JP2013084822A - Material for ceramic circuit board and ceramic circuit board manufacturing method - Google Patents

Material for ceramic circuit board and ceramic circuit board manufacturing method Download PDF

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JP2013084822A
JP2013084822A JP2011224390A JP2011224390A JP2013084822A JP 2013084822 A JP2013084822 A JP 2013084822A JP 2011224390 A JP2011224390 A JP 2011224390A JP 2011224390 A JP2011224390 A JP 2011224390A JP 2013084822 A JP2013084822 A JP 2013084822A
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circuit board
resist film
resist
circuit pattern
printing
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Toshiyuki Imamura
寿之 今村
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Proterial Ltd
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Hitachi Metals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

PROBLEM TO BE SOLVED: To provide a material for a ceramic circuit board which hardly generates irregularities produced in a circuit pattern peripheral edge, and a manufacturing method thereof.SOLUTION: The present invention provides a material for a ceramic circuit board used for forming a circuit substrate including a conductive part formed on a ceramic substrate. When forming a desired circuit pattern of the conductive part, an average thickness in a center part of a circuit pattern of an etching resist film after curing which has been applied with use of a printing mask is set to 30 μm to 60 μm, while a maximum thickness of a circuit pattern peripheral edge is thicker than the average thickness in the center part of the circuit pattern by 5 μm or more.

Description

本発明は、セラミックス基板を用いたセラミックス回路基板及びその製造方法に関する。   The present invention relates to a ceramic circuit board using a ceramic substrate and a manufacturing method thereof.

近年では、例えば電動車両用およびハイブリッド車、電気自動車などのインバーター等に高電圧、大電流動作が可能なパワー半導体モジュール（ＩＧＢＴ、ＭＯＳ−ＦＥＴモジュール等）が広く利用されている。このような半導体モジュールでは、半導体チップが動作中は高温となり、絶縁性ならびに応答性などに劣化が生じて安定動作の確保が困難となる。このため、半導体チップからの放熱効率を高める必要があり、そこで上記半導体チップを搭載する回路基板として、セラミックス基板の中でも破壊靱性および機械強度に優れ、熱伝導率も比較的高い窒化珪素（Ｓｉ３Ｎ４）基板が注目されている。 In recent years, for example, power semiconductor modules (IGBT, MOS-FET modules, etc.) capable of high voltage and large current operation are widely used for inverters for electric vehicles, hybrid vehicles, electric vehicles and the like. In such a semiconductor module, the temperature of the semiconductor chip becomes high during operation, and insulation and response are deteriorated, making it difficult to ensure stable operation. For this reason, it is necessary to increase the heat dissipation efficiency from the semiconductor chip. Therefore, as a circuit board on which the semiconductor chip is mounted, silicon nitride (Si 3) having excellent fracture toughness and mechanical strength among ceramic substrates and having a relatively high thermal conductivity. N 4 ) substrates are drawing attention.

一般に半導体モジュールでは、窒化珪素基板の一面側に、アルミ合金あるいは銅合金等、比較的電気伝導率の高い金属で回路板が形成される。この回路板を構成する金属と、窒化珪素基板との接合は、直接接合法（ＤＢＣ：Ｄｉｒｅｃｔ
Ｂｏｎｄｅｄ Ｃｏｐｐｅｒ）あるいは活性金属ろう付け法（ＡＭＢ：Ａｃｔｉｖｅ Ｍｅｔａｌ Ｂｏｎｄｉｎｇ）等で行われる。前者は、予め銅および銅合金板あるいは窒化珪素基板を熱処理することで、表面部に酸化膜を形成させ、続いてＣｕ−Ｏの融点近傍にて加圧圧着を行う接合方法である。また、後者では、回路板を形成する金属箔又は金属板を窒化珪素基板の表面にろう材相を介して不活性ガス又は真空雰囲気中で加熱圧着接合する方法である。用いるろう材は回路板の種類により異なり、アルミおよびアルミ合金の場合は、Ａｌ−Ｓｉ系合金またはこれに防錆効果のあるＧｅ、低融点化剤のＭｇを微量添加したＡｌ−Ｓｉ−Ｇｅ系またはＡｌ−Ｓｉ−Ｍｇ系のろう材金属が用いられる。また、回路板が無酸素銅および銅合金の場合には、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、ハフニウム（Ｈｆ）等の活性金属とともに低融点合金を作る銀（Ａｇ）、銅（Ｃｕ）等の金属を混合したもの、又はこれらの合金をろう材として用いる。 In general, in a semiconductor module, a circuit board is formed of a metal having a relatively high electrical conductivity such as an aluminum alloy or a copper alloy on one surface side of a silicon nitride substrate. The metal constituting the circuit board and the silicon nitride substrate are bonded by a direct bonding method (DBC: Direct
Bonded Copper) or active metal brazing (AMB) is used. The former is a bonding method in which a copper and copper alloy plate or a silicon nitride substrate is heat-treated in advance to form an oxide film on the surface portion, and then pressure bonding is performed near the melting point of Cu-O. The latter is a method in which a metal foil or a metal plate forming a circuit board is thermocompression bonded to the surface of a silicon nitride substrate through a brazing filler metal phase in an inert gas or vacuum atmosphere. The brazing material to be used varies depending on the type of circuit board. In the case of aluminum and aluminum alloys, Al-Si-Ge alloy with a small amount of Al-Si alloy or Ge having a rust-preventing effect and Mg as a low melting point agent is added. Alternatively, an Al—Si—Mg based brazing metal is used. When the circuit board is made of oxygen-free copper and copper alloy, silver (Ag), copper (Cu), etc. that form a low melting point alloy with an active metal such as titanium (Ti), zirconium (Zr), hafnium (Hf), etc. A mixture of these metals or an alloy thereof is used as a brazing material.

続いて、半導体チップ搭載やワイヤーボンディングが施される回路板あるいは温度センサー（サーミスター）などが搭載される微小電極部などの所定の回路板の形成には、塩化第２鉄溶液または塩化第２銅溶液を用いたエッチング法が広く用いられている。これらのエッチング液は、上述した銅の直接接合法の場合には、銅−窒化珪素間の銅―酸化物からなる反応生成物は導電性を有しないため、問題なくエッチング処理して、所望の回路板を形成することができる。しかし、これらのエッチング液は、活性金属ろう材を用いた接合方法においては、銅および銅合金からなる金属板を溶かすことはできるものの、ろう材およびろう材とセラミックス基板との反応生成物を溶解することができず、これらが回路板間または基板の縁面部に散在することとなる。これらろう材および反応生成物は導電性のため、回路板間または基板の表裏間を絶縁するという回路基板の本来必要な特性を満足することができなくなる不具合が生じる。さらにはんだ濡れ性の維持と回路表面の耐食性向上のために、回路板にＮｉ−ＰおよびＮｉ−Ｂなどの無電解めっきあるいはＮｉなどの無電解めっきを施した際には、前記、ろう材および反応生成物の上にめっき層が堆積し、使用中に剥離しやすいという不具合も生じる。   Subsequently, in order to form a predetermined circuit board such as a circuit board on which a semiconductor chip is mounted or wire bonding is performed, or a microelectrode portion on which a temperature sensor (thermistor) is mounted, a ferric chloride solution or a second chloride is used. An etching method using a copper solution is widely used. In the case of the above-described direct bonding method of copper, these etching solutions are subjected to an etching process without any problem because a reaction product composed of copper-oxide between copper and silicon nitride has no conductivity. A circuit board can be formed. However, these etching solutions can dissolve the metal plate made of copper and copper alloy in the joining method using the active metal brazing material, but dissolve the reaction product of the brazing material and the brazing material with the ceramic substrate. Cannot be done, and these will be scattered between the circuit boards or at the edge of the substrate. Since these brazing materials and reaction products are conductive, there arises a problem that the circuit board or between the front and back of the board cannot be satisfied with the originally required characteristics of the circuit board. Furthermore, in order to maintain solder wettability and improve the corrosion resistance of the circuit surface, when the circuit board is subjected to electroless plating such as Ni-P and Ni-B or electroless plating such as Ni, the brazing material and A plating layer is deposited on the reaction product, and there is a problem that it easily peels off during use.

これらを解決する手段として、特許文献１には、金属板を接合した後に、金属板の表面の所定の部分にエッチングレジスト膜（以下、「レジスト膜」ともいう）を塗布して金属板の不要部分をエッチング処理することにより回路板を形成した後、レジスト膜を維持したまま、不要なろう材およびろう材とセラミックス基板との反応生成物を除去し、その後、レジスト膜を剥離することにより、金属−セラミックス接合回路基板の形状を少ない工数または低コストで容易に制御することができ、且つ耐熱衝撃性または絶縁性に対してより高信頼性を有する金属−セラミックス接合回路基板の製造方法に関する発明がなされている。 As means for solving these problems, Patent Document 1 discloses that after joining metal plates, an etching resist film (hereinafter also referred to as “resist film”) is applied to a predetermined portion of the surface of the metal plate to eliminate the need for the metal plate. After forming the circuit board by etching the part, removing the unnecessary brazing material and the reaction product of the brazing material and the ceramic substrate while maintaining the resist film, and then peeling the resist film, An invention relating to a method of manufacturing a metal / ceramic bonding circuit board that can easily control the shape of the metal / ceramic bonding circuit board with less man-hours or at low cost and has higher reliability with respect to thermal shock resistance or insulation. Has been made.

特開２００３−１１０２２２号JP 2003-110222 A

特許文献１に記載の技術では、ろう材および反応生成物を溶かすための薬液としてキレート剤と過酸化水素水から得られる薬液、キレート剤と過酸化水素水とｐＨ調整剤とから得られる薬液、または弗化物系の薬品を使用することにより、セラミックス基板へのアタックやダメージを抑制することができ、フッ化水素の混酸などを用いた場合と比較して、信頼性において有利となる特徴を有する。特に、薬液のｐＨをｐＨ３〜６．５に規定してアルカリ剥離型レジストの耐液性の維持とろう材の溶解速度の制御を計っている。   In the technique described in Patent Document 1, a chemical solution obtained from a chelating agent and a hydrogen peroxide solution as a chemical solution for dissolving the brazing filler metal and the reaction product, a chemical solution obtained from a chelating agent, a hydrogen peroxide solution, and a pH adjuster, Alternatively, by using fluoride chemicals, attack and damage to the ceramic substrate can be suppressed, and it has a feature that is advantageous in reliability compared to the case of using a mixed acid of hydrogen fluoride. . In particular, the pH of the chemical solution is regulated to pH 3 to 6.5 to maintain the liquid resistance of the alkali peeling resist and control the dissolution rate of the brazing material.

しかしながら、上記の特許文献１に記載の方法を用いて回路基板を製造した場合に、特にろう材およびろう材とセラミックス基板との反応生成物の除去を完全に行うために、フッ化物の添加量の多いろう材除去液を用いた場合には、回路板に色ムラが生じる外観不良、回路板表面に凹凸が生じる面粗度の悪化、はんだ付け部が剥離する接着不良、めっきが付着しにく付着不良が発生し、特にこれらの不具合は回路板周縁部に発生しやすいという問題があった。本発明者らがこの問題に関して、鋭意検討したところ、回路板周縁部において、レジスト膜がエッチング液、ろう材除去液により溶解し部分的に薄くなったり、レジスト膜端部が剥離したりし、部分的に回路板が露出し、回路板表面が腐食されることにより、回路板表面に凹凸が出来、このような不具合が発生することがわかった。 However, when a circuit board is manufactured by using the method described in Patent Document 1, the amount of fluoride added, particularly in order to completely remove the brazing material and the reaction product between the brazing material and the ceramic substrate. When using a brazing filler metal removal solution with a large amount of color, the appearance of color unevenness on the circuit board, surface roughness resulting in unevenness on the surface of the circuit board, poor adhesion where the soldering part peels off, and plating adhere to the surface. In particular, there is a problem that adhesion failure occurs, and in particular, these defects are likely to occur at the peripheral portion of the circuit board. As a result of diligent investigations on this problem, the inventors of the present invention, the peripheral edge of the circuit board, the resist film is dissolved and partially thinned by the etching solution, brazing material removal liquid, or the resist film edge is peeled off, It was found that when the circuit board was partially exposed and the surface of the circuit board was corroded, irregularities were formed on the surface of the circuit board, causing such a problem.

そこで、本発明者らは硬化後のレジスト膜のエッチング液、ろう材除去液への耐性をさらに上げるためにレジスト膜を硬化する目的で紫外線硬化法や熱処理硬化法などのポストベーキング処理と呼ばれる処理を施してさらなる硬化を行ったが、回路板周縁部のめっき付着不良等の発生頻度は減少するものの不良の発生が無くなることはなかった。また、レジスト膜自体の厚さを厚くして、エッチング液、ろう材除去液に対する耐性を持たせようと試みたが、厚肉のレジスト膜にＵＶ硬化を行っても、特にレジスト膜表面から離れた金属板に近いレジスト膜部分が硬化せず、硬化が不十分な半生状態となり、金属板と密着不足のため、エッチング液やろう材除去液が浸入して、半生状態のレジストを溶かすことがあり、逆にエッチング液、ろう材除去液に対する耐性が落ちて溶解しやすくなるという問題もあった。また、厚肉のレジスト膜の場合には熱風による外部加熱を行うことにより加熱硬化させる方法もあるが、レジスト膜表面からの加熱となりレジスト膜の基板側のレジスト膜が硬化しづらいために長時間の処理が必要となりコストが上昇することや、短時間で処理を済ませる為には高温処理が必要となり、基板を加熱するため加熱処理後に基板自体に反りが生じる可能性があった。 Therefore, the present inventors have conducted a process called post-baking such as an ultraviolet curing method or a heat treatment curing method for the purpose of curing the resist film in order to further improve the resistance to the etching solution of the resist film after curing and the brazing material removing solution. However, although the frequency of occurrence of poor plating adhesion at the periphery of the circuit board was reduced, the occurrence of defects was not eliminated. In addition, we tried to increase the thickness of the resist film itself to make it resistant to the etching solution and the brazing material removal solution. However, even if UV curing is applied to the thick resist film, it is particularly far from the resist film surface. The resist film part close to the metal plate does not harden, it becomes a semi-lived state that is not sufficiently cured, and due to insufficient adhesion with the metal plate, the etchant or brazing material removal solution may enter and dissolve the semi-lived resist On the other hand, there is also a problem that resistance to the etching solution and the brazing material removing solution is lowered and the solution is easily dissolved. In addition, in the case of a thick resist film, there is a method of heating and curing by performing external heating with hot air. However, since the resist film is heated from the surface of the resist film and the resist film on the substrate side of the resist film is hard to be cured, it takes a long time. In order to complete the processing in a short time, high temperature processing is required, and the substrate itself is heated, and thus the substrate itself may be warped after the heat processing.

