JPH032383A - Surface treatment of copper and copper alloy - Google Patents
Surface treatment of copper and copper alloyInfo
- Publication number
- JPH032383A JPH032383A JP13702089A JP13702089A JPH032383A JP H032383 A JPH032383 A JP H032383A JP 13702089 A JP13702089 A JP 13702089A JP 13702089 A JP13702089 A JP 13702089A JP H032383 A JPH032383 A JP H032383A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- alkylimidazole
- acid
- chemical conversion
- dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 11
- 238000004381 surface treatment Methods 0.000 title claims 4
- 239000000126 substance Substances 0.000 claims abstract description 20
- JQEVCCUJHLRAEY-UHFFFAOYSA-N 5-methyl-2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=C(C)N1 JQEVCCUJHLRAEY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 47
- 239000000975 dye Substances 0.000 abstract description 23
- -1 alkyl imidazole Chemical compound 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract 3
- 229910045601 alloy Inorganic materials 0.000 abstract 3
- 230000000007 visual effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000007739 conversion coating Methods 0.000 description 10
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 9
- 229940012189 methyl orange Drugs 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- 230000003993 interaction Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- ZHFPEICFUVWJIS-UHFFFAOYSA-M sodium 2-hydroxy-5-[(3-nitrophenyl)diazenyl]benzoate Chemical compound [Na+].Oc1ccc(cc1C([O-])=O)N=Nc1cccc(c1)[N+]([O-])=O ZHFPEICFUVWJIS-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LYNVLWLRSACENL-UHFFFAOYSA-N 2-decyl-1h-imidazole Chemical compound CCCCCCCCCCC1=NC=CN1 LYNVLWLRSACENL-UHFFFAOYSA-N 0.000 description 1
- LEHNQGSPRXHYRT-UHFFFAOYSA-N 2-dodecyl-1h-imidazole Chemical compound CCCCCCCCCCCCC1=NC=CN1 LEHNQGSPRXHYRT-UHFFFAOYSA-N 0.000 description 1
- RFWOZDRUDBNGSY-UHFFFAOYSA-N 2-heptadecyl-5-methyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC(C)=CN1 RFWOZDRUDBNGSY-UHFFFAOYSA-N 0.000 description 1
- CHZUJMWAUOTJFG-UHFFFAOYSA-N 2-pentyl-1h-imidazole Chemical compound CCCCCC1=NC=CN1 CHZUJMWAUOTJFG-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OLQDGRQSFFQIIZ-UHFFFAOYSA-N copper;1h-imidazole Chemical compound [Cu].C1=CNC=N1 OLQDGRQSFFQIIZ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
-
- 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
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、銅あるいは銅合金の表面に、アルキルイミダ
ゾール化合物の着色化成被膜を形成する方法に関するも
のであり、本発明方法は銅あるいは銅合金の一般的な防
錆処理のばか特にプリント配線基板における回路のプリ
フラックス処理として好適である。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for forming a colored chemical conversion film of an alkylimidazole compound on the surface of copper or copper alloy. It is suitable for anti-corrosion treatment, especially as a pre-flux treatment for circuits on printed wiring boards.
従来の技術
銅あるいは銅合金の表面をアルキルイミダゾール化合物
を含む水溶液中に浸漬させて、金属表面に０．３μ前後
のアルキルイミダゾールの化成被膜を形成する方法は公
知である。（特公昭４６−１７０４２、特公昭４８−２
５６２１及び特公昭４９−２６１８３号公報）また特開
昭５６−９８４７９号公報には、銅及び銅合金の表面を
アルキルイミダゾール化合物を含む水溶液に接触させた
のち、これを染料溶液に浸漬して化成被膜を着色する方
法が提案されている。2. Description of the Related Art A method is known in which the surface of copper or copper alloy is immersed in an aqueous solution containing an alkylimidazole compound to form a chemical conversion coating of alkylimidazole with a thickness of about 0.3 μm on the metal surface. (Tokuko Sho 46-17042, Sho 48-2
5621 and Japanese Patent Publication No. 49-26183) Also, in Japanese Patent Application Laid-open No. 56-98479, the surface of copper and copper alloy is brought into contact with an aqueous solution containing an alkylimidazole compound, and then immersed in a dye solution to undergo chemical conversion. A method of coloring the film has been proposed.
