JP3495890B2 - Conductive paste composition, method for producing conductive paste composition, method for forming surface conductor, and ceramic multilayer substrate - Google Patents
Conductive paste composition, method for producing conductive paste composition, method for forming surface conductor, and ceramic multilayer substrateInfo
- Publication number
- JP3495890B2 JP3495890B2 JP27445197A JP27445197A JP3495890B2 JP 3495890 B2 JP3495890 B2 JP 3495890B2 JP 27445197 A JP27445197 A JP 27445197A JP 27445197 A JP27445197 A JP 27445197A JP 3495890 B2 JP3495890 B2 JP 3495890B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive paste
- paste composition
- firing
- silver
- rhodium oxide
- 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 - Fee Related
Links
- 239000004020 conductor Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 53
- 239000000919 ceramic Substances 0.000 title claims description 27
- 239000000758 substrate Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 78
- 238000010304 firing Methods 0.000 claims description 52
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 46
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 46
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 27
- 239000002344 surface layer Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 13
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002241 glass-ceramic Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 description 50
- 239000004332 silver Substances 0.000 description 50
- 238000007747 plating Methods 0.000 description 28
- 229910000679 solder Inorganic materials 0.000 description 18
- 239000000843 powder Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000009736 wetting Methods 0.000 description 11
- 239000010937 tungsten Substances 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000010344 co-firing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000000611 regression analysis Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001364 causal effect Effects 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XBBXDTCPEWHXKL-UHFFFAOYSA-N rhodium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Rh+3].[Rh+3] XBBXDTCPEWHXKL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Conductive Materials (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、焼成処理されるこ
とによって基板上に導体を形成する導電ペースト組成物
と、その導電ペースト組成物の製造方法、前記導電ペー
スト組成物を使った表層導体形成方法、および前記導電
ペースト組成物を使って作製されたセラミック多層基板
に関する。TECHNICAL FIELD The present invention relates to a conductive paste composition for forming a conductor on a substrate by firing, a method for producing the conductive paste composition, and formation of a surface layer conductor using the conductive paste composition. The present invention relates to a method and a ceramic multilayer substrate made using the conductive paste composition.
【０００２】[0002]
【従来の技術】近年、移動体通信分野の進展が著しく、
それら高周波用途で用いるのに適した材料として、低抵
抗導体を用い、低ロスであるガラスセラミックが注目さ
れている。この種のガラスセラミックは、１０００℃以
下での低温焼成が可能で、通常の焼成温度は８４０〜９
５０℃の範囲にあることが多い。また、結晶化ガラス
や、ガラスとフィラーとを反応させるようなタイプで
は、焼成時における最高温度での保持時間が、例えば３
０分〜２時間と比較的長い。2. Description of the Related Art In recent years, remarkable progress has been made in the field of mobile communication.
As a material suitable for use in such high frequency applications, a glass ceramic, which uses a low resistance conductor and has a low loss, has been drawing attention. This kind of glass ceramic can be fired at a low temperature of 1000 ° C. or lower, and the usual firing temperature is 840-9.
It is often in the range of 50 ° C. In the case of crystallized glass or a type in which glass and a filler are reacted, the holding time at the highest temperature during firing is, for example, 3
It is relatively long, from 0 minutes to 2 hours.
【０００３】[0003]
【発明が解決しようとする課題】ところで、上記ガラス
セラミックを用いた製品の表層導体の材料には、従来
は、銀をはじめとする各種貴金属材料が用いられてき
た。しかしながら、融点が９６０℃程度の銀をはじめ、
融点が１０００℃前後の貴金属材料は、上述の如きガラ
スセラミックとの同時焼成を行った際に、基板上の表層
導体が過焼結ぎみになって、表層導体がポーラスな組織
になってしまうことが多々あった。そして、このような
過焼結状態になると、表層導体が高抵抗になったり、メ
ッキのりやハンダ濡れが悪くなる等、この種の導体に必
要な特性が大幅に劣化するという問題があった。また、
ポーラスな組織となった表層導体にメッキ処理を施す
と、表層導体のポアから酸やアルカリ等の処理液が浸入
し、表層導体内部の組織間、あるいは表層導体と基板と
の界面を侵し、表層導体の密着強度が大幅に劣化すると
いう問題もあった。By the way, conventionally, various noble metal materials such as silver have been used as the material of the surface layer conductor of the product using the above glass ceramic. However, including silver with a melting point of about 960 ° C,
When a precious metal material with a melting point of about 1000 ° C. is co-fired with the glass ceramic as described above, the surface conductor on the substrate becomes oversintered and the surface conductor has a porous structure. There were many. Then, in such an over-sintered state, there has been a problem that the surface layer conductor has a high resistance, the plating paste and the solder wettability are deteriorated, and the properties required for this type of conductor are significantly deteriorated. Also,
When the surface conductor with a porous structure is plated, the treatment liquid such as acid or alkali penetrates from the pores of the surface layer conductor, and the structure inside the surface layer conductor or the interface between the surface layer conductor and the substrate is invaded. There is also a problem that the adhesion strength of the conductor is significantly deteriorated.
【０００４】ここで、単に表層導体の過焼結を避けるこ
とだけを考えれば、内層配線を形成した基板を表層導体
の無い状態で焼成した後、表層に２次メタライズでメッ
キ性の良い銀導体を焼き付ける方法はある。しかし、こ
れでは工数の増加になるため、コスト的に不利である。
また、キャビティを有する形状の製品の場合、キャビテ
ィ内に銀導体を２次メタライズで形成するのは困難であ
る。Here, considering only to avoid oversintering of the surface conductor, a silver conductor having a good plating property is formed by firing the substrate on which the inner layer wiring is formed without the surface conductor and then secondary metallizing the surface layer. There is a way to burn. However, this increases the man-hours, which is disadvantageous in cost.
In the case of a product having a cavity, it is difficult to form a silver conductor in the cavity by secondary metallization.
【０００５】また、銀／Ｐｄ、銀／Ｐｔといった銀系合
金を用いれば、メッキ処理が不要な表層導体を形成でき
るので、メッキ処理の処理液によって引き起こされる問
題は解決される。しかし、銀／Ｐｄを用いる方法は、同
時焼成時に内層の銀導体との接続部分に互いの熱拡散速
度の違いから断線（カーケンドール効果）を起こしやす
いので、同時焼成によるコストの低下は望めない。一
方、銀／Ｐｔを用いる方法は、同時焼成時に内層の銀導
体との接続性は良好であるが、銀入りハンダ以外のハン
ダに対する耐久性に問題がある。If a silver-based alloy such as silver / Pd or silver / Pt is used, a surface layer conductor which does not require plating can be formed, so that the problems caused by the plating solution can be solved. However, in the method using silver / Pd, disconnection (Kirkendall effect) is likely to occur in the connection portion with the silver conductor in the inner layer due to the difference in thermal diffusion rate between them during co-firing, so cost reduction due to co-firing cannot be expected. . On the other hand, the method using silver / Pt has good connectivity with the silver conductor of the inner layer at the time of simultaneous firing, but has a problem in durability against solder other than silver-containing solder.
