JPH0541110A - Conductive paste - Google Patents
Conductive pasteInfo
- Publication number
- JPH0541110A JPH0541110A JP21477191A JP21477191A JPH0541110A JP H0541110 A JPH0541110 A JP H0541110A JP 21477191 A JP21477191 A JP 21477191A JP 21477191 A JP21477191 A JP 21477191A JP H0541110 A JPH0541110 A JP H0541110A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- paste
- weight
- conductor
- adhesive strength
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 claims abstract description 67
- 239000004020 conductor Substances 0.000 claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 24
- 229910000679 solder Inorganic materials 0.000 abstract description 29
- 239000000758 substrate Substances 0.000 abstract description 18
- 239000000919 ceramic Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 17
- 239000011265 semifinished product Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000007718 adhesive strength test Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Ceramic Products (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、導体ペ−ストに関し、
特に、低温焼成セラミック基板を製造する際、該表面に
導体を形成するために用いる改良された厚膜用Ａｇ−Ｐ
ｔ系導体ペ−ストに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductor paste,
In particular, an improved thick film Ag-P used for forming a conductor on a surface of a low temperature fired ceramic substrate when the substrate is manufactured.
The present invention relates to a t-based conductor paste.
【０００２】[0002]
【従来の技術】厚膜用導体ペ−ストは、種々の組成のも
のが既に知られており、そのうちの一つとして、Ａｇ粉
末、Ｐｔ粉末、ガラスフリット及び有機質ビヒクルをベ
−ス（以下これをベ−ス組成物という。）とし、これに
目的に応じて種々の添加物を配合したＡｇ−Ｐｔ系導体
ペ−スト組成物が幾つか開発されている。2. Description of the Related Art Thick-film conductor pastes having various compositions are already known, and one of them is Ag powder, Pt powder, glass frit and organic vehicle base (hereinafter referred to as "base"). Is referred to as a base composition), and various Ag-Pt-based conductor paste compositions in which various additives are mixed according to the purpose have been developed.
【０００３】上記既開発のＡｇ−Ｐｔ系導体ペ−スト組
成物を列挙すれば、(1) 前記ベ−ス組成物にチタネ−ト
系カップリング剤を配合し、これによって、ペ−ストを
混練した際に生じるフレ−クを減少させるＡｇ−Ｐｔ系
導体ペ−スト（特開昭59−155988号公報）、(2) 前記ベ
−ス組成物に酸化ビスマスとリンを添加し、これによっ
て、電極露出部に生じるステインによる半田濡れ性を防
止するＡｇ−Ｐｔ系導体ペ−スト（特開昭61−251101号
公報）、(3) 結晶化ガラスからなるホ−ロ−被覆基板に
導体を形成するために、前記ベ−ス組成物に酸化ビスマ
スと酸化銅を配合し、これによって、導体の接着強度の
改良を意図したＡｇ−Ｐｔ系導体ペ−スト（特開昭62−
55805号公報）、等が知られている。The above-mentioned Ag-Pt-based conductor paste compositions that have already been developed are listed as follows: (1) A titanium-based coupling agent is added to the base composition, whereby a paste is prepared. Ag-Pt-based conductor paste (Japanese Patent Laid-Open No. 59-155988), which reduces flakes generated when kneading, (2) Bismuth oxide and phosphorus are added to the base composition, thereby , An Ag-Pt-based conductor paste (Japanese Patent Laid-Open No. 61-251101) that prevents solder wettability due to stains generated on the electrode exposed portion, and (3) a conductor on a hollow-coated substrate made of crystallized glass. In order to form the base composition, bismuth oxide and copper oxide are blended with the above-mentioned base composition, whereby an Ag-Pt-based conductor paste intended to improve the adhesive strength of the conductor (JP-A-62-
55805), etc. are known.
