JPH11193482A - Method for preventing discoloration of copper or copper alloy material and copper or copper alloy material - Google Patents
Method for preventing discoloration of copper or copper alloy material and copper or copper alloy materialInfo
- Publication number
- JPH11193482A JPH11193482A JP36660497A JP36660497A JPH11193482A JP H11193482 A JPH11193482 A JP H11193482A JP 36660497 A JP36660497 A JP 36660497A JP 36660497 A JP36660497 A JP 36660497A JP H11193482 A JPH11193482 A JP H11193482A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- discoloration
- preventing
- copper alloy
- alloy material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅または銅合金材
の変色防止方法に関するものである。特には、リードフ
レームやプリント配線板などの銅または銅合金素材の変
色防止方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing discoloration of copper or a copper alloy material. In particular, the present invention relates to a method for preventing discoloration of a copper or copper alloy material such as a lead frame or a printed wiring board.
【０００２】[0002]
【従来の技術】近年、リードフレーム等の電子部品材料
には高速部分銀めっきが行われることが多い。例えば、
金製のボンディングワイヤーを使用してのボンディング
に際しては、その接合性の向上のためにリードフレーム
のボンディング部分に高速部分銀めっきが施される。こ
の高速部分銀めっきは、通常以下のようにして行われ
る。先ず、リードフレーム等の電子部品材料に用いられ
る基材を脱脂及び酸洗後、被覆される銀めっき被膜と基
材との密着性を良くするため、銅ストライクめっきが施
される。次に、銅ストライクめっきが施された基材は、
水洗後基材を銀めっき液に浸漬した時に銀の置換析出を
防止するための前処理を行った後、必要部分のみに高速
電気銀めっきを行う。2. Description of the Related Art In recent years, high-speed partial silver plating is often performed on electronic component materials such as lead frames. For example,
In bonding using a gold bonding wire, high-speed partial silver plating is applied to the bonding portion of the lead frame in order to improve the bonding property. This high-speed partial silver plating is usually performed as follows. First, after a base material used for an electronic component material such as a lead frame is degreased and pickled, copper strike plating is performed to improve the adhesion between the coated silver plating film and the base material. Next, the substrate that has been subjected to copper strike plating is
After rinsing, the base material is subjected to a pretreatment for preventing substitutional precipitation of silver when immersed in a silver plating solution, and then high-speed electric silver plating is performed only on necessary portions.
【０００３】ここで、銀の置換析出を防止するための前
処理は、被めっき基材を銀置換析出防止液中に浸漬する
ことによって実施されるのが普通であるが、このような
前処理が必要な理由は次の通りである。即ち、高速電気
銀めっき液は銀濃度が高いため、これにより銀より卑な
金属から成る基材を浸漬すると浸漬しただけで銀が大量
に置換析出してしまう。この置換析出層は基材に対する
密着性が極めて悪く、この上に銀を電気めっきしても密
着性は改善されずにめっき被膜の剥がれ乃至は加熱時の
膨れや変色を生じる原因となるので、上記置換析出層を
極力抑えるべく前記前処理を施すことが必要となるので
ある。なお、前処理で使用する処理液はこのような銀の
置換防止剤を含有しており、基材表面に薄い置換防止被
膜を形成することにより銀の置換を防止するもので、銀
の置換防止剤としては例えば、チオカルボン酸もしくは
その塩、２，２’−ジピリジル等の含窒素複素環化合
物、２−チオバルビツル酸等のチオウレイレン基を環内
に含む化合物等が用いられる。電子部品材料として用い
られる基材の部分的な電気銀めっきは上述のような要領
で行われるが、この高速部分銀めっきを実施した場合、
種々の理由により、前記基材の銀めっき不要部分にも銀
がめっきされたり銀の析出が起きたりすることが多い。
このような銀の異常析出部を放置しておくと、銀のマイ
グレーションが起こる可能性があり、電子材料の信頼性
が低下する。従って、このような銀の異常析出部は、銀
の剥離液を用いて選択的に溶解除去される。Here, the pretreatment for preventing the substitutional precipitation of silver is usually carried out by immersing the substrate to be plated in a silver displacement prevention liquid. Is necessary for the following reason. That is, since the high-speed electro-silver plating solution has a high silver concentration, when a base material made of a metal lower than silver is immersed therein, a large amount of silver is replaced and precipitated by immersion. The substitutional deposition layer has extremely poor adhesion to the substrate, and even if electroplating silver thereon, the adhesion is not improved, and peeling of the plating film or swelling or discoloration during heating is caused. It is necessary to perform the pre-treatment in order to minimize the above-mentioned substitution precipitation layer. The treatment liquid used in the pretreatment contains such a silver substitution inhibitor, and prevents silver substitution by forming a thin substitution prevention film on the substrate surface. As the agent, for example, a thiocarboxylic acid or a salt thereof, a nitrogen-containing heterocyclic compound such as 2,2′-dipyridyl, a compound containing a thioureylene group in the ring such as 2-thiobarbituric acid, and the like are used. The partial electro-silver plating of the substrate used as an electronic component material is performed in the manner described above, but when this high-speed partial silver plating is performed,
For various reasons, silver is often plated or silver is also deposited on portions of the substrate that do not require silver plating.
