JPS6220880A - Surface treatment of zinc-aluminum alloy plated steel sheet - Google Patents
Surface treatment of zinc-aluminum alloy plated steel sheetInfo
- Publication number
- JPS6220880A JPS6220880A JP15801685A JP15801685A JPS6220880A JP S6220880 A JPS6220880 A JP S6220880A JP 15801685 A JP15801685 A JP 15801685A JP 15801685 A JP15801685 A JP 15801685A JP S6220880 A JPS6220880 A JP S6220880A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- zinc
- aluminum alloy
- plated steel
- alloy plated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
-
- 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
- C23C22/73—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 characterised by the process
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本究明はアルミニウム含有量が１〜７０％の亜鉛−アル
ミニウム合金めっき鋼板の表面処理方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present study relates to a method for surface treatment of zinc-aluminum alloy plated steel sheets having an aluminum content of 1 to 70%.
従来より亜鉛めっき鋼板を塗装するに際し、６価クロム
化合物を主剤としたクロメート水溶液で亜鉛めっき鋼板
を処理してクロメート皮膜を化成させて塗装下地性を向
上させ、ることが良く知られている。最近公害上の間鴎
から６価クロム含有水を工場外に排出することが出来な
くなったので、【亜鉛めっき鋼板に６価クロム及びシリ
カを含む酸性の塗布型クロメート水心液を塗布して水洗
することなくぞのま筐乾譲して塗装下地とするクロメー
ト処理法がとられるようになった。Conventionally, when painting galvanized steel sheets, it is well known that the galvanized steel sheets are treated with a chromate aqueous solution containing a hexavalent chromium compound as the main ingredient to form a chromate film and improve the coating base properties. Recently, due to pollution concerns, it has become impossible to discharge water containing hexavalent chromium from the factory outside the factory. A chromate treatment method was started in which the housing was left to dry and used as a base for painting.
近年めっき鋼板自体の耐食性を向上させる為種々の合金
めっき鋼板が１ｉｉｌ ’ｔｆｓされているが、その中
で亜鉛−アルミニウム合金めつきｗ４阪が注目され市場
にも出ている。この亜鉛−アルミニウム合金めっきはめ
っき皮ｊ戻中に１〜７０％のアルミニウムを言有すせる
もので、従来の溶融亜鉛めっきに比較して裸めっき板の
耐食性が格段に良好になる。しかし、この亜鉛−アルミ
ニウム合金めっき鋼板に前記塗布型のクロメート水溶液
にて塗・装下地皮膜を形成させてもその効果は余りなく
、３年問屋外曝露後の前記合金めっき鋼板の切断部の塗
装ふくれ状態を観察すると無処理と殆ど差がなかった。In recent years, various alloy-plated steel sheets have been subjected to 1iil'tfs in order to improve the corrosion resistance of the plated steel sheets themselves, and among them, zinc-aluminum alloy plated W4 has attracted attention and is now on the market. This zinc-aluminum alloy plating contains 1 to 70% aluminum during re-plating, and the corrosion resistance of the bare plated sheet is much better than that of conventional hot-dip galvanizing. However, even if a coating/base film is formed on this zinc-aluminum alloy plated steel sheet with the above-mentioned paint-type chromate aqueous solution, the effect is not very effective, and the coating of the cut portion of the above alloy-plated steel sheet after being exposed outdoors for three years is not effective. When observing the state of swelling, there was almost no difference from untreated.
本発明は亜鉛−アルミニウム合金めっき鋼板表面に塗布
型クロメート水溶液を塗布する前に表面調整を行って、
従来のクロメート塗布法よりも屋外４真性を向上させる
ことを目的としている。The present invention performs surface conditioning before applying a coating type chromate aqueous solution to the surface of a zinc-aluminum alloy plated steel sheet.
The objective is to improve outdoor chromate properties compared to conventional chromate coating methods.