発明が解決しようとする課題
アルキルイミダゾールの化成被膜は、経時もしくは乾燥
処理により茶系統の色に変わるけれども、処理の直後は
ほとんど無色であるため、化成被膜が適確な厚さに形成
されているかどうかを簡単に判定することができなかっ
た。Problems to be Solved by the Invention Alkylimidazole chemical conversion coatings change to a brownish color over time or through drying treatment, but since they are almost colorless immediately after treatment, it is difficult to determine whether the chemical conversion coating has been formed to an appropriate thickness. It was not possible to easily determine whether
アルキルイミダゾールの化成被膜を測定する方法として
は、化成被膜を酸水溶液で溶出させ、紫外分光光度計を
用いて溶液中のイミダゾール濃度を求めなければならず
、その作業管理が甚だ煩わしいものであった。The method for measuring alkylimidazole chemical conversion coatings requires eluting the chemical conversion coating with an acid aqueous solution and determining the imidazole concentration in the solution using an ultraviolet spectrophotometer, which is extremely cumbersome to manage. .
またアルキルイミダゾールの化成被膜を形成したのち、
染色処理を行う方法は、化成被膜の表面部が特に染色さ
れるけれども、このような化成被膜は、染色されていな
い化成被膜に比べて、熱処理後の半田付は性が低下する
という難点があった。In addition, after forming a chemical conversion film of alkylimidazole,
In the dyeing method, the surface of the chemical conversion coating is particularly dyed, but such a chemical conversion coating has the disadvantage that the solderability after heat treatment is lower than that of an undyed chemical conversion coating. Ta.
課題を解決するための手段
本発明者はこのような問題を解消するために試験研究を
重ねた結果、銅及び銅合金の表面を２位に長鎖アルキル
基を有するイミダゾール化合物、有機酸及び染料を含む
水溶液と接触させることによって、所期の目的を達成し
たものである。Means for Solving the Problems As a result of repeated testing and research in order to solve these problems, the inventor of the present invention discovered that the surface of copper and copper alloys can be coated with an imidazole compound having a long-chain alkyl group at the 2-position, an organic acid, and a dye. The intended purpose was achieved by contacting with an aqueous solution containing.
本発明の実施に適するアルキルイミダゾール化合物は、
２−アミルイミダゾール、２−へブチルイミダゾール、
２−デシルイミダゾール、２−ウンデシルイミダゾール
、２−ウンデシル−４−メチルイミダゾール、２−ドデ
シルイミダゾール。Alkylimidazole compounds suitable for the practice of this invention include:
2-amylimidazole, 2-hebutylimidazole,
2-decylimidazole, 2-undecylimidazole, 2-undecyl-4-methylimidazole, 2-dodecylimidazole.
２−トリデシルイミダゾール２−ヘプタデシルイミダゾ
ール、２−ヘプタデシル−４−メチルイミダゾール等で
あり、これらは水に対して０．０１〜５％の範囲、好ま
しくは０．５〜２％の割合で添加する。2-tridecylimidazole 2-heptadecyl imidazole, 2-heptadecyl-4-methylimidazole, etc., and these are added in a range of 0.01 to 5%, preferably 0.5 to 2% relative to water. do.
本発明方法の実施においては、前記アルキルイミダゾー
ル化合物の水に対する溶解性を高めるために、有機酸を
加えて水に可溶性の塩とすべきである。In carrying out the method of the present invention, an organic acid should be added to form a water-soluble salt in order to increase the solubility of the alkylimidazole compound in water.
本発明の実施に適する有機酸は、酢酸９カプリン酸、グ
リコール酸、パラニトロ安息香酸、パラトルエンスルフ
ォン酸、ピクリン酸、ｉ酸、ｔｉ珀酸、マレイン酸、フ
マール酸、酒石酸、アジピン酸等であり、これら有機酸
は水に対して０．０１〜１０％の範囲、好ましくは０．
０５〜２％の割合で添加する。Organic acids suitable for the practice of the present invention include acetic acid, 9-capric acid, glycolic acid, para-nitrobenzoic acid, para-toluenesulfonic acid, picric acid, i-acid, ti-silicic acid, maleic acid, fumaric acid, tartaric acid, adipic acid, and the like. , these organic acids are contained in a range of 0.01 to 10%, preferably 0.01 to 10%, based on water.