If such an abnormal silver deposition portion is left, silver migration may occur, and the reliability of the electronic material is reduced. Therefore, such an abnormal silver deposition portion is selectively dissolved and removed using a silver stripper.
【０００４】このようにして製造された電子部品材料に
おいて、その運搬や貯蔵等を行っている際、異常析出部
の銀を剥離した後に露出した銅または銅合金基材表面若
しくは銅ストライクめっき処理を施した銅めっき面が変
色するという問題点があることが認識されるようになっ
た。なお、この変色は、特に銀を剥離した後に露出した
銅または銅合金の露出面が運搬や貯蔵等のために重ねら
れた部位で著しかった。この変色の原因については未だ
明瞭な結論が出ていないが、変色部に酸化銅が生成して
いることが確認されていることから、 ａ）銀を剥離した直後なので該部分の銅または銅合金が
活性である、 ｂ）銀と銅または銅合金との間に電位差が発生して銅ま
たは銅合金表面が活性となる、 等の理由によって銀を剥離した銅または銅合金の露出面
部分が酸化されることが変色の原因であると考えられ
る。何れにしろ、この銅または銅合金の酸化変色は、モ
ールディング性、はんだ付け性等のアセンブリ特性に悪
影響を与え、電子材料の信頼性を低下させることから大
きな問題となるものであった。[0004] In the electronic component material manufactured as described above, during transport or storage, the surface of the copper or copper alloy substrate or copper strike plating that is exposed after the silver in the abnormally deposited portion is peeled off. It has been recognized that there is a problem that the applied copper plating surface is discolored. The discoloration was remarkable particularly at a portion where the exposed surface of the copper or copper alloy exposed after the silver was peeled off was overlapped for transportation, storage and the like. Although no clear conclusion has yet been reached as to the cause of this discoloration, it has been confirmed that copper oxide has been formed in the discolored portion. Is active, b) The potential difference is generated between silver and copper or copper alloy, and the surface of copper or copper alloy becomes active. Is considered to be the cause of discoloration. In any case, the oxidative discoloration of the copper or copper alloy adversely affects assembly characteristics such as molding properties and solderability, and is a serious problem because it lowers the reliability of electronic materials.
【０００５】この問題を解決するために、本出願人は先
に、銀めっき不要部分に付着した銀を剥離した後の銀剥
離面の銅の変色を防止するための処理液として、５−メ
チル−１Ｈ−ベンゾトリアゾール、５，６−ジメチル−
１Ｈ−ベンゾトリアゾール及び２−メルカプトピリミジ
ンから選ばれる１種または２種以上を含有する無機酸及
び／または有機酸の酸性溶液からなり、更に必要に応じ
てｐＨ緩衝剤をも含有する銅変色防止液を提案した（特
開平４−１６０１７３号）。しかしながら、その後の検
討により、上記銅変色防止液は通常環境化での変色防止
効果には大変優れているものの、処理面の耐熱性がそれ
ほど良好ではなく、例えば大気中で２８０℃程度に３０
分間ほど加熱されると変色防止液で処理済みのものであ
っても銅または銅合金の露出面部分に剥離しやすい酸化
被膜が形成されがちであることが明らかとなった。[0005] In order to solve this problem, the applicant of the present invention has previously disclosed 5-methyl-treating solution as a treatment liquid for preventing discoloration of copper on a silver-exfoliated surface after exfoliating silver adhering to a portion not requiring silver plating. -1H-benzotriazole, 5,6-dimethyl-
Copper discoloration preventive solution comprising an acidic solution of an inorganic acid and / or an organic acid containing one or more selected from 1H-benzotriazole and 2-mercaptopyrimidine, and further containing a pH buffer if necessary. (JP-A-4-160173). However, according to a subsequent study, although the copper discoloration preventing liquid has a very good discoloration preventing effect in a normal environment, the heat resistance of the treated surface is not so good.
It has been clarified that when heated for about a minute, an oxide film that tends to peel off tends to be formed on the exposed surface of the copper or copper alloy even if it has been treated with the anti-tarnish liquid.
