JP3056852B2 - Ceramic substrate with copper circuit - Google Patents
Ceramic substrate with copper circuitInfo
- Publication number
- JP3056852B2 JP3056852B2 JP3289337A JP28933791A JP3056852B2 JP 3056852 B2 JP3056852 B2 JP 3056852B2 JP 3289337 A JP3289337 A JP 3289337A JP 28933791 A JP28933791 A JP 28933791A JP 3056852 B2 JP3056852 B2 JP 3056852B2
- Authority
- JP
- Japan
- Prior art keywords
- ceramic substrate
- copper plate
- copper
- circuit
- substrate
- 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
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
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
-
- 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
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
Landscapes
- Manufacturing Of Printed Wiring (AREA)
- Structure Of Printed Boards (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電子部品のパワーモジ
ュール等に使用される銅回路を有するセラミックス基板
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic substrate having a copper circuit used for a power module of an electronic component.
【０００２】近年、ロボットやモーター等の産業機器の
高性能化に伴い、大電力・高能率インバーターなど大電
力モジュールの変遷が進んでおり、半導体素子から発生
する熱も増加の一途をたどっている。この熱を効率よく
放散するため、大電力モジュール基板では従来よりさま
ざまな方法がとられてきた。特に最近、良好な熱伝導率
を有するセラミックス基板が利用できるようになったた
め、基板上に銅板などの金属板を接合し、回路を形成
後、そのままあるいはメッキ等の処理を施してから半導
体素子を実装する構造も採用されつつある。In recent years, high performance modules such as high power and high efficiency inverters have been transitioning along with high performance of industrial equipment such as robots and motors, and the heat generated from semiconductor elements has been increasing steadily. . In order to efficiently dissipate this heat, various methods have been used for high power module substrates. In particular, recently, ceramic substrates having good thermal conductivity have become available, so that a metal plate such as a copper plate is bonded onto the substrate, and after forming a circuit, the semiconductor element is processed as it is or after plating. A mounting structure is also being adopted.
【０００３】金属とセラミックスを接合する方法には種
々あるが、回路基板の製造という点からは、Mo−Mn法、
活性金属ろう付け法、硫化銅法、ＤＢＣ法、銅メタライ
ズ法などがあげられる。[0003] There are various methods for joining metal and ceramics, but from the viewpoint of manufacturing circuit boards, the Mo-Mn method,
Active metal brazing, copper sulfide, DBC, copper metallization and the like can be mentioned.
【０００４】特に大電力モジュール基板では、従来のア
ルミナにかわって高熱伝導性の窒化アルミニウム基板が
注目されており、銅板との接合方法としては、銅板と窒
化アルミニウム基板との間に活性金属を含むろう材（以
下、単に「ろう材」という）を介在させ、加熱処理して
接合体とする活性金属ろう付け法（例えば特開昭60−17
7634号公報）や表面を酸化処理した窒化アルミニウム基
板と銅板を銅の融点以下でCu−O の共晶温度以上で加熱
接合するＤＢＣ法（例えば特開昭56−163093号公報）な
どが用いられている。In particular, in the case of high power module substrates, aluminum nitride substrates having high thermal conductivity have been attracting attention in place of conventional alumina, and a method of bonding with a copper plate includes an active metal between the copper plate and the aluminum nitride substrate. An active metal brazing method in which a brazing material (hereinafter simply referred to as "brazing material") is interposed and heat-treated to form a joined body (for example, Japanese Patent Application Laid-Open No. 60-17 / 1985)
No. 7634) and a DBC method (for example, Japanese Patent Application Laid-Open No. 56-163093) in which an aluminum nitride substrate whose surface is oxidized and a copper plate are heated and joined at a temperature lower than the melting point of copper and higher than the eutectic temperature of Cu—O. ing.
【０００５】活性金属ろう付け法は、ＤＢＣ法に比べて
以下の利点がある。 １）上記接合体を得るための処理温度が低いので、窒化
アルミニウムと銅板の熱膨張差によって生じる残留応力
が小さい。 ２）ろう材が延性金属であるので、ヒートショックやヒ
ートサイクルに対して耐久性が大である。[0005] The active metal brazing method has the following advantages over the DBC method. 1) Since the processing temperature for obtaining the above joined body is low, the residual stress caused by the difference in thermal expansion between the aluminum nitride and the copper plate is small. 2) Since the brazing material is a ductile metal, it has high durability against heat shock and heat cycle.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、活性金
属ろう付け法を用いても、ヒートショックやヒートサイ
クルなどの熱衝撃、熱履歴によって生じる損傷に対して
十分な耐久性があるとはいえず新しい技術の提案が待た
れていた。However, even if the active metal brazing method is used, it cannot be said that it is sufficiently durable against damage caused by heat shock and heat history such as heat shock and heat cycle, and a new method is used. Technology proposals were awaited.
