JPH0142612B2 - - Google Patents
Info
- Publication number
- JPH0142612B2 JPH0142612B2 JP58169981A JP16998183A JPH0142612B2 JP H0142612 B2 JPH0142612 B2 JP H0142612B2 JP 58169981 A JP58169981 A JP 58169981A JP 16998183 A JP16998183 A JP 16998183A JP H0142612 B2 JPH0142612 B2 JP H0142612B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- sintered body
- varistor
- composition
- insulating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 48
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 10
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000464 lead oxide Inorganic materials 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 2
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 14
- 238000005245 sintering Methods 0.000 description 12
- 238000009413 insulation Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 7
- 239000012212 insulator Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000007606 doctor blade method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Description
本発明は改良された積層型の電圧非直線抵抗器
（以下バリスタと称す）に関する。
一般に電子部品の高密度実装化指向が強く望ま
れる昨今、バリスタにおいても例外でなくこのよ
うな要請にこたえたものとして各種回路基板に直
接ハンダ付けできるようにした内部構造が積層化
した積層型バリスタが提案されている。しかして
従来積層型バリスタとしては特公昭58−23921号
公報に開示されたものがある。すなわち該公報に
開示されたものは第１図および第２図に示すよう
に複数の内部電極１とZnOを主成分とした焼結体
２とが積層構造となつており、前記内部電極１の
外部取り出し電極部３以外を前記焼結体２で囲ま
れた構造からなるものである。しかしてこのよう
な構成になるバリスタの外部取り出し電極部３間
絶縁は第３図に示すように焼結体２の粒界層部分
すなわちZnOの良導電結晶４間に存在する絶縁層
５で維持するために電界が絶縁層５に集中し絶縁
耐力が低く焼結体２表面での放電劣化が発生し、
さらに耐湿度試験やサージ試験によつて絶縁層５
部分に水分が付着し放電劣化を促進し焼結体２の
表面が変質し低電流領域の漏れ電流が急激に増大
し信頼性に劣る欠点をもつていた。また上記公報
に開示された技術は内部電極１を配した生シート
を複数枚積み重ね一体化した後に焼結をする手段
である。すなわち内部電極１と生シートが同時に
焼結が進むことになり生シート中に含まれる成分
の中で特にビスマスは第３図に示すように内部電
極１に拡散することになり内部電極１のほとんど
が高抵抗化部６となり内部電極１の焼結状態が変
化し抵抗値上昇の大きな要因となる点を考慮し、
ビスマスの添加量をBi2O3に換算して0.05モル％
以下としたものである。しかしながら反面ビスマ
スの添加量が少ないため電圧非直線性（α）が小
さく、さらに制限電圧比（V10A／V1ｍＡ）が大
きくなるなどバリスタ特性そのものが低下する欠
点をもつていた。
本発明は上記の点に鑑みてなされたもので、内
部電極の表裏いずれか一方が焼結後に絶縁体にな
る組成物に接し、かつ最外層に絶縁体が位置する
ようにすることによつて電圧非直線性、制限電圧
比さらには耐湿性および耐サージ性などの諸特性
がすぐれた積層型の電圧非直線抵抗器を提供する
ことを目的とするものである。
以下本発明について図面を参照して説明する。
すなわち第５図および第６図に示すように複数の
内部電極１１とバリスタ組成物焼結体１２および
絶縁組成物焼結体１３が積層化してなる構造にお
いて前記内部電極１１の表裏いずれか一方が絶縁
組成物焼結体１３に接し、かつ最外層が絶縁組成
物焼結体１３からなり前記内部電極１１が外部取
り出し部電極１４と接続する部分を除いて前記バ
リスタ組成物焼結体１２および絶縁組成物焼結体
１３で囲まれている構造としたものであり、その
製造手段の一例につき説明すると、まず焼結後バ
リスタ機能を有する焼結体となる原料として酸化
亜鉛を主成分とし添加物として酸化ビスマスとそ
のほかに酸化コバルト、酸化マンガン、酸化ニツ
ケル、酸化クロム、酸化マグネシウム、酸化鉛、
酸化アルミニウム、酸化チタン、酸化バリウム、
酸化アンチモン、酸化硅素、酸化硼素などの中か
ら３種以上加えボールミルで混合し乾燥後600〜
950℃で仮焼し、しかるのち粉砕し有機バインダ
ーとともに溶媒中に分散させスラリー状とする。
つぎにこれをドクター・ブレード法によつて10μ
mm〜３mm厚程度の均一な焼結後バリスタ機能を有
する生シートを形成する。また一方焼結後絶縁体
となる原料として酸化亜鉛を主成分とし添加物と
して酸化銅、酸化リチウム、酸化カリウム、酸化
銀などの酸化亜鉛絶縁体化成分の中の１種以上に
酸化コバルト、酸化マンガン、酸化ニツケル、酸
化クロム、酸化硅素、酸化マグネシウム、酸化
鉛、酸化チタン、酸化アルミニウム、酸化硼素、
酸化バリウム、酸化アンチモン、酸化ストロンチ
ウム、酸化鉄などの中から１種以上加えまたは必
要に応じてごく少量の酸化ビスマスを加えボール
ミルで混合し乾燥後600〜950℃で仮焼し、しかる
のち粉砕し有機バインダとともに溶媒中に分散さ
せスラリー状とする。つぎにこれをドクター・ブ
レード法によつて10μｍ〜500μｍ厚程度の均一な
焼結後絶縁機能を有する生シートを形成する。し
かして前記焼結後バリスタ機能を有する生シート
の上下両面に金、白金、パラジウム、銀、ロジウ
