫度調節等熱介質、電、微波、超聲波的加熱法等。就生產成本的觀點而言，可適宜地利用使用油溫度調節等熱介質、電的加熱方式。另外，也可為利用微波照射或超聲波照射進行的加熱。As the production process in step B, a batch method or a continuous reactor that heats a stainless steel container is used, and as a heating method, heating methods using heat media such as oil temperature control, electricity, microwaves, and ultrasonic waves, etc. are used. From the viewpoint of production cost, a heating method using a heating medium such as oil temperature control or electricity can be suitably utilized. In addition, heating by microwave irradiation or ultrasonic irradiation may be used.
在步驟B中，為了改善鎳奈米粒子的分散性、或者賦予用於防止氧化的防銹劑等的功能，可在不妨礙接合性的範圍內添加分散劑或用於賦予功能的添加劑。In step B, in order to improve the dispersibility of the nickel nanoparticles, or to impart functions such as a rust inhibitor for preventing oxidation, a dispersant or an additive for imparting functions may be added within a range that does not interfere with bondability.
[有機金屬化合物的添加] 本實施形態中所使用的有機金屬化合物若為具有與親核試劑相同的性質（親核性），且作用於金屬錯合物的化合物，則並無特別制約。作為優選的有機金屬化合物，就鎳奈米粒子的粒子徑或粒子徑分佈的控制容易性、安全性、簡便性、生產性的觀點而言，可列舉：烷基、烷氧基等有機基與鹼金屬配位而成的鹼金屬系有機金屬化合物、以及所述有機基與鹼土金屬配位而成的鹼土金屬系有機金屬化合物。以下，將鹼金屬系有機化合物及鹼土金屬系有機化合物總稱為“本有機金屬化合物”。本有機金屬化合物也可為含有氯、溴、碘等鹵化物的有機金屬鹵化物。所述情況下，也分別稱為鹼金屬系有機金屬鹵化物及鹼土金屬系有機金屬鹵化物。鹼金屬系有機金屬鹵化物為鹼金屬系有機金屬化合物的一形態，鹼土金屬系有機金屬鹵化物為鹼土金屬系有機金屬化合物的一形態。 [Addition of organometallic compounds] The organometallic compound used in this embodiment is not particularly limited as long as it has the same properties (nucleophilicity) as a nucleophile and acts on a metal complex. As a preferable organometallic compound, from the viewpoint of the ease of control of the particle size or particle size distribution of nickel nanoparticles, safety, simplicity, and productivity, organic groups such as alkyl groups and alkoxy groups are listed. An alkali metal-based organometallic compound in which an alkali metal is coordinated, and an alkaline-earth metal-based organometallic compound in which the organic group is coordinated to an alkaline-earth metal. Hereinafter, the alkali metal-based organic compound and the alkaline-earth metal-based organic compound are collectively referred to as "the present organometallic compound". The organometallic compound may be an organometallic halide containing a halide such as chlorine, bromine, or iodine. In these cases, they are also called alkali metal-based organometallic halides and alkaline-earth metal-based organometallic halides, respectively. An alkali metal organometallic halide is one form of an alkali metal organometallic compound, and an alkaline earth metal organometallic halide is one form of an alkaline earth metal organometallic compound.
作為構成鹼金屬系有機金屬化合物的鹼金屬，例如可列舉鋰、鈉、鉀、銣、銫，可適宜地使用含有反應性高的鋰的有機鋰。 另外，作為構成鹼土金屬系有機金屬化合物的鹼土金屬，例如可列舉鈹、鎂、鈣、鍶、鋇，可適宜地使用含有反應性良好的鎂的有機鎂鹵化物。再者，烷基與鋁配位而成的烷基鋁由於易燃性強，因此就安全性及簡便性的觀點而言，可更適宜地使用鹼金屬系的有機金屬化合物。 Examples of the alkali metal constituting the alkali metal-based organometallic compound include lithium, sodium, potassium, rubidium, and cesium, and organolithium containing highly reactive lithium can be suitably used. In addition, examples of the alkaline earth metal constituting the alkaline earth metal-based organometallic compound include beryllium, magnesium, calcium, strontium, and barium, and organomagnesium halides containing magnesium with good reactivity can be suitably used. Furthermore, an alkylaluminum compound in which an alkyl group is coordinated with aluminum is highly flammable, and therefore an alkali metal-based organometallic compound can be more suitably used from the viewpoint of safety and simplicity.
本有機金屬化合物例如優選為作為通過四氫呋喃、己烷、甲苯、環己烷、丁基醚、二丁基醚等有機溶媒而稀釋的稀釋溶液來使用，就與鎳錯合化反應液的親和性的方面而言，特別適宜的是甲苯、二丁基醚溶液。稀釋溶液的濃度並無限制，但在為微量便影響粒子徑的情況下，低濃度的情況更容易控制，因此優選。For example, the organometallic compound is preferably used as a dilute solution diluted with an organic solvent such as tetrahydrofuran, hexane, toluene, cyclohexane, butyl ether, dibutyl ether, etc. In terms of aspects, toluene and dibutyl ether solutions are particularly suitable. The concentration of the dilute solution is not limited, but in the case where the particle diameter is affected by a small amount, a low concentration is easier to control and is therefore preferable.
