JPH0362287B2 - - Google Patents
Info
- Publication number
- JPH0362287B2 JPH0362287B2 JP60232364A JP23236485A JPH0362287B2 JP H0362287 B2 JPH0362287 B2 JP H0362287B2 JP 60232364 A JP60232364 A JP 60232364A JP 23236485 A JP23236485 A JP 23236485A JP H0362287 B2 JPH0362287 B2 JP H0362287B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resistor
- glass
- carbonate
- resistance
- 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 - Lifetime
Links
- 239000000463 material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 13
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 11
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims 2
- 235000011837 pasties Nutrition 0.000 claims 1
- 229910001934 tungsten pentoxide Inorganic materials 0.000 claims 1
- 239000012298 atmosphere Substances 0.000 description 14
- 239000004020 conductor Substances 0.000 description 13
- 238000010304 firing Methods 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Conductive Materials (AREA)
- Non-Adjustable Resistors (AREA)
Description
〔産業上の利用分野〕
本発明は、非酸化雰囲気中での焼成によつて厚
膜抵抗体又はこれに類似の抵抗体を形成すること
ができ、且つ耐湿性の高い抵抗体を提供すること
ができるペースト状抵抗材料に関する。
〔従来の技術〕
未焼成セラミツクシート即ちグリーンシートに
ニツケル等の卑金属の導体ペーストを塗布し、且
つ硼化モリブデンと弗化物とガラスとを含有する
抵抗体ペーストを塗布したものを非酸化雰囲気中
で焼成し、厚膜導体と厚膜抵抗体との両方を有す
る多層セラミツク回路基板を作成する方法は、本
件出願人に係わる特願昭59−197655号明細書に開
示されている。この方法においては、厚膜導体及
び厚膜抵抗の形成に貴金属が使用されないので、
多層セラミツク回路基板のコストの低減ができ
る。
〔発明が解決しようとする問題点〕
しかし、上記出願に係わる抵抗材料で形成され
た厚膜抵抗は十分な耐湿特性を有さない。例え
ば、温度60℃、相対湿度95%の環境下に1000時間
放置した場合の抵抗変化率は+5%〜+10%程度
になる。
そこで、本発明の目的は、非酸化雰囲気中での
焼成で抵抗体を形成することができ、且つ耐湿試
験における抵抗変化率が±2%以内の抵抗体を得
ることができる抵抗材料を提供することにある。
〔問題点を解決するための手段〕
上記目的を達成するための本発明に係わる抵抗
材料は、酸化タングステン20〜80重量%と、ガラ
ス10〜70重量%と、炭酸カルシウム(CaCO3)、
炭酸ストロンチウム(SrCO3)、炭酸バリウム
(BaCO3)の内の少なくとも1種の炭酸塩10〜70
重量%とから成る混合物の粉末と、有機結合剤
と、溶剤(ビヒクル)とからなる。
〔作 用〕
上記組成のペースト状抵抗材料をグリーンシー
ト上に印刷し、非酸化雰囲気で焼成すれば、耐湿
試験における抵抗変化率が±2%以内の厚膜抵抗
体が得られる。従つて、ニツケル等の卑金属の導
体ペーストによる厚膜導体の形成と同時に卑金属
厚膜抵抗を形成することが出来る。
実施例 1
次に、本発明の実施例に係わる抵抗材料及びこ
れを使用した多層セラミツク回路基板の形成方法
について述べる。
まず、二酸化珪素(SiO2)78.0重量%、酸化亜
鉛(ZnO)5.5重量%、酸化ジルコニウム(ZrO2)
12.0重量%、炭酸カルシウム(CaCO3)3.0重量
%、及び酸化アルミニウム(Al2O3)1.5重量%を
混合し、アルミナルツボ中、1400℃で30分間溶融
し、この溶融液を水中に投入し、急冷させた。こ
の急冷物を取り出してアルミナ乳鉢に入れ、約
50μm程度になるまで粉砕し、更にこれをエタノ
ールと共にポリエチレン製ポツトミルの中に入
れ、アルミナボールで150時間粉砕し、粒径が
10μm以下の粉末状のガラスを得た。
次に、上記ガラスと、酸化タングステン
(WO2、W2O5、WO3の1種以上)とを表に示す
割合に秤量し、ボールミルに入れて撹拌した。次
いで、これをアルゴンガス雰囲気中1200℃で1時
間熱処理し、しかる後、エタノールと共にポリエ
チレン製のポツトミル中に入れ、アルミナボール
で24時間粉砕し、10μm以下の酸化タングステン
とガラスとの混合物の粉末を得た。即ち、表の試
料No.1〜30に示されている種々の割合のガラスと
酸化タングステンの混合粉末を得た。
次に、ガラスと酸化タングステンと炭酸塩
(CaCO3、SrCO3、BaCO3の1種以上)との割合
が表の試料No.1〜30の組成の欄に示すようになる
ように、上述のガラスと酸化タングステンの混合
粉末に対して炭酸塩を添加し、混合することによ
つて本発明に係わる抵抗材料の混合物の粉末を得
た。即ち、試料No.1においては、抵抗材料の混合
物の組成をガラス10重量%、WO280重量%、
CaCO310重量%とし、残りの試料No.2〜30にお
いても組成の欄に示す重量割合の組成とした。
次に、各試料の抵抗材料の混物の粉末100重量
部に、有機結合剤としてのエチルセルロース10重
量部を溶剤としてのブチルカルビトール90重量部
に溶かしたものから成る有機バインダ溶液即ちビ
ヒクル25重量部を加えて3本ロールミルで混練し
て約800ポイズの抵抗体ペーストを得た。
一方、上記抵抗体ペーストを印刷するためのグ
リーンシートを次の方法で作製した。Al2O3粉末
50重量%、SiO2粉末20重量%、SrO粉末25重量
%、Li2O粉末1重量%、及びMgO粉末4重量%
からなるセラミツク原料粉末と、アクリル酸エス
テルポリマーの水溶液からるバインダーと、グリ
セリンと、カルボン酸塩及び水と、をそれぞれボ
ールミルに入れて混合して、スリツプを作製し、
脱泡処理した後にドクターブレード法により厚さ
200μmの長尺のグリーンシートを作製した。そし
て、このグリーンシートから、9mm×9mmと6mm
×9mmの2種類のグリーンシート片を切り抜い
た。
