JP3668767B2 - Surface treatment method for metals such as solder, electroless solder, silver, nickel and zinc - Google Patents

Surface treatment method for metals such as solder, electroless solder, silver, nickel and zinc Download PDF

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JP3668767B2
JP3668767B2 JP35475893A JP35475893A JP3668767B2 JP 3668767 B2 JP3668767 B2 JP 3668767B2 JP 35475893 A JP35475893 A JP 35475893A JP 35475893 A JP35475893 A JP 35475893A JP 3668767 B2 JP3668767 B2 JP 3668767B2
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acid
group
solder
chemical formula
alkyl group
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JPH06299374A (en
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秀明 山口
正樹 鵜尾
和彦 加藤
吉司 松本
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Murata Co Ltd
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Murata Co 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
    • 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
    • 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
    • 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
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0562—Details of resist
    • H05K2203/0591—Organic non-polymeric coating, e.g. for inhibiting corrosion thereby preserving solderability
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
    • H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Description

【０００１】
【産業上の利用分野】
この発明は、はんだ、無電解はんだ、ニッケル、銀、亜鉛等の金属の防錆、はんだ荒れ防止、変色防止、耐アルカリ性、耐湿性、耐薬品性、耐熱性、はんだ付け性を向上させる処理方法に関するものであり、特にこれらの金属のはんだ付け性を長期間良好な状態に維持することや、プリント配線板製造時のアルカリ性溶液による表面荒れ防止に好適な方法を提供するものである。また、接合した異種金属の両者共に処理できるため、めっきのピンホールの防錆にも最適で無電解はんだのピンホール防錆や、コネクターのニッケル・金めっき後の封孔処理剤として好適なものである。
【０００２】
【従来の技術】
パターンめっき法によるプリント配線板の製造方法は、銅張積層板に穴をあけ、化学銅めっき、電気銅めっき、続いてアルカリ水溶液に可溶のアルカリ現像型感光性フィルムを銅張積層板上に陰画回路を形成し、次いで電気銅めっき、はんだめっきを行いその後、アルカリ性水溶液と接触させてアルカリ現像型感光性フィルムを除く。
この時アルカリ性水溶液ではんだめっき表面が侵され、銅素材が露出することがあり、この場合、アルカリエッチング液で銅がエッチングされ回路が切断される。また、銅素材が露出するまでには至らないではんだめっきを残し、はんだスルホール基板を製造する場合、このままでははんだ付け性が悪くフュージング処理等を行う必要がある。
プリント配線板のはんだ接合技術の１つとしての無電解はんだは、置換めっき法により行われ、その皮膜は非常に薄く、粗い表面である。このため多孔質な皮膜となり素材の銅表面が露出している。また、析出も鉛、錫個別に行われる為に、両者の混合皮膜となっている。このためはんだ付け性の悪い銅−錫合金の生成や鉛、錫の酸化が起きやすく、めっき後フュージングをしなければ良好なはんだ付け性を長期間維持できない。
ニッケルは強固な酸化膜を形成しやすく、元来はんだ付け性は悪い。そのためプリント配線板やコネクターでは、はんだ付けの必要な場合、ニッケル上に金めっきを施し、酸化防止をしている。
銀、亜鉛の防錆にはクロメート処理が行われるが、有害な６価クロム化合物を使用するため問題がある。また、銀の防錆にはパラフィン等を溶剤に溶解して塗布するが、溶剤を使用しなければならない等、環境汚染上の問題がある。
【０００３】
【発明が解決しようとする課題】
