KR100744918B1 - Dielectric compositions for Y5V type multilayer ceramic Chip Capacitors, and manufacturing method thereof - Google Patents
Dielectric compositions for Y5V type multilayer ceramic Chip Capacitors, and manufacturing method thereof Download PDFInfo
- Publication number
- KR100744918B1 KR100744918B1 KR1020040022087A KR20040022087A KR100744918B1 KR 100744918 B1 KR100744918 B1 KR 100744918B1 KR 1020040022087 A KR1020040022087 A KR 1020040022087A KR 20040022087 A KR20040022087 A KR 20040022087A KR 100744918 B1 KR100744918 B1 KR 100744918B1
- Authority
- KR
- South Korea
- Prior art keywords
- bctz
- composition
- sio
- mlcc
- sol
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000000919 ceramic Substances 0.000 title description 8
- 239000003990 capacitor Substances 0.000 title description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- 238000010923 batch production Methods 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 63
- 238000003980 solgel method Methods 0.000 claims description 8
- 239000013557 residual solvent Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 description 19
- 239000000654 additive Substances 0.000 description 15
- 238000009413 insulation Methods 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000004703 alkoxides Chemical group 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- -1 sintering aids Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
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
- H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
- H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Y5V특성이 우수한 MLCC용 유전체조성물 및 그 제조방법이 제공된다.Provided are a dielectric composition for MLCC excellent in Y5V characteristics and a method of manufacturing the same.
본 발명은, (BaxCa1-x)M(TiyZr1-y)O3로 조성되고 0.99≤x≤1, 0.8≤y≤0.84, 1.001≤M≤ 1.004를 만족하는 BCTZ 조성에, 상기 BCTZ 조성에 대한 중량%로, SiO2졸, TEOS 및 MTMS로 이루어진 Si화합물중 선택된 1종이상을 0.1~2.0%범위로 추가로 첨가하여 조성되는 Y5V특성이 우수한 MLCC용 유전체조성물과, The present invention relates to a BCTZ composition composed of (Ba x Ca 1-x ) M (Ti y Zr 1-y ) O 3 and satisfying 0.99 ≦ x ≦ 1, 0.8 ≦ y ≦ 0.84, 1.001 ≦ M ≦ 1.004, A dielectric composition for MLCC having excellent Y5V characteristics, which is added by adding at least one selected from Si compounds consisting of SiO 2 sol, TEOS, and MTMS in a weight% of the BCTZ composition in a range of 0.1% to 2.0%,
BaCO3,CaCO3,TiO2 및 ZrO2로 조성된 원료분말을 통상의 조건으로 혼합,하소한후 분쇄하여, (BaxCa1-x)M(TiyZr1-y)O3로 조성되고 0.99≤x≤1, 0.8≤y≤0.84, 1.001≤M≤ 1.004를 만족하는 BCTZ분말을 제조하는 공정; 및 후속하는 배치공정에서 상기와 같이 제조된 BCTZ 분말에, 그 분말에 대한 중량%로 SiO2졸, TEOS 및 MTMS로 이루어진 Si화합물중 선택된 1종이상을 0.1~2.0%범위로 추가로 첨가하여 공정;을 포함하는 Y5V특성이 우수한 MLCC용 유전체조성물의 제조방법에 관한 것이다. The raw material powder composed of BaCO 3 , CaCO 3 , TiO 2 and ZrO 2 was mixed and calcined under normal conditions, and then pulverized to form (Ba x Ca 1-x ) M (Ti y Zr 1-y ) O 3 . Preparing a BCTZ powder satisfying 0.99 ≦ x ≦ 1, 0.8 ≦ y ≦ 0.84, and 1.001 ≦ M ≦ 1.004; And further adding at least one selected from Si compounds consisting of SiO 2 sol, TEOS and MTMS to the BCTZ powder prepared as described above in a subsequent batch process in a range of 0.1% to 2.0% by weight. It relates to a method for producing a dielectric composition for MLCC excellent Y5V characteristics including;
Y5V, 유전체조성, MLCC, BCTZY5V, Dielectric Composition, MLCC, BCTZ
Description
도 1은 고상법으로 제조된 BCTZ분말에 첨가제를 혼합하여 MLCC를 제조하는 통상의 공정도이다. 1 is a conventional process chart for preparing an MLCC by mixing an additive with a BCTZ powder prepared by a solid phase method.
도 2는 본 발명에 따른 Y5V특성이 우수한 MLCC 유전체조성물의 제조공정도이다. 2 is a manufacturing process diagram of the MLCC dielectric composition excellent in the Y5V characteristics according to the present invention.
본 발명은 F(Y5V)특성이 우수한 적층칩세라믹캐패시터용(multi layer ceramic capacitor:이하, MLCC라 한다) 유전체조성물에 관한 것으로, 보다 상세히는, BCTZ 기본분말조성에 액상 소결첨가제로서 종래의 Li2O-SiO2(-CaO)계 유리상이 아니라 SiO2졸이나 Si 첨가 고분자를 사용함으로써 절연저항이 우수한 MLCC용 유전체조성물에 관한 것이다. The present invention F (Y5V) characteristics are excellent multi-layer chip for ceramic capacitors (multi layer ceramic capacitor: hereinafter, MLCC quot;) relates to a dielectric composition, more particularly, BCTZ Li 2 prior art as a liquid phase sintering additive to the base powder composition The present invention relates to a dielectric composition for MLCC having excellent insulation resistance by using a SiO 2 sol or a Si-added polymer rather than an O-SiO 2 (-CaO) -based glass phase.
최근 적층세라믹 캐패시터의 제조원가 절감을 위하여 내부전극을 Pd에서 Ni등의 base metal로 사용하기 위한 연구가 활발히 진행되어 오고 있다. 이들 base metal은 산화성 분위기에서 소성하면, 쉽게 산화되기 때문에 소성분위기를 환원성으로 유지시켜야 한다. 따라서, 환원성분위기 소성에서도 절연저항을 유지시키기 위한 내환원성 조성을 갖는 유전체가 개발되어 오고 있으며, 개발된 대부분의 Y5V용 유전체들은 (Ba1-xCax)m(Ti1-zZrz)O3(이하, BCTZ라 한다), (Ba1-x-yCaxSry)m(Ti1-zZrz )O3 (이하, BCSTZ라 한다)등과 같은 다원소의 BaTiO3계 복합 페롭스카이트들이다. Recently, research has been actively conducted to use internal electrodes as base metals such as Ni in Pd in order to reduce manufacturing costs of multilayer ceramic capacitors. Since these base metals are easily oxidized when fired in an oxidizing atmosphere, the minor component must be kept reducing. Therefore, dielectrics having a reduction resistance composition have been developed to maintain insulation resistance even in reducing crisis firing. Most of the developed dielectrics for Y5V are (Ba 1-x Ca x ) m (Ti 1-z Zr z ) O 3 BaTiO 3 -based composite perovskites such as (hereinafter referred to as BCTZ) and (Ba 1-xy Ca x Sr y ) m (Ti 1-z Zr z ) O 3 (hereinafter referred to as BCSTZ).