【０００６】つまり、上述の如き手段では、ガラスセラ
ミック基板と表層導体との同時焼成によるコストダウン
を図りながら、メッキのり、ハンダ濡れ、および密着強
度といった特性のすべてに優れた表層導体を得ること
は、きわめて困難であった。本発明は、上記問題を解決
するためになされたものであり、その目的は、ガラスセ
ラミック基板と表層導体との同時焼成を行った場合で
も、メッキのり、ハンダ濡れ、および密着強度といった
特性のすべてに優れた表層導体を得ることのできる新規
な導電ペースト組成物を提供することにある。また、そ
の導電ペースト組成物の製造方法、前記導電ペースト組
成物を使った表層導体形成方法、および前記導電ペース
ト組成物を使って作製されたセラミック多層基板を提供
することにある。That is, according to the above-mentioned means, it is possible to obtain a surface layer conductor excellent in all of the characteristics such as plating, solder wetting, and adhesion strength while reducing the cost by simultaneously firing the glass ceramic substrate and the surface layer conductor. It was extremely difficult. The present invention has been made to solve the above problems, and its object is to achieve all of the characteristics such as plating paste, solder wetting, and adhesion strength even when co-firing a glass ceramic substrate and a surface layer conductor. Another object of the present invention is to provide a novel conductive paste composition capable of obtaining an excellent surface layer conductor. Another object of the present invention is to provide a method for manufacturing the conductive paste composition, a method for forming a surface layer conductor using the conductive paste composition, and a ceramic multilayer substrate manufactured using the conductive paste composition.
【０００７】[0007]
【課題を解決するための手段、および発明の効果】この
課題を解決するために、本発明の導電ペースト組成物
は、請求項１記載のように、銀粉末、平均粒径０．５〜
２μｍのタングステン粉末、酸化ロジウム、および有機
ビヒクルが混合されてペースト化された混合物であっ
て、前記銀粉末に対する重量比で、タングステン粉末を
３〜５％、酸化ロジウムを１００〜６００ｐｐｍ含有し
ていることを特徴とする。Means for Solving the Problem and Effect of the Invention In order to solve this problem, the conductive paste composition of the present invention has a silver powder and an average particle size of 0.5 to 0.5 as described in claim 1.
2μm of tungsten powder, oxidation rhodium and organic
It is a mixture formed by mixing a vehicle and a paste, and contains 3 to 5% of tungsten powder and 100 to 600 ppm of rhodium oxide in a weight ratio with respect to the silver powder.
【０００８】この導電ペースト組成物において、銀（Ａ
ｇ）粉末は、最終的に銀導体を形成する成分である。銀
粉末については、この種の導電ペースト組成物において
一般に用いられるものであれば特に限定されない。より
具体的な例を挙げるとすれば、例えば平均粒径１〜１０
μｍ程度の銀粉末を用いるとよい。In this conductive paste composition, silver (A
g) Powder is a component that finally forms a silver conductor. The silver powder is not particularly limited as long as it is one generally used in this kind of conductive paste composition. To give a more specific example, for example, the average particle size is 1 to 10
It is preferable to use silver powder of about μm.
【０００９】また、タングステン（Ｗ）粉末は、焼成に
より得られる銀導体の表面に微細な窪みを形成する作用
を有する。この窪みには、銀導体表面にメッキ処理を施
す際に、メッキ被膜の一部が侵入する。そのため、これ
がアンカーとなって銀導体に対するメッキ被膜の密着性
が高まる。すなわち、上記窪みによる投錨効果が現れ
る。また、このメッキ処理が無電解メッキである場合
は、タングステンを添加した結果形成された前記窪み
に、触媒となるパラジウム核が析出しやすくなるため、
触媒活性を高めるという効果もある。The tungsten (W) powder has the function of forming fine depressions on the surface of the silver conductor obtained by firing. A part of the plating film penetrates into the recess when the silver conductor surface is plated. Therefore, this serves as an anchor to improve the adhesion of the plated coating to the silver conductor. That is, the anchoring effect due to the depression appears. Further, when the plating treatment is electroless plating, in the recess formed as a result of adding tungsten, palladium nuclei serving as a catalyst are easily deposited,
It also has the effect of increasing the catalytic activity.
【００１０】ここで、このタングステン粉末について
は、銀粉末に対する重量比で３〜５％含有されているこ
とが重要である。タングステン粉末の含有量が銀粉末に
対する重量比で３％を下回ると、メッキ被膜の密着力が
弱くなり、メッキはがれが生じやすくなる。その一方、
５％を上回ると、タングステン粉末が銀導体表面に浮
き、良好なメッキ性を確保することが困難になる。ま
た、タングステン粉末は、平均粒径０．５〜２μｍのも
のを用いることも重要である。平均粒径が０．５μｍを
下回るものを用いると、上記窪みが小さくなりすぎ、一
方、平均粒径が２μｍを上回るものでは、上記窪みが大
きくなりすぎる。いずれの場合も投錨効果が弱まって、
銀導体に対するメッキ被膜の密着性は低下することにな
る。Here, it is important that the tungsten powder is contained in an amount of 3 to 5% by weight with respect to the silver powder. When the content of the tungsten powder is less than 3% by weight with respect to the silver powder, the adhesion of the plated coating becomes weak and the plating is liable to peel off. On the other hand,
If it exceeds 5%, the tungsten powder floats on the surface of the silver conductor, making it difficult to secure good plating properties. It is also important to use tungsten powder having an average particle size of 0.5 to 2 μm. If the average particle diameter is less than 0.5 μm, the above-mentioned depressions become too small, while if the average particle diameter exceeds 2 μm, the above-mentioned depressions become too large. In any case, the anchoring effect weakens,
The adhesion of the plated coating to the silver conductor will be reduced.
【００１１】さらに、酸化ロジウム（Ｒｈ2 Ｏ3 ）は、
焼成により得られる銀導体が、ポーラスな組織になるの
を抑制する作用を有する。そのため、銀導体表面にメッ
キ処理を施す際に使用する薬液が、銀導体の組織内に浸
入しにくくなる。その結果、銀導体の基材に対する密着
性が良好に保たれることになる。Further, rhodium oxide (Rh 2 O 3 ) is
It has the effect of suppressing the silver conductor obtained by firing from becoming a porous structure. Therefore, it becomes difficult for the chemical solution used for plating the surface of the silver conductor to enter the structure of the silver conductor. As a result, good adhesion of the silver conductor to the base material is maintained.