It is added at a rate of 0.05 to 2%.
本発明の実施に適する染料は、アルキルイミダゾール水
溶液に良く溶けるもので且つアルキルイミダゾール化合
物と相互作用を有することが不可欠な要件であり、その
代表的なものとしでは、メチルオレンジ、アリザリンイ
エロー等である。またこれらの染料は水溶液中に０．０
０５〜２％の割合で添加すべきである。It is essential that the dye suitable for carrying out the present invention is well soluble in an aqueous alkylimidazole solution and has interaction with the alkylimidazole compound; representative examples include methyl orange, alizarin yellow, etc. . Also, these dyes have a concentration of 0.0 in aqueous solution.
It should be added at a rate of 0.05-2%.
本発明方法の処理態様を説明すると、銅あるいは銅合金
の表面を機械的処理あるいは酸洗いなどの化学的処理に
よって清浄に仕上げ、このように表面処理された金属面
を２０°Ｃないし６０℃の温度に維持した処理液に、５
秒ないし数分間接触すれば良い。To explain the treatment mode of the method of the present invention, the surface of copper or copper alloy is finished clean by mechanical treatment or chemical treatment such as pickling, and the thus surface-treated metal surface is heated at 20°C to 60°C. The treatment solution maintained at a temperature of 5
All you need to do is touch for a few seconds or a few minutes.
作用
２位に長鎖アルキル基を有するイミダゾール化合物は、
酸性水溶液でよく溶け、酸性水溶液中でイオン化したア
ルキルイミダゾールは、銅と強い化学反応性を示し、銅
表面に銅錯体の単分子膜を形成する。このようにしてで
きた単分子の膜の上に長鎖アルキル基のファンデルワー
ルスの結合力によって、アルキルイミダゾールが次々と
集合して膜が成長し、またイミダゾール同士の水素結合
力によりしっかりした膜になる。An imidazole compound having a long chain alkyl group at the 2nd position of action is
Alkylimidazoles, which dissolve well in acidic aqueous solutions and are ionized in acidic aqueous solutions, exhibit strong chemical reactivity with copper and form a monomolecular film of copper complexes on the copper surface. Due to the Van der Waals bonding force of the long-chain alkyl groups, the alkylimidazoles aggregate one after another to form a film on the monomolecular film formed in this way, and the hydrogen bonding force between the imidazoles also makes the film firm. become.
本発明において使用される染料は、アルキルイミダゾー
ルの水溶液に良く溶けるものであり、且つアルキルイミ
ダゾールと相互作用を示すものである。The dye used in the present invention is one that is well soluble in an aqueous solution of alkylimidazole and exhibits interaction with alkylimidazole.
染料とイミダゾール化合物の相互作用は必ずしも明確で
ないが、例えばポリビニルイミダゾールとメチルオレン
ジの系は高分子−溶質相互作用という観点から数人の人
達によって研究されており〔ジャーナル オン フィズ
イ力ルケミストリ（Ｊ、Ｒｈｙｓ、Ｃｈｅｍ、）６９．
１２４８（１９６５）、マクロモリキュールズ（Ｍａｃ
ｒｏｍｏｌｅｃｕｌｅｓ） １４．１７００（１９８１
）。ジャーナル オン アプライドポリマー サイエン
ス（Ｊ、＾ｐｐ１．Ｐｏｌｙｍ、ｓｃｉ、）２９．３３
９１（１９８４）、 ）ポリビニルイミダゾールとメチ
ルオレンジの水中における主要な結合の要因は、結合し
た染料の積み重なりを伴うポリマーと溶質量の静電気的
及びファンデルワールスの結合力であり、さらに結合過
程においてはエントロピーの変化とか水素結合が存在す
ると考えられている。Although the interaction between dyes and imidazole compounds is not necessarily clear, for example, the system of polyvinylimidazole and methyl orange has been studied by several people from the perspective of polymer-solute interactions [Journal on Fizi Power Chemistry (J, Rhys. , Chem, )69.