前期、プリント配線板の従来製造法に於けるエッチングレジスト膜としてのはんだめっき皮膜は信頼性に劣り、製造不良が発生し易いのである。そこで、アルカリ現像型感光性フィルムの剥離時や、」アルカリエッチング時に発生するはんだ表面の荒れを防止し、良好な回路を経営する事が望まれ、尚且つはんだ付け性を良好な状態に保つことが求められている。また、無電解はんだにおいては、基板に大きなサーマルストレスを与えてしまうという品質面及び、コスト面からフュージングを行わずにはんだ付け性を維持したいと言う要望が強い。更にニッケルにおいては高価な金めっきを施さずに変色防止とはんだ付け性を維持したいと言う要求がある。銀、亜鉛については、有害な６価クロムを含有しない安全な処理で、長期間変色を防止したり、良好なはんだ付け性を維持することが切望されている。
【０００４】
【課題を解決するための手段】
本発明は、このような事情に鑑み、鋭意検討を重ねた結果なされたものである。はんだ、無電解はんだ、銀、ニッケル、亜鉛等に優れた防錆性を付与する手段として、その有効成分の主剤が（化１）〜（化３）で表される化合物又はその誘導体の塩で、これらを少なくとも１種以上含む水溶液に当該金属を接触させることを特徴とする。（化１）〜（化３）で表される化合物又はその誘導体の塩は、少なくともその１種以上を酸水溶液に対し０．１〜５．０％の割合で添加すれば良い。
本発明の実施において用いられる酸としては、酢酸、ヨード酢酸、ブロオモ酢酸、ジメチル酢酸、ジエチル酢酸、α−ブロモ酢酸、パラニトロ安息香酸、パラトルエンスルホン酸、ピクリン酸、蓚酸、蟻酸、コハク酸、マレイン酸、アクリル酸、フマール酸、酒石酸、アジピン酸、乳酸、オレイン酸、クエン酸、メタスルホン酸、スルファミン酸等の有機酸、塩酸、硫酸、亜りん酸、燐酸等の無機酸、その他のカルボン酸、ハロゲン化脂肪酸、ハロゲン化芳香族脂肪酸等があり、水に対し０．０１〜２０％の割合で添加すれば良い。
本発明の実施において使用される金属イオンを供給する化合物の代表的なものとしては、リチウム、ベリリウム、カリウム、マグネシウム、酢酸亜鉛、蟻酸亜鉛、乳酸亜鉛、クエン酸亜鉛、安息香酸亜鉛、蓚酸亜鉛、水酸化亜鉛、臭化亜鉛、燐酸亜鉛、酸化亜鉛、塩化亜鉛、酢酸鉛、水酸化鉛、臭化亜鉛、ヨウ化鉛、蓚酸鉛、ほう酸鉛、塩化第一鉄、塩化第二鉄、臭化第一銅、臭化第二銅、ヨウ化第一銅、蟻酸銅、塩化ニッケル、酢酸ニッケル、塩化第一銅、塩化第二銅、酸化第一銅、酸化第二銅、、水酸化銅燐酸銅、炭酸銅、酢酸銅、硫酸銅等の金属化合物であり、水に対して０．００１〜５．０％の割合で添加すれば良い。
本発明の実施において用いられるハロゲン化芳香族カルボン酸としては、３−ブロモー４メチル安息香酸、４−（ブロモメチル）フェニル酢酸、α−ブロモフェニル酢酸、α−ブロモテトラデカン酸、２−ブロモフェニル酢酸、３−ブロモフェニル酢酸、４−ブロモフェニル酢酸等であり、水溶液に対して０．０１〜２０．０％の範囲、このましくは０．１〜５．０％の割合で添加すれば良い。
本発明において用いられるハロゲン化脂肪酸としては、ブロモ酢酸、３−ブロモー２−（ブロモメチル）プロピオン酸、２−ブロモブタン酸、４−ブロモブタン酸、２−ブロモヘキサデカン酸、２−ブロモヘキサン酸、２−ブロモー３−メチルブタン酸、２−ブロモ２−メチルプロピオン酸、２−ブロモオクタン酸、８−ブロモオクタン酸、２−ブロモプロピオン酸、３−ブロモプロピオン酸、２−ブロモペンタン酸、５−ブロモペンタン酸、クロロ酢酸、クロロ酪酸、クロロプロピオン酸等であり、水溶液に対して０．０１〜２０．０％の範囲、好ましくは０．１〜５．０％の割合で添加すれば良い。
本発明の実施において、（化１）〜（化３）で表される化合物、酸、金属化合物、ハロゲン化芳香族カルボン酸及び、ハロゲン化脂肪酸の溶解が困難となる場合には、乳化あるいは、メタノール、エタノール、イソプロピルアルコール、ブタノール、アセトン等の水溶性溶媒を夫々単独で用いることが出来る他、任意の割合で混合して使用することも可能である。
前記水溶性溶媒は単独で用いられる他、酸等と併用することも出来る。特に酸単独では、（化１）〜（化３）で表される化合物あるいはその誘導体の溶解が困難となる場合には、水溶性溶媒を含有することが好ましく、この場合の含有率は０．０１〜６０．０％とすることが適当である。尚処理液には、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することは、水溶液のｐＨの安定性を高めるばかりでなく皮膜形成速度を速めるために有効である。
本発明の金属表面処理液により防錆化成皮膜、耐熱性化成皮膜、耐薬品性化成皮膜を金属表面に施すには、金属と処理液を接触させる。接触させる方法としては浸漬、噴霧、塗布による方法を用いる。接触させる処理液の温度は、０〜１００℃の温度範囲で、浸漬時間は数秒〜数十分の処理が適当である。又防錆化成皮膜形成後、耐湿性、耐熱性、耐薬品性をさらに向上させる処理として、赤外線、近赤外線、遠赤外線、紫外線照射処理を０〜３００℃の温度範囲で、処理時間数秒〜数十分の処理が効果的である。
【０００５】
【作用】
上記した処理法によれば、はんだ、無電解はんだ、ニッケル、銀、亜鉛等の金属表面の防錆に有効な、（化１）〜（化３）を主体とする防錆化成皮膜、耐熱性化成皮膜、耐薬品性化成皮膜が形成される。この化成皮膜は撥水性で耐湿性、耐熱性、耐薬品性にも優れ金属表面を長期間保護すると共に、ポストフラックスとの相溶性があるため、後工程のはんだ付け時のはんだ上がり性、濡れ性を良好に保つのである。
【０００６】
【実施例】