【００１２】ここで、酸化ロジウムについては、銀粉末
に対する重量比で１００〜６００ｐｐｍ含有されている
ことが重要である。酸化ロジウムが１００ｐｐｍを下回
ると、８４０〜９５０℃での基板との同時焼成時に発生
する銀導体の異常粒成長を抑制しきれず、銀導体がポー
ラスな組織になりやすい。その一方、６００ｐｐｍを上
回ると、銀粉末の焼成が抑制され過ぎて、メタライズ厚
みの差により焼け具合にむらが出てしまい、良好なメッ
キ性を確保することが難しくなる。Here, it is important that the rhodium oxide is contained in a weight ratio of 100 to 600 ppm relative to the silver powder. If the rhodium oxide content is less than 100 ppm, the abnormal grain growth of the silver conductor that occurs during simultaneous firing with the substrate at 840 to 950 ° C. cannot be suppressed, and the silver conductor tends to have a porous structure. On the other hand, when the amount exceeds 600 ppm, the firing of the silver powder is excessively suppressed, and unevenness in the degree of burning occurs due to the difference in the metallized thickness, making it difficult to secure good plating properties.
【００１３】さらに、ペースト化に当たって必要な成分
として、有機ビヒクルが加えられる。但し、有機ビヒク
ルは、その添加量等が、本発明の本質に影響を及ぼすも
のではない。 Further , the components necessary for forming the paste
As an organic vehicle is added. However, organic
In addition, the addition amount and the like do not affect the essence of the present invention.
【００１４】以上説明したような導電ペースト組成物に
よれば、上記のような特徴的な組成となっているため、
各成分の作用により、ガラスセラミック基板との同時焼
成を行った場合でも、形成される銀導体がポーラスな組
織とならない。その結果、メッキのり、ハンダ濡れ、お
よび密着強度などの特性に優れた銀導体を得ることがで
きる。According to the conductive paste composition as described above, since it has the characteristic composition as described above,
Due to the action of each component, the formed silver conductor does not have a porous structure even when co-firing with the glass ceramic substrate. As a result, it is possible to obtain a silver conductor having excellent characteristics such as plating glue, solder wetting, and adhesion strength.
【００１５】ちなみに、本発明の導電ペースト組成物に
おいて、酸化ロジウムについては、酸化ロジウムの粉末
を添加してあればもちろんよいが、これ以外にも、酸化
雰囲気下での加熱処理によって酸化ロジウムとなるよう
なロジウム系物質を混合しておいて、混合物中において
酸化ロジウムを生成してもよい。このようなロジウム系
物質としては、例えば有機ロジウムを考え得る。有機ロ
ジウムを含有する導電ペースト組成物としては、既に日
本国特許第２５０３９７４号の特許発明が公知である。
しかし、上記特許発明は、基材に塗布される導電ペース
ト組成物中に有機ロジウムを含有させてあるものであ
る。そのため、特に、有機ロジウムの含有量が１００ｐ
ｐｍを上回るような場合には、有機ロジウムが原因とな
って、焼成前のセラミックグリーン体を樹脂抜きする工
程でメタライズはがれを起こしやすい。また、ペースト
のチクソトロピー性を悪化させて、導電ペーストのスク
リーン印刷が困難になるなどの問題が生じやすい。これ
に対し、本発明の導電ペースト組成物は、仮に有機ロジ
ウムを添加した場合であっても、あらかじめ加熱処理を
施すなどして、導電ペースト組成物中の有機ロジウムが
酸化ロジウムに変えられ、その上で基材に塗布されるこ
とになるので、上述の如き問題を招くことはない。By the way, in the conductive paste composition of the present invention, as for rhodium oxide, of course, it is sufficient if powder of rhodium oxide is added, but in addition to this, it is converted into rhodium oxide by heat treatment in an oxidizing atmosphere. Such rhodium-based substances may be mixed and rhodium oxide may be produced in the mixture. As such a rhodium-based substance, for example, organic rhodium can be considered. As a conductive paste composition containing an organic rhodium, the patented invention of Japanese Patent No. 2503974 is already known.
However, in the above-mentioned patented invention, organic rhodium is contained in the conductive paste composition applied to the substrate. Therefore, especially when the content of organorhodium is 100 p
When it exceeds pm, metallization peeling is likely to occur in the step of removing the resin from the ceramic green body before firing due to organic rhodium. In addition, the thixotropy of the paste is deteriorated, which makes it difficult to screen-print the conductive paste. On the other hand, the conductive paste composition of the present invention, even if the organic rhodium is added, is subjected to heat treatment in advance, the organic rhodium in the conductive paste composition is changed to rhodium oxide, Since it is applied to the base material above, the above problems do not occur.
【００１６】ところで、本発明の導電ペースト組成物
は、上述の主要な成分を適宜混合することによっても得
られるが、より望ましくは、請求項２記載のように、前
記銀粉末および前記酸化ロジウムの混合物が、２００〜
４００℃の範囲で５〜３０分間加熱処理され、その加熱
処理された混合物に対して前記タングステン粉末および
前記有機ビヒクルが混合されているものであるとよい。By the way, the conductive paste composition of the present invention can be obtained by appropriately mixing the above-mentioned main components, but more preferably, as described in claim 2, the silver powder and the rhodium oxide are used. The mixture is 200 ~
Heat treatment is performed in the range of 400 ° C. for 5 to 30 minutes, and the tungsten powder and the tungsten powder are added to the heat-treated mixture.
It is preferable that the organic vehicle is mixed.
【００１７】このような導電ペースト組成物は、銀粉末
と酸化ロジウムとが確実に接触する状態で加熱処理を受
けているため、導電ペースト組成物中において、銀粉末
および酸化ロジウムが相互に固定された複合粒子となっ
ている。そして、この複合粒子と他の成分（タングステ
ン粉末および有機ビヒクル）とが混合された物となって
いる。そのため、他の成分（タングステン粉末および有
機ビヒクル）によって銀粉末との接触が阻害された状態
にある酸化ロジウムは激減する。これにより、酸化ロジ
ウムによる銀導体の異常粒成長を抑制する効果が高ま
る。その結果、焼成により得られる銀導体がポーラスな
組織になるのを、より確実に防止できるようになる。Since such a conductive paste composition is subjected to heat treatment in a state where the silver powder and the rhodium oxide are surely in contact with each other, the silver powder and the rhodium oxide are fixed to each other in the conductive paste composition. It is a composite particle. The composite particles are mixed with other components ( tungsten powder and organic vehicle) . Therefore, other components ( tungsten powder and
The rhodium oxide in the state where the contact with the silver powder is blocked by the machine vehicle) is drastically reduced. This enhances the effect of suppressing abnormal grain growth of the silver conductor due to rhodium oxide. As a result, it is possible to more reliably prevent the silver conductor obtained by firing from having a porous structure.