次に、第1図に示す如く、前者のグリーンシー
ト片1上に、ニツケル(Ni)粉末と有機バイン
ダ溶液(エチルセルロース10重量部をテレピン油
90重量部に溶かしたもの)とを3:1の比で混練
した導体ペーストを200メツシユのスクリーンを
用いて印刷し、125℃、10分間乾燥することによ
つて第1図に示す如くNi導体膜2を形成した。
次に、本発明に係わる抵抗体ペーストを導体ペ
ーストと同様にスクリーン印刷し、乾燥すること
によつて、第1図に示す如く抵抗体膜3を形成し
た。
次に、グリーンシート片1の上に鎖線で示す大
きさのもう一方のグリーンシート片4を積層し、
100℃、150Kg/cm2で熱圧着し、これを酸化雰囲気
中500℃で熱処理して有機結合剤及び溶剤(有機
ビヒクル)を飛散及び分解し、N2(98.5容積%)
+H2(1.5容積%)の還元雰囲気中で1100℃、2
時間焼成し、第2図に示す如く、磁器層1a,4
aの中に、厚膜導体2aと厚膜抵抗体3aとを有
する混成集積回路用の多層セラミツク回路基板を
完成させた。なお、抵抗体3aの導体2aにかか
らない部分の大きさは、3mm×3mmであり、厚膜
は18μmである。また、抵抗体3aの組成は、焼
成前の抵抗材料の無機質の組成にほぼ一致してい
る。
次に、この抵抗体3aの25℃におけるシート抵
抗R0(Ω/□)をデイジタルマルチメータで測定
した。次いで、各試料(多層セラミツク回路基
板)を温度60℃、相対湿度95%の環境下に1000時
間放置し、その後、デイジタルマルチメータで再
びシート抵抗R1(Ω/□)を測定し、この耐湿試
験による厚膜導体2aの抵抗変化率△Rを(R1
−R0/R0)×100%で求めた。表の特性の欄には
上記のR0と△Rとが示されている。なお、R0の
値の欄のkは×103を意味する。
[Industrial Application Field] The present invention provides a resistor that can be formed into a thick film resistor or a similar resistor by firing in a non-oxidizing atmosphere and has high moisture resistance. The present invention relates to a paste-like resistance material that can be used. [Prior art] An unfired ceramic sheet (green sheet) coated with a conductor paste of a base metal such as nickel and a resistor paste containing molybdenum boride, fluoride, and glass is heated in a non-oxidizing atmosphere. A method of firing a multilayer ceramic circuit board having both thick film conductors and thick film resistors is disclosed in commonly assigned Japanese Patent Application No. 1976-197. In this method, no precious metals are used to form the thick film conductors and thick film resistors;
The cost of multilayer ceramic circuit boards can be reduced. [Problems to be Solved by the Invention] However, the thick film resistor formed from the resistive material according to the above application does not have sufficient moisture resistance. For example, when left in an environment with a temperature of 60°C and a relative humidity of 95% for 1000 hours, the rate of change in resistance will be about +5% to +10%. Therefore, an object of the present invention is to provide a resistor material that can be formed into a resistor by firing in a non-oxidizing atmosphere and that can have a resistance change rate within ±2% in a humidity test. There is a particular thing. [Means for solving the problem] The resistance material according to the present invention for achieving the above object includes 20 to 80% by weight of tungsten oxide, 10 to 70% by weight of glass, calcium carbonate (CaCO 3 ),
At least one carbonate of strontium carbonate (SrCO 3 ) and barium carbonate (BaCO 3 ) 10 to 70
% by weight, an organic binder, and a solvent (vehicle). [Function] If a paste-like resistance material having the above composition is printed on a green sheet and fired in a non-oxidizing atmosphere, a thick film resistor having a resistance change rate within ±2% in a humidity test can be obtained. Therefore, it is possible to form a base metal thick film resistor simultaneously with the formation of a thick film conductor using a base metal conductor paste such as nickel. Example 1 Next, a resistor material according to an example of the present invention and a method of forming a multilayer ceramic circuit board using the same will be described. First, silicon dioxide (SiO 2 ) 78.0% by weight, zinc oxide (ZnO) 5.5% by weight, zirconium oxide (ZrO 2 )