作為鹼金屬系有機金屬化合物，可適宜地使用廉價且通用的正丁基鋰或苯基鋰，就安全性及簡便性的觀點而言，特別適宜的是苯基鋰的二丁基醚溶液。As the alkali metal-based organometallic compound, inexpensive and general-purpose n-butyllithium or phenyllithium can be suitably used, and a dibutyl ether solution of phenyllithium is particularly suitable from the viewpoint of safety and convenience.
本有機金屬化合物的添加量只要選定與目標粒子徑相應的添加量即可，因此並無特別限制。具體而言，相對於鎳錯合物100 g，本有機金屬化合物的添加量優選為0.001 g～30 g的範圍內，更優選為0.003 g～10 g的範圍內。The amount of the organometallic compound to be added is not particularly limited as long as it is selected in accordance with the target particle size. Specifically, the amount of the organometallic compound added is preferably within a range of 0.001 g to 30 g, more preferably within a range of 0.003 g to 10 g, based on 100 g of the nickel complex.
本有機金屬化合物只要於自步驟A至在步驟B中對錯合化反應液進行加熱為止的期間的任一時間點添加即可。例如，本有機金屬化合物可在步驟A中將鎳鹽及還原劑混合並去除多餘的水分後添加，也可在製備錯合化反應液後添加。另外，本有機金屬化合物由於因水分而失活並失去效果，從而難以控制粒度分佈，因此優選為於即將在步驟B中對錯合化反應液進行加熱之前添加。通過添加本有機金屬化合物，可明顯減小鎳奈米粒子的粒子徑。其作用機制尚不明確，但推測可能是具有親核性的本有機金屬化合物作用於鎳錯合物，促進鎳核的生成。The organometallic compound may be added at any point in the period from step A to heating the complexation reaction liquid in step B. For example, the organometallic compound may be added after mixing the nickel salt and the reducing agent in step A and removing excess water, or after preparing the complexation reaction solution. In addition, since the organometallic compound is deactivated by moisture and loses its effect, it is difficult to control the particle size distribution, so it is preferable to add it immediately before heating the complexation reaction liquid in step B. The particle size of nickel nanoparticles can be significantly reduced by adding the organometallic compound. Its mechanism of action is not yet clear, but it is speculated that this organometallic compound with nucleophilicity acts on nickel complexes to promote the formation of nickel nuclei.
本發明的鎳奈米粒子可與公知的樹脂混合製成膏材料。例如，可使用樹脂作為有機黏合劑。有機黏合劑具有在膏材料中抑制鎳奈米粒子的沉降或凝聚而保持分散性的作用。另外，通過使鎳奈米粒子彼此或鎳奈米粒子與其他粒子連結並製成廣範圍的網路結構，從而有助於形成具有高接合強度的接合層。 作為所述公知的樹脂，若為能夠溶解於有機溶媒的黏合劑，則可並無特別限制地使用，例如可列舉：酚樹脂、環氧樹脂、不飽和聚酯樹脂、脲樹脂、三聚氰胺樹脂等熱硬化性樹脂、或聚乙烯樹脂、丙烯酸樹脂、甲基丙烯酸樹脂、尼龍樹脂、縮醛樹脂、聚乙烯縮醛樹脂等熱塑性樹脂。這些中，優選為聚乙烯縮醛樹脂，尤其是更優選為在分子內具有縮醛基的單元、乙醯基的單元、以及羥基的單元的聚乙烯縮醛樹脂。 The nickel nanoparticles of the present invention can be mixed with known resins to make a paste material. For example, a resin can be used as an organic binder. The organic binder has the function of inhibiting the sedimentation or aggregation of nickel nanoparticles in the paste material and maintaining the dispersion. In addition, nickel nanoparticles are connected to each other or nickel nanoparticles to other particles to form a wide network structure, which contributes to the formation of a bonding layer with high bonding strength. As the above-mentioned known resin, as long as it is a binder that can be dissolved in an organic solvent, it can be used without particular limitation, for example, phenol resin, epoxy resin, unsaturated polyester resin, urea resin, melamine resin, etc. Thermosetting resins, or thermoplastic resins such as polyethylene resins, acrylic resins, methacrylic resins, nylon resins, acetal resins, and polyvinyl acetal resins. Among these, polyvinyl acetal resins are preferable, and polyvinyl acetal resins having an acetal group unit, an acetyl group unit, and a hydroxyl group unit in the molecule are more preferable.