1248 (1965), Macro Molecules (Mac
14.1700 (1981
). Journal on Applied Polymer Science (J, ^pp1. Polym, sci,) 29.33
91 (1984), ) The main binding factors of polyvinylimidazole and methyl orange in water are the electrostatic and van der Waals binding forces of the polymer and solute mass with the stacking of the bound dye, and furthermore, in the binding process. It is thought that entropy changes and hydrogen bonds exist.
本発明方法におけるアルキルイミダゾール化合物は、高
分子ではないが銅表面におけるアルキルイミダゾールは
、銅を媒体としたポリメリックな錯体を形成しているた
め、〔アクタ クリスフログラフイカ（Ａｃｔａ Ｃｒ
ｙｓｔａｌｌｏ（Ｈｒａｐｈｉｃａ）１３．１０２７（
１９６０）、ケースウェスタン・リザーブ大学研究報告
〕前記ポリマー溶質問の相互作用と同様の理由により着
色すると思われる。アルキルイミダゾール水溶液に添加
して銅金属の表面に着色被膜を形成しうる分子構造の明
確な染料としては、メチルオレンジのほかにアリザリン
イエローＣＧがある。これらは共にイミダゾール水溶液
に比較的良好な溶解度を示し、水中でアニオンとなるジ
アゾ系の染料である。Although the alkylimidazole compound used in the method of the present invention is not a polymer, the alkylimidazole on the copper surface forms a polymeric complex using copper as a medium.
ystallo (Hraphica) 13.1027 (
(1960), Case Western Reserve University Research Report] It is thought that the coloring occurs for the same reason as the interaction between the polymer and the solute. In addition to methyl orange, alizarin yellow CG is a dye with a distinct molecular structure that can be added to an aqueous alkylimidazole solution to form a colored film on the surface of copper metal. Both of these are diazo dyes that exhibit relatively good solubility in imidazole aqueous solutions and become anions in water.
アルキルイミダゾール化合物は銅と錯体を形成するが、
イミダゾール・銅錯体は酸により銅とイミダゾ−ル間の
結合が切られ、アルキルイミダゾール化合物は酸に溶解
して除去されるので、プリント配置ｇ仮における回路の
プリフラックス処理に適している。Alkylimidazole compounds form complexes with copper;
The imidazole-copper complex is suitable for preflux treatment of circuits in printed layouts because the bond between copper and imidazole is broken by acid, and the alkylimidazole compound is dissolved in acid and removed.
銅あるいは銅合金をアルキルイミダゾール化合物を含む
溶液に接触し、次いで染料を溶かした溶液に接触して着
色させた場合、化成被膜における染色の度合いは、表面
部が濃く内部が薄くなり、殊に最上部には染料のみの膜
が存在し、これがアルキルイミダゾールに比べて、ポス
トフランクスに対する溶解性が低いため、酸によるアル
キルイミダゾール及び染料の除去が狙害され、半田付は
性が低下する。When copper or copper alloy is colored by contacting it with a solution containing an alkylimidazole compound and then contacting it with a solution containing a dye, the degree of dyeing in the chemical conversion coating is such that the surface becomes darker and the interior becomes lighter, especially at the very end. There is a dye-only film on the top, which has lower solubility in post-Franks than alkylimidazole, so removal of alkylimidazole and dye by acid is targeted and the solderability is reduced.
これに対して本発明方法によれば、アルキルイミダゾー
ル化合物と染料を含む水溶液で銅表面の処理を行った場
合には、化成被膜が均一に染色され、被膜内に分布して
いる染料は、酸によりイミダゾールと共に容易に除去さ
れるため、半田付は性に殆ど影響を与えない。In contrast, according to the method of the present invention, when the copper surface is treated with an aqueous solution containing an alkylimidazole compound and a dye, the chemical conversion coating is uniformly dyed, and the dye distributed within the coating is Soldering has little effect on the properties since it is easily removed together with imidazole.
