JPH07331360A - New copper alloy powder and its production - Google Patents
New copper alloy powder and its productionInfo
- Publication number
- JPH07331360A JPH07331360A JP6123371A JP12337194A JPH07331360A JP H07331360 A JPH07331360 A JP H07331360A JP 6123371 A JP6123371 A JP 6123371A JP 12337194 A JP12337194 A JP 12337194A JP H07331360 A JPH07331360 A JP H07331360A
- Authority
- JP
- Japan
- Prior art keywords
- alloy powder
- copper alloy
- powder
- particle
- copper
- 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.)
- Withdrawn
Links
- 239000000843 powder Substances 0.000 title claims abstract description 128
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002245 particle Substances 0.000 claims abstract description 59
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004332 silver Substances 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000009689 gas atomisation Methods 0.000 claims abstract description 14
- 239000001307 helium Substances 0.000 claims abstract description 14
- 229910052734 helium Inorganic materials 0.000 claims abstract description 14
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 23
- 239000011261 inert gas Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 14
- UDWPONKAYSRBTJ-UHFFFAOYSA-N [He].[N] Chemical compound [He].[N] UDWPONKAYSRBTJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 18
- 238000007650 screen-printing Methods 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000012856 packing Methods 0.000 abstract description 5
- 229910001316 Ag alloy Inorganic materials 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract description 3
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 abstract 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 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
- 239000011812 mixed powder Substances 0.000 description 1
- 229920005615 natural polymer Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 phenol compound Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新しい銅合金粉末及びそ
れを用いた導電性ペースト材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new copper alloy powder and a conductive paste material using the same.
【０００２】[0002]
【従来の技術】エレクトロニクスの飛躍的進歩に伴い種
々の導電性ペースト材料が提案され各種の電子機器・電
子部品・電子回路に使用されている。中でも銅系金属粉
末を主成分とする導電性ペーストは銅金属固有の高周波
特性の良さ、耐エレクトロマイグレーション性の良さか
ら高信頼性が要求される産業用途や各種通信用途をはじ
め広く民生機器にまで使用されている。とりわけ銅系ペ
ーストの中でも特開平４−２６８３８１号公報に記載さ
れているような銅合金粉末の粒子表面の銀濃度が粒子の
平均の銀濃度より高い銅系金属粉末を用いた導電性ペー
ストは耐酸化性に優れる材料として注目されている。2. Description of the Related Art With the rapid progress of electronics, various conductive paste materials have been proposed and used in various electronic devices, electronic parts and electronic circuits. Among them, the conductive paste containing copper-based metal powder as the main component is widely used in consumer products such as industrial applications and various communication applications where high reliability is required due to good high frequency characteristics unique to copper metal and good electromigration resistance. It is used. Among the copper-based pastes, a conductive paste using a copper-based metal powder having a silver concentration on the particle surface of the copper alloy powder as described in JP-A-4-268381 is higher than the average silver concentration of the particles is acid resistant. It is attracting attention as a material with excellent chemical properties.
【０００３】しかしながら、一般に不活性ガスアトマイ
ズ法で作製した銅合金粉末は、導電性ペーストとして実
用上必要な粘度特性（チクソトロピー性）が不十分であ
り、導電性ペーストを印刷するために有機溶媒で希釈す
るとスクリーン印刷が綺麗にできないことや、ペースト
を常温で長期間保存すると粒子沈降による粒子分離がお
こりやすいことなど、この材料は粒子自体の優れた性質
を有するにも拘らず、工場での取扱い性や量産性になお
問題があり、なお一層の改良が望まれていた。また、例
えばこの銅合金粉末を熱硬化性の有機バインダーで硬化
して導電性回路として使用する場合、銅合金粉末自体は
金属銅と同程度の導電率であるにも拘らず、実際にスク
リーン印刷で形成し、熱硬化させて作製した導電回路の
抵抗値はやや高く、また塗布膜厚や硬化条件によってそ
の抵抗値がばらつきやすいなど、一定品質の導電性回路
を量産する上で改良が望まれていた。However, generally, the copper alloy powder prepared by the inert gas atomization method has insufficient viscosity characteristics (thixotropic property) practically required as a conductive paste, and is diluted with an organic solvent for printing the conductive paste. Then, screen printing cannot be done cleanly, and if the paste is stored at room temperature for a long period of time, particle separation easily occurs due to particle sedimentation, etc.Although this material has excellent properties of particles themselves, it is easy to handle in the factory. There is still a problem in mass production and further improvement is desired. Further, for example, when the copper alloy powder is cured with a thermosetting organic binder and used as a conductive circuit, the copper alloy powder itself is actually screen-printed even though it has a conductivity similar to that of metallic copper. The resistance value of the conductive circuit formed by heat-curing is slightly high, and the resistance value is likely to vary depending on the coating film thickness and the curing conditions.Therefore, improvement is desired in mass production of conductive circuit of constant quality. Was there.
【０００４】また低温焼成用の銅導体ペーストで、超微
細銅粉末の添加によって焼結性を向上させる方法が開示
されている。（特開平３−１６７７１３号公報，特開平
２−２６３７３１号公報）しかし微細微粉はそれ単独で
は凝集して二次粒子を形成しやすく取扱いが困難であ
り、これを防ぐため特開平３−１６７７１３号公報のよ
うに湿式で十分な予備混合が必要になるなど、取扱いが
煩雑で生産性が悪く生産コスト高になる。また微細な銅
粉末が開示されている従来技術では銅粉末の表面積が大
きくなるため酸化の影響をより大きくうけやすくなり、
銅粉末自体の欠点である耐酸化性の問題がより顕著に現
れる結果となった。Also disclosed is a method for improving the sinterability by adding ultrafine copper powder in a copper conductor paste for low temperature firing. (JP-A-3-167713, JP-A-2-263731) However, fine fine powder alone tends to agglomerate to form secondary particles and is difficult to handle. To prevent this, JP-A-3-167713. As in the publication, wet pre-mixing is necessary, and the handling is complicated, the productivity is poor, and the production cost is high. Further, in the prior art which discloses a fine copper powder, the surface area of the copper powder becomes large, and thus the influence of oxidation is more easily received,
As a result, the problem of oxidation resistance, which is a drawback of the copper powder itself, becomes more prominent.
【０００５】[0005]
【発明が解決しようとする課題】本発明は前記の特開平
４−２６８３８１号公報に記載されている銅合金粉末の
粒子表面の銀濃度が粒子の平均の銀濃度より高い銅系金
属粉末を用いた導電性ペースト材料を実際に工業的に使
用する場合の種々の問題点を解決し、使い勝手のよい製
品に仕上げたものである。即ち、従来の銅合金粉末の欠
点であったスクリーン印刷特性の向上、ペーストの保存
安定性の大幅な改善、導電性回路を形成した場合の低抵
抗化、導電特性の品質安定化などを図ったものである。DISCLOSURE OF THE INVENTION The present invention uses the copper-based metal powder described in JP-A-4-268381, in which the silver concentration on the particle surface of the copper alloy powder is higher than the average silver concentration of the particles. This product solves various problems in the case of actually using the conductive paste material industrially and finishes the product into a convenient product. That is, the screen printing characteristics, which were the defects of the conventional copper alloy powder, were improved, the storage stability of the paste was significantly improved, the resistance was reduced when a conductive circuit was formed, and the quality of the conductive characteristics was stabilized. It is a thing.
【０００６】[0006]
【課題を解決するための手段】本発明は、一般式Ａｇx
Ｃｕy （０．００１≦ｘ≦０．４，０．６≦ｙ≦０．９
９９（原子比））で表され、且つ粒子表面の銀濃度が粒
子の平均の銀濃度より高い銅合金粉末において、該銅合
金粉末が平均粒子径１〜１０μｍであって、粒子径０．
１〜１μｍの微粒子が全粒子の５〜８０重量％であるこ
とを特徴とする銅合金粉末を提供することによって上記
問題点を解決したものである。The present invention provides a general formula Ag x
Cu y (0.001 ≦ x ≦ 0.4, 0.6 ≦ y ≦ 0.9
99 (atomic ratio)), and the silver concentration on the particle surface is higher than the average silver concentration of the particles, the copper alloy powder has an average particle diameter of 1 to 10 μm and a particle diameter of 0.
The above problem is solved by providing a copper alloy powder characterized in that fine particles of 1 to 1 μm account for 5 to 80% by weight of all particles.