【０００４】[0004]
【発明が解決しようとする課題】上述した(1)〜(3)のＡ
ｇ−Ｐｔ系導体ペ−ストは、ＡＩ2Ｏ3を少なくとも90重
量％以上含有するいわゆるアルミナ基板用として、或い
は、特殊なホ−ロ−被覆基板用として開発されたもので
ある。ところで、最近、低温焼成セラミック基板が着目
され、この基板が大量に製造されるようになっている。
該基板は、例えばアルミナ粉末とガラス粉末とを１：１
（重量比）前後で混合して生シ−トを成形し、内部導体
用のＡｇペ−ストをスクリ−ン印刷法で印刷し、積層、
圧着、焼成の各工程を経て半製品を製造し、次いで、こ
の半製品の表面に前述した(1)〜(3)のＡｇ−Ｐｔ系導体
ペ−ストを印刷法により配線パタ−ンを形成し、焼成し
た後、更に、抵抗体その他のペ−ストを印刷し、焼成す
ることにより製造されていた。その場合、各焼成工程に
おける温度は、いずれも1000℃以下が一般的である。な
お、半製品とは、生シ−トが少なくとも１回の焼成工程
を経たものをいう。[Problems to be Solved by the Invention] A of the above (1) to (3)
g-Pt-based conductor Bae - strike, as a so-called alumina substrate the AI 2 O 3 containing at least 90 wt% or more, or special E - B - were developed for the coated substrate. By the way, recently, attention has been paid to a low temperature fired ceramic substrate, and this substrate has been manufactured in a large amount.
The substrate is made of, for example, 1: 1 alumina powder and glass powder.
(Weight ratio) Mixing before and after to form a green sheet, print Ag paste for internal conductor by screen printing method, stack,
A semi-finished product is manufactured through each process of pressure bonding and firing, and then the wiring pattern is formed on the surface of the semi-finished product by printing the Ag-Pt-based conductor paste of (1) to (3) described above. Then, after firing, a resistor and other pastes are printed and fired. In that case, the temperature in each firing step is generally 1000 ° C. or lower. The semi-finished product refers to a raw sheet that has undergone at least one firing step.
【０００５】上記工程における半製品表面の印刷に使用
される(1)〜(3)のＡｇ−Ｐｔ系導体ペ−ストは、前記し
たとおり、特に低温焼成セラミック基板製造用に開発さ
れたものではなかったが、ＡＩ2Ｏ3を少なくとも90重量
％以上含有するいわゆるアルミナ基板用、又は、特殊な
ホ−ロ−被覆基板用として開発したものをそのまま転用
して用いていた。したがって、従来の方法では、該導体
ペ−ストを、ガラスを多量に含む半製品表面に印刷し、
焼成していたので、そのガラスが焼成過程で導体中に拡
散してガラスリッチとなり、結果として導体の半田濡れ
性を低下させる一方、接着強度、特にエ−ジング後の接
着強度を低下させ、基板としての信頼性を低くするとい
う欠点を有していた。As described above, the Ag-Pt-based conductor pastes (1) to (3) used for printing the surface of the semi-finished product in the above process are not particularly developed for the production of low temperature fired ceramic substrates. However, what was developed for a so-called alumina substrate containing at least 90% by weight of AI 2 O 3 or for a special hollow-coated substrate was used as it was. Therefore, in the conventional method, the conductor paste is printed on a semi-finished product surface containing a large amount of glass,
Since it was fired, the glass diffused into the conductor in the firing process to become glass-rich, and as a result, the solder wettability of the conductor was lowered, while the adhesive strength, particularly the adhesive strength after aging, was lowered. It had a drawback of lowering the reliability as.
【０００６】そこで、本発明者等は、低温焼成セラミッ
ク基板を製造する過程で半製品表面に配線パタ−ンを形
成する際、半田濡れ性と接着強度の両方が良好なＡｇ−
Ｐｔ系導体ペ−ストを開発すべく、従来のベ−ス組成物
を中心に追求した結果、本発明を完成したものであっ
て、本発明の目的は、低温焼成セラミック基板を製造す
る際、該表面に導体を形成するために用いる改良された
厚膜用Ａｇ−Ｐｔ系導体ペ−ストを提供するにあり、詳
細には、ガラス成分を多量に含む低温焼成セラミック基
板の製造過程において、その表面に導体ペ−ストを用い
て配線パタ−ンを形成したとき、半田濡れ性、接着強度
の双方が向上する導体ペ−ストを提供するにある。[0006] Therefore, the inventors of the present invention, when forming a wiring pattern on the surface of a semi-finished product in the process of manufacturing a low temperature fired ceramic substrate, Ag- which has good solder wettability and adhesive strength.
The present invention has been completed as a result of pursuing mainly a conventional base composition in order to develop a Pt-based conductor paste, and an object of the present invention is to produce a low temperature fired ceramic substrate. There is provided an improved thick film Ag-Pt-based conductor paste used for forming a conductor on the surface, and more particularly, in the process of manufacturing a low temperature fired ceramic substrate containing a large amount of a glass component, Another object of the present invention is to provide a conductor paste in which both the solder wettability and the adhesive strength are improved when a wiring pattern is formed on the surface by using the conductor paste.
