JPH07118880A - Metal surface protective agent and treatment using the same - Google Patents

Abstract

PURPOSE:To improve preventing properties with respect to rust, solder leach and discoloration, alkali resistance, humidity resistance, chemical resistance and heat resistance of various metals by treating the surfaces of the metals with an aq. solution contg. a specific compound, an organic acid and a metallic compound. CONSTITUTION:A printing circuit board, etc., is immersed at 0 to 100 deg.C in an aq. solution contg. about 1% concn. of one of the compounds represented by the formula I to V and 0. 001 to 5% concn. of an organic acid such as acetic acid, formic acid, carboxylic acid, etc., and a metallic compound such as zinc formate, zinc phosphate, ferric chloride, etc., or additionally, >=30ppm of barium ions and halogen ions from a salt such as barium bromide, barium chloride, etc. Then the board is heated and dried in the air or in a nitrogen atmosphere by using the near infrared reflow furnace. Subsequently, the soldering is performed through attaching a solder powder on the board and thereafter the board is subjected to alkaline solution treatment and alkaline etching solution treatment. Thus, various metallic parts or printed circuit boards having excellent various characteristics can be formed on the surfaces of metals.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】この発明は、銅、銅合金、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
方法として好適なものである。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、無電解はんだのピンホールの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。また、高密度表面実装用電子部品のチップ及びパッ
ケージ等の接続用プリント配線板として好適なものであ
る。また、はんだ粉のはんだ加熱処理、アルカリ性エッ
チング液処理の銅スルーホールプリント配線板の製造と
して好適なものである。BACKGROUND OF THE INVENTION This invention relates to rust prevention, solder roughening, discoloration prevention, alkali resistance, moisture resistance and chemical resistance of metals such as copper, copper alloys, solders, electroless solders, nickel, silver and zinc. It is suitable as a treatment method for improving heat resistance and solderability. Further, since both dissimilar metals joined can be treated, it is suitable as a rust preventive for plating pinholes, a rust preventive for electroless solder pinholes, and a sealing agent after nickel / gold plating of a connector. It is also suitable as a printed wiring board for connection of chips and packages of high-density surface mounting electronic components. Further, it is suitable for producing a solder through heat treatment of solder powder and a copper through hole printed wiring board treated with an alkaline etching solution.

【０００２】[0002]

【従来の技術】従来、プリント配線板の銅又は銅合金か
らなる回路部を防錆し、はんだ付け性を保持する目的で
使用されているプリフラックスは、大別してプリント配
線板全体をコーティングするロジン系プリフラックス
と、選択的に銅又は銅合金と化学反応させるアルキルイ
ミダゾール系プリフラックスの２種類がある。前者は天
然ロジン、ロジンエステル、ロジン変成マレイン酸樹脂
等を、有機溶剤に溶解させたものをロールコターで塗布
するか、噴霧又は浸漬によつてプリント配線板全体に塗
布し、乾燥して被膜を形成する方法で用いられる。この
ため有機溶剤の揮散によって作業環境及び安全性が著し
く損われる欠点がある。又、ロジン系プリフラックスは
揮発性溶剤を使用しているため作業時引火の危険が伴う
という欠点も有している。他方、アルキルイミダゾール
系プリフラックスは水溶性であり、作業環境の面でも安
全性の面でも優れているが、化学反応したアルキルイミ
ダゾール銅錯体が高温に曝されると空気中の酸素と銅の
触媒作用で変質してポストフラックスの作用を阻害し
て、はんだ付け性を悪くするという欠点を有している。
プリント配線板の製造方法は、銅張積層板に穴あけ、化
学銅めっき、電気めっき、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イルムを銅張積層板上に陰画
回路を形成し、次いで電気めっき、はんだめっき後、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イ
ルムを除き、アルカリ性エッチング液で処理する。この
ため、はんだめっき後のアルカリ現像型感光性フイルム
剥離において、はんだ表面が侵され銅素材が露出するこ
とがある。この場合後工程のアルカリエッチングで銅が
エッチングされるという欠点を有している。2. Description of the Related Art Pre-flux, which has been conventionally used for the purpose of preventing corrosion of a circuit portion made of copper or a copper alloy of a printed wiring board and maintaining solderability, is roughly classified into rosins for coating the entire printed wiring board. There are two types of pre-flux, an alkyl-imidazole-based pre-flux that selectively chemically reacts with copper or a copper alloy. For the former, apply natural rosin, rosin ester, rosin-modified maleic acid resin, etc. dissolved in an organic solvent with a roll coater, or apply it to the entire printed wiring board by spraying or dipping, and then dry to form a film. Used in the method. Therefore, there is a drawback in that the working environment and safety are significantly impaired by the volatilization of the organic solvent. In addition, since rosin-based preflux uses a volatile solvent, it also has a drawback that it may cause a fire when working. On the other hand, the alkyl imidazole pre-flux is water-soluble and is excellent in terms of working environment and safety, but when the chemically reacted alkyl imidazole copper complex is exposed to high temperature, it is a catalyst of oxygen and copper in the air. It has a drawback that it is deteriorated by the action and hinders the action of the post-flux to deteriorate the solderability.
A method for manufacturing a printed wiring board is as follows: a hole is formed in a copper clad laminate, chemical copper plating, electroplating, and subsequently an alkali developing photosensitive film soluble in an alkaline aqueous solution is formed into a negative circuit on the copper clad laminate, and then a negative circuit is formed. After electroplating and solder plating, the film is brought into contact with an alkaline aqueous solution to remove the alkali developing type photosensitive film and treated with an alkaline etching solution. Therefore, in peeling the alkali-developable photosensitive film after solder plating, the solder surface may be attacked and the copper material may be exposed. In this case, there is a drawback that copper is etched in the subsequent alkaline etching.

