JPH07331457A - Zinc phosphate treating plated metallic sheet bright in color tone and its production - Google Patents
Zinc phosphate treating plated metallic sheet bright in color tone and its productionInfo
- Publication number
- JPH07331457A JPH07331457A JP12136194A JP12136194A JPH07331457A JP H07331457 A JPH07331457 A JP H07331457A JP 12136194 A JP12136194 A JP 12136194A JP 12136194 A JP12136194 A JP 12136194A JP H07331457 A JPH07331457 A JP H07331457A
- Authority
- JP
- Japan
- Prior art keywords
- zinc phosphate
- zinc
- film
- steel sheet
- plating
- 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
Landscapes
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
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。BACKGROUND OF THE INVENTION The present invention is suitable for use as a base material for coating in home appliances, building materials, automobiles and the like.
Zinc phosphate-plated metal plate (typically a steel plate) with a bright color that has been treated with zinc phosphate as the 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 electroplating and zinc-based alloy electroplating are collectively referred to as "zinc-based electroplating") are more workable than zinc-based hot-dip galvanized steel sheets. It has good characteristics, 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。The zinc-based electroplated steel sheet is generally subjected as a post-treatment to a chromate treatment for the purpose of improving corrosion resistance or a zinc phosphate treatment for the purpose of improving coatability. Therefore, when a zinc-based electroplated steel sheet is coated and used, a zinc phosphate treatment is usually performed as a coating base treatment for improving coating adhesion. The zinc phosphate coating formed on the plating surface by this treatment not only improves the coating adhesion, but also functions as a solid lubricating coating. Zinc phosphate treatment may be applied to improve the sex.
【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。The zinc phosphate treatment is carried out by dipping or spraying a zinc-based electroplated steel sheet whose surface has been adjusted, if necessary, using a zinc phosphate treatment solution.
After this treatment, washing with water and sealing treatment with a dilute aqueous solution of chromic acid are usually performed. In addition to zinc phosphate, the zinc phosphate treatment liquid used usually contains a small amount of Ni ions to improve coating performance, and a small amount of nitrate ions and a small amount of fluoride ions to accelerate 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-based electroplated steel sheets are treated with zinc phosphate, the surface tone becomes black and the whiteness decreases. This decrease in whiteness is not a problem when a coating is applied on it to completely hide the underlying color. However, recently, there is a tendency for the coating film to become thin for the purpose of cost reduction and improvement of processability, and because painting such as silk printing to transmit the color of the undercoat has become popular especially in the field of home appliances. ,
The base color may affect the surface color tone of the product, and a product steel sheet with higher whiteness (L value of Hunter color difference meter of 60 or more) is required from the user. Further, even when used without coating, a steel plate having such a bright color tone is preferable.
This demand for improving whiteness cannot be met by conventional zinc phosphate-treated plated steel sheets.
【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 Laid-Open No. 59-107084
JP-A-62-47488 and JP-A-62-47488 disclose a zinc phosphate treatment method for a zinc-based electroplated steel sheet capable of forming a zinc phosphate coating with high whiteness by adjusting the composition of the zinc phosphate treatment liquid. Has been done. Specifically, it is a method in which the nitric acid concentration in the zinc phosphate treatment liquid is 2.5 g / L or more. Nitric acid has a function of oxidizing hydrogen gas generated during the formation of zinc phosphate crystals to remove the hydrogen gas, thereby facilitating the formation reaction of the crystals. Also, nitric acid dissolves the surface of the plated steel sheet,
It contributes to the whitening of the steel sheet by melting nickel that adversely affects the whitening. However, nitric acid produces ammonia which adversely affects the zinc phosphate treatment reaction in the course of the reaction, so that the deterioration of the zinc phosphate treatment liquid is promoted and the life thereof is significantly shortened.
【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 treatment plated steel sheet by another means.
