JP2833477B2 - Brightly tinted zinc phosphate treated plated metal sheet and method for producing the same - Google Patents
Brightly tinted zinc phosphate treated plated metal sheet and method for producing the sameInfo
- Publication number
- JP2833477B2 JP2833477B2 JP12136194A JP12136194A JP2833477B2 JP 2833477 B2 JP2833477 B2 JP 2833477B2 JP 12136194 A JP12136194 A JP 12136194A JP 12136194 A JP12136194 A JP 12136194A JP 2833477 B2 JP2833477 B2 JP 2833477B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- zinc phosphate
- film
- plating
- steel sheet
- 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.)
- Expired - Lifetime
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、家電製品、建材、自動
車等の用途に塗装下地母材として使用するのに適した、
塗装下地処理としてりん酸亜鉛処理が施された、色調の
明るいりん酸亜鉛処理めっき金属板 (代表的には鋼板)
とその製造方法に関する。The present invention is suitable for use as a base material for painting in home appliances, building materials, automobiles, etc.
Brightly tinted zinc phosphate-treated metal sheet (typically steel sheet) that has been treated with zinc phosphate as a coating base treatment
And its manufacturing method.
【０００２】[0002]
【従来の技術】亜鉛系電気めっき鋼板 (本発明では、亜
鉛電気めっきと亜鉛系合金電気めっきとを総称して「亜
鉛系電気めっき」という) は、亜鉛系溶融めっき鋼板と
比べて、加工性がよい、めっき量が少ない、表面が平滑
であるといった特徴を有している。2. Description of the Related Art Zinc-based electroplated steel sheets (in the present invention, zinc-electroplated and zinc-based alloy-electroplated are collectively referred to as “zinc-based electroplated”) are more workable than zinc-based hot-dip coated steel sheets. However, it has the characteristics of good plating, a small amount of plating, and a smooth surface.
【０００３】亜鉛系電気めっき鋼板は、一般に後処理と
して、耐食性向上を目的とするクロメート処理か、塗装
性向上を目的とするりん酸亜鉛処理が施される。従っ
て、亜鉛系電気めっき鋼板を塗装して使用する場合に
は、塗装密着性を改善する塗装下地処理として、通常は
りん酸亜鉛処理が施される。この処理でめっき表面に形
成されたりん酸亜鉛皮膜は、塗装密着性を改善する以外
に、固形潤滑皮膜としての機能も有しており、無塗装で
使用される亜鉛系電気めっき鋼板に、潤滑性改善のため
にりん酸亜鉛処理が施されることもある。[0003] Zinc-based electroplated steel sheets are generally subjected to post-treatment such as chromate treatment for improving corrosion resistance or zinc phosphate treatment for improving paintability. Therefore, when a zinc-based electroplated steel sheet is used by coating, zinc phosphate treatment is usually applied as a coating base treatment for improving coating adhesion. The zinc phosphate film formed on the plating surface by this treatment has a function as a solid lubricating film in addition to improving the coating adhesion, and is used for lubricating zinc-based electroplated steel sheets used without painting. In some cases, zinc phosphate treatment is applied to improve the properties.
【０００４】りん酸亜鉛処理は、必要により表面調整さ
れた亜鉛系電気めっき鋼板に対して、りん酸亜鉛処理液
を用いて浸漬または噴霧処理することにより行われる。
この処理の後、通常はさらに水洗と薄いクロム酸水溶液
によるシーリング処理とが行われる。使用するりん酸亜
鉛処理液には、りん酸亜鉛に加えて、塗装性能の向上の
ために微量のNiイオンと、皮膜形成の促進のために少量
の硝酸イオンおよび微量のフッ素イオンとが通常は添加
されている。[0004] The zinc phosphate treatment is carried out by immersing or spraying a zinc-based electroplated steel sheet whose surface has been adjusted as required using a zinc phosphate treatment liquid.
After this treatment, washing with water and sealing treatment with a dilute chromic acid aqueous solution are usually performed. The zinc phosphate treatment solution used usually contains, in addition to zinc phosphate, a small amount of Ni ions for improving coating performance, and a small amount of nitrate ions and a small amount of fluorine ions for promoting film formation. Has been added.
【０００５】[0005]
【発明が解決しようとする課題】一般に、亜鉛系電気め
っき鋼板にりん酸亜鉛処理を施すと、表面の色調が黒く
なり、白色度が低下することが知られている。この白色
度の低下は、その上に塗装を施して、下地の色が完全に
隠れる場合には問題ない。しかし、最近ではコスト削
減、加工性改善を目的として塗膜が薄膜化する傾向があ
り、またシルク印刷などの下地の色が透過するような塗
装が特に家電製品分野で行われるようになったために、
下地の色が製品の表面色調に影響することがあり、ユー
ザーより白色度の高い (ハンター色差計のＬ値で60以上
の) 製品鋼板が要求されている。また、無塗装で使用す
る場合にも、このような明るい色調の鋼板が好ましい。
この白色度の向上要求には、従来のりん酸亜鉛処理めっ
き鋼板では対応することができなかった。It is generally known that when zinc phosphate treatment is applied to a zinc-based electroplated steel sheet, the surface tone becomes black and the whiteness decreases. This decrease in whiteness is not a problem when the paint is applied thereon and the underlying color is completely hidden. However, recently, there has been a tendency for coatings to become thinner in order to reduce costs and improve workability, and painting that allows the color of the underlayer to be transmitted, such as silk printing, has been performed especially in the field of home appliances. ,
The color of the base may affect the surface color of the product, and there is a demand for a product steel plate with higher whiteness (L value of a Hunter color difference meter of 60 or more) than the user. Further, even when used without painting, a steel sheet having such a bright color is preferable.
