JP3095718B2 - Zinc phosphate treated steel sheet with excellent color tone and coating adhesion - Google Patents
Zinc phosphate treated steel sheet with excellent color tone and coating adhesionInfo
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- JP3095718B2 JP3095718B2 JP09212210A JP21221097A JP3095718B2 JP 3095718 B2 JP3095718 B2 JP 3095718B2 JP 09212210 A JP09212210 A JP 09212210A JP 21221097 A JP21221097 A JP 21221097A JP 3095718 B2 JP3095718 B2 JP 3095718B2
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- Prior art keywords
- zinc phosphate
- steel sheet
- coating
- film
- color tone
- Prior art date
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、家庭用電気製品、
配電盤、電話交換機パネル、自動車車体、自動車部品、
建材等の素材として好適に使用できるりん酸亜鉛処理鋼
板に関するものであり、殊に色調および塗膜密着性を改
善したりん酸亜鉛処理鋼板に関するものである。TECHNICAL FIELD The present invention relates to a household electric appliance,
Switchboards, telephone exchange panels, car bodies, car parts,
The present invention relates to a zinc phosphate treated steel sheet which can be suitably used as a material for building materials and the like, and particularly to a zinc phosphate treated steel sheet having improved color tone and coating film adhesion.
【０００２】[0002]
【従来の技術】上記した各種用途においては、Ｚｎめっ
き鋼板やＺｎ合金めっき鋼板（以下、Ｚｎめっき鋼板で
代表することがある）を素地鋼板とし、この表面に塗装
が施された表面処理鋼板が汎用されている。そしてこう
した表面処理鋼板を製造するに当たっては、塗装皮膜の
密着性および耐食性を向上させるという観点から、塗装
前にりん酸亜鉛処理がめっき表面に施されている。以下
では、Ｚｎめっき鋼板のめっき表面にりん酸亜鉛処理が
施された状態の鋼板を、りん酸亜鉛処理鋼板と呼ぶ。2. Description of the Related Art In the above-mentioned various applications, a Zn-coated steel sheet or a Zn alloy-coated steel sheet (hereinafter sometimes referred to as a Zn-coated steel sheet) is used as a base steel sheet, and a surface-treated steel sheet whose surface is coated is used. It is widely used. In manufacturing such a surface-treated steel sheet, a zinc phosphate treatment is applied to the plating surface before painting from the viewpoint of improving the adhesion and corrosion resistance of the coating film. Hereinafter, the steel sheet in which the zinc phosphate treatment is applied to the plating surface of the Zn-plated steel sheet is referred to as a zinc phosphate treated steel sheet.
【０００３】りん酸亜鉛処理鋼板を製造するに当たって
は、まず素地鋼鈑としてのＺｎめっき鋼板の表面を、水
酸化ナトリウム、ケイ酸ナトリウム、炭酸ナトリウム等
のアルカリ性溶液によって脱脂した後、表面調整してめ
っき表面にチタンコロイドを析出させ、その後めっき表
面にりん酸亜鉛皮膜が形成されるのが一般的である。そ
してりん酸亜鉛皮膜を形成するときのりん酸亜鉛処理液
は、基本的にりん酸二水素亜鉛塩[Zn(H2SO4)2]を含むり
ん酸酸性溶液からなり、この溶液からの析出反応によっ
て生成する白色透明なホパイト結晶[Zn3Zn3 (PO4)2・4H2
O ] が主成分となってりん酸亜鉛皮膜が形成される。In manufacturing a zinc phosphate treated steel sheet, first, the surface of a Zn-plated steel sheet as a base steel sheet is degreased with an alkaline solution such as sodium hydroxide, sodium silicate, sodium carbonate, and the like, and the surface is adjusted. Generally, titanium colloid is deposited on the plating surface, and then a zinc phosphate film is formed on the plating surface. The zinc phosphate treatment solution used to form the zinc phosphate film basically consists of a phosphoric acid solution containing zinc dihydrogen phosphate [Zn (H 2 SO 4 ) 2 ]. Transparent white whipite crystals generated by the reaction [Zn 3 Zn 3 (PO 4 ) 2・ 4H 2
O] is a main component to form a zinc phosphate film.
