JP2834776B2 - Copper and copper alloy surface treatment method - Google Patents
Copper and copper alloy surface treatment methodInfo
- Publication number
- JP2834776B2 JP2834776B2 JP1164291A JP16429189A JP2834776B2 JP 2834776 B2 JP2834776 B2 JP 2834776B2 JP 1164291 A JP1164291 A JP 1164291A JP 16429189 A JP16429189 A JP 16429189A JP 2834776 B2 JP2834776 B2 JP 2834776B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- zinc
- seconds
- acid
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
Description
【発明の詳細な説明】 産業上の利用分野 本発明は銅及び銅合金の表面に耐熱性に優れたアルキ
ルイミダゾールを主成分とする被膜を形成する方法に関
するものであり、特にプリント配線板における回路部の
プリフラックス処理として、好適な方法を提供するもの
である。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a coating mainly composed of alkylimidazole having excellent heat resistance on the surface of copper and a copper alloy, and particularly to a circuit for a printed wiring board. This is to provide a suitable method for preflux treatment of the part.
従来の技術 銅あるいは銅合金の表面に、２−アルキルイミダゾー
ル化合物の被膜を形成する表面処理方法は、特公昭46−
17046号、同48−11454号、同48−25621号、同49−1983
号、同49−26183号、同58−22545号、同61−41988号及
び特開昭61−90492号の各公報に記載されている。2. Description of the Related Art A surface treatment method for forming a film of a 2-alkylimidazole compound on the surface of copper or a copper alloy is disclosed in
17046, 48-11454, 48-25621, 49-1983
No. 49-26183, No. 58-22545, No. 61-41988 and JP-A No. 61-90492.
発明が解決しようとする課題 銅あるいは銅合金の表面に形成した２−アルキルイミ
ダゾール化合物の被膜は、室温近辺においては安定であ
るが高温下では比較的短時間に変色し、膜表面のはんだ
付けに支障を来す惧れがある。プリント配線板に対する
電子部品の接合方法として、近年表面実装法が多く採用
されているが、この方法によればチップ部品の仮止め、
部品装置の両面装着あるいはチップ部品とディスクリー
ト部品の混載などのため、特にプリント配線板が高温下
に曝されるようになった。Problems to be Solved by the Invention A coating film of a 2-alkylimidazole compound formed on the surface of copper or a copper alloy is stable at around room temperature, but discolors in a relatively short time at high temperatures, making it difficult to solder the film surface. There is a fear that it will cause trouble. In recent years, a surface mounting method has been widely used as a method for bonding electronic components to a printed wiring board.
In particular, printed wiring boards have been exposed to high temperatures due to double-sided mounting of component devices or mixed mounting of chip components and discrete components.
従って良好なはんだ付け性を得るためには、プリフラ
ックスとして使用されているアルキルイミダゾールの被
膜の耐熱性を向上させる必要があった。Therefore, in order to obtain good solderability, it is necessary to improve the heat resistance of the alkylimidazole film used as the preflux.
課題を解決するための手段 本発明者等は、種々の試験を繰り返した結果、銅ある
いは銅合金の表面に２位に炭素数５〜17のアルキル基を
有するアルキルイミダゾール化合物及び有機酸を含む水
溶液を接触させ、続いて前記処理がされた金属表面に亜
鉛化合物を含む水溶液を接触させることにより、従来の
方法に比べて耐熱性に優れた化成被膜が得られることを
見い出し、本発明を完遂した。Means for Solving the Problems As a result of repeating various tests, the present inventors have found that an aqueous solution containing an alkylimidazole compound having an alkyl group having 5 to 17 carbon atoms at the 2-position on the surface of copper or a copper alloy and an organic acid And then contacting the treated metal surface with an aqueous solution containing a zinc compound, it has been found that a chemical conversion film having excellent heat resistance can be obtained as compared with the conventional method, and the present invention has been completed. .