고상합성법으로 제조된 복합 페롭스카이트 세라믹 파우더에 첨가제를 혼합하여 MLCC를 제조하는 공정이 도 1에 나타나 있다. 즉, 도 1에 나타난 바와같이, 원료물질(BaCO3,CaCO3,TiO2,ZrO2)의 혼합과 하소, 그리고 분쇄에 따른 고상합성법으로 BCTZ 파우더가 제조되며, 제조된 BCTZ 파우더는 후속하는 Batch 공정에서 첨가제, 소결조제, binder, 가소제 및 solvent와 혼합된다. 그리고, Batch공정에서 나온 슬러리는 에이징공정을 거쳐 혼합한 다음 성형, 적층, 압축 및 최종 열처리 공정을 거쳐 MLCC 유전체를 제조한다. 1 shows a process of preparing an MLCC by mixing an additive with a composite perovskite ceramic powder prepared by a solid phase synthesis method. That is, as shown in Figure 1, the BCTZ powder is prepared by the solid phase mixing method of mixing and calcining the raw materials (BaCO 3 , CaCO 3 , TiO 2 , ZrO 2 ) and grinding, the prepared BCTZ powder is a subsequent batch In the process, it is mixed with additives, sintering aids, binders, plasticizers and solvents. In addition, the slurry from the batch process is mixed through an aging process, and then produced, MLCC dielectric through a molding, lamination, compression and final heat treatment process.
이러한 유전체조성물의 일예로 일본특공소56-46641공보에 기재된 발명을 들 수 있다. 여기에는,[(Ba1-xCax)O]k(Ti1-yZry)O로 정의되고, 0.02≤x≤0.22, 0≤y≤0.20, 1.005≤k≤1.03를 만족하는 유전체조성물이 제시되어 있다. 그러나 상기 공보에 개시된 유전체조성물을 이용하여 Ni로된 내부전극을 갖는 MLCC를 제조하 는 경우, 환원분위기에서 1300℃이상의 온도에서 소성할 필요가 있고, Ni페이스트중 Ni입자가 입성장함과 동시에 입자의 응집이 발생하여 양호한 내부전극을 형성하기 어렵다는 문제가 있었다. As an example of such a dielectric composition, the invention described in JP 56-46641 A is mentioned. Here, a dielectric composition defined by [(Ba 1-x Ca x ) O] k (Ti 1-y Zr y ) O and satisfying 0.02 ≦ x ≦ 0.22, 0 ≦ y ≦ 0.20, 1.005 ≦ k ≦ 1.03 Is presented. However, when manufacturing an MLCC having an internal electrode made of Ni using the dielectric composition disclosed in the above publication, it is necessary to fire at a temperature of 1300 ° C. or higher in a reducing atmosphere. There is a problem in that aggregation occurs and it is difficult to form a good internal electrode.
이러한 종래기술의 문제점을 해결하기 위하여, BCTZ 기본조성에 액상 소결 첨가제로서 저융점 Li2O-SiO2 글래스를 첨가하는 기술이 일본 특개평 10-139539호 공보에 제시되어 있다. 구체적으로 상기 공보에서는, 금속원소로서 적어도 Ba, Ca, Ti 및 Zr을 함유하고, 이들의 금속원소산화물의 조성식을, [(Ba1-xCax)O](Ti1-y Zry)O2로 표시될때, 0.02≤x≤0.12, 0.05≤y≤0.24, 1.00≤k≤1.03를 만족하는 주성분과, 상기 주성분 100중량부에 대하여, Li2O-SiO2글래스를 0.15~0.80중량부를 함유함과 아울러, 상기 Li2O-SiO2글래스중 Li2O가 5~70mol% 인 것을 특징으로 하는 유전체조성물을 제시하고 있다. 그런데 이때 MLCC의 액상 소결 첨가제로 첨가된 Li2O-SiO2계 유리상은 미분화된 모재 조성에 비해서 입자가 큰 반면 분쇄가 어렵고, 또한 분산성이 좋지 않기 때문에 편석을 유발하여 MLCC의 절연저항과 고온 가속수명이 열화되는 문제점이 있다. In order to solve this problem of the prior art, a technique of adding a low melting point Li 2 O—SiO 2 glass as a liquid sintering additive to the BCTZ basic composition is disclosed in Japanese Patent Laid-Open No. 10-139539. Specifically, the publication contains at least Ba, Ca, Ti, and Zr as metal elements, and the compositional formulas of these metal element oxides are represented by [(Ba 1-x Ca x ) O] (Ti 1-y Zr y ) O When represented by 2 , the main component satisfying 0.02 ≦ x ≦ 0.12, 0.05 ≦ y ≦ 0.24, 1.00 ≦ k ≦ 1.03, and 0.15 to 0.80 parts by weight of Li 2 O—SiO 2 glass based on 100 parts by weight of the main component. also and at the same time, the Li 2 O-SiO Li 2 O 2 of the glass presents a dielectric composition, characterized in that 5 ~ 70mol%. However, at this time, the Li 2 O-SiO 2 glass phase added as a liquid phase sintering additive of MLCC has larger particles than the undifferentiated base material composition but is difficult to crush and disperses, causing segregation. There is a problem that the accelerated life is deteriorated.