以下実施例及び参考例によって、本発明を具体的に説明
する。The present invention will be specifically explained below using Examples and Reference Examples.
実施例１
２−ウンデシル−４−メチルイミダゾール１；Ｏｇに酢
酸０．４０−を加えて２−ウンデシル−４−メチルイミ
ダゾールを溶解し、さらに純水１００ｍを加え、よく攪
拌して均一な溶液としくｐＨ４，７５） 、これにメチ
ルオレンジ０．１ｇを加えてよく攪拌し、不溶解のメチ
ルオレンジを濾過して除くことにより処理液を造った。Example 1 2-Undecyl-4-methylimidazole 1; Add 0.40-acetic acid to Og to dissolve 2-undecyl-4-methylimidazole, then add 100ml of pure water and stir well to make a homogeneous solution. (pH 4.75), 0.1 g of methyl orange was added thereto, stirred well, and undissolved methyl orange was removed by filtration to prepare a treatment liquid.
他方４ Ｃ１ｌ Ｘ ４ ａａの銅張積層板の銅表面を
スコッチブライトを用いて湿式研磨し、０．５％塩酸水
溶液に３０秒間浸漬したのち水洗して、この銅張積層板
を揺動しながら、５０°Ｃに維持した前記処理液に１分
間浸漬して取り出し水洗したところ、銅張積層板の銅表
面に均一なオレンジ色のイミダゾール被膜を生じた。こ
の銅張積層板を温度５５度、湿度９５％の恒温恒湿槽に
９６時間放置するかあるいは１５０“Ｃの乾燥器の中に
３０分間放置したのち、ポストフランクス（ツルドック
スＦＲ２０７（）ピファスナ工業■製）〕を塗布し、２
５５°Ｃのハンダ浴の中に３秒浸漬したのち、銅表面の
ハンダのぬれを観察した。その結果メチルオレンジの入
ったイミダゾール水溶液によって処理したものは、染料
を含まないイミダゾールで処理したブランクと同程度の
ハンダのぬれ性を示した。On the other hand, the copper surface of a 4 C1l x 4 aa copper clad laminate was wet polished using Scotchbrite, immersed in a 0.5% hydrochloric acid aqueous solution for 30 seconds, washed with water, and polished while rocking the copper clad laminate. When the copper clad laminate was immersed in the treatment solution maintained at 50° C. for 1 minute, taken out and washed with water, a uniform orange imidazole film was formed on the copper surface of the copper clad laminate. This copper-clad laminate was left in a constant temperature and humidity chamber at a temperature of 55 degrees and a humidity of 95% for 96 hours, or in a dryer at 150"C for 30 minutes, and then dried. 2)
After being immersed in a solder bath at 55°C for 3 seconds, the wetting of the solder on the copper surface was observed. As a result, those treated with an aqueous imidazole solution containing methyl orange showed the same level of solder wettability as the blank treated with imidazole containing no dye.
実施例２
前記実施例において、２−ウンデシル−４−メチルイミ
ダゾールの代わりに２−ウンデシルイミダゾールを同量
用いた以外は全く同じようにして処理液を造り、他方銅
張積層板を前記と同様に表面処理し、実施例１と同じよ
うに処理液に浸漬し、後処理を行ったところ、銅張積層
板の銅表面には均一なオレンジ色のイミダゾール被膜を
形成することができた。Example 2 A treatment solution was prepared in exactly the same manner as in the previous example except that the same amount of 2-undecyl-4-methylimidazole was used instead of 2-undecyl-4-methylimidazole, and a copper-clad laminate was prepared in the same manner as above. When the copper clad laminate was surface-treated, immersed in a treatment solution and post-treated in the same manner as in Example 1, a uniform orange imidazole coating could be formed on the copper surface of the copper-clad laminate.
また実施例１と同様にして本品のハンダ付は性を調べた
結果、染料を含まないイミダゾール処理のものと同程度
のハンダぬれ性があった。Further, the solderability of this product was examined in the same manner as in Example 1, and as a result, it was found that the solder wettability of this product was comparable to that of a product treated with imidazole that did not contain dye.