【０００３】[0003]

【発明が解決しょうとする課題】近年プリント配線板に
電子部品をはんだ付けする方法として表面実装法が多く
採用されている。この表面実装法、電子部品の仮止め低
融点クリームはんだのリフロー等、プリント配線板が高
温に曝される機会が多くなり、プリント配線板のはんだ
付け性を保持するために用いられるプリフラックスの耐
熱性、即ちプリント配線板が高温に曝された後での低融
点クリームはんだの濡れ性、拡がり性、はんだ付け性が
優れていることがプリフラックスの性能に要求されるよ
うになった。又、大気汚染等に問題を有する揮発性溶剤
を使用せず、且つ高温に曝された後でもクリームはんだ
の濡れ性、はんだ付け性の優れたプリフラックスの開発
が切望されている。また、パターンめっき法によるプリ
ント配線板の製造方法では、エッチングレジスト膜の信
頼性に劣り製造不良が発生しやすい、そこで、アルカリ
現像型感光性フイルム剥離時、アルカリエッチング時の
はんだ荒れを防止し、良好な回路形成を得ると共にはん
だ付け性を良好な状態に保つ。また、無電解はんだにお
いては、基板へのサーマルストレスが強いばかりでなく
コストも高いフュージングを行なわず防錆処理により良
好なはんだ付け性を維持する。ニッケルにおいては高価
な金めっきを使用せずに変色を防止しまた良好なはんだ
付け性を維持する。銀、亜鉛については、有害な６価ク
ロム化合物を含有しない安全な溶液で処理し、長期間変
色を防止したりはんだ付け性を良好なはんだ付け性を維
持する。プリント配線板の製造方法では、クリームはん
だ印刷時のずれ、はんだの膜厚、生産性、コスト等が悪
い。そこで金属の露出部のみ選択的に粘着性化成被膜を
反応させた後、はんだ粉を付着させリフロー処理後の、
はんだ膜厚の均一性、膜厚のコントロールの優れたはん
だ基板の開発が切望されている。In recent years, the surface mounting method has been widely adopted as a method for soldering electronic components to a printed wiring board. Due to this surface mounting method, reflow of low melting point cream solder for temporary fixing of electronic parts, the printed wiring board is exposed to high temperatures frequently, and the heat resistance of the pre-flux used to maintain the solderability of the printed wiring board. Of the low melting point cream solder after the printed wiring board is exposed to a high temperature, the wettability, spreadability and solderability of the low melting point solder paste are required to be excellent in the performance of the preflux. Further, it is desired to develop a preflux which does not use a volatile solvent having a problem in air pollution and has excellent wettability and solderability of cream solder even after being exposed to a high temperature. Further, in the method of manufacturing a printed wiring board by the pattern plating method, the reliability of the etching resist film is inferior and the manufacturing failure is likely to occur, and therefore, when the alkali development type photosensitive film is peeled off, it prevents the solder roughening during the alkali etching, Good circuit formation is obtained and solderability is kept in a good state. Further, in the electroless solder, not only thermal stress to the substrate is strong but also costly fusing is not performed, but good solderability is maintained by rust preventive treatment. Nickel does not use expensive gold plating to prevent discoloration and maintain good solderability. Silver and zinc are treated with a safe solution containing no harmful hexavalent chromium compound to prevent discoloration for a long period of time and maintain good solderability. In the method of manufacturing a printed wiring board, the deviation during cream solder printing, the solder film thickness, the productivity, the cost, etc. are poor. Therefore, after selectively reacting the adhesive chemical conversion coating only on the exposed part of the metal, after the solder powder is attached and the reflow treatment is performed,
It is earnestly desired to develop a solder substrate excellent in uniformity of solder film thickness and control of film thickness.