本発明者は、前記目的を達成させる為に、塗布型クロメ
ート処理するにあたり予め亜鉛−アルミニウム合金めっ
き材表面のアルミニウムを選択的に除去することを検討
した。その結果亜鉛−アルミニウム合金めっき材を金属
イオン、特にコバルト、鉄、ニッケル、マンガンの１穐
又は２種以上の金属イオンを含み且つ該金属イオンが醪
存するに必要な量の錯化剤を含む、Ｈ１１以上のアルカ
リ水溶液で前処理することにより、該めっき材表面に偏
析濃化していたアルミニウムを除去し、七の後シリカを
含む塗布型クロメート水溶液全塗布することにより本発
明の目的全達成させることが出来た。又その後塗装する
のであるが、下塗塗料としてエポキシ樹脂塗料を用いる
と、他の塗料に比べ型外″１％１性が更に優れているこ
とがわかった。In order to achieve the above object, the present inventor has considered selectively removing aluminum on the surface of a zinc-aluminum alloy plated material in advance of coating-type chromate treatment. As a result, the zinc-aluminum alloy plating material contains metal ions, particularly one or more metal ions of cobalt, iron, nickel, and manganese, and also contains a complexing agent in an amount necessary for the metal ions to exist. By pre-treating with an alkaline aqueous solution of H11 or higher, the aluminum that has been segregated and concentrated on the surface of the plated material is removed, and after that, the entire object of the present invention is achieved by applying a coated chromate aqueous solution containing silica. was completed. Furthermore, it was found that when an epoxy resin paint is used as an undercoat for subsequent painting, the outside-mold 1%1 property is even better than that of other paints.
本発明に於けるアルカリ水容液に含まれる金属イオンは
硝酸塩、硫酸塩、炭酸塩、塩化物等の無機塩、その他水
容液又はアルカリに可痔な化合物として供給する。その
濃度は金属換算で０．０１〜１０曽、好ましくは０．０
５〜５竹である。そしてこれらの金属イオンがアルカリ
水宕腹中で尋存状態で維持されるように錯化剤で充分錯
化されていなげればならないが、その錯化剤は通常０．
１〜２０４の濃度で１史い、その錯化剤としては縮合り
ん酸塩、アンモニア等の無機錯化剤、そして有機鉛化剤
としてマロン酸、フマル酸等のようなジカルボン酸、グ
リシンのようなアミノ酸部、クエン酸、グルコ／酸、乳
酸のようなヒドロキ７カルボン酸類、ソルビトール、１
−２エタンジオールのようなポリヒドロキ７脂肪族化合
物、サリチル酸、フタル酸のようなフェノールカルボン
酸類、エチレンジアミンテトラ酢酸のようなアミンカル
ボン酸類、ジェタノールアミノメタンホスホネートのよ
うなポリアミノ酸、リグノスルホン酸塩類などである。The metal ions contained in the alkaline aqueous solution in the present invention are supplied as inorganic salts such as nitrates, sulfates, carbonates, chlorides, and other compounds that are compatible with the aqueous solution or alkali. Its concentration is 0.01 to 10 so, preferably 0.0 in terms of metal.
5-5 bamboo. These metal ions must be sufficiently complexed with a complexing agent so that they can be maintained in a preserved state in alkaline water, but the complexing agent is usually 0.
The complexing agents include inorganic complexing agents such as condensed phosphates and ammonia, and the organic lead-forming agents include dicarboxylic acids such as malonic acid and fumaric acid, and glycine. amino acids, citric acid, gluco/acid, hydroxy-7 carboxylic acids such as lactic acid, sorbitol, 1
-Polyhydroxy7 aliphatic compounds such as 2-ethanediol, phenolic carboxylic acids such as salicylic acid and phthalic acid, amine carboxylic acids such as ethylenediaminetetraacetic acid, polyamino acids such as jetanolaminomethanephosphonate, lignosulfonates, etc. It is.
特に好ましいのはへキサヒドロキ７ヘプトン酸、グルコ
ン酸ナトリウム、エチレンジアミンテトラ酢酸のナトリ
ウム塩である。Particularly preferred are the sodium salts of hexahydroxyheptonic acid, sodium gluconate, and ethylenediaminetetraacetic acid.
