JPH07207452A - Metal powder composition and production of metallized substrate using the same - Google Patents

Metal powder composition and production of metallized substrate using the same

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Publication number
JPH07207452A
JPH07207452A JP2321594A JP2321594A JPH07207452A JP H07207452 A JPH07207452 A JP H07207452A JP 2321594 A JP2321594 A JP 2321594A JP 2321594 A JP2321594 A JP 2321594A JP H07207452 A JPH07207452 A JP H07207452A
Authority
JP
Japan
Prior art keywords
metal powder
metallized
substrate
metallizing
powder composition
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.)
Pending
Application number
JP2321594A
Other languages
Japanese (ja)
Inventor
Yohei Watabe
洋平 渡部
Shinichi Iwata
伸一 岩田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokin Corp
Original Assignee
Tokin Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokin Corp filed Critical Tokin Corp
Priority to JP2321594A priority Critical patent/JPH07207452A/en
Publication of JPH07207452A publication Critical patent/JPH07207452A/en
Pending legal-status Critical Current

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  • Conductive Materials (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Powder Metallurgy (AREA)

Abstract

PURPOSE:To obtain a metal powder composition for metallizing having high adhesion strength to a ceramic substrate with which a metal oxide film having small volume resistance can be obtd., and to produce a metallized substrate by specifying the chemical compsn. of the metal powder. CONSTITUTION:The metal powder compsn. for metallizing essentially consists of Cu and Ti and contains at least one of Ag, Al, Zr as a subcomponent. The compsn. contains the main component metal powder by 90-99.5wt.% and the subcomponent metal powder by 0.5-10wt.%. The optimum compsn. ratio of the main component is 85-99wt.% Cu and 1-15wt.% Ti. Apaste for metallizing comprising this metal powder compsn. for metallizing, dispersant and binder is prepared and applied on a ceramic substrate once or several times to obtain 80mum or more thickness by screen printing. Then the paste is baked in vacuum or inert gas atmosphere. Thus, a metallized substrate having high adhesion strength to a ceramic substrate can be obtd.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、厚膜電子回路の導体層
形成、及びセラミックス基板上の実装された電子機器用
素子、部品等が動作することによって発生する熱を拡散
するための銅回路を形成するための、メタライズ用金属
粉末組成物及びメタライズ基板に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper circuit for forming a conductor layer of a thick film electronic circuit and for diffusing heat generated by the operation of electronic device elements, parts, etc. mounted on a ceramic substrate. The present invention relates to a metal powder composition for metallization and a metallized substrate for forming.

【0002】[0002]

【従来の技術】一般に、電子回路を構成するための基板
としては、金属絶縁基板、有機基板、セラミックス基板
があるが、絶縁性が高いこと、機械的強度が確保される
こと、他の電子素子を劣化させないこと、金属導体と容
易に接合体を形成できること、熱伝導率が大きいこと等
の性質が要求されている。この要求を満足する材料とし
てはセラミックス基板があり、この基板として、アルミ
ナ、窒化アルミニウム等がある。しかし、セラミックス
単体では、電子機器に用いられるトランジスタ、ダイオ
ード、IC、LSI、その他、各種電子部品を直接実装
することができない。
2. Description of the Related Art Generally, a substrate for forming an electronic circuit includes a metal insulating substrate, an organic substrate, and a ceramic substrate. However, they have a high insulating property, mechanical strength is secured, and other electronic elements. Properties such as not deteriorating, forming a bonded body with a metal conductor easily, and having high thermal conductivity are required. A ceramic substrate is a material that satisfies this requirement, and alumina, aluminum nitride, or the like is used as the substrate. However, the ceramics alone cannot directly mount transistors, diodes, ICs, LSIs and various other electronic components used in electronic devices.

【0003】そのため、セラミックス基板表面に金属化
膜を形成し、導体層として使用するか、又は金属化膜を
介して導体金属箔とを接合することにより、電子回路を
構成している。その方法として、導体金属ペーストによ
るセラミックス基板上への金属化膜による回路形成は、
10〜30μm程度の厚みに、スクリーン印刷−乾燥−
焼成を行い回路形成を行う方法と、導体金属箔とセラミ
ックス基板の間にろう付け用のペーストや金属ろう箔を
挿入して接合を行い、回路形成を行う方法がある。
Therefore, an electronic circuit is formed by forming a metallized film on the surface of a ceramic substrate and using it as a conductor layer, or by joining it to a conductor metal foil via the metallized film. As a method, forming a circuit with a metallized film on a ceramics substrate with a conductor metal paste,
Screen printing-drying-to a thickness of about 10 to 30 μm
There are a method of forming a circuit by firing and a method of inserting a brazing paste or a metal brazing foil between the conductive metal foil and the ceramics substrate and joining them to form a circuit.