【０００４】またりん酸亜鉛皮膜には、塗装密着性およ
び塗装後の耐食性を向上させるという観点から、上記ホ
パイト結晶中に亜鉛以外の重金属を共析させるのが通常
である。こうした重金属としては、例えばＦｅ，Ｎｉ，
Ｍｎ，Ｃｏ，Ｃｒ等、様々なものが挙げられるが、Ｎｉ
を共析させる場合が多い。りん酸亜鉛皮膜にＮｉを共析
させことによる作用は下記の通りである。[0004] In addition, from the viewpoint of improving coating adhesion and corrosion resistance after coating, a heavy metal other than zinc is usually co-deposited in the above-mentioned whipite crystal in the zinc phosphate film. Such heavy metals include, for example, Fe, Ni,
Various materials such as Mn, Co, Cr and the like can be mentioned.
Are often eutectoid. The effect of eutectoid Ni on the zinc phosphate coating is as follows.
【０００５】上記した様にりん酸亜鉛皮膜中には、４分
子の結晶水が結合しているホパイト結晶が存在するが、
塗装時の焼き付けによって脱水されて２水塩になる。し
かしながら、その後水溶液に浸漬されるともとの４水塩
に復水する。復水すると体積膨張が生じ、これが原因と
なって塗装後に密着性が低下することになる。そしてり
ん酸亜鉛皮膜中にＮｉが共析していると、りん酸亜鉛結
晶の規則性が乱れ、またその結晶格子間隔が小さくな
り、これが復水の防止に効果を発揮する。即ち、Ｎｉを
共析したりん酸亜鉛皮膜は機械的強度が保持され、塗装
後の皮膜の密着性が向上することになる。またりん酸亜
鉛皮膜にＮｉを共析させると、耐アルカリ性が改善され
ることになって、塗装後の耐食性が向上することにもな
る。As described above, in the zinc phosphate film, there is a whipite crystal to which four molecules of water of crystallization are bonded.
It is dehydrated by baking during painting to become dihydrate. However, after that, it is immersed in the aqueous solution and then returned to the original tetrahydrate. Condensation occurs when the condensate is condensed, which causes the adhesion to decrease after coating. If Ni is eutectoid in the zinc phosphate film, the regularity of the zinc phosphate crystals is disturbed, and the crystal lattice spacing is reduced, which is effective in preventing water condensate. That is, the zinc phosphate film in which Ni is eutectoid retains the mechanical strength, and the adhesion of the film after coating is improved. Further, when Ni is codeposited on the zinc phosphate film, the alkali resistance is improved, and the corrosion resistance after coating is also improved.
【０００６】[0006]
【発明が解決しようとする課題】上記のように、りん酸
亜鉛皮膜にＮｉを共析させることは、塗膜の密着性や塗
装後の耐食性の向上に有用であるが、その一方でりん酸
亜鉛皮膜の表面が黒くなり、りん酸亜鉛皮膜鋼板の外観
を著しく損なうという問題がある。りん酸亜鉛皮膜を下
地とする塗装は、通常白色系であることが多く、りん酸
亜鉛皮膜鋼板の外観が黒ずんでくると、塗装による遮蔽
力が低下することになる。即ち、りん酸亜鉛皮膜鋼板の
外観が黒くなると、塗膜の付着量を多くしなければなら
ないという問題が生じる。こうした不都合を解消すると
いう観点から、Ｎｉの含有量を極力低下させることも考
えられるが、りん酸亜鉛皮膜鋼板の外観が黒ずまない程
度にＮｉの含有量を低下させることは、Ｎｉを共析させ
ることによる基本的な作用である塗膜密着性や塗装後の
耐食性の向上が発揮されなくなる。As described above, the eutectoid deposition of Ni on a zinc phosphate film is useful for improving the adhesion of the coating film and the corrosion resistance after coating. There is a problem that the surface of the zinc coating becomes black and the appearance of the zinc phosphate coated steel sheet is significantly impaired. The coating with the zinc phosphate coating as a base is usually a white coating, and when the appearance of the zinc phosphate coating steel sheet becomes dark, the shielding power by the coating decreases. That is, when the appearance of the zinc phosphate coated steel sheet becomes black, there arises a problem that the coating amount of the coating film must be increased. From the viewpoint of resolving such inconveniences, it is conceivable to reduce the Ni content as much as possible. However, reducing the Ni content to such an extent that the appearance of the zinc phosphate coated steel sheet is not darkened means that the Ni content is reduced. The improvement of the adhesion of the coating film and the corrosion resistance after coating, which are the basic functions of the precipitation, are not exhibited.
