JP3646788B2

JP3646788B2 - Method and apparatus for activation treatment of base material surface

Info

Publication number: JP3646788B2
Application number: JP2001265032A
Authority: JP
Inventors: 英夫吉田; 正人曽根; 健太郎阿部
Original assignee: 英夫吉田
Priority date: 2001-08-31
Filing date: 2001-08-31
Publication date: 2005-05-11
Anticipated expiration: 2021-08-31
Also published as: JP2003073868A

Description

【０００１】
【発明の属する技術分野】
本発明は、例えば電気メッキ等の電気化学的処理における前処理に好適で、安全かつ安価な溶液によって、金属等母材表面の脱脂処理と酸化被膜除去とを同時かつ効率良く合理的に行なえ、生産性の向上と設備費の低減を図れるとともに、廃液処理を合理化し、その再利用と環境汚染の防止を図れるようにした母材表面の活性化処理方法およびその処理装置に関する。
【０００２】
【従来の技術】
例えば、電気メッキ等の電気化学的処理では、その前処理工程の脱脂洗浄や酸洗いによって、被処理物である金属表面の油脂分や酸化皮膜を除去し、金属表面を活性化処理して、良好な金属皮膜を被覆可能にしている。
【０００３】
前記脱脂洗浄は、アルカリ水溶液に被処理物を浸漬し、また前記酸洗いは、硫酸または塩酸を希釈した酸性水溶液に被処理物を浸漬して行なわれ、この後これらを水洗いし、その排液に酸性またはアルカリ性薬剤を投入して中和し、これを工場から排出していた。
【０００４】
したがって、従来の前処理工程は専用の浴槽と水洗い槽を要し、設備が大掛かりになるとともに、種々の薬剤と多量の水を要して処理コストが嵩み、しかも脱脂処理と酸洗いとの間に水洗いが介在して時間が掛かり、生産性が悪いばかりか、前記中和処理では鉛や亜鉛、スズ等の重金属を除去できず、そのための排水処理設備を要する等して、設備費が増大していた。
【０００５】
更に、従来の前処理工程は、処理液の飛散や有害なガスが発生する状況下での作業を強いられて作業環境が悪く、しかも前記酸洗い工程で発生する水素ガスによって、被処理物が水素脆性を起す惧れがあり、この水素脆性の除去に別途の手段を要する等の問題があった。
【０００６】
このような問題を解決するものとして、特開２０００−７３１９１号公報では、有機溶媒であるホスフィンを含有させた溶液を用い、該溶液中に被処理物を浸漬し、若しくはこれを刷毛やスプレ−で塗布して、強酸やシアン等の危険な薬剤や有毒な薬剤を要せず、実質的に母材を侵すことなく、油脂分や酸化皮膜を除去するようにしている。
【０００７】
しかし、前記ホスフィンは高価で生産コストの上昇を助長するとともに、油脂分や酸化皮膜を十分に除去できない、という問題があった。
【０００８】
ところで、半導体や精密機械部品等の洗浄方法として、超臨界流体や亜臨界の高密度流体を洗浄溶媒に用いる洗浄方法は、例えば特開２０００−３０８８６２号公報等で提案されている。
しかし、前記方法は、機械部品等に付着した油脂分の除去には対応できるが、機械部品等の酸化皮膜の除去には対応できず、その場合は別途に酸化皮膜の除去処理を要して、生産性が悪く設備費の上昇を助長する。
【０００９】
また、他の方法として、洗浄媒体である二酸化炭素を加圧し、粒子状のドライアイスを洗浄ガンから噴出し、これを被洗浄部材の表面に吹き付けて、前記部材表面の油脂分を吹き飛ばすようにした方法が知られている。
しかし、この方法も前述と同様で、油脂分の除去には対応できるが、酸化皮膜の除去には対応できない、という問題がある。
【００１０】
【発明が解決しようとする課題】
本発明はこのような問題を解決し、例えば電気メッキ等の電気化学的処理における前処理に好適で、安全かつ安価な溶液によって、金属等母材表面の脱脂処理と酸化被膜除去とを同時かつ効率良く合理的に行なえ、生産性の向上と設備費の低減を図れるとともに、廃液処理を合理化し、その再利用と環境汚染の防止を図れるようにした母材表面の活性化処理方法およびその処理装置を提供することを目的とする。
【００１１】
【課題を解決するための手段】
請求項１の発明は、加圧二酸化炭素を被接触部材に接触し、被処理部材表面の油脂を分離若しくは剥離するとともに、前記加圧二酸化炭素を水に溶解して酸化皮膜除去溶液を生成し、該酸化皮膜除去溶液を被処理部材に接触させて、被処理部材表面の酸化皮膜を除去し、前記脱脂洗浄と酸化皮膜除去処理とを同時に処理する母材表面の活性化処理方法において、前記脱脂洗浄と酸化皮膜除去処理とを開放空間で行ない、脱脂洗浄と酸化皮膜除去処理を迅速かつ効率良く安価で合理的に行ない、生産性の向上と設備費の低減を図れ、設備ないしその設置スペ−スのコンパクト化を図るとともに、従来のような密閉した容器内での処理法に比べ、作業スペ−スを容易に確保し作業性を向上し得るようにしている。
【００１２】
請求項２の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、酸素の供給を遮断した開放空間で行ない、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られるようにしている。
請求項３の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、二酸化炭素の雰囲気下で行ない、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られるようにしている。
請求項４の発明は、前記脱脂洗浄と酸化皮膜除去処理後、酸素の供給を遮断しおよびまたは二酸化炭素の雰囲気下でメッキ処理するようにして、母材表面の酸化を防止し、その活性化した表面状態を維持して、良好な金属皮膜を得られるようにしている。
【００１３】
請求項５の発明は、前記脱脂洗浄または酸化皮膜除去処理後の処理液の再利用時、重度に汚損した処理液を減圧して二酸化炭素の溶解度を低下し、下水へ排水可能にして、処理液の十分な再利用を図るとともに、処理液の酸性濃度を低下し、中和設備を要することなく安全かつ安価に排水可能にしている。
【００１４】
請求項６の発明は、加圧二酸化炭素を被接触部材に接触可能にし、被処理部材表面の油脂を分離若しくは剥離可能にするとともに、前記加圧二酸化炭素を水に溶解して酸化皮膜除去溶液を生成可能にし、該酸化皮膜除去溶液を被処理部材に接触可能にして、被処理部材表面の酸化皮膜を除去可能にし、前記脱脂洗浄と酸化皮膜除去処理とを同時に処理可能にした母材表面の活性化処理装置において、前記脱脂洗浄と酸化皮膜除去処理とを開放空間で実行可能にし、脱脂洗浄と酸化皮膜除去処理を迅速かつ効率良く安価で合理的に行ない、生産性の向上と設備費の低減を図れ、設備ないしその設置スペ−スのコンパクト化を図るとともに、従来のような密閉した容器内での処理装置に比べ、作業スペ−スを容易に確保し作業性を向上し得るようにしている。
【００１５】
請求項７の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、酸素の供給を遮断した開放空間で実行可能にし、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られるようにしている。
請求項８の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、二酸化炭素の雰囲気下で実行可能にし、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られるようにしている。
請求項９の発明は、前記脱脂洗浄と酸化皮膜除去処理後、酸素の供給を遮断しおよびまたは二酸化炭素の雰囲気下でメッキ処理可能にし、母材表面の酸化を防止し、その活性化表面を維持して、良好な金属皮膜を得られるようにしている。
【００１６】
請求項１０の発明は、前記酸化皮膜除去溶液と、超臨界二酸化炭素とを吹付ガンに導き、これらを吹付ガンに設けた各噴口から同時に噴出可能にし、小形軽量な装置によって、脱脂洗浄と酸化皮膜除去の同時処理を高精密に実行可能にしている。
【００１７】
請求項１１の発明は、前記超臨界二酸化炭素の噴口の周囲に、圧縮空気源に連通する環状口を設け、環状の空気流によって超臨界二酸化炭素の擾乱を防止し、安定した脱脂洗浄を得られるようにしている。
【００１８】
請求項１２の発明は、前記各噴口を離間して配置し、前記超臨界二酸化炭素の噴口側へ吹付ガンを移動可能にし、前記酸化皮膜除去溶液と超臨界二酸化炭素とを吹付け、脱脂洗浄を酸化皮膜除去に先行して自然に行なえ、酸化皮膜除去を精密かつ合理的に処理できるようにしている。
【００１９】
請求項１３の発明は、前記酸化皮膜除去溶液の噴口の外側に、前記超臨界二酸化炭素の噴口を同心円状に配置し、吹付ガンの移動方向を規制することなく、吹付ガンの全ゆる移動方向に対し、脱脂洗浄を酸化皮膜除去に先行可能にし、酸化皮膜除去を精密かつ合理的に処理できるようにしている。
【００２０】
【発明の実施の形態】
以下、本発明の基本構成を電気メッキ（ニッケルメッキ）の前処理である脱脂および酸化皮膜除去（以下、酸洗いと云う）工程に適用した図示の実施形態について説明すると、図１および図２において１はステンレス鋼製の有底筒状の耐圧性の脱脂槽若しくは酸洗い槽（以下、浴槽と呼ぶ）で、その内面を塩化ビニ−ルや硬質ゴムでライニングしており、その上側の開口部に蓋体２が気密かつ着脱可能に装着されている。
【００２１】
前記浴槽１内に、脱脂および酸化皮膜除去対象物である被処理部材３が出し入れ可能に収容され、その底部にスタ−ラ等の撹拌子４が収容されている。
また、前記浴槽１内に水道水、純水等の水５が収容され、その上部周面に給水管６が接続され、該管６が給水源７に連通している。
【００２２】
図中、８は前記給水管６に介挿した開閉弁、９は浴槽１の周面に装着したヒ−タで、前記水５を所定温度、実施形態では５０〜１５０℃に加熱可能にしているこの場合、前記温度に加温した温水を浴槽１へ供給してもよい。
【００２３】
前記浴槽１の外部に、安全で安定した加圧液体若しくは加圧気体である、例えば二酸化炭素を収容したガス容器１０が設置され、そのガス導管１１が圧縮ポンプ１２および開閉弁１３を介して、浴槽１の下部周面に接続されている。
【００２４】
前記圧縮ポンプ１２は、前記二酸化炭素を所定圧、実施形態では二酸化炭素を大気圧以上、望ましくは２気圧以上から亜臨界若しくは超臨界圧以上の範囲で、可及的に高圧に加圧し、これを浴槽１内に供給して前記水５に溶解させ、炭酸（Ｈ₂ＣＯ₃）水を生成可能にしている。この場合の圧力値は、酸化皮膜除去溶液の酸性度に関係するため、酸化皮膜の状況によって適宜最適に調整される。
【００２５】
前記浴槽１の下部に連通管１４が接続され、該管１４に開閉弁１５が介挿され、その下流側端部を貯留タンク１６に接続している。
前記貯留タンク１６は、前記浴槽１と実質的に同一かつ略同容積に構成され、その周面にヒ−タ１７を装着していて、前記タンク１７内に収容した貯留液１８を所定温度に加熱可能にしている。
実施形態では貯留液１８を略５０℃に加熱し、該貯留液１８の主成分である炭酸水を水と二酸化炭素に分解可能にしている。
【００２６】
前記貯留タンク１６にリタ−ンパイプ１９，２０が接続され、それらの他端が前記浴槽１と圧縮ポンプ１２に接続され、これらに前記分解した水と二酸化炭素とを還流可能にしている。
図中、２１，２２は前記リタ−ンパイプ１９，２０に介挿した開閉弁、２３はリタ−ンパイプ１９に介挿したフィルタ若しくはイオン交換樹脂である。
【００２７】
前記貯留タンク１６の下部に排出管２４が接続され、その下流側端部が下水道に連通しており、２５は前記排出管２４に介挿した開閉弁である。
【００２８】
このように構成した母材表面の活性化処理装置の基本構成は、密閉可能な耐圧性の浴槽１と、該浴槽１に水５を供給可能な給水源７と、前記浴槽１に液体若しくは気体状、前記基本構成では密度の高い液体二酸化炭素を供給可能なガス容器１０と、前記浴槽１の脱脂および酸化皮膜除去処理後の処理液を一時的に収容可能な貯留タンク１６とを備えている
【００２９】
したがって、従来のように専用の脱脂槽や酸洗い槽、および各水洗槽および中和槽を要しないから、設備が簡潔で設備費の低減と設置スペ−スのコンパクト化を図れるとともに、構成が簡単であるから、容易かつ安価に製作できる。
しかも、前記処理後の処理液は、後述のように貯留タンク１６によって水と二酸化炭素に分解され、かつ前記処理液に沈殿した酸化皮膜等の夾雑物を除去後、再利用可能にしているから、それらの有効利用と消費の節減を図れる。
【００３０】
次に、前記処理装置によって脱脂および酸化皮膜除去処理を行なう場合は、浴槽１内に被処理部材３を収容し、蓋２を装着して内部を密閉した後、水源７から水５を浴槽１へ供給し、該水５の中に前記被処理部材３を浸漬させる。
【００３１】
前記水５を定量供給後、ガス容器１０から二酸化炭素を浴槽１へ供給し、これを圧縮ポンプ１２で加圧し、更にヒ−タ９を介して前記水５を加熱する。また、これと前後して撹拌子４を作動し、前記水５を撹拌する。
このため、水５内の二酸化炭素が微粒化して高速移動し、その大量の微粒状二酸化炭素が被処理部材３に衝突して、該部材３表面に付着した油脂分を剥離し、脱脂する。
【００３２】
この場合、前記二酸化炭素は浴槽１の下方から供給され、これが水中５をバブリング状態で上昇するから、前記二酸化炭素が水５に速やかに溶解して飽和し、溶解度の上昇を促すとともに、前記撹拌子４と相俟って一様かつ精密な撹拌効果が得られ、前記脱脂作用を増進する。
【００３３】
なお、前記方法の代わりに、前記水５を浴槽１内に霧状に噴霧し、同時に前記二酸化炭素を供給して、それらを混合すれば、それらの接触面積が更に増大して、溶解度の上昇を促すとともに、精密な撹拌効果が得られ、前記脱脂作用が一層増進する。
【００３４】
そして、前記撹拌と同時に前記二酸化炭素が水５に溶解し、炭酸（Ｈ₂ＣＯ₃）を生成して、前記水５が酸性を呈する。
この場合、前記二酸化炭素は高圧に加圧されているから、水５に対する溶解が促進され、かつその溶解量は圧力に比例する。
したがって、前記酸性が上昇し、酸洗いに十分な酸性（ＰＨ３〜４）が速やかに形成されて、前記脱脂後の被処理部材３表面の酸化皮膜に接触し、該酸化皮膜を分解して除去する。
しかも、前記水５は加熱されているから、二酸化炭素の溶解が促進され、前記酸性度の上昇を促して、前記酸化皮膜の分解作用が促進される。
【００３５】
こうして、被処理部材３の脱脂と酸化皮膜除去が同時に行なわれ、その油脂分と酸化皮膜が浴槽１の底部に沈殿する。そして、所定時間前記処理を実行し、十分な脱脂と酸化皮膜除去効果を得られたところで、二酸化炭素の供給を停止し撹拌子４の駆動を停止し、開閉弁１５を開弁する。