本発明は、上記の問題点を解消するために、レジスト膜のエッチング液、ろう材除去液への耐性を向上させる技術を検討することにより、低コストで回路板周縁部表面に凹凸を生成させずに、凹凸にともなう外観不良、面粗度の悪化、接着不良、めっき不良の発生しにくい回路基板を得ることを目的とする。 In order to solve the above-mentioned problems, the present invention makes it possible to generate irregularities on the peripheral surface of the circuit board at a low cost by examining a technique for improving resistance to an etching solution of a resist film and a brazing material removing solution. In addition, an object is to obtain a circuit board that is less susceptible to appearance defects, surface roughness deterioration, adhesion defects, and plating defects due to unevenness.

本発明者らは、上記課題に対応すべく鋭意検討した結果、回路板形成時に用いるレジスト膜の形状を工夫することにより、レジスト膜のエッチング液、ろう材除去液への耐性を向上させることが出来ることを見出し、本発明に想到した。
すなわち、本発明は、セラミックス基板上に形成された回路板を含んだ回路基板を形成するためのセラミックス回路基板用素材であって、前記回路板を所望の回路パターンに形成する際に、印刷マスクを用いて金属板上に塗布されたエッチングレジスト膜の硬化後の回路パターン中央部の平均厚さを３０μｍ〜６０μｍとするとともに回路パターン周縁部の最大厚さを回路パターン中央部の平均厚さよりも５μｍ以上厚く形成したことを特徴とする。 As a result of intensive studies to cope with the above problems, the present inventors have improved the resistance of the resist film to the etching solution and the brazing material removing solution by devising the shape of the resist film used at the time of circuit board formation. I found out what I could do and came up with the present invention.
That is, the present invention relates to a ceramic circuit board material for forming a circuit board including a circuit board formed on a ceramic substrate, and the printing mask is formed when the circuit board is formed into a desired circuit pattern. The average thickness of the center portion of the circuit pattern after curing of the etching resist film applied on the metal plate using 30 to 30 μm to 60 μm and the maximum thickness of the peripheral portion of the circuit pattern is larger than the average thickness of the center portion of the circuit pattern It is characterized by being formed with a thickness of 5 μm or more.

前記エッチングレジスト膜の回路パターン周縁部の最大厚さを回路パターン中央部の平均厚さよりも５μｍ〜５０μｍ厚くすると好ましい。   It is preferable that the maximum thickness of the peripheral portion of the circuit pattern of the etching resist film is 5 μm to 50 μm thicker than the average thickness of the central portion of the circuit pattern.

前記エッチングレジスト膜の回路パターン周縁部の最大厚さを４０μｍ〜８０μｍとすると好ましい。   The maximum thickness of the peripheral edge portion of the circuit pattern of the etching resist film is preferably 40 μm to 80 μm.

本発明のセラミックス回路基板の製造方法は、セラミックス基板と金属板とを接合する工程、前記金属板にエッチングレジストを所望形状の回路パターンに印刷する工程、エッチングレジストを硬化する工程、前記金属板の不要部分を除去するエッチング工程、エッチングレジストを保持したまま不要ろう材を除去する工程、エッチングレジストを剥離する工程を順に行うセラミックス回路基板の製造方法において、前記金属板にエッチングレジストを所望形状の回路パターンに印刷する際に、回転型粘度計を用いて温度：２５℃で測定した回転速度１００rpmにおける粘度が５Ｐａ・ｓ〜３０Ｐａ・ｓであるエッチングレジスト液を透過体積３０ｃｍ3/ｍ2〜９０ｃｍ3/ｍ2のエッチングレジスト印刷用マスクを用いて、スキージ速度を１００ｍｍ/sec〜３００mm/secで印刷することを特徴とする。 The method for manufacturing a ceramic circuit board of the present invention includes a step of bonding a ceramic substrate and a metal plate, a step of printing an etching resist on the metal plate in a circuit pattern having a desired shape, a step of curing the etching resist, In a method for manufacturing a ceramic circuit board, in which an etching process for removing unnecessary portions, a process for removing unnecessary brazing material while retaining an etching resist, and a process for removing the etching resist are sequentially performed, the etching resist is applied to the metal plate in a circuit having a desired shape. when printing a pattern, temperature using a rotary viscometer: 25 transmitting an etching resist solution viscosity at speed 100rpm measured at ℃ is 5Pa · s~30Pa · s volume 30cm 3 / m 2 ~90cm 3 A squeegee speed of 10 using an etching resist printing mask of / m 2 Printing is performed at 0 mm / sec to 300 mm / sec.

前記金属板にエッチングレジストを所望形状の回路パターンに印刷する際に用いるエッチングレジスト印刷用マスクのメッシュ径を５μｍ〜８０μｍとすると好ましい。 It is preferable that the mesh diameter of the mask for etching resist printing used when printing the etching resist on the metal plate in a circuit pattern having a desired shape is 5 μm to 80 μm.

前記金属板にエッチングレジストを所望形状の回路パターンに印刷する際に用いるエッチングレジスト印刷用マスクの目開きを３０μｍ〜１５０μｍとすると好ましい。 It is preferable that the opening size of the etching resist printing mask used when printing the etching resist on the metal plate in a circuit pattern having a desired shape is 30 μm to 150 μm.

本発明によれば、エッチング処理前のレジスト膜の形状を工夫することにより、回路パターン周縁部表面に凹凸を生成させずに、凹凸にともなうめっき不良、外観不良、面粗度の悪化、接着不良の少ないセラミックス回路基板とすることができる。また、そのようなセラミックス回路基板の製造方法を提供することができる。   According to the present invention, by devising the shape of the resist film before the etching process, without generating irregularities on the peripheral surface of the circuit pattern, plating defects, poor appearance, poor surface roughness, poor adhesion due to the irregularities The ceramic circuit board can be reduced. Moreover, the manufacturing method of such a ceramic circuit board can be provided.

図１．本発明の実施の形態に係る断面模式図。
図２．本発明の実施の形態に係る断面模式拡大図。
図３．本発明の実施の形態に係る製造フロー図。
図４．本発明の実施の形態に係るレジスト膜の形状測定結果を示す図。 FIG. The cross-sectional schematic diagram which concerns on embodiment of this invention.
FIG. The cross-sectional model enlarged view which concerns on embodiment of this invention.
FIG. The manufacturing flowchart which concerns on embodiment of this invention.
FIG. The figure which shows the shape measurement result of the resist film which concerns on embodiment of this invention.

以下、本発明を図面に従い具体的に説明するが、それら実施例により本発明が限定されるものではない。
図１に、本発明に係るセラミックス回路基板用素材の断面図の模式図を示す。
本発明に係るセラミックス回路基板用素材は、図1に示すように窒化珪素などからなるセラミックス基板１の上に所定の回路パターンの回路板が得られるようにろう材２を塗布し、その上に銅板等からなる金属板３を設け、接合により１，２，３が一体化されており、金属板３の上にろう材と平面視輪郭が略一致するようにレジスト膜４が形成されている。また、絶縁基板１の下側にろう材２を塗布し、その下側に放熱板として用いられる銅板等からなる金属板３を同様に設ける。図１においては、セラミックス基板である窒化珪素からなる絶縁基板１の上にろう材を用いて銅板からなる金属板３を設けているが、絶縁基板と金属板の接合は直接接合法を用いてもかまわない。図２に図１のレジスト膜端面の拡大断面模式図を示すがレジスト膜の中央部の平均厚さＴ１を３０μｍ〜６０μｍとするとともに、レジスト膜の周縁部５の最大厚さＴ２はレジスト膜中央部の平均厚さＴ１よりも５μｍ以上厚く形成されている。
ここで、回路パターン周縁部５とは、図２に示すように、金属板上に形成されたレジスト膜の端部６から少なくとも２００μｍよりも外側の部分をいう。さらに、レジスト膜の回路パターン周縁部の最大厚さ部７が、エッチング処理により不要な金属板を除去した後の回路パターン周縁部よりも内側に形成されると好ましい。
本発明に係るセラミックス回路基板用素材において、エッチング液、ろう材除去液への薬液耐性の確保には、レジスト膜厚さとその周縁部形状の制御が必要不可欠である。 Hereinafter, the present invention will be specifically described with reference to the drawings. However, the present invention is not limited to the examples.
In FIG. 1, the schematic diagram of sectional drawing of the raw material for ceramic circuit boards which concerns on this invention is shown.
As shown in FIG. 1, a ceramic circuit board material according to the present invention is coated with a brazing material 2 on a ceramic substrate 1 made of silicon nitride or the like so that a circuit board having a predetermined circuit pattern is obtained. A metal plate 3 made of a copper plate or the like is provided, and 1, 2 and 3 are integrated by bonding, and a resist film 4 is formed on the metal plate 3 so that the brazing material and the outline in plan view substantially coincide. . Also, a brazing material 2 is applied to the lower side of the insulating substrate 1, and a metal plate 3 made of a copper plate or the like used as a heat sink is similarly provided on the lower side. In FIG. 1, a metal plate 3 made of a copper plate is provided using a brazing material on an insulating substrate 1 made of silicon nitride, which is a ceramic substrate, but the insulating substrate and the metal plate are joined using a direct joining method. It doesn't matter. FIG. 2 shows an enlarged schematic sectional view of the end face of the resist film of FIG. 1. The average thickness T1 of the central portion of the resist film is set to 30 μm to 60 μm, and the maximum thickness T2 of the peripheral portion 5 of the resist film is the center of the resist film. The thickness is 5 μm or more thicker than the average thickness T1 of the portion.
Here, as shown in FIG. 2, the circuit pattern peripheral portion 5 refers to a portion at least outside 200 μm from the end portion 6 of the resist film formed on the metal plate. Furthermore, it is preferable that the maximum thickness portion 7 at the peripheral portion of the circuit pattern of the resist film is formed on the inner side of the peripheral portion of the circuit pattern after the unnecessary metal plate is removed by the etching process.
In the material for a ceramic circuit board according to the present invention, control of the resist film thickness and its peripheral portion shape is indispensable for ensuring the chemical resistance to the etching solution and the brazing material removing solution.

レジスト膜回路パターン中央部の平均厚さを３０μｍ〜６０μｍとするのは、以下の理由による。エッチング工程、不要ろう材除去工程においてレジスト膜の薬液耐性が維持でき、レジスト膜印刷後のＵＶ硬化過程での収縮による割れの発生がないレジスト膜が得られる厚み範囲である。レジスト膜の回路パターン中央部の平均厚さが３０μｍ未満の場合には、エッチング工程、不要ろう材除去工程においてレジスト膜が溶解してしまい、その箇所でエッチング液、ろう材除去液のアタックを受け回路板面に凹凸を生じる不具合が生じる場合がある。また、６０μｍ超の場合には、レジスト膜印刷後のＵＶ硬化の過程においてＵＶ照射がレジスト膜の深部まで行き届かずレジスト膜の深部が硬化せず、逆にレジスト膜の薬液耐性を低下させる不具合が生じる場合がある。したがって、レジスト膜の回路パターン中央部の平均厚さを３０μｍ〜６０μｍとする。より好ましい範囲は４０μｍ〜５０μｍである。 The reason why the average thickness of the central part of the resist film circuit pattern is 30 μm to 60 μm is as follows. This is a thickness range in which the resist film chemical resistance can be maintained in the etching process and the unnecessary brazing material removing process, and a resist film free from cracking due to shrinkage in the UV curing process after printing the resist film is obtained. If the average thickness of the resist film circuit pattern center is less than 30 μm, the resist film dissolves in the etching process and the unnecessary brazing material removal process, and the resist is attacked by the etching liquid and brazing material removal liquid. There may be a problem that the circuit board surface is uneven. If the thickness exceeds 60 μm, the UV irradiation does not reach the deep part of the resist film during the UV curing process after printing the resist film, and the deep part of the resist film is not hardened. May occur. Therefore, the average thickness of the central portion of the circuit pattern of the resist film is set to 30 μm to 60 μm. A more preferable range is 40 μm to 50 μm.

レジスト膜の形状は、回路パターン周縁部の最大厚さを回路パターン中央部の平均厚さよりも５μｍ以上厚くするのは以下の理由による。回路パターン周縁部はエッチング液、ろう材除去液により膜厚が薄くなりやすく、局所的にレジスト膜を厚くしてエッチング液、ろう材除去液への薬液耐性を向上させる必要があるためである。また、厚さの差が５μｍ未満の場合には、回路パターン周縁部におけるエッチング液およびろう材除去液に対する耐性の向上が期待できなくなる。
また、レジスト膜の回路パターン周縁部が部分的に厚肉化されていても、内部までＵＶ硬化するのは、全体が厚肉の場合にはレジスト膜表面に対して垂直方向のみからのＵＶ照射となるが、回路パターン周縁部のみ厚肉の場合には周縁部のレジスト膜表面に斜面部が形成され、表面積がレジスト膜中央部よりも大きくなるとともに、斜め方向からのＵＶ照射を受けやすくなる効果もあるために硬化するためである。
さらに好ましくは、回路パターン周縁部の最大厚さを回路パターン中央部の厚さよりも５μｍ〜５０μｍ厚くするとよい。厚さの差を５０μｍよりも大きくすると、レジスト塗布時に保形性を維持するためにレジスト液の粘性を高くする必要があり、回路パターン周縁部以外のレジスト膜の後述するレベリング性が低くなり、レジスト膜の膜厚がばらつくなどのレジスト膜形成時に問題が生じやすくなるとともに、レジスト膜のUV硬化時には、回路パターン周縁部ではレジスト膜が厚膜の為に表面部のみ硬化してしまい、レジスト膜の中心まで紫外線が届かずに硬化が不十分な半生の状態になり、エッチング液、ろう材除去液耐性が維持できない場合がある。更に好ましくは回路パターン周縁部の最大厚さを回路パターン中央部の平均厚さよりも８〜３５μｍ厚くすると良い。 Regarding the shape of the resist film, the maximum thickness of the peripheral portion of the circuit pattern is made 5 μm or more thicker than the average thickness of the central portion of the circuit pattern for the following reason. This is because the peripheral portion of the circuit pattern tends to be thinned by the etching solution and the brazing material removing solution, and it is necessary to locally increase the resist film to improve the chemical resistance to the etching solution and the brazing material removing solution. Further, when the difference in thickness is less than 5 μm, improvement in resistance to the etching solution and the brazing material removing solution at the peripheral portion of the circuit pattern cannot be expected.
Further, even if the peripheral portion of the circuit pattern of the resist film is partially thickened, UV curing to the inside is performed only when the whole is thick, UV irradiation only from the direction perpendicular to the resist film surface. However, when only the peripheral portion of the circuit pattern is thick, a slope portion is formed on the resist film surface at the peripheral portion, the surface area becomes larger than the central portion of the resist film, and UV irradiation from an oblique direction is easily received. This is because it also has an effect and is cured.
More preferably, the maximum thickness of the peripheral edge portion of the circuit pattern is 5 to 50 μm thicker than the thickness of the central portion of the circuit pattern. When the difference in thickness is larger than 50 μm, it is necessary to increase the viscosity of the resist solution in order to maintain the shape retention at the time of applying the resist, and the leveling property described later of the resist film other than the peripheral portion of the circuit pattern is lowered, Problems are likely to occur during resist film formation, such as variations in resist film thickness, and at the time of UV curing of the resist film, the resist film is cured only at the surface due to the thick film at the periphery of the circuit pattern. In some cases, the ultraviolet rays do not reach the center of the film, and the curing is in a half-life state, and the resistance to the etching solution and the brazing material removal solution cannot be maintained. More preferably, the maximum thickness of the peripheral portion of the circuit pattern is 8 to 35 μm thicker than the average thickness of the central portion of the circuit pattern.