所述膏材料可包含其他粒子作為任意成分。即，可製成包含所述鎳奈米粒子與其他粒子的膏材料。此處，其他粒子的材質及形狀並無限制，可列舉作為燒結材的熱傳導性優異的、錫、鈦、鈷、銅、鉻、錳、鐵、鋯、鎢、鉬、釩等賤金屬、金、銀、鉑、鈀、銥、鋨、釕、銠、錸等貴金屬等金屬元素。這些可單獨含有或含有兩種以上。更優選為熱傳導性及燒結性優異的鈷、銀、銅、焊錫。The paste material may contain other particles as optional constituents. That is, a paste material containing the nickel nanoparticles and other particles can be produced. Here, the material and shape of other particles are not limited, and examples thereof include base metals such as tin, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tungsten, molybdenum, vanadium, and gold, which are excellent in thermal conductivity as sintered materials. , silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium and other precious metals and other metal elements. These may be contained alone or in combination of two or more. Cobalt, silver, copper, and solder, which are excellent in thermal conductivity and sinterability, are more preferable.
由於所述膏材料含有本發明的鎳奈米粒子作為必需成分，因此在形成薄膜時作用於膏內部的張力變得均勻，容易形成均勻的超薄膜。另外，向槽等的填充性、或配線的直線性優異。因此，例如可適宜地用於MLCC等需要多層薄膜層疊的用途中。另外，也可以防止配線的滲出或擴散為目的作為向印刷形成的槽中填充膏的材料，而廣泛利用於製造電磁波遮罩體或觸控式螢幕等的用途中。Since the paste material contains the nickel nanoparticles of the present invention as an essential component, the tension acting on the inside of the paste becomes uniform when forming a thin film, and a uniform ultra-thin film is easily formed. In addition, it is excellent in fillability to grooves and the like, and linearity of wiring. Therefore, for example, it can be suitably used in applications requiring multilayer thin film lamination, such as MLCC. In addition, it can also be used as a material for filling paste into grooves formed by printing for the purpose of preventing bleeding or spreading of wiring, and is widely used in the manufacture of electromagnetic wave shields, touch screens, and the like.
再者，以下對將所述膏材料用於MLCC用途中、尤其是使用鎳奈米粒子作為MLCC的電極用材料的情況進行例示。In addition, below, the case where the said paste material is used for MLCC application, and nickel nanoparticle is used especially as an electrode material for MLCC is exemplified.
[層疊陶瓷電容器用的內部電極] 本實施形態的層疊陶瓷電容器的內部電極（以下，也簡稱為“內部電極”）是通過將本實施形態的鎳奈米粒子膏化並印刷於陶瓷基板上來製造。 進行所述膏化時，可將有機載體（organic vehicle）、水系載體等公知的黏度調整劑混合。通過混合黏度調整劑，可對所述膏賦予適度的流動性或揮發性，可在陶瓷基板上形成平滑的內部電極。 有機載體例如是將樹脂溶解於有機溶劑中而成。有機載體中使用的樹脂並無特別限定，只要從乙基纖維素、聚乙烯醇縮丁醛等通常的各種樹脂中適宜選擇即可。另外，所使用的有機溶劑也無特別限定，只要根據印刷法或片材法等利用的方法，從萜品醇、丁基卡必醇、丙酮、甲苯等各種有機溶劑中適宜選擇即可。 另外，水系載體例如可列舉聚乙烯醇、纖維素、水溶性丙烯酸樹脂。 陶瓷電介質可使用公知的電介質，例如可列舉：為鈣鈦礦系電介質、且鈦酸鋇或其鈦的一部分置換為鋯石的電介質、鋇的一部分置換為鍶或鈣等的電介質。 內部電極的印刷方法若為可均勻地形成層的方法，則並無特別限定，例如可列舉：絲網印刷法、凹版印刷法、蒸鍍法、濺射法、噴墨法。 [Internal electrodes for multilayer ceramic capacitors] The internal electrodes of the laminated ceramic capacitor of the present embodiment (hereinafter also simply referred to as “internal electrodes”) are produced by pasting and printing the nickel nanoparticles of the present embodiment on a ceramic substrate. When performing the above-mentioned creaming, known viscosity modifiers such as organic vehicles (organic vehicles) and aqueous vehicles can be mixed. By mixing a viscosity modifier, appropriate fluidity or volatility can be imparted to the paste, and smooth internal electrodes can be formed on the ceramic substrate. An organic vehicle is obtained by dissolving a resin in an organic solvent, for example. The resin used for the organic vehicle is not particularly limited, and may be appropriately selected from various usual resins such as ethyl cellulose and polyvinyl butyral. In addition, the organic solvent used is not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, and toluene according to the method used such as printing method or sheet method. In addition, examples of water-based carriers include polyvinyl alcohol, cellulose, and water-soluble acrylic resins. Known dielectrics can be used as the ceramic dielectric, for example, perovskite-based dielectrics in which barium titanate or part of its titanium is substituted by zircon, and dielectrics in which part of barium is substituted by strontium or calcium. The printing method of the internal electrodes is not particularly limited as long as it can form a layer uniformly, and examples thereof include screen printing, gravure printing, vapor deposition, sputtering, and inkjet.