【０００６】このため、本出願人はさらに、“分子内に
窒素又は硫黄あるいはこれら両方を含んでいて銅のイン
ヒビターとして働く複素環状化合物”を含有する溶液に
銅よりも貴な金属又はその塩を添加して成る、銅又は銅
合金の変色防止液を提案した（特願平８−１２２３４３
号）。この変色防止液を用いると、「銅よりも貴な金
属」（代表的には銀）の置換被膜層が１０〜１０００Å
程度の厚さで均一に薄く形成されるため銅又は銅合金は
運搬・貯蔵環境から保護され変色が防止され、しかもこ
の「銅よりも貴な金属」の置換層被膜は耐熱性に富むた
め比較的高温の環境下に置かれた場合でも自身の酸化及
び銅又は銅合金面の酸化を防止することができ酸化膜の
剥離といった不都合を来すことはなかった。ところが、
上記の変色防止処理を行った場合には、変色防止処理直
後の耐熱性は上がるものの、数ヶ月の放置後には著しく
耐熱性が低下することが指摘された。[0006] For this reason, the present applicant further proposes that a solution containing a "heterocyclic compound containing nitrogen and / or sulfur in a molecule and acting as an inhibitor of copper" contains a metal or a salt thereof which is more noble than copper. A discoloration preventive liquid for copper or copper alloy is proposed (Japanese Patent Application No. 8-122343).
issue). When this anti-tarnish liquid is used, the substitution coating layer of “metal nobler than copper” (typically silver) has a thickness of 10 to 1000 °.
Copper or copper alloy is protected from transportation and storage environment and discoloration is prevented because it is formed to a uniform thickness of about the same thickness, and the replacement layer coating of "a metal nobler than copper" is rich in heat resistance. Even when placed in an environment of an extremely high temperature, the oxidation of itself and the oxidation of the copper or copper alloy surface can be prevented, and there was no inconvenience such as peeling of the oxide film. However,
It was pointed out that when the above-described discoloration prevention treatment was performed, the heat resistance immediately after the discoloration prevention treatment was increased, but the heat resistance was significantly reduced after standing for several months.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、耐変色性に
優れると同時に、長期間の保存の後も耐熱性の低下がな
いような変色防止処理表面を得るための銅又は銅合金材
の変色防止手段を確立することを目的とした。DISCLOSURE OF THE INVENTION The present invention relates to a copper or copper alloy material which is excellent in discoloration resistance and has a discoloration prevention treated surface which does not decrease in heat resistance even after long-term storage. The purpose was to establish means for preventing discoloration.
【０００８】[0008]
【課題を解決するための手段】本発明者は、上記目的を
達成すべく鋭意研究を行った結果、銅または銅合金材の
耐熱性低下は、高速部分銀めっきの前に行う銀置換防止
剤、銀めっきの添加剤、銀剥離剤等に含まれる有機物
が、最終工程まで残留することに起因することがわかっ
た。即ち、銅または銅合金材の表面に吸着した有機被膜
の大部分は高速部分銀めっき、不要部の銀剥離処理で除
去されるが、銀めっきや銀剥離の条件によっては一部銅
面に残留し、その上に銅変色防止被膜が形成されること
になる。そこで、銅の変色防止処理工程の前に残留する
有機被膜を酸，アルカリで洗浄することにより、良好な
銅変色防止被膜が形成され、良好な耐熱性、耐食性を示
すことが明らかになった。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that the heat resistance of copper or a copper alloy material is reduced by a silver displacement inhibitor which is performed before high-speed partial silver plating. It was found that organic substances contained in silver plating additives, silver release agents and the like remained until the final step. In other words, most of the organic film adsorbed on the surface of the copper or copper alloy material is removed by high-speed partial silver plating and silver removal treatment of unnecessary parts, but part of the organic film remains on the copper surface depending on the conditions of silver plating and silver peeling. Then, a copper discoloration prevention coating is formed thereon. Therefore, it was clarified that by washing the organic film remaining before the copper discoloration prevention treatment step with an acid and an alkali, a good copper discoloration prevention film was formed and exhibited good heat resistance and corrosion resistance.