実施例３
実施例１において酢酸０．４０ｍの代わりに５０％乳酸
０．７８ｇを用いた以外は全（同じようにして処理液を
造り、前記実施例と同様の前処理を行った同張積層板を
前記と同じように処理液に浸漬し、後処理を行ったとこ
ろ、銅張積層板の銅表面に均一なオレンジ色のイミダゾ
ール被膜ができた。Example 3 All samples were prepared in Example 1 except that 0.78 g of 50% lactic acid was used instead of 0.40 m of acetic acid (a treatment solution was prepared in the same manner and the same pretreatment as in the previous example was performed). When the board was immersed in the treatment solution and post-treated in the same manner as above, a uniform orange imidazole film was formed on the copper surface of the copper-clad laminate.
また実施例１と同様にして本品のハンダ付は性を調べた
結果、染料を含まないイミダゾール処理のものと同程度
のハンダぬれ性があった。Further, the solderability of this product was examined in the same manner as in Example 1, and as a result, it was found that the solder wettability of this product was comparable to that of a product treated with imidazole that did not contain dye.
実施例４
２−ウンデシル−４−メチルイミダゾール１．０ｇに酢
酸０．４０ｔｒｔｆｌを加えて２−ウンデシル−４−メ
チルイミダゾールを溶解し、さらに純水を１００ｍ１加
えて均一な溶液とし、これにアリザリンイエローＣＧ０
．１ｇを加えて室温でよく攪拌したのち、不溶解アリザ
リンイエローＧＧを濾別して処理液を造り、以下実施例
１と同様な操作を行った結果、銅張積層板の銅表面には
均一な赤色のイミダゾール被膜が形成され、また実施例
１と同様にしてハンダ付は性を調べたところ、ブランク
のものと同程度であった。Example 4 Add 0.40 trtfl of acetic acid to 1.0 g of 2-undecyl-4-methylimidazole to dissolve 2-undecyl-4-methylimidazole, and then add 100 ml of pure water to make a homogeneous solution, and add Alizarin Yellow to this. CG0
．． After adding 1 g and stirring well at room temperature, the insoluble alizarin yellow GG was filtered out to prepare a treatment solution, and the same operation as in Example 1 was performed. As a result, a uniform red color was formed on the copper surface of the copper-clad laminate. An imidazole film was formed, and the solderability was examined in the same manner as in Example 1 and found to be comparable to that of the blank.
実施例５
実施例１において、染料のメチルオレンジの代わりにジ
アゾ系染料〔商品名ｒＡＢ１０４Ｊ、三菱化成■製〕を
用いた以外は同様な操作を行ったところ、銅張積層板の
銅表面に青色の化成被膜ができ、明確に銅表面との区別
ができた。Example 5 The same procedure as in Example 1 was carried out except that a diazo dye [trade name rAB104J, manufactured by Mitsubishi Kasei ■] was used instead of the dye methyl orange, and a blue color appeared on the copper surface of the copper-clad laminate. A chemical conversion film was formed, which could be clearly distinguished from the copper surface.
また実施例１と同様にして本品のハンダ付は性を調べた
結果、ブランクのものとほぼ同じであった。Further, as in Example 1, the solderability of this product was examined and found to be almost the same as that of the blank.
参考例１
２−ウンデシル−４−メチルイミダゾール１．０ｇに酢
酸０．４０ｄを加えて２−ウンデシル−４−メチルイミ
ダゾールを溶解し、さらに純水１００ｄを加えてよく攪
拌して均一な第１処理液を造り、他方メチルオレンジ０
．１ｇを１００ ｍｌｌの純水に加えて室温でよく撹拌
したのち、不熔解物を濾別して第２処理液を造った。Reference Example 1 Add 0.40 d of acetic acid to 1.0 g of 2-undecyl-4-methylimidazole to dissolve 2-undecyl-4-methylimidazole, and then add 100 d of pure water and stir well to obtain a uniform first treatment. Make a liquid and add methyl orange 0 to the other side.
．． After adding 1 g to 100 ml of pure water and stirring well at room temperature, undissolved substances were filtered off to prepare a second treatment liquid.