The demand for improving the whiteness cannot be met by the conventional zinc phosphated plated steel sheet.
【０００６】白色度の向上に関して、特開昭59−107084
号および同62−47488 号各公報には、りん酸亜鉛処理液
の組成の調整により、白色度の高いりん酸亜鉛皮膜を形
成することができる亜鉛系電気めっき鋼板のりん酸亜鉛
処理方法が開示されている。具体的には、りん酸亜鉛処
理液中の硝酸濃度を2.5 g/L 以上とする方法である。硝
酸は、りん酸亜鉛結晶の生成時に発生した水素ガスを水
に酸化させて除去し、この結晶の生成反応を円滑にする
働きがある。また、硝酸はめっき鋼板表面を溶解させ、
白色化に悪影響を与えるニッケルを溶解することによっ
て鋼板の白色化に寄与するものである。しかし、硝酸
は、その反応過程で、りん酸亜鉛処理反応に悪影響を与
えるアンモニアを生成するので、りん酸亜鉛処理液の劣
化が促進され、その寿命が著しく低下するという悪影響
がある。Regarding the improvement of whiteness, Japanese Patent Application Laid-Open No.
And JP-A-62-47488 disclose a method of treating zinc-based electroplated steel sheets which can form a zinc phosphate film having high whiteness by adjusting the composition of the zinc phosphate treatment solution. Have been. Specifically, this is a method in which the concentration of nitric acid in the zinc phosphate treatment liquid is set to 2.5 g / L or more. Nitric acid has the function of oxidizing and removing hydrogen gas generated during the formation of zinc phosphate crystals into water, thereby facilitating the formation reaction of the crystals. Also, nitric acid dissolves the surface of the plated steel sheet,
By dissolving nickel which has an adverse effect on whitening, it contributes to whitening of the steel sheet. However, nitric acid produces ammonia which adversely affects the zinc phosphate treatment reaction in the course of the reaction, so that deterioration of the zinc phosphate treatment solution is promoted, and the life of the solution is significantly reduced.
【０００７】よって、本発明の目的は、りん酸亜鉛処理
液の組成の調整によるのではなく、別の手段でりん酸亜
鉛処理めっき鋼板の表面白色度を改善することにより、
りん酸亜鉛処理液の劣化を生ずることなく、色調の明る
いりん酸亜鉛処理めっき鋼板または金属板を製造するこ
とができる方法を提供することである。本発明の別の目
的は、亜鉛系めっき皮膜の改良によって、ハンターＬ値
が70以上、かつりん酸亜鉛処理前後のハンターＬ値の差
が８未満という、色調が明るく、かつりん酸亜鉛処理に
よる白色度低下の少ないりん酸亜鉛処理めっき鋼板また
は金属板とその製造方法とを提供することである。Therefore, the object of the present invention is not to adjust the composition of the zinc phosphate treatment liquid, but to improve the surface whiteness of the zinc phosphate treated plated steel sheet by another means.
An object of the present invention is to provide a method capable of producing a zinc phosphate-treated plated steel sheet or metal sheet having a bright color tone without causing deterioration of the zinc phosphate treatment solution. Another object of the present invention is to improve the zinc-based plating film so that the Hunter L value is 70 or more, and the difference between the Hunter L values before and after the zinc phosphate treatment is less than 8, the color is bright, and the zinc phosphate treatment is used. An object of the present invention is to provide a zinc phosphate-treated plated steel sheet or a metal sheet with less decrease in whiteness and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく検討を重ねた結果、電気亜鉛系めっき段階
においてめっき浴中に特定濃度のイオウ含有有機化合物
を添加すると、形成された亜鉛系電気めっき皮膜中のめ
っき結晶の粒子形状が変化し、りん酸亜鉛処理後の白色
度が向上することを見出し、本発明に到達した。Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have found that when a specific concentration of a sulfur-containing organic compound is added to a plating bath in an electro-zinc plating step, a sulfur-containing organic compound is formed. It has been found that the particle shape of the plating crystals in the zinc-based electroplated film changes, and that the whiteness after zinc phosphate treatment is improved, and the present invention has been achieved.