【０００７】本発明は上記した従来の問題を解消する為
になされたものであって、その目的は、りん酸亜鉛皮膜
鋼板の外観が黒くなるという問題を回避しつつ、Ｎｉを
共析させることによる塗膜密着性や塗装後の耐食性の向
上を発揮させることのできるりん酸亜鉛処理鋼板を提供
しようとするものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and has as its object to eutect Ni while avoiding the problem that the appearance of a zinc phosphate coated steel sheet becomes black. An object of the present invention is to provide a zinc phosphate treated steel sheet which can exhibit improved coating film adhesion and corrosion resistance after painting.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決した本発
明のりん酸亜鉛処理鋼板とは、Ｚｎめっき鋼板またはＺ
ｎ合金めっき鋼板の表面がりん酸塩処理されたりん酸亜
鉛処理鋼板であって、形成されたりん酸亜鉛皮膜中にお
けるＮｉ／ＺｎをＸ（質量％）、りん酸亜鉛皮膜付着量
をＹ（ｇ／ｍ2）、ＺｎめっきまたはＺｎ合金めっき層
中のＮｉ含有量（質量％）をＺとしたとき、下記（１）
〜（４）式を満足するものである点に要旨を有するもの
である。 Ｙ≦−２Ｘ＋３．４ …（１） Ｘ≧０．０５ …（２） １．０≦Ｙ≦２．５ …（３） Ｙ≦−１８．７５Ｚ＋２．５ …（４）The zinc phosphate treated steel sheet of the present invention which has solved the above-mentioned problems is a zinc-coated steel sheet or a Z-plated steel sheet.
The surface of an n-alloy-plated steel sheet is a phosphate-treated zinc phosphate-treated steel sheet, wherein Ni / Zn in the formed zinc phosphate film is X (% by mass), and the zinc phosphate film adhesion amount is Y ( g / m 2 ), and when the Ni content (% by mass) in the Zn plating or Zn alloy plating layer is Z, the following (1)
This has a gist in satisfying Expressions (4) to (4). Y ≦ −2X + 3.4 (1) X ≧ 0.05 (2) 1.0 ≦ Y ≦ 2.5 (3) Y ≦ −18.75Z + 2.5 (4)
【０００９】[0009]
【発明の実施の形態】本発明者らは上記目的を達成させ
るべく、様々な角度から検討した。その結果、りん酸亜
鉛皮膜中およびめっき層中のＮｉ含有量、並びにりん酸
亜鉛皮膜付着量等を厳密に規定すれば、色調と塗膜密着
性を両立できることを見出し、本発明を完成した。本発
明が完成された経緯を説明しつつ、本発明の作用につい
て説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have studied from various angles to achieve the above object. As a result, they found that if the Ni content in the zinc phosphate film and the plating layer and the amount of the zinc phosphate film attached were strictly defined, it was possible to achieve both color tone and coating film adhesion, and completed the present invention. The operation of the present invention will be described while explaining how the present invention was completed.
【００１０】本発明者らの検討によると、りん酸亜鉛処
理鋼板の色調および塗膜密着性は、りん酸亜鉛皮膜の付
着量、該皮膜中のＮｉ濃度、およびＺｎめっき層中のＮ
ｉ含有量に依存することが明らかになった。即ち、色調
はりん酸亜鉛皮膜の付着量が多くなるほど黒くなり、ま
た皮膜中およびＺｎめっき層中におけるＮｉ含有量が多
くなるほど黒くなる。一方、塗膜密着性は、りん酸亜鉛
皮膜の付着量が所定の範囲以下になると低下し、またり
ん酸亜鉛皮膜中のＮｉ含有量が少なくなると劣化する。According to the study of the present inventors, the color tone and coating film adhesion of the zinc phosphate treated steel sheet are determined by the amount of the zinc phosphate coating, the Ni concentration in the coating, and the N content in the Zn plating layer.
It became clear that it depends on the i content. That is, the color tone becomes black as the amount of the zinc phosphate film attached increases, and the color tone becomes black as the Ni content in the film and the Zn plating layer increases. On the other hand, the adhesion of the coating film decreases when the amount of the zinc phosphate film attached falls below a predetermined range, and deteriorates when the Ni content in the zinc phosphate film decreases.