【０００９】本発明は、この知見に基づいて、 １．銅または銅合金の表面に残留する銅変色防止機能を
有する被膜以外の有機被膜を実質的に除去し、銅変色防
止機能を有する被膜を表面に形成することを特徴とする
銅または銅合金材の変色防止方法 ２．銅または銅合金材に対して酸洗浄またはアルカリ洗
浄を行った後、変色防止処理を行うことを特徴とする請
求項１記載の銅または銅合金材の変色防止方法 ３．銀置換防止処理とそれに引き続く銀めっきを行った
銅または銅合金材に対して、残留する有機被膜を酸また
はアルカリで洗浄・除去し、その後変色防止処理を行う
ことを特徴とする銅または銅合金材の変色防止方法 ４．銅または銅合金材に対して、銅のインヒビターに銅
よりも貴な金属またはその塩を添加して成る変色防止液
による変色防止処理を施す前または後に酸洗浄またはア
ルカリ洗浄を行うことを特徴とする請求項１記載の銅ま
たは銅合金材の変色防止方法 ５．銀置換防止処理とそれに引き続く銀めっきを行った
銅または銅合金材に対して、銅のインヒビターに銅より
も貴な金属またはその塩を添加して成る変色防止液によ
る変色防止処理を施す前または後に酸洗浄またはアルカ
リ洗浄を行うことを特徴とする請求項１記載の銅または
銅合金材の変色防止方法 ６．銅または銅合金の表面に残留する銅変色防止機能を
有する被膜以外の有機被膜が実質的に除去され、銅変色
防止機能を有する被膜が表面に形成されていることを特
徴とする銅または銅合金材 を提供するものである。The present invention has been made based on this finding. A copper or copper alloy material characterized by substantially removing an organic film other than a film having a copper discoloration preventing function remaining on the surface of copper or a copper alloy and forming a film having a copper discoloration preventing function on the surface. 1. Discoloration prevention method 2. The method for preventing discoloration of a copper or copper alloy material according to claim 1, wherein a discoloration preventing treatment is performed after the copper or copper alloy material is subjected to acid cleaning or alkali cleaning. Copper or copper alloy characterized by washing and removing the remaining organic film with acid or alkali from copper or copper alloy material that has been subjected to silver substitution prevention treatment and subsequent silver plating, and then subjected to discoloration prevention treatment 3. How to prevent discoloration of the material Copper or copper alloy material is subjected to acid cleaning or alkali cleaning before or after performing a color change prevention treatment with a color change prevention liquid formed by adding a metal nobler than copper or a salt thereof to a copper inhibitor. 4. The method for preventing discoloration of a copper or copper alloy material according to claim 1. Before copper or copper alloy material that has been subjected to silver substitution prevention treatment and subsequent silver plating, is subjected to a discoloration prevention treatment with a discoloration prevention liquid that is a copper inhibitor added with a metal nobler than copper or a salt thereof. 5. The method for preventing discoloration of a copper or copper alloy material according to claim 1, wherein acid cleaning or alkali cleaning is performed thereafter. An organic film other than a film having a function of preventing copper discoloration remaining on the surface of copper or copper alloy is substantially removed, and a film having a function of preventing copper discoloration is formed on the surface of the copper or copper alloy. It provides materials.
【００１０】[0010]
【発明の実施の形態】本発明における変色防止処理を施
される基材としての「銅または銅合金材」とは、銅ある
いは銅合金のみからなる無垢の材料はもちろんのこと、
鉄または鉄合金、ニッケルまたはニッケル合金等といっ
た金属に銅ストライクめっき処理を施したものなど、銅
あるいは銅合金の表面が存在する材料の全てを包含する
ものである。BEST MODE FOR CARRYING OUT THE INVENTION The term “copper or copper alloy material” as a substrate to be subjected to a discoloration prevention treatment in the present invention means not only a solid material consisting of copper or a copper alloy, but also
It includes all materials having a surface of copper or a copper alloy, such as a metal such as iron or an iron alloy, nickel or a nickel alloy subjected to a copper strike plating treatment.
【００１１】銅または銅合金材は、その表面に残留する
銅変色防止機能を有する被膜以外の有機被膜を実質的に
除去され、銅変色防止機能を有する被膜を表面に形成さ
れる。表面に残留する銅変色防止機能を有する被膜以外
の有機被膜を除去するために変色防止工程の前に酸洗浄
またはアルカリ洗浄を行う。通常、銀置換防止処理とそ
れに引き続く銀めっきを行った後、酸洗浄またはアルカ
リ洗浄を行うが、酸洗浄またはアルカリ洗浄工程は、銀
めっきの後、さらに銀剥離工程の後に行っても良いし、
あるいは銀剥離工程の前に行っても構わない。酸洗浄ま
たはアルカリ洗浄は、主成分として、酸またはアルカリ
を０．１％以上、５０％以下、好ましくは１〜１０％含
有する水溶液によって行えば良い。酸としては、無機
酸、有機酸のいずれも使用することが可能であり、例え
ば、塩酸、硫酸、リン酸、ホウ酸、スルホン酸、酢酸、
クエン酸などが代表的に挙げられる。アルカリとして
は、水酸化カリウム、水酸化ナトリウム、シアン化カリ
ウム、シアン化ナトリウム等の無機アルカリ、アミン等
の有機アルカリが代表的に挙げられる。酸またはアルカ
リ濃度が低すぎると効果がなく、濃度が高すぎると素材
のエッチングが激しすぎるため好ましくない。In the copper or copper alloy material, an organic film other than a film having a function of preventing copper discoloration remaining on the surface is substantially removed, and a film having a function of preventing copper discoloration is formed on the surface. In order to remove the organic film other than the film having the function of preventing discoloration of copper remaining on the surface, acid washing or alkali washing is performed before the discoloration preventing step. Usually, after silver substitution prevention treatment and subsequent silver plating are performed, acid cleaning or alkali cleaning is performed.The acid cleaning or alkali cleaning step may be performed after silver plating and further after the silver peeling step,
Alternatively, it may be performed before the silver peeling step. The acid washing or alkali washing may be performed with an aqueous solution containing 0.1% or more and 50% or less, preferably 1 to 10%, of an acid or alkali as a main component. As the acid, any of an inorganic acid and an organic acid can be used. For example, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sulfonic acid, acetic acid,
Representatively, citric acid and the like. Representative examples of the alkali include inorganic alkalis such as potassium hydroxide, sodium hydroxide, potassium cyanide and sodium cyanide, and organic alkalis such as amines. If the acid or alkali concentration is too low, there is no effect, and if the concentration is too high, the etching of the material is too severe, which is not preferable.