【０００４】[0004]

【課題を解決するための手段】本発明者は、このような
事情に鑑み、高温に曝された後でも低融点クリームはん
だの濡れ性、拡がり性。リフロー後のはんだ上がり性、
濡れ性の良い耐熱水溶性プリフラックス剤。また、アル
カリ現像型感光性フイルム剥離時、アルカリエッチング
時のはんだ荒れ、変色防止のためのはんだ防錆剤、無電
解はんだ防錆剤。また、コネクター部品、ニッケル基板
等の防錆、耐湿性、耐熱性、はんだ付け性の優れた防錆
剤。また、金属の露出部のみ選択的に粘着膜を反応させ
金属粉を付着させる粘着剤。また、銅の回路部に化成被
膜を形成させアルカリエッチング液に耐える表面保護剤
に関して鋭意検討を重ねた結果、本発明の実施において
用いられる有機酸としては、酢酸、ヨード酢酸、ブロモ
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、ハロゲン化芳香族カ
ルボン酸等があり水に対して０．０１〜２０％の割合で
添加すれば良い。有効成分として（化１）〜（化５）で
表わされる化合物を１種類又は２種類以上を酸水溶液に
対して０．１〜５％の割合で添加すれば良い。本発明方
法の実施において使用される金属イオンとしての化合物
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
ウン酸亜鉛、安息香酸亜鉛、蓚酸亜鉛、水酸化亜鉛、臭
化亜鉛、リン酸亜鉛、酸化亜鉛、塩化亜鉛、酢酸鉛、水
酸化鉛、臭化鉛、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、
リン酸銅、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％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−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％の範
囲、好ましくは０．１〜５％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−ブロモヘキサンデカン酸、２−ブロモヘキサン
酸、２−ブロモ−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％の範囲、好ま
しくは０．１〜５％の割合で添加すれば良い。本発明の
実施においては、（化１）〜（化５）で表わされる化合
物及び有機酸、金属化合物、ハロゲン化芳香族カルボン
酸、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
独に用いることができる他、任意の割合で混合して使用
することも可能である。例えば上記水溶性溶媒は単独で
用いられる他有機酸等と併用することもでき、特に有機
酸等単独では、（化１）〜（化５）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
溶媒を含有させることが好ましく、この場合の含有率は
０．０１〜６０％とすることが適当である場合が多い。
本発明方法の実施において使用されるバリウムイオンと
しての化合物の代表的なものとしては酢酸バリウム、臭
化バリウム、塩化バリウム、弗化バリウム、炭酸バリウ
ム、水酸化バリウム、硝酸バリウム、燐酸バリウム、酸
化バリウム、蓚酸バリウム等であり、処理液に対して、
バリウムイオン濃度が３０ｐｐｍ以上、好ましくは２０
０〜５０００ｐｐｍの割合で添加すれば良い。また、バ
リウムイオンとハロゲンイオン共存させる場合に、ハロ
ゲンイオン供給源として使用する化合物は、塩化ナトリ
ウム、塩化カリウム、沃化ナトリウム、弗化ナトリウ
ム、弗化カリウム、塩化バリウム、臭化バリウム、塩化
バリウム、塩化アンモニウム、臭化アンモニウム等のア
ルカリ金属、及びアンモニウムイオン、のハロゲン化
物、塩酸、臭化水素酸等のハロゲン化水素酸、塩化クロ
ム、塩化亜鉛、臭化亜鉛、塩化鉛、塩化ニッケル、臭化
ニッケル、臭化第一銅、臭化第二銅、ヨウ化銅、塩化第
二銅等の金属のハロゲン化物であり、処理液に対して、
ハロゲンイオン濃度は３０ｐｐｍ以上、好ましくは２０
０〜５０００ｐｐｍの割合で添加すれば良い。なお処理
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被膜形成速度を速めるために有効で
ある。本発明方法の実施において使用される（化１）〜
（化５）で表される化合物及び有機酸、金属化合物並び
に約３０ｐｐｍ以上のバリウムイオンとハロゲンイオン
を含む水溶液に、接触させることによって、化成被膜の
耐熱性、はんだ濡れ性、はんだ広がり性がさらに高める
ことが出来る。本発明の金属表面処理剤により防錆化成
被膜、粘着性化成膜、耐薬品性化成被膜を金属表面に施
すには、金属と処理液とを接触させる。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。又防錆化成被膜
形成後、耐湿性、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。In view of such circumstances, the present inventors have found that the low melting point cream solder has wettability and spreadability even after being exposed to a high temperature. Solderability after reflow,
Heat-resistant water-soluble pre-flux agent with good wettability. Also, a solder rust preventive and an electroless solder rust preventive to prevent solder roughening and discoloration during alkaline etching when peeling an alkaline development type photosensitive film. In addition, it is a rust preventive agent with excellent rust prevention, moisture resistance, heat resistance, and solderability for connector parts and nickel substrates. Also, an adhesive that selectively reacts the adhesive film only on the exposed portion of the metal to attach the metal powder. In addition, as a result of extensive studies on a surface protective agent that forms a chemical conversion film on a circuit portion of copper and resists an alkaline etching solution, as an organic acid used in the practice of the present invention, acetic acid, iodoacetic acid, bromoacetic acid, dimethylacetic acid , Diethyl acetic acid, α-bromoacetic acid,