【００１１】上記した知見に基づき本発明者らは、りん
酸亜鉛処理鋼板の色調および塗膜密着性の両方が良好に
なる皮膜付着量および皮膜中のＮｉ含有量の範囲につい
て更に検討したところ、図１の斜線部では上記両特性の
いずれもが良好になり得ることを明らかにした。尚、こ
のときの色調はＬ値で評価した。このＬ値は日本電色工
業株式会社製の「ＳＺＳ−Σ９０色差計」（商品名）に
て測定したものであり、Ｌ値が高くなるほど色調は白く
なる。また図１において、「○」印はＬ値が６５以上で
色調が優れていることを示し、「×」印はＬ値が６５未
満で色調が劣ることを示している。Based on the above findings, the present inventors further studied the range of the coating amount and the Ni content in the zinc phosphate-treated steel sheet in which both the color tone and the coating adhesion were good, In the hatched portion of FIG. 1, it was clarified that both of the above characteristics can be improved. The color tone at this time was evaluated by the L value. This L value was measured by “SZS-Σ90 color difference meter” (trade name) manufactured by Nippon Denshoku Industries Co., Ltd. The higher the L value, the whiter the color tone. In FIG. 1, a mark “○” indicates that the color value is excellent when the L value is 65 or more, and a mark “×” indicates that the color tone is poor when the L value is less than 65.
【００１２】次に、塗膜密着性はりん酸亜鉛皮膜鋼板に
「デリコン７００」（商品名：大日本塗料株式会社製）
をバーコード塗装し、２０分間セッテイングした後、１
４０℃で２０分間焼き付けした後評価した。このときの
塗装膜の厚みは２５μｍとした。そして塗膜密着性は、
一次と二次の両方で評価した。即ち、塗膜一次密着性
は、塗装板にカッターナイフで素地鋼板に達成するよう
に１ｍｍ間隔の碁盤目（１００個）を切り、エリクセン
加工（押し出し高さ：６ｍｍ）を施した後、セロテープ
剥離を行い、塗膜の残存率にて評価した。また塗膜二次
密着性は、塗装板を脱イオン沸騰水中に２時間浸漬後、
前記一次試験と同様の評価を行った。Next, the adhesiveness of the coating film was measured on a zinc phosphate coated steel sheet using "DELICON 700" (trade name, manufactured by Dainippon Paint Co., Ltd.)
After coating with a bar code and setting for 20 minutes,
It was evaluated after baking at 40 ° C. for 20 minutes. At this time, the thickness of the coating film was 25 μm. And coating film adhesion,
Evaluated both primary and secondary. That is, the primary adhesion of the coating film was obtained by cutting a grid (100 pieces) at intervals of 1 mm on the coated plate with a cutter knife to achieve a base steel plate, performing Erichsen processing (extrusion height: 6 mm), and then peeling off the cellophane tape. And evaluated by the residual ratio of the coating film. Also, the coating film secondary adhesion, after immersing the coated plate in deionized boiling water for 2 hours,
The same evaluation as in the primary test was performed.
【００１３】前記図１から次の様に考察できる。まずり
ん酸亜鉛皮膜中におけるＮｉとＺｎの比（Ｎｉ／Ｚｎ）
をＸ（質量％）、りん酸亜鉛皮膜付着量をＹ（ｇ／
ｍ2）としたときに、Ｙ≦−２Ｘ＋３．４の関係を満足
する範囲内であれば色調が良好になることがわかる。ま
たりん酸亜鉛皮膜自体のＬ値がＺｎめっきままのＬ値に
比べて低いため、りん酸亜鉛皮膜付着量が増加するほ
ど、りん酸亜鉛皮膜のＬ値は低下する。更に、Ｘ＜０．
０５、Ｙ＜１．０、Ｙ＞２．５のいずれかのときには、
塗膜密着性が低下している。From FIG. 1, the following can be considered. First, the ratio of Ni and Zn in the zinc phosphate coating (Ni / Zn)
Is X (mass%), and the zinc phosphate coating weight is Y (g / g).
m 2 ), it can be seen that the color tone becomes good within a range satisfying the relationship of Y ≦ −2X + 3.4. Further, since the L value of the zinc phosphate film itself is lower than the L value of the as-plated Zn, the L value of the zinc phosphate film decreases as the amount of zinc phosphate film attached increases. Furthermore, X <0.
05, Y <1.0, Y> 2.5,
Coating adhesion is low.