12.0% by weight, 3.0% by weight of calcium carbonate (CaCO 3 ), and 1.5% by weight of aluminum oxide (Al 2 O 3 ) were mixed and melted at 1400°C for 30 minutes in an alumina crucible, and this melt was poured into water. , rapidly cooled. Take out this quenched material and put it in an alumina mortar, about
Grind it to about 50 μm, then put it in a polyethylene pot mill with ethanol and grind it with alumina balls for 150 hours until the particle size is reduced.
A powdered glass with a size of 10 μm or less was obtained. Next, the above glass and tungsten oxide (one or more of WO 2 , W 2 O 5 , and WO 3 ) were weighed in the proportions shown in the table, and the mixture was placed in a ball mill and stirred. Next, this was heat-treated at 1200°C for 1 hour in an argon gas atmosphere, and then placed in a polyethylene pot mill with ethanol and ground for 24 hours with an alumina ball to form a powder of a mixture of tungsten oxide and glass with a size of 10 μm or less. Obtained. That is, mixed powders of glass and tungsten oxide in various proportions shown in Sample Nos. 1 to 30 in the table were obtained. Next, the above-mentioned composition was prepared so that the ratio of glass, tungsten oxide, and carbonate (one or more of CaCO 3 , SrCO 3 , and BaCO 3 ) was as shown in the composition column of sample Nos. 1 to 30 in the table. Carbonate was added to a mixed powder of glass and tungsten oxide, and the mixture was mixed to obtain a powder of a mixture of resistance materials according to the present invention. That is, in sample No. 1, the composition of the resistance material mixture was 10% by weight of glass, 80% by weight of WO 2 ,
The content of CaCO 3 was 10% by weight, and the remaining samples Nos. 2 to 30 had the same weight proportions as shown in the composition column. Next, 25 parts by weight of an organic binder solution or vehicle consisting of 10 parts by weight of the mixed powder of the resistance material of each sample and 10 parts by weight of ethyl cellulose as an organic binder dissolved in 90 parts by weight of butyl carbitol as a solvent was added. and kneaded in a three-roll mill to obtain a resistor paste of about 800 poise. On the other hand, a green sheet for printing the above resistor paste was produced by the following method. Al2O3 powder
50% by weight, 20% by weight of SiO2 powder, 25% by weight of SrO powder, 1% by weight of Li2O powder, and 4% by weight of MgO powder.
A ceramic raw material powder consisting of a powder, a binder consisting of an aqueous solution of an acrylic acid ester polymer, glycerin, a carboxylic acid salt, and water are placed in a ball mill and mixed to prepare a slip,
After degassing, the thickness is measured using the doctor blade method.
A 200 μm long green sheet was produced. And from this green sheet, 9mm x 9mm and 6mm
Two types of green sheet pieces measuring 9 mm were cut out. Next, as shown in FIG.