【００３６】
このようにすると、浴槽１内が減圧され、前記ニ酸化炭素の溶解度が低下して、その処理液が連通管１４に導かれて貯留タンク１６へ押し出され、その全量が貯留タンク１６へ移動したところで、開閉弁１５を閉弁する。この状況は図２のようである。
【００３７】
前記貯留タンク１６内の貯留液１８は、減圧されてニ酸化炭素の溶解度が低下するため、その酸性濃度が急速に低下し、弱酸性になって実害の惧れがなくなる。
そこで、開閉弁２５を開弁し、前記貯留液１８を排出管２４を介して、下水へそのまま排出することができる。
【００３８】
その際、貯留液１８内に重金属が存在する場合、前記液１８中からニ酸化炭素が消失することで、炭酸水から分離し、前記貯留タンク１６内に沈殿する。
したがって、排出管２４に設けたフィルタ（図示略）を介して、他の異物や酸化皮膜と一緒に回収可能になり、前記排水の安全性を確保し、環境汚染を防止するとともに、その回収後は通常の廃棄物として処理し得る。
【００３９】
一方、本発明の基本構成は前記貯留液１８を再利用することができ、その場合は、ヒ−タ１７を加熱し、貯留タンク１６内の貯留液１８を略５０℃に加熱する。
このようにすると、貯留液１８の炭酸水が二酸化炭素と水に分解され、これらが気液二層に分離される。つまり、気体状の二酸化炭素が上位に位置し、水が下位に位置する。
【００４０】
そこで、開閉弁２１，２２を開弁すれば、前記分解した二酸化炭素と水が、リタ−ンパイプ１９，２０に導かれて、浴槽１および圧縮ポンプ１２へ移動し、それらの再利用が可能になる。
その際、前記二酸化炭素と水は、各リタ−ンパイプ１９，２０に介挿したフィルタ２３によって、重金属や酸化皮膜、異物を除去される。
この場合、前記分解によって貯留液１８から二酸化炭素が完全に抜け出るから、前記重金属や酸化皮膜等が完全に沈殿し、これらを精度良く回収できる。
【００４１】
なお、貯留タンク１６は前記浴槽１と実質的に同一に構成されているから、例えば貯留タンク１６内に別の被処理部材３を収容し、この後、前記貯留液１８を貯留タンク１６へ導き、該タンク１６にガス容器１０から高圧の二酸化炭素を補給し、かつ水５を給水源７から補給して、貯留タンク１６内を前記圧力および温度条件に設定すれば、該タンク１６においても被処理部材３の脱脂および酸化皮膜除去を行なえ、その生産性が増大する。
【００４２】
そして、貯留タンク１６の前記処理後、貯留液１８の汚損度をチェックし、汚損している場合は減圧して弱酸性にし、下水へ排水する。
一方、貯留液１８の汚損が軽度であれば、前記タンク１６を減圧し、貯留液１８を水と二酸化炭素とに分解して、それらの再利用を図れる。
【００４３】
また、前記浴槽１または貯留タンク１６の二酸化炭素の圧力、およびヒ−タ９，１７による加熱温度を可及的に高圧高温に設定すれば、前記脱脂および酸化皮膜除去処理を高精度かつ高能率良く行なえる。したがって、二酸化炭素を超臨界状態にすれば、前記脱脂および酸化皮膜除去処理を一層高精度かつ高能率良く行なえる。
【００４４】
このように、本発明の基本構成は水と二酸化炭素の安価な素材で、被処理部材３の脱脂洗浄や酸化皮膜除去を同時に行ない、かつそれらの間の煩雑な水洗いを要しないから、この種の処理作業を容易かつ迅速に行なえ、生産性の向上を図れる。
また、脱脂洗浄や酸化皮膜除去媒体として、従来の有害なアルカリや酸性の薬剤の使用を要しないから、有害なガス発生下の作業環境を改善し、これを安全で迅速かつ容易に行える。
【００４５】
しかも、脱脂や酸化皮膜除去後の処理液を安全かつ速やかに処理し、その合理化と安全性を確保するとともに、従来の煩雑な中和作業を廃し、簡単な方法で前記処理液の安全な排水処理と再利用を図るようにしたものである。
【００４６】
図３乃至図５は本発明の実施形態を示し、前述の基本構成と対応する部分に同一の符号を用いている。
この実施形態は、前記浴槽１と同様な炭酸水生成槽２６を設け、該槽２６に前述の基本構成と同様に水と高圧の二酸化炭素を供給して、所定の酸性濃度の炭酸水２７を生成している。
【００４７】
そして、前記炭酸水２７を、導管２８を介して吹付ガン２９へ導き、また該吹付ガン２９に導管３０を介して、ガス容器１０から高圧の二酸化炭素を導いている。
図中、３１，３２は前記導管２８，２９に介挿した開閉弁、３３は導管３０の可及的に下流側（吹付ガン２９内でも可）に設けたヒ−タで、導管３３の二酸化炭素を超臨界状態に形成可能に加熱している。
【００４８】
前記吹付ガン２９のノズル３４は、図４のように前記導管２８，３０に連通する噴口３５，３６を離間して形成し、噴口３６の外側に圧縮空気源（図示略）に連通する環状孔３７を形成している。
図５は前記噴口３５，３６の他の配置形態を示し、これらを内外同心円状に配置し、二酸化炭素の噴口３６の外側に、圧縮空気源（図示略）に連通する環状孔３７を形成している。図中、３８は脱脂および酸洗い作業スペ−スである。
【００４９】
すなわち、この実施形態は前述のように、密閉した浴槽１内に被処理部材３を収容し、その密閉スペ−スで脱脂および酸化皮膜除去を処理する代わりに、被処理部材３を開放した作業スペ−ス３８に収容し、該被処理部材３に吹付ガン２９を介して、炭酸水２７と超臨界状態の二酸化炭素を吹付けている。
このようにすると、超臨界状態の二酸化炭素が噴口３６から噴出し、炭酸水２７が噴口３５から噴出し、これらが被処理部材３に吹付けられる。
【００５０】
その際、前記二酸化炭素は噴出時に断熱膨張し、その気化熱によってドライアイスに生成され、このドライアイスが勢い良く噴出する際、微粒状化して被処理部材３に衝突し、該部材３表面の油脂分を剥離し、吹き飛ばして脱脂する。
【００５１】
一方、前記炭酸水２７は脱脂後の被処理部材３に衝突し、当該部の酸化皮膜を分解して除去し、吹き飛ばす。
その際、炭酸水２７は導管２８の移動過程で冷却され、二酸化炭素の溶解度が低下して酸性濃度が低下し、前記酸化皮膜除去作用が低下する惧れがある。
そこで、炭酸水２７を高温に加熱するとともに、吹付ガン２９のノズル３４周辺を適宜加熱し、前記二酸化炭素の溶解度低下ないし前記酸化皮膜除去作用の低下を阻止する。
【００５２】
こうして、炭酸水２７および超臨界二酸化炭素を被処理部材３に吹付け後、当該吹付け面は前記ドライアイスが昇華し、かつ炭酸水が勢い良く飛散して、瞬時に乾燥する。
【００５３】
なお、前記吹付ガン２９の操作は、例えばノズル３４を図４の矢視方向へ移動し、被処理部材３の処理面に先ず超臨界二酸化炭素を吹付け、その脱脂処理後、炭酸水２７を吹付けて酸化皮膜を除去する。
この場合、図５の例では噴口３６が噴口３５の外側に位置し、被処理部材３の処理面に対し、超臨界二酸化炭素の吹付けが炭酸水２７を吹付けに先行するから、吹付ガン２９の操作方向に関係なく、所期の手順、つまり脱脂−酸化皮膜除去を自然に得られる利点がある。
【００５４】
また、超臨界二酸化炭素の噴出口３６の周囲の環状口３７から、環状の空気流が同軸状に噴出し、前記ドライアイスの噴流の擾乱を防止して、その整形を促すから、ノズル３４が被処理部材３から離間した際の処理位置の確実性を得られる
【００５５】
このようにこの実施形態は、被処理部材３の脱脂と酸化皮膜除去を同時に行なう。しかも、作業スペ−ス３８を開放スペ−スとすることで、当該スペ−スを容易に得られる。
一方、作業スペ−ス３８を周囲から遮断し、つまり酸素供給を断ち、二酸化炭素の雰囲気下で行なえば、脱脂および酸化皮膜除去後の被処理部材３の酸化を防止でき、そのような雰囲気の下で次期メッキ処理を行なえば、良好な金属皮膜を得られる。
【００５６】
【発明の効果】
以上のように、請求項１の発明は、脱脂洗浄と酸化皮膜除去処理とを開放空間で行ない、脱脂洗浄と酸化皮膜除去処理を迅速かつ効率良く安価で合理的に行なうから、生産性の向上と設備費の低減を図れ、設備ないしその設置スペ−スのコンパクト化を図れるとともに、従来のような密閉した容器内での処理法に比べ、作業スペ−スを容易に確保し作業性を向上することができる。
【００５７】
請求項２の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、酸素の供給を遮断した開放空間で行なうから、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られる効果がある。
請求項３の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、二酸化炭素の雰囲気下で行なうから、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られる効果がある。
請求項４の発明は、前記脱脂洗浄と酸化皮膜除去処理後、酸素の供給を遮断しおよびまたは二酸化炭素の雰囲気下でメッキ処理するようにして、母材表面の酸化を防止し、その活性化した表面状態を維持して、良好な金属皮膜を得られる効果がある。
【００５８】
請求項５の発明は、前記脱脂洗浄または酸化皮膜除去処理後の処理液の再利用時、重度に汚損した処理液を減圧して二酸化炭素の溶解度を低下し、下水へ排水可能にするから、処理液の十分な再利用を図れるとともに、処理液の酸性濃度を低下し、中和設備を要することなく安全かつ安価に排水することができる。
【００５９】
請求項６の発明は、脱脂洗浄と酸化皮膜除去処理とを開放空間で実行可能にしたから、脱脂洗浄と酸化皮膜除去処理を迅速かつ効率良く安価で合理的に行なえ、生産性の向上と設備費の低減を図れ、設備ないしその設置スペ−スのコンパクト化を図れるとともに、従来のような密閉した容器内での処理装置に比べ、作業スペ−スを容易に確保し作業性を向上することができる。
【００６０】
請求項７の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、酸素の供給を遮断した開放空間で実行可能にしたから、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られる効果がある。
請求項８の発明は、前記脱脂洗浄と酸化皮膜除去処理とを、二酸化炭素の雰囲気下で実行可能にしたから、前記処理後の母材表面の酸化を防止し、その活性化を促して、例えば次期メッキ処理時に良好な金属皮膜を得られる効果がある。
請求項９の発明は、前記脱脂洗浄と酸化皮膜除去処理後、酸素の供給を遮断しおよびまたは二酸化炭素の雰囲気下でメッキ処理可能にしたから、母材表面の酸化を防止し、その活性化表面を維持して、良好な金属皮膜を得られる効果がある。
【００６１】
請求項１０の発明は、前記酸化皮膜除去溶液と、超臨界二酸化炭素とを吹付ガンに導き、これらを吹付ガンに設けた各噴口から同時に噴出可能にしたから、小形軽量な装置によって、脱脂洗浄と酸化皮膜除去の同時処理を高精密に実行することができる。
【００６２】
請求項１１の発明は、前記超臨界二酸化炭素の噴口の周囲に、圧縮空気源に連通する環状口を設けたから、環状の空気流によって超臨界二酸化炭素の擾乱を防止し、安定した脱脂洗浄を行なうことができる。
【００６３】
請求項１２の発明は、前記各噴口を離間して配置し、前記超臨界二酸化炭素の噴口側へ吹付ガンを移動可能にし、前記酸化皮膜除去溶液と超臨界二酸化炭素とを吹付け可能にしたから、脱脂洗浄を酸化皮膜除去に先行して自然に行なえ、酸化皮膜除去を精密かつ合理的に処理することができる。
【００６４】
請求項１３の発明は、前記酸化皮膜除去溶液の噴口の外側に、前記超臨界二酸化炭素の噴口を同心円状に配置したから、吹付ガンの移動方向を規制することなく、吹付ガンの全ゆる移動方向に対し、脱脂洗浄を酸化皮膜除去に先行可能にし、酸化皮膜除去を精密かつ合理的に処理することができる。
【図面の簡単な説明】
【図１】本発明の基本構成を示す説明図で、密閉した浴槽で酸化皮膜除去処理溶液を作成し、該溶液に被処理部材を浸漬して、その脱脂処理と酸化皮膜除去処理とを同時に行なっている状況を示している。
【図２】前記脱脂処理と酸化皮膜除去処理後に使用後の処理液を別の容器（貯留タンク）に移し替え、その排水若しくは分解または再生している状況を示している。
【図３】本発明の実施形態を示し、密閉した浴槽で酸化皮膜除去処理溶液を作成し、該溶液と超臨界炭素とを吹付ガンへ供給し、開放空間に収納した被処理部材の脱脂処理と酸化皮膜除去処理とを同時に行なっている。
【図４】前記吹付ガンのノズルの状況を示す正面図である。
【図５】前記吹付ガンのノズルの別の形態を示す正面図である。
【符号の説明】
１浴槽
３被処理部材
５水
１６容器（貯留タンク）
２９吹付ガン
３５，３６噴口
３７環状孔
３８開放空間（作業スペ−ス） [0001]
BACKGROUND OF THE INVENTION
The present invention is suitable for pretreatment in, for example, electrochemical treatment such as electroplating, and by using a safe and inexpensive solution, the degreasing treatment and removal of the oxide film on the surface of the base material such as metal can be performed simultaneously and efficiently, The present invention relates to a method for activation treatment of a base material surface and a treatment apparatus thereof that can improve productivity and reduce equipment costs, streamline waste liquid treatment, and prevent reuse and environmental pollution.
[0002]
[Prior art]
For example, in the electrochemical treatment such as electroplating, the pre-treatment step of degreasing and pickling removes the fat and oxide film on the metal surface that is the object to be treated, and activates the metal surface, A good metal film can be coated.
[0003]
The degreasing cleaning is performed by immersing the object to be processed in an alkaline aqueous solution, and the pickling is performed by immersing the object to be processed in an acidic aqueous solution diluted with sulfuric acid or hydrochloric acid. The product was neutralized with an acidic or alkaline chemical, and discharged from the factory.