【００１８】以上の説明から明らかなように、本発明の
導電ペースト組成物を製造するに当たっては、請求項３
記載のように、銀粉末に対し、酸化ロジウムを銀粉末に
対する重量比で１００〜６００ｐｐｍ混合し、その銀粉
末および酸化ロジウムの混合物を、２００〜４００℃の
範囲で５〜３０分間加熱処理し、その加熱処理された銀
粉末および酸化ロジウムの混合物に対し、平均粒径０．
５〜２μｍ、銀粉末に対する重量比で３〜５％のタング
ステン粉末と、有機ビヒクルとを混合するとよい。As is apparent from the above description, in producing the conductive paste composition of the present invention, the method of claim 3 is used.
As described, rhodium oxide was mixed with silver powder in a weight ratio of 100 to 600 ppm with respect to silver powder, and the mixture of the silver powder and rhodium oxide was heat-treated in the range of 200 to 400 ° C. for 5 to 30 minutes, The heat-treated mixture of silver powder and rhodium oxide had an average particle size of 0.
It is advisable to mix an organic vehicle with a tungsten powder having a weight ratio of 5 to 2 μm and a weight ratio to the silver powder of 3 to 5% .
【００１９】このような製造方法によれば、請求項２に
記載したような優れた導電ペースト組成物を得ることが
できる。次に、本発明の表層導体形成方法は、請求項４
記載のように、請求項１または請求項２記載の導電ペー
スト組成物を、基材表面に塗布して焼成することによ
り、基材表面に所要形状の表層導体を形成する表層導体
形成方法であって、焼成温度Ｔ（℃）を、前記酸化ロジ
ウムの含有量Ｙ（ｐｐｍ）との関係で、６８４．７×Ｙ
0.044 ≦Ｔ≦９５０の範囲に調節して、前記焼成を行う
ことを特徴とする。According to such a manufacturing method, an excellent conductive paste composition as described in claim 2 can be obtained. Next, the method for forming a surface layer conductor according to the present invention comprises:
As described above, a method for forming a surface layer conductor, which comprises forming a surface layer conductor having a desired shape on the surface of a base material by applying the conductive paste composition according to claim 1 or 2 onto the surface of the base material and baking the composition. Then, the firing temperature T (° C.) is 684.7 × Y in relation to the content Y (ppm) of the rhodium oxide.
It is characterized in that the firing is performed by adjusting the range of 0.044 ≤ T ≤ 950.
【００２０】ここで、上記温度条件の上限値は、銀の融
点に起因する制限である。すなわち、この上限値を上回
る焼成温度では、銀が自由に流動し得る状態になりやす
いので、所期のパターンを描く表層導体を形成すること
は困難になる。一方、上記温度条件の下限値は、発明者
が多くの実験を重ねる中で得た知見であり、酸化ロジウ
ムの含有量Ｙと焼成温度Ｔの下限値との因果関係を、明
確に説明することは難しい。Here, the upper limit of the above temperature condition is a limit due to the melting point of silver. That is, at a firing temperature higher than this upper limit, silver tends to be in a state in which it can freely flow, so that it is difficult to form a surface layer conductor that draws a desired pattern. On the other hand, the lower limit value of the temperature condition is a finding obtained by the inventor through many experiments, and clearly explains the causal relationship between the rhodium oxide content Y and the lower limit value of the firing temperature T. Is difficult
【００２１】焼成温度Ｔは、通常、基材側から要求され
る温度条件等によって左右される。一方、上記酸化ロジ
ウムの含有量Ｙは、銀導体の面積や厚さなどに応じて妥
当な値が選定される。但し、酸化ロジウムがある含有量
となっている場合に、焼成時の温度条件がある下限値を
下回っていると、銀導体のメッキのり、ハンダ濡れ、密
着強度などの特性が劣化することがある。そのため、最
適な酸化ロジウムの含有量を選定するには、焼成温度を
も考慮する必要があり、このような選定作業は、必ずし
も容易なことではなかった。The firing temperature T usually depends on the temperature conditions required from the substrate side. On the other hand, as the content R of the rhodium oxide, an appropriate value is selected according to the area and thickness of the silver conductor. However, when the content of rhodium oxide is a certain content and the temperature condition during firing is below a certain lower limit value, the characteristics such as plating of silver conductor, solder wetting and adhesion strength may deteriorate. . Therefore, in order to select the optimum rhodium oxide content, it is necessary to consider the firing temperature as well, and such selection work has not always been easy.
【００２２】そこで、発明者は、まず酸化ロジウムの含
有量Ｙと焼成温度Ｔを種々組み合わせて実験を行い、そ
の関係をグラフ上にプロットしてみた。その結果、発明
者は、酸化ロジウムの含有量Ｙが大きくなるほど、焼成
温度Ｔの下限値を高くしないと、必要な特性を備えた銀
導体を得られない傾向があることを見いだした。この傾
向は、グラフから判断する限り、Ｔ＝ａ×Ｙb なる関係
式で近似可能であると考えられたため、電子計算機を使
った回帰分析により、上記温度条件の下限値を算出し、
上記条件を決定するに至った。Therefore, the inventor first carried out an experiment with various combinations of the rhodium oxide content Y and the firing temperature T, and plotted the relationship on a graph. As a result, the inventor has found that, as the content Y of rhodium oxide increases, unless the lower limit of the firing temperature T is increased, a silver conductor having necessary characteristics tends to be not obtained. This tendency was considered to be approximated by the relational expression T = a × Y b as far as it was judged from the graph. Therefore, the lower limit value of the temperature condition was calculated by regression analysis using an electronic calculator,
The above conditions were decided.
【００２３】このようにして完成された本発明の表層導
体形成方法によれば、焼成温度と酸化ロジウムの含有量
との関係を、従来よりも容易かつ速やかに決定すること
ができ、その条件下で形成された銀導体は、メッキの
り、ハンダ濡れ、密着強度などの特性に優れたものとな
る。According to the surface layer conductor forming method of the present invention completed in this way, the relationship between the firing temperature and the content of rhodium oxide can be determined more easily and quickly than before, under the conditions. The silver conductor formed in step 1 has excellent characteristics such as plating paste, solder wetting, and adhesion strength.
【００２４】次に、本発明のセラミック多層基板は、請
求項５記載の通り、請求項１または請求項２記載の導電
ペースト組成物を、セラミックグリーンシートに印刷し
て、同時焼成することにより、表層配線回路を形成した
ことを特徴とする。Next, in the ceramic multilayer substrate of the present invention, as described in claim 5, the conductive paste composition according to claim 1 or 2 is printed on a ceramic green sheet and simultaneously fired, It is characterized in that a surface wiring circuit is formed.