【0004】[0004]

【発明が解決しようとする課題】しかしながら、上記の
導体金属ペーストを用いて金属化膜を形成する方法の場
合、導体厚みが10〜30μmと薄いため、回路に流せ
る電流が10A以下と使用範囲が限定されてしまう欠点
があり、後者の導体金属箔による接合基板の場合、金属
箔によって回路を構成するため、導体厚みを200〜5
00μmにすることは可能であるが、回路のパターンを
金型によって作製した金属箔を精度良く設置したり、あ
るいは塩化物や酸によるエッチングで回路を形成する等
の製造プロセスが複雑であった。
However, in the case of the method of forming a metallized film using the above conductor metal paste, since the conductor thickness is as thin as 10 to 30 μm, the current that can be passed through the circuit is 10 A or less and the range of use is small. However, in the latter case, the conductor metal foil has a conductor thickness of 200 to 5 because the circuit is composed of the metal foil.
Although it is possible to set the thickness to 00 μm, a manufacturing process such as accurately setting a metal foil in which a circuit pattern is manufactured by a mold or forming a circuit by etching with chloride or acid is complicated.

【0005】そこで、本発明の技術的課題は、前述の導
体金属ペーストを用いて導体金属層の厚みを80μm以
上形成することで、100A以上の電流を流すことの可
能な導体回路を、スクリーン印刷法で一回あるいは数回
塗りという簡略なプロセスによって得ることのできる、
メタライズ用金属組成物及びそれを用いてメタライズ基
板を作製する製造方法を提供することにある。
Therefore, a technical object of the present invention is to screen print a conductor circuit capable of passing a current of 100 A or more by forming the conductor metal layer with a thickness of 80 μm or more using the above-mentioned conductor metal paste. It can be obtained by a simple process of applying once or several times by the method,
It is to provide a metal composition for metallization and a manufacturing method for producing a metallized substrate using the same.

【0006】[0006]

【課題を解決するための手段】本発明によれば、Cu,
Tiを主成分とし、Ag,Al及びZrのうち、少なく
とも一種を副成分として、主成分の金属粉末が重量%で
90〜99.5%、副成分の金属粉末が0.5〜10%か
らなることを特徴するメタライズ用金属粉末組成物が得
られる。なお、主成分の組成比は、重量%でCu85〜
99%、Ti1〜15%が最適である。
According to the present invention, Cu,
Ti as a main component, and at least one of Ag, Al and Zr as a subcomponent, the main component metal powder is 90 to 99.5% by weight, and the subcomponent metal powder is 0.5 to 10%. A metal powder composition for metallization is obtained. In addition, the composition ratio of the main components is from 85 to 85% by weight.
The optimum values are 99% and Ti 1 to 15%.

【0007】又、本発明によれば、前記のメタライズ用
金属粉末と分散剤、結合剤とを含むことを特徴とするメ
タライズ用ペーストが得られる。
Further, according to the present invention, there is obtained a metallizing paste containing the above metallizing metal powder, a dispersant and a binder.

【0008】又、本発明によれば、セラミックス基板上
に、前記のメタライズ用ペーストをスクリーン印刷法に
より、80μm以上の厚みを一回あるいは数回塗りで形
成し、真空及び不活性雰囲気下で焼付けて金属化膜を形
成することを特徴とするメタライズ基板の製造方法が得
られる。
Further, according to the present invention, the above metallizing paste is formed on the ceramics substrate by screen printing to a thickness of 80 μm or more once or several times, and baked under vacuum and an inert atmosphere. A metallized film manufacturing method is obtained, which is characterized by forming a metallized film.