Organic acids such as para-nitrobenzoic acid, para-toluenesulfonic acid, picric acid, oxalic acid, formic acid, succinic acid, maleic acid, acrylic acid, fumaric acid, tartaric acid, adipic acid, lactic acid, oleic acid, citric acid, metasulfonic acid, sulfamic acid, etc. , Inorganic acids such as hydrochloric acid, sulfuric acid, phosphorous acid, phosphoric acid, and other carboxylic acids, halogenated fatty acids, halogenated aromatic carboxylic acids, etc., and they may be added in a proportion of 0.01 to 20% with respect to water. . One or more compounds represented by (Chemical formula 1) to (Chemical formula 5) may be added as an active ingredient at a ratio of 0.1 to 5% with respect to the acid aqueous solution. Typical compounds used as metal ions in the practice of the method of the present invention include lithium, beryllium, potassium, magnesium, zinc acetate, zinc formate, zinc lactate, zinc counate, zinc benzoate, zinc oxalate, and water. Zinc oxide, zinc bromide, zinc phosphate, zinc oxide, zinc chloride, lead acetate, lead hydroxide, lead 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,
It is a metal compound such as copper phosphate, copper carbonate, copper acetate, and copper sulfate, and may be added in a proportion of 0.001 to 5% with respect to water. The halogenated aromatic carboxylic acid used in the practice of the present invention includes 3-bromo-4methylbenzoic acid,
4- (bromomethyl) phenylacetic acid, α-bromophenylacetic acid, α-bromotetradecanoic acid, 2-bromophenylacetic acid, 3-bromophenylacetic acid, 4-bromophenylacetic acid, etc., and 0.01 to 20 with respect to the aqueous solution. %, Preferably 0.1 to 5%.
The halogenated fatty acid used in the practice of the present invention includes bromoacetic acid and 3-bromo-2- (bromomethyl).
Propionic acid, 2-bromobutanoic acid, 4-bromobutanoic acid, 2-bromohexanedecanoic acid, 2-bromohexanoic acid, 2-bromo-3-methylbutanoic acid, 2-bromo2-
Methylpropionic acid, 2-bromooctanoic acid, 8-bromooctanoic acid, 2-bromopropionic acid, 3-bromopropionic acid, 2-bromopentanoic acid, 5-bromopentanoic acid, chloroacetic acid, chlorobutyric acid, chloropropionic acid, etc. Therefore, it may be added in the range of 0.01 to 20%, preferably 0.1 to 5% 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 5) and organic acids, metal compounds, halogenated aromatic carboxylic acids, and halogenated fatty acids, emulsification or methanol Water-soluble solvents such as ethanol, isopropyl alcohol, butanol, and acetone can be used alone, or can be used by mixing them at an arbitrary ratio. For example, the above water-soluble solvent may be used alone or in combination with other organic acids, etc. In particular, when the organic acid alone is used, it is difficult to dissolve the compound represented by (Chemical formula 1) to (Chemical formula 5) or its derivative. In such a case, it is preferable to include a water-soluble solvent, and in this case, the content ratio is often appropriate to be 0.01 to 60%.