（化１）〜（化３）で表される化合物（表１記載の化合物）を１％、コハク酸、カルボン酸、アンモニア水、塩化第二銅、イオン交換水等を含む各種類の水溶液を作り、１００ｍＬ容器に入れ、液温を４０℃に加熱して調整した。他方、１ｃｍ×５ｃｍ×０．３ｍｍの銅板に、▲１▼電気はんだめっき、▲２▼無電解はんだめっき、▲３▼ニッケルめっき、▲４▼銀めっきをした。次いで脱脂、水洗、ソフトエッチング、水洗、酸洗、水洗し表面を洗浄して、上記（化１）〜（化３）で表される化合物を有効成分とする各種類の１％溶液に６０秒間浸漬した。その後水洗した▲１▼〜▲４▼の試験片を準備次いで、（１）▲１▼〜▲２▼の試験片を熱風乾燥機に入れ２００℃で５分間加熱して測定前にポストフラックスに浸漬してはんだ濡れ試験機を用いて濡れ時間を測定した。（２）▲１▼〜▲３▼の試験片を耐湿（ＭＩＬ−ＳＴＤ−２０２Ｆ−Ｍ−１０６Ｅ）処理した後、試験片をポストフラックスに浸漬してはんだ濡れ性試験機を用いて濡れ時間を測定した。（３）アルカリ性溶液を４０℃に加熱し、▲１▼〜▲２▼試験片を５分間浸漬した。その後水洗して表面状態（荒れ性、変色性）を見る。（４）▲４▼の試験片をガス腐食試験（１±０．３ｐｐｍＨ２Ｓ，２５±２℃、５％ＲＨ，１０日間）後の金属の表面状態（荒れ性、変色性）を見る。この試験の結果を表１に示した。
【表１】

Figure 0003668767
Figure 0003668767
Figure 0003668767
【０００７】
【発明の効果】
本発明の金属防錆処理方法によれば、はんだ、無電解はんだ、ニッケル、銀、亜鉛等の金属表面に、耐湿性、耐薬品性、耐熱性に優れた化成皮膜が形成し、金属表面を防錆するばかりでなく、はんだの濡れ性、はんだの広がり性、及びリフロー後のはんだ上がり性、濡れ性が良好という効果で、プリント配線板の電子部品を表面実装するのに特に顕著な効果を発揮しうるものである。また、パターンめっき法によるプリント配線板製造時のアルカリ性水溶液処理時のはんだ荒れ防止、回路切断の危険性をなくすばかりでなく、はんだ付け部のはんだを残しフュージング処理なしではんだ付け性を良好な状態に保ち得るものである。また、作業環境、安全性の面からも優れたプリント配線板、金属部品の製造ができうる。[0001]
[Industrial application fields]
The present invention relates to a processing method for improving the rust prevention, solder roughening prevention, discoloration prevention, alkali resistance, moisture resistance, chemical resistance, heat resistance and solderability of metals such as solder, electroless solder, nickel, silver and zinc. In particular, the present invention provides a method suitable for maintaining the solderability of these metals in a good state for a long period of time and for preventing the surface from being roughened by an alkaline solution during production of a printed wiring board. In addition, since both dissimilar metals can be treated, it is ideal for rust prevention of plated pinholes, and is suitable as a pinhole rust preventive for electroless solder, and as a sealant after nickel / gold plating of connectors It is.
[0002]
[Prior art]
A printed wiring board is manufactured by pattern plating. A copper-clad laminate is perforated, and chemical copper plating, electrolytic copper plating, and subsequently an alkali-developable photosensitive film soluble in an alkaline aqueous solution are placed on the copper-clad laminate. A negative circuit is formed, followed by electrolytic copper plating and solder plating, and then contacted with an alkaline aqueous solution to remove the alkali developing type photosensitive film.