【０００７】[0007]
【課題を解決するための手段】そして、本発明は、従来
のベ−ス組成物に、ＭｎＯ2粉末及びＣｒ2Ｏ3粉末の所
定量を配合することを特徴とし、これによって、上記半
田濡れ性、接着強度の双方が向上する導体ペ−ストが得
られるものである。即ち、本発明は、Ａｇ粉末、Ｐｔ粉
末、ガラスフリット及び有機質ビヒクルよりなるペ−ス
トに、Ａｇ粉末とＰｔ粉末の合量に対しＭｎＯ2粉末0.2
〜2重量％及びＣｒ2Ｏ3粉末0.3〜3重量％配合してなる
ことを特徴とする導体ペ−ストである。The present invention is characterized in that a conventional base composition is compounded with a predetermined amount of MnO 2 powder and Cr 2 O 3 powder, whereby the solder wetting is achieved. It is possible to obtain a conductor paste in which both properties and adhesive strength are improved. That is, according to the present invention, a MnO 2 powder is added to a paste composed of Ag powder, Pt powder, glass frit and an organic vehicle based on the total amount of Ag powder and Pt powder.
Conductors and characterized by being 2 wt% and Cr 2 O 3 powder 0.3 to 3 wt% blending Bae - a strike.
【０００８】[0008]
【作用】本発明において、従来のベ−ス組成物に対し
て、ＭｎＯ2粉末とＣｒ2Ｏ3粉末とを配合することによ
り、上記したとおり、半田濡れ性、接着強度が向上する
作用が生ずるが、これは、次の理由によるものと考えら
れる。ベ−ス組成物にＭｎＯ2粉末、Ｃｒ2Ｏ3粉末を併
用・配合した本発明の導体ペ−ストを半製品表面に印刷
し、再度低温焼成したとき、該導体ペ−ストに含まれる
ガラス成分が溶融して半製品表面の凹部に拡散するのを
助け、かつ、半製品に含まれるガラスが導体へ拡散する
のを防ぎ、更に、冷却時にあって結晶化すると共にアン
カ−効果を発揮して接着効果を向上させ、同時に、導体
表面を金属リッチにするため、半田濡れ性をも向上する
ものと考えられる。In the present invention, by adding MnO 2 powder and Cr 2 O 3 powder to the conventional base composition, the solder wettability and adhesive strength are improved as described above. However, this is considered to be due to the following reasons. The glass contained in the conductor paste when the conductor paste of the present invention, in which MnO 2 powder and Cr 2 O 3 powder are used in combination with the base composition, is printed on the surface of a semi-finished product and is fired again at a low temperature. Helps the components to melt and diffuse into the recesses on the surface of the semi-finished product, and prevents the glass contained in the semi-finished product from diffusing to the conductor, and also exhibits the anchor effect as it crystallizes during cooling. Therefore, it is considered that the adhesive effect is improved and, at the same time, the conductor surface is made metal-rich, so that the solder wettability is also improved.
【０００９】以下、本発明を詳細に説明すると、本発明
は、従来のベ−ス組成物にＭｎＯ2粉末とＣｒ2Ｏ3粉末
の所定量を添加、つまり、両化合物を併用することが目
的達成上最も肝要である。ＭｎＯ2粉末は、半田濡れ性
及び高温エ−ジング後の接着強度双方の改良に作用する
ものと考えられ、その配合量は、Ａｇ粉末とＰｔ粉末の
合量に対し0.2重量％未満では、該接着強度が極端に悪
くなるので好ましくない。そして、その量が0.2〜2重量
％まではその効果を発揮し、2重量％を超えても殆ど該
効果は変わらないが、シ−ト抵抗の増大など別の好まし
くない面が顕現する。したがって、本発明は、ＭｎＯ2
粉末の好ましい配合割合は0.2〜2重量％であり、より好
ましくは0.3〜1.5重量％である。The present invention will be described in detail below. The purpose of the present invention is to add a predetermined amount of MnO 2 powder and Cr 2 O 3 powder to a conventional base composition, that is, to use both compounds in combination. The most important thing to achieve. The MnO 2 powder is considered to act to improve both the solder wettability and the adhesive strength after high temperature aging. If the content of the MnO 2 powder is less than 0.2% by weight based on the total amount of the Ag powder and the Pt powder, It is not preferable because the adhesive strength becomes extremely poor. When the amount is 0.2 to 2% by weight, the effect is exhibited, and when the amount exceeds 2% by weight, the effect is almost the same, but another undesirable aspect such as an increase in sheet resistance is revealed. Therefore, the present invention provides MnO 2
The preferable blending ratio of the powder is 0.2 to 2% by weight, more preferably 0.3 to 1.5% by weight.