Representative of the compounds as barium ions used in the practice of the method of the invention are barium acetate, barium bromide, barium chloride, barium fluoride, barium carbonate, barium hydroxide, barium nitrate, barium phosphate, barium oxide. , Barium oxalate, etc.
Barium ion concentration is 30 ppm or more, preferably 20
It may be added at a rate of 0 to 5000 ppm. When coexisting with barium ions and halogen ions, the compounds used as the halogen ion source are sodium chloride, potassium chloride, sodium iodide, sodium fluoride, potassium fluoride, barium chloride, barium bromide, barium chloride, Alkali metals such as ammonium chloride and ammonium bromide, and halides of ammonium ions, hydrohalic acid such as hydrochloric acid and hydrobromic acid, chromium chloride, zinc chloride, zinc bromide, lead chloride, nickel chloride, bromide Nickel, cuprous bromide, cupric bromide, copper iodide, a halide of a metal such as cupric chloride, with respect to the treatment liquid,
Halogen ion concentration is 30 ppm or more, preferably 20
It may be added at a rate of 0 to 5000 ppm. It should be noted that adding a substance having a buffering action such as aqueous ammonia or amines to the treatment liquid is effective not only for enhancing the stability of PH of the aqueous solution but also for accelerating the film formation rate. Used in the implementation of the method of the present invention
By bringing the compound represented by (Chemical Formula 5), an organic acid, a metal compound, and an aqueous solution containing about 30 ppm or more of barium ions and halogen ions into contact, the heat resistance, solder wettability, and solder spreadability of the chemical conversion film are further improved. Can be raised. In order to apply a rust-proof chemical conversion coating film, a tackifying film formation, and a chemical resistance chemical conversion coating film on the metal surface with the metal surface treatment agent of the present invention, the metal and the treatment liquid are brought into contact with each other. As a method of contacting, a method of dipping, spraying or coating is used. It is suitable that the temperature of the treatment liquid to be brought into contact is in the temperature range of 0 to 100 ° C. and the immersion time is several seconds to several tens of minutes. In addition, after the formation of the rust-proof chemical conversion film, infrared, near-infrared, far-infrared, and ultraviolet irradiation treatments are used as treatments to further improve moisture resistance and chemical resistance.
It is effective to perform the treatment at a temperature range of up to 300 ° C for a treatment time of several seconds to several tens of minutes.