[0004]
Therefore, the conventional pretreatment process requires a dedicated bathtub and a washing tank, which requires a large amount of equipment, requires various chemicals and a large amount of water, increases the treatment cost, and further includes degreasing and pickling. In addition to poor productivity, the neutralization treatment cannot remove heavy metals such as lead, zinc, and tin, and requires a wastewater treatment facility. It was increasing.
[0005]
Furthermore, in the conventional pretreatment process, the work environment is poor due to being forced to work under the situation where the treatment liquid is scattered and harmful gas is generated, and furthermore, the hydrogen gas generated in the pickling process causes the object to be treated. There is a possibility of causing hydrogen embrittlement, and there is a problem that a separate means is required for removing the hydrogen embrittlement.
[0006]
In order to solve such a problem, Japanese Patent Application Laid-Open No. 2000-73191 uses a solution containing phosphine, which is an organic solvent, and immerses an object to be treated in the solution, or uses this solution with a brush or spray. The oil and fat and the oxide film are removed without applying dangerous chemicals such as strong acid and cyanide or toxic chemicals and substantially not damaging the base material.
[0007]
However, the phosphine is expensive and promotes an increase in production cost, and there is a problem that the fat and oil and the oxide film cannot be sufficiently removed.
[0008]
By the way, as a cleaning method for semiconductors, precision machine parts and the like, a cleaning method using a supercritical fluid or a subcritical high density fluid as a cleaning solvent has been proposed in, for example, Japanese Patent Application Laid-Open No. 2000-308862.
However, although the above method can cope with the removal of oil and fat adhering to machine parts, etc., it cannot deal with the removal of oxide films on machine parts, etc. In that case, a separate oxide film removal treatment is required. , Productivity is poor, which helps increase equipment costs.
[0009]
As another method, carbon dioxide as a cleaning medium is pressurized, particulate dry ice is ejected from a cleaning gun, and this is sprayed on the surface of the member to be cleaned, so that the oil and fat on the surface of the member is blown away. The method is known.
However, this method is also the same as described above, and there is a problem that it can cope with the removal of oil and fat but cannot cope with the removal of the oxide film.
[0010]
[Problems to be solved by the invention]
The present invention solves such a problem, and is suitable for pretreatment in electrochemical treatment such as electroplating. For example, the degreasing treatment and removal of the oxide film on the surface of a base material such as metal can be performed simultaneously with a safe and inexpensive solution. A method for activating the surface of a base material that can be performed efficiently and rationally, improve productivity and reduce equipment costs, streamline waste liquid treatment, and reuse and prevent environmental pollution. An object is to provide an apparatus.
[0011]
[Means for Solving the Problems]
  According to the first aspect of the present invention, the pressurized carbon dioxide contacts the contacted member.And separating or peeling off the oil and fat on the surface of the member to be treated, generating the oxide film removing solution by dissolving the pressurized carbon dioxide in water, and bringing the oxide film removing solution into contact with the member to be treated. The oxide film on the surface of the member is removed, and the degreasing cleaning and the oxide film removal process are performed simultaneously.In the activation treatment method of the base material surface,Perform degreasing and oxide film removal treatment in an open space, and perform degreasing and oxide film removal processing quickly, efficiently and inexpensively to improve productivity and reduce equipment costs. -The space can be made compact and the work space can be easily secured and the workability can be improved as compared with the conventional processing method in a closed container.I am doing so.
[0012]
  The invention of claim 2 provides the degreasing cleaning.WhenOxide film removalThe treatment is performed in an open space in which the supply of oxygen is shut off, and the surface of the base material after the treatment is prevented from being oxidized and activated. For example, a good metal film can be obtained during the next plating process.I am doing so.
  Invention of Claim 3 is the said degreasing washing | cleaning and oxide film removal processWhenThe, Performed in an atmosphere of carbon dioxide, preventing oxidation of the surface of the base material after the treatment, promoting its activation, for example, obtaining a good metal film during the next plating treatmentI am doing so.
  Invention of Claim 4 is the said degreasing washing | cleaning and an oxide film removal processAfter that, the supply of oxygen is cut off and / or plating is performed in an atmosphere of carbon dioxide to prevent oxidation of the surface of the base material and maintain its activated surface state to obtain a good metal film.I try to do it.
[0013]
  The invention of claim 5When reusing the treatment liquid after the degreasing or oxide film removal treatment, the heavily contaminated treatment liquid is depressurized to reduce the solubility of carbon dioxide, allowing it to be drained into sewage, and sufficient reuse of the treatment liquid. As well as reducing the acid concentration of the treatment liquid, it can be drained safely and inexpensively without the need for neutralization equipment.I have to.
[0014]
  According to the sixth aspect of the present invention, the pressurized carbon dioxide contacts the contacted member.EnableWhile allowing the oil and fat on the surface of the treated member to be separated or peeled off,SaidDissolve pressurized carbon dioxide in waterTo produce an oxide film removal solution,Contact the treated member with the oxide film removal solutionEnablePossible to remove the oxide film on the surface of the workpieceThe degreasing and oxide film removal process can be performed simultaneously.In the activation treatment apparatus for the base material surface,Perform degreasing and oxide film removal in an open spaceEnableDegreasing and oxide film removal treatment can be performed quickly, efficiently, inexpensively and rationally to improve productivity and reduce equipment costs. Compared to the processing equipment in the container, the work space can be easily secured and workability can be improved.I am doing so.