本発明方法において用いられる２位に炭素数５〜17の
アルキル基を有するアルキルイミダゾール化合物の代表
的なものとしては、２−アミルイミダゾール、２−ヘプ
チルイミダゾール、２−デシルイミダゾール、２−ウン
デシルイミダゾール、２−ドデシルイミダゾール、２−
トリデシルイミダゾール、２−テトラデシルイミダゾー
ル、２−ヘプタデシルイミダゾール、２−ウンデシル−
４−メチルイミダゾール、２−ヘプタデシル−４−メチ
ルイミダゾール及びこれらの塩があり、特に２−ウンデ
シルイミダゾールと２−ウンデシル−４−メチルイミダ
ゾール及びこれらの塩が好適である。Representative examples of the alkylimidazole compound having an alkyl group having 5 to 17 carbon atoms at the 2-position used in the method of the present invention include 2-amilimidazole, 2-heptylimidazole, 2-decylimidazole, and 2-undecylimidazole. , 2-dodecylimidazole, 2-
Tridecylimidazole, 2-tetradecylimidazole, 2-heptadecylimidazole, 2-undecyl-
There are 4-methylimidazole, 2-heptadecyl-4-methylimidazole and salts thereof, and in particular, 2-undecylimidazole, 2-undecyl-4-methylimidazole and salts thereof are preferable.
本発明方法の実施に当たっては、水に対して２位長鎖
アルキルイミダゾール化合物を0.01〜５％の範囲、好ま
しくは0.1〜２％の割合で添加すればよい。In carrying out the method of the present invention, the 2-position long-chain alkylimidazole compound may be added to water in a range of 0.01 to 5%, preferably 0.1 to 2%.
本発明方法の実施においては、２−アルキルイミダゾ
ールは水に対して離溶性であるため、これらを水に溶解
させるには、２−アルキルイミダゾールを有機酸と反応
させて、水に可溶な塩とすればよい。In the practice of the method of the present invention, 2-alkylimidazole is soluble in water. To dissolve them in water, the 2-alkylimidazole is reacted with an organic acid to form a water-soluble salt. And it is sufficient.
本発明方法の実施において用いられる有機酸として
は、蟻酸、酢酸、乳酸、プロピオン酸、カプリン酸、グ
リコール酸、アクリル酸、安息香酸、パラニトロ安息香
酸、パラブチル安息香酸、パラトルエンスルフォン酸、
ピクリル酸、サリチル酸、ｍ−トルイル酸、蓚酸、琥珀
酸、マレイン酸、フマール酸、酒石酸、アジピン酸等が
あり、水に対して0.01〜15％の範囲、好ましくは0.2〜
５％の割合で添加すればよい。The organic acids used in the practice of the method of the present invention include formic acid, acetic acid, lactic acid, propionic acid, capric acid, glycolic acid, acrylic acid, benzoic acid, paranitrobenzoic acid, parabutylbenzoic acid, paratoluenesulfonic acid,
There are picrylic acid, salicylic acid, m-toluic acid, oxalic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, adipic acid, etc., in the range of 0.01 to 15% with respect to water, preferably 0.2 to 15%.
It may be added at a rate of 5%.
本発明方法の実施において使用することができる亜鉛
化合物の代表的なものとしては、蟻酸亜鉛、酢酸亜鉛、
蓚酸亜鉛、乳酸亜鉛、クエン酸亜鉛、安息香酸亜鉛、サ
リチル酸亜鉛、硫酸亜鉛、硝酸亜鉛、リン酸亜鉛等があ
り、水に対して0.02〜10％の範囲、好ましくは0.1〜５
％の割合で添加すればよい。Representative zinc compounds that can be used in the practice of the method of the present invention include zinc formate, zinc acetate,
There are zinc oxalate, zinc lactate, zinc citrate, zinc benzoate, zinc salicylate, zinc sulfate, zinc nitrate, zinc phosphate, etc., in the range of 0.02 to 10% with respect to water, preferably 0.1 to 5%.