【００２５】このセラミック多層基板によれば、上記本
発明の導電ペースト組成物を用いて銀導体を形成してい
るので、同時焼成を行っても、メッキのり、ハンダ濡
れ、密着強度などの特性に優れた銀導体が形成されたも
のとなる。また特に、請求項６記載のセラミック多層基
板のように、前記セラミックグリーンシートが、８４０
〜９５０℃で焼成可能な低温焼成ガラスセラミックから
なるものは、特に同時焼成に長時間を要する場合も多い
が、その場合でも、メッキのり、ハンダ濡れ、および密
着強度といった特性のすべてに優れた銀導体が形成され
たものとなる。According to this ceramic multi-layer substrate, since the silver conductor is formed by using the above-mentioned conductive paste composition of the present invention, even if co-firing is performed, it is possible to obtain characteristics such as plating glue, solder wetting and adhesion strength. An excellent silver conductor is formed. Further, in particular, as in the ceramic multilayer substrate according to claim 6, the ceramic green sheet is 840.
Those made of low-temperature fired glass ceramics that can be fired at ~ 950 ° C often require a long time especially for co-firing, and even in that case, silver excellent in all characteristics such as plating glue, solder wetting, and adhesion strength. A conductor is formed.
【００２６】さらに、請求項７記載のセラミック多層基
板のように、前記導電ペースト組成物および前記セラミ
ックグリーンシートが、焼成温度Ｔ（℃）を、前記酸化
ロジウムの含有量Ｙ（ｐｐｍ）との関係で、６８４．７
×Ｙ 0.044 ≦Ｔ≦９５０の範囲に調節して、同時焼成さ
れていると、焼成温度と酸化ロジウムの含有量が最適な
関係に調節された状態で焼成が行われているので、銀導
体のメッキのり、ハンダ濡れ、密着強度などの特性が、
より確実に優れたものとなる。Further, the ceramic multi-layer substrate according to claim 7.
Like the plate, the conductive paste composition and the ceramic
The green sheet at the firing temperature T (° C.)
684.7 in relation to the rhodium content Y (ppm)
× Y 0.044Adjust within the range of ≦ T ≦ 950 and co-fire
The optimum firing temperature and rhodium oxide content.
Since firing is performed in a state adjusted to the relationship,
Properties such as body plating, solder wetting, and adhesion strength
It will definitely be superior.
【００２７】[0027]
（１）銀ペーストの調製
まず、平均粒径３μｍの銀粉末１００ｇに対して、平均
粒径０．１μｍの酸化ロジウムを添加、混合した。酸化
ロジウムの添加量は、銀粉末に対する重量比で、９０，
１００，１１０，１６０，３００，５００，６００，６
５０，７００ｐｐｍの９種類とした。(1) Preparation of silver paste First, to 100 g of silver powder having an average particle size of 3 μm, rhodium oxide having an average particle size of 0.1 μm was added and mixed. The addition amount of rhodium oxide is 90, by weight ratio to silver powder.
100, 110, 160, 300, 500, 600, 6
Nine kinds of 50,700 ppm were used.
【００２８】続いて、この９種類の銀粉末と酸化ロジウ
ムとの混合物を、オーブン炉で最高温度４００℃で１０
分間加熱処理し、その後、平均粒径１．３μｍのタング
ステン粉末を添加、混合した。タングステン粉末の添加
量は、銀粉末に対する重量比で、２．５，３．５，４．
５，５．５％の４種類とした。Subsequently, the mixture of 9 kinds of silver powders and rhodium oxide was heated in an oven furnace at a maximum temperature of 400 ° C. for 10 times.
Heat treatment was performed for one minute, and then tungsten powder having an average particle diameter of 1.3 μm was added and mixed. The amount of the tungsten powder added was 2.5, 3.5, 4.
It was set to four kinds of 5, 5.5%.
【００２９】その後、有機ビヒクルとしてエチルセルロ
ース５ｇ、ＢＣＡ（ブチルカルビトールアセテート）２
０ｇを添加、混合した後、３本ロールミルで混練し、銀
ペーストを作製した。
（２）セラミックグリーンシートの調製
セラミック原料粉末としては、アルミナホウケイ酸ガラ
スの粉末とアルミナ粉末を用意した。ガラス粉末はＳｉ
Ｏ2 ：４３重量％、Ａ１2 Ｏ3 ：２８重量％、Ｂ
2 Ｏ3 ：８重量％、ＭｇＯ：８重量％、ＣａＯ：８重量
％、ＺｒＯ2 ：１重量％の割合でそれぞれの酸化物粉末
を混合し、溶融後、急冷してカレット状にし、さらに粉
砕して、平均粒径５μｍになるように作製した。一方、
アルミナ粉末は市販の低ソーダのα−アルミナ粉末で、
平均粒径３μｍのものを用意した。Thereafter, 5 g of ethyl cellulose and BCA (butyl carbitol acetate) 2 were used as an organic vehicle.
After adding and mixing 0 g, the mixture was kneaded with a three-roll mill to prepare a silver paste. (2) Preparation of Ceramic Green Sheet As the ceramic raw material powder, powder of alumina borosilicate glass and alumina powder were prepared. Glass powder is Si
O 2 : 43% by weight, A1 2 O 3 : 28% by weight, B
2 O 3 : 8% by weight, MgO: 8% by weight, CaO: 8% by weight, ZrO 2 : 1% by weight, the respective oxide powders are mixed, melted and then rapidly cooled to a cullet shape, and further crushed. Then, an average particle diameter of 5 μm was obtained. on the other hand,
Alumina powder is a commercially available low-soda α-alumina powder,
An average particle size of 3 μm was prepared.
【００３０】バインダーとしては、メタクリル酸エチル
系のアクリル樹脂を用意した。次に、アルミナ製のポッ
トに、上記のガラス粉末とアルミナ粉末を６：４の割合
で、総量が１０００ｇになるように入れた。更に溶剤と
してＭＥＫ（メチルエチルケトン）を２００ｇ、上記の
アクリル系樹脂を１００ｇ、可塑剤としてＤＯＰ（ジオ
クチルフタレート）を５０ｇ、分散剤を５ｇ、上記ポッ
トに入れて１０時間混合し、スラリーを得た。このスラ
リーから、公知のドクターブレード法により厚み０．４
ｍｍのセラミックグリーンシートを作製した。
（３）試料の作製
上記（２）のセラミックグリーンシートを４枚積層した
後、６０ｍｍ角に切断し、上記（１）の銀ペーストを用
いて、図１に示すように、１２個の２．４ｍｍ角の引っ
張り試験用パッド１０を、セラミックグリーンシート１
２に対してスクリーン印刷した。１２０℃で１０分間乾
燥した後、２５０℃で１０時間樹脂抜きを行った。その
後、連続ベルト炉を用いてセラミックと銀導体とを同時
焼成した。この時の焼成温度は、８４０，８６０，８８
０，９００，９１０，９３０，９５０℃の７種類とし、
それぞれ焼成時間は３０分とした。焼成後の収縮率は８
３％で、引っ張り試験用パッド１０の焼き上げ寸法は２
ｍｍ角、厚みは２０μｍとなっていた。
（４）試験方法
以下の試験Ａ〜Ｃを行った。An ethyl methacrylate-based acrylic resin was prepared as the binder. Next, the glass powder and the alumina powder were placed in an alumina pot at a ratio of 6: 4 so that the total amount was 1000 g. Further, 200 g of MEK (methyl ethyl ketone) as a solvent, 100 g of the above acrylic resin, 50 g of DOP (dioctyl phthalate) as a plasticizer, and 5 g of a dispersant were placed in the pot and mixed for 10 hours to obtain a slurry. From this slurry, a thickness of 0.4 is obtained by a known doctor blade method.