ムまたはこれらの内の２つ以上の合金からなる金
属ペーストを用いて所定の大きさにスクリーン印
刷によつて内部電極を形成し、上下面に前記焼結
後絶縁機能を有する生シートを積み重ね圧着した
のち所定の大きさに切断し900〜1200℃で0.5〜８
時間焼結し内部電極を導出させた両端に銀電極を
塗布し450〜850℃で焼付けてなるようにしたもの
である。
以上のような構成になる積層型のバリスタによ
れば第７図に示すように絶縁組成物焼結体１３を
構成する結晶粒１５自体が絶縁体化しているため
電界は表面全体に分散し絶縁組成物焼結体１３表
面での放電劣化はなくすぐれた絶縁効果を発揮で
きると同時に耐湿およびサージ試験によつて信頼
性が失われることはない。またバリスタ組成物焼
結体１２にすぐれたバリスタ特性を得るだけのビ
スマスが添加されていたとしても第８図に示すよ
うに内部電極１１の片面が接する絶縁組成物焼結
体１３にはたとえ添加されたとしてもきわめて少
量のビスマスしか添加されていないため、ビスマ
ス拡散による内部電極１１の高抵抗化部１６は片
側のみで内部電極１１の絶縁組成物焼結体１３側
は抵抗値上昇などの劣化はなく内部電極１１の劣
化による直列抵抗分による制限電圧動性の悪化は
完全に防止できる。さらに内部電極１１の劣化を
絶縁組成物焼結体１３側で防止できたことにより
バリスタ組成物焼結体１２中のビスマスの量を
0.05モル％をはるかに越えて２モル％まで添加で
きることが可能であり、従来構造では得ることの
できない効果を得ることができる。
つぎに本発明の効果について実施例によつて説
明する。
実施例 １
表１に示す１〜７のバリスタ組成比により秤量
した原料に純水を加えボールミルで24時間混合し
水分を乾燥させた後600〜950℃で２時間仮焼し、
さらに粉砕し有機バインダ、分散剤、溶媒を加え
スラリーとしドクター・ブレード法によつて焼結
後の厚みが500μｍになる生シートを形成し、焼
結後内部電極の上下クロス部分が５×５mmになる
白金からなる内部電極材を印刷した生シートを３
層積層圧着し８×10mmに打ち抜き、900〜1250℃
で２時間焼結し内部電極の引出部に外部電極とし
て銀電極を塗布し650℃で焼付けてなる従来例(B)
それぞれと、同じく表１に示す８〜14のバリスタ
組成比により秤量した原料に純水を加え従来例と
同じ方法にてバリスタ組成生シートを形成し、該
生シートとは別に表１の絶縁物組成比により秤量
した原料に純水を加えボールミルで24時間混合し
水分を乾燥した後600〜950℃で２時間仮焼し、さ
らに粉砕し有機バインダ、分散剤、溶媒を加えス
ラリーとしドクター・ブレード法によつて厚さ
50μｍの絶縁組成生シートを形成し、前記バリス
タ組成生シート両面に白金からなる内部電極材を
印刷したバリスタ組成生シート上下面に絶縁組成
生シートを積層圧着し８×10mmに打ち抜き、900
〜1250℃で２時間焼結し内部電極の引出部に外部
電極として銀電極を塗布し650℃で焼付けてなる
本発明(A)それぞれとの電圧非直線性（α）と制限
電圧比（V10A／V1ｍＡ）の特性を比較した結果
第１表および第９図ならびに第１０図に示すよう
になつた。なお第１０図は便宜上ビスマスの添加
量に対する（α）および（V10A／V1ｍＡ）特性
を示した。
The present invention relates to an improved multilayer voltage nonlinear resistor (hereinafter referred to as a varistor). Nowadays, there is a strong desire for high-density packaging of electronic components, and varistors are no exception to this demand.The multilayer varistor has a laminated internal structure that allows it to be directly soldered to various circuit boards. is proposed. However, as a conventional multilayer varistor, there is one disclosed in Japanese Patent Publication No. 58-23921. That is, as shown in FIGS. 1 and 2, the device disclosed in the publication has a laminated structure of a plurality of internal electrodes 1 and a sintered body 2 mainly composed of ZnO, and the internal electrodes 1 have a laminated structure. It has a structure in which the sintered body 2 surrounds the parts other than the external lead-out electrode part 3. However, the insulation between the external electrode parts 3 of the varistor with such a configuration is maintained by the grain boundary layer part of the sintered body 2, that is, the insulation layer 5 existing between the highly conductive ZnO crystals 4, as shown in FIG. Therefore, the electric field concentrates on the insulating layer 5, resulting in low dielectric strength and discharge deterioration on the surface of the sintered body 2.
Furthermore, the insulation layer 5 was tested by humidity resistance test and surge test.