本発明に於ける処理工程は、亜鉛−アルミニウム合金め
っき材をスプレー又は浸漬法に依って本発明に於ける常
温〜沸騰温度のアルカリ水溶液で前記めっき材表面のア
ルミニウムを選択的にエツチング除去するに必要な時間
処理し、水洗後シリカを含んだクロメート水溶液にて塗
布する工程からなる。本発明に於けるアルカリ水溶液に
よる実用土満足な前処理としては連続フープラインの場
合、通常処理ｍ度５０〜８０℃、処理時間４〜１０秒で
行われるが、高温高濃度のアルカリ水溶液ヲ用いれは更
に短時間でも処理可能である。本発明に於げるシリカを
含むクロメート水溶液の亜鉛−アルミニウム合金めっき
鋼板表面に対する塗布量は乾燥温度で１０〜４００−で
ある。１０ ”ｆ７．、を未満だと本発明の効果を発揮
するのに充分でなく、４００−より上まわると塗料付着
性を低下させて実用的でない。The treatment step in the present invention involves selectively etching and removing aluminum on the surface of a zinc-aluminum alloy plated material with an alkaline aqueous solution at room temperature to boiling temperature by spraying or dipping the material. It consists of a process of treating for the required time, washing with water, and then coating with a chromate aqueous solution containing silica. In the present invention, in the case of a continuous hoop line, a satisfactory pretreatment of practical soil with an alkaline aqueous solution is carried out at a temperature of 50 to 80°C for a treatment time of 4 to 10 seconds; can be processed even in a shorter time. The amount of the chromate aqueous solution containing silica applied to the surface of the zinc-aluminum alloy plated steel sheet according to the present invention is 10 to 400% at drying temperature. If it is less than 10" f7., it is not sufficient to exhibit the effects of the present invention, and if it is more than 400, the paint adhesion will be reduced and it is not practical.
クロメート水溶液中の６価クロムイオンは無水クロム酸
から誘導され、シリカとしてはコロイダルシリカから誘
導される。又クロメート水溶液に５価クロムイオン及び
／又はリン酸イオンが含まれるのが好ましい。３価クロ
ムは、６価クロムを含有するクロメート水溶液に、でん
ぷん、しゆう酸、タンニン、アルコール等の還元剤を添
加することによって含有させる。クロメート水ｆａＱ中
のシリカ／６価クロムイオン重量比は０．６〜１５が好
ましい。クロメート水溶液中の５価クロムイオン／６価
クロムイオン重量比は０．２〜１が好ましい。The hexavalent chromium ion in the chromate aqueous solution is derived from chromic anhydride, and the silica is derived from colloidal silica. Further, it is preferable that the aqueous chromate solution contains pentavalent chromium ions and/or phosphate ions. Trivalent chromium is contained by adding a reducing agent such as starch, oxalic acid, tannin, or alcohol to a chromate aqueous solution containing hexavalent chromium. The silica/hexavalent chromium ion weight ratio in the chromate water faQ is preferably 0.6 to 15. The weight ratio of pentavalent chromium ions to hexavalent chromium ions in the chromate aqueous solution is preferably 0.2 to 1.
クロメート水塔液中のＰＯ４／ ６価クロムイオン重量
比は０．６〜６が好ましい。The weight ratio of PO4/hexavalent chromium ion in the chromate water column liquid is preferably 0.6 to 6.
本発明に於けるアルカリ水４液の亜鉛−アルミニウム合
金めっき材表面のアルミニウムの選択エツチング性につ
いて行った試験ｆＪ ｋ示す。A test fJ k conducted on the selective etching property of aluminum on the surface of a zinc-aluminum alloy plated material using four liquids of alkaline water in the present invention is shown.
試験例
「スーパージンク」の商標で市販されている亜鉛−アル
ミニウム合金（Ｚｎ９０〜９６．５％、Ａｌ３．５〜１
０％）めっき鋼板を第１表記載のＰＨ１３，５〜１６．
７ の処理液で浴温５７〜６３℃にて５秒間スプレー処
理した。鉄はＦｅ （ＮＯｓ ）ｓ ’ｆｔ、ニッケル
はＮｔ（Ｎｏ３）ｔとして、コバルトはＣｏ （ＮＯｘ
）ｔとし″′Ｃ叱用した。それぞれの金属イオンのａ
度は険相した薬剤の金属換算値である。処理後水洗乾燥
し、この処理板の表ｍｌを螢光Ｘ線分析装置（ＦＸＡ
）にてＡｌ −Ｋａ を管球：Ｃｒ、分光結晶： ＥＤ
ＤＴ、電圧５０ＫＶ、を流３０ｒｎＡ、積分時間２０秒
で、またＺｎＫａを管球：Ｗ、分光結晶： Ｌｉｄ、
電圧２０ＫＶ、電流２ ｍＡ、積分時間１０秒の条件で
測定し、Ａ１のカウント及びＺｎのカウントからＡ＋／
Ｚｎ比を算出した。その結果を第１表に示す。Test Example Zinc-aluminum alloy (Zn 90-96.5%, Al 3.5-1
0%) The plated steel sheet was heated to a pH of 13.5 to 16.0% as listed in Table 1.