[層疊陶瓷電容器] 本實施形態的層疊陶瓷電容器可通過將所述內部電極與陶瓷電介質交替重疊為層狀並進行壓接、煆燒且加以一體化來製造。陶瓷電介質可使用公知的電介質，可列舉所述鈦酸鋇等。將其膏化，在所述內部電極上形成陶瓷電介質層。進行膏化時，也可將有機載體、水系載體等公知的黏度調整劑混合。通過混合黏度調整劑，可對所述膏賦予適度的流動性或揮發性，可在陶瓷基板上形成平滑的內部電極層及陶瓷電介質層。有機載體例如是將樹脂溶解於有機溶劑中而成。有機載體中使用的樹脂並無特別限定，只要從乙基纖維素、聚乙烯醇縮丁醛等通常的各種樹脂中適宜選擇即可。另外，所使用的有機溶劑也無特別限定，只要根據印刷法或片材法等利用的方法，從萜品醇、丁基卡必醇、丙酮、甲苯等各種有機溶劑中適宜選擇即可。 另外，水系載體例如可列舉聚乙烯醇、纖維素、水溶性丙烯酸樹脂。 陶瓷電介質的印刷方法若為可均勻地形成層的方法，則並無特別限定，例如可列舉：絲網印刷法、凹版印刷法、蒸鍍法、濺射法、噴墨法。 內部電極與陶瓷電介質的層及層厚並無限定，例如為幾層～1000層，各層厚為0.1 μm～2 μm。 [Laminated Ceramic Capacitors] The multilayer ceramic capacitor according to this embodiment can be manufactured by alternately stacking the internal electrodes and the ceramic dielectric in layers, crimping them, firing them, and integrating them. Known dielectrics can be used as the ceramic dielectric, and examples thereof include barium titanate and the like. This is pasted to form a ceramic dielectric layer on the internal electrodes. When performing creaming, known viscosity modifiers such as organic vehicles and water-based vehicles can also be mixed. By mixing a viscosity modifier, appropriate fluidity or volatility can be imparted to the paste, and smooth internal electrode layers and ceramic dielectric layers can be formed on the ceramic substrate. An organic vehicle is obtained by dissolving a resin in an organic solvent, for example. The resin used for the organic vehicle is not particularly limited, and may be appropriately selected from various usual resins such as ethyl cellulose and polyvinyl butyral. In addition, the organic solvent used is not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, and toluene according to the method used such as printing method or sheet method. In addition, examples of water-based carriers include polyvinyl alcohol, cellulose, and water-soluble acrylic resins. The printing method of the ceramic dielectric is not particularly limited as long as it can form a layer uniformly, and examples thereof include screen printing, gravure printing, vapor deposition, sputtering, and inkjet. The layers and layer thicknesses of the internal electrodes and the ceramic dielectric are not limited, for example, several layers to 1000 layers, and each layer thickness is 0.1 μm to 2 μm.
接下來，對如此獲得的內部電極與陶瓷電介質的多層結構進行壓接並一體成型，切割成規定的大小（晶片的尺寸），進行煆燒而形成晶片。 煆燒溫度例如為1000℃～1300℃。煆燒後，在晶片的兩端面塗布金屬膏，進行熱處理，在其表面實施鍍覆，由此形成外部電極。 Next, the multilayer structure of internal electrodes and ceramic dielectrics obtained in this way is press-bonded and integrally molded, cut into a predetermined size (wafer size), and fired to form a wafer. The firing temperature is, for example, 1000°C to 1300°C. After firing, a metal paste is applied to both end surfaces of the wafer, heat-treated, and the surface is plated to form external electrodes.
如此製造的本發明的實施形態所涉及的層疊陶瓷電容器通過焊接等安裝於印刷基板上等，被用於各種電子設備等中。 此種電子設備由於使用本發明的鎳奈米粒子，因此能夠實現小型、高容量化，可靠性、高壽命性優異，可提高電子零件的高溫負荷壽命。 [實施例] The multilayer ceramic capacitor according to the embodiment of the present invention manufactured in this way is mounted on a printed circuit board or the like by soldering or the like, and is used in various electronic devices or the like. Since such electronic devices use the nickel nanoparticles of the present invention, they can be reduced in size and capacity, have excellent reliability and long life, and can improve the high-temperature load life of electronic parts. [Example]
以下，通過實施例具體地說明本發明，但本發明不受這些實施例的任何限定。再者，在以下的實施例中，只要並無特別說明，則測定、評價是基於如下內容。Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. In addition, in the following examples, unless otherwise specified, measurement and evaluation are based on the following content.