【０００５】[0005]

【作用】上記した処理方法によれば、銅、銅合金、はん
だ、無電解はんだ、ニッケル、銀、亜鉛等の金属表面に
防錆に有効な、（化１）〜（化５）を主体とする防錆化
成被膜、粘着性化成被膜、耐薬品性化成被膜が形成され
る。これらの化成被膜は揆水性で耐湿性、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、低融点
クリームはんだの濡れ性、拡がり性、リフロー後のはん
だ上がり性、濡れ性が良好である。また、粘着性化成被
膜にはんだ粉を付着させリフロー処理後ののはんだ膜厚
の均一性が良好である。また必要な銅回路部に耐薬品性
化成被膜を形成させた後アルカリエッチング液処理して
銅スルーホール配線板の製造成が良好である。且つ作業
環境、安全性の面からも優れたプリント配線板の製造が
できる。According to the above treatment method, (Chemical formula 1) to (Chemical formula 5) which are effective for rust prevention on metal surfaces such as copper, copper alloy, solder, electroless solder, nickel, silver and zinc are mainly used. A rustproof chemical conversion coating, an adhesive chemical conversion coating, and a chemical resistant chemical conversion coating are formed. These chemical conversion coatings are water-repellent, have excellent moisture resistance, heat resistance, and chemical resistance, and protect the metal surface for a long period of time, as well as the wettability, spreadability, solder rise after reflow, and wettability of low melting point cream solder. It is good. Further, the uniformity of the solder film thickness after the solder powder is adhered to the adhesive chemical conversion film and the reflow treatment is performed is good. Further, a chemical resistant chemical conversion film is formed on a required copper circuit portion and then treated with an alkali etching solution, whereby the production of a copper through-hole wiring board is good. In addition, it is possible to manufacture a printed wiring board excellent in terms of work environment and safety.

【０００６】[0006]

【実施例】（化１）〜（化５）で表される化合物（表１
の記載の化合物）を１％、蟻酸、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°Ｃに加
熱し調整した。他方、１ｃｍ×５ｃｍ×０．３ｍｍの銅
板に、硫酸銅めっき、無電解銅めっき、電気はん
だめっき、無電解はんだめっき、銀めっき、ニッ
ケルめっきをした。〜の試料片を準備し、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５）で表される化合物
を有効成分とする各種類の１％水溶液に６０秒間浸漬し
た。その後水洗した後ち、（１）熱風乾燥機に入れ２０
０℃で１０分間加熱して測定前にポストフラックスに浸
漬しはんだ濡れ性試験機を用いて濡れ時間を測定した。
（２）耐湿（９０％ＲＨ／４０℃／９６ｈｒ）処理後の
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）アルカリ現像型
感光性フイルム剥離液を４０℃に加熱し、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）アルカリエッチング剥離液を４０℃
に加熱し、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。（５）（化１）〜
（化５）で表される化合物を有効成分とする各種１％水
溶液に３分間浸漬した。その後水洗しはんだ粉を塗布し
て粘着性およびリフロー後の膜の均一性を見る。この試
験結果は表１に示した。EXAMPLES Compounds represented by (Chemical formula 1) to (Chemical formula 5) (Table 1
1% of the above compound), make each kind of aqueous solution containing formic acid, carboxylic acid, ammonia water, cupric chloride, ion-exchanged water, etc., put it in a 100 ml container, and heat it to 40 ° C to adjust it. did. On the other hand, a copper plate of 1 cm x 5 cm x 0.3 mm was plated with copper sulfate, electroless copper, electric solder, electroless solder, silver and nickel. Sample pieces of to are prepared, and then degreased, washed with water, soft etching, washed with water, pickled, washed with water to wash the surface, and each containing the compound represented by the above (Chemical formula 1) to (Chemical formula 5) as an active ingredient. It was immersed in a 1% aqueous solution of one kind for 60 seconds. Then, after washing with water, (1) put it in a hot air dryer and
It was heated at 0 ° C. for 10 minutes, immersed in post flux before measurement, and the wetting time was measured using a solder wettability tester.
(2) The test piece after the moisture resistance (90% RH / 40 ° C./96 hr) treatment was dipped in post flux and the wetting time was measured using a solder wettability tester. (3) The alkali developing type photosensitive film stripping solution was heated to 40 ° C. and the test piece was immersed for 5 minutes. After that, wash with water and check the surface condition (roughness, discoloration). (4) Alkaline etching stripper at 40 ° C
Then, the test piece was immersed for 5 minutes. After that, wash with water and check the surface condition (roughness, discoloration). (5) (Chemical formula 1)
It was dipped in various 1% aqueous solutions containing the compound represented by (Chemical Formula 5) as an active ingredient for 3 minutes. Then, wash with water and apply solder powder to check the adhesiveness and uniformity of the film after reflow. The test results are shown in Table 1.

