JP2014181346A - Method of producing metal-ceramic circuit board - Google Patents
Method of producing metal-ceramic circuit board Download PDFInfo
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- JP2014181346A JP2014181346A JP2013054595A JP2013054595A JP2014181346A JP 2014181346 A JP2014181346 A JP 2014181346A JP 2013054595 A JP2013054595 A JP 2013054595A JP 2013054595 A JP2013054595 A JP 2013054595A JP 2014181346 A JP2014181346 A JP 2014181346A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 28
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 30
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012964 benzotriazole Substances 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000011630 iodine Substances 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229910000679 solder Inorganic materials 0.000 abstract description 26
- 230000002265 prevention Effects 0.000 abstract description 18
- 239000000243 solution Substances 0.000 abstract description 17
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- 238000005476 soldering Methods 0.000 description 11
- 230000003449 preventive effect Effects 0.000 description 9
- 239000012086 standard solution Substances 0.000 description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005219 brazing Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- DQAXFLUHYIOXJB-UHFFFAOYSA-N ICl.CC(O)=O Chemical compound ICl.CC(O)=O DQAXFLUHYIOXJB-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- FBOZXECLQNJBKD-ZDUSSCGKSA-N L-methotrexate Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 FBOZXECLQNJBKD-ZDUSSCGKSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Landscapes
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- ing And Chemical Polishing (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、金属−セラミックス回路基板の製造方法に関し、特に、金属回路板がセラミックス基板に接合した金属−セラミックス回路基板の製造方法に関する。 The present invention relates to a method for manufacturing a metal-ceramic circuit board, and more particularly, to a method for manufacturing a metal-ceramic circuit board in which a metal circuit board is bonded to a ceramic substrate.
近年、パワーモジュールなどに使用する回路基板として、銅回路板がセラミックス基板上に直接またはろう材を介して接合した金属−セラミックス回路基板が使用されている。また、このような金属−セラミックス回路基板の回路パターンとなる銅回路板の表面の変色を防止するとともに、半田付け工程における半田濡れ性や、耐腐食性や耐熱性などの耐候性を向上させるために、Ｎｉ、Ａｕまたはこれらの合金などのめっきや防錆処理が行われている。 In recent years, a metal-ceramic circuit board in which a copper circuit board is joined to a ceramic board directly or via a brazing material is used as a circuit board used for a power module or the like. In addition, to prevent discoloration of the surface of the copper circuit board that becomes the circuit pattern of such a metal-ceramic circuit board, and to improve the weather resistance such as solder wettability, corrosion resistance and heat resistance in the soldering process In addition, Ni, Au, or an alloy thereof is plated or rust-proofed.
このような回路基板の防錆処理として、回路基板の一方の面に形成された金属回路と他方の面に形成された金属放熱板を化学研磨して表面粗さＲａを０．１〜１．０μｍ（またはＲｍａｘを１．０〜５．０μｍ）にした後に、金属回路と金属放熱板にめっきを施さずにベンゾトリアゾール（ＢＴＡ）系の防錆剤を付与して厚さ０．０５〜１０μｍの防錆層を形成し、金属回路間の基板表面に残留する防錆剤を有機溶剤で洗浄して除去する方法が提案されている（例えば、特許文献１参照）。 As a rust-proofing treatment for such a circuit board, the metal circuit formed on one surface of the circuit board and the metal heat sink formed on the other surface are chemically polished to have a surface roughness Ra of 0.1 to 1. After 0 μm (or Rmax is 1.0 to 5.0 μm), a benzotriazole (BTA) -based rust preventive agent is applied without plating the metal circuit and the metal heatsink, and the thickness is 0.05 to 10 μm. There has been proposed a method in which a rust preventive layer is formed and the rust preventive remaining on the substrate surface between metal circuits is removed by washing with an organic solvent (for example, see Patent Document 1).