종래 MLCC 기종중 Y5V 온도 특성을 위한 유전체조성물은 BCTZ(Ba, Ca, Ti, Zr)에, Mn과 Y등의 산화물과 Li2O-SiO2(-CaO)계 유리를 사용함이 일반적이다. 그런 데 이 유리조성은 분산성이 나쁘고, SiO2는 BCTZ 모재 원소인 Ba 또는 Ca와 반응하거나 모재 원소가 Glass로 뭉쳐질 수 있다. 또한 세라믹의 첨가제들이 결정립 내부와 입계에 다르게 존재함으로써 그 원소비[즉,Ti와 Zr원소의 합에 대한 Ba와 Ca원소의 합(Ba+Ca/Ti+Zr)의 비(A/B 몰비)]가 다르게 되어 초기 조성 설계비와 값이 틀려지고, 아울러 재료 특성의 불균일성을 야기할 수 있다. 이로부터 고온에서 생성되는 산소 공공의 움직임을 막기 힘들어 고온 저항이 감소하고, BaTiO3의 A위치와 B위치 원소의 비율 등이 변해 불균일한 입자 크기 및 유전율 변화 등을 초래할 수 있었다. The dielectric composition for the Y5V temperature characteristics of the conventional MLCC type is generally used for BCTZ (Ba, Ca, Ti, Zr), oxides such as Mn and Y and Li 2 O-SiO 2 (-CaO) -based glass. However, this glass composition is poor in dispersibility, and SiO 2 may react with Ba or Ca, which is a BCTZ base element, or the base element may be agglomerated into glass. In addition, the additives of ceramics exist differently in the grains and the grain boundaries, so that the element ratio (ie, the ratio of Ba and Ca elements (Ba + Ca / Ti + Zr) to the sum of Ti and Zr elements (A / B molar ratio)). ] Can lead to different initial compositional design ratios and values, and can lead to non-uniformity of material properties. As a result, it is difficult to prevent the movement of oxygen vacancies generated at high temperatures, thereby reducing the high temperature resistance and changing the ratios of A and B elements of BaTiO 3 , resulting in uneven particle size and dielectric constant.
따라서 본 발명은 상술한 종래기술의 문제점을 해결하기 위하여 마련된 것으로, BCTZ 기본분말조성에 입자 크기가 작고 분산성이 좋은 SiO2졸이나 Si 첨가된 고분자를 소결조제로 첨가함으로써 소결 조제의 뭉침을 방지하여 절연저항 및 고온 가속수명특성이 우수한 MLCC용 유전체조성물 및 그 제조방법을 제공함을 그 목적으로 한다.Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and prevents agglomeration of sintering aids by adding SiO 2 sol or Si-added polymers with small particle size and good dispersibility to the BCTZ basic powder composition as a sintering aid. Accordingly, an object of the present invention is to provide a dielectric composition for MLCC excellent in insulation resistance and high temperature accelerated life characteristics, and a method of manufacturing the same.
상기 목적을 달성하기 위한 본 발명은,The present invention for achieving the above object,
(BaxCa1-x)M(TiyZr1-y)O3로 조성되고 0.99≤x≤1, 0.8≤y≤0.84, 1.001≤M≤ 1.004를 만족하는 BCTZ 조성에, 상기 BCTZ 조성에 대한 중량%로, SiO2졸, TEOS 및 MTMS로 이루어진 Si화합물중 선택된 1종이상을 0.1~2.0%범위로 추가로 첨가하여 조성되는 Y5V특성이 우수한 MLCC용 유전체조성물에 관한 것이다. BCTZ composition having (Ba x Ca 1-x ) M (Ti y Zr 1-y ) O 3 and satisfying 0.99 ≦ x ≦ 1, 0.8 ≦ y ≦ 0.84, 1.001 ≦ M ≦ 1.004, and the BCTZ composition The present invention relates to a dielectric composition for MLCC having excellent Y5V characteristics by additionally adding at least one selected from Si compounds consisting of SiO 2 sol, TEOS, and MTMS in a range of about 0.1% by weight.
또한 본 발명은 상기 BCTZ 조성에 대한 중량%로, MnO2:0~0.5%와 Y2O3:0~0.6%를 추가로 첨가하여 조성되는 Y5V특성이 우수한 MLCC용 유전체조성물에 관한 것이다. In another aspect, the present invention relates to a dielectric composition for MLCC excellent in Y5V characteristics, which is added by the addition of MnO 2 : 0 to 0.5% and Y 2 O 3 : 0 to 0.6% by weight based on the BCTZ composition.
또한 본 발명은 상기 SiO2졸은 자체중량%로, 졸-겔법으로 제조된 SiO2분말:20~40%와 잔여 용매 EG(에틸렌 글리콜)로 조성된 것임을 특징으로 하는 Y5V특성이 우수한 MLCC용 유전체조성물에 관한 것이다. In another aspect, the present invention, the SiO 2 sol is a weight percent of the SiO 2 powder produced by the sol-gel method: 20 to 40% and the residual solvent EG (ethylene glycol) is characterized in that Y5V excellent dielectric dielectric for MLCC It relates to a composition.
나아가, 본 발명은,Furthermore, the present invention,
BaCO3,CaCO3,TiO2 및 ZrO2로 조성된 원료분말을 통상의 조건으로 혼합,하소한후 분쇄하여, (BaxCa1-x)M(TiyZr1-y)O3로 조성되고 0.99≤x≤1, 0.8≤y≤0.84, 1.001≤M≤ 1.004를 만족하는 BCTZ분말을 제조하는 공정; 및 The raw material powder composed of BaCO 3 , CaCO 3 , TiO 2 and ZrO 2 was mixed and calcined under normal conditions, and then pulverized to form (Ba x Ca 1-x ) M (Ti y Zr 1-y ) O 3 . Preparing a BCTZ powder satisfying 0.99 ≦ x ≦ 1, 0.8 ≦ y ≦ 0.84, and 1.001 ≦ M ≦ 1.004; And
후속하는 배치공정에서 상기와 같이 제조된 BCTZ 분말에, 그 분말에 대한 중량%로 SiO2졸, TEOS 및 MTMS로 이루어진 Si화합물중 선택된 1종이상을 0.1~2.0%범위로 추가로 첨가하여 공정;을 포함하는 Y5V특성이 우수한 MLCC용 유전체조성물의 제 조방법에 관한 것이다. Adding to the BCTZ powder prepared as described above in a subsequent batch process by adding at least one selected from Si compounds consisting of SiO 2 sol, TEOS and MTMS in a weight% of the powder in the range of 0.1 to 2.0%; It relates to a method for producing a dielectric composition for MLCC excellent Y5V characteristics including.
또한 본 발명은 상기 BCTZ 조성에 대한 중량%로, MnO2:0~0.5%와 Y2O3:0~0.6%를 추가로 첨가하여 조성되는 Y5V특성이 우수한 MLCC용 유전체조성물 제조방법에 관한 것이다. The present invention also relates to a dielectric composition for MLCC having excellent Y5V characteristics by adding MnO 2 : 0 to 0.5% and Y 2 O 3 : 0 to 0.6% by weight based on the BCTZ composition. .