【０００７】即ち、特開平４−２６８３８１号公報に記
載されている銅合金粉末は一般に１μｍ未満の微粒子の
含有量が低いため、この銅合金固有の特性の良さを活か
したペースト組成設計を行うのが困難であった。これに
対し本発明は０．１〜１μｍの微粒子成分、即ちサブミ
クロンの微粒子成分を全微粒子の５〜８０重量％含有せ
しめることによって、従来の銅合金粉末の欠点であった
スクリーン印刷特性の向上、ペーストの保存安定性の大
幅な改善、導電性回路を形成した場合の低抵抗化、導電
特性の品質安定化などを図ることができた。本発明にお
いて０．１〜１μｍの微粒子成分の含有量は好ましくは
５〜８０重量％であり、さらに好ましい含有量は２０〜
７０重量％であって、その時の銅合金粉末の平均粒子径
は１〜５μｍであることが好ましい。That is, since the copper alloy powder described in Japanese Patent Application Laid-Open No. 4-268381 generally has a low content of fine particles of less than 1 μm, the paste composition is designed by taking advantage of the characteristics peculiar to this copper alloy. Was difficult. On the other hand, in the present invention, the fine particle component of 0.1 to 1 μm, that is, the fine particle component of submicron is contained in an amount of 5 to 80% by weight based on the total fine particles to improve the screen printing characteristics, which is a drawback of the conventional copper alloy powder. In addition, it was possible to significantly improve the storage stability of the paste, reduce the resistance when forming a conductive circuit, and stabilize the quality of the conductive characteristics. In the present invention, the content of the fine particle component of 0.1 to 1 μm is preferably 5 to 80% by weight, and the more preferable content is 20 to
It is preferably 70% by weight, and the average particle diameter of the copper alloy powder at that time is preferably 1 to 5 μm.
【０００８】本発明において、０．１〜１μｍの微粒子
成分が５重量％未満では本発明の狙いであるペーストの
保存安定性や印刷特性の改善が不十分であり、また８０
重量％を超えても微細な粒子が揃いすぎる結果となり、
印刷特性、チクソ性が不十分となる。導電性ペースト組
成物に含有せしめられる金属粉末のサイズ、粒度分布は
それぞれの金属微粉末の性質に応じて最適化を図るべき
であるが、本発明においては１μｍ未満の微粒子と１μ
ｍ以上の粒子とがバランス良く存在している必要があ
る。このためには前述の０．１〜１μｍの微粒子が適当
量存在し全粒子の平均サイズが１〜５μｍの範囲になる
ように種々のサイズに分布した金属粉から構成されてい
ることが最も好ましい。また粒子サイズの異なる粉末は
微粉と粗粉ができるだけ良く混合された状態で存在して
いることが好ましいため、予め作製された微粉と粗粉と
を後で混合するより、粉末の製造過程で直接微粉と粗粉
とが同時に製造されることが最も好ましい。微粉が別の
工程で製造されたものを後で別の粉末と混合するのは微
粉同士の凝集を解してやる必要があり多大の労力が分散
工程で要求され、それでもなお微粉の一次粒子にまで分
散できないことが多い。In the present invention, if the fine particle component of 0.1 to 1 μm is less than 5% by weight, the storage stability and printing characteristics of the paste, which is the object of the present invention, is insufficiently improved.
Even if it exceeds the weight%, the result is that the fine particles are too uniform,
Printing characteristics and thixotropy are insufficient. The size and particle size distribution of the metal powder contained in the conductive paste composition should be optimized according to the properties of each metal fine powder, but in the present invention, fine particles less than 1 μm and 1 μm are used.
It is necessary that particles of m or more are present in a well-balanced manner. For this purpose, it is most preferable that the above-mentioned fine particles of 0.1 to 1 μm are present in an appropriate amount and that the metal particles are distributed in various sizes so that the average size of all particles is in the range of 1 to 5 μm. . Further, it is preferable that powders having different particle sizes exist in a state in which fine powder and coarse powder are mixed as well as possible, and therefore, it is preferable to directly mix fine powder and coarse powder produced in advance in a process of manufacturing the powder. Most preferably, the fine and coarse powders are produced simultaneously. It is necessary to break up the agglomeration of the fine powders in order to mix fine powders produced in a separate process with another powder later, and a great deal of labor is required in the dispersion process, but even the primary particles of the fine powders are dispersed. I often cannot.
【０００９】本発明において微粉は細かければ細かいほ
ど良いわけではなく、０．１μｍ未満の微粒子は余り多
量に存在するとペーストの安定性や印刷特性を阻害する
ことが分かっている。このため小さな粒子として０．１
〜１μｍのサイズの小さな粒子の比率を規定し、且つ１
μｍ以上の大きな粒子が共存して粒子全体として平均粒
径が１〜１０μｍになるように粒子分布を規定してい
る。In the present invention, the finer the finer the finer the finer the powder is, and it has been found that the presence of too much fine particles of less than 0.1 μm impairs the stability and printing characteristics of the paste. Therefore, 0.1 as a small particle
Defines the proportion of small particles of ˜1 μm size, and 1
The particle distribution is specified so that large particles having a size of μm or more coexist and the average particle size of the particles as a whole is 1 to 10 μm.
【００１０】このため本発明の銅合金粉末はヘリウムガ
スを含むガスアトマイズ法で作製されたものが好まし
い。ヘリウムガスを含むガスアトマイズ法により作製さ
れた銅合金粉末は、前述の０．１〜１μｍの微粒子が適
当量存在し、かつ微粒子同士がくっついたり微粒子がや
や大きい粒子にくっついているいわゆるサテライト構造
粉が極めて少ないため導電性ペーストを作製するための
分散が容易でありかつ粒子の充填密度を高めることがで
きることが分かった。この適当な含有量のサブミクロン
粉末の存在と、一次粒子の分散のしやすさ、粒子の充填
密度の向上が、従来の銅合金粉末の欠点であったスクリ
ーン印刷特性の向上、ペーストの保存安定性の大幅な改
善、導電性回路を形成した場合の低抵抗化、導電特性の
品質安定化などの大幅な特性改善につながったものと推
定される。Therefore, the copper alloy powder of the present invention is preferably produced by a gas atomizing method containing helium gas. The copper alloy powder produced by the gas atomizing method containing helium gas is a so-called satellite structure powder in which the above-mentioned fine particles of 0.1 to 1 μm are present in an appropriate amount, and the fine particles are attached to each other or the fine particles are attached to a slightly large particle. It was found that the amount is extremely small, so that the dispersion for producing the conductive paste is easy and the packing density of particles can be increased. The presence of this appropriate amount of submicron powder, the ease of dispersion of primary particles, and the improvement of the packing density of the particles improve the screen printing characteristics, which were the drawbacks of conventional copper alloy powders, and the storage stability of paste. It is presumed that this has led to a great improvement in the characteristics, a lower resistance when a conductive circuit is formed, and a quality improvement of the conductive characteristics.
【００１１】本発明で用いられる銅合金粉末は一般式Ａ
ｇx Ｃｕy （０．００１≦ｘ≦０．４，０．６≦ｙ≦
０．９９９（原子比））で表されるが、ｘが０．００１
未満では十分な耐酸化性が得られず、０．４を越える場
合には耐エレクトロマイグレーション性が不十分であ
る。しかも０．００１≦ｘ≦０．４の範囲で不活性ガス
アトマイズ法によって作製された銅合金粉末は粉末表面
の銀濃度が平均の銀濃度より高いものである。この粉末
表面及び表面近傍の銀濃度はＸ線光電子分光分析装置で
表面からの深さ５０Å程度の表面濃度として求めること
ができる。平均の銀濃度の測定は試料を濃硝酸中で溶解
し、ＩＣＰ（高周波誘導結合型プラズマ発光分析計）を
用いることができる。本発明の銅合金粉末は粉末表面の
銀濃度が平均の銀濃度より高いものであるが、耐酸化性
等の特性がより好適に発現されるためには好ましくは粉
末表面の銀濃度が平均の銀濃度の１．４倍以上であり、
さらに好ましくは２．５倍以上である。また銀濃度比率
は製造上の限界から２０倍を超える材料を提供すること
が困難であり、一般には２．５〜１０倍の銀濃度のもの
が、最も好ましい。The copper alloy powder used in the present invention has the general formula A
g x Cu y (0.001 ≦ x ≦ 0.4, 0.6 ≦ y ≦
0.999 (atomic ratio)), x is 0.001
If it is less than 0.4, sufficient oxidation resistance cannot be obtained, and if it exceeds 0.4, electromigration resistance is insufficient. In addition, the copper alloy powder produced by the inert gas atomization method in the range of 0.001 ≦ x ≦ 0.4 has a silver concentration on the powder surface higher than the average silver concentration. The silver concentration on the surface of the powder and in the vicinity of the surface can be determined as a surface concentration at a depth of about 50Å from the surface by an X-ray photoelectron spectroscopy analyzer. The average silver concentration can be measured by dissolving the sample in concentrated nitric acid and using an ICP (high frequency inductively coupled plasma emission spectrometer). In the copper alloy powder of the present invention, the silver concentration on the powder surface is higher than the average silver concentration, but in order for the characteristics such as oxidation resistance to be expressed more suitably, the silver concentration on the powder surface is preferably the average. More than 1.4 times the silver concentration,
More preferably, it is 2.5 times or more. Further, it is difficult to provide a material having a silver concentration ratio of more than 20 times due to manufacturing limitation, and a silver concentration of 2.5 to 10 times is most preferable.
