JP2011018898A - Barium titanate powder, nickel paste, manufacturing method, and laminated ceramic capacitor - Google Patents
Barium titanate powder, nickel paste, manufacturing method, and laminated ceramic capacitor Download PDFInfo
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- JP2011018898A JP2011018898A JP2010131546A JP2010131546A JP2011018898A JP 2011018898 A JP2011018898 A JP 2011018898A JP 2010131546 A JP2010131546 A JP 2010131546A JP 2010131546 A JP2010131546 A JP 2010131546A JP 2011018898 A JP2011018898 A JP 2011018898A
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- nickel
- sulfur
- barium titanate
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 359
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 151
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 145
- 239000000843 powder Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000011593 sulfur Substances 0.000 claims abstract description 142
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 142
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 55
- 239000000919 ceramic Substances 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052788 barium Inorganic materials 0.000 claims description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 3
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- 238000005245 sintering Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000002003 electrode paste Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
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- 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 7
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 7
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
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- -1 triazine thiols Chemical class 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- IGODOXYLBBXFDW-UHFFFAOYSA-N alpha-Terpinyl acetate Chemical compound CC(=O)OC(C)(C)C1CCC(C)=CC1 IGODOXYLBBXFDW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FAFMZORPAAGQFV-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] propanoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)CC)C[C@@H]1C2(C)C FAFMZORPAAGQFV-BREBYQMCSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- DIICMQCJAQLQPI-UHFFFAOYSA-N isobornyl propionate Natural products CCC(=O)C1CC2CCC1(C)C2(C)C DIICMQCJAQLQPI-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、積層セラミックコンデンサの内部電極形成に使用されるチタン酸バリウム粉末及びそれを含有したニッケルペースト及びその製造方法、更に積層セラミックコンデンサに関するものである。 The present invention relates to a barium titanate powder used for forming an internal electrode of a multilayer ceramic capacitor, a nickel paste containing the same, a method for manufacturing the same, and a multilayer ceramic capacitor.
従来、積層セラミックコンデンサ（以下、ＭＬＣＣとも称する。）の内部電極には、Ｐｄ粉末が使用されていた。近年においては、コストダウンのために上記電極にニッケル粉末が使用されている。特許文献１には、ＭＬＣＣ内部電極形成材料に用いるニッケル粉末が開示されている。ニッケル粉末を使用したＭＬＣＣの内部電極の一般的な製造方法は、次のとおりである。 Conventionally, Pd powder has been used for internal electrodes of multilayer ceramic capacitors (hereinafter also referred to as MLCCs). In recent years, nickel powder has been used for the electrode for cost reduction. Patent Document 1 discloses a nickel powder used as an MLCC internal electrode forming material. The general manufacturing method of the internal electrode of MLCC using nickel powder is as follows.
ニッケル粉末とバインダーと溶剤とを混合して、ニッケル粉と誘電体セラミックス粉末をビヒクル中に分散させたニッケルペーストを内部電極材料として、誘電体セラミックのセラミックグリーンシートにスクリーン印刷などにより塗布する。次いで、セラミックグリーンシートの多層積層体を積層圧着工程により多層化し加熱圧着して一体化する。更に、酸化性雰囲気又は不活性雰囲気中にて５００℃以下で脱バインダー処理を行い、所定の大きさに裁断した後、還元雰囲気中で焼成して、ＭＬＣＣを製造する。 A nickel paste in which nickel powder, a binder, and a solvent are mixed and nickel powder and dielectric ceramic powder are dispersed in a vehicle is applied as an internal electrode material to a ceramic green sheet of dielectric ceramic by screen printing or the like. Next, the multilayered body of ceramic green sheets is multilayered by a laminating and crimping process and integrated by thermocompression bonding. Further, the binder removal treatment is performed at 500 ° C. or less in an oxidizing atmosphere or an inert atmosphere, and after cutting into a predetermined size, the MLCC is manufactured by firing in a reducing atmosphere.
ＭＬＣＣの小型化、多層化および大容量化を促進するうえで、内部電極を薄層化することが重要な技術となっている。従って、小型、大容量のＭＬＣＣの製造にニッケルペーストを用いる場合には、非常に少ない塗布量で焼成時にクラックや剥離が発生しにくく、低抵抗な電極材料としてのニッケル粉末を使用するのが好ましい。 In order to promote the miniaturization, multilayering, and capacity increase of MLCC, it is an important technique to make the internal electrodes thinner. Therefore, when nickel paste is used for the production of small and large-capacity MLCCs, it is preferable to use nickel powder as a low-resistance electrode material because cracks and peeling hardly occur during firing with a very small coating amount. .
ＭＬＣＣ電極の薄膜化には、特許文献１に開示されているように、内部電極形成に用いるニッケル粉末の粒子の大きさと共に、その粒子形状が球状であることが重要である。ＭＬＣＣの製造工程において、球状微粒子は電極ペースト塗膜内の充填密度を高くして、薄膜電極の形成を容易にし、クラックや剥離を生じさせない効果を奏する。特に、特許文献１には、ニッケル微粒子が球状を呈することに関して、ペースト中に含有する硫黄の含有率が影響することが記載されている。 In order to reduce the thickness of the MLCC electrode, as disclosed in Patent Document 1, it is important that the particle shape of the nickel powder used for forming the internal electrode is spherical, as well as the particle shape. In the MLCC manufacturing process, the spherical fine particles increase the packing density in the electrode paste coating film, facilitate the formation of a thin film electrode, and have the effect of preventing cracks and peeling. In particular, Patent Document 1 describes that the content of sulfur contained in the paste affects the nickel fine particles having a spherical shape.
通常のニッケル粉末においては不純物として硫黄が極めて微量しか含有していない。かかる通常のニッケル粉末を用いたニッケルペーストによって内部電極形成を行う場合には、脱バインダー工程においてバインダーの熱分解がニッケル粒子表面の触媒作用により誘発されてバインダー成分ガスが発生する。このとき、バインダーの熱分解はニッケル粒子の表面近傍に集中し、その他のバインダーはほとんどが分解されないため、この部分分解によって発生したガスは閉じ込められ、セラミック誘電体層とニッケル内部電極層との間を拡幅してしまい、構造欠陥を生じさせる。 Ordinary nickel powder contains a very small amount of sulfur as an impurity. When the internal electrode is formed using a nickel paste using such a normal nickel powder, thermal decomposition of the binder is induced by the catalytic action on the surface of the nickel particles in the binder removal step, and a binder component gas is generated. At this time, the thermal decomposition of the binder is concentrated in the vicinity of the surface of the nickel particles, and most of the other binders are not decomposed. Therefore, the gas generated by this partial decomposition is confined, and between the ceramic dielectric layer and the nickel internal electrode layer. Is widened, causing structural defects.
一方、特許文献２、３及び４には、硫黄成分を含有させたニッケルペーストがＭＬＣＣの製造工程において焼結遅延効果を奏し、上記構造欠陥の発生の抑制に寄与することが開示されている。 On the other hand, Patent Documents 2, 3, and 4 disclose that nickel paste containing a sulfur component has a sintering delay effect in the MLCC manufacturing process and contributes to suppression of the occurrence of the structural defects.
特許文献２〜４に開示された硫黄添加ニッケルペーストを以下に検証する。
まず、特許文献２の場合、バインダーを溶剤に溶解したビヒクル中に、ニッケル粉が分散されると共に、トリアジンチオール類や硫酸根含有化合物の硫黄含有有機化合物を混入させている。例えば、硫酸根含有化合物は、硫酸根ＳＯ３を含む脂肪族又は芳香族の炭化水素化合物若しくはその塩であり、具体的にはドデシル硫酸ナトリウムＣＨ３(ＣＨ２)１１ＳＯ３Ｎａ、ドデシルベンゼンスルホン酸ナトリウムＣ１２Ｈ２５Ｃ６Ｈ４ＳＯ３Ｎａなどである。このため、硫黄含有量は微量であっても、ニッケルペースト中に有機成分が余分に混入し、特にベンゼンなどは環境負荷物質であり人体の健康や環境に与える影響は大きく、焼成により分解させても焼成後も残留カーボンとして存在するほか、Ｎａが不純物としてＭＬＣＣの電気特性に悪影響を与えるおそれが生ずる。
The sulfur-added nickel paste disclosed in Patent Documents 2 to 4 will be verified below.
First, in Patent Document 2, nickel powder is dispersed in a vehicle in which a binder is dissolved in a solvent, and triazine thiols and a sulfur-containing organic compound such as a sulfate group-containing compound are mixed therein. For example, the sulfate group-containing compound is an aliphatic or aromatic hydrocarbon compound containing sulfate group SO 3 or a salt thereof. Specifically, sodium dodecyl sulfate CH 3 (CH 2 ) 11 SO 3 Na, dodecylbenzenesulfone Acid sodium C 12 H 25 C 6 H 4 SO 3 Na and the like. For this reason, even if the sulfur content is very small, extra organic components are mixed in the nickel paste, and especially benzene is an environmentally hazardous substance and has a significant impact on human health and the environment. In addition to being present as residual carbon after firing, Na as an impurity may adversely affect the electrical characteristics of MLCC.