【０００７】本発明者らは、以上のような問題点を解決
するために鋭意検討を重ねた結果、セラミックス基板や
ろう材成分あるいは回路構造の大幅な変更等を行うこと
なく、裏面の銅板の沿面距離を小さくすることによっ
て、銅回路を有するセラミックス基板の熱衝撃や熱履歴
に対する耐久性、すなわち耐ヒートショック性と耐ヒー
トサイクル性を向上できることを見出し、本発明を完成
させたものである。The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, without making significant changes in the ceramic substrate, the brazing material components or the circuit structure, etc. It has been found that by reducing the creepage distance, the durability of a ceramic substrate having a copper circuit to thermal shock and thermal history, that is, heat shock resistance and heat cycle resistance can be improved, and the present invention has been completed.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明は、セ
ラミックス基板の表裏面に接合された銅板を化学エッチ
ングを行い、その表面には沿面距離が１．０〜２．０ｍ
ｍ、厚さ０．１ｍｍ以上の銅回路を、また、その裏面に
は沿面距離が０．１〜０．３ｍｍのヒートシンク等への
取り付け用銅板を形成させてなるものであることを特徴
とするセラミックス基板である。 That SUMMARY OF THE INVENTION The present invention is Se
Chemically etch the copper plate bonded to the front and back of the Lamix board
The surface has a creepage distance of 1.0 to 2.0 m
m, a copper circuit with a thickness of 0.1 mm or more, and on the back surface
Is suitable for heat sinks with creepage distances of 0.1 to 0.3 mm.
Characterized by forming a copper plate for mounting
Ceramic substrate.
【０００９】以下、さらに詳しく本発明について説明す
る。Hereinafter, the present invention will be described in more detail.
【００１０】本発明における沿面距離とは、セラミック
ス基板の端面と接合された銅板の端部との距離をいう。
通常、回路が形成されている面の反対側の面（裏面）に
は、基板をヒートシンク等に半田付け等するために回路
が形成されていない１枚の銅板（裏銅板）が接合されて
いる。この裏銅板としては、従来、セラミックス基板よ
りも少し小さいものが使用されてきた。それは、基板端
面より裏銅板がはみだすと絶縁特性が低下したからであ
る。The creepage distance in the present invention refers to the distance between the end face of the ceramic substrate and the end of the joined copper plate.
Normally, one copper plate (back copper plate) on which no circuit is formed is bonded to the surface (back surface) opposite to the surface on which the circuit is formed, for soldering the substrate to a heat sink or the like. . As the back copper plate, a plate slightly smaller than the ceramic substrate has been used. The reason for this is that when the back copper plate protrudes from the end face of the substrate, the insulating properties are reduced.
【００１１】一方、回路の形成法としては、予めパター
ン形状に加工された銅板をセラミックス基板に接合する
搭載法と、板状の銅板をセラミックス基板に接合した
後、化学エッチングによって回路パターンを形成するエ
ッチング法があり、さらには前者を改良したプッシュバ
ック法（特開平３ー１０２８９１号公報）や後者を改良
したハーフエッチ法（特開平３ー１０２８９２号公報）
などがある。いずれの方法においても、沿面距離と公差
を大きく取った方が歩留りの点で有利である。何故な
ら、セラミックス基板は焼成時の収縮のバラツキ等によ
って大きさが変化するのでそれをなくしたり、接合時の
銅板ズレやレジスト印刷時の位置ズレなどによって生じ
る不良を軽減するためである。これらを考慮して、従来
より、沿面距離は0.５〜1.０mmが採用されてきた。On the other hand, as a circuit forming method, there are a mounting method of joining a copper plate previously processed into a pattern shape to a ceramic substrate, and a circuit pattern is formed by joining a plate-like copper plate to a ceramic substrate and then chemically etching. There is an etching method, and further, a pushback method (JP-A-3-102891) in which the former is improved, and a half-etch method (JP-A-3-102892) in which the latter is improved
and so on. In any of the methods, it is advantageous to increase the creepage distance and the tolerance in terms of yield. This is because the size of the ceramic substrate changes due to variations in shrinkage during firing or the like, and this is eliminated, and defects caused by displacement of the copper plate at the time of bonding or displacement at the time of resist printing are reduced. In consideration of these, a creepage distance of 0.5 to 1.0 mm has been conventionally employed.