【００１２】本発明の銅合金粉末の平均粒子径の測定
は、レーザー回折型粒度分布計で測定することができる
が、特にサブミクロンの粒子分布は分散不良や測定機器
等により誤差を生じやすいので、ＳＥＭでの画像解析か
ら求めることができる。本発明に用いられる銅合金粉末
は、ヘリウムガスを含有した不活性ガスによるガスアト
マイズ法で作ることができる。このガスアトマイズ法は
次のような方法がその一例である。まず銅、銀の混合物
もしくは合金を不活性ガス中あるいは真空中で高周波誘
導加熱を用いてるつぼ中で融解する。融解後、るつぼ先
端より融液を不活性ガス雰囲気中へ噴出する。噴出と同
時に圧縮された不活性ガスを断熱膨張させて発生した高
速気流を融液に向かって噴出し銅合金粉末を作製するこ
とができる。このガスアトマイズでは酸素ガスなどの活
性ガスが０．１％以下さらに好ましくは０．０１％以下
になっていることが望ましい。活性ガスの濃度が０．１
％を超えると目的とする銅合金粉末の表面と反応し、銅
合金粉末を劣化することがあり好ましくない。ヘリウム
ガスは高純度であれば良いがこの一部が窒素ガスで置換
された混合ガスは特に好適なガス組成である。ヘリウム
ガスの混合比率が１０〜９９体積％のヘリウム−窒素混
合ガスは特に好適な粒度分布を持つ銅合金粉末を作製す
ることができ、充填密度の高い導電回路を形成すること
ができる。製造コスト、粒度分布、ペースト特性を勘案
し好適な比率のヘリウム−窒素混合ガスを使用すること
が工業的に極めて有用な手段である。The average particle size of the copper alloy powder of the present invention can be measured by a laser diffraction type particle size distribution meter. However, particularly in the submicron particle distribution, errors are likely to occur due to poor dispersion or measuring equipment. , SEM image analysis. The copper alloy powder used in the present invention can be produced by a gas atomization method using an inert gas containing helium gas. An example of this gas atomizing method is as follows. First, a mixture or alloy of copper and silver is melted in an inert gas or vacuum in a crucible using high frequency induction heating. After melting, the melt is jetted from the crucible tip into an inert gas atmosphere. It is possible to produce a copper alloy powder by ejecting a high-speed airflow generated by adiabatic expansion of the compressed inert gas at the same time as the ejection to the melt. In this gas atomization, the active gas such as oxygen gas is preferably 0.1% or less, more preferably 0.01% or less. Active gas concentration is 0.1
%, It reacts with the surface of the intended copper alloy powder and may deteriorate the copper alloy powder, which is not preferable. The helium gas may have a high purity, but a mixed gas in which a part of the helium gas is replaced with nitrogen gas has a particularly suitable gas composition. A helium-nitrogen mixed gas having a helium gas mixing ratio of 10 to 99% by volume can produce a copper alloy powder having a particularly suitable particle size distribution, and can form a conductive circuit having a high packing density. It is an industrially extremely useful means to use a helium-nitrogen mixed gas in a suitable ratio in consideration of production cost, particle size distribution and paste characteristics.
【００１３】本発明においてヘリウム−窒素混合ガスに
よるアトマイズがサブミクロンの微粒子を生成するのに
有効な理由は、ヘリウムガスと窒素ガスとの中間的な次
のような混合ガスとしての物性値、例えば高速気流の速
度、不活性ガスの流量、不活性ガスによる冷却速度、不
活性ガスの動粘度などでは単純に説明できず、あたかも
ヘリウムガスと窒素ガスとの相乗効果として観測される
ものである。In the present invention, the reason why atomization with a helium-nitrogen mixed gas is effective for producing submicron fine particles is the following intermediate physical property value of helium gas and nitrogen gas, for example, It cannot be simply explained by the speed of the high-speed air flow, the flow rate of the inert gas, the cooling rate by the inert gas, the kinematic viscosity of the inert gas, etc., and it is observed as a synergistic effect of helium gas and nitrogen gas.
【００１４】粒子形状は不活性ガスアトマイズ法で得ら
れる球状が一般的であるが、この形状にはこだわらず、
例えばこれを機械的に偏平化したものも使用することが
できる。本発明で用いられる銅合金粉末は、特性を損な
わない程度であれば特に限定されないが、例えば溶融時
にＡｌ，Ｚｎ，Ｓｎ，Ｐｂ，Ｓｉ，Ｍｎ，Ｎｉ，Ｆｅ，
Ｂｉ，Ｍｏ，Ｃｒ，Ｉｒ，Ｎｂ，Ｓｂ，Ｂ，Ｐ，Ｍｇ，
Ｌｉ，Ｃ，Ｎａ，Ｂａ，Ｔｉ，Ｉｎ，Ａｕ，Ｐｄ，Ｐ
ｔ，Ｒｈ，Ｒｕ，Ｚｒ，Ｈｆ，Ｙ，Ｌａなどの金属、半
金属及びそれらの化合物を添加しても構わないし、ま
た、本発明で用いる粉末と同時に、Ａｌ，Ｚｎ，Ｓｎ，
Ｐｂ，Ｓｉ，Ｍｎ，Ｎｉ，Ｆｅ，Ｂｉ，Ｍｏ，Ｃｒ，Ｉ
ｒ，Ｎｂ，Ｓｂ，Ｂ，Ｐ，Ｍｇ，Ｌｉ，Ｃ，Ｎａ，Ｂ
ａ，Ｔｉ，Ｉｎ，Ａｕ，Ｐｄ，Ｐｔ，Ｒｈ，Ｒｕ，Ｚ
ｒ，Ｈｆ，Ｙ，Ｌａなどの金属、半金属およびそれらの
化合物からなる粉末を混合しても構わない。また、特性
を損なわない範囲で、本発明の銅合金粉末の一部を銅金
属粉末や銀金属粉末で置き換えることも可能である。こ
のとき用いられる銅金属粉末はアトマイズ粉末である必
要はなく、例えば電解銅粉、化学還元銅粉、銀メッキ銅
粉であってもよい。The particle shape is generally spherical obtained by the inert gas atomizing method, but the shape is not limited to this.
For example, a mechanically flattened version of this can also be used. The copper alloy powder used in the present invention is not particularly limited as long as it does not impair the characteristics, but for example, Al, Zn, Sn, Pb, Si, Mn, Ni, Fe,
Bi, Mo, Cr, Ir, Nb, Sb, B, P, Mg,
Li, C, Na, Ba, Ti, In, Au, Pd, P
Metals such as t, Rh, Ru, Zr, Hf, Y and La, semimetals and their compounds may be added, and Al, Zn, Sn, and
Pb, Si, Mn, Ni, Fe, Bi, Mo, Cr, I
r, Nb, Sb, B, P, Mg, Li, C, Na, B
a, Ti, In, Au, Pd, Pt, Rh, Ru, Z
Powders composed of metals such as r, Hf, Y and La, metalloids and their compounds may be mixed. Further, a part of the copper alloy powder of the present invention can be replaced with copper metal powder or silver metal powder as long as the characteristics are not impaired. The copper metal powder used at this time does not have to be atomized powder, and may be, for example, electrolytic copper powder, chemically reduced copper powder, or silver-plated copper powder.