また、ベンゾトリアゾール（ＢＴＡ）系の防錆剤を使用しない防錆処理として、リードフレームの表面に非ベンゾトリアゾール（非ＢＴＡ）系の防錆剤を塗布した後、ダイボンディングとワイヤボンディングを行う方法が提案されている（例えば、特許文献２参照）。この方法で使用する非ＢＴＡ系の防錆剤は、ＢＴＡ系の防錆剤のように耐熱温度が高い防錆層を形成することなく、（ワイヤボンディングの際の温度より低い）２５０℃前後の低温で完全に分解する防錆被膜を形成する。そのため、この方法では、ワイヤボンディングの際に防錆被膜が分解して残留物を生成しないので、リードフレームの素地が露出して、信頼性の高いワイヤボンディングが可能になる。 Also, as a rust prevention treatment that does not use a benzotriazole (BTA) rust inhibitor, a method of performing die bonding and wire bonding after applying a non-benzotriazole (non BTA) rust inhibitor to the surface of the lead frame Has been proposed (see, for example, Patent Document 2). The non-BTA rust preventive agent used in this method does not form a rust preventive layer having a high heat resistance temperature like the BTA rust preventive agent, and is around 250 ° C. (lower than the temperature at the time of wire bonding). Forms a rust-proof coating that decomposes completely at low temperatures. Therefore, in this method, since the rust preventive film is not decomposed and a residue is not generated at the time of wire bonding, the lead frame substrate is exposed, and highly reliable wire bonding becomes possible.
さらに、有機溶剤を使用しない洗浄方法として、銅ベース板とダイレクトボンディングカッパー基板（ＤＢＣ）基板との間に半田付けされる領域のみをプラズマ照射により洗浄する方法が提案されている（例えば、特許文献３参照）。 Furthermore, as a cleaning method that does not use an organic solvent, there has been proposed a method in which only a region to be soldered between a copper base plate and a direct bonding copper substrate (DBC) substrate is cleaned by plasma irradiation (for example, Patent Documents). 3).
しかし、銅回路板がセラミックス基板上に接合した金属−セラミックス回路基板では、（めっきを施さずに）防錆処理した銅回路板の表面に半導体チップなどの電子部品を半田付けする際に、短時間で半田付け温度まで昇温させると、ボイド欠陥が発生して半田濡れ性が低下するという問題がある。このようなボイド欠陥の発生は、半田付けする前に、防錆剤を有機溶剤やプラズマなどにより洗浄すれば防止することができるが、工程が増加して製造コストが上昇する。 However, with a metal-ceramic circuit board in which a copper circuit board is bonded onto a ceramic board, it is difficult to solder an electronic component such as a semiconductor chip onto the surface of a rust-proof copper circuit board (without plating). When the temperature is raised to the soldering temperature over time, there is a problem that void defects occur and solder wettability decreases. The occurrence of such void defects can be prevented by washing the rust inhibitor with an organic solvent or plasma before soldering, but the number of processes increases and the manufacturing cost increases.
一方、銅回路板に防錆処理を行わなければ、ボイド欠陥が発生するという問題はないが、銅回路板の表面の経時変化による酸化を十分に抑制することができずに半田濡れ性が低下するという問題がある。 On the other hand, if the copper circuit board is not rust-proofed, there will be no problem of void defects. However, oxidation due to aging of the surface of the copper circuit board cannot be sufficiently suppressed and solder wettability is reduced. There is a problem of doing.
したがって、本発明は、このような従来の問題点に鑑み、金属回路板がセラミックス基板に接合した金属−セラミックス回路基板の製造方法において、金属回路板を防錆処理した後に洗浄しなくても半田付け濡れ性が良好な金属−セラミックス回路基板を製造することができる、金属−セラミックス回路基板の製造方法を提供することを目的とする。 Therefore, in view of such a conventional problem, the present invention provides a metal-ceramic circuit board manufacturing method in which a metal circuit board is bonded to a ceramic board. It is an object of the present invention to provide a method for producing a metal-ceramic circuit board, which can produce a metal-ceramic circuit board having good wettability.
本発明者らは、上記課題を解決するために鋭意研究した結果、セラミックス基板の少なくとも一方の面に接合した金属回路板の表面を、防錆剤の濃度が０．０１３〜０．０７体積％の非ベンゾトリアゾール系の防錆剤の水溶液で防錆処理することにより、金属回路板を防錆処理した後に洗浄しなくても半田付け濡れ性が良好な金属−セラミックス回路基板を製造することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the concentration of the rust inhibitor is 0.013 to 0.07% by volume on the surface of the metal circuit board bonded to at least one surface of the ceramic substrate. It is possible to produce a metal-ceramic circuit board with good soldering wettability even if the metal circuit board is not washed after being rust-proofed by rust-proofing with an aqueous solution of a non-benzotriazole-based rust-proofing agent. The present inventors have found that this can be done and have completed the present invention.