【０００９】ここに、本発明は、少なくとも片面に、可
溶性のイオウ含有有機化合物を含有する酸性浴中での陰
極電解により形成されたＣ含有量 0.001〜10重量％、付
着量３g/m2以上の複合亜鉛または亜鉛系合金電気めっき
皮膜と、その上に形成されたりん酸亜鉛皮膜とを有する
ことを特徴とする、色調の明るいりん酸亜鉛処理めっき
金属板を要旨とする。Here, the present invention relates to a method for producing a composition, comprising: at least one side having a C content of 0.001 to 10% by weight formed by cathodic electrolysis in an acidic bath containing a soluble sulfur-containing organic compound, and an adhesion amount of 3 g / m 2 or more. The present invention provides a zinc-phosphate-plated metal sheet having a bright color tone, characterized by having a composite zinc or zinc-based alloy electroplating film and a zinc phosphate film formed thereon.
【００１０】別の側面から、本発明は、１種または２種
以上の可溶性のイオウ含有有機化合物を合計0.01〜100
g/L の量で含有する酸性浴中で金属板を陰極電解処理し
て、金属板の少なくとも片面にＣ含有量 0.001〜10重量
％の複合亜鉛または亜鉛系合金電気めっき皮膜を３g/m2
以上の付着量で形成し、得られた電気めっき鋼板をりん
酸亜鉛処理して、上記めっき皮膜上にりん酸亜鉛皮膜を
形成することを特徴とする、色調の明るいりん酸亜鉛処
理めっき金属板の製造方法である。[0010] In another aspect, the present invention provides one or more soluble sulfur-containing organic compounds in a total amount of 0.01 to 100.
The metal plate is subjected to cathodic electrolysis in an acid bath containing an amount of 3 g / m 2 on at least one surface of the metal plate with a C content of 0.001 to 10% by weight of a composite zinc or zinc-based alloy.
A zinc phosphate-treated plated metal sheet having a bright color tone, characterized by forming a zinc phosphate film on the plated film by subjecting the resulting electroplated steel sheet to zinc phosphate treatment. It is a manufacturing method of.
【００１１】以下では、説明の簡略化のために、めっき
母材が鋼板であるりん酸亜鉛処理めっき鋼板の場合を例
にとって本発明を説明するが、めっき母材が他の金属板
(例、アルミニウム合金板) である場合も事情はほぼ同
じである。In the following, for the sake of simplicity, the present invention will be described by taking as an example the case of a zinc phosphate-treated plated steel sheet, in which the plated base material is a steel sheet.
The situation is almost the same in the case of (for example, an aluminum alloy plate).
【００１２】[0012]
【作用】本発明は、硫酸塩浴や塩酸塩浴といった酸性浴
による亜鉛系電気めっきの後、りん酸亜鉛処理を行うり
ん酸亜鉛処理めっき鋼板の製造において、めっき浴に特
定量のイオウ含有有機化合物を添加した点に特徴があ
る。この有機化合物の添加により、陰極電解により形成
された亜鉛系めっき皮膜中に有機化合物が分解して共析
し、炭素分を含有する複合亜鉛系電気めっき皮膜が形成
される。その結果、理由は定かではないが、従来の亜鉛
系電気めっき皮膜に比べて、めっき粒子が細粒化され、
表面光沢の高いめっき皮膜が得られる。The present invention relates to a method for producing a zinc phosphate-treated coated steel sheet in which zinc-based electroplating is performed in an acidic bath such as a sulfate bath or a hydrochloride bath, and then a zinc phosphate treatment is performed. The feature is that a compound is added. With the addition of the organic compound, the organic compound is decomposed and co-deposited in the zinc-based plating film formed by the cathodic electrolysis, and a composite zinc-based electroplating film containing carbon is formed. As a result, although the reason is not clear, compared to the conventional zinc-based electroplating film, the plating particles are finer,
Plating film with high surface gloss can be obtained.
【００１３】このめっき皮膜の上に、常法に従って、り
ん酸亜鉛処理を施すと、予想外にも、表面白色度が非常
に高い (ハンターＬ値が70以上の) 、色調の明るいりん
酸亜鉛処理めっき鋼板を得ることができる。しかも、こ
のめっき鋼板は、りん酸亜鉛処理による白色度低下が非
常に少ない (りん酸亜鉛処理前後での上記Ｌ値の差が８
未満) という利点も有している。その理由としては、細
粒化された細かいめっき粒子が個々にりん酸亜鉛と反応
して行くため、緻密で平滑なりん酸亜鉛皮膜が形成さ
れ、表面白色度が高くなるのではないかと推察される。When a zinc phosphate treatment is applied to this plating film in a usual manner, unexpectedly, zinc phosphate having a very high surface whiteness (Hunter L value of 70 or more) and a bright color tone is unexpectedly obtained. A treated plated steel sheet can be obtained. In addition, in this plated steel sheet, the decrease in whiteness caused by the zinc phosphate treatment is extremely small (the difference in the L value before and after the zinc phosphate treatment is 8%).
Less). The reason is presumed that the fine and fine plated particles individually react with zinc phosphate, so that a dense and smooth zinc phosphate film is formed and the surface whiteness increases. You.