【００１４】尚、図１によればりん酸皮膜中のＮｉ／Ｚ
ｎ（質量％）が高くなるほど、Ｌ値が低下しており、そ
の原因についてはその全てを解明し得た訳ではないが、
Ｎｉはりん酸亜鉛皮膜中の前記ホパイト結晶中のＺｎの
位置に析出すると言われており、こうした位置にＮｉが
析出してホパイト結晶の結晶格子が歪むことが、Ｌ値の
低下の一因になるものと推定される。According to FIG. 1, Ni / Z in the phosphoric acid film
As the value of n (mass%) increases, the L value decreases, and the cause of the decrease cannot be completely clarified.
It is said that Ni precipitates at the position of Zn in the above-mentioned whipite crystal in the zinc phosphate film, and the precipitation of Ni at such a position and distortion of the crystal lattice of the whipite crystal contributes to a decrease in the L value. It is estimated that
【００１５】以上のことから、色調および塗膜密着性の
両特性に優れたりん酸亜鉛処理鋼板を得る為には、下記
（１）〜（３）式を満足させる必要があることがわか
る。 Ｙ≦−２Ｘ＋３．４ …（１） Ｘ≧０．０５ …（２） １．０≦Ｙ≦２．５ …（３）From the above, it can be seen that in order to obtain a zinc phosphate treated steel sheet having both excellent color tone and excellent coating film adhesion properties, it is necessary to satisfy the following equations (1) to (3). Y ≦ −2X + 3.4 (1) X ≧ 0.05 (2) 1.0 ≦ Y ≦ 2.5 (3)
【００１６】ところで、りん酸亜鉛処理鋼板の色調は、
Ｚｎめっき層中のＮｉ含有量にも大きく依存する。通常
Ｎｉは、Ｚｎめっき層中に不純物としても含有するが、
Ｚｎめっき層中の鋼板の耐食性およびプレス成形性を良
好にするという観点から、めっき層中に意図的にＮｉが
含有される場合がある。Incidentally, the color tone of the zinc phosphate treated steel sheet is as follows.
It largely depends on the Ni content in the Zn plating layer. Usually, Ni is also contained as an impurity in the Zn plating layer,
From the viewpoint of improving the corrosion resistance and press formability of the steel sheet in the Zn plating layer, Ni may be intentionally contained in the plating layer.
【００１７】図２は、めっき層中のＮｉ含有量やりん酸
亜鉛皮膜付着量がりん酸亜鉛処理鋼板の色調や塗膜密着
性に与える影響を示すグラフである。図２において色調
は前記図１と同様に、図中の「○」印はＬ値が６５以上
であることを意味し、「×」印はＬ値が６５未満である
ことを示している。図２から明らかな様に、めっき層中
のＮｉ含有量をＺ（質量％）としたとき、このＺがりん
酸亜鉛皮膜付着量Ｙとの関係が下記（４）式を満足する
範囲では、りん酸亜鉛処理鋼板の色調を良好にできるこ
とがわかる。 Ｙ≦−１８．７５Ｚ＋２．５ …（４）FIG. 2 is a graph showing the effect of the Ni content in the plating layer and the amount of the zinc phosphate film deposited on the color tone and coating film adhesion of the zinc phosphate treated steel sheet. In FIG. 2, as in FIG. 1, a mark “○” in the figure indicates that the L value is 65 or more, and a mark “x” indicates that the L value is less than 65 in FIG. As is clear from FIG. 2, when the Ni content in the plating layer is Z (% by mass), the relationship between Z and the zinc phosphate coating amount Y satisfies the following equation (4): It can be seen that the color tone of the zinc phosphate treated steel sheet can be improved. Y ≦ −18.75Z + 2.5 (4)
【００１８】めっき層中のＮｉ含有量が多くなると、り
ん酸亜鉛処理鋼板の色調が悪くなるが、その原因につい
てはおそらく次の様に考えることができる。即ち、めっ
き層中のＮｉ含有量が多くなると、それに伴ってりん酸
亜鉛処理皮膜中に取りまれるＮｉ含有量も多くなるの
で、りん酸亜鉛処理皮膜の表面が黒ずんでくるものと考
えられる。尚前記図１、２は、電気亜鉛めっき鋼板（Ｚ
ｎ付着量：３ｇ／ｍ2 ）についてのデータを示したもの
であるが、素地鋼板として例えば溶融亜鉛めっき鋼板と
使用しても同様の結果が得られた。When the Ni content in the plating layer increases, the color tone of the zinc phosphate treated steel sheet deteriorates. The cause can be considered as follows. That is, as the Ni content in the plating layer increases, the Ni content taken in the zinc phosphate treated film also increases, and it is considered that the surface of the zinc phosphate treated film darkens. FIGS. 1 and 2 show electrogalvanized steel sheets (Z
Although the data on n adhesion amount: 3 g / m 2 ) are shown, similar results were obtained when a base steel sheet, for example, a hot-dip galvanized steel sheet was used.