% May be added.
本発明方法の実施に当たっては、亜鉛化合物を含む水
溶液に有機酸、無機酸及びアンモニア水あるいはアミン
類等の緩衝作用を有する物質を添加して、溶液のpHを安
定にすべきである。In carrying out the method of the present invention, an organic acid, an inorganic acid and a substance having a buffering action such as aqueous ammonia or amines should be added to an aqueous solution containing a zinc compound to stabilize the pH of the solution.
本発明方法を実施するには、銅あるいは銅合金の表面
に研磨、脱脂、ソフトエッチング、酸洗浄等の処理を行
ったのち、金属表面を処理液中に浸漬するかあるいは金
属表面に処理液を塗布または噴霧すれば良い。In order to carry out the method of the present invention, the surface of copper or a copper alloy is polished, degreased, soft-etched, or subjected to a treatment such as acid cleaning, and then the metal surface is immersed in the treatment liquid or the treatment liquid is applied to the metal surface. It may be applied or sprayed.
本発明方法においては、銅あるいは銅合金の表面に、
処理液を約20℃から60℃の温度範囲で５秒ないし数分間
接触させれば良い。In the method of the present invention, on the surface of copper or copper alloy,
The treatment solution may be contacted at a temperature range of about 20 ° C. to 60 ° C. for 5 seconds to several minutes.
作 用 銅あるいは銅合金の表面を２位に炭素数５〜17のアル
キル基を有するアルキルイミダゾール化合物及び有機酸
を含む水溶液に接触させると、２−アルキルイミダゾー
ル化合物と銅との錯体形成反応及び２−アルキルイミダ
ゾール化合物間の水素結合とファンデルワールス力の両
作用により、局部的に銅錯体となった２−アルキルイミ
ダゾール化合物の化成被膜が銅表面上に形成される。こ
のようにして形成された化成被膜を放置しあるいは加熱
すると、銅表面から銅の移行が起こり、２−アルキルイ
ミダゾールの大部分が２−アルキルイミダゾール銅錯体
となり、空気中高温下では、銅の触媒作用により比較的
容易に酸化分解を起こす。亜鉛は２−アルキルイミダゾ
ールと容易に錯体を形成し、しかも、形成された２−ア
ルキルイミダゾール亜鉛錯体は、その銅錯体よりも熱的
にかなり安定である。従って、銅あるいは銅合金の表面
を、２−アルキルイミダゾール化合物及び有機酸を含む
水溶液に接触させ、続いて前記処理がされた金属表面を
亜鉛化合物を含む水溶液に接触させると、銅表面からの
銅の移行が殆ど起こらず、亜鉛化合物を含む水溶液から
亜鉛が化成被膜中に取り込まれて、一部２−アルキルイ
ミダゾール銅錯体が含まれるものの、大部分が２−アル
キルイミダゾール亜鉛錯体からなる化成被膜が形成さ
れ、耐熱性が向上する。なお銅あるいは銅合金の表面
に、２−アルキルイミダゾール化合物、有機酸及び亜鉛
化合物を含む水溶液を接触させる方法によれば、本発明
方法と比べて金属表面に形成された化成被膜に含まれる
２−アルキルイミダゾール亜鉛錯体が半減するので、化
成被膜の耐熱性も劣る。When the surface of copper or a copper alloy is brought into contact with an aqueous solution containing an alkylimidazole compound having an alkyl group having 5 to 17 carbon atoms at the 2-position and an organic acid, a complex-forming reaction between the 2-alkylimidazole compound and copper and the 2 Due to both the hydrogen bonding between the -alkylimidazole compounds and the van der Waals force, a conversion coating of the 2-alkylimidazole compound which has locally become a copper complex is formed on the copper surface. When the thus formed chemical conversion coating is left or heated, the migration of copper from the copper surface occurs, and most of the 2-alkylimidazole becomes a 2-alkylimidazole copper complex. Oxidative decomposition occurs relatively easily by action. Zinc readily forms complexes with 2-alkylimidazoles, and the formed 2-alkylimidazole zinc complexes are significantly more thermally stable than their copper complexes. Therefore, when the surface of copper or a copper alloy is brought into contact with an aqueous solution containing a 2-alkylimidazole compound and an organic acid, and then the treated metal surface is brought into contact with an aqueous solution containing a zinc compound, Transfer hardly occurs, and zinc is taken into the chemical conversion coating from the aqueous solution containing the zinc compound, and although a part of the conversion coating containing the 2-alkylimidazole zinc complex is included in the conversion coating containing the 2-alkylimidazole copper complex, Formed, and heat resistance is improved. According to the method in which an aqueous solution containing a 2-alkylimidazole compound, an organic acid, and a zinc compound is brought into contact with the surface of copper or a copper alloy, compared to the method of the present invention, the conversion coating film formed on the metal surface has a smaller amount of 2- Since the amount of the alkylimidazole zinc complex is reduced by half, the heat resistance of the conversion coating is also inferior.