【００１２】しかしながら、量産性の点で有利なエッチ
ング法が主流となったため銅板ズレはあまり問題とはな
らず、基板の大きさを予めサイズごとに分けておいて、
印刷時にスクリーン版の位置や大きさを変えれば位置ズ
レも歩留りには殆んど影響しないことから、技術的には
０．５ｍｍ未満の沿面距離にも十分対応できるようにな
った。本発明においては、熱衝撃や熱履歴の耐久性を向
上させるための沿面距離は０．１ｍｍ〜０．３ｍｍであ
る。耐熱衝撃性向上の点からは沿面距離０ｍｍが最も好
ましいが、歩留りの点で問題がある。 However, since the etching method that is advantageous in terms of mass productivity has become mainstream, displacement of the copper plate does not cause much problem, and the size of the substrate is divided in advance for each size.
If the position and size of the screen plate are changed at the time of printing, the positional deviation hardly affects the yield, so that it has become technically possible to sufficiently cope with a creepage distance of less than 0.5 mm. In the present invention, the creepage distance for improving the durability of thermal shock and thermal history is 0.1 mm to 0.3 mm.
You. From the viewpoint of improving thermal shock resistance, the creepage distance of 0 mm is the best.
Better yet, there is a problem in terms of yield.
【００１３】熱衝撃や熱履歴を受けた際には、脆性材料
であるセラミックス基板に損傷が発生することがある
が、この原因となるのは、銅板とセラミックス基板の熱
膨張差によって生じる熱応力である。従って、最も損傷
を受けやすいのは銅板とセラミックス基板の接合端部で
ある。セラミックス基板には、両面に銅板が接合される
ため、この端部位置が一致するとその位置が受ける熱応
力は倍加して破壊的損傷が生じやすくなり、時にはセラ
ミックス基板を貫通するクラックを生じることがある
が、回路面と裏面の端部位置をずらすことによって、こ
れを解決することができる。When subjected to thermal shock or thermal history, the ceramic substrate, which is a brittle material, may be damaged. This is due to the thermal stress caused by the difference in thermal expansion between the copper plate and the ceramic substrate. It is. Therefore, the most susceptible to damage is the joint end between the copper plate and the ceramic substrate. Since the copper plate is bonded to both sides of the ceramic substrate, if the end positions match, the thermal stress applied to that position will be doubled, causing destructive damage and sometimes causing cracks to penetrate the ceramic substrate. However, this can be solved by shifting the end positions of the circuit surface and the back surface.
【００１４】しかるに、回路面の沿面距離は、絶縁特性
を保つため、１．０ｍｍ〜２．０ｍｍ程度であるので、
裏面の沿面距離を小さくすれば、両面の接合端部位置の
差が大きくなって熱衝撃や熱履歴に対する耐久性を高め
ることができる。However, since the creepage distance of the circuit surface is about 1.0 mm to 2.0 mm in order to maintain insulation properties,
If the creeping distance of the back surface is reduced, the difference between the joining end positions of both surfaces increases, and the durability against thermal shock and thermal history can be increased.
【００１５】本発明における銅回路とは、銅を含む導電
性の金属板であれば特に制限はないが、コスト、加工
性、導電性等から、通常は銅板が用いられる。ＤＢＣ法
ではタフピッチ銅板を、また活性金属ろう付け法では無
酸素銅板が好適に使用されるが、十分な接合強度があれ
ばこれに限られるものではない。銅板の厚さについて
も、通常使用されている0.１〜0.３mm程度のものでよ
い。しかし、あまりにも薄いと大電流を流すのに不適当
であり、またあまりにも厚いと接合時の熱応力によりセ
ラミックス基板に損傷を生じやすくなるので、0.１〜0.
５mm特に0.１５〜0.４mmが適切である。The copper circuit in the present invention is not particularly limited as long as it is a conductive metal plate containing copper, but usually a copper plate is used in view of cost, workability, conductivity and the like. A tough pitch copper plate is preferably used in the DBC method, and an oxygen-free copper plate is preferably used in the active metal brazing method. However, the present invention is not limited to this as long as the bonding strength is sufficient. The thickness of the copper plate may be about 0.1 to 0.3 mm which is usually used. However, if it is too thin, it is inappropriate for flowing a large current, and if it is too thick, the ceramic substrate is likely to be damaged by thermal stress at the time of joining, so that 0.1 to 0.1.
5 mm, especially 0.15 to 0.4 mm, is suitable.
【００１６】熱応力の発生を防ぐ措置、例えば低熱膨張
性合金板の使用や、クラック発生防止スリット（特願平
３−142644号明細書参照）の採用等により、さらに厚い
銅板の使用も可能である。Measures to prevent the occurrence of thermal stress, such as the use of a low thermal expansion alloy plate and the use of a crack prevention slit (see Japanese Patent Application No. 3-142644), allow the use of a thicker copper plate. is there.
【００１７】本発明におけるセラミックス基板とは、銅
回路を接合して使用できるものであれば特に制限される
ものではないが、通常、アルミナ又は窒化アルミニウム
を主成分とするものが最もよく使用される。特に、銅回
路を有するセラミックス基板は、高熱伝導性の基板が好
適であるので、それには窒化アルミニウムを含む基板が
好ましい。The ceramic substrate in the present invention is not particularly limited as long as it can be used by joining a copper circuit. Usually, a substrate mainly composed of alumina or aluminum nitride is most often used. . In particular, a ceramic substrate having a copper circuit is preferably a substrate having high thermal conductivity, and thus a substrate containing aluminum nitride is preferable.
【００１８】本発明における銅回路のセラミックス基板
への接合方法も、特に制限されるものではなく、通常の
方法でかまわないが、量産性やコストの点からＤＢＣ法
や活性金属ろう付け法が多用される。特に活性金属ろう
付け法は信頼性に優れているので本発明には好適であ
る。The method of joining the copper circuit to the ceramic substrate in the present invention is not particularly limited, and may be an ordinary method, but the DBC method and the active metal brazing method are frequently used in terms of mass productivity and cost. Is done. In particular, the active metal brazing method is suitable for the present invention because of its excellent reliability.
【００１９】ろう材成分の活性金属についても各種の金
属が知られており、本発明では特に制限されるものでは
ないが、接合の安定性、入手の容易さ、安全性などを考
慮すると、Ti、TiH2、Zr、ZrH2のうち少なくとも一種を
含むことが好適である。また、ろう材は合金箔の形で使
用することもできるが、各成分粉末と有機溶剤を混合し
て、必要に応じてバインダー等を加え、ペースト状にし
て塗布することもできる。活性金属と共に使用されるろ
う材の他の金属成分としては、AgやAg−Cuを主成分とす
るものが一般的である。Various metals are also known as the active metal of the brazing filler metal component, and are not particularly limited in the present invention. However, considering the stability of joining, the availability and the safety, etc., Ti , TiH 2 , Zr, and ZrH 2 . The brazing material can be used in the form of an alloy foil, but it can also be applied in the form of a paste by mixing each component powder and an organic solvent, adding a binder or the like as necessary. As other metal components of the brazing filler metal used together with the active metal, those containing Ag or Ag-Cu as a main component are generally used.
【００２０】[0020]
【実施例】以下、実施例と比較例をあげて本発明を具体
的に説明する。The present invention will be described below in detail with reference to examples and comparative examples.
【００２１】実施例１〜８ 比較例１〜５ ４０mm×４０mm×0.６３５mmt の窒化アルミニウム基板
（熱伝導率１４０ｗ／ｍ・ｋ）とアルミナ基板（熱伝導
率２０ｗ／ｍ・ｋ）に、表１に示すような各種組成の活
性金属を含むろう材を用いた活性金属ろう付け法又はＤ
ＢＣ法によって厚さ0.１〜0.４mmの銅板を接合し、スク
リーン版を用いてレジスト印刷した後エッチング法によ
り回路を形成した。回路面の沿面は1.５mm、裏面は0.１
〜1.５mmとした。Examples 1 to 8 Comparative Examples 1 to 5 Tables were prepared on a 40 mm × 40 mm × 0.635 mmt aluminum nitride substrate (thermal conductivity 140 w / mk) and an alumina substrate (thermal conductivity 20 w / mk). An active metal brazing method using a brazing material containing active metals of various compositions as shown in FIG.
A copper plate having a thickness of 0.1 to 0.4 mm was joined by a BC method, and a resist was printed using a screen plate, and then a circuit was formed by an etching method. The creepage of the circuit surface is 1.5 mm, the back surface is 0.1
と し た 1.5 mm.
【００２２】これらの試料を各１０枚作製し、以下の条
件で耐ヒートショック性と耐ヒートサイクル性の試験を
行なった。 （１）耐ヒートショック性試験 液中で−４０℃で５分間浸漬後、１５０℃で５分間保持
を１サイクルとして１００サイクル繰り返した。 （２）耐ヒートサイクル性試験 気中−４０℃で３０分保持後、２５℃で１０分、さらに
１２５℃で３０分後、２５℃で１０分間放置を１サイク
ルとして１００サイクル繰り返した。Ten samples of each of these samples were prepared and tested for heat shock resistance and heat cycle resistance under the following conditions. (1) Heat shock resistance test After immersion in a liquid at -40 ° C for 5 minutes, holding at 150 ° C for 5 minutes as one cycle was repeated 100 cycles. (2) Heat cycle resistance test After holding at -40 ° C for 30 minutes in the air, 25 minutes at 10 minutes, 125 ° C for 30 minutes, and then standing at 25 ° C for 10 minutes, one cycle was repeated 100 times.