Moisture adheres to the parts, promoting discharge deterioration, deteriorating the surface of the sintered body 2, and causing a rapid increase in leakage current in the low current region, resulting in poor reliability. Further, the technique disclosed in the above-mentioned publication is a means of stacking and integrating a plurality of green sheets on which internal electrodes 1 are arranged, and then sintering them. In other words, the internal electrode 1 and the raw sheet are sintered at the same time, and among the components contained in the raw sheet, bismuth in particular is diffused into the internal electrode 1 as shown in Figure 3, and most of the internal electrode 1 is Considering that this becomes the high resistance part 6 and changes the sintering state of the internal electrode 1, which is a major factor in increasing the resistance value,
The amount of bismuth added is 0.05 mol% converted to Bi 2 O 3
It is as follows. However, on the other hand, since the amount of bismuth added is small, the voltage nonlinearity (α) is small, and the limiting voltage ratio (V10A/V1mA) becomes large, resulting in a deterioration of the varistor characteristics itself. The present invention has been made in view of the above-mentioned points, and is made by making one of the front and back sides of the internal electrode contact a composition that becomes an insulator after sintering, and the insulator is located in the outermost layer. The object of the present invention is to provide a multilayer voltage nonlinear resistor that has excellent characteristics such as voltage nonlinearity, limiting voltage ratio, moisture resistance, and surge resistance. The present invention will be explained below with reference to the drawings.
That is, as shown in FIGS. 5 and 6, in a structure in which a plurality of internal electrodes 11, a varistor composition sintered body 12, and an insulating composition sintered body 13 are laminated, either the front or back of the internal electrode 11 is The varistor composition sintered body 12 and the insulation are in contact with the insulating composition sintered body 13, and the outermost layer is made of the insulating composition sintered body 13, and the inner electrode 11 is connected to the external lead-out electrode 14. It has a structure surrounded by a composition sintered body 13, and to explain an example of its manufacturing method, first, zinc oxide is the main component and additives are added as a raw material that becomes a sintered body having a varistor function after sintering. In addition to bismuth oxide, cobalt oxide, manganese oxide, nickel oxide, chromium oxide, magnesium oxide, lead oxide,
aluminum oxide, titanium oxide, barium oxide,
Add at least three types of antimony oxide, silicon oxide, boron oxide, etc., mix in a ball mill, and after drying 600 ~
It is calcined at 950°C, then crushed and dispersed in a solvent with an organic binder to form a slurry.
