JPH01312081A - Surface-treated metallic material - Google Patents
Surface-treated metallic materialInfo
- Publication number
- JPH01312081A JPH01312081A JP14268988A JP14268988A JPH01312081A JP H01312081 A JPH01312081 A JP H01312081A JP 14268988 A JP14268988 A JP 14268988A JP 14268988 A JP14268988 A JP 14268988A JP H01312081 A JPH01312081 A JP H01312081A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- layer
- plating layer
- film
- phosphate
- 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.)
- Pending
Links
- 239000007769 metal material Substances 0.000 title claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 238000007747 plating Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 24
- 230000007797 corrosion Effects 0.000 abstract description 24
- 239000011701 zinc Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 8
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 abstract description 4
- 239000011592 zinc chloride Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 8
- 239000011247 coating layer Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- -1 phosphate compound Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は耐食性および塗装性に優れた表面処理金属材料
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a surface-treated metal material with excellent corrosion resistance and paintability.
［従来の技術］
例えば家庭電気製品の外箱や自動車車体等において耐食
性が要求される部分についてはＺｎめっき鋼板やＺｎ合
金めっき鋼板など表面処理を施した金属材料が広く用い
られている。これら金属材料はそのままで使用されるこ
とは殆んどなく通常は塗装を施して用いられている。[Prior Art] Surface-treated metal materials such as Zn-plated steel sheets and Zn alloy-plated steel sheets are widely used for parts that require corrosion resistance, such as outer boxes of home appliances and automobile bodies. These metal materials are rarely used as they are and are usually coated.
塗装を施す際には、その前処理として塗料の密着性を向
上させるための燐酸塩処理、或は耐食性を向上させるた
めのクロメート処理等の化成処理が施されている。When painting, chemical conversion treatments such as phosphate treatment to improve paint adhesion or chromate treatment to improve corrosion resistance are performed as pre-treatments.
前記燐酸塩処理は金属表面に主に燐酸亜鉛系の結晶皮膜
を析出させ、その結晶皮膜表面の凹凸効果、更には皮膜
表面と塗膜間に水素結合を生じさせること等によって塗
膜表面との密着性を向上させるものである。The above-mentioned phosphate treatment deposits a crystalline film mainly based on zinc phosphate on the metal surface, and creates an uneven effect on the surface of the crystalline film and also creates hydrogen bonds between the film surface and the paint film, thereby improving the relationship between the film surface and the paint film. This improves adhesion.
またクロメート処理は金属表面にクロム酸や水酸化クロ
ム等からなるクロム化合物層を形成して耐食性を大幅に
向上させると共に、合せて塗膜密着性をも向上させるも
のである。In addition, chromate treatment forms a chromium compound layer made of chromic acid, chromium hydroxide, etc. on the metal surface to significantly improve corrosion resistance, and also improves paint film adhesion.
［発明が解決しようとする課題］
上記の様に燐酸塩処理は塗膜の密着性向上には有効であ
るが、耐食性の向上効果については元々期待できるほど
のものは無い。一方クロメート処理においては塗膜密着
性および耐食性共に良好となるが、有毒な六価クロムを
使用する必要があるため公害等の問題から使用が制限さ
れている。[Problems to be Solved by the Invention] As described above, phosphate treatment is effective in improving the adhesion of a coating film, but the effect of improving corrosion resistance is not as expected. On the other hand, chromate treatment improves both paint film adhesion and corrosion resistance, but its use is restricted due to problems such as pollution because it requires the use of toxic hexavalent chromium.
この様な状況に鑑み本発明においては、公害等の問題が
なく且つ処理作業性においても比較的容易な燐酸塩処理
に着目し、燐酸塩ＩＡ理技術を改善することによって、
塗膜密着性及び耐食性の両方を満足することのできる表
面処理金属材料を提供するとし＼う目的をたてた。In view of this situation, in the present invention, we focused on phosphate treatment that does not cause problems such as pollution and is relatively easy to process, and by improving phosphate IA technology,
The objective was to provide a surface-treated metal material that can satisfy both coating adhesion and corrosion resistance.