特許文献３の場合、ニッケル粉末を特定量の硫黄を含むガスと接触処理するなどして、ニッケル粉末の表面を硫黄又は硫酸基で被覆した硫黄被覆ニッケル粒子を用いている。ニッケル粉末自体は、一般に化学気相反応法ないし湿式法により製造されるが、特許文献３の硫黄被覆ニッケル粒子製法によれば、ニッケル粉末製造工程で余分の硫黄被覆処理が必要となる。従って、特許文献３の場合には硫黄被覆処理のためにニッケル粉末製造工程を変更することになり製造装置が複雑化し量産規模で低コストなＮｉ粉を生産することが困難である問題点や、また、硫黄被覆処理過程で硫化水素を使用するため人体の健康に与える影響を考えると装置の作業性や安全性に問題がある。更に硫黄被覆処理過程でニッケル粒子同士を結合、再凝集させてしまい、ニッケルペーストとして薄膜の電極形成に悪影響を与えるおそれがあった。 In the case of Patent Document 3, sulfur-coated nickel particles are used in which the surface of nickel powder is coated with sulfur or sulfate groups by, for example, contacting nickel powder with a gas containing a specific amount of sulfur. The nickel powder itself is generally manufactured by a chemical vapor reaction method or a wet method, but according to the sulfur-coated nickel particle manufacturing method of Patent Document 3, an extra sulfur coating process is required in the nickel powder manufacturing process. Therefore, in the case of Patent Document 3, the nickel powder production process is changed for the sulfur coating treatment, and the production apparatus becomes complicated, and it is difficult to produce low-cost Ni powder on a mass production scale, In addition, since hydrogen sulfide is used in the process of sulfur coating, there is a problem in workability and safety of the apparatus considering the effect on human health. Furthermore, nickel particles are bonded and re-aggregated in the process of sulfur coating, which may adversely affect the formation of a thin film electrode as a nickel paste.
特許文献４の場合の製法では、ニッケル粉を生成する時に硫化水素ガスを反応装置内に導入し硫黄を含有させた硫黄含有ニッケル粉を製造する。そして、含有される硫黄原子が酸化されて脱離してしまうのを防止するため、例えば、ニッケル粒子を気相中、高温で酸化性ガスと接触させた後に急冷することにより表面を瞬時に酸化させる表面酸化処理を行っている。しかし、特許文献４の場合においても、反応ガスとして硫化水素ガスを使用しており人体の健康に与える影響を考えると装置の作業性や安全性に問題があるほか、ニッケル粒子の表面酸化処理方法が反応管の出口側に接続された冷却管を通ってニッケル粉が冷却される際に大量に空気を送り込むことによって一気に表面を酸化するため、ニッケル粒子の酸化度合いの制御が難しく、なかには酸化が進行して、電極形成後のＭＬＣＣの電気特性に悪影響を与えるおそれがあった。 In the manufacturing method in the case of patent document 4, the sulfur-containing nickel powder which introduce | transduced hydrogen sulfide gas into the reaction apparatus and was made to contain sulfur at the time of producing | generating nickel powder is manufactured. In order to prevent the contained sulfur atoms from being oxidized and desorbed, for example, the surface is instantaneously oxidized by bringing nickel particles into contact with an oxidizing gas at a high temperature in the gas phase and then rapidly cooling. Surface oxidation treatment is performed. However, in the case of Patent Document 4, hydrogen sulfide gas is used as a reaction gas, and there are problems in the workability and safety of the apparatus when considering the influence on human health. When the nickel powder is cooled through the cooling pipe connected to the outlet side of the reaction pipe, the surface is oxidized at a stretch by sending a large amount of air, so it is difficult to control the degree of oxidation of the nickel particles. There was a risk that the electrical characteristics of the MLCC after electrode formation would be adversely affected.
本発明の目的のひとつは、上記課題に鑑み、積層セラミックコンデンサの製造段階における焼成時のクラック等の発生が抑制され、コンデンサ製造の歩留まりを向上させることのできる、積層セラミックコンデンサ生成用ニッケルペーストに用いる硫黄含有チタン酸バリウムを提供することである。また、本発明の別の目的は、積層セラミックコンデンサの製造段階における焼成時のクラック等の発生が抑制され、高品質に内部電極を形成することができる、前記硫黄含有チタン酸バリウムを含むニッケルペースト及びその製造方法を提供することである。更に、本発明の目的は、硫黄含有チタン酸バリウムを含むニッケルペーストを用いて形成され、クラック等の欠陥のない内部電極を有する積層セラミックコンデンサを提供することである。 One of the objects of the present invention is to provide a nickel paste for producing a multilayer ceramic capacitor capable of suppressing the occurrence of cracks during firing in the production stage of the multilayer ceramic capacitor and improving the yield of capacitor production in view of the above problems. The sulfur-containing barium titanate used is provided. Another object of the present invention is to provide a nickel paste containing sulfur-containing barium titanate, which can suppress the generation of cracks and the like during firing in the production stage of a multilayer ceramic capacitor and can form internal electrodes with high quality. And a method of manufacturing the same. Furthermore, an object of the present invention is to provide a multilayer ceramic capacitor formed using a nickel paste containing sulfur-containing barium titanate and having an internal electrode free from defects such as cracks.
本発明の第１の形態は、積層セラミックコンデンサの内部電極に用いるニッケルペーストであって、ニッケル粉と、バインダー剤と、溶剤と、チタン酸バリウム粉に硫黄を混在させた硫黄含有チタン酸バリウムとを含むニッケルペーストである。 1st form of this invention is nickel paste used for the internal electrode of a multilayer ceramic capacitor, Comprising: Nickel powder, a binder agent, a solvent, Sulfur containing barium titanate which mixed sulfur with barium titanate powder, Nickel paste containing
本発明の第２の形態は、第１の形態において、前記チタン酸バリウム粉が前記ニッケル粉に対して１〜３０重量％を含有し、且つ前記硫黄が前記チタン酸バリウム粉に対して０．０１〜１重量％を含有したニッケルペーストである。 According to a second aspect of the present invention, in the first aspect, the barium titanate powder contains 1 to 30% by weight with respect to the nickel powder, and the sulfur has a concentration of 0.1% to the barium titanate powder. It is a nickel paste containing 01 to 1% by weight.
本発明の第３の形態は、第１又は第２の形態において、前記硫黄含有チタン酸バリウム粉の格子定数比（ｃ軸とａ軸の比：ｃ／ａ比）が１．００４０〜１．０１００の範囲であるニッケルペーストである。 According to a third aspect of the present invention, in the first or second aspect, the sulfur-containing barium titanate powder has a lattice constant ratio (ratio of c-axis to a-axis: c / a ratio) of 1.040-1. Nickel paste in the range of 0100.
本発明の第４の形態は、第１、第２又は第３の形態において、前記硫黄含有チタン酸バリウム粉のバリウム（Ｂａ）とチタン（Ｔｉ）の組成比（Ｂａ／Ｔｉ）が０．９９〜１．０１であるニッケルペーストである。 According to a fourth aspect of the present invention, in the first, second or third aspect, the composition ratio (Ba / Ti) of barium (Ba) and titanium (Ti) of the sulfur-containing barium titanate powder is 0.99. Nickel paste that is ˜1.01.
本発明の第５の形態は、第１〜第４のいずれかの形態において、前記硫黄含有チタン酸バリウム粉が１０〜１００ｎｍ以下の平均粒子径を有し、且つ正方晶であり、高結晶性球状を具備した硫黄含有チタン酸バリウム粉を含むニッケルペーストである。 According to a fifth aspect of the present invention, in any of the first to fourth aspects, the sulfur-containing barium titanate powder has an average particle diameter of 10 to 100 nm and is tetragonal, and has high crystallinity. It is a nickel paste containing sulfur-containing barium titanate powder having a spherical shape.
本発明の第６の形態は、第１〜第５のいずれかの形態に係るニッケルペーストに添加される硫黄含有チタン酸バリウム粉であって、硫黄を含有し、１０〜１００ｎｍ以下の平均粒子径を有し、且つ正方晶であり、高結晶性球状を具備した硫黄含有チタン酸バリウム粉である。 The sixth aspect of the present invention is a sulfur-containing barium titanate powder added to the nickel paste according to any one of the first to fifth aspects, containing sulfur and having an average particle diameter of 10 to 100 nm or less. It is a sulfur-containing barium titanate powder that is tetragonal and has a highly crystalline sphere.
本発明の第７の形態は、バインダー剤及び溶剤を溶解させたビヒクルにニッケル粉と、チタン酸バリウム粉に硫黄を混在させた硫黄含有チタン酸バリウムとを混入させて、積層セラミックコンデンサの内部電極形成用ニッケルペーストを製造するニッケルペーストの製造方法である。 According to a seventh aspect of the present invention, a nickel powder and a sulfur-containing barium titanate in which sulfur is mixed in a barium titanate powder are mixed in a vehicle in which a binder and a solvent are dissolved, and an internal electrode of a multilayer ceramic capacitor It is the manufacturing method of the nickel paste which manufactures the nickel paste for formation.