【００１２】なお、洗浄液には必要に応じて、ｐＨ緩衝
剤として、無機酸、有機酸またはその塩などを１〜５０
０ｇ／Ｌ、好ましくは１０〜１００ｇ／Ｌ添加しても良
い。ｐＨ緩衝剤の濃度が低すぎると、ｐＨ緩衝能が低
く、濃度が高すぎてもそれ以上の効果が期待できないた
め好ましくない。If necessary, an inorganic acid, an organic acid or a salt thereof may be used as a pH buffer in the washing solution in an amount of 1 to 50.
0 g / L, preferably 10 to 100 g / L may be added. If the concentration of the pH buffer is too low, the pH buffering capacity is low, and if the concentration is too high, no further effect can be expected.
【００１３】また、必要に応じてアニオン系、カチオン
系、ノニオン系界面活性剤のいずれかまたはその混合物
を１μｇ／Ｌ〜１０ｇ／Ｌ、好ましくは１０μｇ／Ｌ〜
１ｇ／Ｌ添加しても良い。界面活性剤の濃度が低すぎる
と、界面活性能が低く、濃度が高すぎてもそれ以上の効
果が期待できないため好ましくない。If necessary, any one of anionic, cationic and nonionic surfactants or a mixture thereof may be used in an amount of 1 μg / L to 10 g / L, preferably 10 μg / L to 10 μg / L.
1 g / L may be added. If the concentration of the surfactant is too low, the surfactant activity is low, and if the concentration is too high, no further effect can be expected.
【００１４】洗浄液のｐＨは特に限定されない。洗浄液
の液温は５〜８０℃、好ましくは１０〜５０℃とすべき
である。液温が低すぎると洗浄能力が低く、液温が高す
ぎてもそれ以上の効果が期待できず、また、設備の腐食
につながるため好ましくない。The pH of the cleaning solution is not particularly limited. The temperature of the washing solution should be 5 to 80C, preferably 10 to 50C. If the liquid temperature is too low, the cleaning ability is low, and if the liquid temperature is too high, no further effect can be expected, and it leads to corrosion of equipment, which is not preferable.
【００１５】酸洗浄またはアルカリ洗浄の方法は、銅ま
たは銅合金材を洗浄液に浸漬するかまたは、銅または銅
合金材に洗浄液を散布（シャワー、スプレー等）するこ
とによって行えば良い。The method of acid cleaning or alkali cleaning may be performed by immersing a copper or copper alloy material in a cleaning liquid or by spraying (shower, spray, etc.) the cleaning liquid on the copper or copper alloy material.
【００１６】酸洗浄またはアルカリ洗浄処理を行った銅
または銅合金材は、その後、変色防止処理が施される。
変色防止処理は、銅変色防止液に浸漬するかまたは銅変
色防止液を銅または銅合金に散布（シャワー、スプレー
等）することによって行う。銅変色防止液は、一般的な
ベンゾトリアゾール系の変色防止剤を含むもの等の他、
特願平８−１２２３４３号に記載した“分子内に窒素又
は硫黄あるいはこれら両方を含んでいて銅のインヒビタ
ーとして働く複素環状化合物”を含有する溶液に銅より
も貴な金属又はその塩を添加して成るもの、など公知の
銅変色防止液のいずれを用いても構わない。The copper or copper alloy material subjected to the acid cleaning or alkali cleaning treatment is thereafter subjected to a discoloration prevention treatment.
The anti-tarnish treatment is performed by immersing the anti-tarnish liquid in copper or spraying the anti-tarnish liquid on copper or a copper alloy (shower, spray, etc.). Copper discoloration prevention liquid, other than those containing a general benzotriazole-based discoloration inhibitor,
A metal or a salt thereof which is more noble than copper is added to a solution containing a "heterocyclic compound containing nitrogen and / or sulfur or both in the molecule and acting as an inhibitor of copper" described in Japanese Patent Application No. 8-122343. Any of known copper discoloration preventing liquids such as a liquid discoloration preventing liquid may be used.