【００１０】Ｃｒ2Ｏ3粉末は、特に半田濡れ性への影響
が大きい。その配合量は、Ａｇ粉末とＰｔ粉末の合量に
対し0.3重量％未満では、半田濡れ性及び高温エ−ジン
グ後の接着強度が低く、特に前者の半田濡れ性が極端に
低下し、一方、3重量％を越えると半田濡れ性の低下、
シ−ト抵抗の増大が生ずる等いずれも好ましくない。し
たがって、本発明は、Ｃｒ2Ｏ3粉末の好ましい配合割合
は0.3〜3重量％であり、より好ましくは1.5〜2.5重量％
である。The Cr 2 O 3 powder has a great influence on the solder wettability. If the blending amount is less than 0.3% by weight based on the total amount of Ag powder and Pt powder, the solder wettability and the adhesive strength after high temperature aging are low, and particularly the former solder wettability is extremely reduced. If it exceeds 3% by weight, the solder wettability deteriorates,
Any increase in sheet resistance is not preferable. Therefore, in the present invention, the preferable blending ratio of Cr 2 O 3 powder is 0.3 to 3% by weight, and more preferably 1.5 to 2.5% by weight.
Is.
【００１１】本発明において、ＭｎＯ2粉末及びＣｒ2Ｏ
3粉末は、市販されているものが利用できる。それらの
細かさは、本発明で限定するものではないが、平均粒径
で3μｍ以下のものが好ましく、3μｍを越えるものも使
用できるが、この場合慣用手段で適宜粉砕して使用する
ことができる。また、ＭｎＯ2粉末及びＣｒ2Ｏ3粉末の
ベ−ス組成物への配合方法は、慣用手段にしたがって行
なうことができる。In the present invention, MnO 2 powder and Cr 2 O
3 powders available on the market can be used. The fineness thereof is not limited in the present invention, but an average particle diameter of 3 μm or less is preferable, and an average particle diameter of more than 3 μm can be used. In this case, it can be appropriately crushed and used by a conventional means. .. The MnO 2 powder and the Cr 2 O 3 powder can be added to the base composition by conventional means.
【００１２】次に、ベ−ス組成物について説明すると、
Ａｇ粉末及びＰｔ粉末は、通常使用されている平均粒径
0.1〜4μｍのものを用い、また、両者の配合量も、従来
法と同様、前者を90〜99重量部、後者を10〜1重量部の
割合である。ガラスフリットは、650〜900℃で熱処理し
たとき結晶化するもの、例えばチタン酸ケイ酸亜鉛系の
ものが好ましい。結晶化しないガラスフリットを用いた
場合、それを含むＡｇ−Ｐｔ系導体ペ−ストを印刷・焼
成した半製品表面に、次工程で抵抗体ペ−ストを印刷し
て再度焼成を行った際、該導体ペ−スト中のガラス成分
が導体表面に滲み出し、半田濡れ性を低下させるので、
好ましくない。Next, the base composition will be described.
Ag powder and Pt powder have average particle diameters that are commonly used.
As in the conventional method, the former is 90 to 99 parts by weight, and the latter is 10 to 1 parts by weight. The glass frit that crystallizes when heat-treated at 650 to 900 ° C., for example, a zinc titanate silicate-based glass frit is preferable. When a glass frit that does not crystallize is used, when a resistor paste is printed and fired again in the next step on the surface of the semi-finished product on which the Ag-Pt-based conductor paste containing it is printed and fired, Since the glass component in the conductor paste exudes on the conductor surface and reduces the solder wettability,
Not preferable.
【００１３】有機質ビヒクルは、一般に使用されている
例えばメチルセルロ−ス、エチルセルロ−スなどの有機
結合剤をテルピネオ−ル、ブチルカルビト−ルなどの溶
剤で溶解させたものを使用することができる。ガラスフ
リット及び有機質ビヒクルの配合割合は、Ａｇ粉末とＰ
ｔ粉末の合量に対し前者が0.2〜1.5重量％、後者が10〜
40重量％が好ましい。As the organic vehicle, a generally used organic binder such as methyl cellulose or ethyl cellulose dissolved in a solvent such as terpineol or butyl carbitol can be used. The mixing ratio of glass frit and organic vehicle is Ag powder and P
The former is 0.2-1.5% by weight and the latter is 10-
40% by weight is preferred.