本発明の第８の形態は、第１〜第５のいずれかの形態に係るニッケルペーストをセラミック基材に塗膜して焼成し、ニッケルを導電性元素とした内部電極を形成した積層セラミックコンデンサである。 According to an eighth aspect of the present invention, there is provided a multilayer ceramic capacitor in which an internal electrode having nickel as a conductive element is formed by coating a nickel paste according to any one of the first to fifth aspects on a ceramic substrate and firing it. It is.
本発明者は、ＭＬＣＣの内部電極に用いるニッケルペーストの生成にあたり、特許文献３及び４のように、ニッケル粉に硫黄を直接担持させる硫黄添加方法では種々の不具合が生じる点に鑑み、電極ペーストの焼結抑制効果を有するチタン酸バリウム材に着目し、硫黄含有チタン酸バリウムをビヒクルに混入させることにより、焼結遅延効果を一層発揮することの知見を得た。本発明はかかる知見に基づきなされたものであり、本発明の第１の形態によれば、ニッケル粉と、バインダー剤と、溶剤と、チタン酸バリウム粉に硫黄を混在させた硫黄含有チタン酸バリウムとを含むので、優れた焼結遅延効果を奏し、積層セラミックコンデンサの製造段階における焼成時のクラック等の発生を十分に抑制することができる。即ち、含有硫黄により一層、焼結遅延効果が向上した硫黄含有チタン酸バリウムの焼結遅延効果により、ＭＬＣＣの製造工程において、ペースト中のニッケル粒子表面でのバインダー成分の熱分解とそれに伴う急激なガス発生が抑制されるため、焼成段階でのクラックや層間剥離等の構造欠陥が発生するのを防止することができる。従って、本形態に係るニッケルペーストを使用して、積層セラミックコンデンサの製造歩留まりを向上させることができ、高品質の内部電極を有したＭＬＣＣを得ることができる。
なお、本発明者において行った、ニッケル含有率の異なる２種類のニッケルペーストの誘電特性の検証実験（後述の実施例２及び３参照）によれば、硫黄含有チタン酸バリウム粉を用いたニッケルペーストの場合、硫黄を含有しない場合と比較して静電容量値が高く、硫黄含有チタン酸バリウム粉を用いたニッケルペーストがＭＬＣＣの高容量化を実現できることが解明された。従って、硫黄含有チタン酸バリウム粉を用いたニッケルペーストは、静電容量増大効果を奏するため、定格の静電容量値の実現に際してニッケル含有量の削減が可能になり、ＭＬＣＣの薄膜化及び低価格化に寄与することができる。
In the production of nickel paste used for the internal electrode of MLCC, the present inventor considered that various problems occur in the sulfur addition method in which sulfur is directly supported on nickel powder as in Patent Documents 3 and 4, Focusing on the barium titanate material having a sintering inhibiting effect, the inventors have obtained the knowledge that the sintering delay effect is further exhibited by mixing sulfur-containing barium titanate into the vehicle. This invention is made | formed based on this knowledge, and according to the 1st form of this invention, the sulfur containing barium titanate which mixed nickel powder, the binder agent, the solvent, and sulfur with barium titanate powder. Therefore, an excellent sintering delay effect can be obtained, and the occurrence of cracks and the like during firing in the production stage of the multilayer ceramic capacitor can be sufficiently suppressed. In other words, due to the sintering delay effect of sulfur-containing barium titanate, the sintering delay effect of which is further improved by the contained sulfur, the thermal decomposition of the binder component on the surface of the nickel particles in the paste and the abrupt rapidity associated therewith in the MLCC manufacturing process Since gas generation is suppressed, it is possible to prevent occurrence of structural defects such as cracks and delamination in the firing stage. Therefore, by using the nickel paste according to this embodiment, the production yield of the multilayer ceramic capacitor can be improved, and an MLCC having a high quality internal electrode can be obtained.
In addition, according to a verification experiment (see Examples 2 and 3 described later) of dielectric properties of two kinds of nickel pastes having different nickel contents conducted by the present inventor, nickel paste using sulfur-containing barium titanate powder. In this case, it was clarified that the nickel paste using the sulfur-containing barium titanate powder can achieve a higher capacity of MLCC than the case of not containing sulfur. Therefore, the nickel paste using the sulfur-containing barium titanate powder has an effect of increasing the capacitance, so that the nickel content can be reduced when realizing the rated capacitance value, and the MLCC is made thinner and less expensive. It can contribute to the conversion.
特に、本形態においては、ニッケル粉に硫黄を直接担持させず、別途、チタン酸バリウム粉に硫黄を混在させた硫黄含有チタン酸バリウムを用いるので、特許文献３の場合と比べて、ニッケル粉製造段階で反応ガスとして硫化水素ガスを使用せず、人体の健康に与える影響がなく、良好な作業性や安全性を確保でき、また、特許文献４の場合と比べても、ニッケル粒子の表面酸化処理に伴うニッケル粒子の酸化を誘発させず、高品質の内部電極の形成が可能になる。硫黄の担持形態としては、特に限定されるものではなくチタン酸バリウム粉に硫黄粉を粉体混合する場合の他、硫酸根として含有させたり、バリウム粉粒子にコートさせたりしてもよい。特に、硫酸根として含有させる場合には、特許文献２の場合のように、ドデシル硫酸ナトリウムやドデシルベンゼンスルホン酸ナトリウム等の硫酸根含有化合物を使用せずに、ベンゼン等の有機成分やＮａ等の不純物元素が残留しないようにチタン酸バリウムに硫酸根を合成するのが好ましい。 In particular, in this embodiment, since nickel-containing barium titanate in which sulfur is mixed with barium titanate powder is used instead of directly supporting sulfur in nickel powder, nickel powder production is performed as compared with the case of Patent Document 3. No hydrogen sulfide gas is used as a reaction gas at the stage, there is no influence on human health, good workability and safety can be ensured, and the surface oxidation of nickel particles is higher than that in Patent Document 4. High-quality internal electrodes can be formed without inducing oxidation of nickel particles during processing. The form of sulfur support is not particularly limited, and the sulfur powder may be mixed with barium titanate powder as a sulfate radical, or may be coated with barium powder particles. In particular, when it is contained as a sulfate radical, as in Patent Document 2, an organic component such as benzene, Na or the like such as sodium is used without using a sulfate radical-containing compound such as sodium dodecyl sulfate or sodium dodecylbenzenesulfonate. It is preferable to synthesize sulfate radicals in barium titanate so that no impurity elements remain.
本発明におけるニッケル粉は、ＣＶＤ（化学気相成長）法、ＰＶＤ（物理気相成長）法、噴霧熱分解法及び湿式化学還元法、あるいは湿式化学法で合成した水酸化ニッケル粉を還元雰囲気で熱処理をしてニッケル粉を得る製造方法やアトマイズ法等により製造することができる。ニッケル粉の粉形態は平均粒子径１０ｎｍ〜１μｍのものが好ましく、また粒子形態に限らずフレーク粉も使用することができる。更に、ニッケル粉は、上記各種製造方法により得られるニッケル単体粉の他、例えば、ニッケルに耐酸化性等を付与するためのクロム、リン、亜鉛、貴金属、希土類金属等を添加したニッケルの合金材が含まれる。
なお、ニッケル粉には製造段階で発生する不純物としては硫黄が含まれていてもよく、むしろ微量程度含んでおれば、樹脂成分の急激な燃焼を抑止する効果を奏する。
The nickel powder in the present invention is a nickel hydroxide powder synthesized by a CVD (chemical vapor deposition) method, a PVD (physical vapor deposition) method, a spray pyrolysis method and a wet chemical reduction method, or a wet chemical method in a reducing atmosphere. It can be manufactured by a manufacturing method for obtaining nickel powder by heat treatment, an atomizing method, or the like. The powder form of the nickel powder is preferably one having an average particle diameter of 10 nm to 1 μm, and not only the particle form but also flake powder can be used. Furthermore, nickel powder is nickel alloy powder obtained by adding chromium, phosphorus, zinc, noble metal, rare earth metal, etc. for imparting oxidation resistance to nickel in addition to nickel simple powder obtained by the above various production methods. Is included.
In addition, sulfur may be contained in the nickel powder as an impurity generated in the production stage. If the nickel powder is contained in a very small amount, it has an effect of suppressing rapid combustion of the resin component.
本発明における溶剤には、例えば、アルコール、アセトン、プロパノール、酢酸エチル、酢酸ブチル、エーテル、石油エーテル、ミネラルスピリット、その他のパラフィン系炭化水素溶剤、あるいは、ブチルカルビトール、ターピネオールやジヒドロターピネオール、ブチルカルビトールアセテート、ジヒドロターピネオールアセテート、ジヒドロカルビルアセテート、カルビルアセテート、ターピニルアセテート、リナリールアセテート等のアセテート系や、ジヒドロターピニルプロピオネート、ジヒドロカルビルプロピオネート、イソボニルプロピオネートなどのプロピオネート系溶剤、エチルセロソルブやブチルセロソルブなどのセロソルブ類、芳香族類、ジエチルフタレート、その他電極ペーストに使用可能な溶剤全てを使用することができる。 Examples of the solvent in the present invention include alcohol, acetone, propanol, ethyl acetate, butyl acetate, ether, petroleum ether, mineral spirit, other paraffinic hydrocarbon solvents, butyl carbitol, terpineol, dihydroterpineol, and butyl carbitol. Acetate such as tall acetate, dihydroterpineol acetate, dihydrocarbyl acetate, carbyl acetate, terpinyl acetate, linalyl acetate, dihydroterpinyl propionate, dihydrocarbyl propionate, isobornyl propionate, etc. Use propionate solvents, cellosolves such as ethyl cellosolve and butyl cellosolve, aromatics, diethyl phthalate, and other solvents that can be used for electrode paste. Can.