mm ceramic green sheets were produced. (3) Preparation of sample After stacking four ceramic green sheets of (2) above, the ceramic green sheets were cut into a 60 mm square, and using the silver paste of (1) above, as shown in FIG. The 4 mm square tensile test pad 10 is attached to the ceramic green sheet 1
2 was screen printed. After drying at 120 ° C. for 10 minutes, resin was removed at 250 ° C. for 10 hours. After that, the ceramic and the silver conductor were simultaneously fired using a continuous belt furnace. The firing temperature at this time is 840, 860, 88.
7 kinds of 0,900,910,930,950 ° C,
The firing time was 30 minutes. Shrinkage rate after firing is 8
At 3%, the baking size of the tensile test pad 10 is 2
The mm square and the thickness were 20 μm. (4) Test method The following tests A to C were performed.
【００３１】Ａ．メッキのり試験
上記試料を脱脂し、１０％硫酸で洗浄後、塩化パラジウ
ム溶液に浸け、引っ張り試験用パッド上に無電解Ｎｉ−
Ｐメッキを３μｍ、薄付けの置換Ａｕメッキを０．１μ
ｍかけた。洗浄、乾燥後、メッキの付きを外観検査でチ
ェックした。評価は、メッキが良好にのっている場合を
「○」、部分むらがある場合を「△」、メッキがのらな
い場合を「×」とした。A. Plating Glue Test The above sample was degreased, washed with 10% sulfuric acid, immersed in a palladium chloride solution, and electroless Ni-- was placed on the tensile test pad.
P plating 3 μm, thin replacement Au plating 0.1 μm
It took m. After washing and drying, the appearance of plating was checked by visual inspection. The evaluation was evaluated as “◯” when the plating was good, “Δ” when there was partial unevenness, and “x” when there was no plating.
【００３２】Ｂ．ハンダ濡れ試験
上記試験Ａの後、同試料を、２３０℃に加熱した６０％
Ｓｎ−４０％Ｐｂの共晶ハンダ浴に１０秒間ディッピン
グした。エタノールで洗浄した後、ハンダ濡れ性を外観
検査でチェックした。評価は、濡れが良好な場合を
「○」、部分的に濡れない場合を「△」、ほとんど濡れ
ない場合を「×」とした。B. Solder Wetting Test After the above test A, the same sample was heated to 230 ° C. to 60%.
Dip in a eutectic solder bath of Sn-40% Pb for 10 seconds. After washing with ethanol, the solder wettability was checked by visual inspection. In the evaluation, good wetness was evaluated as “◯”, partial wetness was evaluated as “Δ”, and almost no wetness was evaluated as “x”.
【００３３】Ｃ．密着強度試験
上記試験Ｂの後、同試料に対して、図２に示すように、
直径０．８ｍｍのニッケルメッキ付きの銅線１４をハン
ダ付けした。そして、ハンダ１６により固定された銅線
１４を、セラミックグリーンシート１２の表面に対して
９０度に曲げた。その状態で銅線１４を２０ｍｍ／分の
速度で、図示矢印Ｐ方向へ引っ張り、密着強度を測定し
た。評価は、２ｋｇ以上ある場合を合格と考える。
（５）総合評価
まず、酸化ロジウムの添加量と焼成温度について評価す
るため、タングステンの添加量を３．５％とした場合に
おける上記試験Ａ〜Ｃの結果を、下記表１および図３に
示す。なお、図３中においては、試験Ａ，Ｂとも「○」
かつ試験Ｃで２ｋｇ以上となった試料を「○」、残りの
試料を「●」でプロットした。また、表１中、「−」が
表記されている欄は試験未実施である。C. Adhesion Strength Test After the above test B, as shown in FIG.
A nickel-plated copper wire 14 having a diameter of 0.8 mm was soldered. Then, the copper wire 14 fixed by the solder 16 was bent at 90 degrees with respect to the surface of the ceramic green sheet 12. In this state, the copper wire 14 was pulled in the direction of arrow P in the drawing at a speed of 20 mm / min, and the adhesion strength was measured. When the evaluation is 2 kg or more, it is considered to pass. (5) Comprehensive Evaluation First, in order to evaluate the addition amount of rhodium oxide and the firing temperature, the results of the above tests A to C when the addition amount of tungsten is 3.5% are shown in Table 1 and FIG. 3 below. . In addition, in FIG. 3, both of the tests A and B are “◯”.
In addition, the sample that became 2 kg or more in the test C was plotted as "○", and the remaining samples were plotted as "●". Further, in Table 1, the column marked with "-" has not been tested.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表１および図３から明らかなように、酸化
ロジウムの含有量が１００ｐｐｍを下回ると、優れた特
性の銀導体を得ることができない。この傾向は、特に焼
成温度が高くなると顕著になる。これは、酸化ロジウム
の量が少なすぎて、過焼成を十分に抑制できないためと
考えられる。一方、酸化ロジウムの含有量が６００ｐｐ
ｍを上回っても、優れた特性の銀導体を得ることができ
ない。特に、焼成温度が低くなるとその傾向が顕著にな
る。これは、酸化ロジウムの量が多すぎて、焼成が抑制
され過ぎているためと考えられる。As is clear from Table 1 and FIG. 3, if the content of rhodium oxide is less than 100 ppm, a silver conductor having excellent characteristics cannot be obtained. This tendency becomes remarkable especially when the firing temperature is increased. It is considered that this is because the amount of rhodium oxide is too small to sufficiently suppress overfiring. On the other hand, the content of rhodium oxide is 600 pp
Even if it exceeds m, a silver conductor having excellent characteristics cannot be obtained. In particular, the tendency becomes remarkable when the firing temperature is lowered. It is considered that this is because the amount of rhodium oxide was too large and firing was suppressed too much.