7 was sprayed for 5 seconds at a bath temperature of 57 to 63°C. Iron is Fe(NOs)s'ft, nickel is Nt(No3)t, cobalt is Co(NOx
)t and ''C were used.The a of each metal ion was
The degree is the metal equivalent value of the dangerous drug. After the treatment, it was washed with water and dried, and the surface ml of the treated plate was analyzed using a fluorescent X-ray analyzer (FXA).
) with Al-Ka tube: Cr, spectroscopic crystal: ED
DT, voltage 50 KV, current 30 rnA, integration time 20 seconds, ZnKa tube: W, spectroscopic crystal: Lid,
Measured under the conditions of voltage 20 KV, current 2 mA, and integration time 10 seconds, and A+/ from A1 count and Zn count.
The Zn ratio was calculated. The results are shown in Table 1.
＠１表
第１表から明らかな如く無処理に比べ本発明に於けるア
ルカリ水溶液（Ｎｏ、１、Ｎｏ、２、Ｎｏ、３）で処理
したものは亜鉛−アルミニウム合金めっき鋼板のＡｌ量
が減少していることが分かる。@Table 1 As is clear from Table 1, the amount of Al in the zinc-aluminum alloy coated steel sheets is reduced in those treated with the alkaline aqueous solution (No, 1, No, 2, No, 3) of the present invention compared to the untreated sheet. I know what you're doing.
実施例１
「スーパージンク」の商標で市販されている亜鉛−アル
ミニウム合金めっき鋼板を、Ｆｅ （ＮＯｓ ）ｓ ｋ
ＦＣ換算で０．１７７ｚ、Ｎｉ （ＮＯ３）、 ｆ Ｎ
ｉ換算で０．２４１、ヘキサヒドロキシへブト／ソーダ
１ｔ、７’／ｉ、苛性ソーダ２２〜含有するｐＨ１３ｊ
、液温５７〜６３℃のアルカリ水溶液で１０秒間スプレ
ー処理し、水洗し、６価クロム１７．７１含有する水溶
性クロム化合物中に３価クロム９．９１含有し、シリカ
１５．８７ｚ ｆ含んだｐＨ３の液でロールコータ−塗
布し乾燥して１９０シ鷹の皮膜を得た。Example 1 A zinc-aluminum alloy plated steel sheet commercially available under the trademark “Super Zinc” was prepared using Fe (NOs) sk
0.177z in FC conversion, Ni (NO3), f N
0.241 in terms of i, hexahydroxyhebuto/soda 1t, 7'/i, pH 13j containing caustic soda 22~
, Spray treated with an alkaline aqueous solution at a liquid temperature of 57 to 63°C for 10 seconds, washed with water, and a water-soluble chromium compound containing 17.71 hexavalent chromium contained 9.91 trivalent chromium and 15.87z f silica. It was coated with a pH 3 solution using a roll coater and dried to obtain a film of 190 mm.
比較例１としては、浴融亜鉛めっき鋼板及び亜鉛−アル
ミニウム合金めっき鋼板の無処理と、それ等の鋼板にア
ルカリ水ｍ液による処理を除いた以外は実施例１と同一
条件で処理した。Comparative Example 1 was treated under the same conditions as Example 1, except that the bath-dip galvanized steel sheet and the zinc-aluminum alloy-plated steel sheet were not treated, and the steel sheets were not treated with alkaline water.