本発明におけるバインダー剤には、樹脂結合剤が好ましく、例えばエチルセルロース、ポリビニルアセタール、アクリル樹脂、アルキッド樹脂等であり、その他電極塗料に使用される樹脂は全て含まれる。 The binder agent in the present invention is preferably a resin binder, such as ethyl cellulose, polyvinyl acetal, acrylic resin, alkyd resin, and all other resins used for electrode paints.
本発明の第２の形態によれば、前記チタン酸バリウム粉が前記ニッケル粉に対して１〜３０重量％を含有し、且つ前記硫黄が前記チタン酸バリウム粉に対して０．０１〜１重量％を含有するので、電極ペーストの焼結遅延効果を十分に発揮することができ、非常に少ない電極塗布量で高品質の内部電極を備えた小型、大容量のＭＬＣＣを実現することができる。 According to the 2nd form of this invention, the said barium titanate powder contains 1-30 weight% with respect to the said nickel powder, and the said sulfur is 0.01-1 weight with respect to the said barium titanate powder. %, The effect of delaying the sintering of the electrode paste can be sufficiently exerted, and a small and large-capacity MLCC having a high-quality internal electrode can be realized with a very small electrode coating amount.
本発明に係るニッケルペーストに含有させる、硫黄含有チタン酸バリウム粉には、通常の結晶性を備えたチタン酸バリウム材を使用して硫黄含有を施して使用することができるが、特に、高結晶性を具備したチタン酸バリウム材を使用するのが好ましい。即ち、本発明の第３の形態によれば、格子定数比（ｃ軸とａ軸の比：ｃ／ａ比）が１．００４０〜１．０１００の範囲である、高結晶性の硫黄含有チタン酸バリウム粉を添加するので、電極ペーストの焼結遅延効果を十分に発揮するニッケルペーストを実現することができる。 The sulfur-containing barium titanate powder to be included in the nickel paste according to the present invention can be used with a sulfur content using a normal barium titanate material having crystallinity, in particular, a high crystal It is preferable to use a barium titanate material having properties. That is, according to the third aspect of the present invention, a highly crystalline sulfur-containing titanium having a lattice constant ratio (ratio of c-axis to a-axis: c / a ratio) in the range of 1.040 to 1.0100. Since the barium acid powder is added, a nickel paste that sufficiently exhibits the sintering delay effect of the electrode paste can be realized.
本発明の第４の形態によれば、バリウム（Ｂａ）とチタン（Ｔｉ）の組成比（Ｂａ／Ｔｉ）が０．９９〜１．０１である前記硫黄含有チタン酸バリウム粉を添加するので、電極ペーストの焼結遅延効果を十分に発揮するニッケルペーストを実現することができる。 According to the fourth aspect of the present invention, the sulfur-containing barium titanate powder having a composition ratio (Ba / Ti) of barium (Ba) to titanium (Ti) of 0.99 to 1.01 is added. A nickel paste that sufficiently exhibits the sintering delay effect of the electrode paste can be realized.
本発明の第５の形態によれば、１０〜１００ｎｍ以下の平均粒子径を有し、且つ正方晶であり、高結晶性球状を具備した前記硫黄含有チタン酸バリウム粉を添加するので、電極ペーストの焼結遅延効果を十分に発揮するニッケルペーストを実現することができる。 According to the fifth aspect of the present invention, since the sulfur-containing barium titanate powder having an average particle diameter of 10 to 100 nm or less and tetragonal and having a high crystalline sphere is added, the electrode paste It is possible to realize a nickel paste that sufficiently exhibits the sintering delay effect.
本発明の第６の形態によれば、硫黄を含有し、１０〜１００ｎｍ以下の平均粒子径を有し、且つ正方晶であり、高結晶性球状を具備し、高品質のＭＬＣＣ内部電極の形成に好適な硫黄含有チタン酸バリウム粉を提供することができる。 According to the sixth aspect of the present invention, sulfur is contained, has an average particle diameter of 10 to 100 nm or less, is tetragonal, has a highly crystalline sphere, and forms a high-quality MLCC internal electrode. Sulfur-containing barium titanate powder suitable for the above can be provided.
本発明の第７の形態によれば、前記ビヒクルに、ニッケル粉と硫黄含有チタン酸バリウムとを混入させて、ＭＬＣＣの内部電極形成用ニッケルペーストを製造するので、前記硫黄含有チタン酸バリウムの優れた焼結遅延効果により、焼成時のクラック等の欠陥が発生せず、ＭＬＣＣの製造歩留まりを向上させることができ、高品質の内部電極を有した小型、大容量のＭＬＣＣを簡単且つ低価格で製造することができる。 According to the seventh aspect of the present invention, nickel powder and sulfur-containing barium titanate are mixed in the vehicle to produce a nickel paste for forming an internal electrode of MLCC. Therefore, the sulfur-containing barium titanate is excellent. Due to the delayed sintering effect, defects such as cracks during firing do not occur, the production yield of MLCC can be improved, and a small, large-capacity MLCC with high quality internal electrodes can be easily and inexpensively. Can be manufactured.
第１〜第６の形態のいずれかに係るニッケルペーストをセラミック基材に塗膜して焼成し内部電極を形成するので、焼成時のクラック等の欠陥を含まない積層セラミックコンデンサを実現することができる。 Since the nickel paste according to any one of the first to sixth embodiments is coated on a ceramic substrate and fired to form internal electrodes, it is possible to realize a multilayer ceramic capacitor that does not include defects such as cracks during firing. it can.
本発明の実施形態に係る硫黄含有チタン酸バリウムを以下に説明する。
チタン酸バリウム（ＢａＴｉＯ３）に硫黄を添加した硫黄含有チタン酸バリウム粉及びその硫黄含有チタン酸バリウムを添加したチタン酸バリウムペーストの諸物性を測定し、ペースト材の有効性（耐熱性ないし収縮抑制性）を検証した。硫黄含有チタン酸バリウムの試料として、１００ｎｍサイズのチタン酸バリウム粉を用い、硫黄をチタン酸バリウム粉に対して０．１重量％を含有させたもの（ＢＴ２）を作製した。比較のために、同じ粒径１００ｎｍサイズの硫黄を含有しないチタン酸バリウムの試料（ＢＴ１）を作製した。
The sulfur-containing barium titanate according to the embodiment of the present invention will be described below.
Various physical properties of barium titanate powder containing sulfur added to barium titanate (BaTiO 3 ) and barium titanate paste containing sulfur containing barium titanate were measured, and the effectiveness of paste material (heat resistance or shrinkage suppression) ). As a sample of sulfur-containing barium titanate, 100 nm-sized barium titanate powder was used, and a product containing 0.1% by weight of sulfur with respect to the barium titanate powder (BT2) was produced. For comparison, a barium titanate sample (BT1) containing no sulfur having the same particle size of 100 nm was prepared.
図１はＢＴ１のＳＥＭ（走査型電子顕微鏡）写真を示す。図１の（１Ａ）は同図（１Ｂ）の１０／３倍の拡大を示す。図２はＢＴ２のＳＥＭ写真を示す。図２の（２Ａ）は同図（２Ｂ）の１０／３倍の拡大を示す。硫黄含有なしチタン酸バリウムＢＴ１、硫黄含有チタン酸バリウムＢＴ２の比表面積は夫々、１３．９ｍ２／ｇであり、1次粒子径は同じものとし、粒子の大きさの違いによる焼結遅延効果はないものとした。 FIG. 1 shows a SEM (scanning electron microscope) photograph of BT1. FIG. 1 (1A) shows an enlargement of 10/3 times that of FIG. 1 (1B). FIG. 2 shows an SEM photograph of BT2. FIG. 2 (2A) shows an enlargement of 10/3 times that of FIG. 2 (2B). The specific surface areas of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2 are 13.9 m 2 / g, the primary particle diameter is the same, and the sintering delay effect due to the difference in particle size is Not supposed to be.