【００１４】[0014]
【実施例】以下、本発明の実施例を比較例と共に挙げ、
本発明をより詳細に説明する。次に記載するように、ま
ず、Ａｇ−Ｐｔ系導体ペ−ストを試製し、次いで、該導
体ペ−ストを半製品表面に印刷し、更に、低温焼成して
供試体を得た。そして、この供試体における半田濡れ
性、接着強度等の特性を測定し、該測定値により、導体
ペ−ストの良否を評価した。 (1) 使用した原材料 Ａｇ粉末： 昭栄化学社製（平均粒径1μｍ） Ｐｔ粉末： 田中貴金属社製（粒径0.5〜2.0μｍ） ガラスフリット：ＳｉＯ2、ＴｉＯ2、Ａｌ2Ｏ3、Ｂ
2Ｏ3、ＺｎＯ、ＣａＯ（以上純薬） 有機質ビヒクル：エチルセルロ−スをα−テルピネオ−
ルに溶解させたもの ＭｎＯ2粉末： 高純度化学研究所製 試薬（純度99
％）(平均粒径0.9μｍ) Ｃｒ2Ｏ3粉末： 関東化学社製 特級試薬(平均粒径1.6
μｍ) なお、ガラスフリットは、上記ＳｉＯ2、ＴｉＯ2、Ａｌ
2Ｏ3、Ｂ2Ｏ3、ＺｎＯ、ＣａＯを重量で33：13：18：
2：17：17の割合に配合し、1400℃で溶融し、急冷後ボ
−ルミルで粉砕（平均粒径1.5μｍ）し、得られたチタ
ン酸ケイ酸亜鉛系ガラスフリットを使用した。このガラ
スフリットを850℃で熱処理した後、Ｘ線回析で調べた
ところ、結晶が析出していることが確認された。EXAMPLES Examples of the present invention will be given below together with comparative examples.
The present invention will be described in more detail. As described below, first, an Ag-Pt-based conductor paste was trial-produced, then the conductor paste was printed on the surface of a semi-finished product, and further, low-temperature firing was performed to obtain a specimen. Then, characteristics such as solder wettability and adhesive strength of this test piece were measured, and the quality of the conductor paste was evaluated based on the measured values. (1) Raw materials used Ag powder: manufactured by Shoei Chemical Co., Ltd. (average particle size 1 μm) Pt powder: manufactured by Tanaka Kikinzoku Co., Ltd. (particle size 0.5 to 2.0 μm) Glass frit: SiO 2 , TiO 2 , Al 2 O 3 , B
2 O 3 , ZnO, CaO (above pure drug) Organic vehicle: Ethyl cellulose to α-terpineo-
Dissolved in MnO 2 powder: Reagent manufactured by Kojundo Chemical Laboratory (purity 99
%) (Average particle size 0.9 μm) Cr 2 O 3 powder: Kanto Chemical Co., Ltd. special grade reagent (average particle size 1.6
Note that the glass frit is composed of the above-mentioned SiO 2 , TiO 2 , and Al.
2 O 3, B 2 O 3 , ZnO, and CaO by weight 33:13:18:
The zinc titanate silicate-based glass frit thus obtained was blended in a ratio of 2:17:17, melted at 1400 ° C., rapidly cooled, and then pulverized with a ball mill (average particle size: 1.5 μm). When this glass frit was heat treated at 850 ° C. and examined by X-ray diffraction, it was confirmed that crystals were precipitated.
【００１５】(2) Ａｇ−Ｐｔ系導体ペ−ストの試製 Ａｇ粉末98重量部及びＰｔ粉末2重量部の配合物に対
し、ガラスフリット１重量％と、次いで、表１に記載の
割合でＭｎＯ2粉末及び／又はＣｒ2Ｏ3粉末を加え、更
に、有機質ビヒクルを前記配合物に対し30重量％添加し
た後、三本ロ−ルミルで十分混練してそれぞれの試製導
体ペ−ストを製造した。(2) Trial Production of Ag-Pt Conductor Paste A glass frit of 1 wt% was added to a mixture of 98 parts by weight of Ag powder and 2 parts by weight of Pt powder, and then MnO at a ratio shown in Table 1. 2 powder and / or Cr 2 O 3 powder was added, and further 30% by weight of an organic vehicle was added to the above composition, and then thoroughly kneaded with a three roll mill to manufacture respective trial conductor pastes. ..