【００１４】本発明においては、まず、母材の鋼板に酸
性浴（例、硫酸塩浴、塩酸塩浴等）による亜鉛系電気め
っき (即ち、純亜鉛めっきまたは亜鉛系合金めっきのい
ずれか) を施す。前述したように、母材は鋼板に限定さ
れるものではなく、アルミニウムもしくはアルミニウム
合金板、ニッケル基合金板などの亜鉛系電気めっきが可
能な任意の金属板でよい。この亜鉛系電気めっきは、酸
性めっき浴中に特定量のイオウ含有有機化合物を添加す
る点を除いて従来と同様に実施できる。母材鋼板は、必
要に応じて、常法により脱脂などの表面清浄化処理を施
しておく。In the present invention, first, zinc-based electroplating (that is, either pure zinc plating or zinc-based alloy plating) is applied to a base steel sheet using an acidic bath (eg, a sulfate bath, a hydrochloride bath, etc.). Apply. As described above, the base material is not limited to a steel plate, but may be any metal plate capable of zinc-based electroplating, such as an aluminum or aluminum alloy plate or a nickel-based alloy plate. This zinc-based electroplating can be carried out in the same manner as the conventional method except that a specific amount of a sulfur-containing organic compound is added to an acidic plating bath. The base steel sheet is subjected to a surface cleaning treatment such as degreasing according to a conventional method, if necessary.
【００１５】酸性浴として代表的な硫酸塩浴を例にとっ
て説明すると、亜鉛系めっき用硫酸塩浴の主成分は硫酸
亜鉛であり、これにｐＨおよびイオン伝導度の調整のた
めの適当な電解質 (例、アルカリ金属および／またはア
ンモニウムの硫酸塩) が添加される。亜鉛系合金めっき
の場合には、適量の合金元素の化合物 (例、硫酸塩、塩
化物、炭酸塩、次亜りん酸塩、モリブデン酸塩、酢酸
塩、有機金属化合物、或いは金属) が添加される。本発
明においては、このような酸性めっき浴にさらに１種も
しくは２種以上のイオウ含有有機化合物を添加する。Taking a typical sulfate bath as an example of the acidic bath, the main component of the sulfate bath for zinc-based plating is zinc sulfate, which is provided with a suitable electrolyte (for adjusting pH and ionic conductivity). (E.g., sulfates of alkali metals and / or ammonium). In the case of zinc-based alloy plating, an appropriate amount of a compound of an alloying element (eg, sulfate, chloride, carbonate, hypophosphite, molybdate, acetate, organometallic compound, or metal) is added. You. In the present invention, one or more sulfur-containing organic compounds are further added to such an acidic plating bath.
【００１６】本発明において使用できるイオウ含有有機
化合物は特に制限されないが、使用する酸性めっき浴に
可溶性の化合物（即ち、一般には水溶性化合物）を使用
する。好ましいイオウ含有有機化合物としては、チオ尿
素類、チアゾール類、有機スルホン酸類 (その塩を含
む) 、スルホキシド類などが挙げられるが、これらに限
定されるものではない。The sulfur-containing organic compound that can be used in the present invention is not particularly limited, but a compound that is soluble in the acidic plating bath used (that is, a water-soluble compound in general) is used. Preferred sulfur-containing organic compounds include, but are not limited to, thioureas, thiazoles, organic sulfonic acids (including their salts), sulfoxides, and the like.
【００１７】チオ尿素類とは、チオ尿素 [分子式：(N
H2)2C=S]それ自体、ならびにチオ尿素分子中の少なくと
も１個の水素原子を直鎖もしくは分岐鎖の飽和もしくは
不飽和脂肪族基またはフェニル基、ベンジル基などの芳
香族基で置換した有機化合物を包含する。例えば、チオ
尿素、メチルチオ尿素、アリルチオ尿素、フェニルチオ
尿素などが挙げられる。Thioureas are thiourea [molecular formula: (N
H 2 ) 2 C = S] itself, and at least one hydrogen atom in the thiourea molecule is substituted with a linear or branched saturated or unsaturated aliphatic group or an aromatic group such as a phenyl group or a benzyl group. Organic compounds. For example, thiourea, methylthiourea, allylthiourea, phenylthiourea and the like can be mentioned.
【００１８】チアゾール類とは、分子中に窒素および硫
黄原子を各１個以上含有する複素５員環構造を有する有
機化合物を意味し、例えば 1,3−チアゾール、２−メル
カプトベンゾチアゾールナトリウム等が挙げられる。The term "thiazole" means an organic compound having a 5-membered heterocyclic ring structure containing at least one nitrogen and at least one sulfur atom in the molecule. Examples thereof include 1,3-thiazole and sodium 2-mercaptobenzothiazole. No.
【００１９】有機スルホン酸類とは、分子中に１個以上
スルホン基 (−SO3H) を有する有機化合物とその塩 (即
ち、スルホン基中の水素イオン(H+ ) をカチオンで置き
換えた化合物) を意味する。例えば、エチルスルホン酸
(塩) 、タウリン、リグニンスルホン酸 (塩) 等が挙げ
られる。An organic sulfonic acid is an organic compound having one or more sulfone groups (—SO 3 H) in a molecule and a salt thereof (ie, a compound in which a hydrogen ion (H + ) in a sulfone group is replaced by a cation). Means For example, ethyl sulfonic acid
(Salt), taurine, ligninsulfonic acid (salt) and the like.