또한 본 발명은 상기 SiO2졸은 자체중량%로, 졸-겔법으로 제조된 SiO2분말:20~40%와 잔여 용매 EG(에틸렌 글리콜)로 조성된 것임을 특징으로 하는 Y5V특성이 우수한 MLCC용 유전체조성물 제조방법에 관한 것이다. In another aspect, the present invention, the SiO 2 sol is a weight percent of the SiO 2 powder produced by the sol-gel method: 20 to 40% and the residual solvent EG (ethylene glycol) is characterized in that Y5V excellent dielectric dielectric for MLCC It relates to a method for producing the composition.
이하, 본 발명을 MLCC용 유전체조성물을 설명한다.Hereinafter, the dielectric composition for MLCC will be described.
본 발명의 유전체조성물은 (BaxCa1-x)M(TiyZr1-y)O 3로 조성되고 0.99≤x≤1, 0.8≤y≤0.84, 1.001≤M≤ 1.004를 만족하는 BCTZ 기본조성물을 이용한다. 상기 BCTZ 기본조성은 통상적인 것으로 본 발명은 이러한 기본조성물을 제조하는 구체적인 제조공정에 제한되는 것은 아니다. The dielectric composition of the present invention is composed of (Ba x Ca 1-x ) M (Ti y Zr 1-y ) O 3 and has a BCTZ basis satisfying 0.99 ≦ x ≦ 1, 0.8 ≦ y ≦ 0.84, 1.001 ≦ M ≦ 1.004. The composition is used. The BCTZ basic composition is conventional and the present invention is not limited to the specific manufacturing process for producing such a basic composition.
본 발명은 상기와 같은 조성된 BCTZ 조성에 중량%로, SiO2졸, TEOS(에틸 실리케이트) 및 MTMS(메틸트리메톡시 실레인)로 이루어진 Si화합물중 선택된 1종이상 을 0.1~2.0%범위로 추가로 첨가하여 조성되는 유전체조성물을 제공함을 특징으로 한다. The present invention is a weight% to the composition BCTZ composition as described above, at least one selected from Si compounds consisting of SiO 2 sol, TEOS (ethyl silicate) and MTMS (methyltrimethoxy silane) in the range of 0.1 to 2.0% It is characterized by providing a dielectric composition which is further added.
이러한 세가지 종류의 Si 화합물은 분산성을 증가시켜 세라믹의 계면에 고루 존재 할 수 있으므로 세라믹의 강도값과 절연 저항값이 증가시키는 역할을 한다. 또한 기존에 Li2O-SiO2(-CaO)계 유리에서 존재하는 가벼운 원소인 Li의 휘발에 의한 유전율 감소 효과도 없다는 장점도 있다. SiO2졸은 졸-겔 법으로 제조된 것으로 그 평균 입자크기가 수십 nm 정도로 매우 작으므로 입자의 뭉침에 의한 분산성 저하 문제가 없다. TEOS와 MTMS는 모두 Si 원소에 알콕사이트(alkoxide)가 결합되어 있는 전구체(precursor) 형태이므로 물의 제공에 의해 가수분해가 일어남에 따라 급속히 SiO2로 분해되는 경향이 있고, 그 크기는 수 nm에서 수십 nm에 지나지 않는다. These three kinds of Si compounds can increase the dispersibility and evenly exist at the interface of the ceramic, thereby increasing the strength and insulation resistance of the ceramic. In addition, there is also an advantage that there is no effect of reducing the dielectric constant due to volatilization of Li, a light element existing in Li 2 O—SiO 2 (—CaO) glass. SiO 2 sol is prepared by the sol-gel method, the average particle size is very small, such as several tens of nm, there is no problem of deterioration in dispersibility due to aggregation of particles. Since both TEOS and MTMS are precursor forms in which alkoxide is bonded to Si element, they tend to be rapidly decomposed into SiO 2 as hydrolysis occurs by the provision of water. It is only nm.
이들 Si 화합물은 소결시 다른 첨가제와 함께 공융(eutectic)을 형성함으로써 세라믹의 소결 온도를 낮추어 저온에서 소결이 잘 일어나게하는 소결 치밀화제 역할을 한다. 그러나 그 첨가량이 너무 적으면 이 효과가 미비해서 소결이 잘 일어나지 않고, 반대로 첨가량이 너무 많으면, 비정상 입성장이 일어나서 오히려 유전율이 감소하는 경향이 있다. 이에 따라 본 발명에서는 상기 Si화합물의 첨가량의 범위를 0.1~2.0중량%로 제한함이 바람직하다.These Si compounds act as a sinter densification agent that forms eutectic with other additives during sintering, thereby lowering the sintering temperature of the ceramic and sintering well at low temperatures. However, if the addition amount is too small, this effect is inadequate and sintering does not occur easily. On the contrary, if the addition amount is too large, abnormal grain growth tends to occur and the dielectric constant tends to decrease. Accordingly, in the present invention, it is preferable to limit the range of the addition amount of the Si compound to 0.1 to 2.0% by weight.
한편, 본 발명에서 TEOS와 MTMS는 순도 98%이상의 시약을 사용하였다. 이들은 Si를 포함한 전구체(precursor)로서 물과 가수분해 하여 SiO2를 형성할 수 있다.Meanwhile, in the present invention, TEOS and MTMS used a reagent having a purity of 98% or more. These are precursors containing Si and can be hydrolyzed with water to form SiO 2 .
또한 본 발명에서는, 상기 SiO2졸이 자체중량%로, 졸-겔법으로 제조된 SiO2분말:20~40%와 잔여 용매 EG(에틸렌 글리콜)로 조성된 것임이 바람직하다.In addition, in the present invention, it is preferable that the SiO 2 sol is composed of SiO 2 powder: 20-40% prepared by the sol-gel method and the residual solvent EG (ethylene glycol) in its own weight%.
SiO2졸은 제조 공법상 수십 nm의 미분이므로 처리가 용이하고 그 분산성을 좋게 하기 위해서 용매인 EG에 분산시켜 사용함이 바람직하다. EG양에 대하여 SiO2분말량이 너무 많으면 분산성이 좋지 않고, 반대로 너무 적으면 오히려 SiO2졸의 농도가 낮아져서 첨가 효가가 미비해 질 수 있다. Since SiO 2 sol is a fine powder of several tens of nm in the manufacturing method, it is preferable to disperse it in EG, which is a solvent, for easy treatment and good dispersibility. When the amount of SiO 2 powder is too large relative to the amount of EG, dispersibility is not good. On the contrary, when the amount of SiO 2 is too small, the concentration of SiO 2 sol may be lowered, resulting in insufficient addition efficiency.
한편 상기 EG는 바인더로 쓰이는 PVB의 수소 결합을 끊어서 연화점을 낮추는 역할을 한다. On the other hand, the EG serves to lower the softening point by breaking the hydrogen bond of PVB used as a binder.
또한 본 발명에서는 상기 BCTZ 조성에 대한 중량%로, MnO2:0~0.5%와 Y2O3:0~0.6%를 추가로 첨가함이 바람직하다. In the present invention, it is preferable to further add MnO 2 : 0 to 0.5% and Y 2 O 3 : 0 to 0.6% by weight based on the BCTZ composition.
MnO2는 환원분위기 소결에서 생기는 자유 전자의 움직임을 막는 효과가 있다. 내부전극인 Ni의 산화를 방지하기 위해서 환원 분위기 소결이 불가피 한데, 이때 산소 공공(vacancy)과 함께 자유 전자가 발생한다. 첨가된 Mn은 BaTiO3의 Ti 자리에 치환되어서 양의 전하를 가짐으로 인해 자유 전자의 움직임을 방해하고, 세라믹의 전도성을 감소시킨다. 그러나 MnO2 첨가량이 너무 많아지면 세라믹의 유전특성이 나빠져서 유전율이 감소하는 단점이 있다. MnO 2 has the effect of preventing the movement of free electrons in reducing atmosphere sintering. Sintering of the reducing atmosphere is inevitable in order to prevent oxidation of the internal electrode Ni. In this case, free electrons are generated together with oxygen vacancies. The added Mn is substituted in the Ti site of BaTiO 3 to have a positive charge, thereby preventing the movement of free electrons and reducing the conductivity of the ceramic. However, when the amount of MnO 2 is added too much, the dielectric property of the ceramic is deteriorated and thus the dielectric constant is decreased.
Y2O3는 고온에서 산소공공의 움직임을 방해하여 고온 신뢰성을 높이는 역할을 한다. 환원분위기 소성에서 MnO2의 첨가에 따라 산소공공이 생기는데, Y는 BaTiO3의 Ba 자리에 치환되어서 음의 전하를 형성하기 때문에 양의 전하인 산소 공공의 움직임을 약화시킨다. 그러나 그 첨가량이 많아지면 MnO2와 마찬가지로 유전특성이 나빠지는 경향이 있다.Y 2 O 3 interferes with the movement of oxygen vacancies at high temperatures, thereby enhancing high temperature reliability. Oxygen vacancies are generated by the addition of MnO 2 in the reducing atmosphere firing, and Y is replaced with Ba sites of BaTiO 3 to form negative charges, thereby weakening the movement of oxygen vacancies, which are positive charges. However, as the amount added increases, the dielectric properties tend to deteriorate like MnO 2 .
다음으로, 본 발명의 MLCC용 유전체 조성물 제조공정을 설명한다. Next, the manufacturing process of the dielectric composition for MLCC of this invention is demonstrated.
도 2은 본 발명에 따라 유전체조성을 마련하고, 이를 이용하여 Y5V특성용 MLCC를 제조하는 공정을 나타내는 그림이다. 2 is a diagram illustrating a process of preparing a dielectric composition according to the present invention and manufacturing a MLCC for Y5V characteristics using the dielectric composition.
도 2에 나타난 바와 같이, 본 발명에서는 먼저, BCTZ분말을 제조함에 있어서는 통상의 제조공정을 이용한다. 즉, BaCO3,CaCO3,TiO2 및 ZrO2로 조성된 원료분말을 혼합하고 건조시킨다. 이어, 건조된 분말을 하소한후 분쇄함으로써 (BaxCa1-x)M(TiyZr1-y)O3로 조성되고 0.99≤x≤1, 0.8≤y≤0.84, 1.001≤M≤ 1.004를 만족하는 통상의 BCTZ 분말을 제조할 수 있다. As shown in Fig. 2, in the present invention, first, a conventional manufacturing process is used to prepare BCTZ powder. That is, the raw material powder composed of BaCO 3 , CaCO 3 , TiO 2 and ZrO 2 is mixed and dried. Subsequently, the dried powder was calcined and then pulverized to form (Ba x Ca 1-x ) M (Ti y Zr 1-y ) O 3 , and 0.99 ≦ x ≦ 1, 0.8 ≦ y ≦ 0.84, 1.001 ≦ M ≦ 1.004 Ordinary BCTZ powder can be prepared that satisfies.
그러나 본 발명은 상술한 BCTZ 분말의 구체적인 제조공정에 제한되는 것은 아니며, 고상법으로 제조되는 F특성용 BCTZ분말이면 어느 것에나 적용될 수 있다. However, the present invention is not limited to the specific manufacturing process of the above-described BCTZ powder, it can be applied to any BCTZ powder for F characteristics produced by the solid phase method.
다만, 상기 BCTZ분말의 입도를 0.5㎛이하로 제한함이 바람직하다. BCTZ 분말의 입도가 0.5㎛를 초과하면 수십 nm 크기의 첨가제 첨가효과가 저하될 수 있다. 즉, 원료분말의 입도가 크고 첨가제 크기가 상대적으로 너무 작다면, 소결시에 첨가제가 BCTZ에 골고루 퍼지지 못하기 때문에 결국 분산성 저하 문제를 유발한다. However, the particle size of the BCTZ powder is preferably limited to 0.5㎛ or less. If the particle size of the BCTZ powder exceeds 0.5㎛ the addition effect of several tens of nm size may be reduced. In other words, if the particle size of the raw material powder is too large and the additive size is too small, the additive does not evenly spread in the BCTZ during sintering, resulting in a problem of lowering dispersibility.
그런데 상술한 바와 같이, 종래에는 상기와 같이 마련된 BCTZ 분말에 액상의 소결첨가제로서 Li2O-SiO2(-CaO)계 유리를 사용함이 일반적이었다. 그런데 이 유리조성은 분산성이 나쁘고, SiO2는 BCTZ 모재 원소인 Ba 또는 Ca와 반응하거나 모재 원소가 Glass로 뭉쳐질 수 있으므로, 제조된 재료 특성의 불균일성을 야기할 수 있다는 문제가 있었다. By the way, as described above, in the prior art, it was the general use of the Li 2 O-SiO 2 (-CaO ) based glass as a liquid phase sintering additive of the BCTZ powder prepared as described above. However, this glass composition is poor in dispersibility, and since SiO 2 may react with Ba or Ca, which is a BCTZ base material element, or the base material element may be agglomerated with glass, there may be a problem that it may cause non-uniformity of manufactured material properties.