Next, apply this to 10μ using the doctor blade method.
After uniform sintering, a green sheet having a varistor function with a thickness of approximately 3 mm to 3 mm is formed. On the other hand, the raw material that becomes the insulator after sintering is mainly zinc oxide, and the additives include one or more of the zinc oxide insulating components such as copper oxide, lithium oxide, potassium oxide, and silver oxide, as well as cobalt oxide and cobalt oxide. Manganese, nickel oxide, chromium oxide, silicon oxide, magnesium oxide, lead oxide, titanium oxide, aluminum oxide, boron oxide,
Add one or more of barium oxide, antimony oxide, strontium oxide, iron oxide, etc., or if necessary, add a very small amount of bismuth oxide, mix in a ball mill, dry, calcinate at 600-950℃, and then crush. It is dispersed in a solvent together with an organic binder to form a slurry. Next, this is sintered to a uniform green sheet having an insulating function and having a thickness of about 10 μm to 500 μm using a doctor blade method. After the sintering, a metal paste made of gold, platinum, palladium, silver, rhodium, or an alloy of two or more of these is screen printed on both upper and lower surfaces of the raw sheet having a varistor function to a predetermined size. Therefore, internal electrodes were formed, and after sintering, the raw sheets having an insulating function were stacked and crimped on the upper and lower surfaces, and then cut into a predetermined size and heated at 900 to 1200°C for 0.5 to 8.
After time sintering, silver electrodes are coated on both ends from which internal electrodes are drawn out, and then baked at 450 to 850°C. According to the multilayer varistor having the above structure, as shown in FIG. 7, the crystal grains 15 constituting the insulating composition sintered body 13 themselves are insulators, so the electric field is dispersed over the entire surface, resulting in insulation. There is no discharge deterioration on the surface of the composition sintered body 13, and an excellent insulating effect can be exhibited, and at the same time, reliability is not lost in moisture resistance and surge tests. Furthermore, even if bismuth is added to the varistor composition sintered body 12 in an amount sufficient to obtain excellent varistor properties, as shown in FIG. Even if bismuth is added, only a very small amount of bismuth is added, so the high resistance part 16 of the internal electrode 11 due to bismuth diffusion is only on one side, and the part 16 of the internal electrode 11 on the insulating composition sintered body 13 side is deteriorated such as an increase in resistance value. Instead, it is possible to completely prevent deterioration of the limited voltage dynamics due to the series resistance due to deterioration of the internal electrodes 11. Furthermore, by being able to prevent the deterioration of the internal electrode 11 on the insulating composition sintered body 13 side, the amount of bismuth in the varistor composition sintered body 12 can be reduced.
It is possible to add much more than 0.05 mol% up to 2 mol%, and it is possible to obtain effects that cannot be obtained with conventional structures. Next, the effects of the present invention will be explained using examples. Example 1 Pure water was added to the raw materials weighed according to the varistor composition ratios of 1 to 7 shown in Table 1, mixed for 24 hours in a ball mill, dried to remove moisture, and then calcined at 600 to 950°C for 2 hours.
It is further pulverized, an organic binder, a dispersant, and a solvent are added to form a slurry, which is then sintered using the doctor blade method to form a raw sheet with a thickness of 500 μm. After sintering, the upper and lower cross sections of the internal electrodes are 5 x 5 mm. 3 raw sheets printed with internal electrode material made of platinum
Laminate and press-bond, punch out to 8 x 10 mm, and heat at 900 to 1250℃.
Conventional example (B): sintered at 650℃ for 2 hours, coated with a silver electrode as an external electrode on the lead-out part of the internal electrode.
For each, pure water was added to the raw materials weighed according to the varistor composition ratio of 8 to 14 shown in Table 1 to form a varistor composition raw sheet in the same manner as in the conventional example, and separately from the raw sheet, the insulators shown in Table 1 were added. Pure water is added to the raw materials weighed according to the composition ratio, mixed for 24 hours in a ball mill, dried to remove moisture, calcined for 2 hours at 600 to 950℃, further crushed, and an organic binder, dispersant, and solvent are added to form a slurry. Thickness by law
A raw insulating composition sheet of 50 μm was formed, internal electrode material made of platinum was printed on both sides of the raw varistor composition sheet, the raw insulation composition sheet was laminated and crimped on the upper and lower surfaces of the raw varistor composition sheet, and punched into a size of 8 x 10 mm.
