JP2931444B2 - Powder composition for forming conductive patterns for ceramic circuit boards - Google Patents
Powder composition for forming conductive patterns for ceramic circuit boardsInfo
- Publication number
- JP2931444B2 JP2931444B2 JP19701691A JP19701691A JP2931444B2 JP 2931444 B2 JP2931444 B2 JP 2931444B2 JP 19701691 A JP19701691 A JP 19701691A JP 19701691 A JP19701691 A JP 19701691A JP 2931444 B2 JP2931444 B2 JP 2931444B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- conductive pattern
- ceramic circuit
- weight
- circuit board
- 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
- 239000000843 powder Substances 0.000 title claims description 59
- 239000000919 ceramic Substances 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910000679 solder Inorganic materials 0.000 description 18
- 238000010304 firing Methods 0.000 description 15
- 239000011812 mixed powder Substances 0.000 description 15
- 239000004020 conductor Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 4
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- 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 3
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 3
- 229940088601 alpha-terpineol Drugs 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910020410 SiO2—B2O3—PbO Inorganic materials 0.000 description 1
- 229910020816 Sn Pb Inorganic materials 0.000 description 1
- 229910020922 Sn-Pb Inorganic materials 0.000 description 1
- 229910008783 Sn—Pb Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 201000003373 familial cold autoinflammatory syndrome 3 Diseases 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、セラミックス回路基板
用導電パタ−ン形成用粉末組成物に関し、詳細には、低
温焼成によってセラミックス回路基板を製造するにあた
り、セラミックグリ−ンシ−ト上に導電パタ−ンを形成
するためのペ−スト製造用導電粉末に係るセラミックス
回路基板用導電パタ−ン形成用粉末組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder composition for forming a conductive pattern for a ceramic circuit board, and more particularly to a method for manufacturing a ceramic circuit board by firing at a low temperature. The present invention relates to a conductive pattern-forming powder composition for a ceramic circuit board, which relates to a paste-forming conductive powder for forming a pattern.
【０００２】[0002]
【従来の技術】従来、低温焼成により製造されるセラミ
ックス回路基板において、その表面配線及びスル−ホ−
ルを形成するために、電気抵抗の低いＡｇを主成分とす
る導電粉末が用いられている。例えば、特開昭６３−１
６６９７号公報には、導電粉末として「Ａｇ粉末８５〜
８０重量％とＰｄ粉末１５〜２０重量％の粉末混合物」
又は「Ａｇ５０〜９０重量％とＰｄ５０〜１０重量％の
合金粉末」を用いることについて記載されている。そし
て、該導電粉末を有機ビヒクルに混合して導電体ペ−ス
トを調製し、予め作製されたセラミックグリ−ンシ−ト
の表面に、該導電体ペ−ストを所定の導電パタ−ンにな
るように印刷し、焼成（８００〜１０００℃）する方法
が開示されている。なお、上記有機ビヒクルとしては、
一般的には、エチルセルロ−スをα−テルピネオ−ルに
溶解したものが使用されている。2. Description of the Related Art Conventionally, in a ceramic circuit board manufactured by low-temperature sintering, surface wiring and through-hole
In order to form a metal, a conductive powder mainly composed of Ag having a low electric resistance is used. For example, JP-A-63-1
No. 6697 discloses that “Ag powder 85-
Powder mixture of 80% by weight and 15 to 20% by weight of Pd powder "
Alternatively, it is described that “an alloy powder of 50 to 90% by weight of Ag and 50 to 10% by weight of Pd” is used. Then, the conductive powder is mixed with an organic vehicle to prepare a conductive paste, and the conductive paste is formed into a predetermined conductive pattern on the surface of a ceramic green sheet prepared in advance. Printing and baking (800-1000 ° C.). In addition, as said organic vehicle,
Generally, a solution in which ethyl cellulose is dissolved in α-terpineol is used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記従
来法によって、導電パタ−ンを形成して得たセラミック
グリ−ンシ−トは、これを焼成すると、導電パタ−ン形
成用導電体とセラミックグリ−ンシ−トとは、後に詳記
するとおり、焼成収縮過程が異なることから、導電体の
一部が基板から剥離したり、あるいは、セラミックグリ
−ンシ−トのガラス成分が導電体中に浸透したり、ま
た、セラミックスとの密着性向上のために導電ペ−スト
に添加したガラス成分が導電体表面に浮き出し、その結
果、端子部分でハンダが濡れにくい等の欠点を有してい
る。However, when the ceramic green sheet obtained by forming the conductive pattern by the above-mentioned conventional method is fired, the conductive green for forming the conductive pattern and the ceramic green sheet are formed. As described in detail later, since the firing shrinkage process is different from that of the green sheet, a part of the conductor is peeled off from the substrate or the glass component of the ceramic green sheet penetrates into the conductor. In addition, the glass component added to the conductive paste for improving the adhesion to the ceramics floats out on the surface of the conductive material, and as a result, the solder is hardly wet at the terminal portion.