【００１６】(3) 供試体の作製 2インチ角の生シ−トを焼成（850℃、10分間）し、得ら
れた半製品表面にスクリ−ン印刷法で試製導体ペ−スト
のパッド（2×2ｍｍ）20個を形成し、乾燥し、引き続い
て850℃、10分間焼成してそれぞれの供試体を作製し
た。なお、上記生シ−トは、ＡＩ2Ｏ3粉末とホウケイ酸
亜鉛系ガラス粉末を重量比で１：１に配合し、バインダ
−を加えて混練した後、ドクタ−ブレ−ド法によってシ
−ト状（厚さ0.8ｍｍ）に成形し、上記寸法に裁断した
ものである。(3) Preparation of Specimen A 2-inch square raw sheet was baked (850 ° C., 10 minutes), and a pad of a test conductor paste (screen paste) was formed on the surface of the obtained semi-finished product by a screen printing method. Twenty pieces (2 × 2 mm) were formed, dried, and subsequently fired at 850 ° C. for 10 minutes to prepare respective test pieces. The above-mentioned green sheet was prepared by mixing AI 2 O 3 powder and zinc borosilicate glass powder in a weight ratio of 1: 1 and adding a binder and kneading, followed by doctor blade method. It is formed into a dovetail shape (thickness 0.8 mm) and cut into the above dimensions.
【００１７】(4) 供試体の特性試験 半田濡れ性試験は、供試体を230℃のＳｎ−Ｐｂ−Ａｇ
共晶半田浴に5秒間浸漬し、引上げた後、半田によるパ
ッド面の濡れ面積の割合を求めた。この半田濡れ性は、
実用上、少なくとも90％以上であることが望ましい。接
着強度試験は、次のようにして行った。供試体のパッド
にＬ字型のＳｎメッキ銅線（直径0.8ｍｍ）をＰｂ−Ｓ
ｎ半田で接合し、該銅線をパッド面と垂直方向に引張
り、パッドと基板との接着部が破壊されたときの荷重を
接着強度として測定した。この接着強度試験は、接合直
後（初期接着強度）と接合後高温エ−ジング（150℃、1
00時間）した後とについて行った。これら接着強度は、
1.5Ｋｇ以上が好ましく、その点で判断した。以上の半
田濡れ性及び接着強度の各試験結果を表１に記載した。
なお、合わせてシ−ト抵抗測定値も併記した。(4) Specimen Characteristic Test For the solder wettability test, the specimen is Sn-Pb-Ag at 230 ° C.
After immersing in a eutectic solder bath for 5 seconds and pulling it up, the ratio of the wetted area of the pad surface by the solder was determined. This solder wettability is
Practically, it is desirable that it is at least 90% or more. The adhesive strength test was performed as follows. L-shaped Sn-plated copper wire (0.8 mm diameter) is used as the Pb-S pad on the test piece.
Bonding was performed with n solder, the copper wire was pulled in the direction perpendicular to the pad surface, and the load when the bonding portion between the pad and the substrate was broken was measured as the bonding strength. This adhesive strength test is carried out immediately after joining (initial adhesive strength) and after joining by high temperature aging (150 ° C, 1
(00 hours) and then went. These bond strengths are
It is preferably 1.5 kg or more, and it was judged from that point. Table 1 shows the test results of the solder wettability and the adhesive strength.
The sheet resistance measurement values are also shown together.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１から明らかなように、Ａｇ−Ｐｔ系導
体ペ−ストに、Ａｇ粉末とＰｔ粉末の合量に対しＭｎＯ
2粉末0.2〜2重量％及びＣｒ2Ｏ3粉末0.3〜3重量％配合
した実施例１〜７では、半田濡れ性が90％以上であり、
また、接着強度も、その初期強度並びに高温エ−ジング
後の強度共1.5Ｋｇ以上であり、該半田濡れ性、接着強
度のいずれも共に優れていることが理解できる。また、
シ−ト抵抗測定値が7.4ｍΩ／スクエア以下であり、こ
れも良好であることが理解できる。As is clear from Table 1, MnO was added to the Ag-Pt-based conductor paste with respect to the total amount of Ag powder and Pt powder.
In Examples 1 to 7 containing 0.2 to 2% by weight of 2 powder and 0.3 to 3 % by weight of Cr 2 O 3 powder, the solder wettability is 90% or more,
Further, the adhesive strength is 1.5 kg or more in both initial strength and strength after high temperature aging, and it can be understood that both the solder wettability and the adhesive strength are excellent. Also,
It can be understood that the measured sheet resistance is 7.4 mΩ / square or less, which is also good.
