JP3345961B2 - Low-temperature diffusion bonding method of copper or copper alloy and method of manufacturing conductive paste and multilayer wiring board using the same - Google Patents
Low-temperature diffusion bonding method of copper or copper alloy and method of manufacturing conductive paste and multilayer wiring board using the sameInfo
- Publication number
- JP3345961B2 JP3345961B2 JP13440493A JP13440493A JP3345961B2 JP 3345961 B2 JP3345961 B2 JP 3345961B2 JP 13440493 A JP13440493 A JP 13440493A JP 13440493 A JP13440493 A JP 13440493A JP 3345961 B2 JP3345961 B2 JP 3345961B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- oxide film
- conductive paste
- wiring board
- alloy
- 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
Landscapes
- Conductive Materials (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属加工分野やエレクト
ロニクス産業で広く使用されている銅または銅合金の接
合方法と、その原理を応用した導電ペースト及び同じ原
理により製造される多層配線基板の製造方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for joining copper or a copper alloy widely used in the field of metal processing and the electronics industry, a conductive paste applying the principle, and a multilayer wiring board manufactured by the same principle. It is about the method.
【０００２】[0002]
【従来の技術】従来より銅およびその合金は産業分野で
広く使用されてきた。これら金属の加工に際して２つ以
上の部材を接合するために古くから多くの技術が実施さ
れてきたが、一般的な接合方法としては半田付けに代表
される蝋付けが広く行われている。マイクロエレクトロ
ニクス分野においては特殊な例としては超音波接続も行
われているが、一般的に信頼性のある電気的接続をおこ
なおうとすれば半田付けまたは蝋付けによる接続が唯一
のものであった。2. Description of the Related Art Conventionally, copper and its alloys have been widely used in the industrial field. Many techniques have long been used to join two or more members when processing these metals, but brazing represented by soldering is widely performed as a general joining method. Have been made also ultrasonic connection as a special example in the microelectronics field, if attempted generally electrically connected with a reliable connection by soldering or brazing was the only one .
【０００３】一方、各種電気回路においては多層配線基
板が使用されている。多層配線板は配線層間を接続する
ビアホールの製造方法により２種類に分類される。その
一つはビアホール内の導電膜ををめっきで形成する方法
であり、他の一つはビアホールを導電性ペーストで形成
するものである。On the other hand, a multilayer wiring board is used in various electric circuits. Multilayer wiring boards are classified into two types according to the method of manufacturing via holes for connecting wiring layers. One is a method of forming a conductive film in a via hole by plating, and the other is a method of forming a via hole with a conductive paste.
【０００４】導電ペーストを使用する方法はさらに２種
類に分類され、その一つは通常銀スルーホール配線板と
して知られる貴金属粉体とバインダ樹脂とからなる導電
ペーストを用するものである。もう一つは金属粉末と半
田粉末とを導電要素として使用する導電ペーストを使用
するものであり、この場合は加熱することにより半田が
溶融して金属粉末を結合し、導電経路を形成するもので
ある。[0004] The method of using the conductive paste is further classified into two types, one of which uses a conductive paste composed of a noble metal powder and a binder resin, which are usually known as a silver through-hole wiring board. The other uses a conductive paste that uses metal powder and solder powder as conductive elements.In this case, heating melts the solder and combines the metal powder to form a conductive path. is there.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、半田に
よる接続は鉛、錫などの異種金属を使用するため、使用
環境によっては腐食を発生し、かつ、金属間化合物の形
成を伴うため、接続部分が脆弱であって繰り返しストレ
ス等によりクラックを発生し易い問題点がある。超音波
による接続は上記問題は含まないものの、きわめて小さ
な接続面積しか得られず、一般への応用は困難である。
本発明の目的は信頼性に優れた新規な銅または銅合金の
接続方法を提供することである。However, since the connection using solder uses different metals such as lead and tin, corrosion may occur depending on the use environment and the formation of an intermetallic compound may occur, so that the connection portion may not be formed. There is a problem that it is fragile and cracks easily occur due to repeated stress and the like. Although connection by ultrasonic waves does not include the above-mentioned problems, it can obtain only a very small connection area and is difficult to apply to general use.
An object of the present invention is to provide a novel method for connecting copper or copper alloy with excellent reliability.
【０００６】一方、多層配線基板の製造において、めっ
き法によるビアホールは導電層が金属銅であるため、導
電性、信頼性に優れる一方で製造に多くの工数を要し、
さらにメッキ廃液や基板洗浄液のための公害処理施設を
必要とし、製造コストが高いものとなる。一方、導電ペ
ーストによるビアホール（銀スルーホール）は製造工程
は簡単でコストは安く済むものの、スルーホールの導通
抵抗が高く、特に低電流域において導通抵抗が増加する
非オーミック性を示し、使用範囲が限られていた。さら
に、金属粉末と半田粉末を使用する方法は金属伝導によ
るオーミック接続は期待できるものの、その接続はもろ
いものでヒートショック試験などで破壊され易いもので
あり、事実上使用されていない。On the other hand, in the production of a multilayer wiring board, a via hole formed by plating has excellent conductivity and reliability because the conductive layer is made of metallic copper, but requires many man-hours for production.
Further, a pollution treatment facility for a plating waste liquid and a substrate cleaning liquid is required, and the manufacturing cost is high. On the other hand, via holes (silver through holes) made of conductive paste have a simple manufacturing process and low cost, but have high through-hole conduction resistance, exhibit non-ohmic properties that increase conduction resistance especially in low current regions, and have a limited use range. Was limited. Further, although the method using metal powder and solder powder can be expected to achieve ohmic connection by metal conduction, the connection is brittle and easily broken by a heat shock test or the like, and is not practically used.
【０００７】それ故に本発明の他の目的は上記、銅また
は銅合金の新規な接続原理を応用した新規な概念の多層
配線基板とそれに使用される導電ペーストとを提供する
ことである。Therefore, another object of the present invention is to provide a multilayer wiring board having a novel concept applying the above-described novel connection principle of copper or a copper alloy, and a conductive paste used therefor.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するため
の手段として、本発明は 少なくとも一方が銅または銅
合金である金属の接合に際して、銅または銅合金である
金属の接合面に貴金属薄膜層、酸化膜除去剤塗布層また
は銅またはその合金粉末と酸化膜除去剤とを主成分とす
る導電ペースト層のいずれかを形成して後、接合面を重
ね合わせ、１７０℃以上に加熱、加圧して接合すること
を特徴とする。As a means for solving the above-mentioned problems, the present invention relates to a method for joining a metal having at least one of copper and a copper alloy, the method comprising: After forming either an oxide film remover coating layer or a conductive paste layer containing copper or its alloy powder and an oxide film remover as main components, the joining surfaces are overlapped, and heated and pressed to 170 ° C. or more. It is characterized by joining.
【０００９】さらに本発明にかかる多層配線基板の製造
方法は絶縁性接着層の所定の部分に開けた孔に貴金属、
銅またはそれらの合金からなる導電粉末と酸化層除去剤
とを主たる構成要素とする導電ペーストを刷り込んだ
後、１７０℃以上の温度で加熱プレスして酸化膜が除去
された銅箔の表面と前記導電性粉末とを接合界面におけ
る銅原子の拡散により接合させることを特徴とする。さ
らに本発明にかかる多層基板は、絶縁性接着層に形成さ
れた孔に導電性粒子と酸化膜除去剤とを含む導電ペース
トが充填され、前記孔を覆うように銅箔で絶縁性接着層
が挟まれており、酸化膜が除去された銅箔の表面と前記
導電性粉末とが接合界面における銅原子の拡散接合によ
り電気的に接続されていることを特徴とする。Further, the method for manufacturing a multilayer wiring board according to the present invention is characterized in that a noble metal is inserted into a hole formed in a predetermined portion of the insulating adhesive layer.
After imprinting a conductive paste mainly composed of a conductive powder of copper or an alloy thereof and an oxide layer remover, the oxide film is removed by hot pressing at a temperature of 170 ° C. or more.
Between the surface of the copper foil and the conductive powder
The bonding is performed by diffusion of copper atoms . Further, in the multilayer substrate according to the present invention, holes formed in the insulating adhesive layer are filled with a conductive paste containing conductive particles and an oxide film remover, and the insulating adhesive layer is made of copper foil so as to cover the holes. Between the surface of the copper foil from which the oxide film has been removed
The conductive powder is electrically connected to the conductive powder by diffusion bonding of copper atoms at a bonding interface .
【００１０】本発明のもう一つの特徴は上記酸化層除去
剤がカルボン酸またはカルボキシル基を構造中に含むポ
リマまたはオリゴマであることである。さらに、本発明
の他の一つの特徴は導電ペーストのバインダ樹脂に酸化
層除去剤を使用することである。Another feature of the present invention is that the oxidized layer removing agent is a polymer or an oligomer containing a carboxylic acid or carboxyl group in the structure. Still another feature of the present invention is to use an oxide layer removing agent in a binder resin of the conductive paste.
【００１１】[0011]
【作用】少なくとも一方が銅または銅合金である金属同
士の接合に際して、銅または銅合金である金属の接合面
に貴金属薄膜層、酸化膜除去剤塗布層または銅またはそ
の合金粉末と酸化膜除去剤とを主成分とする導電ペース
ト層のいずれかを形成して後，接合面を重ね合わせ、１
７０℃以上に加熱、加圧することにより、接合面の銅原
子が相対する金属の表面に拡散して接合がなされる。When joining metals having at least one of copper or a copper alloy, a noble metal thin film layer, an oxide film remover coating layer, or copper or its alloy powder and an oxide film remover are applied to the joining surface of the copper or copper alloy metal. After forming any one of the conductive paste layers mainly composed of
By heating and pressurizing to 70 ° C. or more, copper atoms on the bonding surface diffuse to the surface of the opposing metal, and bonding is performed.
【００１２】更に上記原理により、絶縁性接着層の所定
の部分すなわちビアホール部分に貴金属、銅またはそれ
らの合金からなる導電粉末と酸化膜除去剤とを主たる構
成要素とする導電ペーストを刷り込んだ後、１７０℃以
上の温度で加熱プレスして製造することにより、絶縁性
接着層を挟んだ上下の銅箔と導電ペースト内の導電粉末
とが金属原子の拡散による金属結合で接合され、製造時
に導電ペーストを使用したにもかかわらず、上下の銅箔
が完全に電気的に接続される。このため、従来の銀スル
ーホール基板と同様に安いコストで製造できるにもかか
わらず、めっき法によるビアホールと同様に低電流域に
おいても接続抵抗が増大することがなく、全ての回路に
使用できる多層配線板が得られる。Further, according to the above principle, after a predetermined portion of the insulating adhesive layer, that is, a via hole portion, is printed with a conductive paste mainly composed of a conductive powder of noble metal, copper or an alloy thereof and an oxide film remover, By heating and manufacturing at a temperature of 170 ° C. or higher, the upper and lower copper foils sandwiching the insulating adhesive layer and the conductive powder in the conductive paste are joined by metal bonding by diffusion of metal atoms, and the conductive paste is produced at the time of manufacturing. However, the upper and lower copper foils are completely electrically connected. For this reason, despite the fact that it can be manufactured at a low cost in the same way as a conventional silver through-hole substrate, the connection resistance does not increase even in a low current region as in the case of the via hole formed by plating, and can be used in all circuits. A wiring board is obtained.
【００１３】[0013]
【実施例】以下、本発明の実施例につき説明する。Embodiments of the present invention will be described below.
【００１４】本発明に使用される銅または銅合金として
は電解銅、圧延銅、青銅、真鍮、ベリリウム銅、砲金な
ど一般の銅またはその合金が使用できる。これらは板
状、箔状、線状、棒状などいかなる形状でもよい。これ
ら金属は表面の酸化皮膜を除去した後に、貴金属メッキ
される。As the copper or copper alloy used in the present invention, general copper or its alloy such as electrolytic copper, rolled copper, bronze, brass, beryllium copper, and gunmetal can be used. These may have any shape such as a plate shape, a foil shape, a line shape, a bar shape, and the like. These metals are plated with a noble metal after removing the oxide film on the surface.
【００１５】めっき前処理としての酸化膜の除去は各種
手段が公知である。例えば、酸によるエッチング、機械
的研磨、還元雰囲気中での加熱など、材料の要求特性、
形状により任意に選択可能であるが、次の工程である貴
金属めっき工程との兼ね合いでバランスの取れた工程を
選ぶことが望ましい。すなわち、めっき工程が湿式で行
われる場合は酸化膜除去も湿式エッチングが好ましく、
めっき工程が真空蒸着、ＣＶＤ、スパッタ等のドライプ
ロセスで行われる場合は酸化膜除去もドライ工程で行わ
れることが好ましい。Various means are known for removing an oxide film as a pretreatment for plating. For example, required properties of materials such as etching with acid, mechanical polishing, heating in a reducing atmosphere,
Although it can be arbitrarily selected depending on the shape, it is desirable to select a balanced process in consideration of the next process of the noble metal plating process. In other words, when the plating step is performed by a wet method, the oxide film is preferably removed by wet etching.
When the plating process is performed by a dry process such as vacuum deposition, CVD, or sputtering, it is preferable that the oxide film is also removed by the dry process.
【００１６】それ故に、銅箔などの連続フィルムは湿式
で連続に行われることが好ましく、単体部品のような小
さな場合は還元雰囲気炉などを使用してもよい。Therefore, it is preferable that a continuous film such as a copper foil is continuously formed by a wet method. In the case of a small piece such as a single component, a reducing atmosphere furnace may be used.
【００１７】酸化膜除去に引き続き薄層の貴金属めっき
を行う。貴金属めっきの目的は銅または銅合金の表面酸
化を防止し、かつ接合時の銅の拡散を妨げないためであ
る。Following the removal of the oxide film, a thin noble metal plating is performed. The purpose of the noble metal plating is to prevent surface oxidation of copper or copper alloy and not to hinder the diffusion of copper during bonding.
【００１８】すなわち、一般に多く実施されているニッ
ケルめっきは表面酸化は防止するものの、同時に銅の拡
散をも妨げるため、表面にニッケルの様な卑金属めっき
を施した銅または銅合金は本発明のような低温で接合す
ることはできない。つまり、本発明の特徴は清浄な銅表
面の貴金属めっきの採用によって初めて可能となるので
ある。このため、貴金属めっき皮膜は薄いもので充分で
ある。例えば、以下の具体的な実施例に見られるごと
く、その厚みは１００Åあれば充分に目的を達する。貴
金属層が厚くても一般的には特に支障はないが、プロセ
スコストが上がるのみであまり意味はない。さらに、電
気回路に使用する場合は銀の使用量が多い場合は信頼性
の低下につながる場合もある。それ故に貴金属メッキ層
は必要最小限の厚みにすることが望ましく、該当製品の
使用条件に合わせて設定すればよい。That is, although nickel plating, which is generally practiced, prevents surface oxidation, it also impedes the diffusion of copper at the same time. Therefore, a copper or copper alloy having a surface coated with a base metal such as nickel is used as in the present invention. Cannot be joined at very low temperatures. In other words, the features of the present invention can be realized only by adopting a noble metal plating on a clean copper surface. Therefore, a thin noble metal plating film is sufficient. For example, as shown in the following specific examples, a thickness of 100 mm is sufficient for the purpose. In general, there is no problem even if the noble metal layer is thick, but it does not make much sense because it only increases the process cost. Further, when used in an electric circuit, a large amount of silver may lead to a decrease in reliability. Therefore, it is desirable that the noble metal plating layer has a minimum necessary thickness, and may be set in accordance with the use conditions of the product.
【００１９】貴金属めっきの方法としては種々の方法が
知られているが、被めっき物の形状に応じて種々選択可
能である。例えば、連続した銅箔などの場合は電気めっ
きにより行うことが効率的かつ管理が容易である。これ
に対し、単体部品などの場合は無電界めっき法を採用す
る方が形状に依存せずに均一なメッキ膜厚が得られる。
さらに、連続したフィルム状のものであれば真空蒸着
法、ＣＶＤ法、スパッタ法なども採用できる。Various methods of noble metal plating are known, and various methods can be selected according to the shape of the object to be plated. For example, in the case of a continuous copper foil or the like, it is efficient and easy to manage by electroplating. On the other hand, in the case of a single component or the like, adopting the electroless plating method can obtain a uniform plating film thickness without depending on the shape.
Furthermore, a vacuum evaporation method, a CVD method, a sputtering method, or the like can be adopted as long as the film is a continuous film.
【００２０】めっきに使用する貴金属としては、金、
銀、白金、パラジウム、ロジウム等が挙げられるが、経
済性等を考慮すると金または銀の使用が望ましい。ただ
し、銀めっきした後、室内で長期保存すると硫化を受け
るため、銀メッキ後接合までは開放系で長時間の保存は
避けることが望ましい。The noble metals used for plating include gold,
Silver, platinum, palladium, rhodium and the like can be mentioned, but use of gold or silver is desirable in view of economy and the like. However, after silver plating, if stored in a room for a long period of time, sulfuration occurs, so it is desirable to avoid long-term storage in an open system until bonding after silver plating.
【００２１】めっきに代えて酸化膜除去剤を塗布して接
合するに際し、接合しようとする銅または銅合金の酸化
膜が厚い場合はあらかじめ酸化膜を除去することが望ま
しい。前処理としての酸化膜の除去は各種手段が公知で
ある。例えば、酸によるエッチング、機械的研磨、還元
雰囲気中での加熱など、材料の要求特性、形状により任
意に選択可能である。酸化膜が除去されても、銅または
銅合金は空気中で急速に酸化されるためきわめて薄い酸
化膜は存在する。When applying an oxide film removing agent instead of plating and joining, if the oxide film of copper or copper alloy to be joined is thick, it is desirable to remove the oxide film in advance. Various means are known for removing the oxide film as a pretreatment. For example, it can be arbitrarily selected according to the required characteristics and shape of the material, such as etching with an acid, mechanical polishing, and heating in a reducing atmosphere. Even if the oxide film is removed, an extremely thin oxide film exists because the copper or copper alloy is rapidly oxidized in air.
【００２２】銅または銅合金表面に塗布する酸化膜除去
剤としては、カルボン酸またはカルボキシル基を構造中
に含むポリマまたはオリゴマを使用することが望まし
い。これらの例としてはカプロン酸、エナント酸、カプ
リル酸、２ーエチルヘキサン酸、ステアリン酸等の直鎖
または側鎖型の飽和脂肪酸、オレイン酸、リノール酸、
リノレン酸などの不飽和脂肪酸、アビエチン酸、コハク
酸、マロン酸等のカルボン酸、ポリアクリル酸、アルキ
ッド樹脂、末端カルボキシポリブタジエン等がある。な
お、本明細書中で述べる酸化膜除去剤とは、表面を酸化
された銅ないしは貴金属表面を金属状態に変化させる、
ないしは保つ物質のことである。As the oxide film removing agent applied to the copper or copper alloy surface, it is desirable to use a polymer or an oligomer containing a carboxylic acid or a carboxyl group in the structure. Examples of these are straight-chain or side-chain saturated fatty acids such as caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid and stearic acid, oleic acid, linoleic acid,
Examples include unsaturated fatty acids such as linolenic acid, carboxylic acids such as abietic acid, succinic acid, and malonic acid, polyacrylic acid, alkyd resins, and terminal carboxypolybutadiene. Incidentally, the oxide film removing agent described in the present specification, the surface oxidized copper or noble metal surface changes to a metal state,
Or a substance to be kept.
【００２３】これら酸化膜除去剤は直接、または溶剤な
どに溶解して表面に塗布することができる。上記以外
で、従来から半田付けフラックス用として使用されてき
た活性剤例えば、塩酸ジメチルアミン等も酸化膜除去剤
として使用できるが、これら無機系の活性剤を使用した
場合は接合後洗浄して除去することが必要である。These oxide film removing agents can be applied directly or after dissolving in a solvent or the like. In addition to the above, activators conventionally used for soldering fluxes, such as dimethylamine hydrochloride, can also be used as an oxide film remover, but when these inorganic activators are used, they are removed by washing after bonding. It is necessary to.
【００２４】接合に要する温度は少なくとも１７０℃以
上が必要である。温度がこれより低い場合は銅の拡散が
起こらず、接合することが出来ない。温度の上限は特に
ないが、一般的に銅またはその合金は酸化や高温により
により特性変化を受け易いため、接合可能な範囲で低い
温度で接合することが望ましい。当然のこととして接合
温度が高いほど短時間で接合が可能である。さらに、条
件が許せば超音波の併用も効果がある。The temperature required for joining must be at least 170 ° C. or higher. If the temperature is lower than this, diffusion of copper does not occur and bonding cannot be performed. Although there is no particular upper limit on the temperature, copper or an alloy thereof is generally susceptible to a change in characteristics due to oxidation or high temperature. As a matter of course, the higher the bonding temperature, the shorter the bonding time. Furthermore, combined use of ultrasonic waves is effective if conditions permit.
【００２５】本発明に必要とされる圧力は、単に接合部
分の相互の表面同士を近接させるためのものであるか
ら、極端な高圧は不必要であるが、接合圧力を低下させ
るためには接合面の表面粗度を可能な限り小さくするこ
と望ましい。ただし、表面粗度が不良な場合でも、加圧
により弾性の弱い銅または銅合金は塑性変形して接合は
可能となる。さらに、接合に際して接合しようとする銅
または銅合金の間に金、銀などの延性に富む金属を挟む
ことにより低い接合圧力で接合強度を上げることができ
る。Since the pressure required for the present invention is merely for bringing the surfaces of the joining portions close to each other, an extremely high pressure is not necessary. It is desirable to make the surface roughness of the surface as small as possible. However, even when the surface roughness is poor, copper or a copper alloy having low elasticity is plastically deformed by pressurization, so that bonding can be performed. Furthermore, by joining a highly ductile metal such as gold or silver between copper or a copper alloy to be joined at the time of joining, joining strength can be increased at a low joining pressure.
【００２６】本発明は上記板材の接合だけでなく、銅ま
たはその合金粉を導電材料とする樹脂系導電ペーストに
使用することができる。すなわち、導電ペーストのバイ
ンダ樹脂として上記酸化膜除去剤の性質を有する樹脂を
使用するか、またはバインダ樹脂中に酸化膜除去剤を添
加し、ペーストを塗布後、加圧しつつペーストを加熱プ
レスすることにより、ペースト中の銅またはその合金粉
が相互に接合して導電経路を形成することができる。バ
インダ樹脂としては一般に使用されている熱可塑性樹脂
または熱硬化性樹脂が使用できる。ここに得られた導電
経路は金属結合によるものであるため、オーミック性を
示し、非常に微小な電流においても抵抗が増加すること
はない。さらに、上記導電ペーストは電気的用途だけで
なく、銅を接合する際の補助剤として使用することがで
きる。すなわち、接合しようとする銅またはその合金の
表面粗度が不良の場合に、表面の凹部の充填剤としても
使用できるものである。The present invention can be used not only for bonding the above-mentioned plate members but also for a resin-based conductive paste using copper or its alloy powder as a conductive material. That is, a resin having the properties of the oxide film remover is used as a binder resin of the conductive paste, or an oxide film remover is added to the binder resin, and after the paste is applied, the paste is heated and pressed while applying pressure. Thereby, the copper or the alloy powder thereof in the paste can be bonded to each other to form a conductive path. As the binder resin, a generally used thermoplastic resin or thermosetting resin can be used. Since the conductive path obtained here is based on metal bonding, it exhibits ohmic properties, and the resistance does not increase even with a very small current. Further, the above-mentioned conductive paste can be used not only for electrical purposes but also as an auxiliary agent for joining copper. That is, when the surface roughness of copper or its alloy to be joined is poor, it can be used as a filler for concave portions on the surface.
【００２７】本発明に使用する導電粉末としては金、
銀、銅およびそれらの合金の粉末が使用できる。これら
以外の貴金属でも使用可能ではあるが、導通抵抗が高
く、価格も高価でありあまり使用の意味がない。これら
粉末は通常、球状、燐片状、樹脂状などの形状で市場に
供給されているが、本発明においては球状の導電粉末を
使用すると後述するプレス圧力が少なくてすみ、最も都
合がよい。なお、ここに述べる球状とは完全な真球状で
ある必要はなく、多面体を含む板状でないものを示すも
のである。As the conductive powder used in the present invention, gold,
Silver, copper and their alloy powders can be used. Although noble metals other than these can be used, they have high conduction resistance, are expensive, and have little meaning. These powders are usually supplied to the market in the form of spheres, flakes, resins, and the like. However, in the present invention, the use of spherical conductive powders is most convenient because the pressing pressure described below can be reduced. In addition, the spherical shape described here does not need to be a perfect true sphere, but indicates a non-plate-like shape including a polyhedron.
【００２８】酸化膜除去剤としては、従来から半田付け
などにおいて使用されてきた活性剤が使用可能である
が、長期信頼性を考慮すると、無機系の活性剤よりは活
性の緩やかな有機系のカルボン酸またはカルボキシル基
を構造中に含むオリゴマまたはポリマが好ましい。これ
らの例としてはプロピオン酸、カプロン酸、エナント
酸、カプリル酸、２-エチルヘキサン酸、ステアリン酸
などの直鎖または側鎖型の飽和脂肪酸、オレイン酸、リ
ノール酸、リノレン酸などの不飽和脂肪酸や、アビエチ
ン酸、コハク酸、マロン酸、アスパラギン酸、アスコル
ビン酸などの各種カルボン酸またはアミノカルボン酸お
よびその誘導体、ポリアクリル酸、アクリル酸共重合
体、アルキッド樹脂、ポリブタジエン誘導体等側鎖また
は末端ににカルボキシル基を有するオリゴマまたはポリ
マ等が挙げられる。As the oxide film remover, an activator conventionally used in soldering or the like can be used. However, considering long-term reliability, an organic activator having a slower activity than an inorganic activator can be used. Oligomers or polymers containing a carboxylic acid or carboxyl group in the structure are preferred. Examples of these are straight-chain or side-chain saturated fatty acids such as propionic acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid and stearic acid, and unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid. And carboxylic acids such as abietic acid, succinic acid, malonic acid, aspartic acid and ascorbic acid or aminocarboxylic acids and derivatives thereof, polyacrylic acid, acrylic acid copolymers, alkyd resins, polybutadiene derivatives, etc. And an oligomer or polymer having a carboxyl group.
【００２９】低級脂肪酸等沸点が低い活性剤を使用する
場合は実施例１に示すごとく、基板の製造に際してこれ
ら活性剤が作用して導電経路が形成して後、半田付け時
や通常の使用時に導通信頼性に悪影響を与えないため
に、エポキシ樹脂等これら活性剤と反応して安定な化合
物を与える樹脂材料と併用することが望ましい。When an activator having a low boiling point such as a lower fatty acid is used, as shown in Example 1, after the activator acts upon the production of a substrate to form a conductive path, it is used during soldering or during normal use. In order not to adversely affect the conduction reliability, it is desirable to use a resin material such as an epoxy resin which reacts with these activators to give a stable compound.
【００３０】本発明にかかる多層配線基板の製造につ
き、以下図面により説明する。図１（ａ）において絶縁
性接着層１の所定の部分に開けた孔２に上記導電ペース
ト３をスキージ４などを用いて刷り込み、図１（ｂ）に
示すように２枚の銅箔５、５’で挟んでから図１（ｃ）
に示すように１７０℃以上の温度で加熱プレスする。こ
れにより図２（ａ）に示す必要部分に導通経路（ビアホ
ール）６を形成した両面銅貼板７が形成できる。両面銅
貼板７は常法により不要な銅箔部分をエッチングするこ
とにより図２（ｂ）に示す両面配線基板８とすることが
できる。ここに得られたビアホール６内の導電粉末は既
に述べたごとく金属結合により接合されているため導通
抵抗が低く、かつ、ビアホール内の導電粉末は両面の銅
箔とも金属結合しているため、めっき法で製造されたビ
アホールと同様に低電流領域においても抵抗が増大する
こともなく、信頼性に優れた両面配線基板が得られる。The manufacture of the multilayer wiring board according to the present invention will be described below with reference to the drawings. In FIG. 1A, the conductive paste 3 is printed using a squeegee 4 or the like into a hole 2 formed in a predetermined portion of the insulating adhesive layer 1, and two copper foils 5 are formed as shown in FIG. Fig. 1 (c)
And hot pressing at a temperature of 170 ° C. or higher. Thus double-sided copper-clad plate 7 forming a conductive path (via hole) 6 necessary portion shown in FIG. 2 (a) can be formed. The double-sided copper-clad board 7 can be formed into a double-sided wiring board 8 shown in FIG. Since the conductive powder in the via hole 6 obtained here is bonded by metal bonding as described above, the conductive resistance is low, and the conductive powder in the via hole is also metal bonded to both surfaces of the copper foil. Similar to the via hole manufactured by the method, the resistance does not increase even in a low current region, and a double-sided wiring board excellent in reliability can be obtained.
【００３１】こうして得られた複数の両面配線基板８、
８’、８”、を図３（ａ）、（ｂ）に示すように上記導
電ペーストを刷込んだ複数の絶縁製接着層９、９’と共
に加熱プレスすることによりそれぞれ４層ないし６層の
多層配線基板が容易に形成できる。加熱プレスに際して
両面配線基板と絶縁性接着層の数を増やすことにより、
より多層の配線基板が形成できることは当然である。The plurality of double-sided wiring boards 8 thus obtained,
As shown in FIGS. 3 (a) and 3 (b), 8 ′ and 8 ″ are heated and pressed together with the plurality of insulating adhesive layers 9 and 9 ′ on which the conductive paste is imprinted, thereby forming four to six layers. A multi-layer wiring board can be easily formed by increasing the number of double-sided wiring boards and insulating adhesive layers during hot pressing.
Naturally, a multi-layer wiring board can be formed.
【００３２】上記材料組成からなる導電性ペーストを絶
縁性接着層の所定の部分に設けられた孔に刷り込む技術
はスクリーン印刷を用いる方法、ピンを用いる方法、離
形フィルムを張り合わせ、離形フィルムごと孔を開けて
直接刷り込んで後離形フィルムを剥離する方法など公知
の方法を採用することができる。The technique of imprinting a conductive paste having the above-described material composition into a hole provided in a predetermined portion of the insulating adhesive layer includes a method using screen printing, a method using pins, laminating a release film, and attaching the release film together. A known method such as a method in which a hole is formed, the image is directly imprinted, and the post-release film is peeled off can be employed.
【００３３】離型フィルムを使用する方法につき、図４
を用いて説明する。図４（ａ）において、先ず絶縁性接
着層１に離型フィルム１０を貼り合わせ、次いで所定の
場所にビアホ−ル２を離型フィルム１０ごと孔をあけ
る。このビアホ−ル２に導電性ペ−スト３をスキ−ジ４
などを用いて刷り込む。続いて図４（ｂ）に示すように
離型フィルム１０を引きはがすことにより、所定の場所
に導電性ペ−スト３を有し、かつ絶縁性接着層表面には
導電性物質が一切存在しない絶縁性接着層１を得ること
ができる。Referring to the method using a release film, FIG.
This will be described with reference to FIG. In FIG. 4 (a), first, a release film 10 is bonded to the insulating adhesive layer 1, and then a via hole 2 is formed in a predetermined place along with the release film 10. A conductive paste 3 is placed on the via hole 2 with a squeegee 4.
Imprint using such as. Subsequently, as shown in FIG. 4B, the release film 10 is peeled off, so that the conductive paste 3 is provided at a predetermined location and no conductive substance is present on the surface of the insulating adhesive layer. An insulating adhesive layer 1 can be obtained.
【００３４】なお、導電性ペ−スト３の導電材料として
銅粉を使用した場合は絶縁性接着層表面が導電性ペ−ス
ト３で汚染されてもエッチングにより銅粉が除去される
ため、必ずしも離型フィルムを使用する必要はない。When copper powder is used as the conductive material of the conductive paste 3, even if the surface of the insulating adhesive layer is contaminated with the conductive paste 3, the copper powder is removed by etching. There is no need to use a release film.
【００３５】導電ペーストを所定の部分に刷り込んだ絶
縁性接着層は必用に応じ溶剤を乾燥して後２枚の銅箔で
挟み加熱プレスして両面板を製造する。４層以上の多層
板の製造は上記加熱プレス操作の繰り返しにより行うこ
とが出来る。The insulating adhesive layer in which the conductive paste is imprinted on a predetermined portion is dried, if necessary, by a solvent, and then sandwiched between two pieces of copper foil and heated and pressed to produce a double-sided board. The production of a multilayer board having four or more layers can be performed by repeating the above-mentioned hot press operation.
【００３６】加熱プレスに要する温度は１７０℃以上、
好ましくは１８０℃以上である。１７０℃未満の温度で
は上記ペースト中の金属の拡散が生じず、導電ペースト
内の金属同士の接合が生じないため、初期抵抗値は低く
てもオーミックな接続にならず、さらに信頼性試験にお
いて断線ないし抵抗値増加が発生する。The temperature required for the hot press is 170 ° C. or higher,
Preferably it is 180 ° C. or higher. At a temperature lower than 170 ° C., the diffusion of the metal in the paste does not occur, and the metal in the conductive paste does not bond to each other. Or an increase in the resistance value occurs.
【００３７】プレスに要する圧力はペースト中で導体と
して使用する金属材料により変化する。すなわち、金、
銀などの延性に優れた材料は比較的低圧で接合するのに
対し、銅ないしはその合金のように比較的変形しにくい
導体の場合は高めの圧力で接合することが好ましい。The pressure required for pressing varies depending on the metal material used as a conductor in the paste. That is, gold,
A highly ductile material such as silver is joined at a relatively low pressure, whereas a conductor that is relatively difficult to deform, such as copper or an alloy thereof, is preferably joined at a higher pressure.
【００３８】以上本発明について述べてきたが、さら
に、上記導電ペーストは電気的用途だけでなく、一般的
に、貴金属や銅またはその合金をを接合する際の補助剤
として使用することができる。すなわち、接合しようと
する貴金属、銅またはその合金の表面粗度が不良の場合
に、表面の凹部の充填剤としても上記導電ペーストは使
用できるものである以下具体的な実施例により説明す
る。Although the present invention has been described above, the above-mentioned conductive paste can be used not only for electrical applications but also generally as an auxiliary agent for joining a noble metal, copper or an alloy thereof. That is, when the surface roughness of a noble metal, copper, or an alloy thereof to be joined is poor, the above-mentioned conductive paste can be used as a filler for a concave portion on the surface.
【００３９】（実施例１）予め脱脂処理した厚さ０．５
ｍｍの銅板の表面を硫酸ー過酸化水素水溶液でソフトエ
ッチングし、水洗の後表面に電気めっき法により銀めっ
きした。めっき液には市販の非シアン系銀めっき液を使
用し、陽極に銀板を用い０．５Ａ／ｄｍ2の電流密度で
５００Åの銀めっきを行った。この結果、銅板表面は銀
白色になった。(Example 1) Thickness 0.5 preliminarily degreased
The surface of a copper plate having a thickness of 2.5 mm was soft-etched with a sulfuric acid-hydrogen peroxide aqueous solution, washed with water, and then silver-plated on the surface by an electroplating method. A commercially available non-cyanide silver plating solution was used as the plating solution, and a silver plate was used as the anode, and silver plating was performed at a current density of 0.5 A / dm 2 at 500 °. As a result, the surface of the copper plate became silver-white.
【００４０】上記銀めっきした後水洗、乾燥した銅板を
２枚重ね、硬質クロムめっきした鋼板に挟んで加熱プレ
スした。プレス条件は１８０℃、３０分、３００ｋｇ／
ｃｍ 2とした。この結果、２枚の銅板は強固に接合され
た。プレス時に空気に触れていた銅板の銀めっき表面は
酸化を受けて着色していることから、上記プレス温度で
銀めっき面を通して銅の拡散が生じていることが確認さ
れた。接合強度を図るため、引っ張り試験機でせん断剥
離強度の測定を行った結果、接合強度は４００〜５００
ｋｇ／ｃｍ2を示した。After the silver plating, the copper plate washed with water and dried
Two sheets are stacked and sandwiched between hard chrome plated steel sheets.
I did it. Press conditions are 180 ° C, 30 minutes, 300kg /
cm TwoAnd As a result, the two copper plates are firmly joined
Was. The silver plated surface of the copper plate that was in contact with air during pressing
Because it is oxidized and colored, at the above press temperature
It was confirmed that copper diffusion occurred through the silver-plated surface.
Was. Shearing with a tensile tester to achieve joint strength
As a result of measuring the separation strength, the joining strength was 400 to 500.
kg / cmTwoshowed that.
【００４１】比較のため、銅板をソフトエッチング、水
洗、乾燥の後２枚重ねて上記条件で加熱プレスしたが、
接合は生じなかった。さらに比較のため、上記銀めっき
した銅板と、ソフトエッチング、水洗したのみで銀めっ
きを行わなかった銅板とを重ね合わせて上記条件で加熱
プレスを行ったがやはり接合はできなかった。For comparison, a copper plate was soft-etched, washed with water, dried, and two sheets were stacked and heated and pressed under the above conditions.
No bonding occurred. Further, for comparison, the silver-plated copper plate and the copper plate which had been soft-etched and washed with water but not subjected to silver plating were overlapped and heated and pressed under the above-mentioned conditions, but joining was still impossible.
【００４２】以上の結果から、薄層の銀めっきをした銅
板同士を重ねて加熱プレスする、本発明の手法で初めて
銅板同士の接合がなされることが確認された。From the above results, it was confirmed that the copper plates were joined for the first time by the method of the present invention in which thin silver-plated copper plates were stacked and heated and pressed.
【００４３】（実施例２）１８μの銅箔の平滑面に実施
例１と同様にして銀めっきをおこなった。めっき厚みは
１００Åとした。この銅箔を実施例１の銀めっき銅板に
重ね、実施例１の条件で加熱プレスした。ただし圧力は
７５０ｋｇ／ｃｍ2とした。さらに、銅箔の上から１ｍ
ｍの銅板を重ねて箔に均一に圧力がかかるようにした。
この場合も銅箔は銀めっきした銅板には接合したが、均
圧用に設置した銅板と接合することはなかった。Example 2 Silver plating was performed on a smooth surface of an 18 μm copper foil in the same manner as in Example 1. The plating thickness was 100 °. This copper foil was overlaid on the silver-plated copper plate of Example 1 and heated and pressed under the conditions of Example 1. However, the pressure was 750 kg / cm 2 . In addition, 1m from the top of the copper foil
m copper plates were stacked so that pressure was applied evenly to the foil.
Also in this case, the copper foil was bonded to the silver-plated copper plate, but was not bonded to the copper plate installed for equalizing.
【００４４】プレスの結果、銅箔は強固に銅板に接合
し、Ｔ剥離の引剥しテストを行ったが、銅箔が切れて接
合強度の正確な測定はできなかった。As a result of the pressing, the copper foil was firmly bonded to the copper plate, and a peeling test of T peeling was performed. However, the copper foil was cut and the bonding strength could not be measured accurately.
【００４５】（実施例３）表面汚染の影響を見るため
に、実施例１で得られた銀めっき銅板の表面に硬化剤を
含有しないエポキシ樹脂（エポキシ当量１８０のエピク
ロルヒドリンービスフェノールΑタイプ）を塗布し実施
例１の条件で加熱プレスした。この結果、実施例１と同
様の強固な接合が得られた。この結果からたとえ表面に
樹脂成分などが付着していても、接合の邪魔にはならな
いことが確認された。Example 3 An epoxy resin (epichlorohydrin-bisphenol Α type with an epoxy equivalent of 180) containing no curing agent was applied to the surface of the silver-plated copper plate obtained in Example 1 in order to see the effect of surface contamination. Then, it was heated and pressed under the conditions of Example 1. As a result, the same strong bonding as in Example 1 was obtained. From this result, it was confirmed that even if a resin component or the like adhered to the surface, it did not hinder the joining.
【００４６】（実施例４）厚さ０．５ｍｍの銀板と実施
例１で製造した薄層銀めっき銅板とを重ね、実施例１の
条件でプレスした。この場合も実施例１と同様に強固な
接合が得られた。この際、銅に接した銀板表面の銅板の
端部から約０．５ｍｍ付近の銀板表面にまで銅の拡散が
観察され、銀内部に銅原子が拡散して接合に寄与してい
ることがわかった。更に、銀銅の界面を波長分散型ｘ線
マイクロアナライザー（ＸＭＡ)で調べたところ、図５
に示す様に銀、銅それぞれに相手の金属中に数μｍにわ
たって拡散していることが確認された。Example 4 A silver plate having a thickness of 0.5 mm and the thin silver-plated copper plate manufactured in Example 1 were overlaid and pressed under the conditions of Example 1. Also in this case, a strong joint was obtained as in Example 1. At this time, diffusion of copper was observed from the edge of the copper plate on the surface of the silver plate in contact with copper to the surface of the silver plate at about 0.5 mm, and copper atoms diffused inside silver and contributed to the bonding. I understood. Further, when the interface between silver and copper was examined with a wavelength dispersive x-ray microanalyzer (XMA), FIG.
As shown in the figure, it was confirmed that silver and copper were diffused into the metal of the other party over several μm.
【００４７】（実施例５）実施例１において加熱プレス
温度を１７０℃、時間を１時間とした場合は銅板同士の
接合は行われたが、取り出し後、僅かな衝撃で接合が外
れる弱いものであった。Example 5 In Example 1, when the heating press temperature was set to 170 ° C. and the time was set to 1 hour, the copper plates were joined to each other. there were.
【００４８】（実施例６）実施例１において銀のめっき
厚みを１００Åにした場合は実施例１と同様の強固な接
合が得られた。この結果から銀の厚みはきわめて薄くて
も良いことがわかった。Example 6 When the silver plating thickness was set to 100 ° in Example 1, the same strong bonding as in Example 1 was obtained. From this result, it was found that the thickness of silver may be extremely thin.
【００４９】（実施例７）厚さ０．２ｍｍのりん青銅板
に実施例１と同様に５００Å銀メッキした。本めっきり
ん青銅板を重ね、１８０℃、３０分、２０００ｋｇ／ｃ
ｍ2の条件でプレスしたところ、上記りん青銅板は接合
した。しかし、接合力は弱く、接合部分を曲げると剥が
れた。そこで接合温度を２２０℃にしたところ、強固な
接合が得られ、りん青銅の弾性も損なわれることはなか
った。(Example 7) A phosphor bronze plate having a thickness of 0.2 mm was plated with 500 ° silver in the same manner as in Example 1. Laminate this plated phosphor bronze plate, 180 ° C, 30 minutes, 2000kg / c
When pressed under the conditions of m 2, the phosphor bronze plate was joined. However, the joint strength was weak, and the joint peeled off when bent. Then, when the joining temperature was set to 220 ° C., strong joining was obtained, and the elasticity of the phosphor bronze was not impaired.
【００５０】（実施例８）プリント配線板の銅箔に金め
っきを行った。めっき厚みは２００Åとした。一方、配
線板に接続するＱＦＰパッケージのＩＣのリード線の半
田めっき層をエッチングで除去して後、リード線に銅メ
ッキし、さらに銀めっきを行った。めっき厚みはそれぞ
れ５μ、５００Åとした。上記ＩＣのリード線を所定の
配線板上に配置して後、治具でリード線をおさえつつ、
２２０℃で１分間加熱したところ、リード線は強固に配
線板に接続された。Example 8 Gold plating was performed on a copper foil of a printed wiring board. The plating thickness was 200 mm. On the other hand, after the solder plating layer of the lead wire of the QFP package IC connected to the wiring board was removed by etching, the lead wire was plated with copper and further plated with silver. The plating thickness was 5 μ and 500 °, respectively. After arranging the lead wire of the above IC on a predetermined wiring board, hold down the lead wire with a jig,
After heating at 220 ° C. for 1 minute, the lead wire was firmly connected to the wiring board.
【００５１】本接続による回路と、従来の半田による接
続の回路とを冷熱サイクル試験にかけたところ、本実施
例による回路は半田接合による回路に比較し、倍以上の
寿命を示した。又、当然のこととして、半田による回路
は２００℃の加熱で破壊したのに対し、本実施例による
回路は２００℃の加熱でなんら異常を示さなかった。When a circuit based on the actual connection and a circuit based on the conventional solder were subjected to a thermal cycle test, the circuit according to the present example showed a service life twice or more that of the circuit based on the solder joint. As a matter of course, the circuit made of solder was broken by heating at 200 ° C., whereas the circuit according to the present example showed no abnormality at 200 ° C.
【００５２】（実施例９）厚さ２ｍｍの圧延銅板の表面
を#１２００サンドペーパで研磨し、水洗、乾燥した
後、アビエチン酸５％アセトン溶液を塗布し、乾燥して
処理銅板を作製した。上記処理銅板２枚を重ね、１８０
℃、３８０ｋｇ／ｃｍ2で３０分加熱プレスして銅板を
接合した。ここに得られた接合銅板から引張り試験片を
切り出し、せん断引張り試験を行った。この結果、せん
断引張り強さは２４０ないし２６０ｋｇ／ｃｍ2を示
し、強固に接合されていることが判った。Example 9 The surface of a rolled copper plate having a thickness of 2 mm was polished with # 1200 sandpaper, washed with water and dried, and then a 5% acetone solution of abietic acid was applied and dried to prepare a treated copper plate. Two sheets of the above treated copper sheets are stacked and 180
The copper plate was joined by hot pressing at 380 kg / cm 2 for 30 minutes. A tensile test piece was cut out from the bonded copper plate thus obtained, and a shear tensile test was performed. As a result, the shear tensile strength was 240 to 260 kg / cm 2, and it was found that the joint was firmly joined.
【００５３】比較のため、上記圧延銅板を＃１２００サ
ンドペーパで研磨し、水洗、乾燥の後２枚重ねて上記条
件で加熱プレスしたが、接合は生じなかった。For comparison, the above-mentioned rolled copper sheet was polished with # 1200 sandpaper, washed with water, dried, and then two sheets were stacked and heated and pressed under the above-mentioned conditions, but no joining occurred.
【００５４】以上の結果から、銅板表面にアビエチン酸
５％アセトン溶液を塗布し、加熱プレスする、本発明の
手法で初めて銅板同士の接合がなされることが確認され
た。From the above results, it was confirmed that the copper plates were joined for the first time by the method of the present invention, in which a 5% acetone solution of abietic acid was applied to the surface of the copper plate and heated and pressed.
【００５５】（実施例１０）実施例１の処理銅板を厚さ
２ｍｍの銀板に重ね、実施例９と同一条件で加熱プレス
を行った。この結果、両方の板は強固に接合し、引張り
試験の結果、せん断引張り強さは５４０ないし６６０ｋ
ｇ／ｃｍ2を示した。(Example 10) The treated copper plate of Example 1 was overlaid on a silver plate having a thickness of 2 mm, and heated and pressed under the same conditions as in Example 9. As a result, both the plates were firmly joined, and as a result of the tensile test, the shear tensile strength was 540 to 660 k.
g / cm 2 .
【００５６】接合した界面付近を波長分散型ｘ線マイク
ロアナライザー（ＸＭＡ)で調べたところ、図６に示す
ように銀、銅それぞれに相手の金属中に数μｍにわたっ
て拡散していることが確認された。また，加熱プレス条
件を２４０℃、３０分とした場合の界面のＸＭＡ分析結
果を図７に示す。When the vicinity of the joined interface was examined with a wavelength-dispersive x-ray microanalyzer (XMA), it was confirmed that silver and copper were diffused over several μm into the other metal as shown in FIG. Was. FIG. 7 shows an XMA analysis result of the interface when the heating press conditions were 240 ° C. and 30 minutes.
【００５７】（実施例１１）直径１０ｍｍの銅丸棒の先
端部分を直径５ｍｍに削り、先端の平面部分を平滑に仕
上げて後、アビエチン酸溶液を塗布、乾燥した。つい
で、上記丸棒を突き合わせ、直径５ｍｍの平面部分の間
に厚さ０．５ｍｍの銀板を挟んで加熱プレスした。プレ
ス条件は６８０ｋｇ／ｃｍ2、１９５℃３０分とした。
ここに得られた丸棒の引っ張り試験を行ったところ、８
３０ｋｇ／ｃｍ2の破断強度を示し、非常に強固に接合
されていることが判った。(Example 11) A tip of a copper round bar having a diameter of 10 mm was shaved to a diameter of 5 mm, and a flat portion of the tip was finished smoothly, and then an abietic acid solution was applied and dried. Then, the round bars were abutted, and heated and pressed with a silver plate having a thickness of 0.5 mm between flat portions having a diameter of 5 mm. Pressing conditions were 680 kg / cm 2 and 195 ° C. for 30 minutes.
When the tensile test of the obtained round bar was performed,
It showed a breaking strength of 30 kg / cm 2 , and it was found that it was joined very firmly.
【００５８】（実施例１２）銅板表面にアビエチン酸溶
液を塗布して後、直径１ｍｍの金線を重ね、１９５℃の
熱板上で１５分加圧した。この結果、金線は銅板上に接
合した。金線の一部を引き剥してから銅板に直角に引き
剥し試験をしたところ、４．０ｋｇ／ｍｍの引き剥し強
度を示し、強固に接合していることが判った。(Example 12) After coating an abietic acid solution on the surface of a copper plate, a gold wire having a diameter of 1 mm was overlapped and pressed on a hot plate at 195 ° C for 15 minutes. As a result, the gold wire was bonded on the copper plate. A part of the gold wire was peeled off, and a peeling test was performed at right angles to a copper plate. As a result, it was found that the peeling strength was 4.0 kg / mm, and that the bonding was firmly performed.
【００５９】（実施例１３）実施例１において活性剤と
してアビエチン酸に代えて、Ｎ−ラウロイルアスパラギ
ン酸β−ラウリルエステルを使用した。この場合は銅板
を加熱してから活性剤をふりかけて表面で溶融させたと
ころ、実施例１と同様に強固な接合が得られた。Example 13 In Example 1, β-lauryl N-lauroyl aspartate was used as the activator instead of abietic acid. In this case, when the copper plate was heated and the activator was sprinkled and melted on the surface, strong bonding was obtained as in Example 1.
【００６０】（実施例１４）アクリル酸モノマに過酸化
ベンゾイルを０．５％添加し６０℃で加熱撹拌して重合
体を製造した。本ポリマを水に溶解して５％溶液とした
ものを実施例１のアビエチン酸溶液に代えて活性剤とし
て使用した。この場合も、実施例１と同様に強固な接合
が得られた。Example 14 A polymer was prepared by adding 0.5% of benzoyl peroxide to acrylic acid monomer and heating and stirring at 60 ° C. A solution prepared by dissolving this polymer in water to form a 5% solution was used as an activator instead of the abietic acid solution of Example 1. Also in this case, strong bonding was obtained as in Example 1.
【００６１】（実施例１５）実施例１において加熱プレ
ス温度を１７０℃、時間を１時間とした場合は銅板同士
の接合は行われたが、取り出し後、僅かな衝撃で接合が
外れる弱いものであった。(Example 15) In Example 1, when the heating press temperature was 170 ° C. and the time was 1 hour, the copper plates were joined to each other. there were.
【００６２】（実施例１６）直径４〜５μｍの球状銅粉
末（田中貴金属（株）商品名クリスタル銅）７５ｇ、ロ
ジン２５ｇをセロソルブアセテート３５ｇに分散、溶解
して導電ペーストを製造した。本ペーストをガラスーエ
ポキシプリプレグの所定の部分にあけた直径０．５ｍｍ
のスルーホールに刷り込み、両面から３５μｍの銅箔
で挟んで加熱プレスして厚さ０．５ｍｍの両面配線基板
を製造した。プレス条件は１５０ｋｇ／ｃｍ2の圧力で
１８０℃３０分とした。Example 16 75 g of spherical copper powder (crystal copper, trade name of Tanaka Kikinzoku Co., Ltd.) having a diameter of 4 to 5 μm and 25 g of rosin were dispersed and dissolved in 35 g of cellosolve acetate to produce a conductive paste. 0.5mm in diameter when this paste is cut into the specified part of glass-epoxy prepreg
Was printed in the through-holes, sandwiched between both sides with a copper foil of 35 μm, and heated and pressed to produce a double-sided wiring board having a thickness of 0.5 mm. The pressing conditions were 180 ° C. for 30 minutes at a pressure of 150 kg / cm 2 .
【００６３】配線基板はプレス後所定のパターンにエッ
チングしてスルーホール部分の直流抵抗を測定した。こ
の結果、１スルーホール当りの抵抗値は１ｍΩ以下であ
り、この値は高電流から１０μＡの電流範囲において維
持された。After pressing, the wiring substrate was etched into a predetermined pattern, and the DC resistance of the through hole was measured. As a result, the resistance value per through hole was 1 mΩ or less, and this value was maintained in the current range from high current to 10 μA.
【００６４】これに対し、比較に用いた通常のスルーホ
ール配線基板のスルーホール抵抗値は１０ｍΩであり、
電流値が１０ｍＡ 以下になると抵抗が増加した。On the other hand, the through-hole resistance value of the ordinary through-hole wiring board used for comparison is 10 mΩ,
When the current value became 10 mA or less, the resistance increased.
【００６５】この結果から本発明にかかる銅の接合方法
が非常に有効な導電経路形成方法であることが判る。From these results, it can be seen that the copper bonding method according to the present invention is a very effective conductive path forming method.
【００６６】（実施例１７）直径２〜１５μｍの噴霧銅
粉末７５ｇ、ジメチロールプロピオン酸７．５ｇ、をエ
ピクロルヒドリンービスフェノールＡタイプのエポキシ
樹脂（エポキシ等量１８０）１５ｇに分散して導電ペー
ストを製造した。本ペーストをガラスーエポキシプリプ
レグの所定の部分にあけた直径０．５ｍｍのスルーホー
ルに刷り込み、両面から３５μｍの銅箔で挟んで加熱プ
レスして厚さ０．５ｍｍの両面配線基板を製造した。プ
レス条件は１５０ｋｇ／ｃｍ2の圧力で１８０℃３０分
とした。Example 17 A conductive paste was prepared by dispersing 75 g of sprayed copper powder having a diameter of 2 to 15 μm and 7.5 g of dimethylolpropionic acid in 15 g of an epichlorohydrin-bisphenol A type epoxy resin (epoxy equivalent: 180). did. This paste was imprinted into a through-hole with a diameter of 0.5 mm opened in a predetermined portion of a glass-epoxy prepreg, and was hot-pressed with 35 μm copper foil from both sides to produce a double-sided wiring board with a thickness of 0.5 mm. . The pressing conditions were 180 ° C. for 30 minutes at a pressure of 150 kg / cm 2 .
【００６７】製造された配線基板はプレス後所定のパタ
ーンにエッチングしてスルーホール部分の直流抵抗を測
定した。この結果、１スルーホール当りの抵抗値は０．
１ｍΩ以下であり、この値は高電流から１０μＡ の電
流範囲において維持された。After the manufactured wiring board was pressed, the wiring board was etched into a predetermined pattern, and the DC resistance of the through hole was measured. As a result, the resistance value per through hole is 0.
<1 mΩ, which was maintained in the current range from high current to 10 μA.
【００６８】さらにこの基板の２６０℃と２５℃とのヒ
ートサイクル試験を行ったところ、１００回の試験で抵
抗値に異常はみられなかった。Further, when the substrate was subjected to a heat cycle test at 260 ° C. and 25 ° C., no abnormality was found in the resistance value after 100 tests.
【００６９】これに対し、比較に用いた通常のスルーホ
ール配線基板のスルーホール抵抗値は１０ｍΩであり、
電流値が１０ｍＡ以下になると抵抗値の増加が観察され
た。さらに通常のスルーホール配線基板はヒートサイク
ル試験１００回で２０％以上の抵抗値の変化がみられ
た。On the other hand, the through-hole resistance value of the ordinary through-hole wiring board used for comparison is 10 mΩ,
When the current value became 10 mA or less, an increase in the resistance value was observed. Furthermore, the resistance value of the ordinary through-hole wiring board showed a change of 20% or more in 100 heat cycle tests.
【００７０】この結果から本発明にかかる両面配線基板
は上下の銅箔が電気的に完全に接続されていることが確
認された。From the results, it was confirmed that the upper and lower copper foils of the double-sided wiring board according to the present invention were completely electrically connected.
【００７１】（実施例１８）実施例１で得られた両面配
線板２枚で所定の部分に直径０．５ｍｍの孔を開け、実
施例１で製造した導電ペーストを充填したエポキシプリ
プレグを挟み、加熱プレスして４層配線板を製造した。
ここに得られた４層配線板の電気接続も実施例１と同様
に安定した抵抗の低いものであり、本実施例のように簡
単な加熱プレス操作のみで電気的接続性に優れた多層配
線板が製造できることが実証された。(Example 18) A hole having a diameter of 0.5 mm was formed in a predetermined portion of the two double-sided wiring boards obtained in Example 1, and an epoxy prepreg filled with the conductive paste manufactured in Example 1 was sandwiched between the two. A four-layer wiring board was manufactured by hot pressing.
The electrical connection of the four-layer wiring board obtained here is also stable and low in resistance as in the first embodiment, and is a multilayer wiring excellent in electrical connectivity only by a simple heating press operation as in this embodiment. It has been demonstrated that boards can be manufactured.
【００７２】（実施例１９）直径２〜１５μｍの噴霧銅
粉末７５ｇ、ロジン２５ｇをセロソルブアセテート２５
ｇに分散、溶解して導電ペーストを製造した。本ペース
トをガラスーエポキシプリプレグの所定の部分にあけた
直径０．５ｍｍのスルーホールに刷り込み、溶剤を乾燥
の後、両面から３５μｍの銅箔で挟んで加熱プレスして
厚さ０．５ｍｍの両面配線基板を製造した。プレス条件
は１５０ｋｇ／ｃｍ2の圧力で１８０℃３０分とした。Example 19 75 g of sprayed copper powder having a diameter of 2 to 15 μm and 25 g of rosin were added to cellosolve acetate 25.
g to prepare a conductive paste. This paste was applied to a 0.5 mm diameter through-hole formed in a predetermined portion of a glass-epoxy prepreg. After drying the solvent, the paste was sandwiched between both sides with a 35 μm copper foil and hot-pressed to a thickness of 0.5 mm. A double-sided wiring board was manufactured. The pressing conditions were 180 ° C. for 30 minutes at a pressure of 150 kg / cm 2 .
【００７３】配線基板はプレス後所定のパターンにエッ
チングしてスルーホール部分の直流抵抗を測定した。こ
の結果、１スルーホール当りの抵抗値は０．１ｍΩ以下
であり、この値は高電流から１０μＡの電流範囲におい
て維持された。After pressing, the wiring substrate was etched into a predetermined pattern, and the DC resistance of the through hole was measured. As a result, the resistance value per through hole was 0.1 mΩ or less, and this value was maintained in the current range from high current to 10 μA.
【００７４】（実施例２０）実施例１において噴霧銅粉
末に代えて直径１μｍの球状銀粉を使用した導電ペース
トを使用して両面基板を製造した。本実施例においては
プレス圧力を５０Kg／ｃｍ2とし、温度は１９０℃とし
た。この場合も信頼性、導電性に優れた両面基板が得ら
れた。本両面基板のスルーホール部分を観察したとこ
ろ、銀粉は一体化して銀柱となっており、さらに銅箔と
銀柱との界面で銀と銅とが相互に拡散しあって一体化し
ていることがわかった。(Example 20) A double-sided substrate was manufactured by using a conductive paste in which spherical silver powder having a diameter of 1 µm was used instead of the sprayed copper powder in Example 1. In this example, the pressing pressure was 50 kg / cm 2 and the temperature was 190 ° C. Also in this case, a double-sided board excellent in reliability and conductivity was obtained. Observation of the through-hole part of this double-sided board revealed that the silver powder was integrated into a silver pillar, and that silver and copper were mutually diffused and integrated at the interface between the copper foil and the silver pillar. I understood.
【００７５】（実施例２１）実施例１においてジメチロ
ールプロピオン酸とエピクロルヒドリンービスフェノー
ルＡタイプのエポキシ樹脂に代えてスチレンーマレイン
酸（１：１）共重合樹脂を使用した。この場合は導電ペ
ーストの溶剤としてメチルエチルケトンを使用した。本
実施例においても電気的接続性の良好な両面配線基板が
得られた。Example 21 A styrene-maleic acid (1: 1) copolymer resin was used in Example 1 in place of dimethylolpropionic acid and epichlorohydrin-bisphenol A type epoxy resin. In this case, methyl ethyl ketone was used as a solvent for the conductive paste. Also in this example, a double-sided wiring board having good electrical connectivity was obtained.
【００７６】（実施例２２）実施例１において、ジメチ
ロールプロピオン酸に代えて、Ｎーステアロイルアスパ
ラギン酸モノステアリルエステルを使用した場合も電気
的接続性の良好な両面基板が得られた。Example 22 In Example 1, a double-sided substrate having good electrical connectivity was obtained also in the case where N-stearoyl aspartic acid monostearyl ester was used in place of dimethylolpropionic acid.
【００７７】（実施例２３）実施例１においてプレス温
度を１７０℃とし、プレス時間を１時間として両面板を
製造した。この両面板の導通抵抗は実施例１の場合と同
様であったが、ヒートサイクルテスト２０回で断線が生
じた。この結果からプレス温度の下限は１７０℃である
ことがわかった。(Example 23) A double-sided board was manufactured in the same manner as in Example 1 except that the pressing temperature was 170 ° C and the pressing time was 1 hour. The conduction resistance of this double-sided board was the same as that of Example 1, but the disconnection occurred in 20 heat cycle tests. From this result, it was found that the lower limit of the pressing temperature was 170 ° C.
【００７８】[0078]
【発明の効果】以上実施例に記載したごとく、本発明に
かかる銅または銅合金の接合方法は従来の常識を越える
低温での接合を可能にするものであり、また、本発明の
多層配線基板の製造方法は従来の銀スルーホール配線基
板と同様の簡単な製造方法によるにもかかかわらず、め
っき法と同様な非常に優れた導電性を示す配線基板を製
造できるものであり、産業上の効果は大なるものであ
る。As described in the above embodiments, the joining method of copper or copper alloy according to the present invention enables joining at a low temperature exceeding conventional common sense. Despite the simple manufacturing method similar to the conventional silver through-hole wiring board, the manufacturing method can produce a wiring board showing very excellent conductivity similar to the plating method. The effect is great.
【図１】本発明の実施例にかかる両面配線基板の製造方
法を示す概念図FIG. 1 is a conceptual diagram showing a method for manufacturing a double-sided wiring board according to an embodiment of the present invention.
【図２】本発明の実施例にかかる製造方法により製造さ
れた両面配線基板の斜視図FIG. 2 is a perspective view of a double-sided wiring board manufactured by a manufacturing method according to an embodiment of the present invention.
【図３】本発明の実施例にかかる多層配線基板の製造プ
ロセスを示す概念図FIG. 3 is a conceptual diagram showing a manufacturing process of a multilayer wiring board according to an embodiment of the present invention.
【図４】絶縁性接着層の孔に導電ペーストを刷込む方法
の一つを示す概念図FIG. 4 is a conceptual diagram showing one method of imprinting a conductive paste into holes of an insulating adhesive layer.
【図５】本発明の実施例にかかる銅原子の銀板中への拡
散を示す図FIG. 5 is a diagram showing diffusion of copper atoms into a silver plate according to an example of the present invention.
【図６】同実施例にかかる銅原子の銀板中への拡散を示
す図FIG. 6 is a view showing diffusion of copper atoms into a silver plate according to the example.
【図７】同実施例にかかる銅原子の銀板中への拡散を示
す図FIG. 7 is a view showing diffusion of copper atoms into a silver plate according to the example.
１ 絶縁性接着層 ２ 孔 ３ 導電ペースト ４ スキージ ５、５’ 銅箔 ６ 導通経路 ７ 両面銅貼板 ８ 両面配線基板 DESCRIPTION OF SYMBOLS 1 Insulating adhesive layer 2 Hole 3 Conductive paste 4 Squeegee 5, 5 'copper foil 6 Conduction path 7 Double-sided copper bonding board 8 Double-sided wiring board
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０５Ｋ 1/09 Ｈ０５Ｋ 1/09 Ａ 3/32 3/32 Ｃ 3/40 3/40 Ｋ (56)参考文献 特開 昭55−55600（ＪＰ，Ａ) 特開 平２−66803（ＪＰ，Ａ) 特開 平４−96293（ＪＰ，Ａ) 特開 平４−159797（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H05K 3/46 B23K 20/00 H01B 1/22 H05K 1/09 H05K 3/32 H05K 3/40 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI H05K 1/09 H05K 1/09 A 3/32 3/32 C 3/40 3/40 K (56) References JP-A-Showa 55 -55600 (JP, A) JP-A-2-66803 (JP, A) JP-A-4-96293 (JP, A) JP-A-4-159797 (JP, A) (58) Fields investigated (Int. . 7, DB name) H05K 3/46 B23K 20/00 H01B 1/22 H05K 1/09 H05K 3/32 H05K 3/40
Claims (17)
属の接合面を接合界面における銅原子の拡散により接合
させるに当たり、銅または銅合金である金属の接合面に
貴金属薄膜層、酸化膜除去剤塗布層または銅またはその
合金粉末と酸化膜除去剤とを主成分とする導電ペースト
層のいずれかを形成して後、接合面を重ね合わせ、１７
０℃以上に加熱、加圧して接合することを特徴とする銅
または銅合金の低温拡散接合方法。1. A method for removing a noble metal thin film layer and an oxide film removing agent from a bonding surface of a metal of copper or copper alloy when bonding the bonding surface of a metal of at least one of copper or copper alloy by diffusion of copper atoms at the bonding interface. After forming either a coating layer or a conductive paste layer containing copper or its alloy powder and an oxide film remover as main components, the joining surfaces are overlapped, and
A low-temperature diffusion bonding method for copper or a copper alloy, wherein the bonding is performed by heating and pressing at a temperature of 0 ° C. or higher.