以下実施例及び比較例によって、本発明方法を具体的
に説明する。Hereinafter, the method of the present invention will be specifically described with reference to Examples and Comparative Examples.
なお、これらの試験において金属表面における化成被
膜の厚さは、所定の大きさの試験片を0.5％塩酸水溶液
に浸漬して、２−アルキルイミダゾールを抽出させ、紫
外線分光光度計を用いて、この抽出液中に含まれる２−
アルキルイミダゾールの濃度を測定し、化成被膜の厚さ
に換算した。また化成被膜中の２−アルキルイミダゾー
ルの亜鉛錯体の含有率は、原子吸光測定装置を用いて、
前記抽出液中の亜鉛の濃度を測定し、２−アルキルイミ
ダゾールの濃度と亜鉛の濃度より算出した。In these tests, the thickness of the chemical conversion coating on the metal surface was determined by immersing a test piece of a predetermined size in a 0.5% hydrochloric acid aqueous solution to extract 2-alkylimidazole, and using an ultraviolet spectrophotometer. 2- contained in the extract
The concentration of the alkylimidazole was measured and converted to the thickness of the chemical conversion film. The content of the zinc complex of 2-alkylimidazole in the chemical conversion coating was determined using an atomic absorption spectrometer.
The concentration of zinc in the extract was measured and calculated from the concentration of 2-alkylimidazole and the concentration of zinc.
はんだ濡れ時間は、テストピース（5mm×50mm×0.3mm
の銅板）を脱脂し、次いでソフトエッチングしたのち、
各処理液での処理及び加熱処理を行い、測定直前にポス
トフラックス〔商品名「JS−64」（株）弘輝製〕に浸漬
して、はんだ濡れ性試験器（SAT−2000、（株）レスカ
製）を使用して測定した。なお測定条件ははんだ温度24
0℃、浸漬深さ2mm、浸漬スピード16mm/sec.とした。The solder wetting time is the test piece (5mm x 50mm x 0.3mm
Degreased, then soft-etched,
Perform treatment with each treatment solution and heat treatment. Immediately before measurement, immerse in post flux (trade name “JS-64” manufactured by Hiroki Co., Ltd.) and use a solder wettability tester (SAT-2000, Resca Co., Ltd.) Was used for the measurement. The measurement condition was solder temperature 24
The immersion depth was 2 mm and the immersion speed was 16 mm / sec.