[粒度分佈、平均粒子徑及CV值的測定] 粒度分佈、平均粒子徑及CV值的測定是通過以下方法來實施。 利用SEM（掃描電子顯微鏡，日立高科技（Hitachi High-Tech）股份有限公司製造的雷古拉斯（Regulus）8100，加速電壓為15 kV時二次電子解析度為0.8 nm）拍攝試樣的照片，使用粒度分佈分析軟體（貿泰科（Mountech）公司製造 麥克唯優（MacView）），從照片的左側起依次抽出400個拍攝有粒子整體的粒子。將與所選擇的面積相當的圓直徑（黑伍德（Heywood）徑）作為各粒子徑，求出數學平均徑與標準差。算出在所抽出的全部400個鎳奈米粒子中，相對於平均粒子徑的粒子徑為1/2以下的粒子（≦1/2粒子徑）與粒子徑為3/2以上的粒子（≧3/2粒子徑）的比率（%）。 另外，CV值（變異係數）是通過（標準差）÷（數學平均徑）來算出。再者，CV值越小，越表示粒子徑更均勻。 [Measurement of particle size distribution, average particle diameter and CV value] The measurement of particle size distribution, average particle diameter, and CV value was implemented by the following method. A photograph of the sample was taken with a SEM (scanning electron microscope, Regulus 8100 manufactured by Hitachi High-Tech Co., Ltd., with a secondary electron resolution of 0.8 nm at an accelerating voltage of 15 kV) , using a particle size distribution analysis software (MacView manufactured by Mountech), 400 particles were sequentially extracted from the left side of the photograph, and the whole particle was photographed. The diameter of a circle corresponding to the selected area (Heywood diameter) was used as the diameter of each particle, and the mathematical mean diameter and standard deviation were obtained. Among all the 400 nickel nanoparticles extracted, the particles with a particle diameter of 1/2 or less (≦1/2 particle diameter) and the particles with a particle diameter of 3/2 or more (≧3 /2 particle diameter) ratio (%). In addition, the CV value (coefficient of variation) was calculated by (standard deviation) ÷ (mathematical mean diameter). In addition, the smaller the CV value, the more uniform the particle size.
[金屬成分中所含的鎳成分、鹼金屬或鹼土金屬的含量的測定] 利用高頻電感耦合等離子體品質分析（ICP品質分析）法測定鎳奈米粒子中所含的鎳成分、鹼金屬或鹼土金屬的含量（重量份）。 [Measurement of content of nickel component, alkali metal or alkaline earth metal contained in metal component] The content (parts by weight) of nickel components, alkali metals or alkaline earth metals contained in nickel nanoparticles is determined by high-frequency inductively coupled plasma quality analysis (ICP quality analysis).
[有機金屬化合物] 有機金屬化合物（1）：富士膠片和光純藥股份有限公司製造，苯基鋰的約19%二丁基醚溶液（約1.9 mol/L） [Organometallic compound] Organometallic compound (1): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., about 19% dibutyl ether solution of phenyllithium (about 1.9 mol/L)
[油胺] 日油股份有限公司製造的尼桑胺（nissan amine）OB [oleylamine] Nissan amine OB manufactured by NOF Co., Ltd.
（合成例1） 在2 L四口燒瓶中採集油胺600 g，加入乙酸鎳四水合物246.8 g，使氮在2 L/分鐘氣流下、140℃下反應3小時，由此獲得775 g的鎳錯合化反應液A。 (Synthesis Example 1) Collect 600 g of oleylamine in a 2 L four-necked flask, add 246.8 g of nickel acetate tetrahydrate, and react nitrogen at 140°C for 3 hours under 2 L/min air flow, thus obtaining 775 g of nickel complexation reaction Liquid A.
（合成例2） 在2 L四口燒瓶中採集油胺200 g，加入乙酸鎳四水合物82.3 g，使氮在2 L/分鐘氣流下、140℃下反應3小時，由此獲得258 g的鎳錯合化反應液B。 (Synthesis Example 2) Collect 200 g of oleylamine in a 2 L four-necked flask, add 82.3 g of nickel acetate tetrahydrate, and react nitrogen at 140°C for 3 hours under 2 L/min air flow, thus obtaining 258 g of nickel complexation reaction Liquid B.
（實施例1） 向合成例1中所獲得的鎳錯合化反應液A的775 g中添加6 g有機金屬化合物（1），合計設為781 g，一邊以3 L/分鐘向反應液中直接注入（鼓泡）氮氣，一邊調整為動力0.034 kW，利用有罩加熱器（mantle heater）升溫，在210℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖1及表1所示，獲得平均粒子徑為14.9 nm、CV值為0.12的顯示出尖銳的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.85重量份，鋰成分為0.12重量份。 (Example 1) 6 g of the organometallic compound (1) was added to 775 g of the nickel complexation reaction solution A obtained in Synthesis Example 1 to make a total of 781 g, while directly injecting into the reaction solution at 3 L/min (bubbling ) nitrogen, while adjusting the power to 0.034 kW, the temperature was raised using a mantle heater, and the reaction was carried out at 210° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 1 and Table 1, particles showing a sharp particle size distribution with an average particle diameter of 14.9 nm and a CV value of 0.12 were obtained. In addition, the nickel component contained in 100 parts by weight of the metal component was 99.85 parts by weight, and the lithium component was 0.12 parts by weight.