【００３６】さらに、焼成温度は、９５０℃を上限とし
て試験を行っているが、これは、９５０℃を超える温度
で焼成を試みても、銀が流動して所期の表層導体を形成
することができないためである。一方、焼成温度の下限
は、酸化ロジウムの含有量により変動した。酸化ロジウ
ムの含有量Ｙが大きくなるほど、焼成温度Ｔの下限値を
高くしないと、優れた特性を備えた銀導体を得ることが
困難になる傾向がある。この傾向は、図３のグラフから
判断する限り、Ｔ＝ａ×Ｙb なる関係式で近似可能であ
ると考えられる。Further, the firing temperature is tested with an upper limit of 950 ° C. This means that even if firing is attempted at a temperature higher than 950 ° C., silver flows to form the desired surface layer conductor. This is because it cannot be done. On the other hand, the lower limit of the firing temperature varied depending on the content of rhodium oxide. As the content Y of rhodium oxide increases, unless the lower limit of the firing temperature T is increased, it tends to be difficult to obtain a silver conductor having excellent characteristics. It is considered that this tendency can be approximated by the relational expression T = a × Y b as far as judged from the graph of FIG.
【００３７】そこで、電子計算機を使った回帰分析によ
り、図３の縦軸方向最下位置にある「○」を通る最も確
からしい関係式を算出した。その結果、下記数式１を得
た。Therefore, the most probable relational expression passing through "o" at the lowest position in the vertical axis direction in FIG. 3 was calculated by regression analysis using an electronic computer. As a result, the following formula 1 was obtained.
【００３８】[0038]
【数１】Ｔ ＝ ６８４．７ × Ｙ0.044
ちなみに、上記数式１は、図３上では、図中に実線で示
すような曲線となる。以上の結果からは、酸化ロジウム
の含有量を１００〜６００ｐｐｍ、焼成温度Ｔを、酸化
ロジウムの含有量Ｙとの関係で、６８４．７×Ｙ0.044
≦Ｔ≦９５０の範囲に調節して焼成を行えばよいことが
わかる。すなわち、上記条件を満足する場合には、ガラ
スセラミック基板と表層導体との同時焼成を行った場合
でも、メッキのり、ハンダ濡れ、および密着強度といっ
た特性のすべてに優れた表層導体を得ることができると
考えられる。[Number 1] T = 684.7 × Y 0.044 Incidentally, the above equation 1, on Figure 3, a curve shown by a solid line in FIG. From the above results, the content of rhodium oxide is 100 to 600 ppm, the firing temperature T is 684.7 × Y 0.044 in relation to the content Y of rhodium oxide.
It is understood that the firing may be performed by adjusting the range of ≦ T ≦ 950. That is, when the above conditions are satisfied, even when the glass ceramic substrate and the surface layer conductor are co-fired, it is possible to obtain a surface layer conductor having excellent characteristics such as plating glue, solder wetting, and adhesion strength. it is conceivable that.
【００３９】次に、タングステンの添加量と焼成温度に
ついて評価するため、酸化ロジウムの添加量を３００ｐ
ｐｍとした場合における上記試験Ａ〜Ｃの結果を、下記
表２に示す。Next, in order to evaluate the addition amount of tungsten and the firing temperature, the addition amount of rhodium oxide was set to 300 p.
The results of the above tests A to C in the case of pm are shown in Table 2 below.
【００４０】[0040]
【表２】 [Table 2]
【００４１】表２から明らかなように、タングステンの
含有量が３％を下回ると、メッキのりの悪い銀導体にな
る。一方、タングステンの含有量が５％を上回ると、メ
ッキのり、ハンダ濡れの双方の特性に悪影響が現れる。
なお、これらの傾向は、焼成温度が変わってもほぼ同じ
であり、焼成温度による影響はほとんどないと考えられ
る。As is clear from Table 2, when the content of tungsten is less than 3%, the silver conductor has poor plating adhesion. On the other hand, if the content of tungsten exceeds 5%, the characteristics of both plating and solder wetting are adversely affected.
It should be noted that these tendencies are almost the same even if the firing temperature changes, and it is considered that the firing temperature has almost no effect.
【００４２】さらに、タングステンの含有量が３．５％
のものと４．５％のものとを比較すると、４．５％のも
のの方が、より広い焼成温度範囲でメッキのり、ハンダ
濡れに優れた銀導体を作製できる。但し、同じ焼成温度
条件における密着強度を見ると、タングステンの含有量
が３．５％のものの方が、いくらか高い値を示してい
る。したがって、これらを総合的に勘案すれば、タング
ステンの含有量が３．５％のものと４．５％のものは、
いずれが一方的に優れているとは言い難いが、８８０℃
以上での焼成が可能な場合には、タングステンの含有量
を３．５％とすることが望ましいと言える。Furthermore, the content of tungsten is 3.5%.
Comparing the ones of 4.5% and those of 4.5%, the one of 4.5% can produce a silver conductor excellent in plating paste and solder wetting in a wider firing temperature range. However, when looking at the adhesion strength under the same firing temperature condition, a tungsten content of 3.5% shows a somewhat higher value. Therefore, when these are comprehensively taken into consideration, the tungsten contents of 3.5% and 4.5% are
It is hard to say which one is superior, but at 880 ° C
When the above firing is possible, it can be said that the content of tungsten is preferably 3.5%.
【００４３】以上、本発明の実施形態について説明した
が、本発明の実施形態については上記のもの以外にも種
々の具体的形態が考えられる。Although the embodiments of the present invention have been described above, various specific forms of the embodiments of the present invention other than those described above are possible.
【図１】 本発明の導電ペースト組成物を用いて作製し
た引っ張り試験用パッドを備えた試料の正面図である。FIG. 1 is a front view of a sample equipped with a tensile test pad produced using the conductive paste composition of the present invention.
【図２】 上記試料に銅線をハンダ付けした状態を示す
断面図である。FIG. 2 is a sectional view showing a state in which a copper wire is soldered to the sample.
【図３】 酸化ロジウムの含有量を横軸、焼成温度を縦
軸にとり、銀導体の焼成状態の優劣がわかるようにプロ
ットしたグラフである。FIG. 3 is a graph plotting the content of rhodium oxide on the horizontal axis and the firing temperature on the vertical axis so that the superiority or inferiority of the firing state of the silver conductor can be seen.
１０・・・張り試験用パッド、１２・・・セラミックグ
リーンシート、１４・・・銅線、１６・・・ハンダ。10 ... Tension test pad, 12 ... Ceramic green sheet, 14 ... Copper wire, 16 ... Solder.