また、レジスト膜硬化後のレジスト膜の回路パターン周縁部の最大厚さを４０μｍ〜８０μｍとするとよい。これは、エッチング工程と不要ろう材除去工程において薬液耐性が維持できる好ましい厚み範囲である。特に、回路パターン周縁部は、エッチング液、ろう材除去液によるレジスト膜の溶解が著しく、レジスト膜が薄くなる現象が生じやすくなる。このため回路パターン周縁部のレジスト膜の厚さが４０μｍ未満の場合には、レジスト膜が部分的に溶解消滅し、もしくはレジスト膜端部が剥離し、回路パターン周縁部において薬液の影響により回路板が溶解され表面に凹凸が発生しやすくなる場合がある。また、レジスト膜の回路パターン周縁部の厚さが８０μｍ超の場合には、例えばレジスト膜印刷後のＵＶ硬化の過程において、ＵＶ照射が中まで行き届かず中心部が硬化せず、半生状態となり逆にレジスト膜の薬液耐性を低下させる不具合が生じる場合がある。したがって、回路パターン周縁部の厚さは４０μｍ〜８０μｍとすることが好ましい。さらに好ましい範囲は、５０μｍ〜７０μｍである。   The maximum thickness of the peripheral portion of the circuit pattern of the resist film after curing the resist film is preferably 40 μm to 80 μm. This is a preferable thickness range in which chemical resistance can be maintained in the etching step and the unnecessary brazing material removal step. In particular, at the periphery of the circuit pattern, the resist film is remarkably dissolved by the etching solution and the brazing material removing solution, and the phenomenon that the resist film becomes thin easily occurs. For this reason, when the thickness of the resist film at the periphery of the circuit pattern is less than 40 μm, the resist film partially dissolves or disappears, or the end of the resist film is peeled off, and the circuit board is affected by the chemical solution at the periphery of the circuit pattern. May dissolve and the surface may become uneven. In addition, when the thickness of the peripheral part of the circuit pattern of the resist film exceeds 80 μm, for example, in the process of UV curing after printing the resist film, the UV irradiation does not reach the inside and the central part is not cured, resulting in a semi-lived state. Conversely, there may be a problem that the chemical resistance of the resist film is lowered. Therefore, the thickness of the peripheral edge of the circuit pattern is preferably 40 μm to 80 μm. A more preferable range is 50 μm to 70 μm.

また、レジスト膜の表面粗さをＲａ０．２μｍ〜１０μｍとするとよい。レジスト膜の表面粗さは、用いる印刷マスクのメッシュ線径およびレベリング時間（印刷後にレジスト液が膜厚均等に拡がるまでに要する時間）に依存する。表面粗さが小さいほど、膜厚のばらつきの少ないレジスト膜を得ることになるが、この場合には、メッシュ線径を小さく（例えば、２０μｍ径）、また、レベリング時間を長く（例えば３ｍｉｎ）する必要がある。しかしながら、メッシュ線径を小さくすることは、透過体積を低減させることになり、結果としてレジスト膜厚さが不足するという不具合が生じやすくなる。また、レベリング時間を長くすることは、レジスト膜印刷のタクトタイムを長くすることになり、生産性を著しく低下させる。したがって、レジスト膜の表面粗さは、Ｒａ０．２μｍ以上であることが望ましい。一方、Ｒａが１０μｍよりも大きいとレジスト膜の厚さの差が大きくなり過ぎレジスト膜に部分的に薄い部分が出来やすくなり、エッチング処理時、不要ろう材除去時にレジスト膜の薄い部分が溶解し、金属回路面が露出し、回路板表面を溶解する場合があるからである。より好ましいレジスト膜の表面粗さはＲａ０．５μｍ〜５μｍである。   The surface roughness of the resist film is preferably Ra 0.2 μm to 10 μm. The surface roughness of the resist film depends on the mesh wire diameter of the printing mask to be used and the leveling time (the time required for the resist solution to spread evenly after printing). As the surface roughness is smaller, a resist film with less variation in film thickness is obtained. In this case, the mesh wire diameter is reduced (for example, 20 μm diameter), and the leveling time is increased (for example, 3 minutes). There is a need. However, reducing the mesh wire diameter reduces the transmission volume, and as a result, the problem of insufficient resist film thickness is likely to occur. Further, increasing the leveling time increases the takt time for printing the resist film, which significantly reduces productivity. Therefore, the surface roughness of the resist film is desirably Ra 0.2 μm or more. On the other hand, if Ra is larger than 10 μm, the difference in thickness of the resist film becomes too large, and it becomes easy to form a thin part in the resist film, and the thin part of the resist film is dissolved during the removal of the unnecessary brazing material during the etching process. This is because the metal circuit surface may be exposed and the circuit board surface may be dissolved. A more preferable surface roughness of the resist film is Ra 0.5 μm to 5 μm.

本発明のセラミックス回路基板用素材でレジスト膜の回路パターン周縁部の厚さを回路パターン中央部の厚さよりも５μｍ以上厚く形成するためには、印刷マスクを用いてレジスト膜を印刷する際に、レジスト液の粘度、印刷マスクの透過体積、印刷に用いるスキージの速度をバランスすることにより、形成することができる。他の形成方法としては、用いる印刷マスクの回路板周縁部に相当する部分のレジスト液透過性を上げることにより、回路パターン周縁部のレジスト膜の厚さを厚く形成することができる。さらに、回路パターン周縁部にレジスト液を複数回塗布することや、ディスペンサーでレジスト液を周縁部のみ部分的に塗布することにより、回路パターン周縁部のレジスト膜の厚さを中央部よりも厚く形成することができる。 In order to form the thickness of the peripheral part of the circuit pattern of the resist film with the ceramic circuit board material of the present invention to be 5 μm or more thicker than the thickness of the center part of the circuit pattern, when printing the resist film using a printing mask, It can be formed by balancing the viscosity of the resist solution, the transmission volume of the printing mask, and the speed of the squeegee used for printing. As another forming method, by increasing the resist liquid permeability of the portion corresponding to the peripheral portion of the circuit board of the printing mask to be used, the resist film at the peripheral portion of the circuit pattern can be formed thick. Furthermore, the resist film is applied to the peripheral part of the circuit pattern a plurality of times, or the resist solution is partially applied only to the peripheral part with a dispenser, so that the resist film at the peripheral part of the circuit pattern is made thicker than the central part. can do.

次に本発明のセラミックス回路基板の製造方法について説明する。
図３は、本発明のセラミックス回路基板の製造方法を示す一例のフロー図である。
図３においては、セラミックス基板の一方の面に金属回路を形成する工程を示している。本発明の最大の特徴は、図３に示すレジスト印刷工程において、印刷方法を工夫し、形成するレジスト膜の性状を工夫することにより、エッチング工程のみならず、不要ろう材除去工程を、金属板面にレジスト膜を残したまま容易に行うことが可能となるように優れた薬液耐性をレジスト膜に持たせた点にある。以下、更に詳しく本発明を説明する。 Next, the manufacturing method of the ceramic circuit board of this invention is demonstrated.
FIG. 3 is an exemplary flowchart showing a method for manufacturing a ceramic circuit board according to the present invention.
FIG. 3 shows a process of forming a metal circuit on one surface of the ceramic substrate. The greatest feature of the present invention is that in the resist printing process shown in FIG. 3, the printing method is devised, and the properties of the resist film to be formed are devised, so that not only the etching process but also the unnecessary brazing material removing process is performed on the metal plate. The resist film is provided with excellent chemical resistance so that it can be easily performed with the resist film remaining on the surface. Hereinafter, the present invention will be described in more detail.

本発明のセラミックス回路基板の製造方法を示す一例を図３に示すフロー図に従いながら、以下説明する。 An example showing the method for manufacturing a ceramic circuit board of the present invention will be described below with reference to the flowchart shown in FIG.

本発明のセラミックス基板としては、窒化珪素、窒化アルミニウム、窒化ほう素、酸化アルミニウム、及びこれらの複合系を主成分とするものなどが挙げられるが、酸化アルミニウムや窒化アルミニウムが最も一般的である。最近では特にパワー半導体モジュール基板への適用を考えた場合、実装信頼性及び冷熱繰り返し特性の観点から、特に厚さ方向に対する高靭性を有し、かつ、高強度であって、放熱性の観点から高熱伝導性を備えたものが望ましく、窒化珪素の使用が進んでいる。窒化珪素を用いる場合、熱伝導性の観点から窒化珪素基板のβ型窒化珪素結晶粒子の長軸径と短軸径との平均比率である平均アスペクト比が１．５より大きく５以下であることが望ましい。 Examples of the ceramic substrate of the present invention include silicon nitride, aluminum nitride, boron nitride, aluminum oxide, and those having a composite system thereof as a main component, but aluminum oxide and aluminum nitride are the most common. Recently, especially when considering application to power semiconductor module substrates, it has high toughness in the thickness direction and high strength from the viewpoint of mounting reliability and cooling / cooling characteristics, and from the viewpoint of heat dissipation Those having high thermal conductivity are desirable, and silicon nitride is being used. When silicon nitride is used, the average aspect ratio, which is the average ratio of the major axis diameter to the minor axis diameter of the β-type silicon nitride crystal particles of the silicon nitride substrate, is greater than 1.5 and less than or equal to 5 from the viewpoint of thermal conductivity. Is desirable.

セラミックス基板の厚さは、０．２ｍｍより厚く１．０ｍｍ以下であることが望ましい。
セラミックス基板の厚さが０．２ｍｍ以下である場合には、基板自身の剛性の低下により、冷熱繰り返しにともなう回路板の伸縮にともない、セラミックス基板の繰り返し変形量が大きくなり、このため回路板とセラミックス基板との接合信頼性が低下してしまう。また、金属からなる回路板とセラミックス基板の裏面に接合される金属放熱板との間、即ち、セラミックス基板表裏間における絶縁耐圧が低下するため、セラミックス基板としての使用範囲が限定されてしまう。これに対し、セラミックス基板の厚さが１．０ｍｍより厚い場合には、セラミックス基板自体の熱伝導率は、金属からなる回路板の熱伝導率（例えば銅（Ｃｕ）：３９０Ｗ／ｍ・Ｋ）に比較して、窒化珪素の場合９０Ｗ／ｍ・Ｋ、窒化アルミの場合には１７０Ｗ／ｍ・Ｋと低いため、このセラミックス基板の厚さを１．０ｍｍより厚くすると、セラミックス基板としての放熱性を低下させてしまう。好ましいセラミックス基板の厚さは０．２５ｍｍ〜０．８ｍｍである。 The thickness of the ceramic substrate is desirably greater than 0.2 mm and 1.0 mm or less.
When the thickness of the ceramic substrate is 0.2 mm or less, due to the decrease in rigidity of the substrate itself, the amount of repeated deformation of the ceramic substrate increases as the circuit board expands and contracts due to repeated cooling and heating. Bonding reliability with the ceramic substrate is lowered. Moreover, since the withstand voltage between the circuit board made of metal and the metal heat radiating plate bonded to the back surface of the ceramic substrate, that is, between the front and back surfaces of the ceramic substrate is lowered, the range of use as the ceramic substrate is limited. On the other hand, when the thickness of the ceramic substrate is larger than 1.0 mm, the thermal conductivity of the ceramic substrate itself is that of a circuit board made of metal (for example, copper (Cu): 390 W / m · K). Compared to the above, since it is low at 90 W / m · K in the case of silicon nitride and 170 W / m · K in the case of aluminum nitride, if this ceramic substrate is made thicker than 1.0 mm, the heat dissipation as a ceramic substrate Will be reduced. A preferable thickness of the ceramic substrate is 0.25 mm to 0.8 mm.

セラミックス基板は金属板をろう材印刷工程前に表面処理を行うと好ましい。即ち、上記セラミックス基板にブラスト処理を施し、セラミックス基板の表面粗さＲmaxを３μｍより大きく２０μｍ以下に制御する。ブラスト処理には、コンプレッサーエアーで酸化アルミニウム（アルミナ）（Ａｌ２Ｏ３）等の研磨材を被研磨品に吹き付ける乾式ブラスト処理やコンプレッサーエアーで研磨材と溶液の混合物を被研磨品に吹き付ける湿式ブラスト処理がある。 The ceramic substrate is preferably subjected to a surface treatment on the metal plate before the brazing material printing step. That is, the ceramic substrate is subjected to blasting, and the surface roughness Rmax of the ceramic substrate is controlled to be larger than 3 μm and not larger than 20 μm. For the blast treatment, dry blast treatment in which an abrasive such as aluminum oxide (alumina) (Al 2 O 3 ) is blown onto the object to be polished with compressor air, or wet blasting in which a mixture of the abrasive and the solution is blown onto the article to be polished with compressor air. There is processing.

また、本発明で使用されるセラミックス回路基板の金属板は、銅、銅合金、アルミニウム、アルミニウム合金であり、その中でも銅及び銅合金が好ましい。特に高い放熱性が要求されるパワー半導体モジュール用のセラミックス回路基板としては、酸素を僅かに含むタフピッチ銅および無酸素銅板がこれに適している。金属板の厚みは、一般的には０．３ｍｍであるが、パワー半導体素子の発熱密度の増大に伴い、更なる高熱伝導性を有するセラミックス回路基板が必要となり、セラミックス基板の表面に形成される金属回路形成用金属板が厚膜化の傾向にある。この場合０．４ｍｍ以上の銅回路板が用いられ、セラミックスと金属回路板界面の接合信頼性確保といった観点から機械特性に優れた窒化珪素が最適である。好ましくは０．５ｍｍ〜１．０ｍｍである。 Moreover, the metal plate of the ceramic circuit board used by this invention is copper, a copper alloy, aluminum, and an aluminum alloy, Among these, copper and a copper alloy are preferable. Particularly suitable ceramic circuit boards for power semiconductor modules that require high heat dissipation are tough pitch copper and oxygen-free copper plates containing a small amount of oxygen. The thickness of the metal plate is generally 0.3 mm. However, as the heat generation density of the power semiconductor element increases, a ceramic circuit board having higher thermal conductivity is required and is formed on the surface of the ceramic board. Metal circuit forming metal plates tend to be thicker. In this case, a copper circuit board of 0.4 mm or more is used, and silicon nitride having excellent mechanical properties is optimal from the viewpoint of securing the bonding reliability between the ceramic and metal circuit board interface. Preferably it is 0.5 mm-1.0 mm.