【0009】又、本発明によれば、前記のメタライズ基
板の製造方法において、前記セラミックス基板はアルミ
ナ及び窒化アルミニウムのうち少なくとも一種からなる
ことを特徴とするメタライズ基板の製造方法が得られ
る。
Further, according to the present invention, there is provided a method for manufacturing a metallized substrate according to the method for manufacturing a metallized substrate, characterized in that the ceramic substrate is made of at least one of alumina and aluminum nitride.

【0010】又、本発明によれば、前記したいずれかの
メタライズ基板の製造方法において、前記金属化膜上に
Ni膜及びAu膜のうちのいずれか一種を形成すること
を特徴とする導電膜付きメタライズ基板の製造方法が得
られる。
According to the present invention, in any one of the above-described metallized substrate manufacturing methods, one of a Ni film and an Au film is formed on the metallized film. A method of manufacturing a metallized substrate with a substrate is obtained.

【0011】[0011]

【作用】本発明において、メタライズ基板を製造するた
めの金属粉末組成物は、重量%表示で銅粉末及びチタン
粉末からなる主成分が90〜99.5%と、副金属成分
が0.5〜10%とからなる組成を有する。この金属粉
末組成物を分散剤及び結合剤からなるビヒクルと混合し
てペースト状にする。このペーストをアルミナ及び窒化
アルミニウムの表面にスクリーン印刷法を用いて、一回
あるいは数回塗布して80μm以上の厚みを形成し、乾
燥後、高真空雰囲気及び不活性雰囲気のいずれかの雰囲
気中において、熱処理を施すことによって金属化膜を形
成する。この金属化膜(メタライズ層)表面に表面酸化
防止、銅と半田組成のすずとの拡散防止及び半田濡れ性
を確保するために、無電解ニッケルめっき又は金めっき
を施すことによって、セラミックスに対して高い接合強
度が得られ、100A以上の電流を流すことが可能とな
る。
In the present invention, the metal powder composition for producing the metallized substrate contains 90 to 99.5% by weight of copper powder and titanium powder as the main component and 0.5 to 0.5% of the auxiliary metal component. It has a composition of 10%. This metal powder composition is mixed with a vehicle consisting of a dispersant and a binder to form a paste. This paste is applied to the surface of alumina and aluminum nitride by a screen printing method once or several times to form a thickness of 80 μm or more, and after drying, in a high vacuum atmosphere or an inert atmosphere. Then, heat treatment is performed to form a metallized film. The surface of the metallized film (metallized layer) is subjected to electroless nickel plating or gold plating in order to prevent surface oxidation, diffusion of copper and tin in the solder composition, and ensure solder wettability. High bonding strength can be obtained, and a current of 100 A or more can be passed.

【0012】[0012]

【実施例】以下に、本発明の実施例について説明する。EXAMPLES Examples of the present invention will be described below.

【0013】本発明の実施例に係るメタライズ用金属粉
末組成物は、主成分としてのCu,Ti粉末とAg,A
l及びZrのうち、少なくとも一種からなる副成分とか
らなる金属化膜を形成するためのメタライズ用金属粉末
組成物である。主成分としてのCu粉末及びTi粉末が
重量%で90〜99.5%、副成分金属が0.5〜10%
の範囲になるように各粉末の所要量を秤量混合し、結合
剤と分散剤とからなるビヒクルを添加混合して、三本ロ
ールミル等を用いて十分混練し、均一に分散させてスク
リーン印刷に適した粘度に調整して、メタライズ用ペー
ストとする。この場合のペーストの粘度は、一回の印刷
で200〜300μmの厚みを形成させるため、500
〜1000dPa・sとする。メタライズ層の厚みを8
0μm以上に形成するためのスクリーンとして、スクリ
ーンのメッシュはペーストの抜けを良くするため、80
〜125メッシュの開口率の大きいものにし、所定の乳
剤厚みが80〜300μmのものを用いる。スクリーン
と基板の印刷ギャップは、従来100〜150μmであ
ったが、本製造方法ではスクリーンの版離れをよくする
ため、150〜250μmとする。印刷圧力は、ペース
トのスクリーン目詰まりを防止するため、従来の印刷圧
力2.0Kg/mm2に対し0.5〜1Kg/mm2増加さ
せる。又、この混合粉末に添加される結合剤としては、
エチルセルロース、アクリル系樹脂等、従来から使用さ
れているものを用いればよい。
A metal powder composition for metallization according to an embodiment of the present invention comprises Cu and Ti powders as main components and Ag and A powders.
A metal powder composition for metallization for forming a metallized film comprising at least one sub-component of l and Zr. 90% to 99.5% by weight of Cu powder and Ti powder as main components, and 0.5 to 10% of secondary metal components.
The required amount of each powder is weighed and mixed so as to be within the range of, and a vehicle composed of a binder and a dispersant is added and mixed, and sufficiently kneaded using a three-roll mill or the like, and uniformly dispersed for screen printing. Adjust to a suitable viscosity to make a metallizing paste. The viscosity of the paste in this case is 500 to form a thickness of 200 to 300 μm in one printing.
˜1000 dPa · s. Thickness of metallized layer is 8
As a screen for forming 0 μm or more, the mesh of the screen is 80
˜125 mesh with a large aperture ratio and a predetermined emulsion thickness of 80 to 300 μm is used. The printing gap between the screen and the substrate has conventionally been 100 to 150 μm, but in the present manufacturing method, it is set to 150 to 250 μm in order to improve the plate separation of the screen. Printing pressure is to prevent screen clogging of paste to conventional printing pressure 2.0Kg / mm 2 0.5~1Kg / mm 2 is increased. Also, as the binder added to this mixed powder,
Conventional materials such as ethyl cellulose and acrylic resin may be used.