すなわち、本発明による金属−セラミックス回路基板の製造方法は、セラミックス基板の少なくとも一方の面に接合した金属回路板の表面を、防錆剤の濃度が０．０１３〜０．０７体積％の非ベンゾトリアゾール系の防錆剤の水溶液で防錆処理することを特徴とする。 That is, in the method for producing a metal-ceramic circuit board according to the present invention, the surface of the metal circuit board bonded to at least one surface of the ceramic board is coated with a non-benzoic acid having a rust inhibitor concentration of 0.013-0.07% by volume. Rust prevention treatment is performed with an aqueous solution of a triazole rust inhibitor.
この金属−セラミックス回路基板の製造方法において、防錆剤の濃度がヨウ素価法によって求められた濃度であるのが好ましい。また、金属回路板が銅回路板であるのが好ましい。さらに、防錆処理の前に、金属回路板の表面を化学研磨するのが好ましい。 In this metal-ceramic circuit board manufacturing method, the concentration of the rust inhibitor is preferably determined by the iodine value method. The metal circuit board is preferably a copper circuit board. Furthermore, it is preferable to chemically polish the surface of the metal circuit board before the rust prevention treatment.
本発明によれば、金属回路板がセラミックス基板に接合した金属−セラミックス回路基板の製造方法において、金属回路板を防錆処理した後に洗浄しなくても半田付け濡れ性が良好な金属−セラミックス回路基板を製造することができる。 According to the present invention, in a method for manufacturing a metal-ceramic circuit board in which a metal circuit board is bonded to a ceramic substrate, the metal-ceramic circuit has good solder wettability without being washed after the metal circuit board has been rust-prevented. A substrate can be manufactured.
本発明による金属−セラミックス回路基板の製造方法の実施の形態では、セラミックス基板の少なくとも一方の面に接合した銅回路基板などの金属回路板の表面を、好ましくは化学研磨した後、防錆剤の濃度が０．０１３〜０．０７体積％、好ましくは０．０１５〜０．０５体積％の非ベンゾトリアゾール系の防錆剤の水溶液で防錆処理する。 In an embodiment of the method for producing a metal-ceramic circuit board according to the present invention, the surface of a metal circuit board such as a copper circuit board bonded to at least one surface of the ceramic board is preferably chemically polished, and then subjected to a rust inhibitor. Rust prevention treatment is performed with an aqueous solution of a non-benzotriazole rust inhibitor having a concentration of 0.013 to 0.07% by volume, preferably 0.015 to 0.05% by volume.
この金属−セラミックス回路基板の製造方法において、防錆剤の水溶液中の防錆剤の濃度は、例えば、以下のようなヨウ素価法（ウィイス法）により求めることができる。まず、防錆剤の水溶液１Ｌを正確に採取した後、ウィイス液（一塩化ヨウ素の酢酸溶液）６．２５ｍＬを正確に採取して防錆液に添加し、３０秒間攪拌して常温で暗所に１時間以上放置する。次に、１００ｇ／Ｌのヨウ化カリウム溶液５ｍＬを正確に採取して添加し、スターラーで攪拌した後、０．１モル／Ｌのチオ硫酸ナトリウム標準液で滴定する。この溶液が微黄色になったら、１０ｇ／Ｌのデンプン溶液を約５滴加えて滴定を続け、溶液の青〜褐色が消失するときを終点とする。このときの０．１モル／Ｌのチオ硫酸ナトリウム標準液の使用量をＢ（ｍＬ）とする。また、防錆剤の水溶液の希釈水のみで同様のブランクテストを行い、このときの０．１モル／Ｌのチオ硫酸ナトリウム標準液の使用量をＡ（ｍＬ）とし、防錆剤の濃度（体積％）＝０．０１５×（Ａ−Ｂ）×Ｆ−０．００１から、防錆剤の濃度を算出する（なお、式中、Ｆは０．１モル／Ｌのチオ硫酸ナトリウム標準液のファクター＝１．００５である）。 In this method for producing a metal-ceramic circuit board, the concentration of the rust inhibitor in the aqueous solution of the rust inhibitor can be determined, for example, by the following iodine value method (Wiis method). First, after accurately collecting 1 L of an aqueous solution of a rust inhibitor, 6.25 mL of a Wies solution (iodine monochloride acetic acid solution) is accurately collected and added to the rust preventive solution, stirred for 30 seconds and dark at room temperature. Leave for more than 1 hour. Next, 5 mL of 100 g / L potassium iodide solution is