【００１９】りん酸亜鉛処理を施すためのりん酸亜鉛化
成処理浴としては、Ｚｎイオン，Ｎｉイオン，りん酸イ
オン，硝酸イオン等を含む市販の処理液を使用できるが
（例えば、日本パッカーライジング株式会社製の市販
品）、りん酸亜鉛皮膜中のＮｉ／Ｚｎ（質量％）は、該
化成処理浴中の（Ｎｉイオン／Ｚｎイオン）濃度比を変
えることによって変化させることができ、またりん酸亜
鉛皮膜の付着量は、Ｚｎイオン濃度を変化させることに
よって調整することができる。As the zinc phosphate chemical conversion treatment bath for performing the zinc phosphate treatment, a commercially available treatment solution containing Zn ions, Ni ions, phosphate ions, nitrate ions, etc. can be used (for example, Nippon Packer Rising Co., Ltd.). Ni / Zn (mass%) in the zinc phosphate film can be changed by changing the (Ni ion / Zn ion) concentration ratio in the chemical conversion bath. The adhesion amount of the zinc film can be adjusted by changing the Zn ion concentration.
【００２０】りん酸亜鉛皮膜中には、Ｚｎ，Ｎｉ以外に
もＦｅ，Ｃｏ，Ｍｎ，Ｍｇ，Ｃｒ，Ｓｂ等の元素やアル
カリ土類金属等を不純物程度に微量含んでいても良く、
或は添加剤としてのグルコン酸ソーダ、ポリエーテル等
の有機物を含んでいもいっこうに構わない。また前記り
ん酸亜鉛化成処理浴の塗布方法は、浸漬法、スプレー法
のいずれでも行うことができる。但し、りん酸亜鉛処理
の前処理として、コロイダルチタンを含有する表面処理
剤で表面の調整を行うのが一般的である。The zinc phosphate film may contain elements such as Fe, Co, Mn, Mg, Cr, Sb, alkaline earth metals, etc., in addition to Zn and Ni, in trace amounts as impurities.
Alternatively, organic substances such as sodium gluconate and polyether as additives may be contained. The zinc phosphate chemical conversion treatment bath can be applied by either a dipping method or a spray method. However, as a pretreatment before the zinc phosphate treatment, the surface is generally adjusted with a surface treatment agent containing colloidal titanium.
【００２１】以下、本発明を実施例によって更に詳細に
説明するが、下記実施例は本発明を限定する性質のもの
ではなく、前・後記の趣旨に徴して設計変更することは
いずれも本発明の技術的範囲に含まれるものである。Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention. It is included in the technical range of.
【００２２】[0022]
【実施例】電気Ｚｎめっき鋼板（めっき付着量：３ｇ／
ｍ2 ）または溶融亜鉛めっき鋼板（めっき付着量：６０
ｇ／ｍ2 ）を素地鋼鈑として使用し、これに下記の通り
の表面調整およびりん酸亜鉛処理を施した。[Embodiment] Electric Zn-coated steel sheet (coating weight: 3 g /
m 2 ) or hot-dip galvanized steel sheet (coating weight: 60
g / m 2 ) was used as a base steel plate, and the steel plate was subjected to surface conditioning and zinc phosphate treatment as described below.
【００２３】(A) 表面調整 通常のチタンコロイド系の表面調整剤に、素地鋼鈑を常
温で５秒間浸漬した。 (B) りん酸亜鉛処理 日本パッカーライジング株式会社製の処理液に、５０℃
で３０秒間浸漬処理した。(A) Surface Conditioning A base steel plate was immersed in a normal titanium colloidal surface conditioner at room temperature for 5 seconds. (B) Zinc phosphate treatment A treatment solution manufactured by Nippon Packer Rising Co., Ltd.
For 30 seconds.