銅張積層板の銅面を実施例１と同じように前処理したの
ち、銅張積層板を第１処理液に１分間浸漬し、次いでこ
の基板を第２処理液に１分間浸漬して取り出し、水洗し
たところ、イミダゾール被膜は表層のみが黄赤色に染ま
ったものとなり、この銅張積層板を１５０’Ｃと１８０
°Ｃの程度で３０分間加熱し、以下実施例１と同様にし
てハンダのぬれ性を調べたところ、本例の処理をしたも
のは、染料を用いていないブランクのものに比べて、明
らかにハンダのぬれ性が低下した。After pre-treating the copper surface of the copper-clad laminate in the same manner as in Example 1, the copper-clad laminate was immersed in the first treatment solution for 1 minute, and then this substrate was immersed in the second treatment solution for 1 minute and taken out. When washed with water, only the surface layer of the imidazole coating was stained yellow-red, and this copper-clad laminate was heated at 150'C and 180'C.
℃ for 30 minutes, and the wettability of the solder was examined in the same manner as in Example 1. It was found that the solder wettability of the solder treated in this example was clearly superior to that of the blank without dye. Solder wettability decreased.
発明の効果Effect of the invention
Claims (3)
キルイミダゾール化合物、有機酸及び染料を含む水溶液
と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。 一般式 ▲数式、化学式、表等があります▼ ［但し式中Ｒ＿２は長鎖ア ルキル基、Ｒ＿４は水素 原子または低級アル キル基を示す。］(1) A method for surface treatment of copper and copper alloys, which comprises bringing the surfaces of copper and copper alloys into contact with an aqueous solution containing an alkylimidazole compound represented by the following general formula, an organic acid, and a dye. General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ [However, in the formula, R_2 represents a long-chain alkyl group, and R_4 represents a hydrogen atom or a lower alkyl group. ]
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) The method for surface treatment of copper and copper alloys according to claim (1), wherein 2-undecylimidazole is used as the alkylimidazole compound.
シル−４−メチルイミダソ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) The method for surface treatment of copper and copper alloys according to claim (1), wherein 2-undecyl-4-methylimidazole is used as the alkylimidazole compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1137020A JP2834770B2 (en) | 1989-05-29 | 1989-05-29 | Copper and copper alloy surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1137020A JP2834770B2 (en) | 1989-05-29 | 1989-05-29 | Copper and copper alloy surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH032383A true JPH032383A (en) | 1991-01-08 |
| JP2834770B2 JP2834770B2 (en) | 1998-12-14 |
Family
ID=15188959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1137020A Expired - Lifetime JP2834770B2 (en) | 1989-05-29 | 1989-05-29 | Copper and copper alloy surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2834770B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6020417A (en) * | 1997-01-24 | 2000-02-01 | Ntn Corporation | Sheet feed members for image forming devices |
| JP2010077071A (en) * | 2008-09-26 | 2010-04-08 | Shikoku Chem Corp | 2-alkyl-4-(3,4-dichlorophenyl)-5-methylimidazole compound |
| JP2010524122A (en) * | 2007-04-11 | 2010-07-15 | ヒューレット−パッカード デベロップメント カンパニー エル．ピー． | Electronic device locking system |
| JP2010198591A (en) * | 2009-02-24 | 2010-09-09 | Compal Electronics Inc | Engagement mechanism |
-
1989
- 1989-05-29 JP JP1137020A patent/JP2834770B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6020417A (en) * | 1997-01-24 | 2000-02-01 | Ntn Corporation | Sheet feed members for image forming devices |
| JP2010524122A (en) * | 2007-04-11 | 2010-07-15 | ヒューレット−パッカード デベロップメント カンパニー エル．ピー． | Electronic device locking system |
| JP2010077071A (en) * | 2008-09-26 | 2010-04-08 | Shikoku Chem Corp | 2-alkyl-4-(3,4-dichlorophenyl)-5-methylimidazole compound |
| JP2010198591A (en) * | 2009-02-24 | 2010-09-09 | Compal Electronics Inc | Engagement mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2834770B2 (en) | 1998-12-14 |
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