【００１５】特にこのような異種の金属粉末との組み合
わせでは従来の金属粉末固有の欠点を克服し、粉末の混
合による相乗効果が期待できる。例えば、銀金属粉末と
の組み合わせでは、銀ペーストの欠点であるはんだ食わ
れ性が大幅に改善され、また化学還元銅粉とも組み合わ
せでは化学還元銅粉の欠点であるはんだ濡れ性が大幅に
改善されることが分かった。この混合して使用される異
種の金属粉末と本発明の銅合金粉末とを合わせた合計重
量を銅合金粉末の重量とみなし、以下に述べる有機バイ
ンダー、溶媒等の添加剤、成分の添加量を決定すること
ができる。In particular, such a combination with different kinds of metal powders can overcome the drawbacks peculiar to the conventional metal powders and can expect a synergistic effect by mixing the powders. For example, in combination with silver metal powder, solder erosion, which is a drawback of silver paste, is significantly improved, and in combination with chemically reduced copper powder, solder wettability, which is a drawback of chemically reduced copper powder, is significantly improved. I found out. Considering the total weight of the copper alloy powder of the present invention and the different metal powders used by mixing as the weight of the copper alloy powder, the organic binder described below, an additive such as a solvent, the addition amount of the component You can decide.
【００１６】本発明の導電性ペースト材料には、前述の
銅合金粉末以外に種々の添加剤、成分が添加される。本
発明の銅合金粉末は前述のようにヘリウムガスを含むガ
スアトマイズ法によってサブミクロン以下の微粒子を得
ることができるが、さらにサブミクロン以下の微粒子す
なわち０．１〜１μｍの微粒子の比率を高める手段とし
て気流分級機等の適当な分級プロセスを併用するとさら
に導電性ペースト材料としての特性が大きく向上する。
特に０．１〜１μｍの微粒子の比率が全合金粉末の１０
重量％以上であることが好ましく、さらに全合金粉末の
２０〜７０重量％であることがなお一層好ましい。Various additives and components other than the above-mentioned copper alloy powder are added to the conductive paste material of the present invention. As described above, the copper alloy powder of the present invention can obtain submicron or smaller fine particles by the gas atomizing method containing helium gas. As a means for increasing the ratio of submicron or smaller fine particles, that is, 0.1 to 1 μm fine particles. When used in combination with an appropriate classification process such as an air flow classifier, the characteristics of the conductive paste material are further improved.
Especially, the ratio of fine particles of 0.1 to 1 μm is 10 in the total alloy powder.
It is preferably not less than wt%, more preferably 20 to 70 wt% of the total alloy powder.
【００１７】導電性ペースト材料は高温焼成により金属
粉末を焼結せしめて焼結金属配線等に使用されるＣＴＦ
（サーメット・シック・フィルム）型ペースト材料と、
金属粉末を粉体同士の接点で導通をとり熱硬化型のポリ
マーで固めるＰＴＦ（ポリマー・シック・フィルム）型
ペーストに大別される。ＣＴＦ型ペースト材料の場合
は、公知のガラスフリットを添加することができる。ガ
ラスフリットは、所定の温度で溶融し、金属粉末同士、
あるいは金属導体と基板を強固に固着させるためのもの
である。その代表的なものとしてはホウ珪酸亜鉛、ホウ
珪酸鉛、ホウ珪酸ビスマスを主成分としたものである。
これらに必要であれば基板との接着強度をさらに向上さ
せるために、酸化ビスマス、酸化マンガン、酸化チタン
などの金属酸化物や、タングステンなどの金属微粉末を
添加してもよい。ガラスフリットの軟化点は基板との接
着強度、焼結性の点から９５０℃以下３００℃以上が好
ましく、更に３５０℃以上８００℃以下が好ましい。The conductive paste material is a CTF used for sintered metal wiring etc. by sintering metal powder by high temperature firing.
(Cermet thick film) type paste material,
It is roughly classified into PTF (Polymer Thick Film) type paste in which metal powder conducts at the points of contact between powders and is solidified with a thermosetting polymer. In the case of the CTF type paste material, a known glass frit can be added. Glass frit melts at a predetermined temperature, metal powders,
Alternatively, it is for firmly fixing the metal conductor and the substrate. Typical examples thereof include zinc borosilicate, lead borosilicate, and bismuth borosilicate as main components.
If necessary, a metal oxide such as bismuth oxide, manganese oxide or titanium oxide, or a fine metal powder such as tungsten may be added to further improve the adhesive strength with the substrate. The softening point of the glass frit is preferably 950 ° C. or lower and 300 ° C. or higher, more preferably 350 ° C. or higher and 800 ° C. or lower, from the viewpoint of adhesive strength with the substrate and sinterability.
【００１８】特に本発明を７００℃以下の低温焼成型ペ
ーストとして用いる場合には、３５０℃以上６００℃以
下が好ましい。ガラスフリットの構造としては、前述の
ガラスフリット組成物の結晶質、非晶質、あるいはそれ
らの混合ガラスフリットを用いることができる。ガラス
フリットの粒径としては、十分な焼結性を得るために、
０．０１〜３０μｍ程度の平均粒径のものが好ましく、
０．１〜５μｍがより好ましい。ガラスフリットの使用
量は、銅合金粉末１００重量部に対して０．１〜３０重
量部であるが、０．１重量部よりも少ない場合は基板と
の十分な接着強度が得られず、３０重量部を越える場合
にははんだ付け性が悪くなる。より好ましいガラスフリ
ットの使用量は３〜２０重量部である。Particularly when the present invention is used as a low temperature firing type paste of 700 ° C. or lower, it is preferably 350 ° C. or higher and 600 ° C. or lower. As the structure of the glass frit, the crystalline or amorphous of the above-mentioned glass frit composition or a mixed glass frit thereof can be used. Regarding the particle size of the glass frit, in order to obtain sufficient sinterability,
An average particle size of about 0.01 to 30 μm is preferable,
0.1-5 micrometers is more preferable. The amount of the glass frit used is 0.1 to 30 parts by weight with respect to 100 parts by weight of the copper alloy powder, but if it is less than 0.1 parts by weight, sufficient adhesive strength with the substrate cannot be obtained. If it exceeds the weight part, the solderability becomes poor. The more preferable amount of glass frit used is 3 to 20 parts by weight.
【００１９】本発明をＣＴＦ型ペースト材料として用い
る場合、さらに基板との接着強度を向上せしめる目的で
銅酸化物を添加することができる。ＣｕＯ，Ｃｕ2 Ｏも
しくはそれらの混合物を用いることができる。これらの
銅酸化物は平均粒径０．０１〜２０μｍのものが一般的
であり、特に平均粒径０．１〜５μｍのものが好まし
い。銅酸化物の使用量は、銅合金粉末１００重量部に対
して０．０１〜２０重量部であるが、より好ましくは
０．１〜１０重量部である。０．０１重量部より少ない
添加量では、酸素含有量が２０ｐｐｍ以下の窒素ガス雰
囲気中で焼成した場合に基板との十分な接着強度を得る
ことができず、また２０重量部を越える添加量でははん
だ濡れ性を阻害する。When the present invention is used as a CTF type paste material, copper oxide can be added for the purpose of further improving the adhesive strength with the substrate. CuO, Cu 2 O or a mixture thereof can be used. These copper oxides generally have an average particle size of 0.01 to 20 μm, and particularly preferably an average particle size of 0.1 to 5 μm. The amount of the copper oxide used is 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the copper alloy powder. If the amount added is less than 0.01 parts by weight, sufficient bonding strength with the substrate cannot be obtained when firing in a nitrogen gas atmosphere with an oxygen content of 20 ppm or less, and if the amount added exceeds 20 parts by weight. Inhibits solder wettability.
【００２０】本発明の導電性ペースト材料には銅合金粉
末やその他の添加剤を分散し適当な粘度のペーストにす
るために各種の有機バインダーが添加される。ＣＴＦ型
ペースト材料では有機バインダーが焼結の前段階もしく
は焼結の過程で分解せしめるのが一般的であり、主とし
て各種の熱可塑性バインダーから選択される。この有機
バインダーの好ましい添加量は銅合金粉末１００重量部
に対し、０．１〜２０重量部程度である。また、ＰＴＦ
型ペースト材料の場合には主に熱硬化性バインダーから
選択するのが一般的である。この材料に対しては、銅合
金粉末１００重量部に対し、好ましくは５〜１００重量
部である。しかしながら、印刷性そのた種々の目的で熱
可塑性バインダーと熱硬化性バインダーを混合して使用
することもでき、広範な合成高分子化合物あるいは天然
高分子化合物の中から任意に選択することができる。Various organic binders are added to the conductive paste material of the present invention in order to disperse the copper alloy powder and other additives into a paste having an appropriate viscosity. In the CTF type paste material, the organic binder is generally decomposed in the pre-sintering step or the sintering step, and is mainly selected from various thermoplastic binders. The preferable addition amount of this organic binder is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the copper alloy powder. Also, PTF
In the case of the mold paste material, it is common to mainly select from thermosetting binders. The amount of this material is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the copper alloy powder. However, a thermoplastic binder and a thermosetting binder can be mixed and used for various purposes such as printability, and can be arbitrarily selected from a wide range of synthetic polymer compounds or natural polymer compounds.