따라서 본 발명은 이러한 문제점에 착안하여 마련된 것으로서, 상기와 같이 BCTZ분말을 제조한후, 후속하는 배치공정에서 상기 Li2O-SiO2(-CaO)계 유리를 소결첨가제로 사용하지 않고 SiO2졸, TEOS 및 MTMS로 이루어진 Si화합물을 소결첨가제로 이용함을 특징으로 한다. Accordingly, the present invention has been made in view of such a problem, and after preparing the BCTZ powder as described above, in a subsequent batch process, without using the Li 2 O-SiO 2 (-CaO) -based glass as a sintering additive SiO 2 sol Si compound consisting of TEOS and MTMS is used as a sintering additive.
구체적으로 본 발명에서는 배치공정에서 상기와 같이 제조된 통상의 BCTZ 분말에, 그 분말에 대한 중량%로 SiO2졸, TEOS 및 MTMS로 이루어진 Si화합물중 선택된 1종이상을 0.1~2.0%범위로 첨가한다. Specifically, in the present invention, at least one selected from Si compounds consisting of SiO 2 sol, TEOS and MTMS is added in the range of 0.1% to 2.0% by weight of the powder to the conventional BCTZ powder prepared as described above in the batch process. do.
이때, 상기 SiO2졸은 자체중량%로, 졸-겔법으로 제조된 SiO2분말:20~40%와 잔여 용매 EG(에틸렌 글리콜)로 조성되도록 함이 바람직하다. At this time, the SiO 2 sol is by weight of its own, it is preferable to be composed of 20 to 40% SiO 2 powder prepared by the sol-gel method and the residual solvent EG (ethylene glycol).
보다 바람직하게는 상기 BCTZ 조성에 대한 중량%로, MnO2:0~0.5%와 Y2O3:0~0.6%를 추가로 첨가하는 것이다. More preferably, MnO 2 : 0 to 0.5% and Y 2 O 3 : 0 to 0.6% are added as the weight% of the BCTZ composition.
이어, 본 발명에서는 BCTZ분말에 상기와 같이 조성된 첨가제등을 혼합한후 유기용매 바인더 및 분산제를 혼합하여 슬러리를 제조한다. 그리고 제조된 슬러리를 에이징(aging)한후 성형,적층하고, 이어 소성하는 통상의 MLCC 제조공정을 통하여 F특성이 우수한 MLCC를 효과적으로 제조할 수 있다. 이러한 공정은 통상적인 것으로 본 발명은 이러한 구체적인 공정조건에 제한되는 것은 아니다. Subsequently, in the present invention, a slurry is prepared by mixing the BCTZ powder with an additive and the like as described above, followed by mixing an organic solvent binder and a dispersant. In addition, an MLCC having excellent F characteristics can be effectively manufactured through a conventional MLCC manufacturing process of forming, stacking, and then firing the prepared slurry. Such a process is conventional and the present invention is not limited to these specific process conditions.
상술한 제조공정으로부터 마련된 본 발명의 유전체 조성물은 그 유전율 12000이상이며 Grain size가 평균 2㎛일 뿐만 아니라 1200℃~1250℃에서 소결이 가능하며, 아울러, 이를 이용하여 Ni 전극을 인쇄한 MLCC를 제조할 경우, -25~+85℃의 사용온도 범위 내에서 정전용량변화율이 +22~-82%인 Y5V특성을 가지며 절연저항과 고온가속수명이 우수한 특성을 가질 수 있다. The dielectric composition of the present invention prepared from the above-described manufacturing process has a dielectric constant of 12000 or more and a grain size of 2 µm on average, and can be sintered at 1200 ° C to 1250 ° C. In addition, a MLCC printed Ni electrode is manufactured using the same. In this case, it has Y5V characteristics with a capacitance change rate of + 22 ~ -82% within the operating temperature range of -25 ~ + 85 ° C, and excellent insulation resistance and high temperature acceleration life.
또한 본 발명의 유전체조성을 사용함으로서 분산성이 높아져 상온/고온 절연저항등의 특성이 좋아지고, 4㎛이하의 sheet 두께를 가지는 적층형 콘덴서를 효과적으로 제조할 수 있다. In addition, by using the dielectric composition of the present invention, the dispersibility is increased, the characteristics such as room temperature / high temperature insulation resistance are improved, and a multilayer capacitor having a sheet thickness of 4 μm or less can be effectively manufactured.
이하, 본 발명을 실시예를 통하여 상세히 설명하나, 이는 단지 본 발명의 바람직한 일실시예에 불과한 것으로 본 발명의 실시예의 기재내용에 의해 제한되는 것은 아니다. Hereinafter, the present invention will be described in detail by way of examples, which are merely exemplary embodiments of the present invention and are not limited by the description of the embodiments of the present invention.
(실시예 1)(Example 1)
고상법으로 BCTZ분말을 제조하는 통상의 제조공정을 이용하여 (BaxCa1-x)M(TiyZr1-y)O3로 조성되고 0.99≤x≤1, 0.8≤y≤0.84, 1.001≤M≤ 1.004를 만족하는 평균입도 0.5㎛이하의 BCTZ 분말을 제조하였다. 구체적으로 BaCO3,CaCO3,TiO2 및 ZrO2로 조성된 원료분말을 혼합건조한후 5℃/min의 속도로 승온시켜 1140℃에서 2시간 유지하여 하소하였으며, 이어 분쇄하는 통상적인 BCTZ 분말제조공정을 이용하였다. (Ba x Ca 1-x ) M (Ti y Zr 1-y ) O 3 using a conventional manufacturing process for producing BCTZ powder by solid phase method, 0.99≤x≤1, 0.8≤y≤0.84, 1.001 BCTZ powders having an average particle size of 0.5 μm or less satisfying ≦ M ≦ 1.004 were prepared. Specifically, the raw material powder composed of BaCO 3 , CaCO 3 , TiO 2 and ZrO 2 was mixed and dried, and then heated at a rate of 5 ° C./min, calcined by maintaining at 1140 ° C. for 2 hours, and then pulverized. Was used.