accurately sampled and added, stirred with a stirrer, and titrated with a 0.1 mol / L sodium thiosulfate standard solution. When this solution becomes slightly yellow, about 5 drops of 10 g / L starch solution is added and titration is continued until the blue-brown color of the solution disappears. The amount of 0.1 mol / L sodium thiosulfate standard solution used at this time is defined as B (mL). In addition, the same blank test was performed only with the diluted water of the rust inhibitor aqueous solution, and the amount of 0.1 mol / L sodium thiosulfate standard solution used at this time was A (mL), and the concentration of the rust inhibitor ( (Volume%) = 0.015 × (A−B) × F−0.001 to calculate the concentration of the rust preventive agent (where F is a 0.1 mol / L sodium thiosulfate standard solution) Factor = 1.005).
本発明による金属−セラミックス回路基板の製造方法の実施の形態により、金属回路板がセラミックス基板に接合した金属−セラミックス回路基板の製造方法において、金属回路板を防錆処理した後に洗浄しなくても半田付け濡れ性が良好な金属−セラミックス回路基板を製造することができる。特に、従来の金属−セラミックス回路基板では、半田付けの際の昇温速度が１℃／秒程度で半田付けが良好であったものの、昇温速度が２０℃／秒以上になると良好に半田付けを行うことができなかったが、本発明による金属−セラミックス回路基板の製造方法の実施の形態により製造された金属−セラミックス回路基板では、昇温速度が２０℃／秒以上でも良好に半田付けを行うことができる。 In the metal-ceramic circuit board manufacturing method in which the metal circuit board is bonded to the ceramic substrate according to the embodiment of the metal-ceramic circuit board manufacturing method according to the present invention, the metal circuit board does not have to be washed after being rust-proofed. A metal-ceramic circuit board with good solder wettability can be produced. In particular, in the conventional metal-ceramic circuit board, the soldering temperature was good at a temperature rising rate of about 1 ° C./second during soldering, but the soldering was good when the temperature rising rate was 20 ° C./second or more. In the metal-ceramic circuit board manufactured by the embodiment of the method for manufacturing a metal-ceramic circuit board according to the present invention, soldering can be performed well even at a temperature rising rate of 20 ° C./second or more. It can be carried out.
以下、本発明による金属−セラミックス回路基板の製造方法の実施例について詳細に説明する。 Examples of the method for producing a metal-ceramic circuit board according to the present invention will be described in detail below.
［実施例１〜３］
まず、セラミックス基板として長さ５６ｍｍ、幅４７ｍｍ、厚さ０．６３ｍｍの平面形状が略矩形のＡｌＮ基板を用意し、このセラミックス基板の両面に、活性金属として２質量％のＴｉを含むＡｇ−Ｃｕろう材をスクリーン印刷で塗布し、その上に、それぞれ長さ５６ｍｍ、幅４７ｍｍ、厚さ０．２５ｍｍの平面形状が略矩形の無酸素銅からなる銅板を配置し、真空雰囲気中において８５０℃で３０分間加熱してセラミックス基板と銅板を接合して、金属−セラミックス接合基板を作製した。
[Examples 1 to 3]
First, an AlN substrate having a length of 56 mm, a width of 47 mm, and a thickness of 0.63 mm is prepared as a ceramic substrate, and the surface of the ceramic substrate is Ag-Cu containing 2% by mass of Ti as an active metal on both surfaces. A brazing material is applied by screen printing, and a copper plate made of oxygen-free copper having a substantially rectangular shape with a length of 56 mm, a width of 47 mm, and a thickness of 0.25 mm is disposed on the brazing material. The ceramic substrate and the copper plate were bonded by heating for 30 minutes to produce a metal-ceramic bonding substrate.