実施例１ 脱脂及びソフトエッチング処理をしたテストピース
を、２−ウンデシル−４−メチルイミダゾール1.0％及
び乳酸0.57％を含む水溶液に液温50℃で30秒間浸漬した
のち、水洗した。続いて酢酸亜鉛2.0％、酢酸0.09％及
びアンモニア0.04％を含む水溶液に液温50℃で30秒間浸
漬したのち、水洗した。このようにして得られたテスト
ピース表面の化成被膜厚は0.32μｍであり、化成被膜中
の２−ウンデシル−４−メチルイミダゾール亜鉛錯体の
含有率は、72％であった。さらに200℃の温度に設定し
た熱風オーブン中に５分間及び10分間入れて、加熱処理
を行ったのち、はんだ濡れ性を測定し、また比較のため
に加熱処理をしていないテストピースについても同様に
測定した。Example 1 A test piece which had been degreased and soft-etched was immersed in an aqueous solution containing 1.0% of 2-undecyl-4-methylimidazole and 0.57% of lactic acid at a liquid temperature of 50 ° C. for 30 seconds, and then washed with water. Subsequently, the substrate was immersed in an aqueous solution containing 2.0% of zinc acetate, 0.09% of acetic acid and 0.04% of ammonia at a liquid temperature of 50 ° C. for 30 seconds, and then washed with water. The conversion coating thickness on the surface of the test piece thus obtained was 0.32 μm, and the content of the 2-undecyl-4-methylimidazole zinc complex in the conversion coating was 72%. After placing in a hot-air oven set at a temperature of 200 ° C for 5 minutes and 10 minutes and performing heat treatment, the solder wettability was measured, and the same applies to test pieces that were not heat-treated for comparison. Was measured.
その結果はんだ濡れ時間は、加熱処理をしなかった場
合は0.48秒、５分間加熱の場合は0.77秒、10分間加熱の
場合は2.86秒であった。As a result, the solder wetting time was 0.48 seconds without heat treatment, 0.77 seconds with 5 minutes heating, and 2.86 seconds with 10 minutes heating.
実施例２ 実施例１の酢酸亜鉛2.0％、酢酸0.09％及びアンモニ
ア0.04％を含む水溶液の代わりに乳酸亜鉛1.5％、酢酸
0.09％及びアンモニア0.04％を含む水溶液を用いて同様
の処理を行ったところ、テストピース表面の化成被膜厚
は0.33μｍであり、化成被膜中の２−ウンデシル−４−
メチルイミダゾール亜鉛錯体の含有率は、71％であっ
た。Example 2 Instead of the aqueous solution containing 2.0% zinc acetate, 0.09% acetic acid and 0.04% ammonia in Example 1, 1.5% zinc lactate and acetic acid
When the same treatment was performed using an aqueous solution containing 0.09% and 0.04% of ammonia, the conversion coating film thickness on the test piece surface was 0.33 μm, and 2-undecyl-4-
The content of the methylimidazole zinc complex was 71%.
またはんだ濡れ時間は、加熱処理をしなかった場合は
0.45秒、５分間加熱の場合は0.79秒、10分間加熱の場合
は2.91秒であった。Also, the solder wetting time is
It was 0.79 seconds for heating for 0.45 seconds and 5 minutes, and 2.91 seconds for heating for 10 minutes.
実施例３ 実施例１の酢酸亜鉛2.0％、酢酸0.09％及びアンモニ
ア0.04％を含む水溶液の代わりに蟻酸亜鉛3.0％、酢酸
0.09％及びアンモニア0.04％を含む水溶液を用いて同様
の処理を行ったところ、テストピース表面の化成被膜厚
は0.30μｍであり、化成被膜中の２−ウンデシル−４−
メチルイミダゾール亜鉛錯体の含有率は、72％であっ
た。Example 3 Instead of the aqueous solution containing 2.0% zinc acetate, 0.09% acetic acid and 0.04% ammonia in Example 1, 3.0% zinc formate, acetic acid
When the same treatment was performed using an aqueous solution containing 0.09% and 0.04% of ammonia, the conversion coating thickness on the test piece surface was 0.30 μm, and 2-undecyl-4-
The content of the methylimidazole zinc complex was 72%.
またはんだ濡れ時間は、加熱処理をしなかった場合は
0.45秒、５分間加熱の場合は0.81秒、10分間加熱の場合
は2.82秒であった。Also, the solder wetting time is
The heating time was 0.41 second, the heating time was 5 minutes, and the heating time was 0.81 seconds.