[0015]
  The invention of claim 7 provides the degreasing cleaning.WhenOxide film removalThe processing can be performed in an open space where the supply of oxygen is cut off, the surface of the base material after the processing is prevented from being oxidized, and the activation thereof is promoted. For example, a good metal film can be obtained during the next plating processI am doing so.
  The invention of claim 8 provides the degreasing cleaning and oxide film removal treatment.WhenTheUnder the atmosphere of carbon dioxideMake it executable,Prevents oxidation of the surface of the base material after the treatment and promotes its activation, for example, a good metal film can be obtained during the next plating treatmentI am doing so.
  Invention of Claim 9 is the said degreasing washing | cleaning and oxide film removal processAfter that, cut off the supply of oxygen and / or allow plating in an atmosphere of carbon dioxide,Prevents and activates the surface of the base materialKeep the surface,A good metal film is obtained.
[0016]
  Claim10The invention ofThe oxide film removal solution and supercritical carbon dioxide are guided to a spray gun, and these can be ejected simultaneously from the nozzles provided in the spray gun. The small and lightweight device enables simultaneous processing of degreasing and oxide film removal. Precisely feasibleI have to.
[0017]
  Claim11The invention ofAn annular port communicating with a compressed air source is provided around the supercritical carbon dioxide nozzle, and disturbance of the supercritical carbon dioxide is prevented by the annular air flow so that stable degreasing can be obtained.
[0018]
  Claim12The invention ofThe nozzles are arranged apart from each other, the spray gun can be moved to the nozzle side of the supercritical carbon dioxide, the oxide film removing solution and the supercritical carbon dioxide are sprayed, and degreasing is performed prior to the removal of the oxide film. Can be done naturally, and the oxide film removal can be processed precisely and rationallyI am doing so.
[0019]
  Claim13The invention ofThe supercritical carbon dioxide nozzles are arranged concentrically outside the oxide film removal solution nozzle, and the degreasing cleaning is oxidized in all the movement directions of the spray gun without restricting the movement direction of the spray gun. Enables advanced removal of oxide film and enables precise and rational treatment of oxide film removalI am doing so.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, the present inventionBasic configuration1 is applied to a degreasing and oxide film removal (hereinafter referred to as pickling) process, which is a pretreatment of electroplating (nickel plating). It is a bottom-cylinder pressure-resistant degreasing tank or pickling tank (hereinafter referred to as a bathtub), and its inner surface is lined with vinyl chloride or hard rubber, and the lid 2 is airtight in the upper opening. It is detachably attached.
[0021]
In the bathtub 1, a member 3 to be treated which is an object to be degreased and oxide film removed is accommodated so that it can be taken in and out, and a stirrer 4 such as a stirrer is accommodated at the bottom.
Further, water 5 such as tap water or pure water is accommodated in the bathtub 1, a water supply pipe 6 is connected to the upper peripheral surface thereof, and the pipe 6 communicates with a water supply source 7.
[0022]
In the figure, 8 is an on-off valve inserted in the water supply pipe 6, 9 is a heater mounted on the peripheral surface of the bathtub 1, and the water 5 can be heated to a predetermined temperature, in the embodiment, 50 to 150 ° C. In this case, warm water heated to the above temperature may be supplied to the bathtub 1.
[0023]
A gas container 10 containing, for example, carbon dioxide, which is a safe and stable pressurized liquid or pressurized gas, is installed outside the bathtub 1, and its gas conduit 11 is connected via a compression pump 12 and an on-off valve 13, It is connected to the lower peripheral surface of the bathtub 1.
[0024]
The compression pump 12 pressurizes the carbon dioxide to a high pressure as much as possible in the range of atmospheric pressure or higher, preferably 2 atmospheric pressure or higher to subcritical or supercritical pressure in the embodiment. Is supplied into the bathtub 1 and dissolved in the water 5, and carbonic acid (H₂CO_Three) The water can be generated. Since the pressure value in this case is related to the acidity of the oxide film removal solution, it is optimally adjusted appropriately depending on the situation of the oxide film.
[0025]
A communication pipe 14 is connected to the lower part of the bathtub 1, an opening / closing valve 15 is inserted into the pipe 14, and a downstream end thereof is connected to the storage tank 16.
The storage tank 16 is configured to have substantially the same volume and substantially the same volume as the bathtub 1, and a heater 17 is attached to the peripheral surface of the storage tank 16, so that the stored liquid 18 stored in the tank 17 is kept at a predetermined temperature. Heating is possible.
In the embodiment, the stored liquid 18 is heated to approximately 50 ° C., and carbonated water that is the main component of the stored liquid 18 can be decomposed into water and carbon dioxide.
[0026]
Return pipes 19 and 20 are connected to the storage tank 16, and the other ends thereof are connected to the bathtub 1 and the compression pump 12 so that the decomposed water and carbon dioxide can be recirculated thereto.
In the figure, 21 and 22 are on-off valves inserted in the return pipes 19 and 20, and 23 is a filter or ion exchange resin inserted in the return pipe 19.
[0027]
A discharge pipe 24 is connected to the lower part of the storage tank 16, its downstream end communicates with the sewer, and 25 is an on-off valve inserted into the discharge pipe 24.
[0028]