このようにして作製した金属−セラミックス接合基板の銅板上にアルカリ剥離型のエッチングレジストを所定の形状に印刷した後、銅板とろう材の不要部分を塩化第二銅のエッチング液などで除去し、水酸化ナトリウム水溶液でエッチングレジストを剥離することにより、一方の銅板に回路パターンを形成した。 After printing an alkali peeling type etching resist in a predetermined shape on the copper plate of the metal-ceramic bonding substrate thus prepared, unnecessary portions of the copper plate and the brazing material are removed with an etching solution of cupric chloride, etc. A circuit pattern was formed on one copper plate by peeling off the etching resist with an aqueous sodium hydroxide solution.
次に、前処理として硫酸と過酸化水素水からなる化学研磨液に３０秒間浸漬することによって銅板の表面を化学研磨した後、市販の非ベンゾトリアゾール（非ＢＴＡ）系の防錆剤（千代田ケミカル株式会社製のＣ−７１Ｎ）の濃度がそれぞれ０．０５体積％（実施例１）、０．０３体積％（実施例２）、０．０１５体積％（実施例３）になるように水で希釈した水溶液中に５５℃で１分間浸漬して防錆処理を行った。 Next, as a pretreatment, the surface of the copper plate is chemically polished by immersing it in a chemical polishing solution comprising sulfuric acid and hydrogen peroxide solution for 30 seconds, and then a commercially available non-benzotriazole (non-BTA) rust inhibitor (Chiyoda Chemical). Co., Ltd. (C-71N) with a concentration of 0.05% by volume (Example 1), 0.03% by volume (Example 2), and 0.015% by volume (Example 3). Rust prevention treatment was performed by immersing in the diluted aqueous solution at 55 ° C. for 1 minute.
なお、防錆処理の使用した水溶液中の防錆剤の濃度は、以下のようなヨウ素価法により求めた。まず、防錆剤の水溶液１Ｌを正確に採取した後、ウィイス液（和光純薬工業株式会社製の一塩化ヨウ素の酢酸溶液の試薬）６．２５ｍＬを正確に採取して防錆液に添加し、３０秒間攪拌して常温で暗所に１時間以上放置した。次に、１００ｇ／Ｌのヨウ化カリウム溶液５ｍＬを正確に採取して添加し、スターラーで攪拌した後、０．１モル／Ｌのチオ硫酸ナトリウム標準液で滴定した。この溶液が微黄色になったら、１０ｇ／Ｌのデンプン溶液を約５滴加えて滴定を続け、溶液の青〜褐色が消失するときを終点とした。このときの０．１モル／Ｌのチオ硫酸ナトリウム標準液の使用量をＢ（ｍＬ）とする。また、防錆剤の水溶液の希釈水のみで同様のブランクテストを行い、このときの０．１モル／Ｌのチオ硫酸ナトリウム標準液の使用量をＡ（ｍＬ）とし、防錆剤の濃度（体積％）＝０．０１５×（Ａ−Ｂ）×Ｆ−０．００１から、防錆剤の濃度を算出した（なお、式中、Ｆは０．１モル／Ｌのチオ硫酸ナトリウム標準液のファクタであり、Ｆ＝１．００５の標準液を使用した）。 The concentration of the rust inhibitor in the aqueous solution used for the rust prevention treatment was determined by the following iodine value method. First, after accurately collecting 1 L of an aqueous solution of a rust inhibitor, 6.25 mL of a Wiis solution (a reagent for iodine monochloride acetic acid solution manufactured by Wako Pure Chemical Industries, Ltd.) is accurately collected and added to the rust inhibitor. The mixture was stirred for 30 seconds and left in a dark place at room temperature for 1 hour or longer. Next, 5 mL of a 100 g / L potassium iodide solution was accurately collected and added, stirred with a stirrer, and titrated with a 0.1 mol / L sodium thiosulfate standard solution. When this solution turned slightly yellow, about 5 drops of 10 g / L starch solution was added to continue the titration, and the end point was when the blue to brown color of the solution disappeared. The amount of 0.1 mol / L sodium thiosulfate standard solution used at this time is defined as B (mL). In addition, the same blank test was performed only with the diluted water of the rust inhibitor aqueous solution, and the amount of 0.1 mol / L sodium thiosulfate standard solution used at this time was A (mL), and the concentration of the rust inhibitor ( (Volume%) = 0.015 × (A−B) × F−0.001 to calculate the concentration of the rust inhibitor (wherein F is a 0.1 mol / L sodium thiosulfate standard solution). Factor, F = 1.005 standard solution was used).