【００２１】例えば、有機バインダーとしては、エチル
セルロース、ヒドロキシエチルセルロース、メチルセル
ロース、ニトロセルロース、エチルセルロース誘導体、
アクリル系樹脂、ブチラール樹脂、フェノール系樹脂、
ポリウレタン樹脂、ポリエステル系樹脂、アルキッド樹
脂、酢酸ビニル樹脂、エチレン−酢酸ビニル共重合体、
スチレン系樹脂、エポキシ系樹脂、アミノ樹脂、ポリイ
ミド樹脂、メラミンアルキッド樹脂及びそれらの変性樹
脂などから選択することができる。For example, as the organic binder, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose, nitrocellulose, ethyl cellulose derivative,
Acrylic resin, butyral resin, phenolic resin,
Polyurethane resin, polyester resin, alkyd resin, vinyl acetate resin, ethylene-vinyl acetate copolymer,
It can be selected from styrene resins, epoxy resins, amino resins, polyimide resins, melamine alkyd resins and modified resins thereof.
【００２２】代表的ないくつかの樹脂の成分をさらに詳
細に記述すると例えばエポキシ系樹脂としてはビスフェ
ノールＡ型エポキシ樹脂、エポキシフェノールノボラッ
ク型樹脂、ブロム化ビスフェノールＡ型エポキシ樹脂、
脂環式エポキシ樹脂、鎖状エポキシ樹脂、ポリアルキレ
ンエーテル型エポキシ樹脂、ポリグリシジルエーテル型
エポキシ樹脂、ジグリシジルエステル型エポキシ樹脂、
ダイマー酸系ジグリシジルエステル型エポキシ樹脂、エ
ポキシアクリレート樹脂、及びそれらのフェノール性Ｏ
Ｈ末端変性エポキシ樹脂、脂肪酸変性エポキシ樹脂、ウ
レタン変性エポキシ樹脂などが挙げられる。また必要に
応じて公知の反応性希釈剤を用いることもできる。例え
ば、ジグリシジルエーテル、エチレングリコールジグリ
シジルエーテル、１，３−ブタンジオールジグリシジル
エーテル、ジエチレングリコールジグリシジルエーテ
ル、ビニルシクロヘキサンジエポキサイド、トリグリシ
ジルシアヌレート、Ｎ−ジグリシジルアミン、ジビニル
ベンゼンジエポキサイドなどが挙げられるがこれらに限
定するものではない。The components of some typical resins will be described in more detail. Examples of the epoxy resin include bisphenol A type epoxy resin, epoxyphenol novolac type resin, brominated bisphenol A type epoxy resin,
Alicyclic epoxy resin, chain epoxy resin, polyalkylene ether type epoxy resin, polyglycidyl ether type epoxy resin, diglycidyl ester type epoxy resin,
Dimer acid-based diglycidyl ester type epoxy resin, epoxy acrylate resin, and phenolic O thereof
Examples thereof include H-terminal modified epoxy resin, fatty acid modified epoxy resin and urethane modified epoxy resin. Further, a known reactive diluent can be used if necessary. For example, diglycidyl ether, ethylene glycol diglycidyl ether, 1,3-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, vinylcyclohexane diepoxide, triglycidyl cyanurate, N-diglycidyl amine, divinylbenzene diepoxide, etc. may be mentioned. However, the present invention is not limited to these.
【００２３】フェノール系樹脂としては、ノボラック型
フェノール樹脂、レゾール型フェノール樹脂、アンモニ
アレゾール型フェノール樹脂、ｐ−クレゾールやｏ−ク
レゾールとの混合物あるいはｍ−クレゾールあるいは
３，５−ジメチルフェノールを用いるアルキルフェノー
ルレゾール型樹脂、キシレン樹脂変性レゾール型樹脂、
ロジン変性フェノール型樹脂などが挙げられる。As the phenolic resin, novolac type phenolic resin, resol type phenolic resin, ammonia resol type phenolic resin, mixture with p-cresol or o-cresol, or m-cresol or alkylphenol resol using 3,5-dimethylphenol. Type resin, xylene resin modified resol type resin,
Examples include rosin-modified phenol type resins.
【００２４】ポリエステル樹脂としては各種の脂肪族ポ
リエステル樹脂に代表される熱可塑性のポリエステル樹
脂や不飽和ポリエステル樹脂に代表される熱硬化性ポリ
エステル樹脂を挙げることができる。アミノ樹脂として
は例えばメチル化メラミン樹脂、ブチル化メラミン樹
脂、ベンゾグアナミン樹脂、尿素樹脂、ブチル化尿素樹
脂などが挙げられる。アクリル樹脂としては、公知の各
種アクリル酸エステル、メタクリル酸エステルからの選
択、組み合わせが可能であり、さらにこれらのモノマー
と共重合可能な種々のモノマーとの組み合わせからなる
共重合体を挙げることができる。このアクリル樹脂は非
反応性のモノマーを組み合わせて熱可塑性ポリマーとし
ても使用可能であり、また反応性の置換基を導入して熱
硬化性ポリマーとして使用してもよい。さらにアクリル
樹脂はオリゴマーとしても用いられる。Examples of the polyester resin include thermoplastic polyester resins typified by various aliphatic polyester resins and thermosetting polyester resins typified by unsaturated polyester resins. Examples of the amino resin include methylated melamine resin, butylated melamine resin, benzoguanamine resin, urea resin and butylated urea resin. As the acrylic resin, it is possible to select and combine from various known acrylic acid esters and methacrylic acid esters, and further there can be mentioned a copolymer composed of a combination of various monomers copolymerizable with these monomers. . This acrylic resin can be used as a thermoplastic polymer by combining non-reactive monomers, or may be used as a thermosetting polymer by introducing a reactive substituent. Further, the acrylic resin is also used as an oligomer.
【００２５】本発明の導電性ペースト材料には、必要に
応じて種々の有機溶媒が使用される。溶剤量としては、
銅合金粉末と有機バインダーの合計１００重量部に対し
て１０〜１００重量部を含有することが好ましい。本発
明で用いることのできる溶剤としては、樹脂によってこ
となるが、公知の溶剤で構わない。例えば、トルエン、
キシレンなどの芳香族類、メチルエチルケトン、メチル
イソブチルケトンなどのケトン類、酢酸ブチル、酢酸エ
チルなどのエステル類、エチレングリコールモノメチル
エーテル、エチレングリコールモノエチルエーテル、エ
チレングリコールモノブチルエーテル、エチレングリコ
ールジメチルエーテル、エチレングリコール−ｎ−ヘキ
シルエーテル及びそれらのアセテート、ジエチレングリ
コールモノメチルエーテル、ジエチレングリコールモノ
エチルエーテル、ジエチレングリコールモノイソブチル
エーテル、ジエチレングリコールモノヘキシルエーテル
及びそれらのアセテート、トリエチレングリコールモノ
アルキル類及びそのアセテートや、α−テルペノール、
β−テルペノール、ブタノールなどのアルコール類、フ
ェノール類、ジオキサン、ジメチルアセトアミド、ジメ
チルホルムアミド、Ｎ−メチルピロリドン、γ−ラクト
ンより選ばれた１種以上を含むものが好ましい。Various organic solvents are used in the conductive paste material of the present invention, if necessary. As the amount of solvent,
It is preferable to contain 10 to 100 parts by weight based on 100 parts by weight of the total of the copper alloy powder and the organic binder. The solvent that can be used in the present invention depends on the resin, but a known solvent may be used. For example, toluene,
Aromatic compounds such as xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as butyl acetate and ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol- n-hexyl ether and acetates thereof, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether and acetates thereof, triethylene glycol monoalkyls and acetates thereof, α-terpenol,
Those containing one or more selected from alcohols such as β-terpenol and butanol, phenols, dioxane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and γ-lactone are preferable.
【００２６】本発明の導電性ペースト材料には、必要に
応じて粉末表面の銅酸化物を除去しうる添加剤を添加す
ることができる。本発明で用いる添加剤としては、脂肪
酸、ジカルボン酸、オキシカルボン酸及びその金属塩、
フェノール化合物、金属キレート形成剤、高級脂肪族ア
ミン、有機シリコン化合物、有機チタン化合物、ロジ
ン、アントラセン及びその誘導体から選ばれた１種以上
が挙げられる。If necessary, an additive capable of removing the copper oxide on the powder surface can be added to the conductive paste material of the present invention. The additives used in the present invention include fatty acids, dicarboxylic acids, oxycarboxylic acids and metal salts thereof,
One or more selected from a phenol compound, a metal chelate forming agent, a higher aliphatic amine, an organic silicon compound, an organic titanium compound, rosin, anthracene and a derivative thereof can be given.