It is an object of the present invention to provide a method capable of producing a zinc phosphate-treated plated steel sheet or a 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 in the Hunter L value before and after the zinc phosphate treatment is less than 8 and the color tone is bright and the zinc phosphate treatment results in It is an object of the present invention to provide a zinc phosphate-treated plated steel sheet or metal sheet with less whiteness reduction 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 the electrogalvanizing step, the compound is formed. The inventors have found that the particle shape of the plated crystal in the zinc-based electroplating film changes and the whiteness after the zinc phosphate treatment is improved, and the present invention has been accomplished.
【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。According to the present invention, the C content formed by cathodic electrolysis in an acidic bath containing a soluble sulfur-containing organic compound on at least one side is 0.001 to 10% by weight, and the amount of adhesion is 3 g / m 2 or more. The subject is a zinc phosphate-treated metal plate having a bright color tone, which has a composite zinc or zinc-based alloy electroplating film of, 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。From 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 acidic bath containing g / L, and a composite zinc or zinc-based alloy electroplating film having a C content of 0.001 to 10% by weight is applied to at least one side of the metal plate at 3 g / m 2
A zinc phosphate treated plated metal plate having a bright color, characterized in that the electroplated steel sheet formed with the above-mentioned deposition amount is treated with zinc phosphate to form a zinc phosphate coating on the plating coating. Is a manufacturing method.
【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。For the sake of simplification of description, the present invention will be described below by taking as an example the case of a zinc phosphate-treated plated steel plate whose base metal is a steel plate.
The situation is almost the same for (eg, 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。According to the present invention, in the production of zinc phosphate-treated plated steel sheet in which zinc phosphate treatment is performed after zinc-based electroplating in an acid bath such as a sulfate bath or a hydrochloride bath, a specific amount of sulfur-containing organic material is added to the plating bath. It is characterized in that the compound was added. By adding this organic compound, the organic compound is decomposed and co-deposited in the zinc-based plating film formed by 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 made finer,
A 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 zinc phosphate treatment is applied to this plated film according to a conventional method, unexpectedly, the surface whiteness is very high (Hunter L value is 70 or more), and zinc phosphate having a bright color tone is obtained. A treated plated steel sheet can be obtained. In addition, this plated steel sheet has very little reduction in whiteness due to the zinc phosphate treatment (the difference in the L value before and after the zinc phosphate treatment is 8
Less than). The reason for this is speculated that the finely divided finely divided plated particles may individually react with zinc phosphate, resulting in the formation of a dense and smooth zinc phosphate film, resulting in higher surface whiteness. It
【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, the base steel sheet is subjected to zinc-based electroplating (that is, either pure zinc plating or zinc-based alloy plating) in an acid bath (eg, sulfate bath, hydrochloride bath, etc.). Give. As described above, the base material is not limited to the steel plate, and may be any metal plate capable of zinc-based electroplating such as aluminum or aluminum alloy plate and 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 the sulfur-containing organic compound is added to the acidic plating bath. The base steel sheet is subjected to surface cleaning treatment such as degreasing by 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 sulfuric acid bath as an acidic bath as an example, zinc sulfate is mainly composed of zinc sulfate, and a suitable electrolyte for adjusting pH and ionic conductivity is added to this. (Eg, alkali metal and / or ammonium sulfate). In the case of zinc alloy plating, an appropriate amount of alloying element compound (e.g., sulfate, chloride, carbonate, hypophosphite, molybdate, acetate, organometallic compound, or metal) is added. It In the present invention, one kind or two or more kinds of 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 usable in the present invention is not particularly limited, but a compound soluble in the acidic plating bath used (that is, generally a water-soluble compound) is used. Preferred sulfur-containing organic compounds include, but are not limited to, thioureas, thiazoles, organic sulfonic acids (including salts thereof), 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 thioureas [molecular formula: (N
H 2 ) 2 C = S] itself and at least one hydrogen atom in the thiourea molecule are substituted with a linear or branched saturated or unsaturated aliphatic group or an aromatic group such as a phenyl group or a benzyl group. Included 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 structure containing at least one nitrogen atom and one sulfur atom in the molecule, such as 1,3-thiazole and 2-mercaptobenzothiazole sodium. Can be mentioned.