【００２４】得られたりん酸亜鉛処理鋼板について、下
記の方法によって色調、塗膜密着性および塗装後耐食性
を評価した。 (1) 色調 前記のＬ値により評価した。 ○：Ｌ値が６５以上 △：Ｌ値が６０以上、６５未満 ×：Ｌ値が６０未満The zinc phosphate-treated steel sheet thus obtained was evaluated for color tone, coating film adhesion and post-coating corrosion resistance by the following methods. (1) Color Tone The evaluation was made based on the L value. ：: L value is 65 or more Δ: L value is 60 or more and less than 65 ×: L value is less than 60
【００２５】(2) 塗膜密着性 前記の方法により、一次密着性および二次密着性を評価
した。このときの評価基準は、一次密着性および二次密
着性のいずれも下記の通りである。 ○：塗膜残存率が９０％以上 △：塗膜残存率が７０％以上、９０％未満 ×：塗膜残存率が５０％以上、７０％未満 ××：塗膜残存率が５０％未満(2) Coating Film Adhesion Primary adhesion and secondary adhesion were evaluated by the above method. The evaluation criteria at this time are as follows for both the primary adhesion and the secondary adhesion. ：: Residual rate of coating film is 90% or more △: Remaining rate of coating film is 70% or more and less than 90% ×: Remaining rate of coating film is 50% or more and less than 70% XX: Remaining rate of coating film is less than 50%
【００２６】(3) 塗装後耐食性 りん酸亜鉛処理鋼板に、前記塗膜密着性試験と同様のバ
ーコート塗装を施した後、カッターナイフで鋼板素地に
達するスクラッチを入れ、塩水噴霧試験を１０００時間
行った後、スクラッチ部にセロハンテープを粘着して剥
離し、スクラッチ部の塗膜最大膨れ幅を測定した。この
ときの評価基準は下記の通りである。 ○：塗膜最大膨れ幅が１．５ｍｍ未満 △：塗膜最大膨れ幅が１．５ｍｍ以上、２．５ｍｍ未満 ×：塗膜最大膨れ幅が２．５ｍｍ以上、３．５ｍｍ未満 ××：塗膜最大膨れ幅が３．５ｍｍ以上 これらの結果を、素地鋼板の種類、Ｚｎめっき層中のＮ
ｉ含有量、りん酸亜鉛皮膜付着量、およびりん酸亜鉛皮
膜中のＮｉ／Ｚｎ（質量％）等と共に、下記表１，２に
示す。(3) Corrosion resistance after coating A zinc phosphate-treated steel sheet was subjected to the same bar coat coating as in the above-mentioned coating film adhesion test, and a scratch reaching the steel sheet base was put in with a cutter knife, and a salt spray test was conducted for 1000 hours. After performing, the cellophane tape was adhered to the scratch portion and peeled off, and the maximum swollen width of the coating film in the scratch portion was measured. The evaluation criteria at this time are as follows. ：: Maximum swelling width of the coating film is less than 1.5 mm Δ: Maximum swelling width of the coating film is 1.5 mm or more and less than 2.5 mm ×: Maximum swelling width of the coating film is 2.5 mm or more and less than 3.5 mm XX: Coating The maximum swelling width of the film is 3.5 mm or more.
Tables 1 and 2 below show the i content, the zinc phosphate coating amount, the Ni / Zn (% by mass) in the zinc phosphate coating, and the like.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
【００２９】これらの結果から明らかなように、本発明
で規定する要件の全てを満足する実施例（Ｎｏ．１〜３
５）では、色調，塗膜密着性，塗装後耐食性の全てにお
いて優れていることがわかる。これに対し、上記要件の
いずれかを欠く比較例（Ｎo.３６〜５６）では、いずれ
かの特性が劣化していることがわかる。As is apparent from these results, Examples (Nos. 1 to 3) satisfying all the requirements specified in the present invention.
In 5), it can be seen that color tone, coating film adhesion, and corrosion resistance after painting are all excellent. On the other hand, in the comparative examples (Nos. 36 to 56) lacking any of the above requirements, it can be seen that any of the characteristics is deteriorated.
【００３０】[0030]
【発明の効果】本発明は以上の様に構成されており、り
ん酸亜鉛皮膜鋼板の外観が黒くなるという問題を回避し
つつ、Ｎｉを共析させることによる塗膜密着性や塗装後
の耐食性の向上を発揮させることができるりん酸亜鉛処
理鋼板が実現できた。The present invention is constituted as described above, and avoids the problem that the appearance of the zinc phosphate coated steel sheet is blackened, and at the same time, adheres to the coating film by eutectoidizing Ni and the corrosion resistance after coating. A zinc phosphate-treated steel sheet that can exhibit the improvement of the steel is realized.