  The base material surface activation treatment apparatus configured in this wayBasic configurationIs a pressure-resistant bathtub 1 that can be sealed, a water supply source 7 that can supply water 5 to the bathtub 1, and a liquid or gaseous state in the bathtub 1,Basic configurationIs a gas container 10 capable of supplying high-density liquid carbon dioxide and a treatment liquid after the degreasing and oxide film removal treatment of the bath 1.TimeStorage tank 16 that can be accommodated
[0029]
Therefore, the conventional degreasing tank, pickling tank, each washing tank and neutralization tank are not required, so the equipment is simple, the equipment cost can be reduced and the installation space can be made compact, and the configuration can be reduced. Since it is simple, it can be manufactured easily and inexpensively.
Moreover, since the treated liquid after the treatment is decomposed into water and carbon dioxide by the storage tank 16 as will be described later, and after impurities such as an oxide film precipitated in the treated liquid are removed, the treated liquid can be reused. , The effective use and consumption of them can be saved.
[0030]
Next, when degreasing and oxide film removal processing are performed by the processing device, the member 3 to be processed is accommodated in the bathtub 1, the lid 2 is attached and the inside is sealed, and then water 5 is supplied from the water source 7 to the bathtub 1. And the treated member 3 is immersed in the water 5.
[0031]
After the water 5 is supplied in a fixed amount, carbon dioxide is supplied from the gas container 10 to the bathtub 1, pressurized by the compression pump 12, and further heated by the heater 9. Also, the stirrer 4 is operated around this time to stir the water 5.
For this reason, the carbon dioxide in the water 5 atomizes and moves at high speed, and a large amount of the fine carbon dioxide collides with the member 3 to be treated, and the oil and fat adhering to the surface of the member 3 is peeled off and degreased.
[0032]
In this case, since the carbon dioxide is supplied from below the bathtub 1 and rises in the water 5 in a bubbling state, the carbon dioxide quickly dissolves and saturates in the water 5 to promote an increase in solubility and the stirring. Combined with the child 4, a uniform and precise stirring effect is obtained, and the degreasing action is enhanced.
[0033]
Instead of the above method, if the water 5 is sprayed into the bathtub 1 in the form of a mist, and at the same time, the carbon dioxide is supplied and mixed, the contact area further increases and the solubility increases. And a precise stirring effect is obtained, and the degreasing action is further enhanced.
[0034]
Simultaneously with the stirring, the carbon dioxide dissolves in the water 5, and carbonic acid (H₂CO_Three) And the water 5 is acidic.
In this case, since the carbon dioxide is pressurized to a high pressure, dissolution in water 5 is promoted, and the amount of dissolution is proportional to the pressure.
Therefore, the acidity rises, and acidity (PH3-4) sufficient for pickling is quickly formed, contacting the oxide film on the surface of the treated member 3 after degreasing, and decomposing and removing the oxide film. To do.
And since the said water 5 is heated, melt | dissolution of a carbon dioxide is accelerated | stimulated, the raise of the said acidity is promoted, and the decomposition | disassembly effect | action of the said oxide film is accelerated | stimulated.
[0035]
Thus, degreasing and removal of the oxide film of the member to be treated 3 are performed simultaneously, and the oil and fat and the oxide film are deposited on the bottom of the bathtub 1. Then, the processing is executed for a predetermined time, and when sufficient degreasing and oxide film removal effects are obtained, the supply of carbon dioxide is stopped, the drive of the stirrer 4 is stopped, and the on-off valve 15 is opened.
[0036]
  If it does in this way, the inside of the bathtub 1 will be pressure-reduced, the solubility of the said carbon dioxide will fall, and the process liquid will be guide | induced to the communicating pipe 14, and a storage tank16Pushed out into the storage tank16When the valve is moved, the on-off valve 15 is closed. This situation is as shown in FIG.
[0037]
  The storage tank16The stored liquid 18 is depressurized and the solubility of carbon dioxide decreases, so that its acid concentration rapidly decreases and becomes weakly acidic, so that there is no possibility of actual harm.
  Therefore, the on-off valve 25 is opened, and the stored liquid 18 can be discharged into the sewage as it is through the discharge pipe 24.
[0038]
  At that time, when heavy metal is present in the storage liquid 18, carbon dioxide disappears from the liquid 18, so that it is separated from carbonated water,Storagetank16To settle inside.
  Therefore, it can be collected together with other foreign substances and oxide film through a filter (not shown) provided in the discharge pipe 24, ensuring the safety of the drainage, preventing environmental pollution, and after the collection. Can be treated as normal waste.
[0039]
  On the other hand, the present inventionBasic configurationCan reuse the stored liquid 18, in which case the heater 17 is heated and the storage tank is heated.16The stored liquid 18 is heated to about 50 ° C.
  If it does in this way, the carbonated water of the storage liquid 18 will be decomposed | disassembled into a carbon dioxide and water, and these will be isolate | separated into a gas-liquid two layer. That is, gaseous carbon dioxide is located at the upper position and water is located at the lower position.
[0040]
Therefore, if the on-off valves 21 and 22 are opened, the decomposed carbon dioxide and water are guided to the return pipes 19 and 20 and moved to the bathtub 1 and the compression pump 12 so that they can be reused. Become.
At that time, heavy metals, oxide films, and foreign substances are removed from the carbon dioxide and water by the filters 23 inserted in the return pipes 19 and 20.
In this case, carbon dioxide completely escapes from the stored liquid 18 due to the decomposition, so that the heavy metal, oxide film, etc. are completely precipitated and can be recovered with high accuracy.
[0041]
  In addition, since the storage tank 16 is configured substantially the same as the bathtub 1, for example, another member to be processed 3 is accommodated in the storage tank 16, and thereafter, the storage liquid 18 is guided to the storage tank 16. If the tank 16 is replenished with high-pressure carbon dioxide from the gas container 10 and the water 5 is replenished from the water supply source 7 and the inside of the storage tank 16 is set to the pressure and temperature conditions, the tank 16 is also covered. Degreasing the processing member 3 andOxidationRemove filmNaThe productivity increases.