【００２０】スルホキシド類とは、RR'SO (R, R'は炭化
水素基) の構造を有する有機化合物あり、例えば、ジメ
チルスルホキシド、ジエチルスルホキシド等が挙げられ
る。また分子中の炭化水素基R, R' 中の１個以上の水素
原子が水酸基、カルボキシル基などの官能基で置換され
ていてもよい。The sulfoxides are organic compounds having the structure of RR'SO (R and R 'are hydrocarbon groups), and include, for example, dimethyl sulfoxide, diethyl sulfoxide and the like. Further, one or more hydrogen atoms in the hydrocarbon groups R and R 'in the molecule may be substituted with a functional group such as a hydroxyl group or a carboxyl group.
【００２１】イオウ含有有機化合物は１種もしくは２種
以上を合計0.01〜100 g/L の量で酸性めっき浴中に存在
させる。この量が0.01 g/L未満では、めっき皮膜中に複
合されるＣ量が少なく、表面白色度の低下という本発明
の目的が十分に達成できない。一方、イオウ含有有機化
合物の量が100 g/L を超えると、添加した有機化合物の
酸化によるめっき変色などのめっき不良が生じ易くな
る。イオウ含有有機化合物の含有量は、好ましくは0.1
〜10 g/Lの範囲内である。連続めっきの場合には、めっ
き浴中の有機化合物の濃度がほぼ一定に保持されるよう
に、イオウ含有有機化合物を補充することが好ましい。One or more sulfur-containing organic compounds are present in the acid plating bath in a total amount of 0.01 to 100 g / L. If the amount is less than 0.01 g / L, the amount of C compounded in the plating film is small, and the object of the present invention of lowering the surface whiteness cannot be sufficiently achieved. On the other hand, if the amount of the sulfur-containing organic compound exceeds 100 g / L, plating defects such as plating discoloration due to oxidation of the added organic compound are likely to occur. The content of the sulfur-containing organic compound is preferably 0.1
It is in the range of ~ 10 g / L. In the case of continuous plating, it is preferable to replenish the sulfur-containing organic compound so that the concentration of the organic compound in the plating bath is kept almost constant.
【００２２】亜鉛系電気めっき皮膜の付着量は３g/m2以
上必要であり、３g/m2未満ではめっきの表面被覆が不十
分となる。表面被覆の確実性と、めっき時の電気コスト
経済性を考慮すると、好ましいめっき付着量は５〜20g/
m2の範囲内である。The amount of the zinc-based electroplating film must be 3 g / m 2 or more, and if it is less than 3 g / m 2 , the surface coating of the plating becomes insufficient. Considering the reliability of the surface coating and the cost-effectiveness of electricity during plating, the preferred coating weight is 5 to 20 g /
m 2 .
【００２３】このめっき皮膜は、有機化合物の分解・共
析に起因する炭素分をＣ含有量として 0.001〜10重量％
の量で含有する。このＣの共析により、前述のように、
めっき粒子が細かく、表面光沢に優れた複合亜鉛系電気
めっき皮膜が得られる。めっき皮膜中のＣ含有量が 0.0
01重量％未満では、耐食性、表面光沢 (めっきの細粒
化) ともに改善効果が乏しくなる。一方、Ｃ含有量が10
重量％を超えると、めっき皮膜と母材鋼板との密着性が
極端に低下する。めっき浴中のイオウ含有有機化合物の
量が前述のように0.01〜100 g/L の範囲内であると、一
般に、Ｃ含有量が0.001〜10重量％のめっき皮膜が形成
されるが、必要であれば、めっき皮膜中のＣ含有量がこ
の範囲内になるように、めっき浴中の有機化合物添加量
を上記範囲内で調整する。複合めっき皮膜中のＣ含有量
は好ましくは0.01〜３重量％の範囲内である。The plating film has a carbon content of 0.001 to 10% by weight as a C content due to decomposition and codeposition of an organic compound.
In the amount of By the eutectoid of C, as described above,
A composite zinc-based electroplated film having fine plated particles and excellent surface gloss can be obtained. C content in plating film is 0.0
If it is less than 01% by weight, the effect of improving both corrosion resistance and surface gloss (fine graining of plating) is poor. On the other hand, when the C content is 10
If the content exceeds the weight percentage, the adhesion between the plating film and the base steel sheet is extremely reduced. When the amount of the sulfur-containing organic compound in the plating bath is in the range of 0.01 to 100 g / L as described above, a plating film having a C content of 0.001 to 10% by weight is generally formed. If so, the amount of the organic compound added in the plating bath is adjusted within the above range so that the C content in the plating film falls within this range. The C content in the composite plating film is preferably in the range of 0.01 to 3% by weight.