実施例２
実施例１と同様の亜鉛−アルミニウム合金めっき鋼板を
、Ｆｅ （ＮＯｓ ）ｓをＦｅ換算で０．１７’／、、
Ｃｏ （ＮＯＩ ）２をＣｏ換算で０．２４θ、ヘキサ
ヒドロキシヘプトン７−タ２１．７ ｐｚ、 ’Ｒ性７
− タ２２１ を有ス６ ｐＨ１５，ｌｓ、液温５５〜
６０℃のアルカリ水ｍ液で６秒間スプレー処理し、水泳
し、６価クロム１６．５５／７含有する水溶液クロム化
合物中に３価りｐＡ９．９’ｌ／ｚ及びシリカ５４．２
〜を含有し、更にＰｏ、２５．５〜を含んだｐＨ１，５
の液でロールコータ−塗布し乾嫌して２８０％の皮膜を
得た。Example 2 A zinc-aluminum alloy plated steel sheet similar to Example 1 was prepared with Fe (NOs)s of 0.17'/, in terms of Fe.
Co (NOI)2 is 0.24θ in terms of Co, hexahydroxyheptone 7-ta 21.7 pz, 'R property 7
- Contains 221 ml of water, pH 15, ls, liquid temperature 55~
Spray treatment with alkaline water solution at 60°C for 6 seconds, swim, and add trivalent pA 9.9'l/z and silica 54.2 to an aqueous solution chromium compound containing hexavalent chromium 16.55/7.
pH 1,5 containing ~ and further containing Po, 25.5~
The solution was coated with a roll coater and dried to obtain a film of 280%.
比較例２とし【、溶融亜鉛めっき鋼板及び亜鉛−アルミ
ニウム合金めつき鋼板にアルカリ水ｍ液による処理を除
いた以外は実施例２と同一条件で処理した。Comparative Example 2 was prepared under the same conditions as in Example 2, except that the hot-dip galvanized steel sheet and the zinc-aluminum alloy coated steel sheet were not treated with alkaline water solution.
前記処理された合金めつき鋼板に、２コートのものはエ
ポキシ系下塗塗料全膜厚５μになるようにバーコーター
で塗布し、処理温度１νＯ℃で焼付け、次いでポリエス
テル系上塗塗料を１５μになるようにバーコーターで塗
布し、処理温度が２００°Ｃで焼付けた。また１コート
のものはポリエステル系１コート塗料を１４μになるよ
うにバーコーターで塗布し、処理温度２１０℃で焼付け
た。その塗装仮について塗膜密着性及び耐食性試験を行
った結果を８ｇ２表に示す。On the above-treated alloy-plated steel sheet, 2-coat epoxy base coat was applied to a total film thickness of 5μ using a bar coater, baked at a treatment temperature of 1νO℃, and then a polyester topcoat was applied to a total thickness of 15μ. was coated with a bar coater and baked at a processing temperature of 200°C. For the one-coat type, a polyester one-coat paint was applied to a thickness of 14μ using a bar coater, and baked at a processing temperature of 210°C. The results of coating film adhesion and corrosion resistance tests on the temporary coating are shown in Table 8g2.
試験方法は次の如く行った。The test method was as follows.
（リ 折り曲げ試験、衝撃試験
折り曲げ試験は塗装後試験板を二つ折りにして折り曲げ
部分に試験板と同厚みの板片を２枚折り曲げ部に挿入し
万力を用いて締めつけ、折り曲げた而にスコッチテープ
を貼りテープを急激に剥がす。本試験後折り曲げ面に対
する塗膜の剥離面積より評価点金つげる。(Bending test, impact test For the bending test, after painting, the test board was folded in half, two pieces of the same thickness as the test board were inserted into the folded part, tightened using a vise, and then folded. Apply the tape and remove the tape rapidly. After this test, the evaluation score will be increased based on the peeled area of the coating film on the folded surface.
衝撃試験はデュポン式衝撃試験磯によって撃心２“、荷
重１ｋｇ、高さ５０ｃ！ＩＬで行い、凹面にスコッチテ
ープを貼りテープを急激に剥がす。本試験後凹面に対す
る塗膜の剥離面積より評価点をつける。The impact test was conducted using a DuPont impact test rock with a center of impact of 2", a load of 1 kg, and a height of 50 cm! IL. Scotch tape was applied to the concave surface and the tape was rapidly peeled off. After the test, evaluation points were determined based on the peeled area of the paint film on the concave surface. Attach.
評価点の区別は次の通りである。The evaluation points are distinguished as follows.