【００２７】さらに、本発明の導電性ペースト材料に
は、必要に応じて各種の公知の添加剤を添加できる。例
えば、公知の粘度調節剤、希釈剤、沈降防止剤、レベリ
ング剤、消泡剤などを添加してもよい。本発明の導電性
ペースト材料は、通常のペースト製造と同様に、各種ニ
ーダ、プラネタリミキサー、ボールミル、アトライタ、
三本ロールなどの種々の分散、攪拌装置を使用して作製
される。得られた導電性ペースト材料は、スクリーン印
刷、スプレー法、ディップ法、バーコード法、ドクター
ブレード法、マイクロディスペンサー法などの公知の印
刷、塗布方法を用いて使用される。このとき、印刷に用
いられる基板やチップ部品等の加工部品は特に限定され
ないが、通常、アルミナ基板、窒化アルミ基板、低温焼
成用ガラス基板などのセラミックス基板や、アルミ、ス
テンレスなどのメタル基板などの無機基板やガラスエポ
キシ樹脂基板、紙フェノール樹脂基板、ポリイミド基
板、ポリエステル樹脂基板、ＢＴレジン基板、ポリサル
フォン樹脂基板、ポリエーテルサルフォン樹脂基板、ポ
リエーテルイミド樹脂基板、ポリブタジエン樹脂基板、
ガラスポリイミド樹脂基板やフレキシブル基板などの有
機基板が使用される。本発明の導電性ペースト材料は、
各種回路の導体部、チップ部品の端子電極やその接合材
料、はんだ付け下地材、スルーホール用導電材料、電磁
波シールド材料などに使用することができる。Further, various known additives can be added to the conductive paste material of the present invention, if necessary. For example, a known viscosity modifier, diluent, anti-settling agent, leveling agent, defoaming agent and the like may be added. The conductive paste material of the present invention, as in ordinary paste production, various kneaders, planetary mixers, ball mills, attritors,
It is produced by using various dispersing and stirring devices such as a triple roll. The obtained conductive paste material is used by a known printing or coating method such as screen printing, spraying method, dipping method, bar code method, doctor blade method or micro dispenser method. At this time, the processed components such as the substrate and the chip component used for printing are not particularly limited, but usually, a ceramic substrate such as an alumina substrate, an aluminum nitride substrate, a glass substrate for low temperature firing, or a metal substrate such as aluminum or stainless steel. Inorganic substrate, glass epoxy resin substrate, paper phenol resin substrate, polyimide substrate, polyester resin substrate, BT resin substrate, polysulfone resin substrate, polyether sulfone resin substrate, polyetherimide resin substrate, polybutadiene resin substrate,
Organic substrates such as glass-polyimide resin substrates and flexible substrates are used. The conductive paste material of the present invention,
It can be used for conductors of various circuits, terminal electrodes of chip components and their bonding materials, soldering base materials, conductive materials for through holes, electromagnetic wave shielding materials, and the like.
【００２８】[0028]
【００２９】[0029]
【実施例１】 銅合金粉末の作製 窒素ガス、ヘリウムガス及び種々の比率の窒素−ヘリウ
ム混合ガスを用いて同一アトマイズ条件で銅合金粉末を
作製した。銅粒子３１６ｇと銀粒子１５ｇとを黒鉛るつ
ぼ中で高周波誘導加熱を用いて融解した。雰囲気は不活
性ガスアトマイズに用いるガス組成と同一組成にして操
作した。１６００℃まで加熱後、るつぼ先端より落下す
る融液に対して圧力３０ｋ／Ｇの不活性ガスを円周状に
取り付けたノズル（ノズル径１．２ｍｍで円周状に１８
個装着）から噴出し銅銀合金粉末を作製した。得られた
粉末はサイクロンで捕集し、粒度分布及び銅銀合金粉の
表面銀濃度をＸ線光電子分光分析装置で測定した。銀濃
度の測定には測定光電子エネルギーが近いピーク同士で
比較するためＡｇ３ｄ5/2 （ＡｌのＫα線）とＣｕ３ｐ
（ＭｇのＫα線）を選び表面からの深さ５０Ａ程度の表
面濃度として求め、この値とＩＣＰで求めた平均銀濃度
の比を銀濃度比とした。粒度分布はＳＥＭ写真画像から
粒子サイズを測定して求めた。Example 1 Preparation of Copper Alloy Powder A copper alloy powder was prepared under the same atomizing conditions using nitrogen gas, helium gas and nitrogen-helium mixed gas of various ratios. 316 g of copper particles and 15 g of silver particles were melted in a graphite crucible using high frequency induction heating. The atmosphere was the same as the gas composition used for the inert gas atomization. After heating up to 1600 ° C, a nozzle with a circumferentially attached inert gas with a pressure of 30k / G against the melt falling from the tip of the crucible (nozzle diameter 1.2mm, 18
Copper silver alloy powder was prepared by spraying from individual pieces). The obtained powder was collected by a cyclone, and the particle size distribution and the surface silver concentration of the copper-silver alloy powder were measured by an X-ray photoelectron spectroscopy analyzer. In order to compare the peaks having similar measured photoelectron energies, Ag3d 5/2 (Kα ray of Al) and Cu3p were used to measure the silver concentration.
(Mg Kα ray) was selected and determined as the surface concentration at a depth of about 50 A from the surface, and the ratio of this value and the average silver concentration determined by ICP was defined as the silver concentration ratio. The particle size distribution was determined by measuring the particle size from the SEM photograph image.
【００３０】得られた結果を表１に示す。The results obtained are shown in Table 1.
【００３１】[0031]
【比較例１】銅金属のみを用いて実施例１と同様にして
アトマイズ粉を作製し、実施例１と同様に粒子サイズ、
銀濃度比を求めた。得られた結果を表１に示す。[Comparative Example 1] Atomized powder was prepared in the same manner as in Example 1 using only copper metal.
The silver concentration ratio was determined. The results obtained are shown in Table 1.
【００３２】[0032]
【実施例２】 導電性ペースト材料１の作製と評価 実施例１で得られたそれぞれの銅合金粉末２００ｇに対
し、ＰｂＯ−ＺｎＯ−Ｂ2Ｏ3系のガラスフリット（平均
サイズ２．４μｍ）１２ｇ、ハーキュレス社製エチルセ
ルロース０．５ｇ、亜酸化銅粉末３ｇ、２，２，４−ト
リメチル−１，３−ペンタンジオールモノブチレート１
８ｇをプラネタリーミキサーで混合し、さらに三本ロー
ルを通して仕上げ混練して導電性ペースト材料１（ＣＴ
Ｆ）を作製した。Example 2 Preparation and Evaluation of Conductive Paste Material 1 For each 200 g of copper alloy powder obtained in Example 1, 12 g of PbO—ZnO—B 2 O 3 based glass frit (average size 2.4 μm) Hercules ethyl cellulose 0.5 g, cuprous oxide powder 3 g, 2,2,4-trimethyl-1,3-pentanediol monobutyrate 1
8g is mixed with a planetary mixer, and then the mixture is finished and kneaded through a three-roll mill to prepare a conductive paste material 1 (CT
F) was prepared.
【００３３】得られたペースト材料１は９６％アルミナ
基板上にスクリーン印刷法でテストパターンを印刷し、
窒素雰囲気下でピーク温度が９００℃に設定された連続
焼成炉を通過させて焼成した。このとき焼成後の導体膜
厚が約２０μｍになるように印刷条件をコントロールし
た。得られたサンプルは、比抵抗とそのばらつきをｎ＝
１０００で評価した。またペースト材料の保存安定性を
ペーストを５０℃の恒温槽に保管し、粒子沈降の観測さ
れる日数でペーストの保存性を評価した。得られた結果
を表１に示す。The paste material 1 thus obtained was printed with a test pattern on a 96% alumina substrate by a screen printing method,
In a nitrogen atmosphere, it was passed through a continuous firing furnace having a peak temperature set to 900 ° C. and fired. At this time, the printing conditions were controlled so that the conductor film thickness after firing was about 20 μm. The obtained sample shows the specific resistance and its variation n =
It was evaluated by 1000. Further, the storage stability of the paste material was evaluated by storing the paste in a constant temperature bath at 50 ° C. and evaluating the storage stability of the paste by the number of days when particle precipitation was observed. The results obtained are shown in Table 1.