【００２４】こうして形成されたＣが複合化された亜鉛
系電気めっき皮膜を少なくとも片面に有するめっき鋼板
に、従来と同様にりん酸亜鉛処理を施して、上記めっき
皮膜上にりん酸亜鉛皮膜を形成する。このりん酸亜鉛処
理は、市販のりん酸亜鉛処理液を使用して、浸漬または
噴霧などの常法により実施すればよい。りん酸亜鉛皮膜
の付着量には特に制限はないが、通常は 1.0〜2.0 g/m2
の範囲内が好ましい。[0024] A zinc phosphate treatment is applied to the plated steel sheet having a composite zinc-based electroplating film formed on at least one side in the same manner as in the prior art to form a zinc phosphate film on the plating film. I do. This zinc phosphate treatment may be carried out by a conventional method such as immersion or spraying using a commercially available zinc phosphate treatment solution. The amount of the zinc phosphate coating is not particularly limited, but is usually 1.0 to 2.0 g / m 2.
Is preferably within the range.
【００２５】亜鉛系電気めっき工程とりん酸亜鉛処理工
程は、連続して実施しても、或いは別個に実施してもよ
い。いずれの場合も、りん酸亜鉛処理工程は、例えば、
亜鉛系電気めっき鋼板を脱脂した後、水洗し、公知方法
により表面調整 (例、アルカリ水溶液、チタンコロイド
などにより) してから、りん酸亜鉛処理を行い、次いで
水洗し、必要であれば上記のシーリング処理を行うとい
う処理順序となる。[0025] The zinc-based electroplating step and the zinc phosphate treatment step may be performed continuously or separately. In any case, the zinc phosphate treatment step includes, for example,
After degreasing the zinc-based electroplated steel sheet, wash it with water, adjust the surface by a known method (e.g., with an aqueous alkali solution, titanium colloid, etc.), perform zinc phosphate treatment, then wash with water, and if necessary, The processing order is such that the sealing processing is performed.
【００２６】本発明のりん酸亜鉛処理めっき鋼板は、塗
装下地母材として好適であるが、りん酸亜鉛皮膜が緻密
で均一に付着していて、表面が美麗かつ潤滑性に優れて
いるため、無塗装の用途にも使用できる。塗装の種類は
限定されず、通常の塗装、電着塗装、粉体塗装、シルク
印刷などの各種の塗装において、優れた塗装密着性を得
ることができる。Although the zinc phosphate-treated plated steel sheet of the present invention is suitable as a base material for coating, the zinc phosphate coating is dense and uniformly adhered, and the surface is beautiful and excellent in lubricity. Can be used for unpainted applications. The type of coating is not limited, and excellent coating adhesion can be obtained in various coatings such as ordinary coating, electrodeposition coating, powder coating, and silk printing.
【００２７】[0027]
【実施例】めっき母材として、板厚0.8 mmの冷延鋼板を
用いた。この母材鋼板を脱脂および水洗した後、表１に
示す種類および量の有機化合物を含有する硫酸塩めっき
浴による亜鉛系電気めっきを片面に施した。基本となる
亜鉛めっき浴および電解条件は次の通りである。EXAMPLE A cold-rolled steel sheet having a thickness of 0.8 mm was used as a plating base material. After the base steel sheet was degreased and washed with water, one side was subjected to zinc-based electroplating using a sulfate plating bath containing the types and amounts of organic compounds shown in Table 1. The basic zinc plating bath and electrolysis conditions are as follows.
【００２８】ZnSO4・7H2O : 20〜35重量％ Na2SO4 + (NH4)2SO4 : ５〜10重量％ pH : １〜４ 浴温 : 40〜65℃ 電流密度 : 40〜150 A/dm2 液流速 : 0.1 〜３ m/sec 亜鉛系合金電気めっきの場合は、上記の基本めっき浴中
に合金元素を硫酸塩、酢酸塩、炭酸塩、モリブデン酸
塩、次亜りん酸塩、有機金属塩あるいは予め金属を溶解
した状態で、目標組成のめっき皮膜が形成される量で添
加した。めっき時の電流密度は、液流速が高速になるほ
ど高くすることが好ましい。目安としては、液流速が１
m/sec の時に電流密度100 A/dm2 、液流速が0.5 m/sec
では電流密度50 A/dm2が適当である。[0028] ZnSO 4 · 7H 2 O: 20~35 wt% Na 2 SO 4 + (NH 4) 2 SO 4: 5~10 wt% pH: 1 to 4 Bath temperature: 40 to 65 ° C. Current density: 40 150 A / dm 2 solution flow rate: 0.1 to 3 m / sec In the case of zinc-based alloy electroplating, the alloy element is added to the above basic plating bath in the form of sulfate, acetate, carbonate, molybdate, hypophosphorous acid. Salts, organometallic salts or metals dissolved in advance were added in such an amount that a plating film having a target composition was formed. It is preferable that the current density during plating be increased as the liquid flow rate increases. As a guide, the liquid flow rate is 1
Current density 100 A / dm 2 at m / sec, liquid flow rate 0.5 m / sec
In this case, a current density of 50 A / dm 2 is appropriate.