折り曲げ試験及び衝撃試験
（２） コインスクラッチ試験
１０円硬貨により塗面をひっかく。本試験後試験面に塗
膜の剥離面積により評価点をつける。評価点の区別は次
の通りである。Bending test and impact test (2) Coin scratch test The painted surface was scratched with a 10 yen coin. After this test, an evaluation score will be given to the test surface based on the peeled area of the paint film. The evaluation points are distinguished as follows.
（３）耐食性試験
３−１５％塩水噴霧試験
塗装後試験板にナイフで塗面を通して素地に達する傷を
入れた部分、切断部及び折り曲げ都についてＪＩＳ −
Ｚ −２３７１により５％塩水噴霧試験、１コートの場
合二５００時間、２コートの場合： １０００時間行い
、下記の判定基準により判定する。(3) Corrosion Resistance Test 3 - 15% Salt Spray Test After painting, the parts where the test plate was scratched with a knife through the painted surface to reach the base, the cut parts, and the bent areas JIS -
A 5% salt water spray test using Z-2371 was conducted for 2,500 hours for 1 coat and 1,000 hours for 2 coats, and judged according to the following criteria.
３−２ 屋外曝露試験 神奈川系の住宅地に６年間曝廃した。3-2 Outdoor exposure test It was exposed for six years to a residential area in the Kanagawa area.
以上の如く、亜鉛−アルミニウム合金めっき鋼板に、シ
リカをさむクロメート水４液を塗布する前に本発明に於
けるアルカリ水溶液にて処理することにより、塗装後の
屋外８ｍ性を向上させることが出来る。As described above, by treating a zinc-aluminum alloy plated steel sheet with the alkaline aqueous solution of the present invention before applying the 4 liquid chromate water containing silica, it is possible to improve the outdoor 8m performance after painting. .
Claims (6)
アルミニウム合金めっき鋼板にニッケル、鉄、コバルト
、マンガンの群より選ばれた１種又は２種以上の金属イ
オン及び該金属イオンを溶存させるに必要な量の錯化剤
を含むｐＨ１１以上のアルカリ水溶液にて処理を施し、
次いでシリカを含むクロメート水溶液を塗布して乾燥し
、その後塗装することを特徴とする亜鉛−アルミニウム
合金めっき鋼板の表面処理方法。(1) Zinc with an aluminum content of 1 to 70% by weight
An alkaline aqueous solution with a pH of 11 or higher containing one or more metal ions selected from the group of nickel, iron, cobalt, and manganese and a complexing agent in an amount necessary to dissolve the metal ions in an aluminum alloy plated steel sheet. and then
A method for surface treatment of a zinc-aluminum alloy plated steel sheet, which comprises applying a chromate aqueous solution containing silica, drying, and then painting.
料を施すことを特徴とする特許請求の範囲第１項記載の
亜鉛−アルミニウム合金めっき鋼板の表面処理方法。(2) The method for surface treatment of a zinc-aluminum alloy plated steel sheet according to claim 1, characterized in that an epoxy resin paint is applied as an undercoat during the painting.
又はリン酸イオンが含まれることを特徴とする特許請求
の範囲第１項記載の亜鉛−アルミニウム合金めっき鋼板
の表面処理方法。(3) Trivalent chromium ions and/or
2. The method for surface treatment of a zinc-aluminum alloy plated steel sheet according to claim 1, wherein the surface treatment method comprises: or phosphate ions.
れたシリカを含むクロメート水溶液が乾燥皮膜で１０〜
４００ｍｇ／ｍ＾２になるように塗布されていることを
特徴とする特許請求の範囲第１項記載の亜鉛−アルミニ
ウム合金めっき鋼板の表面処理方法。(4) The chromate aqueous solution containing silica applied to the zinc-aluminum alloy plated steel sheet has a dry film of 10 to
2. The method for surface treatment of a zinc-aluminum alloy plated steel sheet according to claim 1, wherein the coating is applied at a concentration of 400 mg/m^2.
オンの重量比が０．６〜１５であり、３価クロム／６価
クロムイオンの重量比が０．２〜１である特許請求の範
囲第３項記載の亜鉛−アルミニウム合金めっき鋼板の表
面処理方法。(5) The weight ratio of silica/hexavalent chromium ions in the chromate aqueous solution is 0.6 to 15, and the weight ratio of trivalent chromium/hexavalent chromium ions is 0.2 to 1. The method for surface treatment of zinc-aluminum alloy plated steel sheet according to item 3.