した銅またはその合金からなり、他方の接合面が貴金属
またはその合金薄膜層をを有する金属からなる請求項１
記載の銅または銅合金の低温拡散接合方法。2. One of the joining surfaces is made of copper or an alloy thereof having an oxide film remover coating layer formed thereon, and the other joining surface is made of a metal having a noble metal or an alloy thin film layer thereof.
A low-temperature diffusion bonding method for copper or a copper alloy according to the above.
シル基を構造中に含むポリマまたはオリゴマである請求
項１記載の銅または銅合金の低温拡散接合方法。3. The method according to claim 1, wherein the oxide film removing agent is a polymer or an oligomer containing a carboxylic acid or a carboxyl group in the structure.
去剤と必要によりバインダ樹脂とを含むことを特徴とす
る低温拡散接合用導電ペースト。4. A conductive paste for low-temperature diffusion bonding, comprising a noble metal, copper or an alloy powder thereof, an oxide film remover and, if necessary, a binder resin.
シル基を構造中に含むポリマまたはオリゴマであること
を特徴とする請求項４記載の低温拡散接合用導電ペース
ト。5. The conductive paste for low-temperature diffusion bonding according to claim 4, wherein the oxide film removing agent is a polymer or an oligomer containing a carboxylic acid or a carboxyl group in the structure.
状である請求項４記載の低温拡散接合用導電ペースト。6. The conductive paste for low-temperature diffusion bonding according to claim 4, wherein the shape of the noble metal, copper or its alloy powder is spherical.
特徴とする請求項４記載の低温拡散接合用導電ペース
ト。7. The conductive paste for low-temperature diffusion bonding according to claim 4, wherein the oxide film removing agent is a binder resin.
熱プレスして製造する多層配線基板の製造において、絶
縁性接着層の所定の部分にあけた穴に、貴金属、銅また
はその合金からなる導電性粉末と、酸化膜除去剤とを主
たる構成要素とする導電ペーストを刷り込んだ後、１７
０℃以上の温度で加熱プレスして酸化膜が除去された銅
箔の表面と前記導電性粉末とを接合界面における銅原子
の拡散により接合させる多層配線基板の製造方法。8. In the production of a multilayer wiring board produced by sandwiching an insulating adhesive layer between two or more copper foils and heating and pressing, a noble metal, copper or copper is inserted into a hole formed in a predetermined portion of the insulating adhesive layer. After imprinting a conductive paste mainly composed of a conductive powder of the alloy and an oxide film remover,
Copper from which oxide film has been removed by hot pressing at a temperature of 0 ° C or higher
Copper atoms at the joining interface between the surface of the foil and the conductive powder
For manufacturing a multilayer wiring board to be joined by diffusion of a metal.
状であることを特徴とする請求項８記載の多層配線基板
の製造方法。9. The method for manufacturing a multilayer wiring board according to claim 8, wherein the shape of the noble metal, copper or its alloy powder is spherical.
キシル基を構造中に含むポリマまたはオリゴマであるこ
とを特徴とする請求項８記載の多層配線基板の製造方
法。10. The method according to claim 8, wherein the oxide film removing agent is a polymer or an oligomer containing a carboxylic acid or a carboxyl group in the structure.
去剤であることを特徴とする請求項８記載の多層配線基
板の製造方法。11. The method according to claim 8, wherein the binder resin of the conductive paste is an oxide film remover.
で鋏んで後、孔あけをし、前記離型フィルムの上から導
電ペーストを刷り込んで後、前記離型フィルムを剥して
製造することを特徴とする請求項８記載の多層配線基板
の製造方法。12. A method in which the insulating adhesive layer is previously scissored with a release film, holes are formed, a conductive paste is printed on the release film, and then the release film is peeled off. The method for manufacturing a multilayer wiring board according to claim 8, wherein
子と酸化膜除去剤とを含む導電ペーストが充填され、前
記孔を覆うように銅箔で前記絶縁性接着層が挟まれ、酸
化膜が除去された銅箔の表面と前記導電性粉末とが接合
界面における銅原子の拡散接合により電気的に接続され
ている多層配線基板。13. A conductive particle is formed in a hole formed in an insulating adhesive layer.
Filled conductive paste containing a child and an oxide film removing agent, wherein the insulating adhesive layer sandwiched between the copper foil so as to cover the hole, acid
The surface of the copper foil from which the oxide film has been removed is joined to the conductive powder.
A multilayer wiring board electrically connected by diffusion bonding of copper atoms at an interface .
銅またはその合金粉末であることを特徴とする請求項１
３記載の多層配線基板。14. The conductive powder in the conductive paste is a noble metal,
2. A copper or alloy powder thereof.
3. The multilayer wiring board according to 3.
球状であることを特徴とする請求項１４記載の多層配線
基板。15. The multilayer wiring board according to claim 14, wherein the shape of the noble metal, copper or its alloy powder is spherical.
去剤を含むことを特徴とする請求項１３記載の多層配線
基板。16. The multilayer wiring board according to claim 13, wherein the binder resin of the conductive paste contains an oxide film removing agent.
キシル基を構造中に含むポリマまたはオリゴマであるこ
とを特徴とする請求項１６記載の多層配線基板。17. The multilayer wiring board according to claim 16, wherein the oxide film removing agent is a polymer or an oligomer containing a carboxylic acid or a carboxyl group in the structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13440493A JP3345961B2 (en) | 1992-06-05 | 1993-06-04 | Low-temperature diffusion bonding method of copper or copper alloy and method of manufacturing conductive paste and multilayer wiring board using the same |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-145276 | 1992-06-05 | ||
| JP14527692 | 1992-06-05 | ||
| JP4-239064 | 1992-09-08 | ||
| JP23906492 | 1992-09-08 | ||
| JP312793 | 1993-01-12 | ||
| JP5-3127 | 1993-01-12 | ||
| JP13440493A JP3345961B2 (en) | 1992-06-05 | 1993-06-04 | Low-temperature diffusion bonding method of copper or copper alloy and method of manufacturing conductive paste and multilayer wiring board using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06262375A JPH06262375A (en) | 1994-09-20 |
| JP3345961B2 true JP3345961B2 (en) | 2002-11-18 |
Family
ID=27453790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13440493A Expired - Fee Related JP3345961B2 (en) | 1992-06-05 | 1993-06-04 | Low-temperature diffusion bonding method of copper or copper alloy and method of manufacturing conductive paste and multilayer wiring board using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3345961B2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6054761A (en) * | 1998-12-01 | 2000-04-25 | Fujitsu Limited | Multi-layer circuit substrates and electrical assemblies having conductive composition connectors |
| EP1220588B1 (en) * | 1999-07-12 | 2006-09-13 | Ibiden Co., Ltd. | Method of manufacturing printed-circuit board |
| TWI325739B (en) * | 2003-01-23 | 2010-06-01 | Panasonic Corp | Electroconductive paste, its manufacturing method, circuit board using the same electroconductive paste, and its manufacturing method |
| JP4078990B2 (en) * | 2003-01-23 | 2008-04-23 | 松下電器産業株式会社 | Conductive paste, circuit forming substrate using the conductive paste, and manufacturing method thereof |
| JP4509757B2 (en) | 2004-12-03 | 2010-07-21 | ソニーケミカル＆インフォメーションデバイス株式会社 | Manufacturing method of multilayer wiring board |
| JP5468199B2 (en) * | 2006-11-22 | 2014-04-09 | 日立化成株式会社 | Conductive adhesive composition, electronic component mounting substrate, and semiconductor device |
| EP2196514B1 (en) * | 2007-10-03 | 2013-01-23 | Hitachi Chemical Company, Ltd. | Adhesive composition, electronic-component-mounted substrate and semiconductor device using the adhesive composition |
| WO2011152423A1 (en) * | 2010-05-31 | 2011-12-08 | 三洋電機株式会社 | Method for bonding metals |
| JP5557698B2 (en) * | 2010-11-04 | 2014-07-23 | 株式会社日立製作所 | Sintered bonding agent, manufacturing method thereof and bonding method using the same |
| JP5728985B2 (en) * | 2011-02-08 | 2015-06-03 | 三菱マテリアル株式会社 | Ag paste for liquid phase diffusion bonding and method for producing power module substrate using this Ag paste for liquid phase diffusion bonding |
| JP2014100711A (en) | 2011-02-28 | 2014-06-05 | Sanyo Electric Co Ltd | Metal joining structure and metal joining method |
| WO2013021567A1 (en) | 2011-08-11 | 2013-02-14 | 三洋電機株式会社 | Bonding method for metal, and metal bonded structure |
| JP2014210267A (en) * | 2011-08-31 | 2014-11-13 | 三洋電機株式会社 | Metal joining device |
| JP6776774B2 (en) * | 2016-09-30 | 2020-10-28 | 日本電気株式会社 | Stacked antenna and its manufacturing method |
| JP7345795B2 (en) * | 2020-01-27 | 2023-09-19 | 日本碍子株式会社 | Joining method and heat exchange member |
-
1993
- 1993-06-04 JP JP13440493A patent/JP3345961B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06262375A (en) | 1994-09-20 |
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