図３に示す本発明のセラミックス回路基板の製造方法を示すフロー図に従い説明する。
（１）ろう材印刷工程
表面処理されたセラミックス基板の表面に活性金属ろう材を用いて金属板を接合する。まず、金属板を接合するためにろう材印刷工程を行う。ろう材としては、金属板が銅及び銅合金の場合、銀（Ａｇ）−銅（Ｃｕ）−チタン（Ｔｉ）系、銅（Ｃｕ）−金（Ａｕ）−チタン（Ｔｉ）系など、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）又はハフニウム（Ｈｆ）等の活性金属と低融点合金を作る銀（Ａｇ）、銅等の金属を混合又は合金としたものを用いる。金属板がアルミおよびアルミ合金の場合、Ａｌ−Ｓｉ系合金またはこれに防錆効果のあるＧｅ、低融点化剤のＭｇを微量添加したＡｌ−Ｓｉ−Ｇｅ系またはＡｌ−Ｓｉ−Ｍｇ系のろう材金属が用いられる。セラミックス基板の所定箇所に上記ろう材のペーストを、用いるろう材粉末の粒度に依存するが、例えば厚さ１０μｍ〜５０μｍ程度の所望の回路基板形状に塗布する。 It demonstrates according to the flowchart which shows the manufacturing method of the ceramic circuit board of this invention shown in FIG.
(1) Brazing material printing process A metal plate is joined to the surface of the ceramic substrate subjected to surface treatment using an active metal brazing material. First, a brazing material printing process is performed to join the metal plates. As the brazing material, when the metal plate is copper or a copper alloy, titanium (such as silver (Ag) -copper (Cu) -titanium (Ti)), copper (Cu) -gold (Au) -titanium (Ti), etc. An active metal such as Ti), zirconium (Zr), or hafnium (Hf) is mixed or alloyed with a metal such as silver (Ag) or copper that forms a low melting point alloy. When the metal plate is aluminum or an aluminum alloy, an Al-Si-based alloy or Al-Si-Mg-based brazing alloy containing a small amount of Ge, which has an anti-corrosive effect, and a low melting point Mg is added thereto. A metal material is used. The brazing paste is applied to a predetermined portion of the ceramic substrate in a desired circuit board shape having a thickness of about 10 μm to 50 μm, for example, depending on the particle size of the brazing powder used.

（２）ろう付け工程
上記ろう材の表面に回路板として厚さ０．３ｍｍ以上の金属箔又は金属板を載置し、例えば、７８０℃〜９００℃で加圧しながら接合する。加圧時間は０．５時間〜７時間が好ましい。 (2) Brazing step A metal foil or metal plate having a thickness of 0.3 mm or more is placed on the surface of the brazing material as a circuit board, and is joined while being pressed at 780 ° C to 900 ° C, for example. The pressing time is preferably 0.5 to 7 hours.

（３）レジスト印刷工程
上記工程により得られた接合体の金属面にレジスト膜が所望の回路パターンに印刷される。レジストの選定は特に重要であり、レジスト膜パターン印刷の後に続く乾燥・硬化等のライン構成を考慮した場合には、即時に乾燥・硬化する紫外線硬化型でアルカリ剥離タイプのものを用いるとよい。 (3) Resist printing step A resist film is printed in a desired circuit pattern on the metal surface of the joined body obtained in the above step. The selection of the resist is particularly important. In consideration of the line configuration such as drying / curing after the resist film pattern printing, it is preferable to use an ultraviolet curable type that is immediately dried / cured and an alkali peeling type.

本発明に用いられるレジスト液のうち、例えば紫外線硬化型レジストは、共重合系アクリレート・オリゴマー、アクリル酸エステル・モノマー、充填剤、光重合開始剤、色素調整剤、および消泡・レベリング剤から構成される。
主成分の共重合系アクリレート・オリゴマーは、縮合・重合反応して硬化する高粘性ポリマーである。主成分である共重合系アクリレート・オリゴマーには、エポキシアクリレート、ウレタンアクリレート、ポリエステルアクリレート、ポリエーテルアクリレートなどからなる共重合樹脂である。
また、アクリル酸エステル・モノマーには、イソアミルアクリレート、ラウリルアクリレート、ステアリルアクリレート、エトキシージーエチレングリコールアクリレート、２ヒドロキシエチルアクリレート、フェノキシエチルアクリレート等である。光重合開始剤のラジカル反応により、アクリル酸エステル・モノマーを伴って高分子ポリマー化する。この場合、重合の度合いによりエッチング液、ろう材除去液への薬液耐性を向上させることができる。また、アクリル酸エステル・モノマーは、上記、高分子ポリマーとしての骨格形成に寄与することに加えて、硬化前のペーストの状態では、流動性を与えるための粘度調整剤として働き、硬化後にはポリマーの可撓性および回路板への密着性の発現に寄与する。 Among the resist solutions used in the present invention, for example, an ultraviolet curable resist is composed of a copolymer acrylate / oligomer, an acrylate ester / monomer, a filler, a photopolymerization initiator, a dye adjusting agent, and a defoaming / leveling agent. Is done.
The main component copolymer acrylate oligomer is a high-viscosity polymer that cures by condensation / polymerization reaction. The copolymer acrylate / oligomer as the main component is a copolymer resin made of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, or the like.
Examples of acrylic acid ester monomers include isoamyl acrylate, lauryl acrylate, stearyl acrylate, ethoxyethylene ethylene glycol acrylate, 2 hydroxyethyl acrylate, and phenoxyethyl acrylate. By the radical reaction of the photopolymerization initiator, the polymer is polymerized with an acrylate ester monomer. In this case, chemical resistance to the etching solution and the brazing material removing solution can be improved depending on the degree of polymerization. In addition to contributing to the formation of a skeleton as a polymer, the acrylate ester monomer acts as a viscosity modifier for imparting fluidity in the state of the paste before curing, and the polymer after curing. This contributes to the development of flexibility and adhesion to the circuit board.

また、充填剤は、ペーストとしての流動性の改善、増容積剤および疎水性の発現に寄与する。充填剤としては、タルク、硫酸バリウムおよびシリカを個々におよび複合添加したものである。
また、光重合開始剤は、水銀灯などの光源により紫外線エネルギーを吸収してラジカル反応を開始し、主成分ポリマーの重合化を促進させる。光重合開始剤としては、ジエトキシアセトフェノン、イソブチルベンゾインエーテル、ヒドロキシシクロヘキシルフェニルケトンおよびベンゾフェノン等である。
また、色素調整剤は、構造骨格中心部にＣｕが配置してこの部分が青色に発色し、紫外線エネルギーの吸収の度合いによって青色から黒色化するため、レジスト膜硬化度および高ポリマー化の尺度となる。色素調整剤としては、フタロシアニンブルー、フタロシアニングリーン等である。色素調整剤としてフタロシアニンブルーを含有した紫外性硬化型レジストを用いると好ましい。フタロシアニンブルーは、紫外線の吸収の度合いで本来の青色から段階的に黒色化する。したがって、黒色化の度合いを定量化することで、レジスト膜の硬化度合を定量化でき、従ってレジスト薬液耐性をモニタリングすることが可能となる。 In addition, the filler contributes to improvement of fluidity as a paste, volume increaser, and expression of hydrophobicity. As the filler, talc, barium sulfate and silica are added individually and in combination.
In addition, the photopolymerization initiator absorbs ultraviolet energy with a light source such as a mercury lamp to initiate a radical reaction, and promotes polymerization of the main component polymer. Examples of the photopolymerization initiator include diethoxyacetophenone, isobutyl benzoin ether, hydroxycyclohexyl phenyl ketone, and benzophenone.
In addition, since the dye adjusting agent has Cu arranged in the central part of the structural skeleton and this part is colored blue, and the color is changed from blue to black depending on the degree of absorption of ultraviolet energy, Become. Examples of the dye adjusting agent include phthalocyanine blue and phthalocyanine green. It is preferable to use an ultraviolet curable resist containing phthalocyanine blue as a dye adjusting agent. Phthalocyanine blue is gradually blackened from the original blue color depending on the degree of absorption of ultraviolet rays. Therefore, by quantifying the degree of blackening, the degree of cure of the resist film can be quantified, and therefore it is possible to monitor the resistance to resist chemicals.

また、消泡・レベリング剤は、ペースト印刷時に巻き込んだ気泡を速やかに発泡させ、また印刷マスクへのレジストの濡れ性および回路板への密着性の改善に寄与する。消泡・レベリング剤は、シリコーン系のものである。
特に主成分である共重合系アクリレート・オリゴマーには、ポリエステルアクリレートあるいはエポキシアクリレートが、アクリル酸エステル・モノマーには、ステアリルアクリレートが、充填剤は、タルク、硫酸バリウムおよびシリカを複合した無機粉末からなり、また、光重合開始剤は、ベンゾフェノンあるいはジエトキシアセトフェノンが好ましい。 Further, the defoaming / leveling agent quickly foams the bubbles involved during paste printing, and contributes to improving the wettability of the resist to the printing mask and the adhesion to the circuit board. The defoaming / leveling agent is a silicone-based one.
In particular, copolymer acrylates / oligomers, which are the main components, are polyester acrylates or epoxy acrylates, acrylic acid esters / monomers are stearyl acrylates, and the filler is an inorganic powder that combines talc, barium sulfate and silica. The photopolymerization initiator is preferably benzophenone or diethoxyacetophenone.

ここで、ろう材除去液耐性の確保には、紫外線照射による硬化したレジスト膜が所定の厚さおよび
形状に制御するには、レジストペーストの粘度に影響する充填剤の種類およびそれら含有量の制御が重要である。 Here, in order to ensure the resistance to the brazing material removal solution, the resist film cured by UV irradiation can be controlled to a predetermined thickness and shape, and the types of fillers that affect the viscosity of the resist paste and the control of their contents is important.

本発明に用いたレジストに含有する充填剤の例としては、平均１次粒子径が１μｍ〜２０μｍのタルクMg3H2(SiO3)4を１０ｗｔ％〜２０ｗｔ％、平均１次粒子径が１μｍ〜３０μｍの硫酸バリウム（ＢａＳＯ４）を２０ｗｔ％〜３０ｗｔ％および平均１次粒子径が５ｎｍ〜２０ｎｍのシリカ（ＳｉＯ２）を１ｗｔ％〜５ｗｔ％とすることが望ましい。それぞれ、規定の下限値未満となると所定の粘度が得られず、印刷後のレジスト膜に流れが発生して保形性が維持できない場合がある。このため、印刷効率向上を意図した１ショットで行う印刷では厚膜化ができなくなる。また、それぞれの規定の上限値を超えるとレジストの流動性が阻害され、この場合には金属板表面への所望形状のレジスト印刷ができなくなる場合がある。したがって、それぞれの充填剤粉末の含有量は、上記の範囲にあることが望ましい。
本発明で用いられるレジストは共重合系アクリレート・オリゴマー：１０ｗｔ％〜２０ｗｔ％、アクリル酸エステル・モノマー：４０ｗｔ％〜５０ｗｔ％、充填材：２５ｗｔ%〜５５ｗｔ%、色素調整剤：０．１ｗｔ％〜１．０ｗｔ％、光重合開始材：１ｗｔ％〜５ｗｔ％、消泡・レベリング剤：０．１ｗｔ％〜１ｗｔ％であると好ましい。 As an example of the filler contained in the resist used in the present invention, talc Mg 3 H 2 (SiO 3 ) 4 having an average primary particle diameter of 1 μm to 20 μm is 10 wt% to 20 wt%, and the average primary particle diameter is 1 μm. It is desirable that -30 μm of barium sulfate (BaSO 4 ) is 20 wt% to 30 wt% and silica (SiO 2 ) having an average primary particle diameter of 5 nm to 20 nm is 1 wt% to 5 wt%. In each case, when it is less than the prescribed lower limit value, a predetermined viscosity cannot be obtained, and a flow may occur in the resist film after printing, and the shape retention may not be maintained. For this reason, it is impossible to increase the film thickness by printing performed in one shot intended to improve printing efficiency. Further, when the upper limit value of each regulation is exceeded, the fluidity of the resist is hindered, and in this case, it may be impossible to print the resist with a desired shape on the surface of the metal plate. Therefore, the content of each filler powder is preferably in the above range.
The resist used in the present invention is copolymerized acrylate / oligomer: 10 wt% to 20 wt%, acrylic acid ester / monomer: 40 wt% to 50 wt%, filler: 25 wt% to 55 wt%, dye adjusting agent: 0.1 wt% to 1.0 wt%, photopolymerization initiator: 1 wt% to 5 wt%, defoaming / leveling agent: 0.1 wt% to 1 wt% are preferable.

さらにレジスト液の粘性は、レジスト膜厚さ、形状に加えて印刷精度に影響する。
レジスト粘度が高い場合には、レベリング性が低下してレジスト膜表面に窪み部が残り、さらに過度に高くなる場合には、レジスト膜は目視においても金属板表面が確認できるような空孔部となる。一方、レジスト粘性が低い場合には、レベリング性は保証されるものの、本発明のレジスト膜の回路パターン周縁部の最大厚さを回路パターン中央部の厚さよりも５μｍ以上厚く形成するような所望のレジスト膜形状に制御することが難しく、さらに過度に低くなる場合にはレジスト膜流れが生じて所望形状のレジスト膜パターンを維持することが困難となる。
したがって、レジスト液を回転型粘度計を用いて温度２５℃で測定した回転数１００ｒｐｍにおける粘度を５Ｐａ・ｓ〜３０Ｐａ・ｓとする。ここで用いられる回転型粘度計は、ＢＲＯＯＫ ＦＩＥＬＤ社製 ＤＶ−２＋Ｐｒｏ ＶＩＳＣＯＭＥＴＥＲで、スピンドルにはＳＣ４−１４型を用いて測定した。更に好ましい粘度は温度２５℃で測定した回転数１００ｒｐｍにおける粘度が７Ｐａ・ｓ〜１５Ｐａ・ｓである。 Furthermore, the viscosity of the resist solution affects the printing accuracy in addition to the resist film thickness and shape.
When the resist viscosity is high, the leveling property is lowered and a recess remains on the surface of the resist film, and when the resist film is excessively high, the resist film has pores so that the surface of the metal plate can be visually confirmed. Become. On the other hand, when the resist viscosity is low, the leveling property is guaranteed, but the maximum thickness of the peripheral portion of the circuit pattern of the resist film of the present invention is desired to be 5 μm or more thicker than the thickness of the central portion of the circuit pattern. It is difficult to control the resist film shape, and when it becomes excessively low, a resist film flow occurs and it becomes difficult to maintain a resist film pattern having a desired shape.
Therefore, the viscosity of the resist solution at a rotation speed of 100 rpm measured at a temperature of 25 ° C. using a rotary viscometer is set to 5 Pa · s to 30 Pa · s. The rotational viscometer used here was DV-2 + Pro VISCOMETER manufactured by BROOK FIELD, and the spindle was measured using SC4-14 type. A more preferable viscosity is 7 Pa · s to 15 Pa · s at a rotation speed of 100 rpm measured at a temperature of 25 ° C.