（實施例2） 向合成例1中所獲得的鎳錯合化反應液A的775 g中添加0.15 g有機金屬化合物（1），合計設為775.15 g，一邊以1 L/分鐘向反應液中直接注入（鼓泡）氮氣，一邊調整為動力0.033 kW，利用有罩加熱器升溫，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖4及表1所示，獲得平均粒子徑為27.9 nm、CV值為0.14的顯示出尖銳的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.0003重量份。 (Example 2) 0.15 g of the organometallic compound (1) was added to 775 g of the nickel complexation reaction solution A obtained in Synthesis Example 1 to make a total of 775.15 g, while directly injecting into the reaction solution at 1 L/min (bubbling ) nitrogen, while adjusting the power to 0.033 kW, using a cover heater to raise the temperature, and reacting at 230° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 4 and Table 1, particles showing a sharp particle size distribution with an average particle diameter of 27.9 nm and a CV value of 0.14 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.0003 weight part.
（實施例3） 向合成例1中所獲得的鎳錯合化反應液A的775 g中添加0.17 g有機金屬化合物（1），合計設為775.17 g，一邊以3 L/分鐘向反應液中直接注入（鼓泡）氮氣，一邊調整為動力0.048 kW，利用有罩加熱器升溫，在到達200℃的階段將氮量切換為0.5 L/分鐘，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖6及表1所示，獲得平均粒子徑為38.2 nm、CV值為0.17的顯示出尖銳的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.0003重量份。 (Example 3) 0.17 g of the organometallic compound (1) was added to 775 g of the nickel complexation reaction solution A obtained in Synthesis Example 1 to make the total 775.17 g, and it was directly injected into the reaction solution at 3 L/min (bubbling ) nitrogen, while adjusting the power to 0.048 kW, use a cover heater to raise the temperature, switch the nitrogen amount to 0.5 L/min when it reaches 200°C, and react at 230°C for 10 minutes, thereby obtaining nickel nanoparticle slurry . As shown in FIG. 6 and Table 1, particles showing a sharp particle size distribution with an average particle diameter of 38.2 nm and a CV value of 0.17 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.0003 weight part.
（實施例4） 向合成例2中所獲得的鎳錯合化反應液B的258 g中添加實施例1中所獲得的鎳奈米粒子漿料13.2 g，合計設為271.2 g，一邊以0.5 L/分鐘向反應液中直接注入（鼓泡）氮氣，一邊調整為動力0.029 kW，利用有罩加熱器升溫，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖8及表1所示，獲得平均粒子徑為41.0 nm、CV值為0.19的顯示出尖銳的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.0006重量份。 (Example 4) To 258 g of the nickel complexation reaction solution B obtained in Synthesis Example 2, 13.2 g of the nickel nanoparticle slurry obtained in Example 1 was added to make the total 271.2 g, and the reaction was carried out at 0.5 L/min. Nitrogen gas was directly injected (bubbled) into the liquid, while the power was adjusted to 0.029 kW, the temperature was raised by a heater with a cover, and the reaction was carried out at 230° C. for 10 minutes to obtain a nickel nanoparticle slurry. As shown in FIG. 8 and Table 1, particles showing a sharp particle size distribution with an average particle diameter of 41.0 nm and a CV value of 0.19 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.0006 weight part.
（實施例5） 向合成例2中所獲得的鎳錯合化反應液B的258 g中添加實施例1中所獲得的鎳奈米粒子漿料5 g，合計設為263 g，一邊以1 L/分鐘向反應液中直接注入（鼓泡）氮氣，一邊調整為動力0.033 kW，利用有罩加熱器升溫，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖10及表1所示，獲得平均粒子徑為49.8 nm、CV值為0.18的顯示出尖銳的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.0004重量份。 (Example 5) To 258 g of the nickel complexation reaction solution B obtained in Synthesis Example 2, 5 g of the nickel nanoparticle slurry obtained in Example 1 was added to make a total of 263 g, and the reaction was carried out at 1 L/min. Nitrogen gas was directly injected (bubbled) into the liquid, while the power was adjusted to 0.033 kW, the temperature was raised by a heater with a cover, and the reaction was carried out at 230° C. for 10 minutes to obtain a nickel nanoparticle slurry. As shown in FIG. 10 and Table 1, particles showing a sharp particle size distribution with an average particle diameter of 49.8 nm and a CV value of 0.18 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.0004 weight part.
（比較例1） 向合成例1中所獲得的鎳錯合化反應液A的775 g中添加6 g有機金屬化合物（1），合計設為781 g，一邊以2 L/分鐘流動氮氣，一邊調整為動力0.033 kW，利用有罩加熱器升溫，在210℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖2及表1所示，獲得平均粒子徑為18.4 nm、CV值為0.29的顯示出寬廣的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.85重量份，鋰成分為0.13重量份。 (comparative example 1) Add 6 g of the organometallic compound (1) to 775 g of the nickel complexation reaction solution A obtained in Synthesis Example 1 to make the total 781 g, and adjust the power to 0.033 kW while flowing nitrogen gas at 2 L/min , using a covered heater to raise the temperature and react at 210° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 2 and Table 1, particles showing a broad particle size distribution with an average particle diameter of 18.4 nm and a CV value of 0.29 were obtained. In addition, the nickel component contained in 100 parts by weight of the metal component was 99.85 parts by weight, and the lithium component was 0.13 parts by weight.