［課題を解決するための手段］
上記課題を解決することのできた本発明とは、金属材料
表面にＺｎ系めっき層が形成され、更に該めっき層上に
０１重量％（以下単に％と記す）以上のＭｇを含有する
燐酸塩系化合物からなる皮膜が形成されていることを要
旨とするものである。[Means for Solving the Problems] The present invention that can solve the above problems is that a Zn-based plating layer is formed on the surface of a metal material, and furthermore, a Zn-based plating layer is formed on the plating layer by 0.1% by weight (hereinafter simply referred to as %). The gist is that a film made of the above Mg-containing phosphate compound is formed.
［作用］
次に本発明に至った経過を述べつつ本発明の詳細な説明
する。[Operation] Next, the present invention will be explained in detail while describing the progress that led to the present invention.
まず本発明者等はＺｎめっき金属材料の耐食性について
種々検討した。その結果、ＭｇをＺｎめっき層中に含有
させておくと耐食性向上効果があるという知見を得た（
この技術に関しては特願昭６２−２８５７１２号として
出願済みである）。First, the present inventors conducted various studies on the corrosion resistance of Zn-plated metal materials. As a result, we found that incorporating Mg in the Zn plating layer has the effect of improving corrosion resistance (
Regarding this technology, an application has been filed as Japanese Patent Application No. 62-285712).
このＭｇは金属元来の状態で効果を発揮するのではなく
、めっき層の溶解によって生じたＭｇイオンとして作用
しＺｎの腐食１［［Ｊ制に効果を発揮するものであるこ
とかわかった。It was found that this Mg does not exhibit its effect in the original state of the metal, but acts as Mg ions generated by dissolution of the plating layer, and is effective against Zn corrosion.
そこでＭｇをＺｎめっキ層中に合金元素として添加する
のではなく、ＭｇイオンになりやすいＭｇ塩の形てＺｎ
系めりき表面にイづ着させてやれは、より優れた効果か
あるのではないかと考え、燐酸塩皮膜中にＭｇ塩を添加
してみたところ、耐食性が大幅に改善されることか確認
された。Therefore, instead of adding Mg as an alloying element to the Zn plating layer, Zn is added in the form of Mg salt, which easily becomes Mg ions.
I thought that attaching Mg salt to the surface of the phosphate coating might have a better effect, and when I added Mg salt to the phosphate film, it was confirmed that the corrosion resistance was greatly improved. Ta.
即ち金属材料表面にＺｎ系め）ぎ層か形成されており、
さらにその上にＭｇを含有する燐酸塩系化合物層か形成
されていると、最外表面にＭｇを含有する塩基性塩化亜
鉛からなる層か形成される。そしてＭｇイオンはＺｎ系
めっき層におりるＺ ｎ −） Ｚ ｎ Ｏの酸化反応
を抑制する作用を有し、ＺｎＯの生成はめっき層の腐食
減量と相関かあるので、ＺｎＯの生成か抑制されるとい
うことは耐食性向上効果があることを意味する。また前
記塩基性塩化亜鉛層は緻密な結晶構造を構成するのて、
金属材料表面に該層か形成されるということは耐食性の
向上にとって一層有用なことである。That is, a Zn-based layer is formed on the surface of the metal material,
Furthermore, if a phosphate compound layer containing Mg is formed thereon, a layer made of basic zinc chloride containing Mg is formed on the outermost surface. Mg ions have the effect of suppressing the oxidation reaction of Zn-)ZnO in the Zn-based plating layer, and the generation of ZnO is correlated with the corrosion loss of the plating layer, so the generation of ZnO is suppressed. This means that there is an effect of improving corrosion resistance. In addition, since the basic zinc chloride layer has a dense crystal structure,
Forming this layer on the surface of the metal material is even more useful for improving corrosion resistance.
第１図に示すグラフは、Ｚｎめっき（めっき付着量２０
ｇ／ｍ２）鋼板上に燐酸塩処理を施し、Ｍｇ含有量の
異なる燐酸塩皮膜（燐酸塩皮膜付着量３ｇ／ｍ２）を形
成させた後、塩水噴霧試験を行なったときの白錆および
赤錆発生時間を示す。The graph shown in Figure 1 is based on Zn plating (plating amount 20
g/m2) After performing phosphate treatment on a steel plate to form phosphate films with different Mg contents (phosphate film adhesion amount: 3 g/m2), occurrence of white rust and red rust when a salt spray test was conducted. Show time.