【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。The organic sulfonic acids are organic compounds having at least one sulfone group (-SO 3 H) in the molecule and salts thereof (that is, compounds in which hydrogen ion (H + ) in the 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 a structure of RR'SO (R and R'are hydrocarbon groups), and examples thereof include dimethyl sulfoxide and diethyl sulfoxide. 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 acidic plating bath in a total amount of 0.01 to 100 g / L. If this 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, that is, the decrease in surface whiteness, cannot be sufficiently achieved. On the other hand, when the amount of the sulfur-containing organic compound exceeds 100 g / L, plating defects such as plating discoloration due to the oxidation of the added organic compound are likely to occur. The content of the sulfur-containing organic compound is preferably 0.1
Within the range of ~ 10 g / L. In the case of continuous plating, it is preferable to supplement the sulfur-containing organic compound so that the concentration of the organic compound in the plating bath is kept substantially 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 to be deposited needs to be 3 g / m 2 or more, and if it is less than 3 g / m 2 , the surface coverage of the plating will be insufficient. Considering the reliability of the surface coating and the economic cost of electricity at the time of plating, the preferable coating amount is 5 to 20 g /
It is within the range of 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。This plating film has a carbon content of 0.001 to 10% by weight as a C content due to decomposition and eutectoid of organic compounds.
Contained in the amount of. By the co-deposition of C, as described above,
A composite zinc-based electroplating film having fine plating particles and excellent surface gloss can be obtained. The C content in the 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) will be poor. On the other hand, the C content is 10
When the content is more than weight%, 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 within 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, but it is not necessary. 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。The thus-formed C-composited zinc-based electroplating film having a zinc-based electroplating film on at least one surface is treated with zinc phosphate in the same manner as in the prior art to form a zinc phosphate film on the plating film. To do. This zinc phosphate treatment may be carried out by a conventional method such as dipping or spraying using a commercially available zinc phosphate treatment liquid. The amount of zinc phosphate coating applied is not particularly limited, but normally 1.0 to 2.0 g / m 2
The range of is preferable.
【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。The zinc-based electroplating step and the zinc phosphate treatment step may be carried out continuously or separately. In either case, the zinc phosphate treatment step is, for example,
After degreasing the zinc-based electroplated steel sheet, washing it with water, adjusting the surface by a known method (for example, with an alkaline aqueous solution, titanium colloid, etc.), performing zinc phosphate treatment, then washing with water, and if necessary, the above The processing order is to perform the sealing processing.
【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。The zinc phosphate-treated plated steel sheet of the present invention is suitable as a base material for coating, but since the zinc phosphate coating is dense and adheres uniformly and the surface is beautiful and has excellent lubricity, It can also 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 plate having a plate thickness of 0.8 mm was used as a plating base material. The base steel sheet was degreased and washed with water, and then zinc-based electroplating was performed on one surface with a sulfate plating bath containing the organic compounds of the types and amounts 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。ZnSO 4 .7H 2 O: 20 to 35% by weight Na 2 SO 4 + (NH 4 ) 2 SO 4 : 5 to 10% by weight pH: 1 to 4 Bath temperature: 40 to 65 ° C. Current density: 40 to 150 A / dm 2 liquid flow rate: 0.1 to 3 m / sec In the case of zinc-based alloy electroplating, the alloying elements in the above basic plating bath are sulfate, acetate, carbonate, molybdate, and hypophosphorous acid. A salt, an organic metal salt, or a metal in which the metal was previously dissolved was added in an amount such that a plating film having a target composition was formed. The current density during plating is preferably higher as the liquid flow velocity becomes higher. 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
A current density of 50 A / dm 2 is suitable for.