【００１７】なお、銅または銅合金材に対して、「銅の
インヒビターに銅よりも貴な金属またはその塩を添加し
て成る変色防止液」を用いる変色防止処理を施す場合に
は、酸洗浄またはアルカリ洗浄はその変色防止処理の後
に行っても良い。これは、「銅のインヒビターに銅より
も貴な金属またはその塩を添加して成る変色防止液」を
用いた変色防止処理を施した場合には表面に「銅よりも
貴な金属」の置換被膜層が形成されることによって変色
防止機能が付与されるが、この変色防止機能を有する置
換被膜層は、通常の有機化合物による銅変色防止被膜と
は異なり、酸洗浄またはアルカリ洗浄によっても銅また
は銅合金基材上に残留し銅変色防止機能を発揮すること
が可能だからである。In the case where the copper or copper alloy material is subjected to a discoloration preventing treatment using “a discoloration preventing liquid obtained by adding a metal or a salt thereof which is nobler than copper to a copper inhibitor”, acid cleaning is performed. Alternatively, the alkali washing may be performed after the discoloration prevention treatment. This is because when a discoloration prevention treatment is performed using a “color change prevention liquid consisting of a copper inhibitor and a metal or a salt thereof that is more noble than copper”, the surface is replaced with a “metal nobler than copper”. Although the discoloration preventing function is imparted by forming the coating layer, the substitution coating layer having the discoloring preventing function is different from the copper discoloration preventing coating formed by a usual organic compound, and is different from the copper or the acid cleaning or the alkali cleaning. This is because it remains on the copper alloy base material and can exhibit the function of preventing copper discoloration.
【００１８】本発明の銅または銅合金材の変色防止方法
においては、主に銀置換防止剤などに含まれ、基材表面
に残留していた有機物被膜が酸洗浄またはアルカリ洗浄
によって洗浄除去されるとともに変色防止処理によって
良好な銅変色防止機能を有する被膜が形成されるため、
不要有機物の残留に起因する耐熱性、耐食性の低下など
を抑制することができる。In the method for preventing discoloration of a copper or copper alloy material according to the present invention, an organic film, which is mainly contained in a silver substitution inhibitor or the like and remains on the substrate surface, is washed and removed by acid washing or alkali washing. Because a film having a good copper discoloration prevention function is formed by the discoloration prevention treatment,
It is possible to suppress a decrease in heat resistance, corrosion resistance, and the like due to the remaining of unnecessary organic substances.
【００１９】[0019]
【実施例】以下、実施例によって本発明を説明するが、
本発明の範囲は実施例によって限定されるものではな
い。厚さ０．１μmの銅ストライクめっきを施した「２
５ｍｍ幅×４０ｍｍ×０．２ｍｍ厚」の銅合金（Cu:97.
77%-Sn:2.0%-Ni:0.2%-P:0.03%）製基材を純水で水洗し
た後、銀置換防止剤である２−チオバルビツル酸を１０
０ｍｇ／Ｌ含むとともに、ｐＨが１０に調整された銀置
換防止液に液温３０℃で１０秒間浸漬し、続いて純水水
流で洗浄した。その後、 ＫＡｇ（ＣＮ）2：１３０ｇ／Ｌ Ｋ2ＨＰＯ4 ：１００ｇ／Ｌ を含むとともにｐＨが８．５に調整された高速電気銀め
っき液に浸漬して電流密度７０Ａ／ｄｍ2で１０秒間銀
めっきを行った。その後、銀めっきした基材を純水で洗
浄してから、中央部（７ｍｍ×６ｍｍ）を除く他の部位
の銀めっき層を市販の銀剥離液を用いて溶解除去し、再
度純水で水洗した後、表１に記載の洗浄液に浸漬するか
または表１に記載の洗浄液を基材表面に散布（シャワ
ー）する処理を行った。Hereinafter, the present invention will be described with reference to Examples.
The scope of the present invention is not limited by the examples. "2" plated with 0.1μm thick copper strike
5mm wide x 40mm x 0.2mm thick "copper alloy (Cu: 97.
77% -Sn: 2.0% -Ni: 0.2% -P: 0.03%) After the base material was washed with pure water, 2-thiobarbituric acid, a silver displacement inhibitor, was added in 10%.
It was immersed in a silver replacement preventing solution containing 0 mg / L and adjusted to pH 10 at a liquid temperature of 30 ° C. for 10 seconds, and then washed with a pure water flow. Then, it was immersed in a high-speed electroplating solution containing 130 g / L of KAg (CN) 2 and 100 g / L of K 2 HPO 4 and adjusted to pH 8.5, and was immersed in silver at a current density of 70 A / dm 2 for 10 seconds. Plating was performed. Thereafter, the silver-plated base material is washed with pure water, and then the silver plating layer at the other portion except for the central part (7 mm × 6 mm) is dissolved and removed using a commercially available silver stripping solution, and washed again with pure water. After that, a treatment of immersing in the cleaning liquid shown in Table 1 or spraying (showing) the cleaning liquid shown in Table 1 on the surface of the substrate was performed.