また、回路パターンの印刷方法としては、スクリーン印刷、ロールコーターなどが適用されるが、レジスト膜印刷後の乾燥・硬化後に、改めて露光、現像および洗浄工程を必要としないで所定のパターンを形成することができるスクリーン印刷法を用いる。 As a circuit pattern printing method, screen printing, roll coater, or the like is applied. After drying / curing after resist film printing, a predetermined pattern is formed without the need for exposure, development, and washing steps. A screen printing method is used.

スクリーン印刷時にはゴム製のワイパー状のスキージが用いられる。印刷時に印刷スクリーンの上にレジスト液を供給した後に、印刷スクリーン上をレジスト液を押し込むようにスキージを移動させることにより、レジスト液を金属板表面に塗布することが出来る。なお、スキージとして、メタル製、樹脂製、ゴム製があるが、接合体表面の反り形状に追従できる樹脂製あるいはゴム製が好ましく、さらに、洗浄時に使用する有機溶剤への耐久性を有するウレタンゴム製が望ましい。
印刷時の印刷スクリーン上をスキージを移動させる速度であるスキージ速度は、レジスト膜厚さおよび連続印刷性に影響するが、特に本発明の特徴であるレジスト膜周縁部の厚さに影響を与える。スクリーン印刷は、速度が遅いと印刷時に金属板表面にレジスト膜を転写（押し込む）すると同時にスキージにより掻き取る作用が働くためレジスト膜を厚膜化することができない。また、スキージ速度が遅いとレジスト液の粘性挙動に大きく影響を受け、印刷ショット間での実際に転写されるレジスト液量にばらつきを生じるため、レジスト膜厚さのばらつきが生じる場合があった。このため、スキージ速度を上げることで、転写（押し込む）作用のみを発現させて厚膜化することが出来るとともに印刷ショット間での実際に転写されるレジスト液量にばらつきを生じにくく、レジスト膜厚さのばらつきが少なくなる。本願発明者らが鋭意検討した結果、さらにスキージ速度を上げていくことで、レジスト膜中央部に比べてレジスト膜周縁部の厚さを厚く形成することが出来ることを見出した。しかし、スキージ速度が早すぎるとレジスト液の粘性挙動に大きく影響を受け、レジスト膜端部を所望形状に制御できないという不具合が生じる場合があった。したがって、印刷時のスキージ速度は、１００ｍｍ/sec〜３００mm/secである。さらに好ましくは１５０mm/sec〜２５０mm/secである。 A rubber wiper squeegee is used for screen printing. After supplying the resist solution onto the printing screen during printing, the resist solution can be applied to the surface of the metal plate by moving the squeegee so as to push the resist solution over the printing screen. The squeegee is made of metal, resin, or rubber, but is preferably made of resin or rubber that can follow the warped shape of the joined body surface, and is also urethane rubber that is durable to organic solvents used during cleaning. It is desirable to make it.
The squeegee speed, which is the speed at which the squeegee moves on the printing screen during printing, affects the resist film thickness and continuous printability, but in particular affects the thickness of the peripheral edge of the resist film, which is a feature of the present invention. In the screen printing, if the speed is low, the resist film cannot be thickened because the resist film is transferred (pushed) onto the surface of the metal plate at the time of printing. In addition, when the squeegee speed is low, the viscosity behavior of the resist solution is greatly affected, and the amount of the resist solution that is actually transferred between print shots varies, which may cause variations in resist film thickness. For this reason, by increasing the squeegee speed, only the transfer (pushing) action can be realized to increase the thickness of the film, and the amount of resist solution that is actually transferred between print shots is less likely to vary. The variation in thickness is reduced. As a result of intensive studies by the inventors of the present application, it has been found that by increasing the squeegee speed further, the thickness of the peripheral portion of the resist film can be formed thicker than the central portion of the resist film. However, if the squeegee speed is too fast, the viscosity behavior of the resist solution is greatly affected, which may cause a problem that the resist film end cannot be controlled to a desired shape. Therefore, the squeegee speed during printing is 100 mm / sec to 300 mm / sec. More preferably, it is 150 mm / sec-250 mm / sec.

本発明における印刷方法は、１回のみのショットで３０μｍ以上厚に印刷するために、印刷時の印刷マスクの透過体積が特に重要である。そのため、用いる印刷マスクのメッシュ線径、目開き、およびレジスト液の粘性を個々に調整する必要がある。透過体積とは１回のショットでペーストが通過できる空間のことであり、透過体積＝（目開き）2／（目開き＋線径）2ｘスクリーン厚さで示される。
本発明に用いる印刷マスクは、その透過体積が３０ｃｍ3/ｍ2〜９０ｃｍ3/ｍ2の範囲である。印刷マスクの透過体積が３０ｃｍ3/ｍ2未満では、上記粘度のレジスト液を用いた場合、所望の厚さを得ることができず、エッチング工程、不要ろう材除去工程の段階でレジスト膜が溶解してしまい、回路表面部に凹凸部が形成される不具合が生じる場合がある。また、印刷マスクの透過体積が９０ｃｍ3/ｍ2超の場合には、レジスト膜自身は印刷できるものの、レジスト膜厚が厚すぎるため、レジスト膜内部で硬化速度、収縮速度に部分的に差が生じるため、割れが生じたり、レジスト液のレベリング効果不足により印刷マスクのマスク線形状に格子状のピットが残存する不具合が生じる場合がある。したがって、用いる印刷マスクの透過体積が３０〜９０ｃｍ3/ｍ2の範囲のものを用いる。さらに好ましい印刷マスクの透過体積は４０ｃｍ3/ｍ2〜７０ｃｍ3/ｍ2である。 In the printing method according to the present invention, since the printing is performed to a thickness of 30 μm or more by only one shot, the transmission volume of the printing mask at the time of printing is particularly important. Therefore, it is necessary to individually adjust the mesh wire diameter, mesh size, and resist solution viscosity of the printing mask to be used. The permeation volume is a space through which the paste can pass in one shot, and is represented by permeation volume = (mesh) 2 / (mesh + wire diameter) 2 xscreen thickness.
Printing mask used in the present invention, the transmission volume in the range of 30cm 3 / m 2 ~90cm 3 / m 2. When the permeation volume of the printing mask is less than 30 cm 3 / m 2 , the desired thickness cannot be obtained when the resist solution having the above viscosity is used, and the resist film is dissolved at the stage of the etching process and unnecessary brazing material removal process. As a result, there may be a problem that irregularities are formed on the circuit surface. In addition, when the transmission volume of the printing mask exceeds 90 cm 3 / m 2 , the resist film itself can be printed, but the resist film thickness is too thick, so there is a partial difference in the curing speed and shrinkage speed inside the resist film. As a result, cracks may occur, and there may be a problem that lattice-like pits remain in the mask line shape of the printing mask due to insufficient leveling effect of the resist solution. Therefore, a printing mask having a transmission volume of 30 to 90 cm 3 / m 2 is used. Further preferred permeation volume of printing masks are 40cm 3 / m 2 ~70cm 3 / m 2.

レジスト膜印刷に用いられる印刷マスクのメッシュ線径は、特に、レジスト膜印刷後のレジスト膜のレベリング性と印刷精度に影響する。
ここでレベリング性とは、印刷後に印刷マスク線クロス部（印刷マスク線が交差した部分）にできるレジスト膜欠乏部をいかに埋めることができるかを示した尺度である。レジスト膜印刷直後は、印刷マスク線クロス部に出来るレジスト膜欠乏部にはレジスト膜が埋まっておらず、印刷マスクが離れた後にこの空間部にレジスト膜が流れ込むことで全体を均一化したレジスト膜となる。
メッシュ線径が太過ぎる場合には、印刷マスク線クロス部の体積が大きくなり、必要なレジスト膜量が多くなるため、上記、空間部を十分に埋めることができなくなり印刷マスク線クロス部のあった部分のレジスト膜表面に窪みが残ることがある。これらの窪みは、レジスト膜が薄いためにエッチング工程、不要ろう材除去工程においてエッチング液、ろう材除去液が選択的にアタックするため、この箇所からレジスト膜溶解が進行し、回路板表面に凹凸が生じる。また、印刷後のレジスト膜端部の直線性も低下する。
一方、メッシュ線径が細過ぎる場合には、レベリング性は問題ないもののマスク自身の厚みがなくなるためレジスト膜を３０μｍ以上の厚さとすることができない。したがって、レジスト膜印刷用マスクのメッシュ線径を５μｍ〜８０μｍとすることが望ましい。好ましいレジスト膜印刷用マスクのメッシュ線径は２０μｍ〜６０μｍである。 The mesh wire diameter of a printing mask used for printing a resist film particularly affects the leveling property and printing accuracy of the resist film after printing the resist film.
Here, the leveling property is a measure showing how a resist film deficient portion that can be formed in a print mask line cross portion (a portion where the print mask lines intersect) after printing can be filled. Immediately after the resist film is printed, the resist film is not filled in the resist film deficient part that can be formed at the crossing part of the print mask line, and the resist film flows into this space part after the print mask is separated, so that the entire resist film is made uniform. It becomes.
If the mesh wire diameter is too large, the volume of the print mask line cross section becomes large and the amount of resist film required increases, so that the above-mentioned space cannot be sufficiently filled and the print mask line cross section is not fully filled. A dent may remain on the surface of the resist film. Since these resist films are thin, the etching solution and brazing material removal solution selectively attack in the etching process and unnecessary brazing material removal process, so that the dissolution of the resist film proceeds from this point, and the circuit board surface is uneven. Occurs. Moreover, the linearity of the resist film edge part after printing also falls.
On the other hand, if the mesh wire diameter is too small, the leveling property is not a problem, but the thickness of the mask itself is lost, so that the resist film cannot be made 30 μm or thicker. Therefore, it is desirable that the mesh wire diameter of the resist film printing mask be 5 μm to 80 μm. The mesh wire diameter of a preferable resist film printing mask is 20 μm to 60 μm.

印刷マスクのメッシュ目開きは、レジスト膜厚さに加えて印刷精度およびＵＶ硬化性に影響する。メッシュ目開きが大きい場合には、レジスト液の透過体積が大きくなるため厚膜化への効果があるが、その一方で、目開きが大きく、また、通常は目開きに応じて太いメッシュ線径であるため、印刷端部の直線部ににじみ現象が生じる。また、ＵＶ硬化時には、目開き部を透過したレジスト同士が再接触する界面において、容易にレベリング性を発揮することができずにレジスト膜厚さに差が生じ、レジスト膜表面は凹凸形状になる。この場合、レジスト液硬化時に収縮挙動の差が生じるためクラック発生の不具合が生じる。一方、目開きが小さい場合には、レジスト液に含有されている主にセラミックス粒子からなる充填剤がメッシュを透過することができず、所望の組成のレジスト膜とすることができなくなることもある。したがって、レジスト膜印刷用マスクの目開きを３０μｍ〜１２０μｍとすることが望ましい。更に好ましいレジスト膜印刷用マスクの目開きは５０μｍ〜１２０μｍである。 The mesh opening of the printing mask affects the printing accuracy and UV curability in addition to the resist film thickness. If the mesh opening is large, the permeation volume of the resist solution is increased, which is effective for increasing the film thickness. On the other hand, the opening is large and the mesh wire diameter is usually large depending on the opening. Therefore, a bleeding phenomenon occurs in the straight line portion at the printing end. Further, at the time of UV curing, the resist film surface becomes uneven because the resist film thickness cannot be easily exhibited at the interface where the resists that have passed through the openings re-contact each other, and the leveling property cannot be easily exhibited. . In this case, since a difference in shrinkage behavior occurs when the resist solution is cured, a problem of crack generation occurs. On the other hand, when the mesh is small, the filler mainly composed of ceramic particles contained in the resist solution cannot pass through the mesh, and may not be a resist film having a desired composition. . Therefore, it is desirable that the opening of the resist film printing mask be 30 μm to 120 μm. A more preferable opening of the resist film printing mask is 50 μm to 120 μm.

（４）レジスト乾燥・硬化工程
所定形状のレジスト膜パターンへの印刷工程後におけるレジスト膜乾燥・硬化方法として、紫外線硬化を用いる場合、紫外線出力を１ｋＷ〜８ｋＷとすることが望ましい。出力が１ｋＷ未満では、レジスト膜硬化不足となり回路板との密着性が維持できない。また、出力が８ｋＷよりも大きくなると、レジスト膜の収縮速度が速くなり、レジスト膜に乾燥クラックが発生する不具合が生ずる。したがって、用いる紫外線硬化装置の照射出力は、１ｋＷ〜８ｋＷとすることが好ましい。さらに２ｋＷ〜５ｋＷとすることが好ましい。
また、紫外線硬化装置内のセラミックス回路基板用素材の搬送速度は２０ｃｍ/ｍｉｎ〜２００ｃｍ／ｍｉｎとすることが望ましい。搬送速度が２０ｃｍ/ｍｉｎ未満では、照射出力が高い場合と同様のレジスト膜に乾燥クラックが発生し、また、２００ｃｍ／ｍｉｎ超では、照射不足となりレジスト膜の硬化が十分でない場合がある。したがって、装置内の搬送速度は２０ｃｍ/ｍｉｎ〜２００ｃｍ／ｍｉｎとすることが好ましい。 (4) Resist drying / curing step When ultraviolet curing is used as a resist film drying / curing method after printing on a resist film pattern having a predetermined shape, it is desirable that the ultraviolet output is 1 kW to 8 kW. If the output is less than 1 kW, the resist film is insufficiently cured and the adhesion to the circuit board cannot be maintained. On the other hand, when the output is larger than 8 kW, the shrinkage rate of the resist film is increased, resulting in a problem that dry cracks are generated in the resist film. Therefore, it is preferable that the irradiation output of the ultraviolet curing device to be used is 1 kW to 8 kW. Furthermore, it is preferable to set it as 2 kW-5 kW.
Moreover, it is desirable that the conveyance speed of the ceramic circuit board material in the ultraviolet curing device is 20 cm / min to 200 cm / min. If the conveyance speed is less than 20 cm / min, dry cracks occur in the resist film as in the case where the irradiation output is high, and if it exceeds 200 cm / min, the irradiation is insufficient and the resist film may not be sufficiently cured. Therefore, it is preferable that the conveyance speed in the apparatus is 20 cm / min to 200 cm / min.