図３は硫黄含有なしチタン酸バリウムＢＴ１、硫黄含有チタン酸バリウムＢＴ２の粒度分布図であり、同図（３Ａ）、（３Ｂ）は夫々ＢＴ１、ＢＴ２の粒度分布を示す。横軸、縦軸は夫々、粒径（μｍ）、体積頻度（％）を示す。図４は硫黄含有なしチタン酸バリウムＢＴ１、硫黄含有チタン酸バリウムＢＴ２の個数分布、体積分布データを夫々示す。粒度分布は市販の粒度分布測定機を使用した。個数分布データのうち、ａｖｅ．は平均粒子径（μｍ）を表し、ＣＶ値は下記の式で示される。
ＣＶ値＝（(標準偏差σ)／（算術径））×１００
また、体積基準分布を基に粒子径分布を算出するソフトを用いて、下記の体積分布値（ＳＰＡＮ）を求めた。
ＳＰＡＮ＝（Ｄ９０ −Ｄ１０）／Ｄ５０
但し、粒子径分布で、Ｄ１０はこれ以下の粒子の比率が１０％である粒径（μｍ）、Ｄ５０は粒子の５０％がこれより大きく、５０％がこれより小さいという粒径（μｍ）、Ｄ９０はこれ以下の粒子の比率が９０％である粒径（μｍ）である。粒度分布の結果からは、硫黄の含有の影響におけるチタン酸バリウム粉の凝集は確認できず、硫黄含有を行った場合、硫黄含有なしチタン酸バリウムと比較しても粗大粒子のない均一な粒度分布をもつ非常に分散性に優れたチタン酸バリウム粉であった。
FIG. 3 is a particle size distribution diagram of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2, and FIGS. 3A and 3B show the particle size distributions of BT1 and BT2, respectively. The horizontal axis and the vertical axis indicate the particle size (μm) and the volume frequency (%), respectively. FIG. 4 shows the number distribution and volume distribution data of sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2, respectively. For the particle size distribution, a commercially available particle size distribution measuring machine was used. Among the number distribution data, ave. Represents an average particle diameter (μm), and the CV value is represented by the following formula.
CV value = ((standard deviation σ) / (arithmetic diameter)) × 100
Moreover, the following volume distribution value (SPAN) was calculated | required using the software which calculates particle diameter distribution based on volume reference | standard distribution.
SPAN = (D90 -D10) / D50
However, in the particle size distribution, D10 is a particle size (μm) in which the ratio of particles below this is 10%, D50 is a particle size (μm) in which 50% of the particles are larger and 50% are smaller than this, D90 is a particle size (μm) in which the ratio of particles below this is 90%. From the results of the particle size distribution, the aggregation of barium titanate powder due to the influence of sulfur content cannot be confirmed, and when sulfur content is included, uniform particle size distribution without coarse particles compared to barium titanate without sulfur content It was a barium titanate powder having excellent dispersibility.
図５は硫黄含有なしチタン酸バリウムＢＴ１、硫黄含有チタン酸バリウムＢＴ２のＴＭＡ（熱機械測定装置）の測定結果を示す。ＴＭＡ測定はＨ２を２％含有した窒素ガス中で行った。図５の横軸、縦軸は夫々、温度（℃）、長さ変化率（％）を示す。ＴＭＡの測定結果からは、硫黄含有なしチタン酸バリウムＢＴ１と硫黄含有チタン酸バリウムＢＴ２を比較すると、硫黄含有チタン酸バリウムＢＴ２が硫黄を含有しないＢＴ１より焼結遅延効果に優れていることがわかる。 FIG. 5 shows the measurement results of TMA (thermomechanical measuring device) of barium titanate BT1 without sulfur and barium titanate BT2 containing sulfur. TMA measurement was performed in nitrogen gas containing 2% of H 2 . The horizontal and vertical axes in FIG. 5 indicate temperature (° C.) and length change rate (%), respectively. From the measurement results of TMA, it can be seen that when sulfur-free barium titanate BT1 and sulfur-containing barium titanate BT2 are compared, sulfur-containing barium titanate BT2 is superior in sintering delay effect to BT1 not containing sulfur.
図６は硫黄含有なしチタン酸バリウムＢＴ１と硫黄含有チタン酸バリウムＢＴ２のＸ線回折結果を示す。同図（６Ａ）、（６Ｂ）は夫々、試料ＢＴ１、ＢＴ２のＸ線回折パターン、ピークを示す。 FIG. 6 shows X-ray diffraction results of barium titanate BT1 without sulfur and barium titanate BT2 with sulfur. FIGS. 6A and 6B show the X-ray diffraction patterns and peaks of samples BT1 and BT2, respectively.
図７は硫黄含有なしチタン酸バリウムＢＴ１と硫黄含有チタン酸バリウムＢＴ２をペースト化したときの試料ＢＴ１、ＢＴ２をＭＬＣＣのパターンで印刷して乾燥させたときの表面粗さの測定結果（Ｒａ、Ｒｍａｘ）を示す。ペースト化は、エチルセルロース粉末、電極ペースト用分散剤、ターピネオールを混合したビヒクルに試料ＢＴ１、ＢＴ２を投入してビーズミルにて分散処理を行った。ＢＴ１の場合、Ｒａが０．０１９μｍ、Ｒｍａｘが０．４４５μｍであった。ＢＴ２の場合、Ｒａが０．０１５μｍ、Ｒｍａｘが０．３３３μｍであった。ペースト化した試料の表面粗さは非常に平滑であり分散性にも大差なく優れており薄膜電極に使用するには適していた。 FIG. 7 shows the measurement results of surface roughness (Ra, Rmax) when samples BT1 and BT2 obtained by pasting sulfur-containing barium titanate BT1 and sulfur-containing barium titanate BT2 into a paste of MLCC and dried. ). For pasting, samples BT1 and BT2 were added to a vehicle in which ethyl cellulose powder, a dispersant for electrode paste, and terpineol were mixed, and dispersion treatment was performed using a bead mill. In the case of BT1, Ra was 0.019 μm and Rmax was 0.445 μm. In the case of BT2, Ra was 0.015 μm and Rmax was 0.333 μm. The surface roughness of the pasted sample was very smooth and excellent in dispersibility, making it suitable for use in thin film electrodes.
図５のＴＭＡ測定結果からわかるように、硫黄含有チタン酸バリウムは、耐熱性、即ち、収縮抑制効果に優れており、ＭＬＣＣの良好な容量特性に寄与するニッケルペースト材として使用することができる。 As can be seen from the TMA measurement results of FIG. 5, sulfur-containing barium titanate is excellent in heat resistance, that is, shrinkage suppression effect, and can be used as a nickel paste material that contributes to good capacity characteristics of MLCC.
以下に、硫黄含有チタン酸バリウムを含有させたニッケルペースト及びそれを用いたＭＬＣＣの実施例を示す。
＜実施例１＞
ニッケルペースト組成は、平均粒子径０．２μｍのニッケル粉を３０重量％、平均粒子径１００ｎｍの硫黄含有高結晶チタン酸バリウム粉、又は硫黄を含有していないチタン酸バリウムセラミックのみからなる高結晶チタン酸バリウム粉を６．０重量％（ニッケル粉に対しては２０重量％）、樹脂固形分（エチルセルロース粉末）を７．０重量％、電極ペースト用分散剤を０．５重量％、溶剤（ターピネオール系溶剤）を５６．５重量％からなる。これらの成分を３本セラミックロールにより分散処理混合してニッケルペーストを２種類（硫黄無をＭ１１、硫黄含有をＭ１２とする。）を作製した。更に、ニッケルペーストＭ１１、Ｍ１２を、チタン酸バリウムセラミックシート（厚さ：約４．０μｍ）に電極パターン印刷して、２０層分積層してＭＬＣＣ試料を作製した。高結晶チタン酸バリウム粉には、格子定数比（ｃ軸とａ軸の比：ｃ／ａ比）が１．００４０〜１．０１００の範囲にあるチタン酸バリウム材を使用するのが好ましい。また、チタン酸バリウム粉には、バリウム（Ｂａ）とチタン（Ｔｉ）の組成比（Ｂａ／Ｔｉ）が０．９９〜１．０１であるチタン酸バリウム材を使用するのが好ましい。
なお、ニッケルペーストＭ１１、Ｍ１２の夫々の無機含有率は３６．０％、３５．９％、また各ニッケル含有率は３０．０％、２９．９％であった。
Examples of nickel paste containing sulfur-containing barium titanate and examples of MLCC using the same are shown below.
<Example 1>
The nickel paste composition is 30% by weight of nickel powder having an average particle size of 0.2 μm, high-concentration titanium comprising only sulfur-containing high-crystal barium titanate powder having an average particle size of 100 nm, or barium titanate ceramic not containing sulfur. 6.0% by weight of barium acid powder (20% by weight with respect to nickel powder), 7.0% by weight of resin solids (ethylcellulose powder), 0.5% by weight of dispersant for electrode paste, solvent (terpineol) System solvent) is 56.5% by weight. These components were dispersed and mixed by three ceramic rolls to prepare two types of nickel paste (M11 is sulfur-free and M12 is sulfur-containing). Further, the nickel pastes M11 and M12 were printed with an electrode pattern on a barium titanate ceramic sheet (thickness: about 4.0 μm), and 20 layers were laminated to prepare an MLCC sample. For the high crystalline barium titanate powder, it is preferable to use a barium titanate material having a lattice constant ratio (ratio of c axis to a axis: c / a ratio) in the range of 1.040 to 1.0100. Moreover, it is preferable to use the barium titanate material whose composition ratio (Ba / Ti) of barium (Ba) and titanium (Ti) is 0.99 to 1.01 for the barium titanate powder.
The inorganic contents of the nickel pastes M11 and M12 were 36.0% and 35.9%, and the nickel contents were 30.0% and 29.9%.