A conductive paste prepared by kneading 90 parts by weight of Ni conductor paste in a ratio of 3:1 was printed using a 200 mesh screen and dried at 125°C for 10 minutes to form a Ni conductor as shown in Figure 1. Film 2 was formed. Next, the resistor paste according to the present invention was screen printed in the same manner as the conductor paste and dried to form a resistor film 3 as shown in FIG. Next, on top of the green sheet piece 1, another green sheet piece 4 of the size indicated by the chain line is laminated,
Thermocompression bonding is carried out at 100℃ and 150Kg/cm 2 , and then heat treated at 500℃ in an oxidizing atmosphere to scatter and decompose the organic binder and solvent (organic vehicle), and N 2 (98.5% by volume)
+H 2 (1.5% by volume) at 1100℃, 2
As shown in FIG. 2, the porcelain layers 1a and 4
A multilayer ceramic circuit board for a hybrid integrated circuit having a thick film conductor 2a and a thick film resistor 3a was completed. The size of the portion of the resistor 3a that does not cover the conductor 2a is 3 mm x 3 mm, and the thickness of the film is 18 μm. Further, the composition of the resistor 3a substantially matches the inorganic composition of the resistor material before firing. Next, the sheet resistance R 0 (Ω/□) of this resistor 3a at 25° C. was measured using a digital multimeter. Next, each sample (multilayer ceramic circuit board) was left in an environment with a temperature of 60°C and a relative humidity of 95% for 1000 hours, and then the sheet resistance R 1 (Ω/□) was measured again using a digital multimeter. The resistance change rate △R of the thick film conductor 2a during the test is (R 1
−R 0 /R 0 )×100%. The above R 0 and ΔR are shown in the characteristics column of the table. Note that k in the R 0 value column means ×10 3 .
本発明は上述の実施例に限定されるものではな
く、例えば次の変形例が可能なものである。
(a) 酸化タングステンとガラスと炭酸塩とを含む
抵抗体ペーストを塗布したグリーンシートの焼
成温度を1000℃〜1200℃の範囲で変化させて
も、抵抗値R0及び抵抗変化率△Rが殆んど変
化しないことが確認されている。例えば、実施
例1の試料No.28と同一組成で焼成温度のみを
1000℃、1050℃、1150℃、1200℃に変化させた
時の抵抗値R0は8.253kΩ/□、8.295kΩ/□、
8.215kΩ/□、8.226kΩ/□であり、また抵抗
変化率△Rは+0.7%、+1.2%、+1.3%、+1.0%
であつた。他の組成においてもほぼ同様な結果
が得られた。
(b) グリーンシートを焼成する時の雰囲気を中性
雰囲気(不活性雰囲気)としてもよい。また、
グリーンシートを焼成する前の有機物を分解及
び飛散させるための酸化性雰囲気の熱処理温度
を例えば400℃〜600℃で変化させてもよい。
(c) ガラスと酸化タングステンとの混合物のアル
ゴン雰囲気中での焼成温度を、例えば900〜
1200℃の範囲で変化させてもよい。またこの焼
成をアルゴンガス以外の不活性雰囲気、又は真
空中、又は中性雰囲気、又は還元性雰囲気で行
つてもよい。
(d) 抵抗体ペーストを作るための有機バインダ溶
液(ビヒクル)は、ニトロセルロース等の樹脂
を、テレピン油、ブチルカルビトールアセテー
ト等の高沸点溶剤に溶かしたものでもよい。ま
た、この有機バインダ溶液の量は15〜35重量部
程度が望ましい。
〔発明の効果〕
上述から明らかな如く、本発明のペースト状抵
抗材料とニツケル等の卑金属の導体ペーストとを
非酸化雰囲気で同時焼成することができ、且つ本
発明の抵抗材料には貴金属が含まれていない。従
つて、多層セラミツク回路基板、又はこれに類似
の電気回路部品の小型化及び低コスト化に寄与す
ることができる。また、本発明の抵抗材料は前述
の特許出願の抵抗材料に比較し、耐湿性の良い抵
抗体を提供することができる。
The present invention is not limited to the embodiments described above, and the following modifications are possible, for example. (a) Even if the firing temperature of a green sheet coated with a resistor paste containing tungsten oxide, glass, and carbonate is varied in the range of 1000℃ to 1200℃, the resistance value R 0 and the resistance change rate △R are almost constant. It has been confirmed that there is no change. For example, with the same composition as sample No. 28 of Example 1, only the firing temperature was changed.