【０００４】そこで、本発明者等は、上記欠点を解消す
る導電パタ−ン形成用導電体（導電体組成物）について
鋭意研究した結果、本発明を完成したものであって、本
発明は、セラミックス基板と導電パタ−ン（導電体）と
が焼成後に剥離せず、しかも、端子のハンダ濡れに優れ
た導電体組成物に係るセラミックス回路基板用導電パタ
−ン形成用粉末組成物を提供することを目的とする。The present inventors have conducted intensive studies on a conductive pattern-forming conductor (conductor composition) which solves the above-mentioned drawbacks, and as a result, have completed the present invention. Provided is a powder composition for forming a conductive pattern for a ceramic circuit board, which is a conductive composition which does not peel off a ceramic substrate and a conductive pattern (conductor) after firing and is excellent in solder wetting of terminals. The purpose is to:
【０００５】[0005]
【課題を解決するための手段】そして、本発明は、上記
目的を達成するため、導電粉末として、（１）所定割合
のＡｇ−Ｐｄ混合粉末を酸化雰囲気中で加熱処理したも
の使用する点及び（２）このＡｇ−Ｐｄ混合粉末を加熱
処理したものに、更に、Ｍｎの酸化物を添加したもの使
用する点にある。Means for Solving the Problems In order to achieve the above object, the present invention provides (1) a method in which a predetermined ratio of Ag-Pd mixed powder which is heat-treated in an oxidizing atmosphere is used as a conductive powder; (2) This Ag-Pd mixed powder is obtained by heat-treating and further adding an Mn oxide.
【０００６】即ち、本発明は、（１）Ａｇ粉末７０〜９
５重量部及びＰｄ粉末５〜３０重量部の混合物を酸化雰
囲気中で加熱処理してなることを特徴とするセラミック
ス回路基板用導電パタ−ン形成用粉末組成物（請求項
１）、（２）Ａｇ粉末７０〜９５重量部及びＰｄ粉末５
〜３０重量部の混合物を酸化雰囲気中で加熱処理してな
る粉末に、Ｍｎの酸化物を添加してなることを特徴とす
るセラミックス回路基板用導電パタ−ン形成用粉末組成
物（請求項３）である。That is, the present invention relates to (1) Ag powder 70 to 9
A powder composition for forming a conductive pattern for a ceramic circuit board, wherein a mixture of 5 parts by weight and 5 to 30 parts by weight of a Pd powder is subjected to a heat treatment in an oxidizing atmosphere. 70 to 95 parts by weight of Ag powder and Pd powder 5
A powder composition for forming a conductive pattern for a ceramic circuit board, characterized in that an oxide of Mn is added to a powder obtained by heat treating a mixture of 30 to 30 parts by weight in an oxidizing atmosphere. ).