Voltage nonlinearity (α) and limiting voltage ratio (V10A) were obtained by sintering at ~1250°C for 2 hours, applying a silver electrode as an external electrode to the lead-out part of the internal electrode, and baking at 650°C. /V1mA), the results are shown in Table 1 and Figures 9 and 10. For convenience, FIG. 10 shows (α) and (V10A/V1mA) characteristics with respect to the amount of bismuth added.
【表】
表１および第９図および第１０図から明らかな
ように従来例(B)はビスマス添加量が0.05モル％で
（α）および（V10A／V1ｍＡ）特性が最もよく
0.05モル％を越えると両特性とも劣化の傾向にあ
るのに対し、本発明(A)のものはビスマス添加量と
して0.05モル％を越えた方が（α）および
（V10A／V1ｍＡ）特性がよくなる傾向を示し2.0
モル％添加量においてもなんら問題なく良好な結
果を示し、すぐれたバリスタ特性を得るだけのビ
スマス添加を保証しながら内部電極へのビスマス
拡散を制御することによる内部電極の抵抗値上昇
を防止できることを実証した。
実施例 ２
つぎにバリスタ組成を同一にし絶縁組成を種々
変えた試料No.15〜37に示す本発明(A)と上記実施例
１に示す試料No.12との特性比較を表２に示した。
試料No.15〜37の製造条件、形状等は実施例１の本
発明(A)の説明で述べたとおりである。なお試料No.
38はBi2O3を0.1モル％を含有した場合の参考例(C)
である。[Table] As is clear from Table 1 and Figures 9 and 10, the conventional example (B) has the best (α) and (V10A/V1mA) characteristics when the amount of bismuth added is 0.05 mol%.
If the bismuth content exceeds 0.05 mol%, both properties tend to deteriorate, whereas in the case of the present invention (A), the (α) and (V10A/V1mA) characteristics become better when the amount of bismuth added exceeds 0.05 mol%. trend 2.0
It showed good results without any problem even at the addition amount of mol%, and it was confirmed that increase in the resistance value of the internal electrodes could be prevented by controlling the bismuth diffusion to the internal electrodes while ensuring that the amount of bismuth added was sufficient to obtain excellent varistor characteristics. Proven. Example 2 Next, Table 2 shows a comparison of the characteristics of the present invention (A) shown in samples Nos. 15 to 37, in which the varistor composition was the same and the insulation composition was varied, and sample No. 12 shown in Example 1 above. .
The manufacturing conditions, shapes, etc. of Samples Nos. 15 to 37 are as described in the explanation of the present invention (A) in Example 1. In addition, sample No.
38 is a reference example (C) containing 0.1 mol% of Bi 2 O 3
It is.
【表】
表２から明らかなように絶縁組成を種々変えて
も電圧非直線性（α）および制限電圧比
（V10A／V1ｍＡ）特性は安定していることが明
らかとなつたと同時に絶縁組成にBi2O3が0.1モル
％含有したものは極端に特性が劣化しBi2O3とし
ては0.05モル％程度にとどめておく必要があるこ
とが明らかになつた。
実施例 ３
酸化亜鉛、酸化コバルト、酸化マンガン、酸化
ニツケル、酸化アンチモン、酸化硼素、酸化ビス
マス、酸化クロム、酸化硅素、酸化マグネシウ
ム、酸化銀、酸化鉛、酸化チタン、酸化アルミニ
ウムをZnO、CoO、MnO、NiO、Sb2O3、B2O3、
Bi2O3、Cr2O3、SiO2、MgO、Ag2O、PbO、
TiO2、Al2O3の形に換算してZnO96.77モル％、
CoO0.5モル％、MnO0.5モル％、NiO0.2モル％、
Sb2O30.5モル％、B2O30.1モル％、Bi2O30.5モル
％、Cr2O30.2モル％、SiO20.1モル％、MgO0.5モ
ル％、Ag2O0.01モル％、PbO0.1モル％、
TiO20.01モル％、Al2O30.01モル％からなるバリ
スタ原料と水をボールミルに入れ24時間混合粉砕
し乾燥したのち600〜950℃で２時間仮焼し再び粉
砕する。しかして有機バインダ、溶媒、分散剤を
加えて適当な粘度に混練したのち圧延ロール機に
かけて厚さ1.5mmのバリスタ組成生シートを形成
し、内部電極の上下クロス部分が５×５mm（焼結
後寸法）になるように白金からなる内部電極材を
印刷した後、前記バリスタ組成生シート上下面に
表３の絶縁物組成欄を示す組成からなり上記バリ
スタ組成生シート製造と同じ圧延ロール方式によ
つて形成した厚さ0.5mmの絶縁組成生シートを積
層圧着し８×10mm（焼結後寸法）になるよう打ち
抜き900〜1250℃で２時間焼結し内部電極の引出
部に外部電極として銀パラジウム電極を塗布し
650℃で焼付けてなる本発明(A)それぞれの電圧非
直線性（α）および制限電圧比（V100A／V1ｍ
Ａ）を測定した結果、表３に示すようになつた。
なお参考までに上記バリスタ組成生シートのみ
を３層積層した従来例(B)のものを試料No.43とし記