【００２０】これに対して、ＭｎＯ2粉末及びＣｒ2Ｏ3
粉末を配合しない比較例１では、半田濡れ性が40％であ
り、また、接着強度も、その初期強度が0.9Ｋｇ、高温
エ−ジング後の強度が0.4Ｋｇであり、いずれも劣って
いた。また、ＭｎＯ2、Ｃｒ2Ｏ3を併用せず単独使用の
場合、例えば、Ｃｒ2Ｏ3粉末のみ配合した比較例２で
は、半田濡れ性、初期接着強度については満足する結果
が得られるものの、高温エ−ジング後の接着強度が0.9
Ｋｇと劣っており、また、ＭｎＯ2粉末のみ配合した比
較例４では、初期接着強度並びに高温エ−ジング後の接
着強度については満足する結果が得られるものの、半田
濡れ性が50％と劣っていた。更に、ＭｎＯ2、Ｃｒ2Ｏ3
を併用した場合であっても、ＭｎＯ2粉末の配合量が本
発明で規定する0.2〜2重量％の範囲外の3.0重量％であ
る比較例３やＣｒ2Ｏ3粉末の配合量が本発明で規定する
0.3〜3重量％の範囲外の4.0重量％である比較例５で
は、そのシ−ト抵抗測定値が10.1ｍΩ／スクエア、10.5
ｍΩ／スクエアであり、いずれも好ましいものではなか
った。On the other hand, MnO 2 powder and Cr 2 O 3
In Comparative Example 1 in which the powder was not mixed, the solder wettability was 40%, and the adhesive strength was inferior because the initial strength was 0.9 kg and the strength after high temperature aging was 0.4 kg. Further, when MnO 2 and Cr 2 O 3 are used alone without being used together, for example, in Comparative Example 2 in which only Cr 2 O 3 powder is mixed, although satisfactory results are obtained with respect to solder wettability and initial adhesive strength, Adhesive strength after high temperature aging is 0.9
Inferior to Kg, and in Comparative Example 4 in which only MnO 2 powder was blended, satisfactory results were obtained with respect to initial adhesive strength and adhesive strength after high temperature aging, but solder wettability was poor at 50%. It was Further, MnO 2 , Cr 2 O 3
Even when used in combination, the compounding amount of MnO 2 powder was 3.0% by weight, which is outside the range of 0.2 to 2% by weight defined in the present invention, and the compounding amount of Cr 2 O 3 powder was the same as that of the present invention. Prescribed by
In Comparative Example 5, which is 4.0% by weight outside the range of 0.3 to 3% by weight, the sheet resistance measurement value is 10.1 mΩ / square, 10.5%.
It was mΩ / square, and neither was preferable.
【００２１】[0021]
【発明の効果】本発明は、以上詳記したとおり、Ａｇ−
Ｐｔ系ペ−ストに、ＭｎＯ2粉末及びＣｒ2Ｏ3粉末の所
定量を配合するものであり、これによって、ガラス成分
を多量に含む低温焼成セラミック基板の製造過程におい
て、その表面に該導体ペ−ストを用いて配線パタ−ンを
形成したとき、半田濡れ性及び接着強度の双方が格段に
向上する効果が生じ、また、シ−ト抵抗が低いものが得
られる効果が生ずる。そして、この半田濡れ性及び接着
強度の両特性は、電子回路形成の際の要となるものであ
り、従って、本発明により、回路の信頼性ひいては歩留
まりの向上に大いに役立つ導体ペ−ストを提供すること
ができる。INDUSTRIAL APPLICABILITY As described in detail above, the present invention is characterized by Ag-
A Pt-based paste is mixed with a predetermined amount of MnO 2 powder and Cr 2 O 3 powder, so that in the process of manufacturing a low temperature fired ceramic substrate containing a large amount of glass components, the conductor paste is formed on the surface thereof. When a wiring pattern is formed using a strike, both solder wettability and adhesive strength are remarkably improved, and a sheet resistance is low. Both of the solder wettability and the adhesive strength are essential for forming an electronic circuit. Therefore, according to the present invention, a conductor paste is provided which is very useful for improving the reliability of the circuit and thus the yield. can do.
Claims (1)
び有機質ビヒクルよりなるペ−ストに、Ａｇ粉末とＰｔ
粉末の合量に対しＭｎＯ2粉末0.2〜2重量％及びＣｒ2Ｏ
3粉末0.3〜3重量％配合してなることを特徴とする導体
ペ−スト。1. An Ag powder and Pt are added to a paste made of Ag powder, Pt powder, glass frit and an organic vehicle.