【０００７】[0007]
【作用】従来から用いられているＡｇ−Ｐｄ導電性粉末
は、セラミックス回路基板焼成時に、導電体として含有
されているＰｄが酸化され、体積膨張を起こし、その後
の熱処理により還元され、Ａｇ−Ｐｄからなる導電層を
形成する。その結果、導電層は、焼成に伴い一度膨張
し、その後収縮するという焼成収縮過程を示す。これに
対して、セラミックグリ−ンシ−トは、焼成に伴い収縮
し、焼結が完了するという焼成収縮過程を示す。この両
者の焼成収縮過程の違いが導電パタ−ン（導電体）の剥
離現象の原因であり、また、この焼成過程において、ガ
ラス層が端子部分表面に形成され、ハンダ濡れを阻害し
ているものと考えられる。In the conventional Ag-Pd conductive powder, Pd contained as a conductor is oxidized during firing of the ceramic circuit board, causing volume expansion, and is reduced by a subsequent heat treatment to reduce the Ag-Pd. Is formed. As a result, the conductive layer shows a firing shrinkage process in which it expands once with firing and then contracts. On the other hand, the ceramic green sheet shrinks with firing and shows a firing shrinkage process in which sintering is completed. The difference in the firing shrinkage process between the two is the cause of the peeling phenomenon of the conductive pattern (conductor), and in this firing process, a glass layer is formed on the surface of the terminal portion, which hinders solder wetting. it is conceivable that.
【０００８】そこで、本発明は、上記導電パタ−ンの収
縮焼結過程を制御するため、Ａｇ−Ｐｄ混合粉末を予め
酸化雰囲気中で加熱処理した粉末を使用するものであ
り、これによって、セラミックス基板と導電パタ−ン
（導電体）とが焼成後に剥離せず、しかも、端子のハン
ダ濡れが優れたセラミックス回路基板が得られるもので
ある。即ち、本発明は、予め酸化雰囲気中で加熱処理す
ることにより、Ａｇ−Ｐｄ混合粉末中のＰｄが主として
酸化され、そのため、前記したＡｇ−Ｐｄからなる導電
層の形成時に、膨張ー収縮という焼成収縮過程のうち、
その膨張を抑制する作用が生ずるものである。Therefore, the present invention uses a powder obtained by heat-treating an Ag-Pd mixed powder in an oxidizing atmosphere in advance to control the shrink sintering process of the conductive pattern. The present invention provides a ceramic circuit board in which the substrate and the conductive pattern (conductor) do not peel off after firing, and have excellent solder wettability of the terminals. That is, according to the present invention, Pd in the Ag-Pd mixed powder is mainly oxidized by heat treatment in an oxidizing atmosphere in advance, and therefore, when forming the conductive layer made of Ag-Pd, sintering called expansion-shrinkage occurs. During the contraction process,
This has the effect of suppressing the expansion.
【０００９】以下、本発明を詳細に説明すると、本発明
において、セラミックス回路基板製造用原料粉末として
は、アルミナ、ムライト又はコ−デュライトなどにＳｉ
Ｏ2−Ｂ2Ｏ3系ガラス、ＰｂＯ−ＳｉＯ2−ＡＩ2Ｏ3−Ｂ
2Ｏ3系ガラス又はＣａＯ−ＳｉＯ2−ＡＩ2Ｏ3−Ｂ2Ｏ3
系ガラス等を複合したものが好ましく、このような原料
粉末を使用することによって、セラミックス回路基板を
低温焼成により製造することができる。また、セラミッ
クグリ−ンシ−トとしては、上記記原料粉末に有機バイ
ンダ−及び溶剤を加えてスラリ−とし、通常のドクタ−
プレイド法等により作製することができる。Hereinafter, the present invention will be described in detail. In the present invention, as a raw material powder for producing a ceramic circuit board, alumina, mullite or cordurite is used.
O 2 -B 2 O 3 based glass, PbO-SiO 2 -AI 2 O 3 -B
2 O 3 based glass or CaO-SiO 2 -AI 2 O 3 -B 2 O 3
A composite of a system glass or the like is preferable. By using such a raw material powder, a ceramic circuit board can be manufactured by low-temperature firing. Further, as a ceramic green sheet, an organic binder and a solvent are added to the above-mentioned raw material powder to form a slurry.
It can be manufactured by a plaid method or the like.