ロムイオンの重量比が０．６〜３である特許請求の範囲
第３項記載の亜鉛−アルミニウム合金めっき鋼板の表面
処理方法。(6) The method for surface treatment of a zinc-aluminum alloy plated steel sheet according to claim 3, wherein the weight ratio of phosphate ions/hexavalent chromium ions in the chromate aqueous solution is 0.6 to 3.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15801685A JPS6220880A (en) | 1985-07-19 | 1985-07-19 | Surface treatment of zinc-aluminum alloy plated steel sheet |
| AU60084/86A AU6008486A (en) | 1985-07-19 | 1986-07-11 | Alkaline treatment of zinc-aluminium alloys |
| GB8617211A GB2178065B (en) | 1985-07-19 | 1986-07-15 | Process for treatment of zinc-aluminium alloy coatings |
| DE8686109842T DE3679866D1 (en) | 1985-07-19 | 1986-07-17 | METHOD FOR TREATING THE SURFACE OF STEEL SHEET PROVIDED WITH A ZINC / ALUMINUM ALLOY. |
| EP19860109842 EP0209143B1 (en) | 1985-07-19 | 1986-07-17 | Surface treatment process for a sheet iron zinc-aluminium alloy coating |
| DE19863624101 DE3624101A1 (en) | 1985-07-19 | 1986-07-17 | METHOD FOR TREATING THE SURFACE OF STEEL SHEET PROVIDED WITH A ZINC / ALUMINUM ALLOY |
| BR8603404A BR8603404A (en) | 1985-07-19 | 1986-07-18 | PROCESS FOR TREATING THE SURFACE OF A ZINC-ALUMINUM ALLOY |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15801685A JPS6220880A (en) | 1985-07-19 | 1985-07-19 | Surface treatment of zinc-aluminum alloy plated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6220880A true JPS6220880A (en) | 1987-01-29 |
| JPH0351797B2 JPH0351797B2 (en) | 1991-08-07 |
Family
ID=15662426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15801685A Granted JPS6220880A (en) | 1985-07-19 | 1985-07-19 | Surface treatment of zinc-aluminum alloy plated steel sheet |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0209143B1 (en) |
| JP (1) | JPS6220880A (en) |
| AU (1) | AU6008486A (en) |
| BR (1) | BR8603404A (en) |
| DE (2) | DE3679866D1 (en) |
| GB (1) | GB2178065B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63218279A (en) * | 1987-03-05 | 1988-09-12 | Nippon Steel Corp | Chromating method for imparting excellent corrosion resistance |
| JPH05331662A (en) * | 1992-05-27 | 1993-12-14 | Sumitomo Metal Ind Ltd | Manufacture of highly corrosion resistant galvannealed steel sheet |
| US7381281B2 (en) | 2001-11-21 | 2008-06-03 | Chiyoda Chemical Co., Ltd | Surface treatment method of metal member, and metal goods |
| JP2014510197A (en) * | 2011-03-22 | 2014-04-24 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Multi-stage corrosion-resistant treatment of metal parts containing zinc |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987001397A1 (en) * | 1985-08-29 | 1987-03-12 | Nisshin Steel Co., Ltd. | Hot-dipped steel plate and process for its production |
| JPH03226584A (en) * | 1990-01-30 | 1991-10-07 | Nippon Parkerizing Co Ltd | Solution for surface-treating galvanized steel sheet and method therefor |
| FR2701754B1 (en) * | 1993-02-18 | 1995-04-07 | Pont A Mousson | Pipe element for buried pipe, corresponding buried pipe, and method for protecting such a pipe element. |
| LT3218B (en) | 1993-03-27 | 1995-04-25 | Chemijos Inst | Method for coating zinc alloy by chromium plating |
| JP3983386B2 (en) | 1998-04-03 | 2007-09-26 | 日本ペイント株式会社 | Chromate antirust treatment agent |
| EP2631333A1 (en) * | 2012-02-24 | 2013-08-28 | Henkel AG & Co. KGaA | Pre-treatment of zinc surfaces before passivation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49135836A (en) * | 1973-05-04 | 1974-12-27 | ||
| JPS5392339A (en) * | 1977-01-25 | 1978-08-14 | Nippon Paint Co Ltd | Metal surface treatment agent |