図８はニッケルペーストＭ１１、Ｍ１２を用いて作製したＭＬＣＣ試料の断面構造写真を示す。図８の（８Ａ）、（８Ｂ）はニッケルペーストＭ１１を用いて作製したＭＬＣＣ試料の断面構造写真を示し、（８Ａ）は（８Ｂ）の２倍の拡大を示す。図８の（８Ｃ）、（８Ｄ）はニッケルペーストＭ１２を用いて作製したＭＬＣＣ試料の断面構造写真を示し、（８Ｃ）は（８Ｄ）の２倍の拡大を示す。ＭＬＣＣ試料の焼成条件は、Ｈ２を３％含有した窒素ガス雰囲気中で１２３０℃、２時間、更に、窒素雰囲気で１０００℃、３時間の再酸化処理を行った。 FIG. 8 shows a photograph of a cross-sectional structure of an MLCC sample prepared using nickel pastes M11 and M12. (8A) and (8B) of FIG. 8 show photographs of the cross-sectional structure of the MLCC sample produced using the nickel paste M11, and (8A) shows an enlargement twice as large as (8B). (8C) and (8D) of FIG. 8 show photographs of the cross-sectional structure of the MLCC sample produced using the nickel paste M12, and (8C) shows an enlargement twice as large as (8D). The firing conditions of the MLCC sample were re-oxidation treatment at 1230 ° C. for 2 hours in a nitrogen gas atmosphere containing 3% of H 2 and further at 1000 ° C. for 3 hours in a nitrogen atmosphere.
図９及び図１０はニッケルペーストＭ１１、Ｍ１２を用いて作製したＭＬＣＣ試料の各電気特性の測定結果を示す。図９の（９Ａ）、（９Ｂ）は夫々、静電容量、絶縁抵抗値を示し、図１０の（１０Ａ）、（１０Ｂ）は夫々、損失係数、直流破壊電圧値を示す。 9 and 10 show the measurement results of the electrical characteristics of the MLCC sample produced using the nickel pastes M11 and M12. (9A) and (9B) in FIG. 9 indicate the capacitance and the insulation resistance value, respectively, and (10A) and (10B) in FIG. 10 indicate the loss coefficient and the DC breakdown voltage value, respectively.
実施例１によれば、ＭＬＣＣの静電容量につき、硫黄含有有りと含有なしの場合で、顕著な差異がみられた。即ち、硫黄含有チタン酸バリウム粉を用いたニッケルペーストＭ１２の場合、静電容量が硫黄を含有しないチタン酸バリウム粉を用いたニッケルペーストＭ１１の場合に比較して、約６％平均して高くなっている。従って、硫黄含有チタン酸バリウム粉を用いたニッケルペーストを使用することにより、所定容量値に対してセラミックシートの積層数の削減が可能になり、原材料コストの低減により安価なＭＬＣＣ製品を提供することが可能になる。また、硫黄含有チタン酸バリウム粉を用いれば、構造欠陥が非常に少なく、小型且つ大容量のＭＬＣＣを実現することができる。 According to Example 1, with respect to the capacitance of MLCC, a significant difference was observed between the case of containing sulfur and the case of containing no sulfur. That is, in the case of nickel paste M12 using sulfur-containing barium titanate powder, the electrostatic capacity is about 6% higher on average than in the case of nickel paste M11 using barium titanate powder containing no sulfur. ing. Therefore, by using nickel paste using sulfur-containing barium titanate powder, it is possible to reduce the number of laminated ceramic sheets for a given capacity value, and to provide an inexpensive MLCC product by reducing raw material costs Is possible. In addition, if sulfur-containing barium titanate powder is used, a small and large-capacity MLCC can be realized with very few structural defects.
実施例１において、ニッケルペーストＭ１１、Ｍ１２を用いたＭＬＣＣ試料における、単位面積当たりのニッケル付着量（ｍｇ／ｃｍ２）は夫々、０．６１、０．６２であった。ニッケル付着量は焼成後の重量値に基づき、ニッケル含有率を考慮して求めた。従って、ニッケル付着量がいずれのニッケルペーストでも変わらないものの、電極の連続性が硫黄含有チタン酸バリウム粉を用いたニッケルペーストの場合が優れており、これからも、硫黄含有チタン酸バリウム粉を用いたニッケルペーストを使用したＭＬＣＣでは、容量特性が良好になっていることがわかる。 In Example 1, the nickel adhesion amount (mg / cm 2 ) per unit area in the MLCC samples using the nickel pastes M11 and M12 was 0.61 and 0.62, respectively. The amount of nickel adhesion was determined based on the weight value after firing and taking into account the nickel content. Therefore, although the nickel adhesion amount does not change with any nickel paste, the continuity of the electrode is excellent in the case of the nickel paste using the sulfur-containing barium titanate powder. From now on, the sulfur-containing barium titanate powder was used. It can be seen that MLCC using nickel paste has good capacity characteristics.
次に、ニッケルペーストの無機含有率及びニッケル含有率を調整した実施例２及び３を説明する。
＜実施例２＞
ニッケルペースト組成は、平均粒子径０．２μｍのニッケル粉を３５．０重量％、平均粒子径１００ｎｍの硫黄含有高結晶チタン酸バリウム粉又は硫黄を含有していないチタン酸バリウムセラミックのみからなる高結晶チタン酸バリウム粉を７．０重量％（ニッケル粉に対しては２０重量％）、樹脂固形分（エチルセルロース粉末）を５．３重量％、電極ペースト用分散剤を０．５重量％、溶剤（ターピネオール系溶剤）を５２．２重量％からなる。これらの成分を３本セラミックロールにより分散処理混合してニッケルペーストを２種類（硫黄無をＭ２１、硫黄含有をＭ２２とする。）作製した。更に、ニッケルペーストＭ２１、Ｍ２２を、チタン酸バリウムセラミックシート（厚さ：約４．０μｍ）に電極パターン印刷して、１０層分積層してＭＬＣＣ試料を作製した。高結晶チタン酸バリウム粉には、格子定数比（ｃ軸とａ軸の比：ｃ／ａ比）が１．００４０〜１．０１００の範囲にあるチタン酸バリウム材を使用するのが好ましい。また、チタン酸バリウム粉には、バリウム（Ｂａ）とチタン（Ｔｉ）の組成比（Ｂａ／Ｔｉ）が０．９９〜１．０１であるチタン酸バリウム材を使用するのが好ましい。なお、ニッケルペーストＭ２１、Ｍ２２の夫々の無機含有率は４２．１２％、４２．１０％、また各ニッケル含有率は３５．１３％、３５．０８％であった。
Next, Examples 2 and 3 in which the inorganic content and nickel content of the nickel paste are adjusted will be described.
<Example 2>
The nickel paste composition is 35.0% by weight of nickel powder having an average particle size of 0.2 μm and high crystal composed only of sulfur-containing high crystalline barium titanate powder having an average particle size of 100 nm or barium titanate ceramic not containing sulfur. 7.0% by weight of barium titanate powder (20% by weight with respect to nickel powder), 5.3% by weight of resin solids (ethylcellulose powder), 0.5% by weight of dispersant for electrode paste, solvent ( A terpineol-based solvent) comprising 52.2% by weight. These components were dispersed and mixed by three ceramic rolls to produce two types of nickel paste (no sulfur is M21 and sulfur is M22). Further, nickel pastes M21 and M22 were printed with an electrode pattern on a barium titanate ceramic sheet (thickness: about 4.0 μm) and laminated for 10 layers to prepare MLCC samples. For the high crystalline barium titanate powder, it is preferable to use a barium titanate material having a lattice constant ratio (ratio of c axis to a axis: c / a ratio) in the range of 1.040 to 1.0100. Moreover, it is preferable to use the barium titanate material whose composition ratio (Ba / Ti) of barium (Ba) and titanium (Ti) is 0.99 to 1.01 for the barium titanate powder. The inorganic contents of the nickel pastes M21 and M22 were 42.12% and 42.10%, and the nickel contents were 35.13% and 35.08%.
図１１はニッケルペーストＭ２１、Ｍ２２を用いて作製したＭＬＣＣ試料の断面構造写真を示す。図１１の（１１Ａ）、（１１Ｂ）はニッケルペーストＭ２１を用いて作製したＭＬＣＣ試料の断面構造写真を示し、（１１Ａ）は（１１Ｂ）の２倍の拡大を示す。図１１の（１１Ｃ）、（１１Ｄ）はニッケルペーストＭ２２を用いて作製したＭＬＣＣ試料の断面構造写真を示し、（１１Ｃ）は（１１Ｄ）の２倍の拡大を示す。ニッケルペーストＭ２１、Ｍ２２を用いたＭＬＣＣ試料の焼成条件は、ニッケルペーストＭ１１、Ｍ１２と同様である。 FIG. 11 shows a photograph of the cross-sectional structure of an MLCC sample prepared using nickel pastes M21 and M22. (11A) and (11B) in FIG. 11 show photographs of the cross-sectional structure of the MLCC sample produced using the nickel paste M21, and (11A) shows an enlargement twice as large as (11B). (11C) and (11D) of FIG. 11 show photographs of the cross-sectional structure of the MLCC sample produced using the nickel paste M22, and (11C) shows an enlargement twice as large as (11D). The firing conditions of the MLCC sample using the nickel pastes M21 and M22 are the same as those of the nickel pastes M11 and M12.