した。[Table] As is clear from Table 2, it has become clear that the voltage nonlinearity (α) and limiting voltage ratio (V10A/V1mA) characteristics are stable even when the insulation composition is varied. It has become clear that a material containing 0.1 mol % of 2 O 3 has extremely poor properties and needs to be kept at around 0.05 mol % of Bi 2 O 3 . Example 3 Zinc oxide, cobalt oxide, manganese oxide, nickel oxide, antimony oxide, boron oxide, bismuth oxide, chromium oxide, silicon oxide, magnesium oxide, silver oxide, lead oxide, titanium oxide, aluminum oxide to ZnO, CoO, MnO , NiO, Sb 2 O 3 , B 2 O 3 ,
Bi2O3 , Cr2O3 , SiO2 , MgO , Ag2O , PbO,
TiO 2 , ZnO 96.77 mol% in terms of Al 2 O 3 form,
CoO0.5mol%, MnO0.5mol%, NiO0.2mol%,
Sb 2 O 3 0.5 mol %, B 2 O 3 0.1 mol %, Bi 2 O 3 0.5 mol %, Cr 2 O 3 0.2 mol %, SiO 2 0.1 mol %, MgO 0.5 mol %, Ag 2 O 0.01 mol %, PbO0.1 mol%,
A ballista raw material consisting of 0.01 mol % of TiO 2 and 0.01 mol % of Al 2 O 3 and water are placed in a ball mill, mixed and pulverized for 24 hours, dried, calcined at 600 to 950° C. for 2 hours, and pulverized again. After adding an organic binder, a solvent, and a dispersant and kneading to an appropriate viscosity, a raw varistor composition sheet with a thickness of 1.5 mm was formed by applying it to a rolling mill. After printing an internal electrode material made of platinum so as to have the same dimensions as above, on the upper and lower surfaces of the raw varistor composition sheet, a material having the composition shown in the insulator composition column of Table 3 was printed using the same rolling roll method as in the production of the raw varistor composition sheet. The raw insulating composition sheets with a thickness of 0.5 mm were laminated and crimped, punched out to a size of 8 x 10 mm (dimensions after sintering), and sintered at 900 to 1250°C for 2 hours. apply the electrode
Voltage nonlinearity (α) and limiting voltage ratio (V100A/V1m) of the present invention (A) baked at 650℃
The results of measuring A) were as shown in Table 3. For reference, a conventional example (B) in which only three layers of the above raw varistor composition sheets were laminated was designated as sample No. 43.
【表】
表３から明らかなように各特性は実施例１また
は実施例２で述べたドクター・ブレード法によつ
て得た結果と同じ傾向を示し、圧延ロール方式に
よつても同効であることが明らかになつた。
実施例 ４
つぎに上記各実施例でとりあげた本発明(A)およ
び従来例(B)の代表的試料を選びだし耐サージ特性
および耐湿特性を調べた結果、表４に示すように
なつた。
なお試験方法のうちサージ試験は８×
20μsec500A−10回印加後の△V1ｍＡ（％）測定
とし耐湿試験は40℃−95％RHで1000時間経過後
の△V1ｍＡ（％）測定とした。[Table] As is clear from Table 3, each characteristic shows the same tendency as the results obtained by the doctor blade method described in Example 1 or Example 2, and the same effect is obtained by the rolling roll method. It became clear. Example 4 Next, representative samples of the present invention (A) and conventional example (B) taken up in each of the above examples were selected and their surge resistance and moisture resistance characteristics were investigated, and the results are shown in Table 4. Of the test methods, the surge test is 8x
ΔV1mA (%) was measured after 10 applications of 500A for 20 μsec, and ΔV1mA (%) was measured after 1000 hours at 40° C. and 95% RH for the humidity test.