| JPS5745833A (en) * | 1980-09-01 | 1982-03-16 | Taeko Nakagawa | Stomack camera |
| JPS59200768A (en) * | 1983-04-26 | 1984-11-14 | Nippon Paint Co Ltd | Corrosion-resistant composition for treating metallic surface with superior adhesive strength to paint film |
| JPS6126784A (en) * | 1984-07-16 | 1986-02-06 | Nippon Paint Co Ltd | Chemical conversion treated alloy steel sheet plated with zinc containing aluminum |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE316668B (en) * | 1963-09-23 | 1969-10-27 | Parker Ste Continentale | |
| GB1234181A (en) * | 1967-06-14 | 1971-06-03 | ||
| FR1596007A (en) * | 1968-04-18 | 1970-06-15 | ||
| US4227946A (en) * | 1979-02-09 | 1980-10-14 | Oakite Products, Inc. | No-rinse pre-paint coating composition and method |
| FR2560894B1 (en) * | 1984-03-07 | 1988-11-18 | Parker Ste Continentale | PROCESS FOR THE PREPARATION OF ZINC SURFACES, ZINC ALLOYS AND STEEL COATED WITH SUCH MATERIALS FOR RECEIVING PAINTS OR VARNISHES |
| JPS61110777A (en) * | 1984-11-02 | 1986-05-29 | Kawasaki Steel Corp | Surface treating method for preventing black change of galvanizing steel plate |
-
1985
- 1985-07-19 JP JP15801685A patent/JPS6220880A/en active Granted
-
1986
- 1986-07-11 AU AU60084/86A patent/AU6008486A/en not_active Abandoned
- 1986-07-15 GB GB8617211A patent/GB2178065B/en not_active Expired
- 1986-07-17 DE DE8686109842T patent/DE3679866D1/en not_active Expired - Fee Related
- 1986-07-17 EP EP19860109842 patent/EP0209143B1/en not_active Expired - Lifetime
- 1986-07-17 DE DE19863624101 patent/DE3624101A1/en not_active Withdrawn
- 1986-07-18 BR BR8603404A patent/BR8603404A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49135836A (en) * | 1973-05-04 | 1974-12-27 | ||
| JPS5392339A (en) * | 1977-01-25 | 1978-08-14 | Nippon Paint Co Ltd | Metal surface treatment agent |
| JPS5745833A (en) * | 1980-09-01 | 1982-03-16 | Taeko Nakagawa | Stomack camera |
| JPS59200768A (en) * | 1983-04-26 | 1984-11-14 | Nippon Paint Co Ltd | Corrosion-resistant composition for treating metallic surface with superior adhesive strength to paint film |
| JPS6126784A (en) * | 1984-07-16 | 1986-02-06 | Nippon Paint Co Ltd | Chemical conversion treated alloy steel sheet plated with zinc containing aluminum |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63218279A (en) * | 1987-03-05 | 1988-09-12 | Nippon Steel Corp | Chromating method for imparting excellent corrosion resistance |
| JPH05331662A (en) * | 1992-05-27 | 1993-12-14 | Sumitomo Metal Ind Ltd | Manufacture of highly corrosion resistant galvannealed steel sheet |
| US7381281B2 (en) | 2001-11-21 | 2008-06-03 | Chiyoda Chemical Co., Ltd | Surface treatment method of metal member, and metal goods |
| JP2014510197A (en) * | 2011-03-22 | 2014-04-24 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Multi-stage corrosion-resistant treatment of metal parts containing zinc |
| US9534301B2 (en) | 2011-03-22 | 2017-01-03 | Henkel Ag & Co. Kgaa | Multi-stage anti-corrosion treatment of metal components having zinc surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8617211D0 (en) | 1986-08-20 |
| DE3679866D1 (en) | 1991-07-25 |
| EP0209143A2 (en) | 1987-01-21 |
| GB2178065B (en) | 1989-07-19 |
| DE3624101A1 (en) | 1987-01-22 |
| BR8603404A (en) | 1987-02-24 |
| AU6008486A (en) | 1987-01-22 |
| JPH0351797B2 (en) | 1991-08-07 |
| GB2178065A (en) | 1987-02-04 |
| EP0209143B1 (en) | 1991-06-19 |
| EP0209143A3 (en) | 1988-10-26 |
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