図１２はニッケルペーストＭ２１、Ｍ２２を用いて作製したＭＬＣＣ試料の各電気特性の測定結果を示す。図１２の（１２Ａ）、（１２Ｂ）、（１２Ｃ）及び（１２Ｄ）は夫々、静電容量、絶縁抵抗値、損失係数、直流破壊電圧値を示す。 FIG. 12 shows the measurement results of the electrical characteristics of the MLCC sample produced using the nickel pastes M21 and M22. (12A), (12B), (12C), and (12D) in FIG. 12 indicate the capacitance, the insulation resistance value, the loss coefficient, and the DC breakdown voltage value, respectively.
＜実施例３＞
ニッケルペースト組成は、平均粒子径０．２μｍのニッケル粉を３７．５重量％、平均粒子径１００ｎｍの硫黄含有高結晶チタン酸バリウム粉又は硫黄を含有していないチタン酸バリウムセラミックのみからなる高結晶チタン酸バリウム粉を７．５重量％（ニッケル粉に対しては２０重量％）、樹脂固形分（エチルセルロース粉末）を４．３重量％、電極ペースト用分散剤を０．５重量％、溶剤（ターピネオール系溶剤）を５０．２重量％からなる。これらの成分を３本セラミックロールにより分散処理混合してニッケルペーストを２種類（硫黄無をＭ３１、硫黄含有をＭ３２とする。）作製した。更に、ニッケルペーストＭ３１、Ｍ３２を、チタン酸バリウムセラミックシート（厚さ：約４．０μｍ）に電極パターン印刷して、１０層分積層してＭＬＣＣ試料を作製した。高結晶チタン酸バリウム粉には、格子定数比（ｃ軸とａ軸の比：ｃ／ａ比）が１．００４０〜１．０１００の範囲にあるチタン酸バリウム材を使用するのが好ましい。また、チタン酸バリウム粉には、バリウム（Ｂａ）とチタン（Ｔｉ）の組成比（Ｂａ／Ｔｉ）が０．９９〜１．０１であるチタン酸バリウム材を使用するのが好ましい。なお、ニッケルペーストＭ３１、Ｍ３２の夫々の無機含有率は４５．０９％、４５．００％、また各ニッケル含有率は３７．５８％、３７．５０％であった。
<Example 3>
The nickel paste composition is 37.5% by weight of nickel powder having an average particle diameter of 0.2 μm and high crystal composed only of sulfur-containing high crystalline barium titanate powder having an average particle diameter of 100 nm or barium titanate ceramic not containing sulfur. 7.5% by weight of barium titanate powder (20% by weight with respect to nickel powder), 4.3% by weight of resin solid content (ethylcellulose powder), 0.5% by weight of dispersant for electrode paste, solvent ( Terpineol-based solvent) is 50.2% by weight. These components were dispersed and mixed by three ceramic rolls to produce two types of nickel paste (M31 for sulfur and M32 for sulfur). Further, nickel pastes M31 and M32 were printed with an electrode pattern on a barium titanate ceramic sheet (thickness: about 4.0 μm), and 10 layers were laminated to prepare an MLCC sample. For the high crystalline barium titanate powder, it is preferable to use a barium titanate material having a lattice constant ratio (ratio of c axis to a axis: c / a ratio) in the range of 1.040 to 1.0100. Moreover, it is preferable to use the barium titanate material whose composition ratio (Ba / Ti) of barium (Ba) and titanium (Ti) is 0.99 to 1.01 for the barium titanate powder. The inorganic contents of the nickel pastes M31 and M32 were 45.09% and 45.00%, and the nickel contents were 37.58% and 37.50%.
図１３はニッケルペーストＭ３１、Ｍ３２を用いて作製したＭＬＣＣ試料のＳＥＭ写真を示す。図１３の（１３Ａ）、（１３Ｂ）はニッケルペーストＭ３１を用いて作製したＭＬＣＣ試料の断面構造写真を示し、（１３Ａ）は（１３Ｂ）の２倍の拡大を示す。図１３の（１３Ｃ）、（１３Ｄ）はニッケルペーストＭ３２を用いて作製したＭＬＣＣ試料の断面構造写真を示し、（１３Ｃ）は（１３Ｄ）の２倍の拡大を示す。ニッケルペーストＭ３１、Ｍ３２を用いたＭＬＣＣ試料の焼成条件は、ニッケルペーストＭ１１、Ｍ１２と同様である。 FIG. 13 shows SEM photographs of MLCC samples prepared using nickel pastes M31 and M32. (13A) and (13B) of FIG. 13 show a cross-sectional structure photograph of the MLCC sample prepared using the nickel paste M31, and (13A) shows an enlargement twice as large as (13B). (13C) and (13D) of FIG. 13 show photographs of a cross-sectional structure of the MLCC sample produced using the nickel paste M32, and (13C) shows an enlargement twice as large as (13D). The firing conditions of the MLCC sample using the nickel pastes M31 and M32 are the same as those of the nickel pastes M11 and M12.
図１４はニッケルペーストＭ３２、Ｍ３３を用いて作製したＭＬＣＣ試料の各電気特性の測定結果を示す。図１４の（１４Ａ）、（１４Ｂ）、（１４Ｃ）及び（１４Ｄ）は夫々、静電容量、絶縁抵抗値、損失係数、直流破壊電圧値を示す。 FIG. 14 shows the measurement results of the electrical characteristics of the MLCC sample prepared using the nickel pastes M32 and M33. (14A), (14B), (14C), and (14D) in FIG. 14 indicate the capacitance, the insulation resistance value, the loss coefficient, and the DC breakdown voltage value, respectively.
実施例２及び実施例３において、ニッケルペーストＭ２１、Ｍ２２、Ｍ３２及びＭ３３を用いたＭＬＣＣ試料における、単位面積当たりのニッケル付着量（ｍｇ／ｃｍ２）は夫々、０．５４６、０．５４０、０．５９６、０．５８３であった。ニッケル付着量は印刷後の重量値に基づき、ニッケル含有率を考慮して求めた。ニッケル粉のＮｉ含有量の違い（３５．０重量％、３７．５重量％）に応じて、Ｎｉ含有率の大きいニッケルペースト（Ｍ３２、Ｍ３３）はニッケルペースト（Ｍ２１、Ｍ２２）よりもニッケル付着量が多くなっている。従って、チタン酸バリウム粉に対する硫黄含有有無にかかわらず、ニッケル含有率によりニッケル付着量の制御が可能である。
ニッケル含有率の異なる２種類のニッケルペーストについて、硫黄含有有無の観点でみれば、硫黄含有チタン酸バリウム粉を用いたニッケルペーストの場合（Ｍ２２、Ｍ３２）、硫黄を含有しない場合（Ｍ２１、Ｍ３１）と比較して、静電容量値が高く、硫黄含有チタン酸バリウム粉を用いたニッケルペーストがＭＬＣＣの高容量化に寄与することがわかる。従って、硫黄含有チタン酸バリウム粉を用いたニッケルペーストの場合（Ｍ２２、Ｍ３２）では、焼結遅延効果により構造欠陥を大幅に縮減できると共に、硫黄を含有しない場合（Ｍ２１、Ｍ３１）に比較して静電容量が向上するので、定格の静電容量値の実現に際してニッケル含有量の削減が可能になり、ＭＬＣＣの高品質化、薄膜化及び低価格化において硫黄含有チタン酸バリウム粉の使用がより効果的となる。
In Example 2 and Example 3, in the MLCC samples using the nickel pastes M21, M22, M32, and M33, the nickel adhesion amount (mg / cm 2 ) per unit area was 0.546, 0.540, 0, respectively. .596, 0.583. The amount of nickel adhered was determined in consideration of the nickel content based on the weight value after printing. Depending on the difference in nickel content of nickel powder (35.0 wt%, 37.5 wt%), nickel paste (M32, M33) with a high Ni content is more than the nickel paste (M21, M22). Is increasing. Therefore, regardless of the presence or absence of sulfur in the barium titanate powder, the amount of nickel deposited can be controlled by the nickel content.
From the viewpoint of the presence or absence of sulfur, nickel paste using sulfur-containing barium titanate powder (M22, M32) and no sulfur (M21, M31) It can be seen that the nickel paste using the sulfur-containing barium titanate powder contributes to the increase in the capacity of MLCC. Therefore, in the case of nickel paste using sulfur-containing barium titanate powder (M22, M32), structural defects can be greatly reduced by the sintering delay effect, and compared with the case where sulfur is not contained (M21, M31). Since the capacitance is improved, the nickel content can be reduced when the rated capacitance value is achieved, and the use of sulfur-containing barium titanate powder is more effective in improving the quality, thinning and price of MLCC. Become effective.