【００２０】[0020]
【表１】 [Table 1]
【００２１】さらに、純水で水洗した後、表１に記載の
変色防止液に基材を１０秒間浸漬する変色防止処理を行
った。なお、変色防止剤として銅インヒビターに銅より
も貴な金属を添加して成る変色防止液を用いた場合につ
いては、該変色防止処理の前に酸洗浄を行った場合（実
施例５）だけでなく該変色防止処理の後に酸洗浄を行っ
た場合（実施例７）も併せて示した。Further, after washing with pure water, a discoloration preventing treatment was performed by dipping the substrate in a discoloration preventing solution shown in Table 1 for 10 seconds. In the case where a discoloration preventing liquid obtained by adding a noble metal than copper to a copper inhibitor was used as a discoloration preventing agent, only when acid cleaning was performed before the discoloration preventing treatment (Example 5). In addition, the case where acid washing was performed after the discoloration prevention treatment (Example 7) is also shown.
【００２２】このような処理を行った各基材について、
「３０分間加熱後、テープによるピールテストで銅酸化
被膜が完全に剥離する温度」を調べて耐熱性の評価を行
った。なお、変色防止処理を行った後１２ヶ月放置した
後に同じ試験を行い、長期間保管後の耐熱性を評価し
た。また、変色防止処理を行った各基材を煮沸純水中に
１０分間浸漬し、銅ストライクめっき部（剥離液によっ
て銀めっき層を除去した部位）の変色を目視により判定
し、耐変色性の評価を行った。ここで、「煮沸純水中に
１０分間浸漬する」という前記熱処理は、大気中に放置
した場合の加速試験として通常に行われている処理であ
る。With respect to each substrate subjected to such treatment,
"The temperature at which the copper oxide film was completely peeled off by a tape peel test after heating for 30 minutes" was examined to evaluate the heat resistance. In addition, the same test was performed after standing for 12 months after performing the discoloration prevention treatment, and the heat resistance after long-term storage was evaluated. Further, each substrate subjected to the discoloration prevention treatment was immersed in boiling pure water for 10 minutes, and the discoloration of the copper strike plating portion (the portion from which the silver plating layer was removed by the stripping solution) was visually judged, and the discoloration resistance was evaluated. An evaluation was performed. Here, the heat treatment of “immersing in boiling pure water for 10 minutes” is a process that is usually performed as an accelerated test when left in the air.
【００２３】なお、比較例として、酸洗浄またはアルカ
リ洗浄を行わずに実施例１，５，６と同じ変色防止処理
を行った場合について、同様の試験を行い、その結果を
評価した。これらの結果を表２に示す。As a comparative example, the same test as in Examples 1, 5, and 6 was performed without acid cleaning or alkali cleaning, and the same test was performed. The results were evaluated. Table 2 shows the results.
【００２４】[0024]
【表２】 [Table 2]
【００２５】表１、２に示した結果から、本発明に係る
変色防止方法を施した場合には、非常に良好な耐熱性、
耐変色性を示すと同時に、１２ヶ月放置後の耐熱性は変
色防止処理直後と同じ高い耐熱性を示した。これに対し
て、比較例では、同じ変色防止を用いて剤理を行った場
合でも酸洗浄またはアルカリ洗浄を行った場合に比べて
耐熱性が低く、また、１２ヶ月放置後の耐熱性は低下す
るという問題があった。From the results shown in Tables 1 and 2, when the method for preventing discoloration according to the present invention was applied, very good heat resistance,
At the same time as showing discoloration resistance, the heat resistance after standing for 12 months showed the same high heat resistance as immediately after the discoloration prevention treatment. On the other hand, in the comparative example, even when the pharmacological treatment was performed using the same discoloration prevention, the heat resistance was lower than that in the case of performing the acid cleaning or the alkali cleaning, and the heat resistance after being left for 12 months was lowered. There was a problem of doing.
【００２６】[0026]
【発明の効果】本発明の銅または銅合金材の変色防止方
法を施すことにより表面に残留する不要有機被膜が実質
的に除去され、銅変色防止被膜が表面に形成された銅ま
たは銅合金材は、非常に良好な耐熱性、耐変色性を示す
と同時に、長期間保管後でも変色防止処理直後と同じ高
い耐熱性を示す。従って、高速部分銀めっきが施された
電子部品材料（例えばリードフレーム）等の信頼性向上
に大きく寄与し得るなど、産業上有用な効果がもたらさ
れる。According to the method for preventing discoloration of a copper or copper alloy material according to the present invention, an unnecessary organic film remaining on the surface is substantially removed, and a copper or copper alloy material having a copper discoloration prevention film formed on the surface. Shows very good heat resistance and discoloration resistance, and at the same time, shows the same high heat resistance even after long-term storage, as it does immediately after the discoloration prevention treatment. Therefore, industrially useful effects are brought about, such as being able to greatly contribute to the improvement of the reliability of electronic component materials (eg, lead frames) that have been subjected to high-speed partial silver plating.
Claims (6)
防止機能を有する被膜以外の有機被膜を実質的に除去
し、銅変色防止機能を有する被膜を表面に形成すること
を特徴とする銅または銅合金材の変色防止方法。1. A copper film, wherein an organic film other than a film having a function of preventing copper discoloration remaining on the surface of copper or a copper alloy is substantially removed, and a film having a function of preventing copper discoloration is formed on the surface. Or a method for preventing discoloration of copper alloy materials.