【図１】りん酸亜鉛皮膜中のＮｉ／Ｚｎ（質量％）およ
びりん酸亜鉛皮膜付着量がりん酸亜鉛処理鋼板の色調や
塗膜密着性に与える影響を示すグラフである。FIG. 1 is a graph showing the effect of Ni / Zn (% by mass) in a zinc phosphate coating and the amount of zinc phosphate coating on the color tone and coating adhesion of a zinc phosphate treated steel sheet.
【図２】めっき層中のＮｉ含有量やりん酸亜鉛皮膜付着
量がりん酸亜鉛処理鋼板の色調や塗膜密着性に与える影
響を示すグラフである。FIG. 2 is a graph showing the effect of the Ni content in a plating layer and the amount of a zinc phosphate coating on the color tone and coating film adhesion of a zinc phosphate-treated steel sheet.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平９−49086（ＪＰ，Ａ) 特開 昭62−47488（ＪＰ，Ａ) 特開 平３−75379（ＪＰ，Ａ) 特開 平２−88777（ＪＰ，Ａ) 特開 平３−68781（ＪＰ，Ａ) 特開 平７−138766（ＪＰ，Ａ) 特開 平３−53079（ＪＰ，Ａ) 特表 平４−507436（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 22/00 - 22/86 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-9-49086 (JP, A) JP-A-62-47488 (JP, A) JP-A-3-75379 (JP, A) JP-A-2- 88777 (JP, A) JP-A-3-68781 (JP, A) JP-A-7-138766 (JP, A) JP-A-3-53079 (JP, A) JP-A-4-507436 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C23C 22/00-22/86
Claims (1)
板の表面がりん酸塩処理されたりん酸亜鉛処理鋼板であ
って、形成されたりん酸亜鉛皮膜中におけるＮｉ／Ｚｎ
をＸ（質量％）、りん酸亜鉛皮膜付着量をＹ（ｇ／
ｍ2）、ＺｎめっきまたはＺｎ合金めっき層中のＮｉ含
有量（質量％）をＺとしたとき、下記（１）〜（４）式
を満足するものであることを特徴とする色調および塗膜
密着性に優れたりん酸亜鉛処理皮膜。 Ｙ≦−２Ｘ＋３．４ …（１） Ｘ≧０．０５ …（２） １．０≦Ｙ≦２．５ …（３） Ｙ≦−１８．７５Ｚ＋２．５ …（４）A zinc-plated steel sheet or a zinc alloy-plated steel sheet whose surface is a zinc phosphate-treated steel sheet having a phosphate treatment, wherein Ni / Zn in the formed zinc phosphate film is provided.
Is X (mass%), and the zinc phosphate coating weight is Y (g / g).
m 2 ), when the Ni content (% by mass) in the Zn plating or Zn alloy plating layer is Z, the color tone and the coating film satisfy the following expressions (1) to (4). Zinc phosphate treated film with excellent adhesion. Y ≦ −2X + 3.4 (1) X ≧ 0.05 (2) 1.0 ≦ Y ≦ 2.5 (3) Y ≦ −18.75Z + 2.5 (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09212210A JP3095718B2 (en) | 1997-08-06 | 1997-08-06 | Zinc phosphate treated steel sheet with excellent color tone and coating adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09212210A JP3095718B2 (en) | 1997-08-06 | 1997-08-06 | Zinc phosphate treated steel sheet with excellent color tone and coating adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1161430A JPH1161430A (en) | 1999-03-05 |
| JP3095718B2 true JP3095718B2 (en) | 2000-10-10 |
Family
ID=16618761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09212210A Expired - Lifetime JP3095718B2 (en) | 1997-08-06 | 1997-08-06 | Zinc phosphate treated steel sheet with excellent color tone and coating adhesion |
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| Country | Link |
|---|---|
| JP (1) | JP3095718B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5130080B2 (en) * | 2008-02-29 | 2013-01-30 | 株式会社神戸製鋼所 | Phosphate-treated electrogalvanized steel sheet |
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1997
- 1997-08-06 JP JP09212210A patent/JP3095718B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1161430A (en) | 1999-03-05 |
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