【表１】 [Table 1]

【０００７】[0007]

【実施例】（化１）〜（化５）で表される化合物（表１
の記載の化合物）を１％、蟻酸、カルボン酸、アンモニ
ア水、塩化第二銅、塩化バリウム、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°Ｃに加熱し調整した。他方、１ｃｍ×５ｃｍ×
０．３ｍｍの銅板に、硫酸銅めっき、無電解銅めっ
き、電気はんだめっき、無電解はんだめっき、銀
めっき、ニッケルめっきをした。〜の試料片を準
備し、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５）で
表される化合物を有効成分とする各種類の１％水溶液に
６０秒間浸漬した。その後水洗した後ち、（１）熱風乾
燥機に入れ２００℃で１０分間加熱して測定前にポスト
フラックスに浸漬しはんだ濡れ性試験機を用いて濡れ時
間を測定した。（２）耐湿（９０％ＲＨ／４０℃／９６
ｈｒ）処理後の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）
アルカリ現像型感光性フイルム剥離液を４０℃に加熱
し、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）アルカリエッチング
剥離液を４０℃に加熱し、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。
（５）（化１）〜（化５）で表される化合物を有効成分
とする各種１％水溶液に３分間浸漬した。その後水洗し
はんだ粉を塗布して粘着性およびリフロー後の膜の均一
性を見る。この試験結果は上記実施例と同じ結果であっ
た。また、水溶液に硫酸根が混入した場合でも塩化バリ
ュウムの効果により良い結果が得られた。EXAMPLES Compounds represented by (Chemical formula 1) to (Chemical formula 5) (Table 1
1%, formic acid, carboxylic acid, ammonia water, cupric chloride, barium chloride, ion-exchanged water, etc., to prepare an aqueous solution of each type, put it in a 100 ml container, and bring the solution temperature to 40 ° C. It was heated and adjusted. On the other hand, 1 cm x 5 cm x
A 0.3 mm copper plate was plated with copper sulfate, electroless copper, electric solder, electroless solder, silver and nickel. Sample pieces of to are prepared, and then degreased, washed with water, soft etching, washed with water, pickled, washed with water to wash the surface, and each containing the compound represented by the above (Chemical formula 1) to (Chemical formula 5) as an active ingredient. It was immersed in a 1% aqueous solution of one kind for 60 seconds. Then, after washing with water, (1) it was put in a hot air drier and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. (2) Moisture resistance (90% RH / 40 ° C / 96
hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. (3)
The alkali developing type photosensitive film stripping solution was heated to 40 ° C. and the test piece was immersed for 5 minutes. After that, wash with water and check the surface condition (roughness, discoloration). (4) The alkaline etching stripping solution was heated to 40 ° C., and the test piece was immersed for 5 minutes. After that, wash with water and check the surface condition (roughness, discoloration).
(5) It was immersed for 3 minutes in various 1% aqueous solutions containing the compounds represented by (Chemical Formula 1) to (Chemical Formula 5) as active ingredients. Then, wash with water and apply solder powder to check the adhesiveness and uniformity of the film after reflow. The test result was the same as that of the above-mentioned example. Also, even when sulfate was mixed in the aqueous solution, good results were obtained due to the effect of barium chloride.

【０００８】[0008]

【発明の効果】本発明の処理方法によれば、金属表面
に、耐湿性、耐熱性、耐薬品性に優れた化成防錆被膜、
粘着性化成被膜、耐薬品化成被膜が形成し、低融点クリ
ームはんだの濡れ性、拡がり性、また、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、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、粘着性化成被膜
は、防錆、耐熱性に優れ、はんだ粉の付着が良くリフロ
ー後のはんだ拡がり性、濡れ性及び均一性に優れ、且つ
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。According to the treatment method of the present invention, a chemical conversion rust-preventive coating excellent in moisture resistance, heat resistance and chemical resistance is formed on a metal surface,
Adhesive chemical conversion coating and chemical resistant chemical conversion coating are formed, and it has the effect of good wettability and spreadability of low melting point cream solder, and solderability after reflow and good wettability. It is possible to exert a remarkable effect. In addition, the pattern plating method not only prevents the solder from becoming rough when processing alkaline aqueous solutions during the manufacture of printed wiring boards and eliminates the risk of circuit disconnection, but also leaves solder at the soldering part and improves solderability without fusing treatment. It can be kept in a state. In addition, the adhesive chemical conversion coating has excellent rust prevention, heat resistance, good adhesion of solder powder, excellent solder spreadability after reflow, wettability, and uniformity, as well as excellent work environment and safety printing. It is possible to manufacture wiring boards and metal parts.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 山口 知浩 埼玉県鴻巣市箕田362−24 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomohiro Yamaguchi 362-24 Minota, Konosu City, Saitama Prefecture