このように防錆処理を行った金属−セラミックス接合基板の半田濡れ性を評価する１０ｍｍ×１０ｍｍの部分に厚さ０．１５ｍｍのＳｎＡｇＣｕ系板半田を載せた。次に、水素１００％の雰囲気中において昇温速度３０℃／秒で加熱して３２０℃（半田付け温度）で２６０秒間（半田付け温度保持時間）保持し、放冷後、半田濡れ性を評価する部分の面積（１００ｍｍ２）に対して溶融半田が濡れて占有する面積の割合（半田の濡れ広がり率）を測定した。なお、半田の濡れ広がり率の評価基準として、半田の濡れ広がり率が９９％以上の場合に半田濡れ性が非常に良好（表１において◎で示す）、９５％以上の場合に半田濡れ性が良好（表１において○で示す）であるとし、９５％未満の場合に半田濡れ性が不良（表１において×で示す）であるとした。その結果、半田濡れ性は、実施例１では良好、実施例２〜３では非常に良好であった。 A SnAgCu-based plate solder having a thickness of 0.15 mm was placed on a 10 mm × 10 mm portion for evaluating the solder wettability of the metal / ceramic bonding substrate subjected to the rust prevention treatment in this way. Next, it is heated in a 100% hydrogen atmosphere at a heating rate of 30 ° C./second, held at 320 ° C. (soldering temperature) for 260 seconds (soldering temperature holding time), allowed to cool, and then evaluated for solder wettability. The ratio of the area occupied by the molten solder wetted with respect to the area (100 mm 2 ) of the soldering area (the solder spreading ratio) was measured. As an evaluation standard for the solder wetting spread rate, solder wettability is very good (indicated by “◎” in Table 1) when the solder wet spreading rate is 99% or more, and when the solder wetting spread rate is 95% or more. The solder wettability was judged to be poor (indicated by x in Table 1) when it was good (indicated by ◯ in Table 1) and less than 95%. As a result, the solder wettability was good in Example 1, and very good in Examples 2-3.
また、防錆処理を行った金属−セラミックス接合基板を恒温恒湿試験機により８５℃で湿度８５％に２００時間保持した後、外観を目視する試験を行った。なお、この恒温恒湿試験の評価基準として、変色がほとんどない場合に非常に良好（表１において◎で示す）、変色が僅かな場合に良好（表１において○で示す）、変色が顕著な場合に不良（表１において×で示す）であるとした。その結果、恒温恒湿試験の結果は、実施例１〜３ではいずれも良好であった。 Moreover, the test | inspection which visually observes an external appearance was done, after hold | maintaining the metal-ceramics bonding board | substrate which performed the antirust process at 85 degreeC and 85% of humidity for 200 hours with a constant temperature and humidity tester. In addition, as an evaluation standard of this constant temperature and humidity test, it is very good when there is almost no discoloration (indicated by １ in Table 1), good when there is little discoloration (indicated by ○ in Table 1), and discoloration is remarkable. In some cases, it was determined to be defective (indicated by x in Table 1). As a result, the results of the constant temperature and humidity test were all good in Examples 1 to 3.