（５）ポストベーク工程
エッチング液、ろう材除去液への薬液耐性を更に向上させる手法として、さらにレジスト硬化工程の紫外線硬化に加えてポストベーク処理を行うと好ましい。この場合、紫外線処理または加熱処理のいずれにおいてもその効果を発現することができる。紫外線硬化法を採用する場合には、紫外線出力を２ｋＷ〜１０ｋＷとすることが望ましい。出力が２ｋＷ未満では、レジスト膜が十分に硬化せずにレジスト膜のエッチング液、ろう材除去液への薬液耐性を維持することができない場合がある。また、出力が１０ｋＷ超となると、レジスト膜が過度に硬化して脆くなりポストベーク処理後の冷却過程においてレジスト膜と金属板との収縮差が生じてレジスト膜が剥離する不具合が生ずる場合がある。したがって、用いる紫外線硬化装置の照射出力は、２ｋＷ以上１０ｋＷ以下とすることが好ましい。さらに３ｋＷ〜５ｋＷとすることが好ましい。
また、装置内の搬送速度は２０ｃｍ/ｍｉｎ〜２００ｃｍ／ｍｉｎとすることが望ましい。装置内の搬送速度が２０ｃｍ/ｍｉｎ未満では、照射出力が高い場合と同様にレジスト膜剥離が生じやすく、また、２００ｃｍ／ｍｉｎ超では、照射不足となりエッチング液、ろう材除去液への薬液耐性を確保できなくなる。したがって、装置内の搬送速度は２０ｃｍ/ｍｉｎ〜２００ｃｍ／ｍｉｎとすることが好ましい。 (5) Post-baking step As a technique for further improving the chemical resistance to the etching solution and the brazing material removing solution, it is preferable to perform a post-baking treatment in addition to the ultraviolet curing in the resist curing step. In this case, the effect can be exhibited in either the ultraviolet treatment or the heat treatment. When the ultraviolet curing method is employed, it is desirable that the ultraviolet output is 2 kW to 10 kW. If the output is less than 2 kW, the resist film may not be sufficiently cured and the chemical solution resistance to the resist film etching solution and brazing material removal solution may not be maintained. When the output exceeds 10 kW, the resist film is excessively hardened and becomes brittle, and there may be a problem that the resist film peels off due to a shrinkage difference between the resist film and the metal plate in the cooling process after the post-baking process. . Therefore, it is preferable that the irradiation output of the ultraviolet curing device to be used is 2 kW or more and 10 kW or less. Furthermore, it is preferable to set it as 3 kW-5 kW.
Further, the conveying speed in the apparatus is desirably 20 cm / min to 200 cm / min. When the conveyance speed in the apparatus is less than 20 cm / min, the resist film is likely to be peeled off similarly to the case where the irradiation output is high, and when it exceeds 200 cm / min, the irradiation is insufficient and the chemical resistance to the etching solution and the brazing material removing solution is reduced. It cannot be secured. Therefore, it is preferable that the conveyance speed in the apparatus is 20 cm / min to 200 cm / min.

また、ポストベーク工程において、加熱硬化法を採用する場合には加熱温度を２００℃〜３００℃、また、保持時間を５分〜３０分とすることが望ましい。加熱温度が２００℃未満、保持時間５分未満では、十分なレジスト膜硬化が達成できない場合がある。また、加熱温度が３００℃超、保持時間３０分超では、レジスト膜が過度に硬化して脆くなり冷却過程においてレジスト膜と金属板との収縮差が生じてレジスト膜が剥離する不具合が生じたり、セラミックス回路基板に曲がりが生じたりする場合がある。したがって、加熱温度を２００℃〜３００℃、保持時間を５分〜３０分とすることが好ましい。さらに好ましくは、２１０℃〜２５０℃である。 In the post-bake process, when a heat curing method is employed, it is desirable that the heating temperature is 200 ° C. to 300 ° C. and the holding time is 5 minutes to 30 minutes. If the heating temperature is less than 200 ° C. and the holding time is less than 5 minutes, sufficient resist film curing may not be achieved. In addition, when the heating temperature is over 300 ° C. and the holding time is over 30 minutes, the resist film is excessively cured and becomes brittle, causing a difference in shrinkage between the resist film and the metal plate during the cooling process, resulting in a problem that the resist film peels off. The ceramic circuit board may be bent. Therefore, it is preferable that the heating temperature is 200 ° C. to 300 ° C. and the holding time is 5 minutes to 30 minutes. More preferably, it is 210 degreeC-250 degreeC.

本発明では、レジスト膜のＵＶによる硬化度合いを測定するための色素調整剤としてフタロシアニンブルーを含有させた紫外性硬化型レジストを用いると好ましい。その場合には、ＵＶによる硬化度合を測定するために分光光度計を用いて青色発光域の波長450ｎｍにおける反射率の範囲を測定すると好ましい。すなわち、ポストベーク処理後におけるレジスト膜表面部の青色発光域の波長450nmにおける反射率が８５％以下となるとレジスト液、不要ろう材除去液に対して十分な耐性を有することから、望ましく、更に好ましくは７５％以下の範囲である。
なお、色素調整剤をフタロシアニングリーンとした場合には、紫外線の吸収の度合いで本来の緑色から段階的に黒色化する。したがってこの場合には、緑色発光域の波長５５０ｎｍにおける反射率の範囲を測定すればよい。 In the present invention, it is preferable to use an ultraviolet curable resist containing phthalocyanine blue as a dye adjusting agent for measuring the degree of curing of the resist film by UV. In that case, in order to measure the degree of curing by UV, it is preferable to measure the reflectance range at a wavelength of 450 nm in the blue emission region using a spectrophotometer. That is, when the reflectance at a wavelength of 450 nm in the blue light emission region of the resist film surface after post-baking is 85% or less, it is desirable and more preferable because it has sufficient resistance to the resist solution and the unnecessary brazing material removing solution. Is in the range of 75% or less.
When the phthalocyanine green is used as the dye adjusting agent, the original green color is gradually blackened according to the degree of absorption of ultraviolet rays. Therefore, in this case, the reflectance range at a wavelength of 550 nm in the green light emission region may be measured.

（６）エッチング工程
次にエッチング液によってレジスト膜が表面に塗布された部分以外の金属板が除去され、回路板表面にはまだレジスト膜が残ったままの金属回路が形成される。エッチング液としては、金属板が銅板又は銅合金板である場合には塩化第２鉄溶液や塩化第２銅溶液が使用される。アルミ板、アルミ合金板の場合にも塩化第２鉄溶液や塩化第２銅溶液が使用されるが、アルミの場合には、銅よりもエッチング速度が速いため、所定の寸法に制御するためには、アルミとの反応速度が緩やかな塩化第２銅溶液が好ましい。 (6) Etching Step Next, the metal plate other than the portion where the resist film is applied to the surface is removed by the etching solution, and a metal circuit with the resist film still remaining is formed on the circuit board surface. As the etching solution, when the metal plate is a copper plate or a copper alloy plate, a ferric chloride solution or a cupric chloride solution is used. In the case of aluminum plates and aluminum alloy plates, ferric chloride solution and cupric chloride solution are also used, but in the case of aluminum, the etching rate is faster than copper, so to control to a predetermined size Is preferably a cupric chloride solution having a slow reaction rate with aluminum.

（７）不要ろう材除去工程
次いで、回路板表面にレジスト膜が残ったままの状態で回路パターン間に存在する不要ろう材をろう材除去液で除去する。 (7) Unnecessary brazing material removing step Next, the unnecessary brazing material present between the circuit patterns is removed with a brazing material removing solution while the resist film remains on the surface of the circuit board.

不要ろう材の除去液は主にフッ素化合物と過酸化水素と水で構成される。フッ素化合物としては、フッ酸及びナトリウム、アンモニウム等のフッ化物があるが、安全性と不要ろう材の除去効果の面からフッ化アンモニウムが好ましい。中でも、水素二フッ化アンモニウムが望ましい。フッ素化合物の濃度としては、１ｗｔ％〜２０ｗｔ％とすることが望ましい。フッ素化合物の濃度が１ｗｔ％よりも小さいと不要ろう材の除去効果が不十分となる場合があり、一方２０ｗｔ％よりも大きいと取扱性と安全性が悪くなり、更には回路パターン部のろう材まで浸食されて必要な接合強度を確保することができなくなる場合がある。特にフッ素化合物の濃度は５ｗｔ％〜１５ｗｔ％が望ましい。 The unnecessary brazing material removal solution is mainly composed of a fluorine compound, hydrogen peroxide and water. Fluorine compounds include fluorides such as hydrofluoric acid, sodium, and ammonium. Ammonium fluoride is preferred in terms of safety and the effect of removing unnecessary brazing material. Of these, ammonium hydrogen fluoride is desirable. The concentration of the fluorine compound is desirably 1 wt% to 20 wt%. If the concentration of the fluorine compound is less than 1 wt%, the removal effect of the unnecessary brazing material may be insufficient. On the other hand, if the concentration is more than 20 wt%, the handleability and safety will deteriorate, and further, the brazing material of the circuit pattern portion will be deteriorated. In some cases, the required bonding strength cannot be ensured. In particular, the concentration of the fluorine compound is desirably 5 wt% to 15 wt%.

過酸化水素は、フッ素化合物による不要ろう材の除去効果を助長させるために使用されるものであり、その濃度としては２ｗｔ％〜４０ｗｔ％が好ましい。２ｗｔ％よりも小さいと上記助長効果が充分でなくなり、また４０ｗｔ％よりも大きいと過酸化水素の分解が激しくなって薬液組成のコントロールが困難となる。 Hydrogen peroxide is used to promote the removal effect of the unnecessary brazing material by the fluorine compound, and the concentration is preferably 2 wt% to 40 wt%. If the amount is less than 2 wt%, the above-mentioned promoting effect is not sufficient, and if it is more than 40 wt%, the decomposition of hydrogen peroxide becomes severe and it becomes difficult to control the chemical composition.

ろう材の薬液による処理温度としては、３０℃〜６０℃が好ましい。３０℃よりも低温では不要ろう材の充分な除去効果は得られず、また６０℃よりも高温であるとろう材除去液中の過酸化水素がレジスト膜と反応して、レジスト膜表面部に気泡が生成し、過度な場合には金属回路板からレジスト膜が剥離してしまい、回路板表面が腐食される不具合が生じる。また、上記、過酸化水素濃度を規定した溶液を用いた場合には、処理時間については３０分〜９０分として、レジスト膜表面への不均一な溶解反応を抑制することが望ましい。不要ろう材除去処理時間が長いと、レジスト厚さが薄い部分が集中的に溶解する不具合が生じやすくなるので、これを抑制する時間が９０分までである。 As processing temperature by the chemical | medical solution of a brazing material, 30 to 60 degreeC is preferable. If the temperature is lower than 30 ° C., a sufficient removal effect of the unnecessary brazing filler metal cannot be obtained. If the temperature is higher than 60 ° C., hydrogen peroxide in the brazing filler metal removal solution reacts with the resist film to form a resist film surface portion. When bubbles are generated and excessive, the resist film is peeled off from the metal circuit board, resulting in a problem that the circuit board surface is corroded. Further, when the above-mentioned solution with a specified hydrogen peroxide concentration is used, it is desirable to suppress the non-uniform dissolution reaction on the resist film surface by setting the treatment time to 30 minutes to 90 minutes. If the unnecessary brazing material removal processing time is long, a problem that the portion where the resist thickness is thin is intensively dissolved is likely to occur, and the time for suppressing this is up to 90 minutes.

（８）ろう材剥離工程
次にＮａＯＨ溶液により金属回路面に残存しているレジスト膜を剥離する。この場合、従来のレジスト膜とは異なり、本発明ではレジスト膜の回路パターン周縁部の厚さを回路パターン中央部の厚さよりも５μｍ以上厚く形成している。そのために、回路パターン周縁部のレジスト膜の薬液耐性が高くなっている。したがって、従来のレジスト膜では、レジスト膜剥離時に、最終仕上げ回路面にエッチング処理時もしくは不要ろう材除去時に回路板表面部が薬液により侵食されたことに起因した凹凸が発生する不具合が生じ、単なる外観不良に留まらずに、極端なはんだ濡れ性劣化が起こっていたのに対し、本発明の場合には、強力なレジスト膜剥離液を用いても、そのような不具合が生じ難い。 (8) Brazing material stripping step Next, the resist film remaining on the metal circuit surface is stripped with an NaOH solution. In this case, unlike the conventional resist film, in the present invention, the thickness of the peripheral portion of the circuit pattern of the resist film is formed to be 5 μm or more thicker than the thickness of the central portion of the circuit pattern. For this reason, the chemical resistance of the resist film at the periphery of the circuit pattern is high. Therefore, in the conventional resist film, when the resist film is peeled off, there is a problem that unevenness is caused due to the erosion of the circuit board surface portion by the chemical solution at the time of etching treatment or unnecessary brazing material removal on the final finished circuit surface. In contrast to the appearance deterioration, the solder wettability has been extremely deteriorated. In the case of the present invention, even when a strong resist film stripping solution is used, such a problem hardly occurs.

本発明では３ｗｔ％〜１０ｗｔ％の濃度のＮａＯＨ水溶液を用い、温度を３０℃〜６０℃として、剥離のための浸漬処理時間を３分〜１５分とすると好ましい。
さらに水洗で２分程度、流水に浸漬・浴動してレジスト膜剥離液の除去を行った。なお、５０℃程度の湯水を用いた場合はその除去効果が高く望ましい。
レジスト膜剥離液のＮａＯＨ濃度が３ｗｔ％未満では、レジスト膜残渣がある場合があり、また、１０ｗｔ％超の高濃度のアルカリ溶液では、レジスト膜剥離は容易にできるものの、その反面、レジスト膜剥離直後の回路板が剥離液に触れるとアルカリ腐食（赤色のアルカリ焼け）が進行して、回路表面に凹凸形状が形成され、Ｈ２ＳＯ４をベースとした酸溶液による処理を施しても所定の面粗さに回復できなくなる場合があった。したがって、ＮａＯＨの濃度は３ｗｔ％〜１０ｗｔ％の水溶液とすることが望ましい。
処理時間が３分未満では、レジスト膜残渣があり、また、１５分超では上記のアルカリ腐食が大きくなる。したがって、レジスト膜剥離のための浸漬処理時間は、３分〜１５分とすることが望ましい。 In the present invention, it is preferable to use an aqueous NaOH solution having a concentration of 3 wt% to 10 wt%, set the temperature to 30 ° C. to 60 ° C., and set the immersion treatment time for peeling to 3 minutes to 15 minutes.
Further, the resist film stripping solution was removed by immersing and bathing in running water for about 2 minutes by washing with water. In addition, when hot water of about 50 ° C. is used, its removal effect is high and desirable.
When the NaOH concentration of the resist film stripping solution is less than 3 wt%, there may be a resist film residue, and with a high concentration alkaline solution exceeding 10 wt%, the resist film can be easily stripped. When the circuit board immediately after that comes into contact with the stripping solution, alkali corrosion (red alkali burning) proceeds to form an uneven shape on the circuit surface. Even if a treatment with an acid solution based on H 2 SO 4 is performed, a predetermined pattern is obtained. In some cases, the surface roughness could not be recovered. Therefore, it is desirable that the NaOH concentration be an aqueous solution of 3 wt% to 10 wt%.
If the treatment time is less than 3 minutes, there is a resist film residue, and if it exceeds 15 minutes, the above alkali corrosion becomes large. Therefore, it is desirable that the immersion treatment time for removing the resist film is 3 minutes to 15 minutes.