이어, 상기와 같이 마련된 BCTZ 분말에 하기 표 1과 같이 소결첨가제인 Si 화합물(SiO2 졸 + TEOS + MTMS)를 그 첨가량을 달리하여 혼합하였으며, 아울러, BCTZ분말에 대한 중량%로, MnO2: 0.2%, Y2O3 :0.4%를 추가로 혼합하였다. 한편 여기에서 SiO2 졸은 졸-겔 법으로 만들어진 SiO2 분말을 EG(에틸렌 글리콜)에 20~40중량%로 섞은 것을 사용하였으며, SiO2 졸이 EG와 골고루 섞임으로서 혼합 용액에서 분산성이 증가한다. Subsequently, the Si compound (SiO 2 sol + TEOS + MTMS), which is a sintering additive, was mixed with the BCTZ powder prepared as described above, by varying the addition amount thereof, and, in addition, in terms of weight% of the BCTZ powder, MnO 2 : 0.2%, Y 2 O 3 : 0.4% was further mixed. In this case, SiO 2 sol is a mixture of SiO 2 powder made by sol-gel method with EG (ethylene glycol) at 20 to 40% by weight.SiO 2 sol is evenly mixed with EG to increase dispersibility in the mixed solution. do.
그리고 상기 혼합분말을 용매, 바인더 및 분산제와 함께 지르코니아 ball mill 혼합하여 슬러리를 제조하였다. 계속하여, 제조된 슬러리를 325mesh의 천을 이용하여 거른 다음, 24시간 이상 에이징하였으며, 이후, 20㎛로 성형한후 1㎜ 두께가 되도록 적층하여 140℃에서 1분간 가압착하였다. In addition, the slurry was prepared by mixing the zirconia ball mill with the solvent, a binder and a dispersant. Subsequently, the prepared slurry was filtered using a cloth of 325mesh, then aged for at least 24 hours, and then molded into 20 μm and laminated to a thickness of 1 mm, followed by pressing at 140 ° C. for 1 minute.
후속하여 85℃ 1000kgf의 하중으로 15분간 CIP(Cool Isostatic Press)를 행한 후 절단하였으며, 절단된 시편들은 300℃에서 열처리하여 결합제를 소각한후 터널로 및 튜브로를 이용하여 분위기를 제어하면서 소결을 행하여 유전특성 측정을 위한 표준시편을 제조하였다.Subsequently, after performing a CIP (Cool Isostatic Press) for 15 minutes under a load of 1000 kgf at 85 ° C., the cut specimens were heat treated at 300 ° C. to incinerate the binder, and then sintered while controlling the atmosphere using a tunnel furnace and a tube furnace. To prepare a standard specimen for dielectric characteristics measurement.
이렇게 얻어진 표준시편들에 대하여 유전체 특성을 평가하였으며, 그 결과를 하기 표 1에 나타내었다. 여기에서, 유전체 조성물의 유전율, 유전손실, 절연저항등의 전기적 특성은 본 발명이 속하는 기술분야에서 통상적으로 사용되는 방법을 이용하여 측정하였다.The dielectric properties were evaluated for the standard specimens thus obtained, and the results are shown in Table 1 below. Here, the electrical properties such as dielectric constant, dielectric loss, insulation resistance of the dielectric composition was measured using a method commonly used in the art.
상기 표 1에 나타난 바와 같이, BCTZ기본조성에 소정함량의 Si화합물을 첨가한 시편(2-3, 6-7, 9-10, 13-14)은 유전율이 12000 이상이였고, 절연저항도 4E+11Ω.cm 이상으로 우수하였다.As shown in Table 1, the specimens (2-3, 6-7, 9-10, 13-14) to which a predetermined amount of Si compound was added to the BCTZ basic composition had a dielectric constant of 12000 or more and an insulation resistance of 4E +. It was excellent in 11 micrometers or more.
이에 반하여, BCTZ 기본조성에 Si화합물이 너무 적게 첨가된 시편(1,5,9,13)은 소결이 잘 되지 않기때문에 유전율이 나빠지고, 너무 과다하게 첨가된 시편(4,8,12,16)은 비정상 입성장이 일어나기 때문에 역시 유전율이 좋지 않았다.In contrast, specimens (1,5,9,13) in which too little Si compound was added to the BCTZ base composition had poor dielectric constant due to poor sintering, and specimens added too much (4,8,12,16). ) Also had poor permittivity because abnormal grain growth occurred.
(실시예 2) (Example 2)
실시예 1과 같은 BCTZ 기본조성에 하기 표 2와 같은 조건으로 Si화합물을 그 첨가량을 달리하여 첨가하여 유전체 조성물을 마련하였으며, 아울러, 이러한 BCTZ분말에 대한 중량%로, MnO2: 0.2%, Y2O3 :0.4%를 추가로 혼합하였다. Si compound was added to the BCTZ basic composition as in Example 1 under the same conditions as in Table 2 to prepare a dielectric composition. In addition, as a weight% of the BCTZ powder, MnO 2 : 0.2%, Y 2 0 3 : 0.4% was further mixed.
그리고 이러한 유전체 조성물을 교대로 적층하고 그 사이에 Ni 내부전극을 형성하여 환원분위기에서 소성하여 적층 세라믹 콘덴서를 제조하였으며, 제조된 콘덴서의 절연저항을 측정하여 하기 표 2에 또한 나타내었다. 한편, 이때 선택된 기종은 4㎛ 100층의 유전체층과 내부전극층의 적층체를 소성한 것으로 이루어져 있으며 용량은 1.0㎌이상, DF은 16%이하, 절연저항은 1.0E+8Ω이상의 제한기준을 적용하였다.The dielectric compositions were alternately stacked, and Ni internal electrodes were formed therebetween, and then fired in a reducing atmosphere to prepare a multilayer ceramic capacitor. The insulation resistance of the manufactured capacitor was also measured and shown in Table 2 below. At this time, the selected model consists of firing a laminate of a dielectric layer and an internal electrode layer of 100 μm of 4 μm and applied a limit of 1.0 kΩ or more, DF of 16% or less, and insulation resistance of 1.0E + 8 kΩ or more.
상기 표 2와 같이, BCTZ기본조성에 소정함량의 Si화합물을 첨가하여 제조된 MLCC(2,5-6,8-9)의 경우 모두 절연저항이 우수함을 알 수 있다.As shown in Table 2, in the case of MLCC (2,5-6,8-9) prepared by adding a predetermined amount of Si compound to the BCTZ basic composition, it can be seen that the insulation resistance is excellent.