【００２９】電解処理後、水洗および乾燥して亜鉛系電
気めっき鋼板を得た。このめっき鋼板のめっき種と付着
量、およびめっき皮膜中のＣ含有量も表１に示す。な
お、めっき皮膜中にＣ含有量は燃焼定量法により測定し
た。また、このめっき鋼板のめっき皮膜密着性を、エリ
クセンにて７mm張り出し後のテープ剥離試験によって試
験した。試験結果は、テープの目視観察で塗膜剥離の認
められない場合を○、剥離が少しでも生じている場合を
×と評価した。さらに、めっき鋼板の表面白色度 (ハン
ター表示のＬ値) をミノルタ製色差計で測定した。After the electrolytic treatment, washing and drying were performed to obtain a zinc-based electroplated steel sheet. Table 1 also shows the type and amount of plating of this plated steel sheet and the C content in the plating film. The C content in the plating film was measured by a combustion determination method. Further, the plating film adhesion of the plated steel sheet was tested by a tape peeling test after extending 7 mm with Erichsen. The test results were evaluated as ○ when no peeling of the coating film was observed by visual observation of the tape, and x when the peeling occurred even a little. Further, the surface whiteness (L value of Hunter display) of the plated steel sheet was measured with a color difference meter manufactured by Minolta.
【００３０】こうして得た亜鉛系電気めっき鋼板を次に
示す処理条件で浸漬法によりりん酸亜鉛処理して、めっ
き面と非めっき面の両面にりん酸亜鉛皮膜を形成した。 りん酸亜鉛処理工程：脱脂→水洗→表面調整→りん酸亜
鉛処理→水洗 表面調整剤 ：チタン系コロイド (3 g/L) 表面調整処理条件 ：室温×10秒 りん酸亜鉛処理液 ：日本パーカライジング社製 PB330
1 りん酸亜鉛処理条件：60℃×30秒 こうして得たりん酸亜鉛処理めっき鋼板のめっき面側の
表面白色度 (ハンターＬ値) を上記と同様に測定した。
表面白色度の評価は、りん酸亜鉛処理後の白色度 (Ｌ
値) とりん酸亜鉛処理前後でのＬ値の差 (白色度差Δ
Ｌ) とに基づいて次の基準で行った。 りん酸亜鉛処理後のＬ値による白色度：Ｌ≧70を○、
Ｌ＜70を×。 りん酸亜鉛処理前後での白色度差ΔＬ：ΔＬ＜８を
○、ΔＬ≧８を×。The zinc-based electroplated steel sheet thus obtained was subjected to a zinc phosphate treatment by an immersion method under the following treatment conditions to form a zinc phosphate film on both the plated surface and the non-plated surface. Zinc phosphate treatment process: degreasing → water washing → surface conditioning → zinc phosphate treatment → water washing Surface conditioner: titanium-based colloid (3 g / L) Surface condition treatment condition: room temperature × 10 seconds Zinc phosphate treatment solution: Nippon Parkerizing Co., Ltd. Made PB330
1 Zinc phosphate treatment condition: 60 ° C. × 30 seconds The surface whiteness (Hunter L value) on the plating side of the zinc phosphate treated plated steel sheet thus obtained was measured in the same manner as described above.
The evaluation of the surface whiteness was determined by the whiteness (L
Value) and the L value before and after zinc phosphate treatment (whiteness difference Δ
L) and the following criteria. Whiteness by L value after zinc phosphate treatment:
× L <70. Whiteness difference ΔL before and after zinc phosphate treatment: ○ for ΔL <8, × for ΔL ≧ 8.
【００３１】[0031]
【表１】 [Table 1]
【００３２】表１からわかるように、本発明のりん酸亜
鉛処理めっき鋼板は、めっき密着性を阻害することな
く、表面白色度に優れていた。一方、めっき浴中にイオ
ウ含有有機化合物を添加しなかったか、その添加量が本
発明の範囲外であって皮膜中のＣ含有量が 0.001〜10重
量％の範囲をはずれると、白色度は低下した。As can be seen from Table 1, the zinc phosphate-treated plated steel sheet of the present invention was excellent in surface whiteness without inhibiting plating adhesion. On the other hand, if the sulfur-containing organic compound was not added to the plating bath, or if the addition amount was out of the range of the present invention and the C content in the film was out of the range of 0.001 to 10% by weight, the whiteness decreased. did.
【００３３】[0033]
【発明の効果】本発明のりん酸亜鉛処理めっき鋼板は、
従来品に比べて高度かつ安定した白色度を有しており、
しかもりん酸亜鉛処理による白色度の低下も小さい。そ
のため、ユーザーの要求を十分に満たす、Ｌ値が70以上
の色調の明るいりん酸亜鉛処理めっき鋼板を安定して供
給することができる。また、めっき皮膜が炭素を含有す
るが、その量が10重量％以下であれば、めっき密着性に
対する悪影響は認められないので、加工性も十分にあ
る。従って、このりん酸亜鉛処理めっき鋼板は、特に家
電や建材用の塗装用下地鋼板母材として有用であり、従
来より色調の優れた塗装鋼板を製造することが可能とな
る。The zinc phosphate-treated plated steel sheet of the present invention
High and stable whiteness compared to conventional products,
Moreover, the decrease in whiteness due to the zinc phosphate treatment is small. Therefore, it is possible to stably supply a bright zinc phosphate-treated plated steel sheet having an L value of 70 or more, which sufficiently satisfies the needs of the user. Further, although the plating film contains carbon, if the amount is 10% by weight or less, there is no adverse effect on the plating adhesion, so that the workability is sufficient. Therefore, the zinc phosphate treated plated steel sheet is particularly useful as a base steel sheet for coating for home appliances and building materials, and it is possible to produce a coated steel sheet having a better color tone than before.