［比較例１〜４］
実施例１〜３と同様の方法により、金属−セラミックス接合基板を作製し、回路パターンを形成し、化学研磨した後、市販の非ベンゾトリアゾール（非ＢＴＡ）系の防錆剤（千代田ケミカル株式会社製のＣ−７１Ｎ）の濃度がそれぞれ１．５体積％（比較例１）、０．２体積％（比較例２）、０．１体積％（比較例３）、０．０１体積％（比較例３）になるように水で希釈した以外は、実施例１〜３と同様の方法により防錆処理を行った。
[Comparative Examples 1-4]
A metal-ceramic bonding substrate was prepared by the same method as in Examples 1 to 3, a circuit pattern was formed, and after chemical polishing, a commercially available non-benzotriazole (non-BTA) rust inhibitor (Chiyoda Chemical Co., Ltd.) The concentration of C-71N produced is 1.5% by volume (Comparative Example 1), 0.2% by volume (Comparative Example 2), 0.1% by volume (Comparative Example 3), and 0.01% by volume (Comparison). Rust prevention treatment was carried out by the same method as in Examples 1 to 3 except that it was diluted with water so as to be Example 3).
このように防錆処理を行った金属−セラミックス接合基板について、実施例１〜３と同様の方法により、半田濡れ性の評価と恒温恒湿試験を行ったところ、半田濡れ性は、比較例４では良好であったが、比較例１〜３では不良であり、恒温恒湿試験の結果は、比較例１〜３では非常に良好であったが、比較例４では不良であった。 For the metal / ceramic bonding substrate thus subjected to the rust prevention treatment, the solder wettability was evaluated and the constant temperature and humidity test was performed in the same manner as in Examples 1 to 3. Was good in Comparative Examples 1 to 3, and the results of the constant temperature and humidity test were very good in Comparative Examples 1 to 3, but poor in Comparative Example 4.
［実施例４〜６］
実施例１〜３と同様の方法により、金属−セラミックス接合基板を作製し、回路パターンを形成し、化学研磨した後、市販の非ベンゾトリアゾール（非ＢＴＡ）系の防錆剤（千代田ケミカル株式会社製のＹ−８５９１）を使用した以外は、それぞれ実施例１〜３と同様の方法により防錆処理を行った。
[Examples 4 to 6]
A metal-ceramic bonding substrate was prepared by the same method as in Examples 1 to 3, a circuit pattern was formed, and after chemical polishing, a commercially available non-benzotriazole (non-BTA) rust inhibitor (Chiyoda Chemical Co., Ltd.) Rust prevention treatment was performed in the same manner as in Examples 1 to 3, except that Y-8591) was used.
このように防錆処理を行った金属−セラミックス接合基板について、実施例１〜３と同様の方法により、半田濡れ性の評価と恒温恒湿試験を行ったところ、半田濡れ性は、実施例４〜５では良好、実施例６では非常に良好であり、恒温恒湿試験の結果は、実施例４〜６ではいずれも良好であった。 For the metal / ceramic bonding substrate subjected to the rust prevention treatment in this manner, evaluation of solder wettability and constant temperature and humidity test were performed in the same manner as in Examples 1 to 3. -5 was good, Example 6 was very good, and the results of the constant temperature and humidity test were all good in Examples 4-6.
［比較例５〜６］
実施例１〜３と同様の方法により、金属−セラミックス接合基板を作製し、回路パターンを形成し、化学研磨した後、市販の非ベンゾトリアゾール（非ＢＴＡ）系の防錆剤（千代田ケミカル株式会社製のＹ−８５９１）の濃度がそれぞれ１．５体積％（比較例５）、０．２体積％（比較例６）になるように水で希釈した以外は、実施例４〜６と同様の方法により防錆処理を行った。
[Comparative Examples 5-6]
A metal-ceramic bonding substrate was prepared by the same method as in Examples 1 to 3, a circuit pattern was formed, and after chemical polishing, a commercially available non-benzotriazole (non-BTA) rust inhibitor (Chiyoda Chemical Co., Ltd.) The same as in Examples 4 to 6 except that the concentration of Y-8591) made by water is 1.5% by volume (Comparative Example 5) and 0.2% by volume (Comparative Example 6). Rust prevention treatment was performed by the method.
このように防錆処理を行った金属−セラミックス接合基板について、実施例１〜３と同様の方法により、半田濡れ性の評価と恒温恒湿試験を行ったところ、半田濡れ性は、比較例５〜６ではいずれも不良であり、恒温恒湿試験の結果は、比較例５〜６ではいずれも非常に良好であった。 For the metal / ceramic bonding substrate subjected to the rust prevention treatment as described above, when the solder wettability evaluation and the constant temperature and humidity test were performed in the same manner as in Examples 1 to 3, the solder wettability was Comparative Example 5. The results of the constant temperature and humidity test were very good in Comparative Examples 5 to 6.