【表】
表４においてNo.３とNo.10、No.５とNo.12、No.43と
No.42はそれぞれ同一バリスタ組成によるものであ
る。しかして表４から明らかなように本発明(A)の
ものは従来例(B)のものと比較して耐サージ特性お
よび耐湿特性とも著しくすぐれている結果を示し
た。
なお積層数は上記各実施例で述べたものに限定
されることなく必要に応じ適宜設定してかまわな
い。またバリスタ焼結体が露出する側面部にガラ
スコート層またはセラミツクコート層を形成すれ
ばさらに耐湿性を向上できる利点を有するもので
ある。
以上述べたように本発明によれば複数の内部電
極が焼結体で囲まれた積層型電圧非直線抵抗器に
おいて、内部電極の表裏いずれか一方がバリスタ
機能のない絶縁組成物焼結体に接し、かつ最外層
が絶縁組成物焼結体が位置するようにすることに
よつて電圧非直線性、制限電圧比はもとより耐サ
ージ性ならびに耐湿性などの諸特性がすぐれた積
層型電圧非直線抵抗器を得ることができる。[Table] In Table 4, No. 3 and No. 10, No. 5 and No. 12, No. 43 and
No. 42 has the same varistor composition. As is clear from Table 4, the sample of the present invention (A) exhibited significantly superior surge resistance and moisture resistance compared to the conventional sample (B). Note that the number of laminated layers is not limited to those described in each of the above embodiments, and may be appropriately set as necessary. Furthermore, if a glass coat layer or a ceramic coat layer is formed on the side surface where the varistor sintered body is exposed, the moisture resistance can be further improved. As described above, according to the present invention, in a multilayer voltage nonlinear resistor in which a plurality of internal electrodes are surrounded by a sintered body, one of the front and back sides of the internal electrodes is made of an insulating composition sintered body without a varistor function. A laminated voltage nonlinear product with excellent characteristics such as voltage nonlinearity, limiting voltage ratio, surge resistance, and moisture resistance by having the insulating composition sintered body in contact with the outermost layer. You can get resistors.
第１図〜第４図は従来例に係り第１図は積層型
電圧非直線抵抗器を示す斜視図、第２図は同断面
図、第３図は第２図イ部拡大図、第４図は第２図
ロ部拡大図、第５図〜第８図は本発明に係り第５
図は積層型電圧非直線抵抗器を示す斜視図、第７
図は第６図イ′拡大図、第８図は第６図ロ′拡大
図、第９図は電圧非直線特性曲線図、第１０図は
制限電圧比特性曲線図である。
１１……内部電極、１２……バリスタ組成物焼
結体、１３……絶縁組成物焼結体、１４……外部
取り出し電極。
1 to 4 relate to a conventional example, and FIG. 1 is a perspective view showing a multilayer voltage nonlinear resistor, FIG. 2 is a sectional view of the same, FIG. 3 is an enlarged view of part A in FIG. The figure is an enlarged view of the lower part of Figure 2, and Figures 5 to 8 are related to the present invention.
The figure is a perspective view showing a multilayer voltage nonlinear resistor.
The figures are an enlarged view of FIG. 6A', FIG. 8 is an enlarged view of FIG. 6B', FIG. 9 is a voltage nonlinear characteristic curve diagram, and FIG. 11... Internal electrode, 12... Varistor composition sintered body, 13... Insulating composition sintered body, 14... External lead-out electrode.