【００１０】次に、本発明のセラミックス回路基板用導
電パタ−ン形成用粉末組成物の製造法について説明する
と、原料粉末であるＡｇ及びＰｄの各粉末としては、導
電体材料として通常使用される平均粒径０．３〜１０μ
ｍ程度のものを用いることができる。特に、２μｍ以下
のＡｇ粉末及びＰｄ粉末の使用は、得られたＡｇ−Ｐｄ
粉末の混合が均一となり、導電パタ−ンの収縮が均一と
なることから、好ましい。このＡｇ粉末とＰｄ粉末とを
慣用手段で混合し、次いで、該混合粉末を酸化雰囲気中
で加熱処理し、目的とする導電パタ−ン形成用粉末組成
物を製造する。なお、酸化雰囲気中とは、酸素含有雰囲
気を指し、空気中又は酸素中等がその例として挙げられ
る。また、加熱処理温度の目安としては、充分な酸化処
理が得られる２００℃以上であり、好ましくは、２５０
℃以上である。Next, the method for producing the conductive pattern forming powder composition for a ceramic circuit board of the present invention will be described. Each of the raw material powders Ag and Pd is usually used as a conductive material. Average particle size 0.3-10μ
m can be used. In particular, the use of Ag powder and Pd powder of 2 μm or less is difficult to obtain the obtained Ag-Pd
This is preferable because the mixing of the powder becomes uniform and the contraction of the conductive pattern becomes uniform. The Ag powder and the Pd powder are mixed by conventional means, and then the mixed powder is heat-treated in an oxidizing atmosphere to produce a desired conductive pattern forming powder composition. Note that the term “in an oxidizing atmosphere” refers to an oxygen-containing atmosphere, such as in air or oxygen. The heat treatment temperature is preferably at least 200 ° C. at which a sufficient oxidation treatment can be obtained.
° C or higher.
【００１１】本発明において、上記したとおり、このＡ
ｇ−Ｐｄ混合粉末の酸化雰囲気中での加熱処理により、
主としてＰｄの酸化が起こり、後の焼成時における導電
パタ−ンの収縮状況を制御することができる。即ち、酸
化雰囲気中での加熱処理により得られるＡｇ−Ｐｄ混合
粉末は、酸化雰囲気中の酸素量の増加に伴ってその収縮
開始温度が低温側に変化する性質を示し、この性質を利
用して、セラミックグリ−ンシ−トの焼成時における収
縮状況とマッチングさせることができる。ここで、含有
される酸素量としては、０．２〜４．７重量％であり、
特に、０．５〜４．５重量％が好ましい。０．２重量％
未満の酸素量では、作製された導電パタ−ンとセラミッ
クス回路基板との密着性が悪く、接着強度として低いも
のとなってしまうので、好ましくない。また、４．７重
量％を越える酸素量の場合には、Ａｇ粉末の酸化が促進
され、導電パタ−ンの抵抗が高くなり、同じく好ましく
ない。In the present invention, as described above, this A
By heat treatment of the g-Pd mixed powder in an oxidizing atmosphere,
Oxidation of Pd mainly occurs, and it is possible to control the state of contraction of the conductive pattern at the time of subsequent firing. That is, the Ag-Pd mixed powder obtained by the heat treatment in the oxidizing atmosphere exhibits such a property that the shrinkage start temperature changes to a lower temperature side with an increase in the amount of oxygen in the oxidizing atmosphere. It can be matched with the shrinkage of the ceramic green sheet during firing. Here, the amount of oxygen contained is 0.2 to 4.7% by weight,
In particular, 0.5 to 4.5% by weight is preferable. 0.2% by weight
If the oxygen content is less than this, the adhesion between the produced conductive pattern and the ceramic circuit board is poor, and the bonding strength is low, which is not preferable. On the other hand, if the amount of oxygen exceeds 4.7% by weight, the oxidation of the Ag powder is promoted, and the resistance of the conductive pattern becomes high, which is not preferable.
【００１２】本発明において、導電パタ−ン形成用粉末
の作製において、Ｍｎの酸化物を添加することは、ハン
ダ濡れの向上のために、特に好ましい。Ｍｎの酸化物添
加によるハンダ濡れ性改善の理由は、定かではないが、
導電体にＭｎの酸化物を添加することにより、ガラス層
の形成を抑制する作用が生ずるものと考えられる。添加
に用いられるＭｎの酸化物としては、ＭｎＯ、Ｍｎ
Ｏ2、Ｍｎ2Ｏ3、Ｍｎ3Ｏ4等が挙げられる。この添加量
としては、ＭｎＯ2換算で１〜５重量部であり、特に３
重量部以下が好ましい。５重量部を越える量を添加する
と、導電体抵抗が高くなり、また、かえってハンダ濡れ
性が悪くなる傾向となるので、好ましくない。In the present invention, it is particularly preferable to add an oxide of Mn in the preparation of the conductive pattern forming powder in order to improve solder wettability. The reason for the improvement of solder wettability by adding Mn oxide is not clear,
It is considered that the addition of the Mn oxide to the conductor has an effect of suppressing the formation of the glass layer. Mn oxides used for the addition include MnO and Mn.