比較例１ 実施例１の酢酸亜鉛2.0％、酢酸0.09％及びアンモニ
ア0.04％を含む水溶液による処理を行わなかった以外
は、前記実施例１と同様の処理を行ったところ、テスト
ピース表面の化成被膜厚は0.34μｍであった。Comparative Example 1 The same treatment as in Example 1 was performed except that the treatment with the aqueous solution containing 2.0% of zinc acetate, 0.09% of acetic acid, and 0.04% of ammonia was not performed. The thickness was 0.34 μm.
またはんだ濡れ時間は、加熱処理をしなかった場合は
0.45秒、５分間加熱の場合は2.73秒、10分間加熱の場合
は10秒以上であった。Also, the solder wetting time is
The heating time was 0.43 seconds, the heating time was 5 minutes, the heating time was 2.73 seconds, and the heating time was 10 minutes.
比較例２ ２−ウンデシル−４−メチルイミダゾール1.0％、乳
酸0.57％及び酢酸亜鉛0.5％を含む水溶液を用いて、且
つ酢酸亜鉛2.0％、酢酸0.09％及びアンモニア0.04％を
含む水溶液に接触させる処理は行わずに実施例１と同様
の処理を行ったところ、テストピース表面の化成被膜厚
は0.36μｍであり、化成被膜中の２−ウンデシル−４−
メチルイミダゾール亜鉛錯体の含有率は、35％であっ
た。またはんだ濡れ時間は、加熱処理をしなかった場合
は0.42秒、５分間加熱の場合は1.51秒、10分間加熱の場
合は5.12秒であった。Comparative Example 2 Treatment using an aqueous solution containing 1.0% of 2-undecyl-4-methylimidazole, 0.57% of lactic acid and 0.5% of zinc acetate, and contacting with an aqueous solution containing 2.0% of zinc acetate, 0.09% of acetic acid and 0.04% of ammonia When the same treatment as in Example 1 was performed without performing the above, the conversion coating thickness on the test piece surface was 0.36 μm, and 2-undecyl-4-
The content of the methylimidazole zinc complex was 35%. The solder wetting time was 0.42 seconds without heat treatment, 1.51 seconds with 5 minutes heating, and 5.12 seconds with 10 minutes heating.
実施例４ 脱脂及びソフトエッチング処理をしたテストピース
を、２−ウンデシル−４−メチルイミダゾール15％及び
酢酸0.40％を含む水溶液に液温50℃で30分間浸漬したの
ち、水洗した。続いて酢酸亜鉛0.50％、酢酸0.09％及び
アンモニア0.04％を含む水溶液に液温50℃で30秒間浸漬
したのち、水洗した。このようにして得られたテストピ
ース表面の化成被膜厚は0.37μｍであり、化成被膜中の
２−ウンデシル−４−メチルイミダゾール亜鉛錯体の含
有率は、68％であった。さらに200℃の温度に設定した
熱風オーブン中に５分間及び10分間入れて、加熱処理を
行ったのち、はんだ濡れ性を測定し、また比較のために
加熱処理をしていないテストピースについても同様に測
定した。Example 4 A test piece that had been degreased and soft-etched was immersed in an aqueous solution containing 15% of 2-undecyl-4-methylimidazole and 0.40% of acetic acid at a liquid temperature of 50 ° C. for 30 minutes, and then washed with water. Subsequently, the substrate was immersed in an aqueous solution containing 0.50% of zinc acetate, 0.09% of acetic acid and 0.04% of ammonia at a liquid temperature of 50 ° C. for 30 seconds, and then washed with water. The conversion coating thickness on the surface of the test piece thus obtained was 0.37 μm, and the content of the 2-undecyl-4-methylimidazole zinc complex in the conversion coating was 68%. After placing in a hot-air oven set at a temperature of 200 ° C for 5 minutes and 10 minutes and performing heat treatment, the solder wettability was measured, and the same applies to test pieces that were not heat-treated for comparison. Was measured.