0.2 to 2 wt% of MnO 2 powder and Cr 2 O based on the total amount of powder
Conductor paste characterized by being mixed with 0.3 to 3 % by weight of 3 powders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21477191A JP2965222B2 (en) | 1991-07-31 | 1991-07-31 | Conductor paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21477191A JP2965222B2 (en) | 1991-07-31 | 1991-07-31 | Conductor paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0541110A true JPH0541110A (en) | 1993-02-19 |
| JP2965222B2 JP2965222B2 (en) | 1999-10-18 |
Family
ID=16661267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21477191A Expired - Fee Related JP2965222B2 (en) | 1991-07-31 | 1991-07-31 | Conductor paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2965222B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000040520A1 (en) * | 1998-12-31 | 2000-07-13 | Ceramic Fuel Cells Limited | Electrically conductive ceramics |
| US6110569A (en) * | 1997-10-16 | 2000-08-29 | Tdk Corporation | Conductive paste and non-reciprocal device using the same |
| EP1184882A1 (en) * | 2000-01-28 | 2002-03-06 | TDK Corporation | Conductor pattern built in multilayer board, multilayer board having built-in conductor pattern, and method of manufacturing multilayer board |
| JP2006332236A (en) * | 2005-05-25 | 2006-12-07 | Murata Mfg Co Ltd | Conductive paste, laminated ceramic electronic component, and manufacturing method thereof |
| US7898822B2 (en) | 2004-08-04 | 2011-03-01 | Epcos Ag | Holder for electric components |
-
1991
- 1991-07-31 JP JP21477191A patent/JP2965222B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110569A (en) * | 1997-10-16 | 2000-08-29 | Tdk Corporation | Conductive paste and non-reciprocal device using the same |
| WO2000040520A1 (en) * | 1998-12-31 | 2000-07-13 | Ceramic Fuel Cells Limited | Electrically conductive ceramics |
| EP1184882A1 (en) * | 2000-01-28 | 2002-03-06 | TDK Corporation | Conductor pattern built in multilayer board, multilayer board having built-in conductor pattern, and method of manufacturing multilayer board |
| US6738251B2 (en) | 2000-01-28 | 2004-05-18 | Tdk Corporation | Conductive pattern incorporated in a multilayered substrate, multilayered substrate incorporating a conductive pattern, and a method of fabricating a multilayered substrate |
| EP1184882A4 (en) * | 2000-01-28 | 2007-12-12 | Tdk Corp | Conductor pattern built in multilayer board, multilayer board having built-in conductor pattern, and method of manufacturing multilayer board |
| US7898822B2 (en) | 2004-08-04 | 2011-03-01 | Epcos Ag | Holder for electric components |
| JP2006332236A (en) * | 2005-05-25 | 2006-12-07 | Murata Mfg Co Ltd | Conductive paste, laminated ceramic electronic component, and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2965222B2 (en) | 1999-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5303552B2 (en) | Conductive paste for ceramic substrate and electric circuit | |
| JP4885781B2 (en) | Conductive paste | |
| JPH09306236A (en) | Conductive paste | |
| JPH0334162B2 (en) | ||
| JP2000048642A (en) | Conductive paste and glass circuit substrate | |
| JP4423832B2 (en) | Glass composition and thick film paste using the same | |
| WO2021221172A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| JP2965222B2 (en) | Conductor paste | |
| TWI662561B (en) | Lead-free thick film resistor composition, lead-free thick film resistor and production method thereof | |
| TWI847266B (en) | Low melting point, high reliability solder particle and resin composite including the same, and electronic devices using the same | |
| JP2795467B2 (en) | Good adhesive metal paste | |
| JP2917457B2 (en) | Conductor paste | |
| KR101739744B1 (en) | Lead-free thick film resistor composition, resistor and method thereof | |
| JPH11130459A (en) | Electrically conductive composition for glass substrate and anti-fog window glass for automobile | |
| JPH0945130A (en) | Conductor paste composite | |
| JP2931450B2 (en) | Conductor paste | |
| US6190790B1 (en) | Resistor material, resistive paste and resistor using the resistor material, and multi-layered ceramic substrate | |
| JP2003267750A (en) | Glass composition for coating resistive element | |
| JPH05128910A (en) | Conductor paste | |
| JP3318299B2 (en) | Pb-free low-temperature firing type conductive paint | |
| JP2004199941A (en) | Conductive paste composition, and circuit board using the same | |
| JP6836184B2 (en) | Composition for forming a thick film conductor and a method for producing a thick film conductor | |
| JPH02263731A (en) | Thick film copper paste | |
| JPH0850806A (en) | Composition for thick film conductor | |
| JPH06223617A (en) | Conductive paste composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |