JP2005071825A - Conductive paste, wiring board, and its manufacturing method - Google Patents

Conductive paste, wiring board, and its manufacturing method Download PDF

Info

Publication number
JP2005071825A
JP2005071825A JP2003300632A JP2003300632A JP2005071825A JP 2005071825 A JP2005071825 A JP 2005071825A JP 2003300632 A JP2003300632 A JP 2003300632A JP 2003300632 A JP2003300632 A JP 2003300632A JP 2005071825 A JP2005071825 A JP 2005071825A
Authority
JP
Japan
Prior art keywords
melting point
particles
point metal
low
low melting
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.)
Granted
Application number
JP2003300632A
Other languages
Japanese (ja)
Other versions
JP4268476B2 (en
Inventor
Koji Nishi
浩二 西
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.)
Kyocera Corp
Original Assignee
Kyocera 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 Kyocera Corp filed Critical Kyocera Corp
Priority to JP2003300632A priority Critical patent/JP4268476B2/en
Publication of JP2005071825A publication Critical patent/JP2005071825A/en
Application granted granted Critical
Publication of JP4268476B2 publication Critical patent/JP4268476B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Landscapes

  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
  • Conductive Materials (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide conductive paste having low resistance and capable of achieving high connection reliability, and to provide a wiring board using it. <P>SOLUTION: This conductive paste contains: low-melting-point metal A particles 5a containing at least tin and having melting points below 230°C; low-melting-point metal B particles 5b containing at least tin and having melting points lower than those of the particles 5a; low-resistance metal particles 5c having melting points over 230°C; and a resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、少なくとも樹脂を含有する絶縁基板と、導電性ペーストを充填してなるビアを具備する配線基板において、ビアの低抵抗化と接続信頼性を向上できる導電性ペーストに関するものである。   The present invention relates to a conductive paste capable of reducing via resistance and improving connection reliability in a wiring board including an insulating substrate containing at least a resin and a via filled with a conductive paste.

近年、エポキシ樹脂、フェノール樹脂等の熱硬化性樹脂を含む絶縁基板の表面に配線層を形成した、いわゆるプリント基板が配線基板や半導体素子等の電気素子を搭載したパッケージ等に適用されている。このようなプリント基板において配線層を形成する方法としては、絶縁基板の表面に銅箔を接着した後、これをエッチングして配線回路を形成する方法、または配線回路に形成された銅箔を絶縁基板に転写する方法、絶縁基板の表面に金属メッキ法によって回路を形成する方法等が用いられている。また、配線の多層化に伴い、異なる層間の配線層をビアによって電気的に接続することも行われている。このビアは一般的に配線基板の絶縁基板の所定の箇所にドリル等でビアホールを開けた後に、ビアホール内の内壁にメッキ等を施して形成される。   In recent years, a so-called printed circuit board in which a wiring layer is formed on the surface of an insulating substrate containing a thermosetting resin such as an epoxy resin or a phenol resin is applied to a package or the like on which an electric element such as a wiring board or a semiconductor element is mounted. As a method of forming a wiring layer in such a printed circuit board, a copper foil is bonded to the surface of an insulating substrate and then etched to form a wiring circuit, or a copper foil formed on the wiring circuit is insulated. A method of transferring to a substrate, a method of forming a circuit on the surface of an insulating substrate by a metal plating method, and the like are used. In addition, with the increase in the number of wiring layers, wiring layers between different layers are also electrically connected by vias. This via is generally formed by opening a via hole at a predetermined location on an insulating substrate of a wiring board with a drill or the like and then plating the inner wall in the via hole.

しかしながら、上記のような方法ではメッキ処理を施すのに用いられる薬品が高価であり、処理時間も長いなど生産性と経済性に難がある。また、内壁にメッキを施して形成されたビアは、多層構造の場合には任意の層間に形成するために一層毎にレジスト形成、メッキ、剥離研磨を行う必要があり、更なる生産性と経済性の悪化となる。配線層の密度を向上するために多層構造の任意の層間に導通をとる導通機構としては、問題がある。   However, in the method as described above, the chemicals used for the plating treatment are expensive, and there are difficulties in productivity and economy such as a long treatment time. In addition, in the case of vias formed by plating the inner wall, in the case of a multilayer structure, it is necessary to perform resist formation, plating, and peeling polishing for each layer in order to form between arbitrary layers. Sexual deterioration. There is a problem as a conduction mechanism that conducts electricity between arbitrary layers of a multilayer structure in order to improve the density of the wiring layer.

このような問題に対して、銀、銅、ハンダなどの金属粉末と熱硬化性樹脂や活性剤とを混合した導体ペーストを用い、これを絶縁基板の表面に塗布したり、ビアホール内に充填し、積層して多層化する方法がある（特許文献１、２参照）。   To solve this problem, a conductive paste in which a metal powder such as silver, copper, or solder is mixed with a thermosetting resin or activator is applied to the surface of an insulating substrate or filled into a via hole. There is a method of stacking and multilayering (see Patent Documents 1 and 2).

ビア用の導電性ペーストは、一般には金属粉末と熱硬化性樹脂との混合物からなるものであるが、特許文献１の導電性ペーストでは、導電性ペースト中の熱硬化性樹脂成分の量が２２．９％と多く、またビアの金属粉末間の接触性が充分でないために、ビアの導電率が低いという問題があった。   The conductive paste for vias is generally composed of a mixture of metal powder and thermosetting resin. However, in the conductive paste of Patent Document 1, the amount of the thermosetting resin component in the conductive paste is 22. There is a problem that the electrical conductivity of the via is low because the contact property between the metal powders of the via is not sufficient and the contact property is low.

また、特許文献２の導電性ペーストでは、熱硬化性樹脂成分の量を減少させているため、初期のビアの抵抗は低いものの、ビアの金属粒子同士の結合力が十分でなく、熱サイクル等により、ビアの抵抗が変化するという問題があった。   Further, in the conductive paste of Patent Document 2, since the amount of the thermosetting resin component is reduced, the initial via resistance is low, but the bonding force between the metal particles of the via is not sufficient, the thermal cycle, etc. As a result, the resistance of the via changes.

このような問題に対して、導電性ペーストにＣｕなどの粉末とともに、Ｐｂ−Ｓｎなどの低融点半田を含有させて、Ｃｕ粒子同士を半田によって接続させ、ビアの導電率を高めることも提案されている（特許文献３参照）。
特開平８−３１５６３７ 特許第２６０３０５３ 特開２００２−１０９９５６ In order to solve this problem, it has also been proposed that the conductive paste contains a low melting point solder such as Pb-Sn together with a powder such as Cu, and the Cu particles are connected to each other by solder to increase the conductivity of the via. (See Patent Document 3).
JP-A-8-315637 Japanese Patent No. 2603053 JP2002-109956

しかしながら、配線基板中のビア構造の核となるＣｕ粒子表面への低融点半田の濡れ性が十分でなかったり、Ｃｕ粒子同士を接続する低温半田のネッキングが不充分な場合には、信頼性が不十分で、ヒートサイクル等でネッキングが切れ、電気抵抗の上昇や、最悪の場合、断線を引き起こすという問題があった。   However, the reliability is low when the low-melting-point solder wettability to the Cu particle surface that is the core of the via structure in the wiring board is insufficient, or the low-temperature soldering that connects the Cu particles is insufficient. There is a problem that necking is cut off due to heat cycle or the like, the electrical resistance is increased, and in the worst case, disconnection is caused.

本発明はこのような問題を解消し、低抵抗で、高い接続信頼性を実現する導電性ペースト及びそれを用いた配線基板を提供することを目的とするものである。   An object of the present invention is to solve such problems and to provide a conductive paste that realizes high connection reliability with low resistance and a wiring board using the same.

本発明の導電性ペーストは、少なくとも錫を含有し、融点が２３０℃以下の低融点金属Ａ粒子と、錫を含有し、低融点金属Ａ粒子よりも融点が低い低融点金属Ｂ粒子と、低抵抗金属粒子と、樹脂とを含有することを特徴とする。   The conductive paste of the present invention contains at least tin and low melting point metal A particles having a melting point of 230 ° C. or lower, low melting point metal B particles containing tin and having a melting point lower than that of the low melting point metal A particles, Resistive metal particles and a resin are contained.

また、本発明の導電性ペーストは、低抵抗金属粒子が少なくともＣｕ、Ａｇ、Ａｕから選ばれる一種を含有することが望ましい。   The conductive paste of the present invention preferably contains at least one kind of low-resistance metal particles selected from Cu, Ag, and Au.

また、本発明の導電性ペーストは、低融点金属Ａ粒子の平均粒子径が低融点金属Ｂ粒子の平均粒子径よりも大きいことが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable for the average particle diameter of the low melting metal A particle to be larger than the average particle diameter of the low melting metal B particle.

また、本発明の導電性ペーストは、低融点金属Ｂ粒子の平均粒径が低融点金属Ａ粒子の平均粒径の８０％以下であることが望ましい。   In the conductive paste of the present invention, the average particle size of the low melting point metal B particles is desirably 80% or less of the average particle size of the low melting point metal A particles.

また、本発明の導電性ペーストは、樹脂が熱硬化性樹脂であることが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable that resin is a thermosetting resin.

また、本発明の導電性ペーストは、樹脂が、トリアリルイソシアヌレートを含有することが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable for resin to contain triallyl isocyanurate.

また、本発明の導電性ペーストは、低融点金属Ａ粒子の含有量をＭ１、低融点金属Ｂ粒子の含有量をＭ２、低抵抗金属粒子の含有量をＭ３としたとき、（Ｍ２）／（Ｍ１＋Ｍ２）が３０〜８０％、（Ｍ３）／（Ｍ１＋Ｍ２＋Ｍ３）が４０〜６０％の関係を満足することが望ましい。   In the conductive paste of the present invention, when the content of the low melting point metal A particles is M1, the content of the low melting point metal B particles is M2, and the content of the low resistance metal particles is M3, (M2) / ( It is desirable that the relationship of (M1 + M2) is 30 to 80% and (M3) / (M1 + M2 + M3) is 40 to 60%.

また、本発明の導電性ペーストは、低融点金属Ａ粒子と低融点金属Ｂ粒子の融点の差が１０℃以上であることが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable for the difference of melting | fusing point of the low melting metal A particle and the low melting metal B particle to be 10 degreeC or more.

また、本発明の導電性ペーストは、低融点金属Ｂ粒子が、Ｂｉを含有していることが望ましい。   In the conductive paste of the present invention, it is desirable that the low melting point metal B particles contain Bi.

また、本発明の導電性ペーストは、低融点金属Ａ粒子、低融点金属Ｂ粒子、低抵抗金属粒子の含有量が合計で８５〜９５質量％、樹脂の含有量が５〜１５質量％であることが望ましい。   The conductive paste of the present invention has a total content of low melting point metal A particles, low melting point metal B particles, and low resistance metal particles of 85 to 95% by mass, and a resin content of 5 to 15% by mass. It is desirable.

このような導電性ペーストを、例えば、配線基板等に用いることにより、高信頼性で低抵抗のビアを形成することができる。   By using such a conductive paste for, for example, a wiring board or the like, a highly reliable and low resistance via can be formed.

また、本発明の配線基板は、少なくとも樹脂を含有する絶縁基板と配線層とが積層され、該配線層間を電気的に接続するために前記絶縁基板内にビアを具備してなる配線基板であって、前記ビアが、以上説明した導電性ペーストを充填して形成されたことを特徴とする。   The wiring board of the present invention is a wiring board in which an insulating substrate containing at least a resin and a wiring layer are laminated, and a via is provided in the insulating substrate to electrically connect the wiring layers. The via is formed by filling the conductive paste described above.

以上説明した導電性ペーストを使用して配線基板を作製することにより、ビアの抵抗を小さくできるとともに、ビアや電気的接続構造の接続信頼性を向上させることができ、電気抵抗の低い配線を有し、信頼性に優れた配線基板を提供できる。   By producing a wiring board using the conductive paste described above, the resistance of the via can be reduced, the connection reliability of the via and the electrical connection structure can be improved, and a wiring having a low electrical resistance can be provided. In addition, a highly reliable wiring board can be provided.

また、本発明の配線基板の製造方法は、少なくとも熱硬化性樹脂を含有する未硬化あるいは半硬化状態の絶縁基板にビアホールを形成する工程と、前記ビアホールに、上記の導電性ペーストを充填した後、前記ビアホール形成部を含む前記絶縁基板の表面に導体層を被着形成する工程と、該絶縁基板を積層して一体化した後、該積層物を前記熱硬化性樹脂の硬化温度に加熱して一括硬化する工程とを具備することを特徴とする。   The method for manufacturing a wiring board according to the present invention includes a step of forming a via hole in an uncured or semi-cured insulating substrate containing at least a thermosetting resin, and after filling the via hole with the conductive paste. A step of depositing and forming a conductor layer on the surface of the insulating substrate including the via hole forming portion, and laminating and integrating the insulating substrates, and then heating the laminate to a curing temperature of the thermosetting resin. And a step of collectively curing.

このような配線基板の製造方法では、一括硬化することにより逐次硬化時に発生する配線基板内層部と外層部の材料物性の変化を低減できるとともに、硬化に関わる工程時間を短縮させることができ、さらに、低抵抗で、接続信頼性に優れた配線基板を提供できる。   In such a method of manufacturing a wiring board, it is possible to reduce the change in the material physical properties of the wiring board inner layer part and the outer layer part that are generated at the time of sequential curing by batch curing, and to shorten the process time related to curing, A wiring board with low resistance and excellent connection reliability can be provided.

本発明の導電性ペーストは、少なくとも錫を含有し、融点が２３０℃以下の低融点金属Ａ粒子と、錫を含有し、低融点金属Ａ粒子よりも融点が低い低融点金属Ｂ粒子と、低抵抗金属粒子と、樹脂とを含有することを特徴とする。   The conductive paste of the present invention contains at least tin and low melting point metal A particles having a melting point of 230 ° C. or lower, low melting point metal B particles containing tin and having a melting point lower than that of the low melting point metal A particles, Resistive metal particles and a resin are contained.

このように融点の異なる２種以上の低融点金属を用いることで、１種類の低融点金属を用いた場合に比べ、太く、強固な導電性粒子同士の接続構造が実現され、低抵抗のビアを実現できる導電性ペーストを提供できる。   By using two or more low melting point metals having different melting points in this way, a thicker and stronger connection structure between conductive particles is realized compared to the case of using one kind of low melting point metal, and a low resistance via is provided. It is possible to provide a conductive paste that can realize the above.

また、本発明の導電性ペーストは、低抵抗金属粒子が少なくともＣｕ、Ａｇ、Ａｕから選ばれる一種を含有することが望ましい。これらの金属あるいは合金は低抵抗であり、導電性ペーストに含有させることで、低抵抗なビア、電気的接続構造を提供することができる。   The conductive paste of the present invention preferably contains at least one kind of low-resistance metal particles selected from Cu, Ag, and Au. These metals or alloys have low resistance, and by including them in a conductive paste, a low resistance via and electrical connection structure can be provided.

また、本発明の導電性ペーストは、低融点金属Ａ粒子の平均粒子径が低融点金属Ｂ粒子の平均粒子径よりも大きいことが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable for the average particle diameter of the low melting metal A particle to be larger than the average particle diameter of the low melting metal B particle.

このように、低融点金属Ｂ粒子よりも高温で溶融する低融点金属Ａ粒子の平均粒子径を低融点金属Ｂ粒子の平均粒子径よりも大きくすることで、低抵抗金属粒子同士を接続する低融点金属Ａ粒子により形成される接続構造を太く、強固にすることができ、また、低融点金属Ｂがより低温で、より広範囲の低抵抗金属粒子、及び低融点金属Ａ粒子を濡らすことが可能になる。また、低融点金属Ｂ粒子の数も増加するために、さらにその効果は顕著になる。   Thus, the low resistance metal particles are connected to each other by making the average particle size of the low melting point metal A particles that melt at a higher temperature than the low melting point metal B particles larger than the average particle size of the low melting point metal B particles. The connection structure formed by the melting point metal A particles can be thick and strong, and the low melting point metal B can wet a wider range of low resistance metal particles and low melting point metal A particles at a lower temperature. become. Moreover, since the number of the low melting point metal B particles is increased, the effect is further remarkable.

また、本発明の導電性ペーストは、低融点金属Ｂ粒子の平均粒径が低融点金属Ａ粒子の平均粒径の８０％以下であることが望ましい。   In the conductive paste of the present invention, the average particle size of the low melting point metal B particles is desirably 80% or less of the average particle size of the low melting point metal A particles.

このように、低融点金属Ｂ粒子の平均粒径を低融点金属Ａ粒子の平均粒径の８０％以下とすることで、低融点金属Ｂ粒子と低融点金属Ａ粒子の平均粒径の差に起因して発生する前述した効果は、より顕著になり、接続信頼性に優れたビアや電気的接続構造を作製することができる。   Thus, by setting the average particle size of the low melting point metal B particles to 80% or less of the average particle size of the low melting point metal A particles, the difference in the average particle size between the low melting point metal B particles and the low melting point metal A particles is increased. The above-described effect caused by the above becomes more prominent, and a via or an electrical connection structure having excellent connection reliability can be manufactured.

また、本発明の導電性ペーストは、樹脂が熱硬化性樹脂であることが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable that resin is a thermosetting resin.

このような導電性ペーストでは、温度が加わり金属による電気的導電経路が形成されるに従い、熱硬化性樹脂も硬化し、剛性が増加して、ビアや電気的接続構造が変形しにくくなるため、熱応力や外力の印加によるビアや電気的接続構造の変形を抑制でき、ビアや電気的接続構造の接続信頼性を向上させることができる。   In such a conductive paste, as the temperature increases and the electrical conductive path is formed by the metal, the thermosetting resin also hardens, the rigidity increases, and the via and the electrical connection structure are not easily deformed. Deformation of vias and electrical connection structures due to application of thermal stress and external force can be suppressed, and connection reliability of vias and electrical connection structures can be improved.

また、本発明の導電性ペーストは、樹脂が、トリアリルイソシアヌレートを含有することが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable for resin to contain triallyl isocyanurate.

トリアリルイソシアヌレートは、軟化点が低いことから、導電性ペーストを低粘度に調整してスクリーン印刷等によるビアホールへの充填性を高めボイドの発生をなくすことができるために、導電性金属同士の接点を確実に確保できる。   Since triallyl isocyanurate has a low softening point, it is possible to adjust the conductive paste to a low viscosity to increase the fillability of via holes by screen printing and the like, and to eliminate the occurrence of voids. Secure contact.

また、本発明の導電性ペーストは、低融点金属Ａ粒子の含有量をＭ１、低融点金属Ｂ粒子の含有量をＭ２、低抵抗金属粒子の含有量をＭ３としたとき、（Ｍ２）／（Ｍ１＋Ｍ２）が３０〜８０％、（Ｍ３）／（Ｍ１＋Ｍ２＋Ｍ３）が４０〜６０％の関係を満足することが望ましい。   In the conductive paste of the present invention, when the content of the low melting point metal A particles is M1, the content of the low melting point metal B particles is M2, and the content of the low resistance metal particles is M3, (M2) / ( It is desirable that the relationship of (M1 + M2) is 30 to 80% and (M3) / (M1 + M2 + M3) is 40 to 60%.

このように、（Ｍ２）／（Ｍ１＋Ｍ２）を３０％以上にすることで低抵抗金属粒子への低融点金属Ａ粒子の被覆面積を広げることができ、また、８０％以下とすることで低抵抗金属粒子同士の接続構造を太く、強固に形成することができるために、ビアや電気的接続構造の抵抗を低くできるとともに、ビアや電気的接続構造の接続信頼性を向上させることができる。   As described above, by setting (M2) / (M1 + M2) to 30% or more, the coating area of the low-melting-point metal A particles on the low-resistance metal particles can be expanded, and by setting it to 80% or less, low resistance is achieved. Since the connection structure between the metal particles can be thick and formed firmly, the resistance of the via and the electrical connection structure can be lowered, and the connection reliability of the via and the electrical connection structure can be improved.

また、（Ｍ３）／（Ｍ１＋Ｍ２＋Ｍ３）を４０％以上にすることで、低抵抗である低抵抗金属粒子が増えるために、ビアの電気抵抗を低くでき、また、（Ｍ３）／（Ｍ１＋Ｍ２＋Ｍ３）を６０％以下にすることで、低抵抗金属粒子同士を接続するネッキングを太く強固に形成することができるために、ビアや電気的接続構造の抵抗を低くできるとともに、ビアや電気的接続構造の接続信頼性を向上させることができる。   Further, by setting (M3) / (M1 + M2 + M3) to 40% or more, low resistance metal particles having a low resistance increase, so that the electrical resistance of the via can be lowered, and (M3) / (M1 + M2 + M3) is set to 60. % Or less, the necking that connects the low-resistance metal particles can be formed thick and firm, so the resistance of the via and the electrical connection structure can be lowered, and the connection reliability of the via and the electrical connection structure can be reduced. Can be improved.

また、本発明の導電性ペーストは、低融点金属Ａ粒子と低融点金属Ｂ粒子の融点の差が１０℃以上であることが望ましい。   Moreover, as for the electrically conductive paste of this invention, it is desirable for the difference of melting | fusing point of the low melting metal A particle and the low melting metal B particle to be 10 degreeC or more.

低融点金属Ａ粒子と低融点金属Ｂ粒子の融点の差を１０℃以上とすることで、低融点金属Ａ粒子と低融点金属Ｂ粒子の軟化、溶融の開始温度に比較的長い時間差を設けることができ、低融点金属Ｂが低抵抗金属粒子表面、低融点金属Ａ粒子表面を十分に濡らすことができる。そのため、低融点金属Ｂ及び低融点金属Ａを介した低抵抗金属粒子同士の接続が、より容易に発生し、ビアや電気的接続構造の接続信頼性を向上させることができる。   By setting the difference between the melting points of the low melting point metal A particles and the low melting point metal B particles to 10 ° C. or more, a relatively long time difference is provided between the softening and melting start temperatures of the low melting point metal A particles and the low melting point metal B particles. The low melting point metal B can sufficiently wet the surface of the low resistance metal particle and the low melting point metal A particle. Therefore, the connection between the low-resistance metal particles via the low-melting point metal B and the low-melting point metal A occurs more easily, and the connection reliability of the via or the electrical connection structure can be improved.

また、本発明の導電性ペーストは、低融点金属Ｂ粒子が、Ｂｉを含有していることが望ましい。低融点金属Ｂ粒子に、Ｂｉを含有させることで、溶融後の低融点金属Ｂの粘性を低下させることができるため、低融点金属Ｂの低抵抗金属粒子及び低融点金属Ａ粒子への濡れ性を向上させることができ、ビアや電気的接続構造の接続信頼性を向上させることができる。   In the conductive paste of the present invention, it is desirable that the low melting point metal B particles contain Bi. By containing Bi in the low melting point metal B particles, the viscosity of the low melting point metal B after melting can be reduced, so that the low melting point metal B wettability to the low resistance metal particles and the low melting point metal A particles The connection reliability of vias and electrical connection structures can be improved.

また、本発明の導電性ペーストは、低融点金属Ａ粒子、低融点金属Ｂ粒子、低抵抗金属粒子の含有量が合計で８５〜９５質量％、樹脂の含有量が５〜１５質量％であることが望ましい。   The conductive paste of the present invention has a total content of low melting point metal A particles, low melting point metal B particles, and low resistance metal particles of 85 to 95% by mass, and a resin content of 5 to 15% by mass. It is desirable.

このように、低融点金属Ａ粒子、低融点金属Ｂ粒子、低抵抗金属粒子などの導電性粉末の量を８５質量％以上とし、樹脂の量を１５質量％以下にすることで導電性金属同士の接点を確実に確保することができるために、導電経路が確保され、ビアや電気的接続構造の抵抗を小さくすることができる。また、導電性粉末の量を９５質量％以下とし、樹脂の量を５質量％以上にすることで導電性ペーストの粘度を適正にでき、例えば、スクリーン印刷等により、ビアホールへ導電性ペーストを充填する際に、充填性を高めることができ、ボイドの発生をなくすことができる。   Thus, the amount of the conductive powder such as the low melting point metal A particle, the low melting point metal B particle, and the low resistance metal particle is 85% by mass or more, and the amount of the resin is 15% by mass or less. Therefore, the conductive path is secured, and the resistance of the via and the electrical connection structure can be reduced. In addition, by setting the amount of conductive powder to 95% by mass or less and the amount of resin to 5% by mass or more, the viscosity of the conductive paste can be made appropriate. For example, the conductive paste is filled into the via hole by screen printing or the like. In doing so, the filling property can be improved and the generation of voids can be eliminated.

また、本発明の配線基板は、少なくとも樹脂を含有する絶縁基板と配線層とが積層され、該配線層間を電気的に接続するために前記絶縁基板内にビアを具備してなる配線基板であって、前記ビアが、以上説明した導電性ペーストを充填して形成されたことを特徴とする。   The wiring board of the present invention is a wiring board in which an insulating substrate containing at least a resin and a wiring layer are laminated, and a via is provided in the insulating substrate to electrically connect the wiring layers. The via is formed by filling the conductive paste described above.

このような導電性ペーストでは、加熱処理を行った場合、まず、低融点金属Ｂが軟化、溶融し、低抵抗金属粒子表面と低融点金属Ａ表面とを、軟化、溶融した低融点金属Ｂが、濡らし、低抵抗金属粒子表面と低融点金属Ａ粒子表面の少なくとも一部に低融点金属Ｂの層が形成される。   In such a conductive paste, when heat treatment is performed, first, the low melting point metal B is softened and melted, and the low resistance metal particle surface and the low melting point metal A surface are softened and melted. The low melting point metal B layer is formed on at least a part of the surface of the low resistance metal particle and the low melting point metal A particle.

このように、低抵抗金属粒子と、低融点金属Ａ表面とに、軟化、溶融して低粘度となった低融点金属Ｂが付着することで、低抵抗金属同士、低融点金属Ａ粒子同士あるいは、低抵抗金属粒子と低融点金属Ａとは軟化、溶融した低融点金属Ｂを介して接触することになる。   In this way, the low resistance metal particles and the low melting point metal A surface adhere to the low melting point metal B which has been softened and melted to have a low viscosity, so that the low resistance metals, the low melting point metal A particles or the The low resistance metal particles and the low melting point metal A come into contact via the softened and melted low melting point metal B.

そして温度が上がるにつれて、低融点金属Ｂは、さらに粘度が低下して、低抵抗金属粒子、低融点金属Ａ粒子の表面に広がっていく。   As the temperature rises, the viscosity of the low melting point metal B further decreases and spreads on the surfaces of the low resistance metal particles and the low melting point metal A particles.

そして低融点金属Ａ粒子の融点に達すると、低融点金属Ａが軟化、溶融して、低融点金属Ｂに覆われた低抵抗金属粒子同士を強固に接続するネッキングを形成する。このとき、低融点金属Ａは低融点金属Ｂよりも高融点であるために、同じ温度であれば、低融点金属Ａは低融点金属Ｂよりも高粘度の流体となるため、変形量は小さくなり、Ｃｕ粒子同士を構造的、電気的に強固に接続することができる。この低融点金属Ａによる接続は低融点金属Ａの変形が少ないために、低融点金属Ａの原料形状を反映した形となり、比較的太く、強固な低融点金属粒子同士の接続構造が実現される。また、配線基板のビアと、ビアの上下に設けられた配線層の界面においても同様の機構が発現し、ビアのみならず、ビアと配線層との接続信頼性が改善される。   When the melting point of the low melting point metal A particles is reached, the low melting point metal A softens and melts to form a necking that firmly connects the low resistance metal particles covered with the low melting point metal B. At this time, since the low melting point metal A has a higher melting point than the low melting point metal B, the low melting point metal A becomes a fluid having a higher viscosity than the low melting point metal B at the same temperature. Thus, the Cu particles can be firmly connected structurally and electrically. The connection with the low melting point metal A has a shape reflecting the raw material shape of the low melting point metal A because the deformation of the low melting point metal A is small, and a relatively thick and strong connection structure between the low melting point metal particles is realized. . In addition, a similar mechanism appears at the interface between the via of the wiring board and the wiring layer provided above and below the via, and the connection reliability between the via and the wiring layer is improved as well as the via.

以上説明した導電性ペーストを使用して配線基板を作製することにより、ビアの抵抗を小さくできるとともに、ビアや電気的接続構造の接続信頼性を向上させることができ、電気抵抗の低い配線を有し、信頼性に優れた配線基板を提供できる。   By producing a wiring board using the conductive paste described above, the resistance of the via can be reduced, the connection reliability of the via and the electrical connection structure can be improved, and a wiring having a low electrical resistance can be provided. In addition, a highly reliable wiring board can be provided.

また、本発明の配線基板の製造方法は、少なくとも熱硬化性樹脂を含有する未硬化あるいは半硬化状態の絶縁基板にビアホールを形成する工程と、前記ビアホールに、上記の導電性ペーストを充填した後、前記ビアホール形成部を含む前記絶縁基板の表面に導体層を被着形成する工程と、該絶縁基板を積層して一体化した後、該積層物を前記熱硬化性樹脂の硬化温度に加熱して一括硬化する工程とを具備することを特徴とする。   The method for manufacturing a wiring board according to the present invention includes a step of forming a via hole in an uncured or semi-cured insulating substrate containing at least a thermosetting resin, and after filling the via hole with the conductive paste. A step of depositing and forming a conductor layer on the surface of the insulating substrate including the via hole forming portion, and laminating and integrating the insulating substrates, and then heating the laminate to a curing temperature of the thermosetting resin. And a step of collectively curing.

このような配線基板の製造方法では、一括硬化することにより逐次硬化時に発生する配線基板内層部と外層部の材料物性の変化を低減できるとともに、硬化に関わる工程時間を短縮させることができ、さらに、低抵抗で、接続信頼性に優れた配線基板を提供できる。   In such a method of manufacturing a wiring board, it is possible to reduce the change in the material physical properties of the wiring board inner layer part and the outer layer part that are generated at the time of sequential curing by batch curing, and to shorten the process time related to curing, A wiring board with low resistance and excellent connection reliability can be provided.

本発明の導電性ペーストは、例えば、配線基板のビアを形成するために用いられ、図１（ａ）に示すように、絶縁層１に形成されたビアホール３に導電性ペースト５を充填し、ビアホール３の上下に配線層７を形成した後、加熱することにより、図１（ｃ）に示すようにビア９を形成し、ビア９の上面に形成された配線層７ａと、ビアの下面に形成された配線層７ｂとを電気的に接続するものである。   The conductive paste of the present invention is used, for example, to form a via of a wiring board. As shown in FIG. 1A, the via paste 3 formed in the insulating layer 1 is filled with the conductive paste 5, A wiring layer 7 is formed above and below the via hole 3 and then heated to form a via 9 as shown in FIG. 1C. A wiring layer 7a formed on the upper surface of the via 9 and a lower surface of the via are formed. The wiring layer 7b thus formed is electrically connected.

本発明の導電性ペーストは、図１（ａ）に示すように、少なくとも錫を含有し、融点が２３０℃以下の低融点金属Ａ粒子５ａと、少なくとも錫を含有し、低融点金属Ａ粒子５ａよりも融点が低い低融点金属Ｂ粒子５ｂと、融点が２３０℃を超える低抵抗金属粒子５ｃと、樹脂（図示せず）とで構成されている。   As shown in FIG. 1 (a), the conductive paste of the present invention contains at least tin and low melting point metal A particles 5a having a melting point of 230 ° C. or less, and at least tin, and low melting point metal A particles 5a. The low melting point metal B particles 5b having a lower melting point, the low resistance metal particles 5c having a melting point exceeding 230 ° C., and a resin (not shown).

なお、図１では樹脂は省略したが、ビアホール３内の低融点金属Ａ粒子５ａと、低融点金属Ｂ粒子５ｂと、低抵抗金属粒子５ｃなどの導電性粒子を除く部分を、樹脂が占めている。   Although the resin is omitted in FIG. 1, the resin occupies a portion excluding conductive particles such as the low melting point metal A particles 5 a, the low melting point metal B particles 5 b, and the low resistance metal particles 5 c in the via hole 3. Yes.

導電性ペースト５に含まれる低抵抗金属粒子５ｃは、加熱処理時には、溶融しないため、導電経路であるビア９の核、あるいは骨格となる材料であり、低抵抗を有するものであり、このような低抵抗金属粒子５ｃとしては、低融点金属Ａ粒子５ａ及び低融点金属Ｂ粒子５ｂよりも高融点の金属を用いる。   Since the low-resistance metal particles 5c contained in the conductive paste 5 do not melt at the time of heat treatment, the low-resistance metal particles 5c are materials that serve as the core or skeleton of the via 9 that is a conductive path, and have low resistance. As the low resistance metal particles 5c, a metal having a melting point higher than those of the low melting point metal A particles 5a and the low melting point metal B particles 5b is used.

特に、安価で、低抵抗で、Ｓｎとの脆い金属間化合物をつくりにくい点からＣｕが望ましい。また、低抵抗で耐酸化性に優れる点からＡｇが望ましく、低抵抗で耐酸化性、耐薬品性に優れる点からＡｕが望ましい。また、これらの粉末を混合してもよく、これらの合金であってもよい。   In particular, Cu is desirable because it is inexpensive, has low resistance, and is difficult to form a brittle intermetallic compound with Sn. Further, Ag is desirable from the viewpoint of low resistance and excellent oxidation resistance, and Au is desirable from the viewpoint of low resistance and excellent oxidation resistance and chemical resistance. Moreover, these powders may be mixed and these alloys may be sufficient.

低融点金属Ａ粒子５ａ並びに低融点金属Ｂ粒子５ｂは、いずれも少なくとも錫を含有し、融点が２３０℃以下の金属からなり、導電性ペースト５の加熱処理時に、時間差をおいて、軟化、溶融し、変形することで、ビア９の核あるいは骨格となる低抵抗金属粒子５ｃと、ビア９に接する配線層７とを接続する機能を有するものである。   The low melting point metal A particles 5a and the low melting point metal B particles 5b are each made of a metal containing at least tin and having a melting point of 230 ° C. or less, and are softened and melted at a time difference during the heat treatment of the conductive paste 5. By deforming, the low-resistance metal particles 5 c that are the core or skeleton of the via 9 and the wiring layer 7 in contact with the via 9 are connected.

低融点金属Ｂ粒子５ｂは、低融点金属Ａ粒子５ａと低抵抗金属５ｃの表面を濡らす機能を発現するために、また、低抵抗金属粒子５ｃを結合させ、ネッキングを太く強くする為に、低融点金属Ａ５ａ粒子よりも低融点であることが重要であり、特に両者の融点の差を１０℃以上とすることで、ビア９の抵抗を下げ、信頼性の高いビア９を有する配線基板を容易に作製することができる。   The low melting point metal B particle 5b is low in order to express the function of wetting the surfaces of the low melting point metal A particle 5a and the low resistance metal 5c, and to bond the low resistance metal particle 5c and make necking thick and strong. It is important that the melting point is lower than that of the melting point metal A5a particles. Particularly, by making the difference between the melting points of 10 ° C. or more, the resistance of the via 9 is lowered, and the wiring board having the highly reliable via 9 can be easily obtained. Can be produced.

低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂは、ビアホール３の上下に配置された配線層７とビアの核となる低抵抗金属粒子５ｃとにスムーズに濡れ広がり、これらを結合させる機能を有している。   The low-melting point metal A particles 5a and the low-melting point metal B particles 5b have a function of smoothly wetting and spreading between the wiring layers 7 disposed above and below the via holes 3 and the low-resistance metal particles 5c serving as the cores of the vias. Have.

本発明の低融点金属Ｂ粒子５ｂは、低融点金属Ａ粒子５ａより先に溶け、低抵抗金属粒子５ｃ表面と低融点金属Ａ粒子５ａ表面とを溶融した低融点金属Ｂ粒子５ｂが濡らし、例えば、低融点金属Ｂ粒子５ｂの層を形成するなどして、接続ポイントを増加させるものである。従って、低融点金属Ｂ粒子５ｂの数を増加させる為に、低融点金属Ｂ粒子５ｂの平均粒子径は低融点金属Ａ粒子５ａより小さいことが望ましい。   The low melting point metal B particle 5b of the present invention is melted before the low melting point metal A particle 5a, and the low melting point metal B particle 5b obtained by melting the surface of the low resistance metal particle 5c and the low melting point metal A particle 5a is wetted. The connection point is increased by forming a layer of the low melting point metal B particles 5b. Therefore, in order to increase the number of the low melting point metal B particles 5b, the average particle diameter of the low melting point metal B particles 5b is desirably smaller than the low melting point metal A particles 5a.

特に、低融点金属Ｂ粒子５ｂの平均粒径が低融点金属Ａ粒子５ａの平均粒径の８０％以下であることが望ましく、さらに５０％以下であることが望ましい。   In particular, the average particle size of the low melting point metal B particles 5b is desirably 80% or less of the average particle size of the low melting point metal A particles 5a, and more desirably 50% or less.

また、樹脂は導電経路を保護、保持する能力に優れた硬化した後に剛性が高くなる熱硬化性樹脂を用いることが望ましい。   Further, it is desirable to use a thermosetting resin that has high rigidity after being cured with excellent ability to protect and retain the conductive path.

また、熱硬化性樹脂は、未硬化の状態においては導電性ペーストを低粘度に調整して、スクリーン印刷等によるビアホール３への充填性を高めボイドの発生を低減させるため、トリアリルイソシアヌレートを含有することが望ましい。   In addition, the thermosetting resin adjusts the conductive paste to a low viscosity in an uncured state, increases the filling property to the via hole 3 by screen printing or the like, and reduces the generation of voids. It is desirable to contain.

また、本発明の導電性ペースト５では、低抵抗金属５ｃへの低融点金属Ａ粒子５ａの被覆面積を広げ、低抵抗金属粒子５ｃ同士を接続するネッキングを太く強固に形成する機能を有し、そのために、（Ｍ２）／（Ｍ１＋Ｍ２）が３０〜８０％であることが望ましく、さらに５０〜８０％であることが望ましい。   Further, the conductive paste 5 of the present invention has a function of expanding the covering area of the low melting point metal A particles 5a to the low resistance metal 5c and forming a thick and strong necking for connecting the low resistance metal particles 5c, Therefore, (M2) / (M1 + M2) is preferably 30 to 80%, and more preferably 50 to 80%.

また、本発明の導電性ペースト５は、低抵抗金属粒子５ｃ同士の接点を増加させ、ビア９の電気抵抗を低下させ、低抵抗金属粒子５ｃ同士を接続するネッキングを太く強固に形成するために、（Ｍ３）／（Ｍ３＋Ｍ１＋Ｍ２）が４０〜６０％であることが望ましい。   Further, the conductive paste 5 of the present invention increases the number of contacts between the low-resistance metal particles 5c, decreases the electrical resistance of the via 9, and forms a thick and firm necking that connects the low-resistance metal particles 5c. , (M3) / (M3 + M1 + M2) is preferably 40 to 60%.

また、本発明の低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂは、低融点金属Ｂ粒子５ｂが低融点金属Ａ粒子５ａより先に溶け、低抵抗金属粒子５ｃ表面と低融点金属Ａ粒子５ａ粒子表面とを溶融した低融点金属Ｂ粒子５ｂが濡らし、低融点金属Ｂ粒子５ｂの層を形成する機能を有しており、低融点金属Ａ粒子５ａがその形状を維持した状態で、低融点金属Ｂ粒子５ｂが変形することが望ましく、低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂとの融点の差が１０℃以上であることが望ましい。   Further, the low melting point metal A particle 5a and the low melting point metal B particle 5b of the present invention are such that the low melting point metal B particle 5b is melted before the low melting point metal A particle 5a, and the surface of the low resistance metal particle 5c and the low melting point metal A particle. The low melting point metal B particles 5b that have melted the surface of the 5a particles have a function of wetting and forming a layer of the low melting point metal B particles 5b. The melting point metal B particles 5b are desirably deformed, and the difference in melting point between the low melting point metal A particles 5a and the low melting point metal B particles 5b is desirably 10 ° C. or more.

また、本発明の低融点金属Ｂ粒子５ｂは、他の導電性粒子を濡らすためにＢｉを含有していることが望ましい。   Moreover, it is desirable that the low melting point metal B particles 5b of the present invention contain Bi in order to wet other conductive particles.

また、本発明の導電性ペーストは、スクリーン印刷等により導電性ペーストをビアホール３へ埋め込む際に、充填性を高め、ボイドの発生をなくすために、導電性粉末を８５〜９５質量％と、熱硬化性樹脂を５〜１５質量％含有することが望ましい。   In addition, the conductive paste of the present invention has a conductive powder of 85 to 95% by mass in order to improve the filling property and eliminate voids when the conductive paste is embedded in the via hole 3 by screen printing or the like. It is desirable to contain 5-15 mass% of curable resin.

また、本発明の配線基板は、少なくとも樹脂を含有する絶縁基板１と、絶縁基板１の表面または内部に形成された複数層の配線層と、該配線層間を電気的にビア９で接続されてなるもので、以上説明した導電性ペーストを用いてビア９が形成されたものである。   The wiring board according to the present invention includes an insulating substrate 1 containing at least a resin, a plurality of wiring layers formed on the surface of or inside the insulating substrate 1, and the wiring layers are electrically connected by vias 9. Thus, the via 9 is formed using the conductive paste described above.

次に、本発明の配線基板の製造方法について説明する。   Next, the manufacturing method of the wiring board of this invention is demonstrated.

先ず、図２（ａ）に示すように、半硬化状の絶縁基板１に、ＵＶ−ＹＡＧレーザ、エキシマレーザ、ＣＯ２レーザなどのレーザ加工機で穴あけ加工を施し、ビアホール３を設ける。 First, as shown in FIG. 2A, the semi-cured insulating substrate 1 is drilled by a laser processing machine such as a UV-YAG laser, an excimer laser, or a CO 2 laser to provide a via hole 3.

次に、図２（ｂ）に示すように、そのビアホール３内に導電性ペースト５を充填する。   Next, as shown in FIG. 2B, a conductive paste 5 is filled in the via hole 3.

次に、図２（ｃ）に示すように、導電性ペースト５を充填したビアホール３の片側あるいは両端部に、樹脂フィルム９に接着剤１１を介して接着された金属箔からなる配線層７を位置あわせし、６０〜１５０℃で加熱し、４．０〜８．０ＭＰａの圧力で加圧する。そして、図２（ｄ）に示すように、接着剤１１と共に樹脂フィルム９をはがすことで配線層７が絶縁基板１に埋設される。   Next, as shown in FIG. 2 (c), a wiring layer 7 made of a metal foil bonded to a resin film 9 with an adhesive 11 is attached to one side or both ends of the via hole 3 filled with the conductive paste 5. Align, heat at 60 to 150 ° C., and pressurize at a pressure of 4.0 to 8.0 MPa. Then, as shown in FIG. 2 (d), the wiring layer 7 is embedded in the insulating substrate 1 by peeling the resin film 9 together with the adhesive 11.

このようにして作製された図２（ｅ）に示すような配線ユニットａを複数作製し、図３（ｆ）に示すように積層させ、一括して絶縁層中の熱硬化性樹脂が硬化する温度、例えば、１８０〜２５０℃に加熱し、１〜１０ＭＰａの圧力で加圧することにより、図３（ｇ）に示すような配線基板Ａを作製することができる。   A plurality of wiring units a as shown in FIG. 2 (e) thus manufactured are manufactured and stacked as shown in FIG. 3 (f), and the thermosetting resin in the insulating layer is cured at once. By heating to a temperature, for example, 180 to 250 ° C. and pressurizing at a pressure of 1 to 10 MPa, a wiring board A as shown in FIG. 3G can be manufactured.

なお、この加熱に伴い、加熱前には、図１（ａ）に示すように絶縁基板１のビアホール３に充填されていた導電性ペースト５の低融点金属Ａ粒子５ａと、低融点金属Ｂ粒子５ｂと、低抵抗金属粒子５ｃとが変化していく。   With this heating, before heating, the low melting point metal A particles 5a and the low melting point metal B particles of the conductive paste 5 filled in the via holes 3 of the insulating substrate 1 as shown in FIG. 5b and the low-resistance metal particles 5c change.

まず、図１（ｂ）に示すように低融点金属Ｂ粒子５ｂが軟化し始め、変形し、低融点金属Ａ粒子５ａと、低抵抗金属粒子５ｃと、配線層７とを結合し始める。   First, as shown in FIG. 1B, the low melting point metal B particles 5b begin to soften and deform, and the low melting point metal A particles 5a, the low resistance metal particles 5c, and the wiring layer 7 start to be bonded.

さらに、温度が上昇するに従い、低融点金属Ａ粒子５ａが変形し、図２（ｃ）に示すように、低融点金属Ｂ粒子５ｂと、低抵抗金属粒子５ｃと、配線層７との間に太く、強固な結合を形成する。   Further, as the temperature rises, the low melting point metal A particle 5a is deformed, and as shown in FIG. 2C, the low melting point metal B particle 5b, the low resistance metal particle 5c, and the wiring layer 7 are interposed. Forms a thick and strong bond.

かくして、本発明の導電性ペースト５を用いて、低抵抗で、信頼性の高いビア９が形成され、図３（ｇ）に示すような、高性能で、信頼性の高い配線基板Ａを作製することができる。   Thus, by using the conductive paste 5 of the present invention, the via 9 having a low resistance and high reliability is formed, and a high-performance and highly reliable wiring board A as shown in FIG. can do.

なお、本発明は上記形態に限定されるものではなく、発明の要旨を変更しない範囲で種々の変更が可能である。例えば、２種以上の融点が２３０℃以下の低抵抗金属を含有している場合は、２３０℃を超える低融点金属を含有していてもかまわない。また、３種以上の低融点金属を用いてもよいことは言うまでもない。   In addition, this invention is not limited to the said form, A various change is possible in the range which does not change the summary of invention. For example, when two or more kinds of melting points contain a low resistance metal having a melting point of 230 ° C. or lower, a low melting point metal having a melting point higher than 230 ° C. may be contained. Needless to say, three or more kinds of low melting point metals may be used.

また、配線基板Ａの形態は、例えば、コア基板の表面に微細配線層を形成したものなどにも用いることができるのは当然である。   Of course, the form of the wiring board A can also be used for, for example, a structure in which a fine wiring layer is formed on the surface of the core board.

表１に示す配合比で、低抵抗金属粒子５ｃである銅粉末と、表１に示す組成の低融点金属Ａ粒子５ａと、低融点金属Ｂ粒子５ｂと、樹脂の混合物をプロペラ式攪拌機にて混練し、導電性ペースト５を作製した。   A mixture of the copper powder as the low-resistance metal particles 5c, the low-melting point metal A particles 5a, the low-melting point metal B particles 5b, and the resin having the composition shown in Table 1 at a blending ratio shown in Table 1 is obtained with a propeller-type stirrer. The conductive paste 5 was produced by kneading.

なお、樹脂はトリアリルイソシアヌレート樹脂と、触媒としての過酸化物ＰＨ２５Ｂとの混合物を用い、トリアリルイソシアヌレート樹脂と過酸化物ＰＨ２５Ｂとの混合比は、９５：５体積％とした。   The resin used was a mixture of triallyl isocyanurate resin and peroxide PH25B as a catalyst, and the mixing ratio of triallyl isocyanurate resin and peroxide PH25B was 95: 5 vol%.

また、低融点金属Ａ粒子５ａと、低融点金属Ｂ粒子５ｂの粒径も表１に示す範囲で変化させた。   The particle diameters of the low melting point metal A particles 5a and the low melting point metal B particles 5b were also changed within the range shown in Table 1.

このようにして、作製した導電性ペースト５を以下の工程に用いて、テスト用配線基板を作製した。   Thus, the produced conductive paste 5 was used in the following steps to produce a test wiring board.

まず、３０μｍ厚みのＰＰＥ（ポリフェニレンエーテル）からなる半硬化状の絶縁基板１に、ＵＶ−ＹＡＧレーザ加工機で１００μｍの穴あけ加工を施し、ビアホール３を形成した。   First, a via hole 3 was formed on a semi-cured insulating substrate 1 made of PPE (polyphenylene ether) having a thickness of 30 μm by drilling 100 μm with a UV-YAG laser processing machine.

次に、表１に示す導電性ペースト５をビアホール３に充填した。   Next, the conductive paste 5 shown in Table 1 was filled in the via hole 3.

次に、この絶縁基板１に形成されたビアホール３の表裏面にパターン化された厚み１０μｍの銅箔からなる配線層７を１５０℃、６．０ＭＰａで転写した。   Next, the wiring layer 7 made of a copper foil having a thickness of 10 μm and patterned on the front and back surfaces of the via hole 3 formed in the insulating substrate 1 was transferred at 150 ° C. and 6.0 MPa.

次に、上記のようにして作製した絶縁基板１を、それぞれのビアホール３と配線層７が電気的に接続されるように６層かさね、位置合わせして、２３０℃に加熱し、５．０ＭＰａの圧力をかけ、積層した。   Next, the insulating substrate 1 manufactured as described above is placed in 6 layers so that each via hole 3 and the wiring layer 7 are electrically connected, aligned, heated to 230 ° C., and 5.0 MPa. Was applied and laminated.

導通信頼性の評価は、初期導通抵抗と試料を温度が−５５℃の条件で３０分、１２５℃の条件で３０分を１サイクルとする温度サイクル試験（ＴＣＴ）を行い、１０００サイクル後のビア９の導通抵抗を測定し、試験前後の導通抵抗の変化率を比較することにより評価した。   Conduction reliability is evaluated by conducting a temperature cycle test (TCT) in which the initial conduction resistance and the sample are 30 minutes at a temperature of −55 ° C. and 30 minutes at a temperature of 125 ° C. (TCT). The conduction resistance of 9 was measured and evaluated by comparing the rate of change of conduction resistance before and after the test.

表１に、ビア一穴当りの初期導通抵抗と試験前後の導通抵抗変化率を示す。

Figure 2005071825
Table 1 shows initial conduction resistance per via hole and conduction resistance change rate before and after the test.
Figure 2005071825

本発明の範囲外である一種類のみの低融点金属を用いた試料Ｎｏ．１、２ではビア９の初期抵抗が１０×１０−６Ωｃｍ以上と高くなり、また、ビア９の熱サイクル試験後の抵抗変化率も５．４％以上と高くなった。 Sample No. using only one kind of low melting point metal which is outside the scope of the present invention. In 1 and 2, the initial resistance of the via 9 was as high as 10 × 10 −6 Ωcm or more, and the resistance change rate after the thermal cycle test of the via 9 was as high as 5.4% or more.

また、２種類の低融点金属を用いてはいるものの、２種類のうち高融点を有する低融点金属の融点が２３０℃を超える試料Ｎｏ．３でも、ビア９の初期抵抗が１３．２×１０−６Ωｃｍ以上と高くなり、また、ビア９の熱サイクル試験後の抵抗変化率も６．７％以上と高くなった。 In addition, although two types of low melting point metals are used, Sample No. No. 2 has a melting point of a low melting point metal having a high melting point exceeding 230 ° C. 3, the initial resistance of the via 9 was as high as 13.2 × 10 −6 Ωcm or more, and the resistance change rate after the thermal cycle test of the via 9 was also as high as 6.7% or more.

一方、本発明の導電性ペースト５を用いた試料Ｎｏ．４〜２１では、いずれも、１０×１０−６Ωｃｍ以下の初期抵抗、５％以下の導通抵抗変化率を有しており、抵抗の低い、高信頼性のビア９となることが判る。 On the other hand, sample No. using the conductive paste 5 of the present invention. 4 to 21 all have an initial resistance of 10 × 10 −6 Ωcm or less and a conduction resistance change rate of 5% or less, and it can be seen that the via 9 has low resistance and high reliability.

低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂの融点の差を変化させた試料Ｎｏ．５、６では、低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂの融点の差が５℃である試料Ｎｏ．５よりも、１０℃である試料Ｎｏ．６の方が初期抵抗、熱サイクル後の抵抗変化率ともに優れている。   Sample No. 5 in which the difference in melting point between the low melting point metal A particles 5a and the low melting point metal B particles 5b was changed. In Samples Nos. 5 and 6, the difference in melting point between the low melting point metal A particles 5a and the low melting point metal B particles 5b is 5 ° C. Sample No. 5 which is 10 ° C. than 5 ° C. 6 is superior in both the initial resistance and the rate of change in resistance after thermal cycling.

また、低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂの平均粒子径を変化させた試料Ｎｏ．６〜８の結果から、低融点金属Ｂ粒子５ｂの平均粒径が低融点金属Ａ粒子５ａの平均粒径よりも小さい方が初期抵抗、熱サイクル後の抵抗変化率ともに優れていることがわかる。低融点金属Ｂ粒子５ｂの平均粒径が低融点金属Ａ粒子５ａの平均粒径の８０％である試料Ｎｏ．７では初期抵抗、導通抵抗変化率が低下しており、更に、低融点金属Ｂ粒子５ｂの平均粒径が低融点金属Ａ粒子５ａの平均粒径の５０％である試料Ｎｏ．８では更に初期抵抗、導通抵抗変化率が低下した。   In addition, Sample No. 5 in which the average particle diameter of the low melting point metal A particles 5a and the low melting point metal B particles 5b was changed. From the results of 6 to 8, it can be seen that the smaller the average particle size of the low melting point metal B particles 5b is smaller than the average particle size of the low melting point metal A particles 5a, both the initial resistance and the rate of change in resistance after thermal cycling are excellent. . Sample No. 5 in which the average particle size of the low melting point metal B particles 5b is 80% of the average particle size of the low melting point metal A particles 5a. 7, the initial resistance and the rate of change in conduction resistance are decreased, and the average particle size of the low melting point metal B particles 5b is 50% of the average particle size of the low melting point metal A particles 5a. In 8, the initial resistance and the rate of change in conduction resistance were further reduced.

また、低融点金属Ａ粒子５ａの含有量をＭ１、低融点金属Ｂの含有量をＭ２としたとき、（Ｍ２）／（Ｍ１＋Ｍ２）の比率、即ち、低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂの比率を変化させた試料Ｎｏ．９〜１３では、（Ｍ２）／（Ｍ１＋Ｍ２）が３０〜８０％の試料Ｎｏ．８〜１２が、より低い初期抵抗、導通抵抗変化率を示した。   Further, when the content of the low melting point metal A particles 5a is M1 and the content of the low melting point metal B is M2, the ratio of (M2) / (M1 + M2), that is, the low melting point metal A particles 5a and the low melting point metal B Sample No. 5 in which the ratio of the particles 5b was changed. In Samples Nos. 9 to 13, Sample No. 8-12 showed the lower initial resistance and the conduction | electrical_connection resistance change rate.

また、低融点金属Ａ粒子５ａの含有量をＭ１、低融点金属Ｂ粒子５ｂの含有量をＭ２、低抵抗金属粒子の含有量をＭ３としたとき、（Ｍ３）／（Ｍ１＋Ｍ２＋Ｍ３）の比率、即ち、低抵抗金属粒子と、低融点金属Ａ粒子５ａと低融点金属Ｂ粒子５ｂとの和の比率を変化させた試料Ｎｏ．１４〜１７では、（Ｍ２）／（Ｍ１＋Ｍ２）が４０〜６０％の試料Ｎｏ．１５、１６が、より低い初期抵抗、導通抵抗変化率を示した。   Further, when the content of the low melting point metal A particles 5a is M1, the content of the low melting point metal B particles 5b is M2, and the content of the low resistance metal particles is M3, the ratio of (M3) / (M1 + M2 + M3), that is, Sample No. 5 in which the ratio of the sum of the low resistance metal particles, the low melting point metal A particles 5a, and the low melting point metal B particles 5b was changed. In Samples Nos. 14 to 17, Sample No. 15 and 16 showed lower initial resistance and conduction resistance change rate.

また、樹脂量を３〜２０質量％の範囲で変化させた試料Ｎｏ．１８〜２１では、樹脂が５〜１５質量％である試料Ｎｏ．１７〜２０で低い初期抵抗、導通抵抗変化率を示した。   In addition, the sample No. in which the resin amount was changed in the range of 3 to 20% by mass. 18-21, sample No. whose resin is 5-15 mass%. 17 to 20 showed low initial resistance and conduction resistance change rate.

また、低融点金属Ｂ粒子５ｂにＢｉを含有している試料については、低融点金属Ｂ粒子５ｂにＢｉを含有していない試料Ｎｏ．４よりも、初期抵抗、導通抵抗変化率が低くなる傾向にあった。   As for the sample containing Bi in the low melting point metal B particle 5b, Sample No. No. containing Bi in the low melting point metal B particle 5b. The initial resistance and conduction resistance change rate tended to be lower than 4.

本発明の導電性ペーストが加熱され、ビアとなる模式図である。It is the schematic diagram by which the electrically conductive paste of this invention is heated and becomes a via | veer. 本発明の配線基板の作製方法を示す工程図である。It is process drawing which shows the preparation methods of the wiring board of this invention. 本発明の配線基板の作製方法を示す工程図である。It is process drawing which shows the preparation methods of the wiring board of this invention.

符号の説明Explanation of symbols

１・・・・絶縁基板
３・・・・ビアホール
５・・・・導電性ペースト
５ａ・・・低融点金属Ａ粒子
５ｂ・・・低融点金属Ｂ粒子
５ｃ・・・低抵抗金属粒子
７・・・・配線層
９・・・・樹脂フィルム
１１・・・接着剤
ａ・・・・配線ユニット
Ａ・・・・配線基板 DESCRIPTION OF SYMBOLS 1 ... Insulating substrate 3 ... Via hole 5 ... Conductive paste 5a ... Low melting point metal A particle 5b ... Low melting point metal B particle 5c ... Low resistance metal particle 7 ... .... Wiring layer 9 ... Resin film 11 ... Adhesive a ... Wiring unit A ... Wiring board

Claims (12)

少なくとも錫を含有し、融点が２３０℃以下の低融点金属Ａ粒子と、少なくとも錫を含有し、低融点金属Ａ粒子よりも融点が低い低融点金属Ｂ粒子と、融点が２３０℃を超える低抵抗金属粒子と、樹脂とを含有することを特徴とする導電性ペースト。 Low-melting point metal A particles containing at least tin and having a melting point of 230 ° C. or lower, low-melting point metal B particles containing at least tin and having a melting point lower than that of the low-melting point metal A particles, and low resistance exceeding 230 ° C. A conductive paste comprising metal particles and a resin. 低抵抗金属粒子が少なくともＣｕ、Ａｇから選ばれる少なくとも一種を含有することを特徴とする請求項１に記載の導電性ペースト。 2. The conductive paste according to claim 1, wherein the low-resistance metal particles contain at least one selected from Cu and Ag. 低融点金属Ａ粒子の平均粒子径が低融点金属Ｂ粒子の平均粒子径よりも大きいことを特徴とする請求項１又は２に記載の導電性ペースト。 The conductive paste according to claim 1 or 2, wherein the average particle size of the low melting point metal A particles is larger than the average particle size of the low melting point metal B particles. 低融点金属Ｂ粒子の平均粒径が低融点金属Ａ粒子の平均粒径の８０％以下であることを特徴とする請求項１乃至３のうちいずれかに記載の導電性ペースト。 The conductive paste according to any one of claims 1 to 3, wherein the average particle size of the low melting point metal B particles is 80% or less of the average particle size of the low melting point metal A particles. 樹脂が熱硬化性樹脂であることを特徴とする請求項１乃至４のうちいずれかに記載の導電性ペースト。 The conductive paste according to claim 1, wherein the resin is a thermosetting resin. 樹脂が、トリアリルイソシアヌレートを含有することを特徴とする請求項１乃至５のうちいずれかに記載の導電性ペースト。 The conductive paste according to any one of claims 1 to 5, wherein the resin contains triallyl isocyanurate. 低融点金属Ａ粒子の含有量をＭ１、低融点金属Ｂ粒子の含有量をＭ２、低抵抗金属粒子の含有量をＭ３としたとき、（Ｍ２）／（Ｍ１＋Ｍ２）が３０〜８０％、（Ｍ３）／（Ｍ１＋Ｍ２＋Ｍ３）が４０〜６０％の関係を満足することを特徴とする請求項１乃至６のうちいずれかに記載の導電性ペースト。 When the content of the low melting point metal A particles is M1, the content of the low melting point metal B particles is M2, and the content of the low resistance metal particles is M3, (M2) / (M1 + M2) is 30 to 80%, (M3 ) / (M1 + M2 + M3) satisfies a relationship of 40 to 60%, and the conductive paste according to any one of claims 1 to 6. 低融点金属Ａ粒子と低融点金属Ｂ粒子の融点の差が１０℃以上であることを特徴とする請求項１乃至７のうちいずれかに記載の導電性ペースト。 The conductive paste according to claim 1, wherein a difference in melting point between the low melting point metal A particles and the low melting point metal B particles is 10 ° C. or more. 低融点金属Ｂ粒子が、Ｂｉを含有することを特徴とする請求項１乃至８のうちいずれかに記載の導電性ペースト。 The conductive paste according to any one of claims 1 to 8, wherein the low melting point metal B particles contain Bi. 低融点金属Ａ粒子、低融点金属Ｂ粒子、低抵抗金属粒子の含有量が合計で８５〜９５質量％、樹脂の含有量が５〜１５質量％であることを特徴とする請求項１乃至９のうちいずれかに記載の導電性ペースト。 10. The content of the low melting point metal A particles, the low melting point metal B particles, and the low resistance metal particles is 85 to 95 mass% in total, and the resin content is 5 to 15 mass%. The electrically conductive paste in any one of these. 少なくとも樹脂を含有する絶縁基板と配線層とが積層され、該配線層間を電気的に接続するために前記絶縁基板内にビアを具備してなる配線基板であって、前記ビアが、請求項１乃至１０のうちいずれかに記載の導電性ペーストを充填して形成されたことを特徴とする配線基板。 An insulating substrate containing at least a resin and a wiring layer are laminated, and the wiring substrate is provided with a via in the insulating substrate for electrically connecting the wiring layers, wherein the via is the claim 1. A wiring board formed by filling the conductive paste according to any one of 1 to 10. 少なくとも熱硬化性樹脂を含有する未硬化あるいは半硬化状態の絶縁基板にビアホールを形成する工程と、前記ビアホールに請求項１乃至１０のうちいずれかに記載の導電性ペーストを充填する工程と、前記絶縁基板の表面に導体層を形成する工程と、前記絶縁基板を積層して一体化した後、前記熱硬化性樹脂の硬化温度に加熱して一括硬化する工程とを具備することを特徴とする配線基板の製造方法。 A step of forming a via hole in an uncured or semi-cured insulating substrate containing at least a thermosetting resin, a step of filling the via hole with the conductive paste according to any one of claims 1 to 10, and A step of forming a conductor layer on the surface of the insulating substrate; and a step of laminating and integrating the insulating substrates and then heating to a curing temperature of the thermosetting resin to collectively cure the insulating substrate. A method for manufacturing a wiring board.
JP2003300632A 2003-08-25 2003-08-25 Conductive paste, wiring board and manufacturing method thereof Expired - Fee Related JP4268476B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003300632A JP4268476B2 (en) 2003-08-25 2003-08-25 Conductive paste, wiring board and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2003300632A JP4268476B2 (en) 2003-08-25 2003-08-25 Conductive paste, wiring board and manufacturing method thereof