At this time, the surface of the solder plating may be eroded with an alkaline aqueous solution, and the copper material may be exposed. In this case, the copper is etched with an alkaline etching solution to cut the circuit. Further, when the solder plating is left without the copper material being exposed and the solder through-hole substrate is manufactured, the soldering property is poor as it is, and it is necessary to perform a fusing process or the like.
Electroless solder as one of the solder joint technologies for printed wiring boards is performed by displacement plating, and its film is very thin and has a rough surface. For this reason, it becomes a porous film and the copper surface of the material is exposed. Moreover, since precipitation is also performed separately for lead and tin, a mixed film of both is formed. For this reason, formation of a copper-tin alloy having poor solderability and oxidation of lead and tin are likely to occur, and good solderability cannot be maintained for a long time unless fusing is performed after plating.
Nickel is easy to form a strong oxide film, and originally has poor solderability. Therefore, in printed wiring boards and connectors, when soldering is necessary, gold is plated on nickel to prevent oxidation.
Chromate treatment is performed for rust prevention of silver and zinc, but there is a problem because a harmful hexavalent chromium compound is used. Moreover, although paraffin etc. are melt | dissolved and apply | coated for a silver rust prevention, there exists a problem on environmental pollution, such as having to use a solvent.
[0003]
[Problems to be solved by the invention]
In the previous period, the solder plating film as the etching resist film in the conventional manufacturing method of the printed wiring board is inferior in reliability and prone to manufacturing defects. Therefore, it is desirable to prevent solder surface roughness that occurs during alkali development type photosensitive film peeling or during alkali etching, and to manage a good circuit, and to maintain good solderability. Is required. In electroless soldering, there is a strong demand for maintaining solderability without performing fusing because of the quality and the cost of giving large thermal stress to the substrate. Furthermore, there is a demand for nickel to prevent discoloration and maintain solderability without expensive gold plating. With regard to silver and zinc, there is an urgent need to prevent discoloration for a long period of time and to maintain good solderability by a safe treatment that does not contain harmful hexavalent chromium.