フロントページの続き (56)参考文献 特開 昭59−107084（ＪＰ，Ａ) 特開 昭59−157286（ＪＰ，Ａ) 特開 昭62−47488（ＪＰ，Ａ) 特開 平６−71225（ＪＰ，Ａ) 特開 昭54−51933（ＪＰ，Ａ) 特開 平２−57695（ＪＰ，Ａ) 特開 平３−247790（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 28/00 - 28/04 C23C 22/00 - 22/86 C25D 5/00 - 5/56 C25D 3/00 - 3/66Continuation of front page (56) References JP-A-57-107084 (JP, A) JP-A-59-157286 (JP, A) JP-A-62-47488 (JP, A) JP-A-6-71225 (JP) JP-A-54-51933 (JP, A) JP-A-2-57695 (JP, A) JP-A-3-247790 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB Name) C23C 28/00-28/04 C23C 22/00-22/86 C25D 5/00-5/56 C25D 3/00-3/66
Claims (2)
有機化合物を含有する酸性浴中での陰極電解により形成
された、Ｃ含有量 0.001〜10重量％、付着量３g/m2以上
の複合亜鉛または亜鉛系合金電気めっき皮膜と、その上
に形成されたりん酸亜鉛皮膜とを有することを特徴とす
る、色調の明るいりん酸亜鉛処理めっき金属板。1. A composite zinc or carbon having a C content of 0.001 to 10% by weight and a deposition amount of 3 g / m 2 or more formed by cathodic electrolysis in an acidic bath containing a soluble sulfur-containing organic compound on at least one surface. A brightly colored zinc phosphate-treated plated metal plate comprising a zinc-based alloy electroplated film and a zinc phosphate film formed thereon.
含有有機化合物を合計0.01〜100 g/L の量で含有する酸
性浴中で金属板を陰極電解処理して、金属板の少なくと
も片面にＣ含有量 0.001〜10重量％の複合亜鉛または亜
鉛系合金電気めっき皮膜を３g/m2以上の付着量で形成
し、得られた電気めっき金属板をりん酸亜鉛処理して、
上記めっき皮膜上にりん酸亜鉛皮膜を形成することを特
徴とする、色調の明るいりん酸亜鉛処理めっき金属板の
製造方法。2. A metal plate is subjected to cathodic electrolysis in an acidic bath containing one or more soluble sulfur-containing organic compounds in a total amount of 0.01 to 100 g / L, so that at least one surface of the metal plate is A composite zinc or zinc-based alloy electroplating film having a C content of 0.001 to 10% by weight is formed with an adhesion amount of 3 g / m 2 or more, and the obtained electroplated metal sheet is treated with zinc phosphate.
A method for producing a zinc phosphate-treated plated metal sheet having a bright color, comprising forming a zinc phosphate film on the plating film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12136194A JP2833477B2 (en) | 1994-06-02 | 1994-06-02 | Brightly tinted zinc phosphate treated plated metal sheet and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12136194A JP2833477B2 (en) | 1994-06-02 | 1994-06-02 | Brightly tinted zinc phosphate treated plated metal sheet and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07331457A JPH07331457A (en) | 1995-12-19 |
| JP2833477B2 true JP2833477B2 (en) | 1998-12-09 |
Family
ID=14809354
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12136194A Expired - Lifetime JP2833477B2 (en) | 1994-06-02 | 1994-06-02 | Brightly tinted zinc phosphate treated plated metal sheet and method for producing the same |
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| Country | Link |
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| JP (1) | JP2833477B2 (en) |
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| JP4862445B2 (en) * | 2006-03-22 | 2012-01-25 | Ｊｆｅスチール株式会社 | Method for producing electrogalvanized steel sheet |
| JP2008046477A (en) * | 2006-08-18 | 2008-02-28 | Toyo Kohan Co Ltd | Reflecting plate for liquid crystal backlight |
| JP5620798B2 (en) * | 2010-12-01 | 2014-11-05 | メタローテクノロジーズジャパン株式会社 | Non-cyan electrolytic gold plating bath for gold bump formation and gold bump formation method |
| JP5655649B2 (en) * | 2011-03-17 | 2015-01-21 | Ｊｆｅスチール株式会社 | Method for producing chemical conversion treated steel sheet |
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1994
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| Publication number | Publication date |
|---|---|
| JPH07331457A (en) | 1995-12-19 |
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