O 2 , Mn 2 O 3 , Mn 3 O 4 and the like can be mentioned. The addition amount is 1 to 5 parts by weight in terms of MnO 2 ,
It is preferably at most part by weight. If the amount exceeds 5 parts by weight, the resistance of the conductor increases and the solder wettability tends to deteriorate, which is not preferable.
【００１３】上記のようにして得られた導電パタ−ン形
成用粉末にビヒクルを添加し、更に、セラミックス基板
との密着性向上を目的として、少量のガラス成分を加
え、例えば、３本ロ−ルミル等の慣用の方法で混合し、
セラミックグリ−ンシ−ト用導電性ペ−ストを調製す
る。このビヒクルとしては、種々の有機ビヒクルを使用
することができるが、エチルセルロ−スをα−テルピネ
オ−ルに溶解したものを使用するのが好ましい。そし
て、この導電性ペ−ストをセラミックグリ−ンシ−トに
所定形状で印刷した後、焼成してセラミックス回路基板
を製造する。A vehicle is added to the conductive pattern forming powder obtained as described above, and a small amount of a glass component is added for the purpose of improving the adhesion to the ceramic substrate. Mixed by a conventional method such as Lumil,
A conductive paste for a ceramic green sheet is prepared. As this vehicle, various organic vehicles can be used, but it is preferable to use one obtained by dissolving ethyl cellulose in α-terpineol. Then, the conductive paste is printed on a ceramic green sheet in a predetermined shape, and then fired to manufacture a ceramic circuit board.
【００１４】[0014]
【実施例】以下、本発明の実施例を比較例と共にあげ、
本発明をより詳細に説明する。 （実施例１〜９）平均粒径１μｍのアルミナ粉末５０重
量％とＳｉＯ2−Ｂ2Ｏ3−ＰｂＯ系ガラス５０重量％と
を混合し、この混合粉末にアクリル樹脂及び溶剤を加え
てスラリ−を作製した。このスラリ−をドクタ−ブレイ
ド装置で塗工し（厚さ０．５ｍｍ）、低温焼成セラミッ
クス回路基板用セラミックグリ−ンシ−トを得た。EXAMPLES Examples of the present invention will be described below together with comparative examples.
The present invention will be described in more detail. (Examples 1 to 9) 50% by weight of alumina powder having an average particle size of 1 μm and 50% by weight of SiO 2 —B 2 O 3 —PbO-based glass were mixed, and an acrylic resin and a solvent were added to the mixed powder to obtain a slurry. Was prepared. The slurry was applied with a doctor blade device (thickness: 0.5 mm) to obtain a ceramic green sheet for a low-temperature fired ceramic circuit board.
【００１５】一方、導電性ペ−スト用原料粉末（Ａｇ粉
末及びＰｄ粉末）を混合し、この混合粉末を空気中で加
熱して導電パタ−ン形成用粉末を作製した（実施例１〜
６）。また、この導電パタ−ン形成用粉末に、ＭｎＯ2
を添加した（実施例７〜９）。このＡｇ粉末とＰｄ粉末
の配合量及びＭｎＯ2の添加量並びに加熱処理温度を表
１に示した。次に、α−テルピネオ−ルにエチルセルロ
−スを溶解してビヒクルを調製し、このビヒクル中に上
記混合粉末を３本ロ−ルミルで混合し、導電性ペ−スト
を得た。この導電性ペ−ストを前記したセラミックグリ
−ンシ−ト上に、幅１５０μｍのパタ−ン及び２ｍｍス
クエアのパタ−ンをスクリ−ン印刷し、４００℃で４時
間脱バインダ−した後、８５０℃で焼成してセラミック
ス回路基板を得た。On the other hand, the raw material powder for conductive paste (Ag powder and Pd powder) was mixed, and this mixed powder was heated in air to prepare a conductive pattern forming powder (Examples 1 to 5).