Publications (2)

Publication Number Publication Date
JP2005071825A true JP2005071825A (en) 2005-03-17
JP4268476B2 JP4268476B2 (en) 2009-05-27

Family

ID=34405482

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2003300632A Expired - Fee Related JP4268476B2 (en) 2003-08-25 2003-08-25 Conductive paste, wiring board and manufacturing method thereof

Country Status (1)

Country Link
JP (1) JP4268476B2 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007042696A (en) * 2005-08-01 2007-02-15 Furukawa Circuit Foil Kk Laminated circuit board
JP2008010858A (en) * 2006-05-30 2008-01-17 Mitsubishi Plastics Ind Ltd Multilayer printed circuit board with cavity portion
JP2008227012A (en) * 2007-03-09 2008-09-25 Mitsubishi Plastics Ind Ltd Multilayer wiring board
JP2008235833A (en) * 2007-03-23 2008-10-02 Mitsubishi Plastics Ind Ltd Interlayer connection bonding sheet for multilayer wiring board
JP2008244061A (en) * 2007-03-27 2008-10-09 Mitsubishi Plastics Ind Ltd Interlayer connection bonding sheet for multilayer wiring circuit board
JP2008244091A (en) * 2007-03-27 2008-10-09 Mitsubishi Plastics Ind Ltd Interlayer connection bonding sheet for multilayer wiring circuit board
WO2009069273A1 (en) 2007-11-28 2009-06-04 Panasonic Corporation Electrically conductive paste, and electrical and electronic device comprising the same
JP2011199250A (en) * 2010-02-25 2011-10-06 Panasonic Corp Multilayer wiring substrate, and method for producing multilayer wiring substrate
US8110749B2 (en) 2008-05-30 2012-02-07 Fujitsu Limited Printed wiring board
US8119925B2 (en) 2008-05-30 2012-02-21 Fujitsu Limited Core substrate and printed wiring board
US8152953B2 (en) 2008-05-30 2012-04-10 Fujitsu Limited Method of making printed wiring board and method of making printed circuit board unit
US8182923B2 (en) * 2008-04-23 2012-05-22 Panasonic Corporation Conductive paste and mounting structure using the same
WO2012086140A1 (en) * 2010-12-21 2012-06-28 パナソニック株式会社 Multilayer wiring substrate, production method for multilayer wiring substrate, and via paste
WO2012090402A1 (en) * 2010-12-29 2012-07-05 パナソニック株式会社 Multilayer wiring board and method for manufacturing multilayer wiring board
JP2013235807A (en) * 2012-05-04 2013-11-21 Samsung Electro-Mechanics Co Ltd Conductive resin composition, multilayer ceramic capacitor including the same, and method for manufacturing the same

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4609850B2 (en) * 2005-08-01 2011-01-12 古河電気工業株式会社 Multilayer circuit board
JP2007042696A (en) * 2005-08-01 2007-02-15 Furukawa Circuit Foil Kk Laminated circuit board
JP2008010858A (en) * 2006-05-30 2008-01-17 Mitsubishi Plastics Ind Ltd Multilayer printed circuit board with cavity portion
JP2008227012A (en) * 2007-03-09 2008-09-25 Mitsubishi Plastics Ind Ltd Multilayer wiring board
JP2008235833A (en) * 2007-03-23 2008-10-02 Mitsubishi Plastics Ind Ltd Interlayer connection bonding sheet for multilayer wiring board
JP2008244061A (en) * 2007-03-27 2008-10-09 Mitsubishi Plastics Ind Ltd Interlayer connection bonding sheet for multilayer wiring circuit board
JP2008244091A (en) * 2007-03-27 2008-10-09 Mitsubishi Plastics Ind Ltd Interlayer connection bonding sheet for multilayer wiring circuit board
US20110049439A1 (en) * 2007-11-28 2011-03-03 Takayuki Higuchi Electrically conductive paste, and electrical and electronic device comprising the same
US8540903B2 (en) 2007-11-28 2013-09-24 Panasonic Corporation Electrically conductive paste, and electrical and electronic device comprising the same
EP2216790A1 (en) * 2007-11-28 2010-08-11 Panasonic Corporation Electrically conductive paste, and electrical and electronic device comprising the same
WO2009069273A1 (en) 2007-11-28 2009-06-04 Panasonic Corporation Electrically conductive paste, and electrical and electronic device comprising the same
EP2216790A4 (en) * 2007-11-28 2010-12-15 Panasonic Corp Electrically conductive paste, and electrical and electronic device comprising the same
US8182923B2 (en) * 2008-04-23 2012-05-22 Panasonic Corporation Conductive paste and mounting structure using the same
US8110749B2 (en) 2008-05-30 2012-02-07 Fujitsu Limited Printed wiring board
US8119925B2 (en) 2008-05-30 2012-02-21 Fujitsu Limited Core substrate and printed wiring board
US8152953B2 (en) 2008-05-30 2012-04-10 Fujitsu Limited Method of making printed wiring board and method of making printed circuit board unit
JP2011199250A (en) * 2010-02-25 2011-10-06 Panasonic Corp Multilayer wiring substrate, and method for producing multilayer wiring substrate
WO2012086140A1 (en) * 2010-12-21 2012-06-28 パナソニック株式会社 Multilayer wiring substrate, production method for multilayer wiring substrate, and via paste
WO2012090402A1 (en) * 2010-12-29 2012-07-05 パナソニック株式会社 Multilayer wiring board and method for manufacturing multilayer wiring board
CN102884872A (en) * 2010-12-29 2013-01-16 松下电器产业株式会社 Multilayer wiring board and method for manufacturing multilayer wiring board
JP2013235807A (en) * 2012-05-04 2013-11-21 Samsung Electro-Mechanics Co Ltd Conductive resin composition, multilayer ceramic capacitor including the same, and method for manufacturing the same

Also Published As

Publication number Publication date
JP4268476B2 (en) 2009-05-27

Similar Documents

Publication Publication Date Title
US7642468B2 (en) Multilayer wiring board and fabricating method of the same
JP3729092B2 (en) Conductive bonding material, multilayer printed wiring board, and method for manufacturing multilayer printed wiring board
JP4268476B2 (en) Conductive paste, wiring board and manufacturing method thereof
JP2012134313A (en) Multilayer wiring board, manufacturing method thereof, and via-hole paste
JP3187373B2 (en) Wiring board
JP2012142450A (en) Multilayer wiring board, and method of manufacturing multilayer wiring board
JP2009065008A (en) Conductive paste composition
JP4787195B2 (en) Conductive paste composition for via hole filling and multilayer wiring board using the same
JP3634984B2 (en) Wiring board
JP4996838B2 (en) Multilayer wiring board
JP3461172B2 (en) Method for manufacturing multilayer wiring circuit board
JP2002290052A (en) Multilayer wiring board
JP3574738B2 (en) Wiring board
JP4468081B2 (en) Conductive paste composition for multilayer wiring board
JP2005119264A (en) Metallic foil with resin film, wiring substrate and its manufacturing method
JP4863543B2 (en) Conductive paste and method for manufacturing wiring board using the same
JP2001291425A (en) Via filling conductive adhesive and method of manufacturing electronic apparatus using the same
JP2000077849A (en) Wiring board and its manufacture
WO1995013901A1 (en) Metallurgically bonded polymer vias
JP4422555B2 (en) Conductive paste composition for multilayer wiring board
JP4965102B2 (en) Conductive paste composition for via hole filling
JP4540273B2 (en) Conductive paste and method of manufacturing wiring board using the same
JP2005039136A (en) Circuit board and method for connection thereof
JP2005136050A (en) Wiring board and its manufacturing method
JP3034238B2 (en) Conductive paste composition for via-hole conductor

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20060210

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20081017

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20081027

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20081226

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20090127

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20090220

R150 Certificate of patent or registration of utility model

Ref document number: 4268476

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120227

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120227

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130227

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140227

Year of fee payment: 5

LAPS Cancellation because of no payment of annual fees