（比較例2） 向合成例1中所獲得的鎳錯合化反應液A的775 g中添加6 g有機金屬化合物（1），合計設為781 g，一邊以4 L/分鐘流動氮氣，一邊調整為動力0.033 kW，利用有罩加熱器升溫，在210℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖3及表1所示，獲得平均粒子徑為20.4 nm、CV值為0.24的顯示出寬廣的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.85重量份，鋰成分為0.12重量份。 (comparative example 2) 6 g of the organometallic compound (1) was added to 775 g of the nickel complexation reaction solution A obtained in Synthesis Example 1 to make a total of 781 g, and the power was adjusted to 0.033 kW while flowing nitrogen gas at 4 L/min. , using a covered heater to raise the temperature and react at 210° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 3 and Table 1, particles showing a broad particle size distribution with an average particle diameter of 20.4 nm and a CV value of 0.24 were obtained. In addition, the nickel component contained in 100 parts by weight of the metal component was 99.85 parts by weight, and the lithium component was 0.12 parts by weight.
（比較例3） 向合成例1中所獲得的鎳錯合化反應液A的775 g中添加0.2 g有機金屬化合物（1），合計設為775.2 g，一邊以3 L/分鐘流動氮氣，一邊調整為動力0.033 kW，利用有罩加熱器升溫，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖5及表1所示，獲得平均粒子徑為27.8 nm、CV值為0.27的顯示出寬廣的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.0007重量份。 (comparative example 3) Add 0.2 g of the organometallic compound (1) to 775 g of the nickel complexation reaction solution A obtained in Synthesis Example 1 to make the total 775.2 g, and adjust the power to 0.033 kW while flowing nitrogen gas at 3 L/min , using a covered heater to raise the temperature and react at 230° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 5 and Table 1, particles showing a broad particle size distribution with an average particle diameter of 27.8 nm and a CV value of 0.27 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.0007 weight part.
（比較例4） 向合成例1中所獲得的鎳錯合化反應液A的775 g中添加0.2 g有機金屬化合物（1），合計設為775.2 g，一邊以3 L/分鐘流動氮氣，一邊調整為動力0.048 kW，利用有罩加熱器升溫，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖7及表1所示，獲得平均粒子徑為36.6 nm、CV值為0.36的包含10 nm～20 nm的微粒子的顯示出寬廣的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.0006重量份。 (comparative example 4) Add 0.2 g of the organometallic compound (1) to 775 g of the nickel complexation reaction solution A obtained in Synthesis Example 1 to make the total 775.2 g, and adjust the power to 0.048 kW while flowing nitrogen gas at 3 L/min , using a covered heater to raise the temperature and react at 230° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 7 and Table 1, particles showing a broad particle size distribution including fine particles of 10 nm to 20 nm with an average particle diameter of 36.6 nm and a CV value of 0.36 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.0006 weight part.
（比較例5） 向合成例2中所獲得的鎳錯合化反應液B的258 g中添加實施例1中所獲得的鎳奈米粒子漿料13.2 g，合計設為271.2 g，一邊以3 L/分鐘流動氮氣，一邊調整為動力0.029 kW，利用有罩加熱器升溫，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖9及表1所示，獲得平均粒子徑為36.5 nm、CV值為0.55的顯示出寬廣的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.001重量份。 (comparative example 5) 13.2 g of the nickel nanoparticle slurry obtained in Example 1 was added to 258 g of the nickel complexation reaction solution B obtained in Synthesis Example 2 to make the total 271.2 g, while flowing nitrogen gas at 3 L/min , while adjusting the power to 0.029 kW, the temperature was raised by a cover heater, and the reaction was carried out at 230° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 9 and Table 1, particles showing a broad particle size distribution with an average particle diameter of 36.5 nm and a CV value of 0.55 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.001 weight part.
（比較例6） 向合成例2中所獲得的鎳錯合化反應液B的258 g中添加實施例1中所獲得的鎳奈米粒子漿料4.0 g，合計設為262 g，一邊以1 L/分鐘流動氮氣，一邊調整為動力0.018 kW，利用有罩加熱器升溫，在230℃下反應10分鐘，由此獲得鎳奈米粒子漿料。如圖11及表1所示，獲得平均粒子徑為49.3 nm、CV值為0.31的顯示出寬廣的粒度分佈的粒子。另外，金屬成分100重量份中所含的鎳成分為99.99重量份，鋰成分為0.0002重量份。 (comparative example 6) 4.0 g of the nickel nanoparticle slurry obtained in Example 1 was added to 258 g of the nickel complexation reaction solution B obtained in Synthesis Example 2 to make the total 262 g, while flowing nitrogen gas at 1 L/min , while adjusting the power to 0.018 kW, the temperature was raised using a cover heater, and the reaction was performed at 230° C. for 10 minutes, thereby obtaining a nickel nanoparticle slurry. As shown in FIG. 11 and Table 1, particles showing a broad particle size distribution with an average particle diameter of 49.3 nm and a CV value of 0.31 were obtained. Moreover, the nickel component contained in 100 weight part of metal components was 99.99 weight part, and the lithium component was 0.0002 weight part.