【００３４】[0034]
【比較例２】比較例１で得られた金属粉末を用いて実施
例２と同様にペーストを作製した。得られた結果を表１
に示す。Comparative Example 2 Using the metal powder obtained in Comparative Example 1, a paste was prepared in the same manner as in Example 2. The results obtained are shown in Table 1.
Shown in.
【００３５】[0035]
【実施例３】 導電性ペースト材料２の作製と評価 実施例１で得られたそれぞれの銅合金粉末２００ｇに対
し、セバシン酸４ｇ、トリエタノールアミン２ｇ、ブチ
ルセロソルブ８０ｇ及びレゾール樹脂の添加量を変化さ
せて導電性ペーストを作製し、ガラスエポキシ樹脂基板
上に塗布したのち、乾燥し、１６０℃で３０分間加熱硬
化したのち導電性を評価した。レゾール樹脂の量を変化
させたとき、得られる比抵抗が最低になる金属粉末の充
填率とその時の比抵抗を表１に示す。Example 3 Preparation and Evaluation of Conductive Paste Material 2 With respect to 200 g of each copper alloy powder obtained in Example 1, 4 g of sebacic acid, 2 g of triethanolamine, 80 g of butyl cellosolve, and the amount of resole resin added were changed. A conductive paste was prepared by applying the composition to a glass epoxy resin substrate, dried, and heat-cured at 160 ° C. for 30 minutes, and then the conductivity was evaluated. When the amount of the resol resin is changed, the filling rate of the metal powder that gives the lowest specific resistance and the specific resistance at that time are shown in Table 1.
【００３６】[0036]
【比較例３】比較例１で得られた金属粉末を用いて実施
例３と同様にペーストを作製した。得られた結果を表１
に示す。Comparative Example 3 A paste was prepared in the same manner as in Example 3 using the metal powder obtained in Comparative Example 1. The results obtained are shown in Table 1.
Shown in.
【００３７】[0037]
【実施例４】実施例１の実験番号３で得られた銅合金粉
末を気流分級機で８μｍ以下の粉体のみが得られるよう
に分級した。得られた粉体は平均粒径３．２μｍで１μ
ｍ未満の微粉は２８重量％含まれていた。（この粉末を
実験番号７とする）この粉末を実施例３の組成で調合
し、実施例３と同一の評価を行った。比抵抗は３．５×
１０-5Ωｃｍとさらに低抵抗になり最適充填率は９２％
と一段と金属粉の充填密度を上げることができた。Example 4 The copper alloy powder obtained in Experiment No. 3 of Example 1 was classified by an air stream classifier so that only powder of 8 μm or less was obtained. The obtained powder has an average particle size of 3.2 μm and 1 μm.
28% by weight of fine powder of less than m was contained. (This powder is designated as Experiment No. 7) This powder was blended with the composition of Example 3 and the same evaluation as in Example 3 was performed. The specific resistance is 3.5 ×
The resistance is even lower at 10 -5 Ωcm, and the optimum filling rate is 92%.
Thus, the packing density of the metal powder could be increased further.
【００３８】実験番号３及び実験番号７の銅合金粉体を
用いて作製した実施例３の組成と同様のペーストと、比
較例３のペーストを用いてスクリーン印刷法で穴径０．
７ｍｍの紙フェノール樹脂基板にスルーホールを形成し
た。乾燥、加熱硬化して得られたスルーホールの導通性
は、１穴あたり以下のようになり、サブミクロンのサイ
ズの粉末の存在が有効なことが確認できた。A paste having a composition similar to that of Example 3 prepared by using the copper alloy powders of Experiment Nos. 3 and 7 and the paste of Comparative Example 3 were used to screen-print a hole diameter of 0.
Through holes were formed in a 7 mm paper phenolic resin substrate. The conductivity of the through holes obtained by drying and heat curing was as follows per hole, and it was confirmed that the presence of powder of submicron size was effective.
【００３９】 実験番号７の粉体を用いたペースト（実施例） １８ｍΩ 実験番号３の粉体を用いたペースト（実施例） ２４ｍΩ 比較例３のペースト（比較例） ４１ｍΩPaste using the powder of Experiment No. 7 (Example) 18 mΩ Paste using the powder of Experiment No. 3 (Example) 24 mΩ Paste of Comparative Example 3 (Comparative Example) 41 mΩ
【００４０】[0040]
【実施例５】実施例４で用いたペースト（実験番号７の
粉体を用いたもの）をガラスエポキシ基板上に乾燥後の
膜厚が３０μｍになるように塗布し、さらに乾燥、加熱
硬化して導電回路を形成した。初期の導電性及び加速劣
化テスト（８５℃、８５ＲＨで１００時間後）後の結果
を表２に示す。また、ペーストの保存安定性について、
４０℃の恒温槽に保管して初期粘度の３０％増まで粘度
が上昇するまでの保存日数を求めた。この結果を同様に
表２に示す。Example 5 The paste used in Example 4 (using the powder of Experiment No. 7) was applied on a glass epoxy substrate so that the film thickness after drying would be 30 μm, and further dried and heat-cured. To form a conductive circuit. The results after the initial conductivity and accelerated deterioration test (after 85 hours at 85 ° C. and 85 RH) are shown in Table 2. Also, regarding the storage stability of the paste,
It was stored in a constant temperature bath at 40 ° C., and the number of storage days until the viscosity increased until the initial viscosity increased by 30% was calculated. The results are also shown in Table 2.
【００４１】[0041]
【比較例４】化学還元銅粉で平均粒径３．３μｍ，１μ
ｍ未満の微粒子の含有量２６重量％の粉体を準備した。
これはちょうど平均粒径および微粒子の含有率で実施例
２の銅合金粉末とほぼ同一のものである。この粉体を用
いて実施例３と同一組成の導電性ペースト材料を作製し
た。実施例５と同様に、前記導電性ペーストを塗布、乾
燥、加熱硬化して導電回路を形成し、初期の導電性及び
加速劣化（８５℃、８５％ＲＨで１０００時間後）後の
結果を求めた。またペーストの安定性についても実施例
５と同様に測定した結果を表２に示す。この結果より純
銅の化学還元銅粉は微粉末が多く存在すると特に表面積
が大きくなり酸化劣化を受けやすいことがわかった。[Comparative Example 4] Chemically reduced copper powder having an average particle diameter of 3.3 μm and 1 μm
A powder having a content of fine particles of less than m of 26% by weight was prepared.
This is almost the same as the copper alloy powder of Example 2 in terms of average particle size and content of fine particles. Using this powder, a conductive paste material having the same composition as in Example 3 was produced. In the same manner as in Example 5, the conductive paste was applied, dried, and heat-cured to form a conductive circuit, and the initial conductivity and the result after accelerated deterioration (after 1000 hours at 85 ° C. and 85% RH) were obtained. It was The stability of the paste was also measured in the same manner as in Example 5, and the results are shown in Table 2. From these results, it was found that the chemically reduced copper powder of pure copper had a large surface area and was susceptible to oxidative deterioration when a large amount of fine powder was present.
【００４２】[0042]
【実施例６】実施例１の実験番号４の粉体のうち、銅合
金粉末の５０重量％を銀粉末で置き換え実施例２と同一
組成のペーストを作製した。これを、塗布、焼結したの
ち、２００μｍ幅のパターンを２３０℃はんだ浴中へ１
０秒間浸漬させ、断線するまでの繰り返し回数ではんだ
食われ性をテストした。その結果実施例では、６回目で
断線した。用いた銀粉末は市販の最大径約８μｍのフレ
ーク状粉末である。Example 6 Among the powders of Experiment No. 4 of Example 1, 50% by weight of the copper alloy powder was replaced with silver powder to prepare a paste having the same composition as in Example 2. After coating and sintering this, a 200 μm wide pattern is placed in a 230 ° C. solder bath.
It was dipped for 0 second, and the solder erosion resistance was tested by the number of repetitions until disconnection. As a result, in the example, the wire was broken at the sixth time. The silver powder used is a commercially available flake powder having a maximum diameter of about 8 μm.
【００４３】[0043]
【比較例５】すべての銅合金粉末を銀粉末で置き換えた
以外は実施例６を同一組成のペーストを作製し、実施例
６と同様のはんだ食われ性テストを行った。用いた銀粉
末は市販の最大径約８μｍのフレーク状粉末である。浸
漬１回目で断線した。Comparative Example 5 A paste having the same composition as in Example 6 was prepared except that all the copper alloy powders were replaced with silver powders, and the same solder erosion resistance test as in Example 6 was conducted. The silver powder used is a commercially available flake powder having a maximum diameter of about 8 μm. The wire was broken at the first immersion.