Claims (8)

【特許請求の範囲】[Claims] 【請求項１】 （化１）〜（化５）で表される化合物又
はその誘導体の塩を含有する水溶液に、接触させること
を特徴とする金属の表面保護剤および処理方法。 【化１】 【化２】 【化３】 【化４】 【化５】 1. A surface protective agent for metal and a treatment method, which comprises contacting with an aqueous solution containing a salt of a compound represented by (Chemical formula 1) to (Chemical formula 5) or a derivative thereof. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] 【請求項２】 （化１）〜（化５）で表される化合物及
び有機酸、金属化合物を含む水溶液に、接触させること
を特徴とする金属の表面保護剤および処理方法。2. A metal surface protective agent and a treatment method, which comprises contacting with an aqueous solution containing a compound represented by (Chemical formula 1) to (Chemical formula 5), an organic acid, and a metal compound. 【請求項３】 （化１）〜（化５）で表される化合物及
び有機酸並びに約３０ｐｐｍ以上のバリウムイオンとハ
ロゲンイオンを含む水溶液に、接触させることを特徴と
する金属の表面保護剤および処理方法。3. A surface protective agent for a metal, which is brought into contact with a compound represented by (Chemical Formula 1) to (Chemical Formula 5), an organic acid, and an aqueous solution containing about 30 ppm or more of barium ion and halogen ion. Processing method. 【請求項４】 （化１）〜（化５）で表される化合物及
び有機酸、金属化合物並びに約３０ｐｐｍ以上のバリウ
ムイオンとハロゲン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保護剤および処理方法。4. A surface of a metal, which is brought into contact with a compound represented by (Chemical Formula 1) to (Chemical Formula 5), an organic acid, a metal compound, and an aqueous solution containing about 30 ppm or more of barium ions and halogen ions. Protective agent and treatment method. 【請求項５】 請求項１〜請求項４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
配線板の製造方法。5. A method of manufacturing a printed wiring board, which comprises performing a soldering treatment after the surface treatment of the metal according to any one of claims 1 to 4. 【請求項６】 請求項１〜請求項４記載の金属の表面処
理後、空気中または窒素雰囲気中で加熱する赤外線リフ
ロー、近赤外線リフロー、遠赤外線リフロー、窒素リフ
ロー、ベーパー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方法。6. After the surface treatment of the metal according to any one of claims 1 to 4, infrared reflow, near infrared reflow, far infrared reflow, nitrogen reflow, vapor reflow treatment of heating in air or a nitrogen atmosphere is performed. A method for manufacturing a characteristic printed wiring board. 【請求項７】 請求項１〜請求項４記載の金属の表面処
理後、はんだ粉を付着させた後、または、はんだ粉を付
着させポストフラックスを塗布した後、赤外線リフロ
ー、近赤外線リフロー、遠赤外線リフロー、窒素リフロ
ー、ベーパーリフロー処理等の加熱処理を行うことを特
徴とするプリント配線板の表面処理方法。7. An infrared reflow, a near infrared reflow, a far-infrared reflow, after the surface treatment of the metal according to any one of claims 1 to 4, after applying solder powder or after applying solder powder and applying post flux. A surface treatment method for a printed wiring board, which comprises performing heat treatment such as infrared reflow, nitrogen reflow, and vapor reflow treatment. 【請求項８】 請求項１〜請求項４記載の金属の表面処
理後、アルカリ性溶液処理、アルカリ性エッチング液処
理を行うことを特徴とするプリント配線板の製造方法。8. A method for producing a printed wiring board, which comprises performing an alkaline solution treatment and an alkaline etching solution treatment after the surface treatment of the metal according to any one of claims 1 to 4.