【００２３】耐ヒートショック性と耐ヒートサイクル性
の試験後は、絶縁不良の原因となる貫通クラックと貫通
クラックへと進展する垂直クラックの発生個数を調べ、
さらに銅板を溶解除去して水平クラックの発生状況を調
べた。水平クラックは、基板表面と平行方向に進展しや
すいクラックで甚しい場合には回路パターンの剥離へつ
ながるものである。以上の結果を表１に示す。After the heat shock resistance and heat cycle resistance tests, the number of penetrating cracks that cause insulation failure and the number of vertical cracks that develop into penetrating cracks are examined.
Further, the copper plate was dissolved and removed, and the occurrence of horizontal cracks was examined. A horizontal crack is a crack that easily develops in a direction parallel to the substrate surface, and in extreme cases, leads to peeling of a circuit pattern. Table 1 shows the above results.
【００２４】[0024]
【表１】 [Table 1]
【００２５】表１から、本発明の実施例は比較例に比べ
て、ヒートショック性とヒートサイクル性において著し
い改善効果が認められた。From Table 1, it can be seen that the Examples of the present invention showed a remarkable improvement in heat shock property and heat cycle property as compared with Comparative Examples.
【発明の効果】本発明によれば、セラミック基板やろう
材成分、あるいは接合法や回路構造の大幅な変更等をす
ることなく、熱衝撃や熱履歴に対する耐久性すなわち耐
ヒートショック性や耐ヒートサイクル性を向上させるこ
とができる。According to the present invention, the durability against heat shock and heat history, that is, the heat shock resistance and heat resistance can be achieved without making significant changes in the ceramic substrate, brazing material components, joining method or circuit structure. Cycleability can be improved.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−101153（ＪＰ，Ａ) 特開 昭63−87790（ＪＰ，Ａ) 特公 平３−61353（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) H05K 1/02 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-101153 (JP, A) JP-A-63-87790 (JP, A) JP-B-3-61353 (JP, B2) (58) Field (Int.Cl. 7 , DB name) H05K 1/02
Claims (1)
板を化学エッチングを行い、その表面には沿面距離が
１．０〜２．０ｍｍ、厚さ０．１ｍｍ以上の銅回路を、
また、その裏面には沿面距離が０．１〜０．３ｍｍのヒ
ートシンク等への取り付け用銅板を形成させてなるもの
であることを特徴とするセラミックス基板。 1. Copper bonded to the front and back surfaces of a ceramic substrate
The board is chemically etched and its surface has a creepage distance
1.0-2.0mm, copper circuit of thickness 0.1mm or more,
On the back surface, a creeping distance of 0.1 to 0.3 mm is used.
Formed from a copper plate for attachment to a heat sink, etc.
A ceramic substrate, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3289337A JP3056852B2 (en) | 1991-10-08 | 1991-10-08 | Ceramic substrate with copper circuit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3289337A JP3056852B2 (en) | 1991-10-08 | 1991-10-08 | Ceramic substrate with copper circuit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05102620A JPH05102620A (en) | 1993-04-23 |
| JP3056852B2 true JP3056852B2 (en) | 2000-06-26 |
Family
ID=17741895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3289337A Expired - Fee Related JP3056852B2 (en) | 1991-10-08 | 1991-10-08 | Ceramic substrate with copper circuit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3056852B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2562283Y2 (en) * | 1993-06-30 | 1998-02-10 | 株式会社ランダム | Water saving tool for water supply |
| DE50307323D1 (en) * | 2002-03-13 | 2007-07-05 | Electrovac Ag | METHOD FOR PRODUCING A METAL CERAMIC SUBTRAT, PREFERABLY OF A COPPER CERAMIC SUBSTRATE |
| DE10212495B4 (en) | 2002-03-21 | 2004-02-26 | Schulz-Harder, Jürgen, Dr.-Ing. | Method for producing a metal-ceramic substrate, preferably a copper-ceramic substrate |
| JP7179550B2 (en) * | 2018-09-20 | 2022-11-29 | 株式会社東芝 | Ceramic circuit board and semiconductor device using the same |
-
1991
- 1991-10-08 JP JP3289337A patent/JP3056852B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05102620A (en) | 1993-04-23 |
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