[表1]
如表1所示，實施例1～實施例5的本發明的鎳奈米粒子在利用加速電壓為15 kV時二次電子解析度為1.0 nm以下的高解析度SEM所拍攝的全部400個鎳奈米粒子中，相對於平均粒子徑的粒子徑為1/2以下的粒子與粒子徑為3/2以上的粒子的合計數量所占的比例為5%以下。即，在粒度分佈中大幅偏離平均粒子徑的粒子的存在比率少，具有尖銳的粒度分佈，因此確認到薄膜形成性或向極窄間隙的填充性優異。As shown in Table 1, all 400 nickel nanoparticles of the present invention in Examples 1 to 5 were captured by a high-resolution SEM with a secondary electron resolution of 1.0 nm or less at an accelerating voltage of 15 kV. In the nanoparticles, the ratio of the total number of particles having a particle diameter of 1/2 or less and particles having a particle diameter of 3/2 or more relative to the average particle diameter is 5% or less. That is, the ratio of particles greatly deviated from the average particle diameter in the particle size distribution is small, and the particle size distribution is sharp, so it has been confirmed that the thin film formability and the filling property into extremely narrow gaps are excellent.
另外，如表1所示，本發明的鎳奈米粒子即便在利用加速電壓為15 kV時二次電子解析度為1.0 nm以下的高解析度SEM進行測定的情況下，CV值也為0.25以下。在高解析度SEM的情況下，可充分檢測到小於20 nm、尤其是小於5 nm的小粒徑的鎳奈米粒子（以下，稱為“小粒徑鎳奈米粒子”）的存在，因此更正確地反映CV值的實際狀態。本發明的鎳奈米粒子與現有技術的鎳奈米粒子相比較，由於小粒徑鎳奈米粒子的含量少，因此即便在利用高解析度SEM進行測定的情況下，CV值也為0.25以下。In addition, as shown in Table 1, the nickel nanoparticles of the present invention have a CV value of 0.25 or less even when measured by a high-resolution SEM with a secondary electron resolution of 1.0 nm or less at an accelerating voltage of 15 kV. . In the case of high-resolution SEM, the existence of small-diameter nickel nanoparticles (hereinafter referred to as "small-diameter nickel nanoparticles") smaller than 20 nm, especially smaller than 5 nm, can be sufficiently detected, so More correctly reflect the actual state of the CV values. Compared with the nickel nanoparticles of the prior art, the nickel nanoparticles of the present invention have a small content of nickel nanoparticles with a small particle size, so even when measured by a high-resolution SEM, the CV value is 0.25 or less. .
以上，出於例示的目的詳細說明了本發明的實施形態，但本發明並不受所述實施形態的制約。As mentioned above, although the embodiment of this invention was demonstrated in detail for the purpose of illustration, this invention is not limited to the said embodiment.
圖1是實施例1中所製備的粒子的掃描式電子顯微鏡（SEM）圖像（20萬倍）。 圖2是比較例1中所製備的粒子的SEM圖像（20萬倍）。 圖3是比較例2中所製備的粒子的SEM圖像（20萬倍）。 圖4是實施例2中所製備的粒子的SEM圖像（10萬倍）。 圖5是比較例3中所製備的粒子的SEM圖像（20萬倍）。 圖6是實施例3中所製備的粒子的SEM圖像（20萬倍）。 圖7是比較例4中所製備的粒子的SEM圖像（20萬倍）。 圖8是實施例4中所製備的粒子的SEM圖像（20萬倍）。 圖9是比較例5中所製備的粒子的SEM圖像（20萬倍）。 圖10是實施例5中所製備的粒子的SEM圖像（20萬倍）。 圖11是比較例6中所製備的粒子的SEM圖像（5萬倍）。 FIG. 1 is a scanning electron microscope (SEM) image (200,000 times) of the particles prepared in Example 1. FIG. 2 is a SEM image (200,000 times) of the particles prepared in Comparative Example 1. FIG. 3 is a SEM image (200,000 times) of the particles prepared in Comparative Example 2. Fig. 4 is a SEM image (100,000 times) of the particles prepared in Example 2. FIG. 5 is a SEM image (200,000 times) of the particles prepared in Comparative Example 3. FIG. Fig. 6 is a SEM image (200,000 times) of the particles prepared in Example 3. FIG. 7 is a SEM image (200,000 times) of the particles prepared in Comparative Example 4. FIG. FIG. 8 is a SEM image (200,000 times) of the particles prepared in Example 4. FIG. 9 is a SEM image (200,000 times) of the particles prepared in Comparative Example 5. FIG. FIG. 10 is a SEM image (200,000 times) of the particles prepared in Example 5. FIG. 11 is a SEM image (50,000 times) of the particles prepared in Comparative Example 6. FIG.
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