[0042]
Then, after the treatment of the storage tank 16, the degree of contamination of the stored liquid 18 is checked. If the storage liquid 18 is contaminated, the storage tank 16 is depressurized to be weakly acidic and drained into sewage.
On the other hand, if the stored liquid 18 is mildly fouled, the tank 16 can be decompressed to decompose the stored liquid 18 into water and carbon dioxide and reuse them.
[0043]
  The bathtub 1 or the storage tankNkIf the pressure of 16 carbon dioxide and the heating temperature by the heaters 9 and 17 are set as high as possible, the degreasing and oxide film removal processes can be performed with high accuracy and high efficiency. Therefore, if the carbon dioxide is brought into a supercritical state, the degreasing and oxide film removing treatments can be performed with higher accuracy and efficiency.
[0044]
  Thus, the present inventionBasic configurationIs an inexpensive material of water and carbon dioxide, which simultaneously degreases and removes the oxide film of the member to be treated 3 and does not require complicated washing between them, so that this kind of treatment can be performed easily and quickly. , Improve productivity.
  In addition, since it is not necessary to use conventional harmful alkali or acidic chemicals as a degreasing and oxide film removal medium, it is possible to improve the working environment under generation of harmful gas, and to perform this safely, quickly and easily.
[0045]
Moreover, the treatment liquid after degreasing and oxide film removal is treated safely and promptly, ensuring its rationalization and safety, eliminating the conventional complicated neutralization work, and safe drainage of the treatment liquid by a simple method. It is intended to be processed and reused.
[0046]
  3 to 5 show the present invention.The fruitShowing the embodiment, the above-mentionedBasic structureCorresponding partsInThe same code is used.
  In this embodiment, a carbonated water generation tank 26 similar to that of the bathtub 1 is provided, andBasic configurationSimilarly to this, water and high-pressure carbon dioxide are supplied to produce carbonated water 27 having a predetermined acidic concentration.
[0047]
The carbonated water 27 is guided to a spray gun 29 via a conduit 28, and high-pressure carbon dioxide is guided from the gas container 10 to the spray gun 29 via a conduit 30.
In the figure, 31 and 32 are on-off valves inserted in the conduits 28 and 29, 33 is a heater provided on the downstream side of the conduit 30 as much as possible (or in the spray gun 29). Carbon is heated to form a supercritical state.
[0048]
As shown in FIG. 4, the nozzle 34 of the spray gun 29 is formed by separating the nozzle holes 35, 36 communicating with the conduits 28, 30, and an annular hole communicating with a compressed air source (not shown) outside the nozzle hole 36. 37 is formed.
FIG. 5 shows another arrangement form of the nozzle holes 35, 36, which are arranged concentrically inside and outside, and an annular hole 37 communicating with a compressed air source (not shown) is formed outside the nozzle hole 36 for carbon dioxide. ing. In the figure, 38 is a degreasing and pickling work space.
[0049]
That is, in this embodiment, as described above, the member to be treated 3 is accommodated in the sealed bathtub 1 and the member to be treated 3 is opened instead of processing the degreasing and oxide film removal in the sealed space. Housed in a space 38, carbonated water 27 and carbon dioxide in a supercritical state are sprayed onto the member to be treated 3 through a spray gun 29.
If it does in this way, the carbon dioxide of a supercritical state will eject from the nozzle hole 36, the carbonated water 27 will eject from the nozzle hole 35, and these will be sprayed on the to-be-processed member 3.
[0050]
At that time, the carbon dioxide is adiabatically expanded at the time of ejection, and is generated in dry ice by the heat of vaporization. When this dry ice is ejected vigorously, it is pulverized and collides with the member 3 to be treated. Remove oil and fat, blow away and degrease.
[0051]
On the other hand, the carbonated water 27 collides with the member 3 to be treated after degreasing, decomposes and removes the oxide film of the part, and blows away.
At this time, the carbonated water 27 is cooled during the movement of the conduit 28, so that the solubility of carbon dioxide is lowered, the acid concentration is lowered, and the oxide film removing action may be lowered.
Therefore, the carbonated water 27 is heated to a high temperature, and the periphery of the nozzle 34 of the spray gun 29 is appropriately heated to prevent the carbon dioxide solubility from being lowered or the oxide film removing action from being lowered.
[0052]
Thus, after the carbonated water 27 and the supercritical carbon dioxide are sprayed on the member 3 to be treated, the dry ice is sublimated on the sprayed surface, and the carbonated water scatters vigorously and is instantly dried.
[0053]
The operation of the spray gun 29 is performed, for example, by moving the nozzle 34 in the direction of the arrow in FIG. 4 and spraying supercritical carbon dioxide on the processing surface of the member 3 to be processed. Spray to remove oxide film.
In this case, in the example of FIG. 5, the nozzle 36 is located outside the nozzle 35, and the spray of supercritical carbon dioxide precedes the spray of carbonated water 27 against the processing surface of the member 3 to be processed. Regardless of the operation direction of 29, there is an advantage that a desired procedure, that is, degreasing-oxide film removal can be naturally obtained.
[0054]
In addition, an annular air flow is coaxially ejected from an annular port 37 around the supercritical carbon dioxide jet port 36 to prevent disturbance of the jet flow of the dry ice and facilitate its shaping. The certainty of the processing position when separated from the member to be processed 3 can be obtained.
[0055]
Thus, in this embodiment, the member 3 to be treated is degreased and the oxide film is removed simultaneously. In addition, by making the work space 38 an open space, the space can be easily obtained.