【0014】こうして得られたペースト状金属粉末組成
物(メタライズ用ペースト)をセラミックス基板の表面
に塗布する。ここで、セラミックス基板は、熱伝導率の
よい酸化物、窒化物、あるいは数%の焼結助剤を含むセ
ラミックス焼結体のいずれでもよい。なお、酸化物とし
て、酸化アルミニウム(Al23)、あるいは窒化物と
して、窒化アルミニウム(AlN)が例示できる。
The paste-like metal powder composition (paste for metallization) thus obtained is applied to the surface of the ceramic substrate. Here, the ceramic substrate may be an oxide, a nitride, or a ceramic sintered body containing a sintering aid of several percent, which has a high thermal conductivity. Aluminum oxide (Al 2 O 3 ) can be used as the oxide, and aluminum nitride (AlN) can be used as the nitride.

【0015】表面に200〜300μmの厚みのメタラ
イズ用ペーストが塗布されたセラミックス基板を高真空
中、又は不活性雰囲気下で熱処理を施すことによって、
メタライズセラミックス基板が得られる。このメタライ
ズセラミックス基板の素子実装時の半田濡れ性を確保
し、銅メタライズ層の表面酸化及び銅の半田への拡散を
防止するため、ニッケルめっき、あるいは金めっきが施
される。この場合のめっきは、メタライズパターンが独
立している時は無電解を用い、連続している時は電気、
あるいは無電解めっき、いずれのめっき法でもよい。
By subjecting the ceramics substrate, whose surface is coated with a metallizing paste having a thickness of 200 to 300 μm, to a heat treatment in a high vacuum or in an inert atmosphere,
A metallized ceramic substrate is obtained. Nickel plating or gold plating is performed in order to secure solder wettability at the time of mounting the element on the metallized ceramics substrate and prevent surface oxidation of the copper metallized layer and diffusion of copper into the solder. In this case, the plating is electroless when the metallization patterns are independent, and electrically when continuous.
Alternatively, electroless plating or any plating method may be used.

【0016】図1に、主成分と副成分との組成比と副成
分の各組成物についてのメタライズ層の抵抗率を示す。
抵抗率は、四端子法で測定を行った。
FIG. 1 shows the composition ratio of the main component and the subcomponent and the resistivity of the metallized layer for each composition of the subcomponent.
The resistivity was measured by the four-terminal method.

【0017】副成分の組成が10重量%を越えると、一
般的に厚膜導体ペーストとして使用されているAg−P
dの体積抵抗率と同等以上になる。
When the composition of the subcomponents exceeds 10% by weight, Ag-P generally used as a thick film conductor paste.
It is equal to or higher than the volume resistivity of d.