Claims (1)
び絶縁組成物焼結体を積層化してなる構造におい
て、該絶縁組成物焼結体が酸化亜鉛を主成分とし
添加物として酸化銅、酸化リチウム、酸化カリウ
ム、酸化銀などの中の１種以上に酸化コバルト、
酸化マンガン、酸化ニツケル、酸化クロム、酸化
硅素、酸化マグネシウム、酸化鉛、酸化チタン、
酸化アルミニウム、酸化硼素、酸化バリウム、酸
化アンチモン、酸化ストロンチウム、酸化鉄など
の中から１種以上を加えたものからなり、前記内
部電極の表裏いずれか一方が前記絶縁組成物焼結
体に接し、かつ最外層を絶縁組成物焼結体とし、
前記内部電極の外部取り出し電極と接続する部分
を除いて前記バリスタ組成物焼結体および絶縁組
成物焼結体で囲まれていることを特徴とする積層
型電圧非直線抵抗器。 ２ 絶縁組成物焼結体が上記組成のほかに少量の
酸化ビスマスを加えたものからなることを特徴と
する特許請求の範囲第１項記載の積層型電圧非直
線抵抗器。 ３ バリスタ組成物焼結体が酸化亜鉛を主成分と
し添加物として酸化ビスマスとそのほかに酸化コ
バルト、酸化マンガン、酸化ニツケル、酸化クロ
ム、酸化マグネシウム、酸化鉛、酸化アルミニウ
ム、酸化チタン、酸化バリウム、酸化アンチモ
ン、酸化硅素、酸化硼素などの中から数種類添加
したものからなることを特徴とする特許請求の範
囲第１項または第２項記載の積層型電圧非直線抵
抗器。[Claims] 1. A structure in which a plurality of internal electrodes, a varistor composition sintered body, and an insulating composition sintered body are laminated, wherein the insulating composition sintered body contains zinc oxide as a main component and as an additive. Cobalt oxide, one or more of copper oxide, lithium oxide, potassium oxide, silver oxide, etc.
Manganese oxide, nickel oxide, chromium oxide, silicon oxide, magnesium oxide, lead oxide, titanium oxide,
The internal electrode is made of one or more of aluminum oxide, boron oxide, barium oxide, antimony oxide, strontium oxide, iron oxide, etc., and either the front or back of the internal electrode is in contact with the insulating composition sintered body, and the outermost layer is an insulating composition sintered body,
A multilayer voltage nonlinear resistor characterized in that a portion of the internal electrode connected to an external electrode is surrounded by the varistor composition sintered body and the insulating composition sintered body. 2. The multilayer voltage nonlinear resistor according to claim 1, wherein the sintered insulating composition is made of the above composition plus a small amount of bismuth oxide. 3. The varistor composition sintered body contains zinc oxide as a main component, and bismuth oxide as an additive, as well as cobalt oxide, manganese oxide, nickel oxide, chromium oxide, magnesium oxide, lead oxide, aluminum oxide, titanium oxide, barium oxide, and other additives. 3. The multilayer voltage nonlinear resistor according to claim 1 or 2, characterized in that the resistor contains several types of antimony, silicon oxide, boron oxide, etc. added thereto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58169981A JPS6060702A (en) | 1983-09-13 | 1983-09-13 | Laminated voltage nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58169981A JPS6060702A (en) | 1983-09-13 | 1983-09-13 | Laminated voltage nonlinear resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6060702A JPS6060702A (en) | 1985-04-08 |
| JPH0142612B2 true JPH0142612B2 (en) | 1989-09-13 |
Family
ID=15896384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58169981A Granted JPS6060702A (en) | 1983-09-13 | 1983-09-13 | Laminated voltage nonlinear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6060702A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0777162B2 (en) * | 1986-10-29 | 1995-08-16 | 松下電器産業株式会社 | Method of manufacturing laminated chip varistor |
| JPH0798678B2 (en) * | 1990-03-26 | 1995-10-25 | 株式会社村田製作所 | Low temperature sintered porcelain composition |
| JP4715248B2 (en) | 2005-03-11 | 2011-07-06 | パナソニック株式会社 | Multilayer ceramic electronic components |
| CN111718192B (en) * | 2012-12-27 | 2023-07-21 | 东莞令特电子有限公司 | Varistor based on zinc oxide and method for manufacturing same |
| JPWO2020194812A1 (en) * | 2019-03-22 | 2020-10-01 |
-
1983
- 1983-09-13 JP JP58169981A patent/JPS6060702A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6060702A (en) | 1985-04-08 |
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| JP3245933B2 (en) | Resistor | |
| JPH04280603A (en) | Laminated varistor |