On the other hand, if the work space 38 is cut off from the surroundings, that is, the supply of oxygen is cut off and performed in an atmosphere of carbon dioxide, oxidation of the member 3 to be treated after degreasing and removal of the oxide film can be prevented. If the next plating process is performed below, a good metal film can be obtained.
[0056]
【The invention's effect】
  As described above, the invention of claim 1Degreasing cleaning and oxide film removal treatment are performed in an open space, and degreasing cleaning and oxide film removal processing are carried out quickly, efficiently, and reasonably at low cost, improving productivity and reducing equipment costs. Space can be made compact, and work space is easily secured and workability is improved compared to conventional processing methods in sealed containers.can do.
[0057]
  The invention of claim 2 provides the degreasing cleaning.WhenOxide film removalSince the treatment is performed in an open space in which the supply of oxygen is shut off, the surface of the base material after the treatment is prevented from being oxidized, and the activation thereof is promoted. For example, a good metal film can be obtained during the next plating treatment. is there.
  Invention of Claim 3 is the said degreasing washing | cleaning and oxide film removal processWhenTheSince it is performed in an atmosphere of carbon dioxide, the surface of the base material after the treatment is prevented from being oxidized, and its activation is promoted. For example, a good metal film can be obtained during the next plating treatment..
  Invention of Claim 4 is the said degreasing washing | cleaning and an oxide film removal processAfter that, the supply of oxygen is cut off and / or plating is performed under an atmosphere of carbon dioxide to prevent the surface of the base material from being oxidized and maintain its activated surface state.There is an effect that a good metal film can be obtained.
[0058]
  Claim5The invention ofWhen reusing the treatment liquid after the degreasing or oxide film removal treatment, the treatment liquid that has been heavily soiled is decompressed to reduce the solubility of carbon dioxide, and can be drained into sewage. In addition to reducing the acid concentration of the treatment liquid, drain water safely and inexpensively without the need for neutralization equipment.be able to.
[0059]
  The invention of claim 6Since degreasing and oxide film removal processing can be performed in an open space, degreasing and oxide film removal processing can be performed quickly, efficiently, and reasonably, improving productivity and reducing equipment costs. In addition, the installation space can be made compact, and the work space can be easily secured and the workability can be improved compared with the conventional processing equipment in a sealed container.Can.
[0060]
  The invention of claim 7 provides the degreasing cleaning.WhenOxide film removalSince the treatment can be performed in an open space where the supply of oxygen is cut off, the surface of the base material after the treatment is prevented from being oxidized and activated so that a good metal film can be obtained, for example, during the next plating process. Has the effectThe
  The invention of claim 8 provides the degreasing cleaning and oxide film removal treatment.WhenTheUnder the atmosphere of carbon dioxideSo thatPrevents oxidation of the surface of the base material after the treatment, promotes its activation, and has an effect of obtaining a good metal film, for example, at the next plating treatment.The
Invention of Claim 9 is the said degreasing washing | cleaning and oxide film removal processAfter that, because the supply of oxygen was cut off and / or the plating treatment was possible under an atmosphere of carbon dioxide, the surface of the base material was prevented from being oxidized, and its activated surface was maintained.There is an effect that a good metal film can be obtained.
[0061]
  Claim10The invention ofThe oxide film removal solution and supercritical carbon dioxide are guided to a spray gun, and these can be ejected simultaneously from each nozzle provided in the spray gun. Execute with high precisionbe able to.
[0062]
  Claim11The invention ofSince an annular port communicating with the compressed air source is provided around the supercritical carbon dioxide nozzle, disturbance of the supercritical carbon dioxide is prevented by the annular air flow, and stable degreasing cleaning is performed.be able to.
[0063]
  Claim12The invention ofSince each of the nozzle holes is spaced apart, the spray gun can be moved to the nozzle hole side of the supercritical carbon dioxide, and the oxide film removing solution and the supercritical carbon dioxide can be sprayed. Naturally prior to removal, precise and rational treatment of oxide film removalbe able to.
[0064]
  Claim13The invention ofSince the supercritical carbon dioxide nozzles are arranged concentrically outside the oxide film removal solution nozzle, degreasing cleaning can be performed for all the movement directions of the spray gun without restricting the direction of movement of the gun. Makes it possible to precede oxide film removal and treat oxide film removal precisely and rationally.be able to.
[Brief description of the drawings]
FIG. 1 of the present inventionBasic configurationFIG. 2 shows a situation where an oxide film removal treatment solution is prepared in a sealed bath, a member to be treated is immersed in the solution, and the degreasing treatment and the oxide film removal treatment are performed simultaneously.
FIG. 2 shows a state in which the used processing liquid is transferred to another container (storage tank) after the degreasing process and the oxide film removing process, and drained or decomposed or regenerated.
FIG. 3The fruitAn embodiment is shown, an oxide film removal treatment solution is prepared in a sealed bath, the solution and supercritical carbon are supplied to a spray gun, and a degreasing treatment and an oxide film removal treatment of a member to be treated stored in an open space are performed. I do it at the same time.
FIG. 4 is a front view showing a state of a nozzle of the spray gun.
FIG. 5 is a front view showing another embodiment of the nozzle of the spray gun.
[Explanation of symbols]
            1 Bathtub
            3 Processed material
            5 Water
          16 container (storage tank)
          29 Spray gun
          35, 36                  Crater
          37                        Annular hole
          38                        Open space (work space)