【００４４】[0044]
【実施例７】比較例４の化学還元銅粉５０重量％と実施
例１の実験番号１の銅合金粉末５０重量％とからなる金
属混合粉末を用い、実施例３の組成の導電性ペースト材
料を準備した。この材料のはんだぬれ性を見るためにリ
フロー炉（ピーク温度２１０℃、通過時間２分間）を２
回通過させた後の共晶はんだ２３０℃に３秒間浸漬し
て、その時のはんだ濡れ面積を測定した。濡れ面積は９
５％以上であった。[Example 7] A conductive paste material having the composition of Example 3 was prepared using a metal mixed powder of 50% by weight of the chemically reduced copper powder of Comparative Example 4 and 50% by weight of the copper alloy powder of Experiment No. 1 of Example 1. Prepared. To see the solder wettability of this material, use a reflow furnace (peak temperature 210 ° C, passage time 2 minutes) 2
The eutectic solder after passing twice was immersed in 230 ° C. for 3 seconds, and the solder wetted area at that time was measured. Wet area is 9
It was 5% or more.
【００４５】[0045]
【比較例６】比較例４の導電性ペースト材料を用い、実
施例７と同様のはんだ濡れテストを実施した。はんだ濡
れ面積は２０％以下であった。COMPARATIVE EXAMPLE 6 Using the conductive paste material of Comparative Example 4, the same solder wetting test as in Example 7 was conducted. The solder wetted area was 20% or less.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【表２】 [Table 2]
【００４８】[0048]
【発明の効果】以上説明したように本発明は、導体回路
の低抵抗化を可能とし、さらにはスクリーン印刷特性、
ペーストの保存安定性を大幅に改良し、バラツキの少な
い高品質で高精細の導体回路の製造を可能にしたもので
ある。また、特に微粉末が粉末中に分散している状態で
含有された本発明の銅合金粉末がヘリウムガスを含有す
る不活性ガスアトマイズ法によって直接かつ簡便に製造
でき、この工業的利点も大きい。As described above, according to the present invention, it is possible to reduce the resistance of the conductor circuit, and further, the screen printing characteristics,
The storage stability of the paste is greatly improved, and it is possible to manufacture a high-quality and high-definition conductor circuit with little variation. Further, in particular, the copper alloy powder of the present invention, which is contained in a state in which fine powder is dispersed in the powder, can be directly and simply manufactured by an inert gas atomizing method containing helium gas, and this has a great industrial advantage.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｂ 1/16 Ｚ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location H01B 1/16 Z
Claims (4)
０．４，０．６≦ｙ≦０．９９９（原子比））で表さ
れ、且つ粒子表面の銀濃度が粒子の平均の銀濃度より高
い銅合金粉末において、該銅合金粉末が平均粒子径１〜
１０μｍであって、粒子径０．１〜１μｍの微粒子が全
粒子の５〜８０重量％であることを特徴とする銅合金粉
末。1. The general formula Ag x Cu y (0.001 ≦ x ≦
0.4, 0.6 ≦ y ≦ 0.999 (atomic ratio)), and in the copper alloy powder having a silver concentration on the particle surface higher than the average silver concentration of the particles, the copper alloy powder has an average particle diameter. 1 to
A copper alloy powder having a particle size of 10 μm and a particle size of 0.1 to 1 μm in an amount of 5 to 80% by weight based on all particles.
も１種の金属銅粉末もしくは少なくとも１種の金属銀粉
末とを含有することを特徴とする導電性ペースト材料。2. A conductive paste material comprising the copper alloy powder according to claim 1 and at least one metal copper powder or at least one metal silver powder.
性ガスアトマイズ法を用いて製造されることを特徴とす
る請求項１記載の銅合金粉末。3. The copper alloy powder according to claim 1, wherein the copper alloy powder is produced by an inert gas atomizing method containing helium gas.
末を製造する方法において、不活性ガスが、混合比率１
０〜９９体積％のヘリウムガスを含有するヘリウム−窒
素混合ガスからなることを特徴とする銅合金粉末の製造
方法。4. A method for producing a copper alloy powder by an inert gas atomizing method, wherein the inert gas is mixed at a mixing ratio of 1.
A method for producing a copper alloy powder, comprising a helium-nitrogen mixed gas containing 0 to 99% by volume of helium gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6123371A JPH07331360A (en) | 1994-06-06 | 1994-06-06 | New copper alloy powder and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6123371A JPH07331360A (en) | 1994-06-06 | 1994-06-06 | New copper alloy powder and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07331360A true JPH07331360A (en) | 1995-12-19 |
Family
ID=14858934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6123371A Withdrawn JPH07331360A (en) | 1994-06-06 | 1994-06-06 | New copper alloy powder and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07331360A (en) |
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|---|---|---|---|---|
| WO2005031760A1 (en) * | 2003-09-26 | 2005-04-07 | Hitachi Chemical Co., Ltd. | Mixed conductive powder and use thereof |
| WO2007040195A1 (en) * | 2005-10-03 | 2007-04-12 | Mitsui Mining & Smelting Co., Ltd. | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder |
| JP2008227364A (en) * | 2007-03-15 | 2008-09-25 | Tdk Corp | Internal electrode formation paste, lamination layer ceramic type electronic component, and method of manufacturing the same |
| JP2013251256A (en) * | 2012-03-26 | 2013-12-12 | Heraeus Precious Metals North America Conshohocken Llc | Low silver content paste composition, and method of making conductive film from said low silver content paste composition |
| WO2015016202A1 (en) * | 2013-08-01 | 2015-02-05 | 積水化学工業株式会社 | Conductive filler, method for producing same, conductive paste and method for producing conductive paste |
| WO2015053222A1 (en) * | 2013-10-09 | 2015-04-16 | 山陽特殊製鋼株式会社 | Agcu-based conductive filler powder |
| JP2016189474A (en) * | 2010-03-02 | 2016-11-04 | 株式会社トクヤマ | Composition for forming wiring pattern |
-
1994
- 1994-06-06 JP JP6123371A patent/JPH07331360A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8029701B2 (en) | 2003-09-26 | 2011-10-04 | Hitachi Chemical Co., Ltd. | Mixed conductive powder and use thereof |
| WO2005031760A1 (en) * | 2003-09-26 | 2005-04-07 | Hitachi Chemical Co., Ltd. | Mixed conductive powder and use thereof |
| JP2010021145A (en) * | 2003-09-26 | 2010-01-28 | Hitachi Chem Co Ltd | Mixed conductive powder and use thereof |
| US7790063B2 (en) | 2003-09-26 | 2010-09-07 | Hitachi Chemical Company, Ltd. | Mixed conductive power and use thereof |
| WO2007040195A1 (en) * | 2005-10-03 | 2007-04-12 | Mitsui Mining & Smelting Co., Ltd. | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder |
| JP2007100155A (en) * | 2005-10-03 | 2007-04-19 | Mitsui Mining & Smelting Co Ltd | Silver nanoparticle-adhered silver-copper composite powder and method for producing the silver nanoparticle-adhered silver-copper composite powder |
| JP2008227364A (en) * | 2007-03-15 | 2008-09-25 | Tdk Corp | Internal electrode formation paste, lamination layer ceramic type electronic component, and method of manufacturing the same |
| JP2016189474A (en) * | 2010-03-02 | 2016-11-04 | 株式会社トクヤマ | Composition for forming wiring pattern |
| JP2013251256A (en) * | 2012-03-26 | 2013-12-12 | Heraeus Precious Metals North America Conshohocken Llc | Low silver content paste composition, and method of making conductive film from said low silver content paste composition |
| WO2015016202A1 (en) * | 2013-08-01 | 2015-02-05 | 積水化学工業株式会社 | Conductive filler, method for producing same, conductive paste and method for producing conductive paste |
| CN105556617A (en) * | 2013-08-01 | 2016-05-04 | 积水化学工业株式会社 | Conductive filler, method for producing same, conductive paste and method for producing conductive paste |
| US10533098B2 (en) | 2013-08-01 | 2020-01-14 | Sekisui Chemical Co., Ltd. | Conductive filler, method for producing same, conductive paste and method for producing conductive paste |
| WO2015053222A1 (en) * | 2013-10-09 | 2015-04-16 | 山陽特殊製鋼株式会社 | Agcu-based conductive filler powder |
| JP2015074806A (en) * | 2013-10-09 | 2015-04-20 | 山陽特殊製鋼株式会社 | AgCu-BASED CONDUCTIVE FILLER POWDER |
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