アルカリ洗浄を行った後、変色防止処理を行うことを特
徴とする請求項１記載の銅または銅合金材の変色防止方
法。2. The method for preventing discoloration of a copper or copper alloy material according to claim 1, wherein a discoloration preventing treatment is performed after the copper or copper alloy material is subjected to acid cleaning or alkali cleaning.
きを行った銅または銅合金材に対して、残留する有機被
膜を酸またはアルカリで洗浄・除去し、その後変色防止
処理を行うことを特徴とする銅または銅合金材の変色防
止方法。3. A copper or copper alloy material which has been subjected to a silver replacement prevention treatment and a subsequent silver plating, wherein a residual organic film is washed and removed with an acid or an alkali, and thereafter a discoloration prevention treatment is performed. To prevent discoloration of copper or copper alloy materials.
ビターに銅よりも貴な金属またはその塩を添加して成る
変色防止液による変色防止処理を施す前または後に酸洗
浄またはアルカリ洗浄を行うことを特徴とする請求項１
記載の銅または銅合金材の変色防止方法。4. An acid washing or an alkali washing before or after a copper or copper alloy material is subjected to a discoloration preventing treatment by adding a noble metal or a salt thereof to a copper inhibitor to a copper inhibitor. 2. The method according to claim 1, wherein
The method for preventing discoloration of a copper or copper alloy material as described above.
きを行った銅または銅合金材に対して、銅のインヒビタ
ーに銅よりも貴な金属またはその塩を添加して成る変色
防止液による変色防止処理を施す前または後に酸洗浄ま
たはアルカリ洗浄を行うことを特徴とする請求項１記載
の銅または銅合金材の変色防止方法。5. A discoloration preventive liquid comprising a copper inhibitor and a noble metal or a salt thereof added to a copper inhibitor to a copper or copper alloy material which has been subjected to a silver replacement prevention treatment and subsequent silver plating. The method for preventing discoloration of a copper or copper alloy material according to claim 1, wherein acid cleaning or alkali cleaning is performed before or after the treatment.
防止機能を有する被膜以外の有機被膜が実質的に除去さ
れ、銅変色防止機能を有する被膜が表面に形成されてい
ることを特徴とする銅または銅合金材。6. An organic film other than a film having a function of preventing copper discoloration remaining on the surface of copper or a copper alloy is substantially removed, and a film having a function of preventing copper discoloration is formed on the surface. Copper or copper alloy material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36660497A JP3994295B2 (en) | 1997-12-26 | 1997-12-26 | Method for preventing discoloration of copper or copper alloy material and copper or copper alloy material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36660497A JP3994295B2 (en) | 1997-12-26 | 1997-12-26 | Method for preventing discoloration of copper or copper alloy material and copper or copper alloy material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11193482A true JPH11193482A (en) | 1999-07-21 |
| JP3994295B2 JP3994295B2 (en) | 2007-10-17 |
Family
ID=18487195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36660497A Expired - Fee Related JP3994295B2 (en) | 1997-12-26 | 1997-12-26 | Method for preventing discoloration of copper or copper alloy material and copper or copper alloy material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3994295B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007321241A (en) * | 2006-06-05 | 2007-12-13 | Mayclean Obutsudan Honpo:Kk | Method for cleaning grease |
| CN113373485A (en) * | 2021-04-19 | 2021-09-10 | 辉门环新（安庆）粉末冶金有限公司 | Powder metallurgy copper plating process |
| CN115161647A (en) * | 2022-07-13 | 2022-10-11 | 江苏富乐华半导体科技股份有限公司 | Method for improving copper surface oxidation after copper-clad ceramic substrate welding |
-
1997
- 1997-12-26 JP JP36660497A patent/JP3994295B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007321241A (en) * | 2006-06-05 | 2007-12-13 | Mayclean Obutsudan Honpo:Kk | Method for cleaning grease |
| JP4553870B2 (en) * | 2006-06-05 | 2010-09-29 | 株式会社メイクリーンお仏壇本舗 | Oil cleaning method |
| CN113373485A (en) * | 2021-04-19 | 2021-09-10 | 辉门环新（安庆）粉末冶金有限公司 | Powder metallurgy copper plating process |
| CN113373485B (en) * | 2021-04-19 | 2024-09-03 | 辉门环新（安庆）粉末冶金有限公司 | Valve seat ring metallurgical copper plating process |
| CN115161647A (en) * | 2022-07-13 | 2022-10-11 | 江苏富乐华半导体科技股份有限公司 | Method for improving copper surface oxidation after copper-clad ceramic substrate welding |
| CN115161647B (en) * | 2022-07-13 | 2023-07-21 | 江苏富乐华半导体科技股份有限公司 | Method for improving oxidation of copper surface of copper-clad ceramic substrate after welding |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3994295B2 (en) | 2007-10-17 |
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