［比較例７〜１１］
実施例１〜３と同様の方法により、金属−セラミックス接合基板を作製し、回路パターンを形成し、化学研磨した後、市販のベンゾトリアゾール（ＢＴＡ）系の防錆剤（日本マクドーミット株式会社製のＭｅｔｅｘ Ｍ−６６７）の濃度がそれぞれ１．５体積％（比較例７）、０．２体積％（比較例８）、０．０５体積％（比較例９）、０．０３体積％（比較例１０）、０．０１５体積％（比較例１１）になるように水で希釈した水溶液中に室温で１分間浸漬して防錆処理を行った。
[Comparative Examples 7 to 11]
A metal-ceramic bonding substrate was prepared by the same method as in Examples 1 to 3, a circuit pattern was formed, and after chemical polishing, a commercially available benzotriazole (BTA) rust inhibitor (manufactured by Nippon McDomit Ltd.) The concentration of Metex M-667) is 1.5% by volume (Comparative Example 7), 0.2% by volume (Comparative Example 8), 0.05% by volume (Comparative Example 9), and 0.03% by volume (Comparative Example). 10), and was immersed in an aqueous solution diluted with water so as to be 0.015% by volume (Comparative Example 11) at room temperature for 1 minute to perform rust prevention treatment.
このように防錆処理を行った金属−セラミックス接合基板について、実施例１〜３と同様の方法により、半田濡れ性の評価と恒温恒湿試験を行ったところ、半田濡れ性は、比較例７〜１１ではいずれも不良であったが、恒温恒湿試験の結果は、比較例７では良好であり、比較例８〜１１ではいずれも非常に良好であった。 For the metal / ceramic bonding substrate subjected to the rust prevention treatment as described above, when the solder wettability evaluation and the constant temperature and humidity test were performed in the same manner as in Examples 1 to 3, the solder wettability was Comparative Example 7. The results of the constant temperature and humidity test were good in Comparative Example 7 and very good in Comparative Examples 8 to 11.
［比較例１２〜１６］
実施例１〜３と同様の方法により、金属−セラミックス接合基板を作製し、回路パターンを形成し、化学研磨した後、市販のベンゾトリアゾール（ＢＴＡ）系の防錆剤（千代田ケミカル株式会社製のＣ−７１ＤＥ）の濃度がそれぞれ１．５体積％（比較例１２）、０．２体積％（比較例１３）、０．０５体積％（比較例１４）、０．０３体積％（比較例１５）、０．０１５体積％（比較例１６）になるように水で希釈した水溶液中に５５℃で１分間浸漬して防錆処理を行った。
[Comparative Examples 12 to 16]
A metal-ceramic bonding substrate was prepared by the same method as in Examples 1 to 3, a circuit pattern was formed, and after chemical polishing, a commercially available benzotriazole (BTA) rust inhibitor (manufactured by Chiyoda Chemical Co., Ltd.). C-71DE) concentrations of 1.5% by volume (Comparative Example 12), 0.2% by volume (Comparative Example 13), 0.05% by volume (Comparative Example 14), and 0.03% by volume (Comparative Example 15) ), And was immersed in an aqueous solution diluted with water so as to be 0.015% by volume (Comparative Example 16) at 55 ° C. for 1 minute for rust prevention treatment.
このように防錆処理を行った金属−セラミックス接合基板について、実施例１〜３と同様の方法により、半田濡れ性の評価と恒温恒湿試験を行ったところ、半田濡れ性は、比較例１２〜１６ではいずれも不良であったが、恒温恒湿試験の結果は、比較例１２〜１６ではいずれも非常に良好であった。 For the metal / ceramic bonding substrate subjected to the rust-proofing treatment as described above, when the solder wettability evaluation and the constant temperature and humidity test were performed in the same manner as in Examples 1 to 3, the solder wettability was found to be Comparative Example 12. Although all were unsatisfactory in -16, the result of the constant temperature and humidity test was very favorable in Comparative Examples 12-16.
これらの実施例および比較例の結果を表１に示す。 The results of these examples and comparative examples are shown in Table 1.
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