[0004]
[Means for Solving the Problems]
In view of such circumstances, the present invention has been made as a result of intensive studies. As a means for imparting excellent antirust properties to solder, electroless solder, silver, nickel, zinc, etc., the main component of the active ingredient is a compound represented by (Chemical Formula 1) to (Chemical Formula 3) or a salt of a derivative thereof. The metal is brought into contact with an aqueous solution containing at least one of these. What is necessary is just to add the salt of the compound or its derivative (s) represented by (Chemical Formula 1) to (Chemical Formula 3) at least in a proportion of 0.1 to 5.0% with respect to the acid aqueous solution.
Examples of acids used in the practice of the present invention include acetic acid, iodoacetic acid, bromoacetic acid, dimethylacetic acid, diethylacetic acid, α-bromoacetic acid, paranitrobenzoic acid, paratoluenesulfonic acid, picric acid, succinic acid, formic acid, succinic acid, maleic acid. Acid, acrylic acid, fumaric acid, tartaric acid, adipic acid, lactic acid, oleic acid, citric acid, metasulfonic acid, sulfamic acid and other organic acids, hydrochloric acid, sulfuric acid, phosphorous acid, phosphoric acid and other inorganic acids, other carboxylic acids, There are halogenated fatty acids, halogenated aromatic fatty acids and the like, and they may be added at a ratio of 0.01 to 20% with respect to water.
Representative compounds for supplying metal ions used in the practice of the present invention include lithium, beryllium, potassium, magnesium, zinc acetate, zinc formate, zinc lactate, zinc citrate, zinc benzoate, zinc oxalate, Zinc hydroxide, zinc bromide, zinc phosphate, zinc oxide, zinc chloride, lead acetate, lead hydroxide, zinc bromide, lead iodide, lead oxalate, lead borate, ferrous chloride, ferric chloride, bromide Cuprous, cupric bromide, cuprous iodide, copper formate, nickel chloride, nickel acetate, cuprous chloride, cupric chloride, cuprous oxide, cupric oxide, copper hydroxide phosphoric acid It is a metal compound such as copper, copper carbonate, copper acetate, copper sulfate, and may be added at a ratio of 0.001 to 5.0% with respect to water.
Examples of the halogenated aromatic carboxylic acid used in the practice of the present invention include 3-bromo-4-methylbenzoic acid, 4- (bromomethyl) phenylacetic acid, α-bromophenylacetic acid, α-bromotetradecanoic acid, 2-bromophenylacetic acid, It may be 3-bromophenylacetic acid, 4-bromophenylacetic acid, etc., and may be added in a range of 0.01 to 20.0%, preferably 0.1 to 5.0% with respect to the aqueous solution.
Examples of the halogenated fatty acid used in the present invention include bromoacetic acid, 3-bromo-2- (bromomethyl) propionic acid, 2-bromobutanoic acid, 4-bromobutanoic acid, 2-bromohexadecanoic acid, 2-bromohexanoic acid, 2-bromo- 3-methylbutanoic acid, 2-bromo-2-methylpropionic acid, 2-bromooctanoic acid, 8-bromooctanoic acid, 2-bromopropionic acid, 3-bromopropionic acid, 2-bromopentanoic acid, 5-bromopentanoic acid, They are chloroacetic acid, chlorobutyric acid, chloropropionic acid, etc., and may be added in a range of 0.01 to 20.0%, preferably 0.1 to 5.0% with respect to the aqueous solution.
In the practice of the present invention, when it becomes difficult to dissolve the compounds represented by (Chemical Formula 1) to (Chemical Formula 3) , acids, metal compounds, halogenated aromatic carboxylic acids, and halogenated fatty acids, emulsification or A water-soluble solvent such as methanol, ethanol, isopropyl alcohol, butanol, and acetone can be used alone, or can be used by mixing at an arbitrary ratio.
The water-soluble solvent can be used alone or in combination with an acid or the like. In particular, when the acid alone is difficult to dissolve the compound represented by (Chemical Formula 1) to (Chemical Formula 3) or a derivative thereof, it is preferable to contain a water-soluble solvent. It is appropriate to set it to 01 to 60.0%. It should be noted that adding a buffering substance such as aqueous ammonia or amines to the treatment solution is effective not only for increasing the pH stability of the aqueous solution but also for increasing the film formation rate.