6). Further, MnO 2 was added to the conductive pattern forming powder.
Was added (Examples 7 to 9). Table 1 shows the amounts of the Ag powder and the Pd powder, the amounts of MnO 2 added, and the heat treatment temperatures. Next, ethyl cellulose was dissolved in α-terpineol to prepare a vehicle, and the mixed powder was mixed in the vehicle with a three-roll mill to obtain a conductive paste. This conductive paste is screen-printed on the above-mentioned ceramic green sheet with a pattern of 150 μm width and a pattern of 2 mm square, and after removing the binder at 400 ° C. for 4 hours, 850. It was fired at ℃ to obtain a ceramic circuit board.
【００１６】得られた回路基板上の導電パタ−ンの剥離
を目視により観察した。また、２ｍｍスクエアを用いて
ハンダ濡れ性をロジン入りフラックス中に侵漬し、２３
０℃でＳｎ−Ｐｂ共晶ハンダ（Ａｇ２％入り）に５秒間
侵漬し、ハンダ濡れ面積率を画像処理により調べた。導
電パタ−ンの接着強度を２ｍｍスクエアのパッド上にφ
０．８ｍｍのＳｎメッキ銅線をハンダ付けし、ピ−ル法
により測定した。その結果を同じく表１に示した。The peeling of the conductive pattern on the obtained circuit board was visually observed. Further, the solder wettability was immersed in a flux containing rosin using a 2 mm square,
It was immersed in Sn-Pb eutectic solder (containing 2% Ag) at 0 ° C for 5 seconds, and the solder wet area ratio was examined by image processing. Adhesion strength of conductive pattern is φ on 2mm square pad.
A 0.8 mm Sn-plated copper wire was soldered and measured by a peel method. The results are also shown in Table 1.
【００１７】（比較例１、２）比較のために、導電パタ
−ン形成用粉末として、ＡｇとＰｄの混合粉末（比較例
１）及びＡｇ、Ｐｄ、ＭｎＯ2の混合粉末（比較例２）
を使用し、そして、該混合粉末を空気中で加熱しない点
を除いて、上記実施例と同一条件で導電ペ−ストを調製
し、セラミックス回路基板を作製した。得られた回路基
板上の導電パタ−ンについて、上記実施例と同一の試験
を行なった。その結果を同じく表１に併記した。Comparative Examples 1 and 2 For comparison, as a conductive pattern forming powder, a mixed powder of Ag and Pd (Comparative Example 1) and a mixed powder of Ag, Pd and MnO 2 (Comparative Example 2)
And a conductive paste was prepared under the same conditions as in the above example, except that the mixed powder was not heated in air, to produce a ceramic circuit board. The same test as in the above embodiment was performed on the conductive pattern on the obtained circuit board. The results are also shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１から明らかなように、導電パタ−ン形
成用粉末として、Ａｇ粉末とＰｄ粉末の混合粉末を予め
空気中で加熱したものを用いた実施例１〜９では、すべ
て剥離が認められず、また、ハンダ濡れ性並びに接着強
度が良好であることが理解できる。これに対して、空気
中で加熱処理しない比較例１、２では、いずれも剥離が
認められた。また、酸素量として０．５〜４．３％含有
する実施例２〜５では、ハンダ濡れ性が９２％以上、接
着強度が１．９Ｋｇ以上を示し、この酸素量範囲外の
０．２％（実施例１）、４．７％（実施例６）のものに
比し、ハンダ濡れ性、接着強度とも優れたものであっ
た。更に、ＭｎＯ2を添加した実施例７〜９では、Ｍｎ
Ｏ2の添加により、添加しないものに比し、ハンダ濡れ
性、接着強度とも優れたものであり、特に、ＭｎＯ2の
添加量が３％である実施例３は、最良の効果が得られ
た。As is clear from Table 1, in Examples 1 to 9 in which a mixed powder of an Ag powder and a Pd powder was previously heated in the air as the conductive pattern forming powder, peeling was all observed. However, it can be understood that solder wettability and adhesive strength are good. On the other hand, in Comparative Examples 1 and 2 in which heat treatment was not performed in the air, peeling was observed in each case. Further, in Examples 2 to 5 containing 0.5 to 4.3% as an oxygen amount, the solder wettability was 92% or more, and the bonding strength was 1.9 kg or more. (Example 1) The solder wettability and the adhesive strength were superior to those of 4.7% (Example 6). Further, in Examples 7 to 9 to which MnO 2 was added, MnO 2 was used.