The resistance value R0 when changing to 1000℃, 1050℃, 1150℃, 1200℃ is 8.253kΩ/□, 8.295kΩ/□,
8.215kΩ/□, 8.226kΩ/□, and the resistance change rate △R is +0.7%, +1.2%, +1.3%, +1.0%.
It was hot. Almost similar results were obtained with other compositions. (b) The atmosphere when firing the green sheet may be a neutral atmosphere (inert atmosphere). Also,
The heat treatment temperature in an oxidizing atmosphere for decomposing and scattering organic matter before firing the green sheet may be varied, for example, from 400°C to 600°C. (c) Set the firing temperature of the mixture of glass and tungsten oxide in an argon atmosphere to, for example, 900 to
It may be varied within a range of 1200°C. Further, this firing may be performed in an inert atmosphere other than argon gas, in vacuum, in a neutral atmosphere, or in a reducing atmosphere. (d) The organic binder solution (vehicle) for making the resistor paste may be one in which a resin such as nitrocellulose is dissolved in a high boiling point solvent such as turpentine oil or butyl carbitol acetate. Further, the amount of this organic binder solution is preferably about 15 to 35 parts by weight. [Effects of the Invention] As is clear from the above, the paste-like resistive material of the present invention and the conductive paste of a base metal such as nickel can be co-fired in a non-oxidizing atmosphere, and the resistive material of the present invention does not contain a noble metal. Not yet. Therefore, it is possible to contribute to miniaturization and cost reduction of multilayer ceramic circuit boards or similar electric circuit components. Furthermore, the resistive material of the present invention can provide a resistor with better moisture resistance than the resistive material of the patent application mentioned above.
第1図は本発明の実施例に係わる多層セラミツ
ク回路基板を作製する際のグリーンシートと導体
膜及び抵抗体膜のパターンを示す平面図、第2図
は第1図の−線に相当する部分の焼成後の多
層セラミツク回路基板を示す断面図である。
1……グリーンシート片、2……導体膜、3…
…抵抗体膜、4……グリーンシート片。
FIG. 1 is a plan view showing patterns of a green sheet, a conductor film, and a resistor film when manufacturing a multilayer ceramic circuit board according to an embodiment of the present invention, and FIG. 2 is a portion corresponding to the - line in FIG. 1. FIG. 3 is a cross-sectional view showing the multilayer ceramic circuit board after firing. 1... Green sheet piece, 2... Conductor film, 3...
...Resistor film, 4... Green sheet piece.
Claims (1)
酸バリウムの内の少なくとも1種の炭酸塩 10〜
70重量%、 から成る混合物の粉末と、 有機結合剤と、 溶剤と、 から成るペースト状抵抗材料。 2 前記酸化タングステンは、2酸化タングステ
ン(WO2)、5酸化2タングステン(W2O5)、及
び3酸化タングステン(WO3)の内の少なくと
も1種である特許請求の範囲第1項記載の抵抗材
料。 3 前記ガラスは、作業点が900〜1200℃の範囲
のものである特許請求の範囲第1項又は第2項記
載の抵抗材料。[Scope of Claims] 1 Tungsten oxide 20-80% by weight, Glass 10-70% by weight, At least one carbonate selected from calcium carbonate, strontium carbonate, and barium carbonate 10-80% by weight
70% by weight of a powder mixture consisting of an organic binder, a solvent, and a pasty resistance material. 2. The tungsten oxide according to claim 1, wherein the tungsten oxide is at least one of tungsten dioxide (WO 2 ), tungsten pentoxide (W 2 O 5 ), and tungsten trioxide (WO 3 ). resistance material. 3. The resistance material according to claim 1 or 2, wherein the glass has a working point in the range of 900 to 1200°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60232364A JPS6292405A (en) | 1985-10-18 | 1985-10-18 | Resistance material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60232364A JPS6292405A (en) | 1985-10-18 | 1985-10-18 | Resistance material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6292405A JPS6292405A (en) | 1987-04-27 |
JPH0362287B2 true JPH0362287B2 (en) | 1991-09-25 |
Family
ID=16938056
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60232364A Granted JPS6292405A (en) | 1985-10-18 | 1985-10-18 | Resistance material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6292405A (en) |
-
1985
- 1985-10-18 JP JP60232364A patent/JPS6292405A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS6292405A (en) | 1987-04-27 |
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