次に、必要に応じて、セラミックス回路基板を構成する回路パターンの表面にニッケルめっきを施す。この処理は、例えば、上記プロセスを経たセラミックス回路基板を、所定温度（例えば、８５℃）を有する無電解ニッケルめっき液中に所定時間（例えば、２０分〜３０分）浸漬して行う。無電解ニッケルめっき液は、ニッケル（Ｎｉ）を主成分としてリン（Ｐ）あるいはボロン（B）等を含有し、リン（Ｐ）の濃度は、例えば、３ｗｔ％〜１１ｗｔ％である。無電解ニッケルめっき液は、リン（Ｐ）の濃度が３ｗｔ％であるものが低リン（Ｐ）タイプ、リン（Ｐ）の濃度が６ｗｔ％〜８ｗｔ％であるものが中リン（Ｐ）タイプ、リン（Ｐ）の濃度が１１ｗｔ％であるものが高リン（Ｐ）タイプとそれぞれ呼ばれている。本発明の実施の形態では、これら何れのタイプの無電解ニッケルめっき液も利用することができる。   Next, if necessary, nickel plating is applied to the surface of the circuit pattern constituting the ceramic circuit board. This treatment is performed, for example, by immersing the ceramic circuit board that has undergone the above process in an electroless nickel plating solution having a predetermined temperature (for example, 85 ° C.) for a predetermined time (for example, 20 to 30 minutes). The electroless nickel plating solution contains nickel (Ni) as a main component and contains phosphorus (P), boron (B), or the like, and the concentration of phosphorus (P) is, for example, 3 wt% to 11 wt%. The electroless nickel plating solution has a low phosphorus (P) type with a phosphorus (P) concentration of 3 wt%, a medium phosphorus (P) type with a phosphorus (P) concentration of 6 wt% to 8 wt%, Those having a phosphorus (P) concentration of 11 wt% are called high phosphorus (P) types, respectively. In the embodiment of the present invention, any of these types of electroless nickel plating solutions can be used.

また、めっきを省略して防錆処理膜のみとする場合もある。この防錆処理膜は、例えば、有機防錆剤であるベンゾトリアゾール系防錆剤をＩＰＡ（イソプロピルアルコール）に溶かした０．５ｗｔ％〜５ｗｔ％溶液を用いて酸溶液処理後のセラミックス回路基板表面部に塗布する。この技術によれば、以下の問題点が解決できる特徴を有する。すなわち、上記の酸溶液処理と無電解Ｎｉ−Ｐめっきを用いた方法で製造されたセラミックス回路基板上に鉛レスのはんだ層を形成すると、回路板表面のめっき層に含まれるＰ（隣）成分と、鉛レスはんだ層とが反応を起こし脆性層が生成される場合がある。これにより、はんだ層が脆くなり半導体モジュールの信頼性が低下するという問題がある。さらに、無電解Ｎｉ−Ｐめっきの工程を行う場合には、このめっき工程だけでなく、めっき前の脱脂、酸化スケール除去および硫酸パラジュウムあるいは塩化パラジュウム溶液などの触媒付与処理、さらに、セラミックス部分の残留パラジュウムの除去処理等、めっき後にはめっき液を洗浄除去する工程等、これに付随して多数の工程も必要になるため、セラミックス回路基板製造コストが上昇するという問題もある。   In some cases, the plating is omitted and only the anticorrosive film is used. This rust-proofing film is, for example, the surface of a ceramic circuit board after acid solution treatment using a 0.5 wt% to 5 wt% solution in which benzotriazole rust preventive agent, which is an organic rust preventive agent, is dissolved in IPA (isopropyl alcohol). Apply to the part. According to this technique, the following problems can be solved. That is, when a lead-less solder layer is formed on a ceramic circuit board manufactured by the above method using acid solution treatment and electroless Ni-P plating, the P (adjacent) component contained in the plating layer on the circuit board surface In some cases, the leadless solder layer reacts to generate a brittle layer. Thereby, there exists a problem that a solder layer becomes weak and the reliability of a semiconductor module falls. Furthermore, when performing an electroless Ni—P plating process, not only this plating process, but also degreasing, plating scale removal and catalyst application treatment such as palladium sulfate or palladium chloride solution before plating, and residual ceramic parts There are also problems that the manufacturing cost of the ceramic circuit board is increased because a number of processes such as a process of removing palladium after the plating, such as a process of removing palladium, etc. are necessary.

（実施例１）
以下、本発明の実施例について説明する。ただし、これら実施例により本発明が限定されるものではない。 Example 1
Examples of the present invention will be described below. However, the present invention is not limited to these examples.

［実施例１］
幅６０ｍｍ×長さ５０ｍｍ×厚さ０．３２ｍｍサイズの窒化珪素製セラミックス基板に対して、スクリーン印刷法により７７ｗｔ％Ａｇ−１５ｗｔ%Ｃｕ−５ｗｔ%Ｉｎ−３ｗｔ％Ｔｉからなるろう材を回路板側では、２８ｍｍ×４８ｍｍの２箇所、放熱板側では、５９ｍｍ×４９ｍｍの１箇所厚さ３０μｍに塗布し、その両側に幅６０ｍｍ×長さ５０ｍｍ×厚さ０．５ｍｍのＣｕ板を配置し、真空炉中において８２０℃で１時間保持し、セラミックス基板とＣｕ板をろう付けした接合体を得た。 [Example 1]
A ceramic substrate made of silicon nitride having a size of width 60 mm × length 50 mm × thickness 0.32 mm is coated with a brazing material made of 77 wt% Ag-15 wt% Cu-5 wt% In-3 wt% Ti by the screen printing method on the circuit board side. Then, two places of 28mm x 48mm, on the heat sink side, 59mm x 49mm, one place 30μm thick, and Cu plates of width 60mm x length 50mm x thickness 0.5mm are placed on both sides, vacuum It was kept at 820 ° C. for 1 hour in a furnace to obtain a joined body in which the ceramic substrate and the Cu plate were brazed.

続いて、表１に示すように印刷マスク、印刷条件を調整することにより、所望の形状の回路パターンに表２に示すように共重合系アクリレート・オリゴマーとアクリル酸エステル・モノマーを併せて６０ｗｔ％混合し、残部が色素調整剤：０．５ｗｔ％、光重合開始材：１ｗｔ％、消泡・レベリング剤：０．５ｗｔ％および残部が平均１次粒子径が５μｍのタルクMg3H2(SiO3)4を１２ｗｔ％、平均１次粒子径が５μｍの硫酸バリウム（ＢａＳＯ４）を２３ｗｔ％および平均１次粒子径が５ｎｍのシリカ（ＳｉＯ２）を３重量％含む充填剤よりなるレジスト液A〜Kの紫外線硬化アルカリ剥離型レジストをスクリーン印刷により所定の厚さに塗布し、紫外線照射装置中を紫外線出力を２ｋＷ、セラミックス回路基板用素材の搬送速度を１００ｃｍ/ｍｉｎで移動させ、レジスト膜を乾燥・硬化させた。 Subsequently, by adjusting the printing mask and printing conditions as shown in Table 1, 60 wt% of the copolymerized acrylate / oligomer and acrylate ester / monomer are combined into a circuit pattern having a desired shape as shown in Table 2. Mix, the balance being a dye adjusting agent: 0.5 wt%, a photopolymerization initiator: 1 wt%, a defoaming / leveling agent: 0.5 wt%, and the balance being an average primary particle diameter of 5 μm talc Mg 3 H 2 (SiO 3 ) Resist solution A comprising a filler containing 12 wt% of 4 and 23 wt% of barium sulfate (BaSO 4 ) having an average primary particle diameter of 5 μm and 3 wt% of silica (SiO 2 ) having an average primary particle diameter of 5 nm. ~ K UV curable alkali-peeling resist is applied to a predetermined thickness by screen printing, UV output is 2 kW in the UV irradiation device, and the conveyance speed of the ceramic circuit board material is 100c. / Is moved in min, and the resist film is dried and cured.

また、レジスト膜印刷・硬化後の表面部の形状および厚さの評価は、３次元形状評価装置（キーエンス社製：ＬＴ−８１００）を用いて行った。図４にその評価例を示す。(実施例Ｎｏ．３４)
レジスト膜中央部の平均厚さは３次元測定によるレジスト凹凸形状の凹部とCu表面の距離を示している。
また、レジスト膜周縁部の最大高さは３次元測定によるレジスト凹凸形状の最大凸部とCu表面の距離を示している。
また、レジスト膜剥離および気泡の有無について５倍の拡大鏡を用いて目視にて評価した。さらに、表1に示す条件で紫外線照射装置によりポストベークを加えることで、レジスト膜の重合化により硬化を促進させた。ポストベーク処理後のレジスト膜の反射率、レジスト印刷精度を評価した。
レジスト表面反射率（％）は日本分光製 分光光度計 V630を用い、450nmの表面反射率を測定した。
レジスト表面の色調変化について、測定波長範囲：350ｎｍから550nmまでの反射率を測定して、
450nmにおける反射率を評価した。
レジスト印刷精度は、レジスト印刷の直線性を示し、評価長さ２ｍｍにおける寸法のばらつきが±５０μｍ以内を○、それ以上を×とした。 In addition, the evaluation of the shape and thickness of the surface portion after printing and curing of the resist film was performed using a three-dimensional shape evaluation apparatus (manufactured by Keyence Corporation: LT-8100). FIG. 4 shows an example of the evaluation. (Example No. 34)
The average thickness at the center of the resist film indicates the distance between the concave portion of the concave and convex shape of the resist and the Cu surface by three-dimensional measurement.
Further, the maximum height of the peripheral edge of the resist film indicates the distance between the maximum convex portion of the resist concave-convex shape and the Cu surface by three-dimensional measurement.
Further, the resist film peeling and the presence or absence of bubbles were visually evaluated using a 5 × magnifier. Further, post-baking was performed with an ultraviolet irradiation device under the conditions shown in Table 1, thereby promoting curing by polymerization of the resist film. The reflectance and resist printing accuracy of the resist film after the post-baking treatment were evaluated.
The resist surface reflectance (%) was measured at 450 nm using a spectrophotometer V630 manufactured by JASCO Corporation.
For the color change of the resist surface, measure the reflectance in the measurement wavelength range: 350nm to 550nm,
The reflectance at 450 nm was evaluated.
The resist printing accuracy indicates the linearity of resist printing, and a dimensional variation within an evaluation length of 2 mm is indicated by ◯, and a value exceeding that is indicated by ×.

次に、７７ｗｔ％塩化第２鉄溶液、３ｗｔ%塩酸からなるエッチング液により銅板の不要部分を除去して回路パターンを形成した。続いて、この回路パターン間や基板の縁面の不要なろう材を除去するため、Ｈ２ＳＯ４水溶液に３０℃で２分間浸漬した後、５ｗｔ％水素二フッ化アンモニウムと３０ｗｔ％過酸化水素水（３５ｗ／ｗ％）および1ｗｔ％Ｈ２ＳＯ４の混合溶液に、液温４５℃で６０分間浸漬して不要ろう材を除去処理を行った。また、レジスト膜剥離および気泡の有無について５倍の拡大鏡を用いて、気泡の有無は、レジスト表面の円形状の盛り上がりが有無を、レジスト剥離については、特に、レジストの青色から白色化するので、その有無で目視にて評価した。 Next, unnecessary portions of the copper plate were removed with an etchant composed of 77 wt% ferric chloride solution and 3 wt% hydrochloric acid to form a circuit pattern. Subsequently, in order to remove unnecessary brazing material between the circuit patterns and the edge of the substrate, the substrate is immersed in an aqueous H 2 SO 4 solution at 30 ° C. for 2 minutes, and then 5 wt% ammonium difluoride and 30 wt% hydrogen peroxide. The unnecessary brazing material was removed by immersing in a mixed solution of water (35 w / w%) and 1 wt% H 2 SO 4 at a liquid temperature of 45 ° C. for 60 minutes. In addition, using a magnifying glass 5 times for resist film peeling and the presence or absence of bubbles, the presence or absence of bubbles indicates the presence or absence of a circular bulge on the resist surface, and the resist peeling particularly whites from the blue color of the resist. The presence or absence was visually evaluated.

続いて、３ｗｔ％ＮａＯＨ溶液を用いてレジスト膜を剥離した。また、回路板周縁部の凹凸の有無について５倍の拡大鏡を用いて目視にて評価した。回路板周辺部が、ろう材除去液に侵されると、周辺部の凹凸が形成され、その部分が赤褐色に変色する。この変色度合いを観察することにより、回路周縁部の凹凸の有無を判断しています。 Subsequently, the resist film was removed using a 3 wt% NaOH solution. Moreover, the presence or absence of the unevenness | corrugation of a circuit board peripheral part was visually evaluated using the 5 times magnifier. When the peripheral portion of the circuit board is attacked by the brazing material removing liquid, irregularities in the peripheral portion are formed, and the portion changes color to reddish brown. By observing the degree of discoloration, the presence or absence of irregularities on the circuit periphery is judged.

Figure 2013084822
Figure 2013084822

Figure 2013084822
Figure 2013084822

以下、表１に本発明の実施例と比較例を示す。
先ず、表１の実施例Ｎｏ.１〜３３より以下の知見が得られた。
Ｎｏ．１〜１２は、印刷マスクの目開きを変更することで透過体積を所定の範囲に制御した場合の、Ｎｏ．１３〜１８は、用いるレジスト液の粘度を変更することで、また、Ｎｏ．１９〜２４は、印刷速度を変更することで、さらに、Ｎｏ．２５〜３３は、印刷マスクのメッシュ線径を変更することで透過体積を所定の範囲に制御した場合の、それぞれ、紫外線乾燥・硬化後のレジスト厚さおよびレジストの割れ、格子状ピットの有無を評価した。さらに、ポストベーク処理後の反射率、レジスト印刷精度、ろう剤除去耐性、回路板表面での凹部の有無を評価した。
本発明では、用いるレジスト液の粘性を５Ｐａ・ｓ〜３０Ｐａ・ｓ、印刷速度を１００ｍｍ／ｓｅｃ〜３００ｍｍ／ｓｅｃ、印刷マスクの透過体積を３０ｃｍ3/ｍ2〜９０ｃｍ3/ｍ2とすることで、ＵＶ乾燥・硬化後のレジスト膜の回路パターン中央部の平均厚さを３０μｍ〜６０μｍとするとともに回路パターン周縁部の最大厚さを回路パターン中央部の平均厚さよりも５μｍ以上厚く形成することでき、これにより、レジスト液のレベリング効果不足により格子状のピットが残存したり、紫外線乾燥・硬化処理の段階で割れるといった不具合が解消される。また、レジスト印刷精度に優れるため、高精度に回路パターン寸法が得られる。さらにエッチング液、不要ろう材除去液への耐性を向上させることが出来たため、特に回路板周縁部表面に凹凸の無いセラミックス回路基板を得ることが出来た。 Table 1 below shows examples of the present invention and comparative examples.
First, the following knowledge was obtained from Example Nos. 1-33 in Table 1.
No. Nos. 1 to 12 show No. 1 when the transmission volume is controlled within a predetermined range by changing the mesh of the printing mask. Nos. 13 to 18 are obtained by changing the viscosity of the resist solution to be used. Nos. 19 to 24 change the printing speed. 25 to 33, when the transmission volume is controlled to a predetermined range by changing the mesh wire diameter of the printing mask, the resist thickness after UV drying / curing and the presence of cracks or lattice pits in the resist, respectively. evaluated. Furthermore, the reflectance after the post-baking treatment, the resist printing accuracy, the brazing agent removal resistance, and the presence or absence of recesses on the circuit board surface were evaluated.
In the present invention, by a 30cm 3 / m 2 ~90cm 3 / m 2 viscous 5Pa · s~30Pa · s of the resist solution, a 100mm / sec~300mm / sec print speed, the transmission volume of the printing mask used The average thickness of the circuit pattern central portion of the resist film after UV drying / curing can be made 30 μm to 60 μm and the maximum thickness of the peripheral edge of the circuit pattern can be made 5 μm or more thicker than the average thickness of the circuit pattern central portion. As a result, problems such as lattice-like pits remaining due to insufficient leveling effect of the resist solution and cracking at the stage of ultraviolet drying / curing treatment are eliminated. Further, since the resist printing accuracy is excellent, the circuit pattern dimensions can be obtained with high accuracy. Furthermore, since the resistance to the etching solution and the unnecessary brazing material removing solution could be improved, a ceramic circuit board having no irregularities on the peripheral surface of the circuit board could be obtained.