With the addition of O 2 , the solder wettability and the adhesive strength were superior to those without the addition, and in particular, Example 3 in which the addition amount of MnO 2 was 3% showed the best effect. .
【００２０】[0020]
【発明の効果】本発明は、以上詳記したとおり、導電パ
タ−ン形成用粉末として、Ａｇ−Ｐｄ系混合粉末を予め
酸化雰囲気中で加熱処理した粉末を使用するものであ
り、これによって、セラミックス基板と導電パタ−ン
（導電体）とが焼成後に剥離することがなく、しかも、
端子のハンダ濡れが良好であり、ハンダ濡れ性並びに接
着強度に優れたセラミックス回路基板が得られる効果が
生ずる。更に、Ｍｎの酸化物を添加することにより、ハ
ンダ濡れ性の改善効果が生じ、より一層ハンダ濡れ性、
接着強度が向上する効果が生ずる。According to the present invention, as described in detail above, a powder obtained by heat-treating an Ag-Pd-based mixed powder in an oxidizing atmosphere in advance is used as the conductive pattern forming powder. The ceramic substrate and the conductive pattern (conductor) do not peel off after firing, and
The terminal has good solder wettability, and the effect of obtaining a ceramic circuit board having excellent solder wettability and adhesive strength is obtained. Further, by adding an oxide of Mn, an effect of improving solder wettability is produced, and solder wettability is further improved.
The effect of improving the adhesive strength is produced.
Claims (4)
５〜３０重量部の混合物を酸化雰囲気中で加熱処理して
なることを特徴とするセラミックス回路基板用導電パタ
−ン形成用粉末組成物。A powder composition for forming a conductive pattern for a ceramic circuit board, wherein a mixture of 70 to 95 parts by weight of an Ag powder and 5 to 30 parts by weight of a Pd powder is heat-treated in an oxidizing atmosphere. .
が０．２〜４．７重量％である請求項１に記載のセラミ
ックス回路基板用導電パタ−ン形成用粉末組成物。2. The powder composition for forming a conductive pattern for a ceramic circuit board according to claim 1, wherein the amount of oxygen in the heat-treated powder composition is 0.2 to 4.7% by weight.
５〜３０重量部の混合物を酸化雰囲気中で加熱処理して
なる粉末組成物に、更に、Ｍｎの酸化物を添加してなる
ことを特徴とするセラミックス回路基板用導電パタ−ン
形成用粉末組成物。3. A powder composition obtained by heat-treating a mixture of 70 to 95 parts by weight of Ag powder and 5 to 30 parts by weight of Pd powder in an oxidizing atmosphere, further comprising adding an oxide of Mn. A powder composition for forming a conductive pattern for a ceramic circuit board.
１〜５重量部である請求項３に記載のセラミックス回路
基板用導電パタ−ン形成用粉末組成物。4. The powder composition for forming a conductive pattern for a ceramic circuit board according to claim 3, wherein the amount of the Mn oxide added is 1 to 5 parts by weight in terms of MnO 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19701691A JP2931444B2 (en) | 1991-07-11 | 1991-07-11 | Powder composition for forming conductive patterns for ceramic circuit boards |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19701691A JP2931444B2 (en) | 1991-07-11 | 1991-07-11 | Powder composition for forming conductive patterns for ceramic circuit boards |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0521919A JPH0521919A (en) | 1993-01-29 |
| JP2931444B2 true JP2931444B2 (en) | 1999-08-09 |
Family
ID=16367379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19701691A Expired - Lifetime JP2931444B2 (en) | 1991-07-11 | 1991-07-11 | Powder composition for forming conductive patterns for ceramic circuit boards |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2931444B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1043208A (en) * | 1996-08-05 | 1998-02-17 | Matsushita Satoyuki | Manufacturing device and method for synthetic resin plate artificial tooth |
-
1991
- 1991-07-11 JP JP19701691A patent/JP2931444B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0521919A (en) | 1993-01-29 |
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