In order to apply a rust-proof chemical film, a heat-resistant chemical film, and a chemical-resistant chemical film to the metal surface with the metal surface treatment liquid of the present invention, the metal and the treatment liquid are brought into contact with each other. As a method for contacting, a method by dipping, spraying or coating is used. The temperature of the treatment liquid to be contacted is in the temperature range of 0 to 100 ° C., and the immersion time is suitably from several seconds to several tens of minutes. In addition, after the formation of the rust-proof chemical film, infrared, near-infrared, far-infrared, and ultraviolet irradiation treatments are performed at a temperature range of 0 to 300 ° C. for several seconds to several hours as treatments for further improving moisture resistance, heat resistance, and chemical resistance. Sufficient treatment is effective.
[0005]
[Action]
According to the processing method described above, the solder, electroless solder, nickel, silver, effective rust of the metal surface such as zinc, (Formula 1) antirust conversion coating mainly to (Formula 3), heat resistance A chemical conversion film and a chemical resistant chemical conversion film are formed. This chemical film is water-repellent, has excellent moisture resistance, heat resistance, and chemical resistance, protects the metal surface for a long period of time, and is compatible with post-flux. Keeps good.
[0006]
【Example】
Various types of aqueous solutions containing 1% of the compounds represented by (Chemical Formula 1) to (Chemical Formula 3) (compounds described in Table 1), succinic acid, carboxylic acid, aqueous ammonia, cupric chloride, ion-exchanged water, etc. The liquid temperature was adjusted to 40 ° C. by heating in a 100 mL container. On the other hand, (1) electric solder plating, (2) electroless solder plating, (3) nickel plating, and (4) silver plating were applied to a 1 cm × 5 cm × 0.3 mm copper plate. Next, degreasing, water washing, soft etching, water washing, acid washing, water washing and washing of the surface are carried out for 60 seconds in each kind of 1% solution containing the compounds represented by (Chemical Formula 1) to (Chemical Formula 3) as active ingredients. Soaked. Then, prepare the test pieces (1) to (4) which were washed with water. (1) Place the test pieces (1) to (2) in a hot air drier and heat them at 200 ° C. for 5 minutes. Immersion time was measured using a solder wetting tester. (2) After the specimens (1) to (3) are treated with moisture resistance (MIL-STD-202F-M-106E), the specimen is immersed in a post flux and the wetting time is set using a solder wettability tester. It was measured. (3) The alkaline solution was heated to 40 ° C., and the test pieces (1) to (2) were immersed for 5 minutes. Then wash with water to see the surface condition (roughness, discoloration). (4) The surface condition (roughness, discoloration) of the metal after the gas corrosion test (1 ± 0.3 ppm H 2 S, 25 ± 2 ° C., 5% RH, 10 days) is observed for the specimen of (4). The results of this test are shown in Table 1.
[Table 1]
Figure 0003668767
Figure 0003668767
Figure 0003668767
[0007]
【The invention's effect】
According to the metal rust preventive treatment method of the present invention, a chemical conversion film excellent in moisture resistance, chemical resistance, and heat resistance is formed on a metal surface such as solder, electroless solder, nickel, silver, zinc, etc. In addition to rust prevention, the solder wettability, solder spreadability, reflow solderability, and good wettability are particularly effective for surface mounting of electronic components on printed wiring boards. It can be demonstrated. In addition to preventing solder roughening during alkaline aqueous solution processing during printed wiring board manufacturing by pattern plating and eliminating the risk of circuit disconnection, leaving solder on the soldered part and maintaining good solderability without fusing treatment It can be kept in. Also, it is possible to manufacture printed wiring boards and metal parts that are excellent in terms of work environment and safety.