Claims (7)
グステン粉末、酸化ロジウム、および有機ビヒクルが混
合されてペースト化された混合物であって、 前記銀粉末に対する重量比で、タングステン粉末を３〜
５％、酸化ロジウムを１００〜６００ｐｐｍ含有してい
ることを特徴とする導電ペースト組成物。1. A silver powder, tungsten powder having an average particle diameter of 0.5 to 2 [mu] m, oxidation rhodium, and an organic vehicle are mixed
A mixture of the tungsten powder and the silver powder in a weight ratio to the silver powder.
A conductive paste composition comprising 5% and 100-600 ppm of rhodium oxide.
いて、 前記銀粉末および前記酸化ロジウムの混合物が、２００
〜４００℃の範囲で５〜３０分間加熱処理され、その加
熱処理された混合物に対して前記タングステン粉末およ
び前記有機ビヒクルが混合されていることを特徴とする
導電ペースト組成物。2. The conductive paste composition according to claim 1, wherein the mixture of the silver powder and the rhodium oxide is 200
Is 5-30 minutes heat treatment in the range of to 400 ° C., Oyo the tungsten powder for the heat treated mixture
And a mixture of the organic vehicle and a conductive paste composition.
対する重量比で１００〜６００ｐｐｍ混合し、 その銀粉末および酸化ロジウムの混合物を、２００〜４
００℃の範囲で５〜３０分間加熱処理し、 その加熱処理された銀粉末および酸化ロジウムの混合物
に対し、平均粒径０．５〜２μｍ、銀粉末に対する重量
比で３〜５％のタングステン粉末と、有機ビヒクルとを
混合することを特徴とする導電ペースト組成物の製造方
法。3. Rhodium oxide is mixed with silver powder in a weight ratio of 100 to 600 ppm with respect to silver powder, and the mixture of the silver powder and rhodium oxide is mixed with 200 to 4 ppm.
Heat treatment is performed in the range of 00 ° C. for 5 to 30 minutes, and the heat-treated mixture of silver powder and rhodium oxide has an average particle diameter of 0.5 to 2 μm and a weight of silver powder.
A method for producing a conductive paste composition, which comprises mixing 3 to 5% by weight of tungsten powder with an organic vehicle .
スト組成物を、基材表面に塗布して焼成することによ
り、基材表面に所要形状の表層導体を形成する表層導体
形成方法であって、 焼成温度Ｔ（℃）を、前記酸化ロジウムの含有量Ｙ（ｐ
ｐｍ）との関係で、６８４．７×Ｙ0.044 ≦Ｔ≦９５０
の範囲に調節して、前記焼成を行うことを特徴とする表
層導体形成方法。4. A method for forming a surface layer conductor, which comprises forming a surface layer conductor having a desired shape on the surface of a base material by applying the conductive paste composition according to claim 1 or 2 onto the surface of the base material and firing the composition. The firing temperature T (° C.) at the rhodium oxide content Y (p
684.7 × Y 0.044 ≦ T ≦ 950
The surface layer conductor forming method is characterized in that the firing is carried out by adjusting to the range.
スト組成物を、セラミックグリーンシートに印刷して、
同時焼成することにより、表層配線回路を形成したこと
を特徴とするセラミック多層基板。5. A ceramic green sheet is printed with the conductive paste composition according to claim 1 or 2,
A ceramic multilayer substrate having a surface wiring circuit formed by simultaneous firing.
いて、 前記セラミックグリーンシートが、８４０〜９５０℃で
焼成可能な低温焼成ガラスセラミックからなることを特
徴とするセラミック多層基板。6. The ceramic multilayer substrate according to claim 5, wherein the ceramic green sheet is made of a low temperature fired glass ceramic capable of firing at 840 to 950 ° C.
ク多層基板において、 前記導電ペースト組成物および前記セラミックグリーン
シートが、焼成温度Ｔ（℃）を、前記酸化ロジウムの含
有量Ｙ（ｐｐｍ）との関係で、６８４．７×Ｙ0.044 ≦
Ｔ≦９５０の範囲に調節して、同時焼成されていること
を特徴とするセラミック多層基板。7. The ceramic multilayer substrate according to claim 5, wherein the conductive paste composition and the ceramic green sheet have a firing temperature T (° C.) and a rhodium oxide content Y (ppm). 684.7 × Y 0.044 ≦
A ceramic multilayer substrate, which is co-fired in a range of T ≦ 950.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27445197A JP3495890B2 (en) | 1997-10-07 | 1997-10-07 | Conductive paste composition, method for producing conductive paste composition, method for forming surface conductor, and ceramic multilayer substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27445197A JP3495890B2 (en) | 1997-10-07 | 1997-10-07 | Conductive paste composition, method for producing conductive paste composition, method for forming surface conductor, and ceramic multilayer substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11111052A JPH11111052A (en) | 1999-04-23 |
| JP3495890B2 true JP3495890B2 (en) | 2004-02-09 |
Family
ID=17541881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27445197A Expired - Fee Related JP3495890B2 (en) | 1997-10-07 | 1997-10-07 | Conductive paste composition, method for producing conductive paste composition, method for forming surface conductor, and ceramic multilayer substrate |
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| Country | Link |
|---|---|
| JP (1) | JP3495890B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3734731B2 (en) | 2001-09-06 | 2006-01-11 | 株式会社ノリタケカンパニーリミテド | Ceramic electronic component and method for manufacturing the same |
| EP2239743B1 (en) * | 2008-01-17 | 2020-03-11 | Nichia Corporation | Method for producing conductive material, conductive material obtained by the method, electronic device containing the conductive material, light-emitting device, and method for manufacturing light-emitting device |
| JP5417861B2 (en) * | 2009-01-23 | 2014-02-19 | 日亜化学工業株式会社 | Conductive material, manufacturing method thereof, electronic device including conductive material, light emitting device |
| EP2390932B1 (en) | 2009-01-23 | 2015-09-09 | Nichia Corporation | Method for manufacturing a semiconductor device |
| EP2390903B1 (en) | 2009-01-23 | 2016-11-02 | Nichia Corporation | Method of producing a semiconductor device by bonding silver oxide or silver on a surface of a semiconductor element with silver oxide or silver on a surface of a lead frame or of a wiring substrate, at least one of said surfaces being provided with silver oxide |
| US8836130B2 (en) | 2009-01-23 | 2014-09-16 | Nichia Corporation | Light emitting semiconductor element bonded to a base by a silver coating |
| EP2407980B1 (en) | 2009-07-21 | 2019-01-23 | Nichia Corporation | Method for producing conductive material, conductive material obtained by the same method, electronic device containing the conductive material, and light-emitting device |
| CN113851253A (en) * | 2021-08-25 | 2021-12-28 | 复旦大学 | Magnetic resonance imaging compatible conductive paste compound and preparation method thereof |
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1997
- 1997-10-07 JP JP27445197A patent/JP3495890B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11111052A (en) | 1999-04-23 |
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