【0018】図2に、主成分と副成分との組成比と副成
分の各組成物についてのメタライズ層とセラミックス基
板との密着強度を示す。密着強度の測定は、一辺が2m
mの正方形パッドにFe−Niネールピンを半田で垂直
に接合し、垂直に引っ張った時の引張力を示している。
FIG. 2 shows the composition ratio of the main component and the subcomponent and the adhesion strength between the metallized layer and the ceramic substrate for each composition of the subcomponent. Adhesive strength is measured at 2m on each side
Fe-Ni nail pins are vertically joined to the square pad of m with solder and the pulling force when pulled vertically is shown.

【0019】メタライズ層の密着強度は、副成分を添加
することにより、メタライズ層内の金属粉末の融点を下
げると共に、溶融を促進させる。副成分量が0.5重量
%未満の場合、メタライズ層の溶融が進まず、その結
果、密着強度が低くなり、素子実装後の熱冷サイクル試
験において剥離を惹き起こした。又、11重量%以上の
場合、メタライズ層の溶融が進みすぎ、メタライズ層の
熱膨張率が大きくなるため、メタライズ層がセラミック
スから剥がれたり、セラミックス基板を破壊してしまう
ため、副成分の添加量は0.5〜10重量%とした。
又、メタライズ層の密着強度も、従来の厚膜メタライズ
基板に比較し、同等以上であった。
As for the adhesion strength of the metallized layer, the melting point of the metal powder in the metallized layer can be lowered and the melting thereof can be promoted by adding the auxiliary component. When the amount of the sub-components was less than 0.5% by weight, the metallized layer did not melt, and as a result, the adhesion strength became low, causing peeling in the thermal cooling cycle test after mounting the device. On the other hand, when the content is 11% by weight or more, the metallized layer is excessively melted and the coefficient of thermal expansion of the metallized layer is increased, so that the metallized layer is peeled from the ceramic or the ceramic substrate is destroyed. Was 0.5 to 10% by weight.
Also, the adhesion strength of the metallized layer was equal to or higher than that of the conventional thick film metallized substrate.

【0020】[0020]

【発明の効果】以上、説明したように、本発明によるメ
タライズ用金属粉末組成物を用いたメタライズ基板の製
造方法によって得られたメタライズ基板は、セラミック
ス基板に対する密着強度が高く、体積抵抗の小さいメタ
ライズ基板を得ることができる。
As described above, the metallized substrate obtained by the method for producing a metallized substrate using the metal powder composition for metallization according to the present invention has a high adhesion strength to a ceramic substrate and a small volume resistance. A substrate can be obtained.

【図面の簡単な説明】[Brief description of drawings]

【図1】主成分と副成分との組成比及び副成分の種類に
対する体積抵抗率の関係をCuとTiの比をパラメータ
として示す特性図。図1(a)は副成分がAgの場合を
示す図、図1(b)は副成分がZrの場合を示す図、図
1(c)は副成分がAlの場合を示す図。
FIG. 1 is a characteristic diagram showing a composition ratio of a main component and a subcomponent and a relationship of a volume resistivity with respect to a kind of the subcomponent, using a ratio of Cu and Ti as parameters. FIG. 1A is a diagram showing a case where the subcomponent is Ag, FIG. 1B is a diagram showing a case where the subcomponent is Zr, and FIG. 1C is a diagram showing a case where the subcomponent is Al.

【図2】主成分と副成分との組成比及び副成分の種類に
対する密着強度の関係をCuとTiの比をパラメータと
して示す特性図。図2(a)は副成分がAgの場合を示
す図、図2(b)は副成分がZrの場合を示す図、図2
(c)は副成分がAlの場合を示す図。
FIG. 2 is a characteristic diagram showing the relationship between the composition ratio of the main component and the subcomponent and the adhesion strength with respect to the type of the subcomponent, using the ratio of Cu and Ti as parameters. FIG. 2A is a diagram showing a case where the accessory component is Ag, and FIG. 2B is a diagram showing a case where the accessory component is Zr.
FIG. 6C is a diagram showing a case where an accessory component is Al.