Claims (6)

（化１）〜（化３）で表される化合物又はその誘導体の塩を少なくとも１種以上含有する水溶液に接触させることを特徴とする金属の表面処理法。
Figure 0003668767
（但し、式中Ｒ１＝水素、アルキル基、フェニルアルキル基、アリル基、Ｒ２＝アルキル基、フェニルアルキル基、Ｒ３＝水素、スルホン酸基、アルキル基、ハロゲン原子、ｎ＝０〜１７、ｘ＝１。）
Figure 0003668767
（但し、式中Ｒ１＝水素、アルキル基、フェニルアルキル基、アリル基、Ｒ２＝水素、アルキル基、フェニルアルキル基、アルキルフェニル基Ｒ３＝水素、スルホン酸基、アルキル基、ハロゲン原子、ｎ＝０〜１７、ｍ＝０〜３、ｘ＝１。）
Figure 0003668767
（但し、式中Ｒ１＝水素、アルキル基、フェニルアルキル基、アリル基、Ｒ２＝アルキル基、Ｒ３＝水素、スルホン酸基、アルキル基、ハロゲン原子、ｎ＝０〜７、ｍ＝０〜７、ｘ＝１。）A metal surface treatment method comprising contacting an aqueous solution containing at least one salt of a compound represented by (Chemical Formula 1) to (Chemical Formula 3) or a derivative thereof.
Figure 0003668767
(In the formula, R 1 = hydrogen, alkyl group, phenylalkyl group, allyl group, R 2 = alkyl group, phenylalkyl group, R 3 = hydrogen, sulfonic acid group, alkyl group, halogen atom, n = 0-17 , X = 1. )
Figure 0003668767
(Wherein R 1 = hydrogen, alkyl group, phenylalkyl group, allyl group, R 2 = hydrogen, alkyl group, phenylalkyl group, alkylphenyl group R 3 = hydrogen, sulfonic acid group, alkyl group, halogen atom, n = 0-17, m = 0-3, x = 1. )
Figure 0003668767
(In the formula, R 1 = hydrogen, alkyl group, phenylalkyl group, allyl group, R 2 = alkyl group, R 3 = hydrogen, sulfonic acid group, alkyl group, halogen atom, n = 0 to 7, m = 0. ~ 7, x = 1. ) （化１）〜（化３）で表される化合物又はその誘導体の塩の少なくとも１種以上と、酸と、金属イオンを含む水溶液に接触させることを特徴とする金属の表面処理法。A metal surface treatment method comprising contacting at least one of the compounds represented by (Chemical Formula 1) to (Chemical Formula 3) or a salt of a derivative thereof, an acid, and an aqueous solution containing a metal ion. （化１）〜（化３）で表される化合物又はその誘導体の塩の少なくとも１種以上と、酸と、金属イオンと、アンモニア塩類を含む水溶液に接触させる事を特徴とする金属の表面処理法。Metal surface treatment characterized by contacting with an aqueous solution containing at least one or more salts of the compound represented by (Chemical Formula 1) to (Chemical Formula 3) or a derivative thereof, an acid, a metal ion, and an ammonia salt. Law. 請求項１〜請求項３記載の金属の表面処理後、はんだリフロー処理を行うことを特徴とするプリント配線板の製造法。A method for producing a printed wiring board, comprising performing a solder reflow treatment after the surface treatment of the metal according to claim 1. 請求項１〜請求項３記載の金属の表面処理後、はんだ付け処理を行うことを特徴とするプリント配線板の製造法。A method for producing a printed wiring board, wherein a soldering process is performed after the surface treatment of the metal according to claim 1. （化１）〜（化３）で表される化合物又はその誘導体の塩の少なくとも１種以上と、有機酸、金属イオンを含む溶液で処理後、アルカリ性溶液処理を行うことを特徴とするプリント配線板の製造法。Printed wiring characterized by performing an alkaline solution treatment after treatment with a solution containing at least one of the compounds represented by (Chemical Formula 1) to (Chemical Formula 3) or a salt thereof and an organic acid or a metal ion. Board manufacturing method.
JP35475893A 1993-02-18 1993-12-24 Surface treatment method for metals such as solder, electroless solder, silver, nickel and zinc Expired - Fee Related JP3668767B2 (en)

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