Claims

Pressurized carbon dioxide is brought into contact with the member to be contacted , oil or fat on the surface of the member to be treated is separated or peeled off, and the pressurized carbon dioxide is dissolved in water to form an oxide film removing solution. In the activation treatment method for the surface of the base material, the degreasing cleaning and the oxide film removal treatment are performed by contacting the member to be treated, removing the oxide film on the surface of the treatment member, and simultaneously performing the degreasing cleaning and the oxide film removal processing. And activating the surface of the base material in an open space .

The degreasing and the oxide film removal process,請 Motomeko 1 activation treatment method of the base material surface according performed in open space blocked the supply of oxygen.

The degreasing and washing the oxide film removal process,請 Motomeko 1 activation treatment method of the base material surface according performed under an atmosphere of carbon dioxide.

After the degreasing and oxide film removal process,請 Motomeko 2 or 3 activation treatment method of the base material surface according to plating in an atmosphere of blocking the supply of oxygen and or carbon dioxide.

The base material surface according to claim 1, wherein when reusing the treatment liquid after the degreasing cleaning or the oxide film removal treatment, the heavily contaminated treatment liquid is depressurized to reduce the solubility of carbon dioxide so that it can be discharged into sewage. Activation processing method.

The pressurized carbon dioxide to allow contact with the contact member, thereby allowing separation or peeling of the oil of the treated member surface, the pressurized carbon dioxide to be generated was dissolved in water oxidation film removal solution, the oxidation In the activation treatment device for the surface of the base material , which makes it possible to contact the member to be treated with the film removing solution, remove the oxide film on the surface of the member to be treated, and simultaneously perform the degreasing cleaning and the oxide film removing treatment . The base material surface activation treatment apparatus characterized in that the degreasing and oxide film removal treatment can be performed in an open space .

The base material surface activation treatment apparatus according to claim 6, wherein the degreasing cleaning and the oxide film removal treatment can be performed in an open space where supply of oxygen is blocked .

The degreasing and the oxide film removal process, the activation processing unit of the base material surface according to claim 6, wherein the executable under an atmosphere of carbon dioxide.

The degreasing cleaning and oxidation after film removal treatment, cut off the supply of oxygen and or activation processor of the base material surface of the 請 Motomeko 7 or 8, wherein the allowed plating under an atmosphere of carbon dioxide.

The base material surface activation treatment apparatus according to claim 6, wherein the oxide film removing solution and supercritical carbon dioxide are guided to a spray gun, and these can be ejected simultaneously from each nozzle provided in the spray gun.

The base material surface activation treatment apparatus according to claim 10, wherein an annular hole communicating with a compressed air source is provided around the supercritical carbon dioxide nozzle.

The surface of the base material according to claim 10, wherein the nozzle holes are arranged apart from each other, the spray gun is movable toward the nozzle hole side of the supercritical carbon dioxide, and the oxide film removing solution and the supercritical carbon dioxide are sprayed. Activation processing device.

The base material surface activation treatment apparatus according to claim 10, wherein the supercritical carbon dioxide nozzles are arranged concentrically outside a nozzle hole of the oxide film removing solution.