【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, it was washed with water and dried to obtain a zinc-based electroplated steel sheet. Table 1 also shows the plating species and the adhesion amount of this plated steel sheet, and the C content in the plating film. The C content in the plating film was measured by the combustion quantitative method. Further, the adhesion of the plating film of this plated steel sheet was tested by a tape peeling test after projecting 7 mm by Erichsen. The test result was evaluated as ◯ when the peeling of the coating film was not observed by visual observation of the tape, and as x when the peeling occurred even a little. Furthermore, 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 treated with zinc phosphate by a dipping method under the following treatment conditions to form a zinc phosphate coating on both the plated surface and the non-plated surface. Zinc phosphate treatment process: Degreasing → Washing → Surface preparation → Zinc phosphate treatment → Water surface conditioning agent: Titanium colloid (3 g / L) Surface conditioning treatment condition: Room temperature × 10 seconds Zinc phosphate treatment liquid: Nihon Parkerizing Co., Ltd. Made PB330
1 Zinc phosphate treatment condition: 60 ° C. × 30 seconds The surface whiteness (Hunter L value) of the zinc phosphate-treated plated steel sheet thus obtained on the plating side was measured in the same manner as above.
The whiteness of the surface is evaluated by the whiteness (L
Value) and the L value before and after zinc phosphate treatment (whiteness difference Δ
L) and the following criteria. Whiteness according to L value after zinc phosphate treatment: ○ for L ≧ 70,
L <70 x. Whiteness difference ΔL before and after zinc phosphate treatment: ◯ when ΔL <8, × when 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 impairing 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 outside the range of the present invention and the C content in the coating 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 is
It has a higher and more stable whiteness than conventional products,
Moreover, the decrease in whiteness due to the zinc phosphate treatment is small. Therefore, it is possible to stably supply a zinc phosphate-treated plated steel sheet having a color tone of L value of 70 or more, which satisfies the user's requirements. Further, the plating film contains carbon, but if the amount is 10% by weight or less, no adverse effect on the plating adhesion is observed, and therefore the workability is sufficient. Therefore, this zinc phosphate-treated plated steel sheet is particularly useful as a base steel sheet base material for painting for home appliances and building materials, and it becomes possible to produce a coated steel sheet having a better color tone than before.
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 having a C content of 0.001 to 10% by weight and an adhesion amount of 3 g / m 2 or more, which is formed by cathodic electrolysis in an acidic bath containing a soluble sulfur-containing organic compound on at least one surface, or A zinc phosphate-treated metal plate having a bright color, which has a zinc 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 electrolytic treatment in an acidic bath containing one or more kinds of soluble sulfur-containing organic compounds in a total amount of 0.01 to 100 g / L, and at least one surface of the metal plate is subjected to cathodic electrolysis. 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 plate is treated with zinc phosphate,
A method for producing a zinc phosphate-treated metal plate having a bright color, which comprises 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 true JPH07331457A (en) | 1995-12-19 |
| JP2833477B2 JP2833477B2 (en) | 1998-12-09 |
Family
ID=14809354
Family Applications (1)
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2833477B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297646A (en) * | 2006-03-22 | 2007-11-15 | Jfe Steel Kk | Method for manufacturing electrogalvanized steel sheet |
| JP2008046477A (en) * | 2006-08-18 | 2008-02-28 | Toyo Kohan Co Ltd | Reflecting plate for liquid crystal backlight |
| JP2012117113A (en) * | 2010-12-01 | 2012-06-21 | Metalor Technologies (Japan) Corp | Non-cyanide gold electroplating bath for gold bump formation and method for forming gold bump |
| JP2012193419A (en) * | 2011-03-17 | 2012-10-11 | Jfe Steel Corp | Method for producing chemical conversion steel plate |
-
1994
- 1994-06-02 JP JP12136194A patent/JP2833477B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297646A (en) * | 2006-03-22 | 2007-11-15 | Jfe Steel Kk | Method for manufacturing electrogalvanized steel sheet |
| JP2008046477A (en) * | 2006-08-18 | 2008-02-28 | Toyo Kohan Co Ltd | Reflecting plate for liquid crystal backlight |
| JP2012117113A (en) * | 2010-12-01 | 2012-06-21 | Metalor Technologies (Japan) Corp | Non-cyanide gold electroplating bath for gold bump formation and method for forming gold bump |
| JP2012193419A (en) * | 2011-03-17 | 2012-10-11 | Jfe Steel Corp | Method for producing chemical conversion steel plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2833477B2 (en) | 1998-12-09 |
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