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】 セラミックス基板上に金属化膜を形成す
るためのメタライズ用金属粉末組成物において、Cu及
びTi粉末を主成分とし、Ag,Al,Zrのうち、少
なくとも一種を副成分とする金属粉末組成物であって、
前記主成分が重量%で90〜99.5%、副成分が0.5
〜10%からなることを特徴とするメタライズ用金属粉
末組成物。
1. A metallizing metal powder composition for forming a metallized film on a ceramic substrate, comprising Cu and Ti powder as main components and at least one of Ag, Al and Zr as a subcomponent. A powder composition,
The main component is 90 to 99.5% by weight, and the auxiliary component is 0.5.
A metal powder composition for metallization comprising 10% to 10%.
【請求項2】 請求項1記載のメタライズ用金属粉末組
成物と分散剤及び結合剤とからなることを特徴とするメ
タライズ用ペースト。
2. A metallizing paste comprising the metallizing metal powder composition according to claim 1, a dispersant and a binder.
【請求項3】 セラミックス基板上に金属化膜を形成し
てなるメタライズ基板の製造方法において、前記セラミ
ックス基板上に、請求項2記載のメタライズ用ペースト
をスクリーン印刷法により80μm以上の厚みを一回、
あるいは数回塗りで形成し、真空または不活性雰囲気下
で焼付けて、金属化膜を形成することを特徴とするメタ
ライズ基板の製造方法。
3. A method for producing a metallized substrate comprising a metallized film formed on a ceramics substrate, wherein the metallizing paste according to claim 2 is applied once to a thickness of 80 μm or more by screen printing on the ceramics substrate. ,
Alternatively, a method for producing a metallized substrate is characterized in that the metallized film is formed by coating several times and baked in a vacuum or an inert atmosphere to form a metallized film.
【請求項4】 請求項3記載のメタライズ基板の製造方
法において、前記セラミックス基板はアルミナ及び窒化
アルミニウムのうち、少なくとも一種からなることを特
徴とするメタライズ基板の製造方法。
4. The method of manufacturing a metallized substrate according to claim 3, wherein the ceramics substrate is made of at least one of alumina and aluminum nitride.
【請求項5】 請求項3又は請求項4記載のメタライズ
基板の製造方法において、前記金属化膜上にNi膜及び
Au膜のうち、いずれか一種を形成することを特徴とす
るメタライズ基板の製造方法。
5. The method of manufacturing a metallized substrate according to claim 3 or 4, wherein any one of a Ni film and an Au film is formed on the metallized film. Method.
JP2321594A 1994-01-24 1994-01-24 Metal powder composition and production of metallized substrate using the same Pending JPH07207452A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2321594A JPH07207452A (en) 1994-01-24 1994-01-24 Metal powder composition and production of metallized substrate using the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2321594A JPH07207452A (en) 1994-01-24 1994-01-24 Metal powder composition and production of metallized substrate using the same

Publications (1)

Publication Number Publication Date
JPH07207452A true JPH07207452A (en) 1995-08-08

Family

ID=12104445

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2321594A Pending JPH07207452A (en) 1994-01-24 1994-01-24 Metal powder composition and production of metallized substrate using the same

Country Status (1)

Country Link
JP (1) JPH07207452A (en)

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WO2012090647A1 (en) * 2010-12-28 2012-07-05 株式会社トクヤマ Metallized substrate, metal paste composition, and method for producing metallized substrate
CN103373860A (en) * 2012-04-27 2013-10-30 比亚迪股份有限公司 Surface metalized coating composition of ceramic matrix, surface metalizing method of ceramic matrix, and coating and ceramic prepared from ceramic matrix
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010113892A1 (en) 2009-03-30 2010-10-07 株式会社トクヤマ Process for producing metallized substrate and metallized substrate
US20120015152A1 (en) * 2009-03-30 2012-01-19 Tokuyama Corporation Process for producing metallized substrate, and metallized substrate
US9301390B2 (en) 2009-03-30 2016-03-29 Tokuyama Corporation Process for producing metallized substrate, and metallized substrate
US9374893B2 (en) 2010-03-02 2016-06-21 Tokuyama Corporation Production method of metallized substrate
WO2012090647A1 (en) * 2010-12-28 2012-07-05 株式会社トクヤマ Metallized substrate, metal paste composition, and method for producing metallized substrate
CN103238380A (en) * 2010-12-28 2013-08-07 株式会社德山 Metallized substrate, metal paste composition, and method for producing metallized substrate
US9462698B2 (en) 2010-12-28 2016-10-04 Tokuyama Corporation Metallized substrate, metal paste composition, and method for manufacturing metallized substrate
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