実施例１〜３では、用いられた全てのニッケルペーストにおいて、ニッケル粉の平均粒子径が０．２μｍであり、チタン酸バリウム粉の平均粒子径が１００ｎｍであったが、表１に示すように、実施例４、５では、ニッケル粉とチタン酸バリウム粉の平均粒子径がより小さなものを用いて、ニッケルペーストを作製している。尚、表１には、各ペーストの作製に用いられたチタン酸バリウム粉とニッケル粉の混合比率（重量％）、平均粒子径（ｎｍ）を記載している。また、チタン酸バリウム粉については、硫黄が含有されているかどうかを表中に記載している。
＜実施例４＞
実施例４において、ニッケルペーストは、平均粒子径１５０ｎｍのニッケル粉を３６．５重量％、平均粒子径２０ｎｍの硫黄含有高結晶チタン酸バリウム粉、又は硫黄を含有していないチタン酸バリウムセラミックのみからなる高結晶チタン酸バリウム粉を４．０重量％（ニッケル粉に対しては約１０．０重量％）、樹脂固形分（エチルセルロース粉末）を３．０重量％、電極ペースト用分散剤を１．０重量％、溶剤（ターピネオール系溶剤）を５５．５重量％含んでいる。これらの成分を３本セラミックロールにより分散処理混合してニッケルペーストを２種類（硫黄無をＭ４１、硫黄含有をＭ４２とする。）を作製した。
更に、ニッケルペーストＭ４１、Ｍ４２を、チタン酸バリウムセラミックシート（厚さ：約４．０μｍ）に電極パターン印刷して、１０層分積層してＭＬＣＣ試料を作製した。尚、前記電極パターン印刷におけるＮｉ付着量は、ニッケルペーストＭ４１、Ｍ４２を用いた場合、夫々０．３００ｍｇ/ｃｍ２、０．３０７ｍｇ/ｃｍ２である。焼成条件は、実施例１の場合と略同一であり、記載を省略する。ニッケルペーストＭ４１、Ｍ４２を用いて作製されたＭＬＣＣ試料の電気特性の測定では、各々の静電容量が平均５７０ｎＦ、６８０ｎＦ程度であることが確かめられている。即ち、ＭＬＣＣ試料の作製に用いたニッケルペーストに硫黄含有高結晶チタン酸バリウム粉を混合したことにより、静電容量が増大している。
In Examples 1 to 3, in all the nickel pastes used, the average particle diameter of the nickel powder was 0.2 μm, and the average particle diameter of the barium titanate powder was 100 nm. In Examples 4 and 5, a nickel paste was prepared using nickel powder and barium titanate powder having smaller average particle diameters. In Table 1, the mixing ratio (% by weight) and average particle diameter (nm) of barium titanate powder and nickel powder used for the preparation of each paste are described. Moreover, about the barium titanate powder, it is described in the table | surface whether sulfur is contained.
<Example 4>
In Example 4, the nickel paste is composed only of 36.5% by weight of nickel powder having an average particle diameter of 150 nm, sulfur-containing highly crystalline barium titanate powder having an average particle diameter of 20 nm, or barium titanate ceramic not containing sulfur. 4.0% by weight of the high crystalline barium titanate powder (about 10.0% by weight with respect to the nickel powder), 3.0% by weight of the resin solid (ethylcellulose powder), and 1. Dispersant for the electrode paste 0% by weight and 55.5% by weight of solvent (terpineol solvent). These components were dispersed and mixed by three ceramic rolls to produce two types of nickel paste (M41 for sulfur and M42 for sulfur).
Furthermore, nickel pastes M41 and M42 were printed with an electrode pattern on a barium titanate ceramic sheet (thickness: about 4.0 μm), and 10 layers were laminated to prepare an MLCC sample. Incidentally, Ni deposition amount in the electrode pattern printing, the case of using a nickel paste M41, M42, respectively 0.300 mg / cm 2, is 0.307mg / cm 2. The firing conditions are substantially the same as in Example 1, and the description is omitted. In the measurement of the electrical characteristics of the MLCC samples prepared using the nickel pastes M41 and M42, it has been confirmed that the respective electrostatic capacities are about 570 nF and 680 nF on average. That is, the electrostatic capacity is increased by mixing the sulfur-containing highly crystalline barium titanate powder with the nickel paste used to prepare the MLCC sample.
＜実施例５＞
実施例５において、ニッケルペーストは、平均粒子径１２０ｎｍのニッケル粉を３６．５重量％、平均粒子径２０ｎｍの硫黄含有高結晶チタン酸バリウム粉又は硫黄を含有していないチタン酸バリウムセラミックのみからなる高結晶チタン酸バリウム粉を４．０重量％（ニッケル粉に対しては約１０．０重量％）、樹脂固形分（エチルセルロース粉末）を５．３重量％、電極ペースト用分散剤を１．５重量％、溶剤（ターピネオール系溶剤）を５２．７重量％含んでいる。これらの成分を３本セラミックロールにより分散処理混合してニッケルペーストを２種類（硫黄無をＭ５１、硫黄含有をＭ５２とする。）作製した。
更に、ニッケルペーストＭ５１、Ｍ５２を、チタン酸バリウムセラミックシート（厚さ：約４．０μｍ）に電極パターン印刷して、１０層分積層してＭＬＣＣ試料を作製した。尚、前記電極パターン印刷におけるＮｉ付着量は、ニッケルペーストＭ５１、Ｍ５２を用いた場合、０．３４６ｍｇ/ｃｍ２、０．３４３ｍｇ/ｃｍ２である。ニッケルペーストＭ５１とＭ５２を用いたＭＬＣＣ試料の電気特性の測定では、静電容量が、夫々６００ｎＦ、７３０ｎＦ程度であることが確かめられている。即ち、実施例４と同様にニッケルペーストに硫黄含有高結晶チタン酸バリウム粉を混合することにより、ＭＬＣＣ試料の電気特性が向上している。
<Example 5>
In Example 5, the nickel paste is composed of only 36.5% by weight of nickel powder having an average particle size of 120 nm and sulfur-containing highly crystalline barium titanate powder having an average particle size of 20 nm or barium titanate ceramic not containing sulfur. 4.0% by weight of high crystalline barium titanate powder (about 10.0% by weight with respect to nickel powder), 5.3% by weight of resin solids (ethylcellulose powder), and 1.5% of a dispersant for electrode paste % By weight and 52.7% by weight of solvent (terpineol-based solvent). These components were dispersed and mixed with three ceramic rolls to produce two types of nickel paste (M51 is sulfur-free and M52 is sulfur-containing).
Further, nickel pastes M51 and M52 were printed with an electrode pattern on a barium titanate ceramic sheet (thickness: about 4.0 μm), and 10 layers were laminated to prepare an MLCC sample. Incidentally, Ni deposition amount in the electrode pattern printing, the case of using a nickel paste M51, M52, 0.346mg / cm 2 , is 0.343mg / cm 2. In the measurement of the electrical characteristics of the MLCC sample using the nickel pastes M51 and M52, it has been confirmed that the capacitances are about 600 nF and 730 nF, respectively. That is, by mixing sulfur-containing highly crystalline barium titanate powder with nickel paste as in Example 4, the electrical characteristics of the MLCC sample are improved.
尚、前記ニッケル粉の平均粒子系は、１０ｎｍ〜１μｍの範囲であることが好ましく、１０ｎｍ未満の場合、超微粒子であるため、大気中で酸化し易く不安定となり、粉塵爆発等の危険性があることから、ニッケルペーストの材料として適していない。また、１μｍを超えると、ニッケルペーストを用いて製造されるＭＬＣＣの電極の薄層化が困難となる。更に、ニッケルペーストにおける硫黄含有高結晶チタン酸バリウム粉の含有量は、ニッケル粉に対して１〜３０重量％の範囲であることが好ましく、１重量％未満の場合、目的とする焼結抑制剤としての十分な効果が得られず、３０重量％を超えると、絶縁物であることからニッケルペーストの導電性を大幅に低減化させ、ＭＬＣＣ等の電子部品に用いることができなくなる。 The average particle system of the nickel powder is preferably in the range of 10 nm to 1 μm, and in the case of less than 10 nm, since it is an ultrafine particle, it is easily oxidized and unstable in the atmosphere, and there is a risk of dust explosion and the like. For this reason, it is not suitable as a material for nickel paste. On the other hand, when the thickness exceeds 1 μm, it is difficult to make the MLCC electrode manufactured using nickel paste thinner. Furthermore, the content of the sulfur-containing highly crystalline barium titanate powder in the nickel paste is preferably in the range of 1 to 30% by weight, preferably less than 1% by weight, with respect to the nickel powder. If the amount exceeds 30% by weight, the conductivity of the nickel paste is greatly reduced and it cannot be used for electronic parts such as MLCC.
尚、本発明は上記実施形態に限定されるものではなく、本発明の技術的思想を逸脱しない範囲における種々変形例、設計変更などをその技術的範囲内に包含するものであることは云うまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and various modifications, design changes and the like within the scope not departing from the technical idea of the present invention are included in the technical scope. Nor.
本発明によれば、硫黄黄含有チタン酸バリウム粉を含むニッケルペーストにより、非常に少ないニッケル付着量でＭＬＣＣの高容量化、薄膜化あるいは小型化を実現でき、しかも構造欠陥の非常に少ない安価且つ小型の高品質のＭＬＣＣを提供することができる。 According to the present invention, the nickel paste containing sulfur yellow-containing barium titanate powder can realize MLCC capacity increase, thinning, or miniaturization with a very small amount of nickel adhesion, and it is inexpensive and has very few structural defects. A small, high-quality MLCC can be provided.
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| KR20160013809A (en) | 2014-07-28 | 2016-02-05 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive paste for internal electrode of multi-layer ceramic capacitor and production method thereof, and multi-layer ceramic capacitor |
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