第１図から明らかな様に燐酸塩皮膜中におけるＭｇ含有
量が０．１％以上になると白錆発生時間および赤錆発生
時間がいずれも長くなり耐食性が大いに向上することが
わかる。尚皮膜中におけるＭｇ含有量の上限については
耐食性の点からは特に制限されないが、５％付近で効果
が飽和に達すると共に５％を超えると皮膜結晶の外観か
悪くなるので５％以下に抑えることが望ましい。As is clear from FIG. 1, when the Mg content in the phosphate film is 0.1% or more, both the white rust generation time and the red rust generation time become longer, and the corrosion resistance is greatly improved. The upper limit of the Mg content in the film is not particularly limited from the viewpoint of corrosion resistance, but the effect reaches saturation at around 5%, and if it exceeds 5%, the appearance of the film crystals deteriorates, so it should be kept below 5%. is desirable.
燐酸塩皮膜の付着量については０．５３７ｍ２未満ては
耐食性や塗膜密着性共に十分な性能か得られず、一方４
ｇ／ｍ２を超えてもそれ以上の効果は望めないので燐
酸塩皮膜の何着量は０．５〜４ ｇ／ｍ２が適当である
。Regarding the amount of phosphate film deposited, if it is less than 0.537 m2, sufficient performance in both corrosion resistance and film adhesion cannot be obtained;
Since no further effect can be expected even if the amount exceeds 0.5 to 4 g/m2, the amount of phosphate film coated is suitably 0.5 to 4 g/m2.
燐酸塩皮膜の下側に形成されるめっき層についてはＺｎ
系のめつきてあれは良く、純Ｚｎめっきの他にＺｎ−Ｎ
ｉ合金、Ｚｎ−Ｆｅ合金等のＺｎ合金めっきであっても
良い。For the plating layer formed under the phosphate film, Zn
It is good to have Zn-N plating in addition to pure Zn plating.
Zn alloy plating such as i alloy or Zn-Fe alloy may be used.
さらに以上の様に形成された表面処理金属材料上に塗装
を施したときは、塗膜の密着性が良好であると共に高耐
食性を示す。Furthermore, when a coating is applied to the surface-treated metal material formed as described above, the coating film has good adhesion and exhibits high corrosion resistance.
本発明の対象となる金属としては、Ｚｎ系めつ籾層が形
成されるものであれは良く、代表的なものとしては軟鋼
を初めとする各種鋼材及び鋳鉄等か非限定的に例示され
る。The metal that is the object of the present invention may be any metal in which a Zn-based layer is formed, and representative examples include, but are not limited to, various steel materials including mild steel, and cast iron. .
［実施例］
電気Ｚｎめっき鋼板（イ」着Ｊｔ ２０ ｇ／ｍ２）を
Ｍｇ含有燐酸塩処理液に浸漬し、Ｍｇ含有量の異なる燐
酸亜鉛皮膜を形成した後、塩水噴霧試験により耐食性を
調へた。その結果を第１表に示す。また燐酸塩処理後ア
クリル系塗料を塗布しく膜厚３０μｍ）その密着性を調
へた。その結果を第１表に示す。尚塗膜密着性はごはん
目エリクセン試験後の塗膜剥離状況で評価した。[Example] After immersing an electrolytic Zn-plated steel sheet (Jt 20 g/m2) in a Mg-containing phosphate treatment solution to form zinc phosphate films with different Mg contents, the corrosion resistance was examined by a salt spray test. Ta. The results are shown in Table 1. After the phosphate treatment, an acrylic paint was applied (film thickness: 30 μm) to check its adhesion. The results are shown in Table 1. The adhesion of the paint film was evaluated based on the peeling status of the paint film after the Erichsen test.
第 １ 表
○・良
×：不良
第１表から明らかな様に皮膜中に０．１％以上のＭｇを
含む燐酸塩皮膜が形成された電気Ｚｎめっき鋼板は耐食
性および塗膜密着性に優れていることがわかる。Table 1 ○/Good ×: Bad As is clear from Table 1, the electrolytic Zn-plated steel sheet with a phosphate film containing 0.1% or more of Mg in the film has excellent corrosion resistance and coating adhesion. I know that there is.