その結果はんだ濡れ時間は、加熱処理をしなかった場
合は0.46秒、５分間加熱の場合は0.82秒、10分間加熱の
場合は2.99秒であった。As a result, the solder wetting time was 0.46 seconds without heat treatment, 0.82 seconds with 5 minutes heating, and 2.99 seconds with 10 minutes heating.
実施例５ 実施例１の２−ウンデシル−４−メチルイミダゾール
1.0％及び乳酸0.57％を含む水溶液の代わりに、２−ウ
ンデシルイミダゾール1.0％及び乳酸0.75％を含む水溶
液を用いて同様の処理を行ったところ、テストピース表
面の化成被膜厚は0.29μｍであり、化成被膜中の２−ウ
ンデシルイミダゾール亜鉛錯体の含有率は、70％であっ
た。Example 5 2-Undecyl-4-methylimidazole of Example 1
When the same treatment was performed using an aqueous solution containing 1.0% of 2-undecylimidazole and 0.75% of lactic acid instead of the aqueous solution containing 1.0% and 0.57% of lactic acid, the conversion coating film thickness on the test piece surface was 0.29 μm. The content of the 2-undecylimidazole zinc complex in the conversion coating was 70%.
またはんだ濡れ時間は、加熱処理をしなかった場合は
0.48秒、５分間加熱の場合は0.79秒、10分間加熱の場合
は2.80秒であった。Also, the solder wetting time is
The heating time was 0.48 seconds, the heating time was 0.79 seconds for 5 minutes, and the heating time was 2.80 seconds for the heating time of 10 minutes.
比較例３ 脱脂及びソフトエッチング処理をしたテストピース
を、２−ウンデシルイミダゾール1.0％及び乳酸0.75％
を含む水溶液に液温50℃で30秒間浸漬したのち、水洗し
た。この時のテストピース表面の化成被膜厚は0.30μｍ
であった。さらに200℃の温度に設定した熱風オーブン
中に５分間及び10分間入れて、加熱処理を行ったのち、
はんだ濡れ性を測定し、また比較のために加熱処理をし
ていないテストピースについても同様に測定した。その
結果はんだ濡れ時間は、加熱処理をしなかった場合は0.
44秒、５分間加熱の場合は3.01秒、10分間加熱の場合は
10秒以上であった。Comparative Example 3 A test piece that had been degreased and soft-etched was treated with 1.0% of 2-undecylimidazole and 0.75% of lactic acid.
Was immersed in an aqueous solution containing at 30 ° C. for 30 seconds, and then washed with water. At this time, the conversion coating thickness on the test piece surface is 0.30 μm.
Met. After placing it in a hot-air oven set at a temperature of 200 ° C for 5 minutes and 10 minutes and performing heat treatment,
Solder wettability was measured, and a test piece not subjected to heat treatment was similarly measured for comparison. As a result, the solder wetting time was 0 if no heat treatment was performed.
44 seconds, 3.01 seconds for 5 minutes heating, 10 minutes for heating
It was more than 10 seconds.
実施例６ 脱脂及びソフトエッチング処理をしたテストピース
を、２−ウンデシルイミダゾール1.5％及び酢酸0.55％
を含み水溶液に液温50℃で30秒間浸漬したのち、水洗し
た。続いて乳酸亜鉛1.50％、酢酸0.09％及びアンモニア
0.04％を含む水溶液に液温50℃で30秒間浸漬したのち、
水洗した。この時のテストピース表面の化成被膜厚は0.
30μｍであり、化成被膜中の２−ウンデシルイミダゾー
ル亜鉛錯体の含有率は、70％であった。さらに、200℃
の温度に設定した熱風オーブン中に５分間及び10分間入
れて、加熱処理を行ったのち、はんだ濡れ性を測定し、
また比較のために加熱処理をしていないテストピースに
ついても同様に測定した。Example 6 A test piece subjected to a degreasing and soft etching treatment was treated with 1.5% of 2-undecylimidazole and 0.55% of acetic acid.