（比較例）
用いたレジスト、無酸素銅と窒化珪素基板からなる接合体は、上記実施例と同様に行い、表１に示す試料１０１および１０２は、レジスト粘性の異なるレジスト液を用い、ＵＶ乾燥・硬化後のレジスト厚さを変更した。
また、試料１０３、１０４および１０７は、レジスト塗布の印刷速度を変更させた。
また、試料１０５、１０６および１０８は、印刷マスクの透過体積を変更した。 (Comparative example)
The resist and the joined body made of oxygen-free copper and silicon nitride substrate were used in the same manner as in the above example. Samples 101 and 102 shown in Table 1 used resist solutions having different resist viscosities, and were subjected to UV drying and curing. The resist thickness was changed.
Samples 103, 104, and 107 were changed in the resist coating printing speed.
Samples 105, 106, and 108 were changed in the transmission volume of the printing mask.

Ｎｏ.１０１は、粘度が５Ｐａ．ｓ未満のレジスト液を用いた場合であり、所望のレジスト厚さが得られない。このため、不要ろう材除去工程においてレジスト剥離、気泡が生じ、回路板表面部に凹凸部が形成され、回路板表面部が白濁する外観不良が生じた。 No. 101 has a viscosity of 5 Pa.s. This is a case where a resist solution of less than s is used, and a desired resist thickness cannot be obtained. For this reason, resist peeling and air bubbles were generated in the unnecessary brazing material removing step, irregularities were formed on the surface portion of the circuit board, and an appearance defect in which the surface portion of the circuit board became cloudy occurred.

Ｎｏ.１０２は、粘度が３０Ｐａ．ｓ超のレジスト液を用いた場合であり、レジストの流動性が悪く、ＵＶ乾燥・硬化後に格子状のピットが形成する。このため、不要ろう材除去工程においてレジスト気泡が生じ、回路板表面部に凹凸部が形成され、回路板表面部が白濁する外観不良が生じた。また、レジスト印刷精度にばらつきが生じ、これにより製品の回路パターン寸法精度が低下した。 No. 102 has a viscosity of 30 Pa.s. This is a case where a resist solution exceeding s is used, and the fluidity of the resist is poor, and lattice-like pits are formed after UV drying / curing. For this reason, resist bubbles were generated in the unnecessary brazing material removing step, and irregularities were formed on the circuit board surface portion, resulting in an appearance defect in which the circuit board surface portion became cloudy. In addition, variations in resist printing accuracy occurred, which lowered the circuit pattern dimension accuracy of the product.

Ｎｏ.１０３は、印刷速度が１００ｍｍ／ｓｅｃ未満であり、この場合には、レジスト粘性挙動に影響され、レジスト印刷精度にばらつきが生じ、これにより製品の回路パターン寸法精度が低下したために製品として使用できない。 No. 103 has a printing speed of less than 100 mm / sec. In this case, it is affected by the resist viscosity behavior, resulting in variations in resist printing accuracy, thereby reducing the circuit pattern dimensional accuracy of the product and using it as a product. Can not.

Ｎｏ.１０４は、印刷速度が３００ｍｍ／ｓｅｃ超であり、この場合にも、レジスト粘性挙動に影響され、特に、印刷方向へのレジスト印刷精度にばらつきが生じ、これにより製品の回路パターン寸法精度が低下したために製品として使用できない。 No. 104 has a printing speed of more than 300 mm / sec. In this case as well, it is affected by the resist viscosity behavior, and in particular, the resist printing accuracy in the printing direction varies, which increases the circuit pattern dimensional accuracy of the product. Cannot be used as a product due to a drop.

Ｎｏ.１０５は、用いる印刷マスクの透過体積を３０ｃｍ3/ｍ2未満とした場合であり、これによりレジスト厚さが回路パターン中央部で２７μｍ、回路パターン周縁部で２９μｍと薄く、不要ろう材除去工程においてレジスト剥離、気泡が生じ、回路板表面部に凹凸部が形成され、回路板表面部が白濁する外観不良が生じた。 No. 105 is the case where the transmission volume of the printing mask to be used is less than 30 cm 3 / m 2. As a result, the resist thickness is as thin as 27 μm at the center of the circuit pattern and 29 μm at the periphery of the circuit pattern, and unnecessary brazing material is removed. In the process, resist peeling and air bubbles occurred, irregularities were formed on the circuit board surface portion, and the appearance defect that the circuit board surface portion became cloudy occurred.

Ｎｏ.１０６は、用いる印刷マスクの透過体積を９０ｃｍ3/ｍ2超とした場合であり、これによりレジスト厚さが回路パターン中央部で７５μｍ、回路パターン周縁部で７９μｍと厚く、紫外線硬化処理の段階でレジスト割れが発生し、また、これに加えてレジストペーストのレベリング効果不足による格子状のピットが残存する不具合が生じた。さらに、不要ろう材除去工程において、レジスト割れおよびピット部からろう材除去液が侵入してレジスト剥離が生じた。これにより、回路板表面部に凹凸部が形成され回路板表面部が白濁する外観不良が生じた。 No. 106 is a case where the transmission volume of the printing mask to be used is more than 90 cm 3 / m 2 , so that the resist thickness is as thick as 75 μm at the center of the circuit pattern and 79 μm at the periphery of the circuit pattern. Resist cracking occurred at this stage, and in addition to this, there was a problem that lattice-like pits remained due to insufficient leveling effect of the resist paste. Furthermore, in the unnecessary brazing material removing step, the resist cracking occurred and the brazing material removing solution entered from the pits, resulting in resist peeling. Thereby, the appearance defect that the uneven part was formed in the circuit board surface part and the circuit board surface part became cloudy occurred.

Ｎｏ.１０７は、粘度が３０Ｐａ．ｓと高めのレジスト液を用いた場合であり、印刷速度が１００ｍｍ／ｓｅｃ未満であり、これによりレジスト厚さが回路パターン中央部で４５μｍ、回路パターン周縁部で４８μｍと中央部と周縁部とで所望の差を得ることが出来ず、不要ろう材除去工程において周縁部にレジスト剥離が生じ、回路板周縁部表面に凹凸部が形成される不具合が生じた。 No. 107 has a viscosity of 30 Pa. s and a higher resist solution are used, and the printing speed is less than 100 mm / sec. Thereby, the resist thickness is 45 μm at the circuit pattern central part, 48 μm at the circuit pattern peripheral part, and at the central part and peripheral part. A desired difference could not be obtained, and in the unnecessary brazing material removing step, resist peeling occurred at the peripheral portion, resulting in a problem that uneven portions were formed on the peripheral surface of the circuit board.

Ｎｏ.１０８は、用いる印刷マスクの透過体積を３０ｃｍ3/ｍ2未満とした場合であり、これによりレジスト厚さが回路パターン中央部で２６μｍ、回路パターン周縁部で３３μｍと中央部と周縁部とで所望の差を得ることが出来ず、不要ろう材除去工程において回路パターン周縁部にレジスト剥離が生じ、回路板周縁部表面に凹凸部が形成される不具合が生じた。 No. 108 is a case where the transmission volume of the printing mask to be used is less than 30 cm 3 / m 2 , whereby the resist thickness is 26 μm at the circuit pattern central part, 33 μm at the circuit pattern peripheral part, and the central part and peripheral part. Thus, a desired difference could not be obtained, and in the unnecessary brazing material removing step, resist peeling occurred at the peripheral portion of the circuit pattern, and a problem was caused in that an uneven portion was formed on the surface of the peripheral portion of the circuit board.

１.セラミックス基板
２.ろう材
３.金属板
４.レジスト
５.レジスト回路パターン周縁部
６．レジスト膜の端部
７．レジスト膜の回路パターン周縁部の最大厚さ部
Ｔ１. レジスト回路パターン中央部高さ
Ｔ２．レジスト回路パターン周縁部高さ
1. Ceramic substrate 2. Brazing material 3. Metal plate 4. Resist 5. Resist circuit pattern peripheral edge 6. 6. Edge of resist film Maximum thickness portion T1 of the peripheral portion of the circuit pattern of the resist film. Height of the central portion of the resist circuit pattern T2. Resist circuit pattern peripheral edge height

本発明の実施の形態に係る断面模式図。The cross-sectional schematic diagram which concerns on embodiment of this invention. 本発明の実施の形態に係る断面模式拡大図。The cross-sectional model enlarged view which concerns on embodiment of this invention. 本発明の実施の形態に係る製造フロー図。The manufacturing flowchart which concerns on embodiment of this invention. 本発明の実施の形態に係るレジスト膜の形状測定結果を示す図。The figure which shows the shape measurement result of the resist film which concerns on embodiment of this invention.

Claims (6)

セラミックス基板上に形成された回路板を含んだ回路基板を形成するためのセラミックス回路基板用素材であって、前記回路板を所望の回路パターンに形成する際に、印刷マスクを用いて金属板上に塗布されたエッチングレジスト膜の硬化後の回路パターン中央部の平均厚さを３０μｍ〜６０μｍとするとともに回路パターン周縁部の最大厚さを回路パターン中央部の平均厚さよりも５μｍ以上厚く形成したことを特徴とするセラミックス回路基板用素材。   A ceramic circuit board material for forming a circuit board including a circuit board formed on a ceramic board, wherein the circuit board is formed on a metal plate using a printing mask when forming the circuit board into a desired circuit pattern. The average thickness of the center portion of the circuit pattern after curing of the etching resist film applied to the substrate is 30 μm to 60 μm, and the maximum thickness of the peripheral portion of the circuit pattern is 5 μm or more thicker than the average thickness of the center portion of the circuit pattern. A ceramic circuit board material characterized by 前記エッチングレジスト膜の回路パターン周縁部の最大厚さを回路パターン中央部の平均厚さよりも５μｍ〜５０μｍ厚くしたことを特徴とする請求項1に記載のセラミックス回路基板用素材。   2. The ceramic circuit board material according to claim 1, wherein the maximum thickness of the peripheral edge portion of the circuit pattern of the etching resist film is 5 μm to 50 μm thicker than the average thickness of the central portion of the circuit pattern. 前記エッチングレジスト膜の回路パターン周縁部の厚さを４０μｍ〜８０μｍとしたことを特徴とする請求項１又は請求項２に記載のセラミックス回路基板用素材。   3. The ceramic circuit board material according to claim 1, wherein a thickness of a peripheral portion of the circuit pattern of the etching resist film is set to 40 μm to 80 μm. セラミックス基板と金属板とを接合する工程、前記金属板にエッチングレジストを所望形状の回路パターンに印刷する工程、エッチングレジストを硬化する工程、前記金属板の不要部分を除去するエッチング工程、エッチングレジストを保持したまま不要ろう材を除去する工程、エッチングレジストを剥離する工程を順に行うセラミックス回路基板の製造方法において、前記金属板にエッチングレジストを所望形状の回路パターンに印刷する際に、回転型粘度計を用いて温度：２５℃で測定した回転速度１００rpmにおける粘度が５Ｐａ・ｓ〜３０Ｐａ・ｓであるエッチングレジスト液を透過体積３０ｃｍ3/ｍ2〜９０ｃｍ3/ｍ2のエッチングレジスト印刷用マスクを用いて、スキージ速度を１００ｍｍ/sec〜３００mm/secで印刷することを特徴とするセラミックス回路基板の製造方法。 A step of bonding a ceramic substrate and a metal plate, a step of printing an etching resist on the metal plate in a circuit pattern of a desired shape, a step of curing the etching resist, an etching step of removing unnecessary portions of the metal plate, an etching resist In the method for manufacturing a ceramic circuit board, in which a step of removing an unnecessary brazing material while being held and a step of removing an etching resist are sequentially performed, when the etching resist is printed on a circuit pattern of a desired shape on the metal plate, a rotary viscometer with temperature using an etching resist printing mask of the transmission volume 30cm 3 / m 2 ~90cm 3 / m 2 an etching resist solution viscosity at speed 100rpm is 5Pa · s~30Pa · s measured at 25 ° C. And printing at a squeegee speed of 100 mm / sec to 300 mm / sec. Ceramic circuit substrate manufacturing method of. 前記金属板にエッチングレジストを所望形状の回路パターンに印刷する際に用いるエッチングレジスト印刷用マスクのメッシュ線径を５μｍ〜８０μｍとすることを特徴とする請求項４に記載のセラミックス回路基板の製造方法。 5. The method of manufacturing a ceramic circuit board according to claim 4, wherein a mesh wire diameter of an etching resist printing mask used when printing an etching resist on the metal plate in a circuit pattern having a desired shape is 5 μm to 80 μm. . 前記金属板にエッチングレジストを所望形状の回路パターンに印刷する際に用いるエッチングレジスト印刷用マスクの目開きを３０μｍ〜１５０μｍとすることを特徴とする請求項４又は請求項５に記載のセラミックス回路基板の製造方法。
6. The ceramic circuit board according to claim 4, wherein an opening of an etching resist printing mask used when printing an etching resist on the metal plate in a circuit pattern having a desired shape is set to 30 μm to 150 μm. Manufacturing method.
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JP7370421B2 (en) 2020-05-01 2023-10-27 マクセル株式会社 3D molded circuit parts
JP2022126684A (en) * 2020-05-01 2022-08-30 マクセル株式会社 Three-dimensional molding circuit component

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