［発明の効果］
本発明は以上の様に構成されているので、本発明の表面
処理金属材料は耐食性に優れ、また塗膜に対する密着性
にも優れたものである。[Effects of the Invention] Since the present invention is configured as described above, the surface-treated metal material of the present invention has excellent corrosion resistance and also excellent adhesion to a coating film.
第１図は燐酸塩皮膜中のＭｇ含有量と白錆・赤錆発生時
間の関係を示す図である。FIG. 1 is a diagram showing the relationship between the Mg content in the phosphate film and the time for white rust/red rust to occur.
Claims (1)
き層上に０．１重量％以上のＭｇを含有する燐酸塩系化
合物からなる皮膜が形成されていることを特徴とする表
面処理金属材料。A surface-treated metal material characterized in that a Zn-based plating layer is formed on the surface of the metal material, and a film made of a phosphate-based compound containing 0.1% by weight or more of Mg is further formed on the plating layer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14268988A JPH01312081A (en) | 1988-06-09 | 1988-06-09 | Surface-treated metallic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14268988A JPH01312081A (en) | 1988-06-09 | 1988-06-09 | Surface-treated metallic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01312081A true JPH01312081A (en) | 1989-12-15 |
Family
ID=15321239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14268988A Pending JPH01312081A (en) | 1988-06-09 | 1988-06-09 | Surface-treated metallic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01312081A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03107469A (en) * | 1989-09-21 | 1991-05-07 | Nippon Parkerizing Co Ltd | Zinc plated material having phosphate chemical conversion coating film excellent in bare corrosion resistance |
| US6555249B1 (en) | 1999-09-17 | 2003-04-29 | Kawasaki Steel Corporation | Surface treated steel sheet and method for production thereof |
| US6649275B1 (en) | 2001-03-27 | 2003-11-18 | Nippon Steel Corporation | Zinc phosphate-treated galvanized steel sheet excellent in corrosion resistance and color tone |
| JP2006057149A (en) * | 2004-08-20 | 2006-03-02 | Jfe Steel Kk | Phosphated galvanized-steel sheet superior in corrosion resistance and blackening resistance |
| JP2006225737A (en) * | 2005-02-18 | 2006-08-31 | Jfe Steel Kk | Phosphatized galvanized steel sheet superior in corrosion resistance and blackening resistance |
-
1988
- 1988-06-09 JP JP14268988A patent/JPH01312081A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03107469A (en) * | 1989-09-21 | 1991-05-07 | Nippon Parkerizing Co Ltd | Zinc plated material having phosphate chemical conversion coating film excellent in bare corrosion resistance |
| US6555249B1 (en) | 1999-09-17 | 2003-04-29 | Kawasaki Steel Corporation | Surface treated steel sheet and method for production thereof |
| US6649275B1 (en) | 2001-03-27 | 2003-11-18 | Nippon Steel Corporation | Zinc phosphate-treated galvanized steel sheet excellent in corrosion resistance and color tone |
| JP2006057149A (en) * | 2004-08-20 | 2006-03-02 | Jfe Steel Kk | Phosphated galvanized-steel sheet superior in corrosion resistance and blackening resistance |
| US7588836B2 (en) | 2004-08-20 | 2009-09-15 | Jfe Steel Corporation | Phosphate-treated zinc-coated steel sheet |
| JP4492254B2 (en) * | 2004-08-20 | 2010-06-30 | Ｊｆｅスチール株式会社 | Phosphate-treated galvanized steel sheet with excellent corrosion resistance and blackening resistance |
| JP2006225737A (en) * | 2005-02-18 | 2006-08-31 | Jfe Steel Kk | Phosphatized galvanized steel sheet superior in corrosion resistance and blackening resistance |
| JP4635638B2 (en) * | 2005-02-18 | 2011-02-23 | Ｊｆｅスチール株式会社 | Phosphate-treated electrogalvanized steel sheet with excellent corrosion resistance and blackening resistance |
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