And immersed in an aqueous solution at a liquid temperature of 50 ° C. for 30 seconds, and then washed with water. Then zinc lactate 1.50%, acetic acid 0.09% and ammonia
After immersing in an aqueous solution containing 0.04% at a liquid temperature of 50 ° C for 30 seconds,
Washed with water. At this time, the conversion coating thickness on the test piece surface was 0.
The content of the 2-undecylimidazole zinc complex in the conversion coating was 70%. 200 ° C
5 minutes and 10 minutes in a hot air oven set to the temperature of, after the heat treatment, measured the solder wettability,
For comparison, a test piece that was not subjected to a heat treatment was measured in the same manner.
その結果はんだ濡れ時間は、加熱処理をしなかった場
合は0.46秒、５分間加熱の場合は0.78秒、10分間加熱の
場合は2.89秒であった。As a result, the solder wetting time was 0.46 seconds without heat treatment, 0.78 seconds with 5 minutes heating, and 2.89 seconds with 10 minutes heating.
発明の効果 本発明方法によれば、銅あるいは銅合金の表面に２位
に炭素数５〜17のアルキル基を有するアルキルイミダゾ
ール化合物を主成分とする耐熱性を有する化成被膜を形
成することが可能であり、特にプリント配線板における
表面実装法の加熱工程後における良好なはんだ付け性を
改善しうるものである。Effect of the Invention According to the method of the present invention, it is possible to form a heat-resistant chemical conversion coating mainly containing an alkylimidazole compound having an alkyl group having 5 to 17 carbon atoms at the 2-position on the surface of copper or a copper alloy. In particular, it can improve the good solderability of the printed wiring board after the heating step of the surface mounting method.
Claims (3)
〜17のアルキル基を有するアルキルイミダゾール化合物
及び有機酸を含む水溶液を接触させ、続いて前記処理が
された金属表面に亜鉛化合物を含む水溶液を接触させる
ことを特徴とする銅及び銅合金の表面処理方法。1. The method according to claim 1, wherein the surface of the copper or copper alloy has 5 carbon atoms at the second position.
Contacting an aqueous solution containing an alkylimidazole compound having an alkyl group of from 1 to 17 and an organic acid, followed by contacting the treated metal surface with an aqueous solution containing a zinc compound. Method.
ウンデシルイミダゾールを用いる請求項（１）に記載の
銅及び銅合金の表面処理方法。2. An alkylimidazole compound, comprising:
The method for surface treating copper and copper alloy according to claim 1, wherein undecyl imidazole is used.
ウンデシル−４−メチルイミダゾールを用いる請求項
（１）に記載の銅及び銅合金の表面処理方法。3. An alkylimidazole compound,
The method for treating a surface of copper and a copper alloy according to claim 1, wherein undecyl-4-methylimidazole is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1164291A JP2834776B2 (en) | 1989-06-26 | 1989-06-26 | Copper and copper alloy surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1164291A JP2834776B2 (en) | 1989-06-26 | 1989-06-26 | Copper and copper alloy surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0328381A JPH0328381A (en) | 1991-02-06 |
| JP2834776B2 true JP2834776B2 (en) | 1998-12-14 |
Family
ID=15790319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1164291A Expired - Fee Related JP2834776B2 (en) | 1989-06-26 | 1989-06-26 | Copper and copper alloy surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2834776B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5929722B2 (en) | 2011-11-30 | 2016-06-08 | Tdk株式会社 | Terminal structure, printed wiring board, module substrate, electronic device, and manufacturing method of terminal structure |
-
1989
- 1989-06-26 JP JP1164291A patent/JP2834776B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0328381A (en) | 1991-02-06 |
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