그러나 Si화합물의 첨가량이 과소하거나 과다한 유전체 조성물을 이용하여 제조된 MLCC(1,3-4,7)의 경우 소결이 잘 안되거나 비정상 입성장이 일어나서 유전율이 감소하였다. 즉, 이때에는 절연저항값이 비록 MLCC의 1E+10Ω까지 감소해서 아직은 유전체의 특징을 가지지만 고온 신뢰성이 나빠질 가능성이 많고, 또한 유전율 감소로 인하여 Y5V의 용량 규격인 -20~80% (Z편차 일 때)의 규격을 벗어 났다. However, in the case of MLCC (1,3-4,7) prepared using a dielectric composition with too little or excessive amount of Si compound, the dielectric constant decreased due to poor sintering or abnormal grain growth. In this case, although the insulation resistance value is reduced to 1E + 10Ω of MLCC and still has characteristics of dielectric, it is likely that the high temperature reliability is deteriorated, and due to the decrease in dielectric constant, the capacity specification of Y5V is -20 to 80% (Z deviation). Is out of the standard).
상술한 바와 같이, 본 발명은 BCTZ 기본조성에 SiO2 졸을 EG 용매에 분산된 형태로 첨가함으로서 혼합 slurry에서 효과적인 분산성을 얻을 수 있었다. 또한 TEOS와 MTMS등도 반응성이 좋은 alkoxide로서 가수분해에 의해서 SiO2로 반응함으로 입자에 고른 분포와 소결 치밀화 역할을 충분히 할 수 있었으며, 이에따라, 절연저항 상승등으로 신뢰성 증가 현상이 뚜렷하였다. 더욱이, 4㎛이하의 sheet 두께로 제작해야 하는 경우 상기 조성으로 제조 시 우수한 내전압 특성과 고온 신뢰성 특성을 얻을 수 있다.As described above, the present invention was able to obtain effective dispersibility in the mixed slurry by adding SiO 2 sol in the BCTZ basic composition in the form of dispersed in EG solvent. In addition, TEOS and MTMS, which are highly reactive alkoxides, reacted with SiO 2 by hydrolysis, and thus could evenly distribute the particles and densify sintered particles. In addition, when the sheet thickness of less than 4㎛ should be produced in the composition can be obtained excellent withstand voltage characteristics and high temperature reliability characteristics.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040022087A KR100744918B1 (en) | 2004-03-31 | 2004-03-31 | Dielectric compositions for Y5V type multilayer ceramic Chip Capacitors, and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040022087A KR100744918B1 (en) | 2004-03-31 | 2004-03-31 | Dielectric compositions for Y5V type multilayer ceramic Chip Capacitors, and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20050096643A KR20050096643A (en) | 2005-10-06 |
| KR100744918B1 true KR100744918B1 (en) | 2007-08-01 |
Family
ID=37276689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020040022087A KR100744918B1 (en) | 2004-03-31 | 2004-03-31 | Dielectric compositions for Y5V type multilayer ceramic Chip Capacitors, and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100744918B1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286663A (en) * | 1996-04-25 | 1997-11-04 | Kyocera Corp | Dielectric porcelain composition |
-
2004
- 2004-03-31 KR KR1020040022087A patent/KR100744918B1/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286663A (en) * | 1996-04-25 | 1997-11-04 | Kyocera Corp | Dielectric porcelain composition |
Non-Patent Citations (1)
| Title |
|---|
| 09286663 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050096643A (en) | 2005-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4521387B2 (en) | Reduction-resistant dielectric ceramic composition | |
| JP5131595B2 (en) | Dielectric ceramic, ceramic electronic component, and multilayer ceramic capacitor | |
| CN100565726C (en) | Laminated ceramic capacitor | |
| US5248640A (en) | Non-reducible dielectric ceramic composition | |
| JP4165893B2 (en) | Semiconductor ceramic, multilayer semiconductor ceramic capacitor, and method of manufacturing semiconductor ceramic | |
| US20010026865A1 (en) | Oxide having perovskite structure, barium titanate, and manufacturing method therefor, dielectric ceramic, and ceramic electronic component | |
| JP5077362B2 (en) | Dielectric ceramic and multilayer ceramic capacitor | |
| KR100307681B1 (en) | Dielectric ceramic composition, Laminated ceramic capacitor and Method for producing the laminate ceramic capacitor | |
| KR19990067988A (en) | Dielectric Ceramic, Method for Producing the Same, Laminated Ceramic Electronic Element, and Method for Producing the Same | |
| US8335073B2 (en) | Dielectric ceramic composition and ceramic electronic component | |
| EP0630032B1 (en) | Non-reducible dielectric ceramic composition | |
| JP4697582B2 (en) | Dielectric ceramic, dielectric ceramic manufacturing method, and multilayer ceramic capacitor | |
| JP5070841B2 (en) | Dielectric ceramic composition, manufacturing method thereof, and multilayer ceramic capacitor | |
| JP5153069B2 (en) | Dielectric porcelain | |
| JP3961454B2 (en) | Low temperature fired dielectric ceramic composition and multilayer ceramic capacitor using the same | |
| JP7037945B2 (en) | Ceramic capacitors and their manufacturing methods | |
| JP2010208905A (en) | Method for manufacturing dielectric ceramic, dielectric ceramic, method for manufacturing laminated ceramic capacitor and the laminated ceramic capacitor | |
| KR100568286B1 (en) | A Method for Dispersed Coating Additive on Ceramic Powder | |
| JP7262640B2 (en) | ceramic capacitor | |
| KR100744918B1 (en) | Dielectric compositions for Y5V type multilayer ceramic Chip Capacitors, and manufacturing method thereof | |
| JP4652595B2 (en) | Dielectric porcelain with excellent temperature characteristics | |
| JP2006036606A (en) | Dielectric ceramic, method for manufacturing dielectric ceramic, and laminated ceramic capacitor | |
| JP4487476B2 (en) | Dielectric porcelain composition and electronic component | |
| JP3791264B2 (en) | Method for producing reduction-resistant dielectric composition and method for producing multilayer ceramic capacitor | |
| JP2004210613A (en) | Dielectric ceramic, its producing method and laminated ceramic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment | ||
| J201 | Request for trial against refusal decision | ||
| E801 | Decision on dismissal of amendment | ||
| B601 | Maintenance of original decision after re-examination before a trial | ||
| J301 | Trial decision |
Free format text: TRIAL DECISION FOR APPEAL AGAINST DECISION TO DECLINE REFUSAL REQUESTED 20060619 Effective date: 20070620 |
|
| S901 | Examination by remand of revocation | ||
| GRNO | Decision to grant (after opposition) | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20130624 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20140701 Year of fee payment: 8 |
|
| LAPS | Lapse due to unpaid annual fee |