JPH09118989A - Galvanized steel sheet excellent in corrosion resistance and lubricity and its manufacture - Google Patents
Galvanized steel sheet excellent in corrosion resistance and lubricity and its manufactureInfo
- Publication number
- JPH09118989A JPH09118989A JP28026695A JP28026695A JPH09118989A JP H09118989 A JPH09118989 A JP H09118989A JP 28026695 A JP28026695 A JP 28026695A JP 28026695 A JP28026695 A JP 28026695A JP H09118989 A JPH09118989 A JP H09118989A
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- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- lubricity
- zinc
- plated steel
- 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.)
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- Application Of Or Painting With Fluid Materials (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
- Coating With Molten Metal (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は耐食性と潤滑性に
優れた亜鉛系めっき鋼板及びその製造方法に関するもの
である。TECHNICAL FIELD The present invention relates to a zinc-based plated steel sheet having excellent corrosion resistance and lubricity, and a method for producing the same.
【０００２】[0002]
【従来の技術】亜鉛系めっき鋼板は、従来から電気めっ
きあるいは溶融めっきにより製造され、そのめっき皮膜
の犠牲防食性により地鉄の腐食を大きく抑制することが
できるため広く使用されている。しかし、亜鉛系めっき
鋼板はその腐食過程において白色の亜鉛錆が生成し、外
観品質が大きく低下する。そこで、この白錆を抑制する
ために、クロム酸、重クロム酸またはその塩類を主体と
したクロメート処理が施される。このクロメート処理
は、耐食性に優れ、かつ比較的簡単に行なうことができ
る経済的な処理方法であるが、６価クロムを使用するも
のであり、クロメート処理工場の管理や廃水処理に多大
の設備と費用が必要となるという問題がある。2. Description of the Related Art Zinc-based plated steel sheets have hitherto been produced by electroplating or hot dip plating, and are widely used because the corrosion of the base steel can be largely suppressed by the sacrificial corrosion resistance of the plating film. However, the zinc-based plated steel sheet produces white zinc rust during the corrosion process, and the appearance quality is greatly deteriorated. Therefore, in order to suppress the white rust, a chromate treatment mainly containing chromic acid, dichromic acid or salts thereof is performed. This chromate treatment is an economical treatment method that has excellent corrosion resistance and can be performed relatively easily, but it uses hexavalent chromium, and it requires a large amount of equipment for managing the chromate treatment plant and treating wastewater. There is a problem that costs are required.
【０００３】また、クロメート処理した亜鉛系めっき鋼
板は潤滑性が悪いので、プレス加工時には防錆潤滑油と
して動植物油、鉱物油または合成油をベースとし、これ
に極圧添加剤等を添加した潤滑剤が一般に使用される
が、その場合加工後の脱脂工程においてクロムを含有す
る脱脂液の脱クロム処理が不可欠になる。Further, since the chromate-treated zinc-plated steel sheet has poor lubricity, it is based on animal and vegetable oils, mineral oils or synthetic oils as a rust-preventing lubricating oil at the time of press working, and lubricated by adding an extreme pressure additive or the like thereto. The agent is generally used, but in that case, dechromization treatment of the degreasing liquid containing chromium is indispensable in the degreasing step after processing.
【０００４】さらに、最近ではプレス加工用素材に対し
てより一層高度なプレス成形性が要求されており、従来
の防錆潤滑油ではこのような要求に十分に対応すること
が困難な状況となりつつある。Further, in recent years, there has been a demand for higher press formability for press working materials, and it has become difficult for conventional rust preventive lubricating oils to sufficiently meet such demands. is there.
【０００５】このようなことから、クロメート処理によ
らず亜鉛系めっき鋼板の白錆を防止する方法が数多く提
案されている。From the above, many methods have been proposed for preventing white rust on zinc-plated steel sheets without using chromate treatment.
【０００６】例えば、次のような方法がある。 （１）モリブデン、タングステンなどポリ金属酸化物を
被覆する方法（特開昭５７ー５８７５号公報等） （２）フィチン酸を主成分とする処理液を用いる方法
（特公昭４８ー４３４０６号公報） （３）タンニン酸を用いる方法（特公昭５１ー２９０２
号公報） しかし、上記の（１）の方法は、モリブデン、タングス
テンなどポリ金属酸化物の腐食に対する安定領域がクロ
ムのそれよりも狭く、クロメート皮膜並の耐食性を得る
のは不可能である。また、（２）や（３）の方法も耐食
性がクロメート皮膜に比べかなり悪い上に、処理によっ
てめっき面が着色し外観が劣る、処理液のコストが高い
等の問題があり、クロメート処理に代替し得る亜鉛系め
っき鋼板の白錆防止方法は未だ開発されていない。For example, there are the following methods. (1) A method of coating a polymetal oxide such as molybdenum or tungsten (JP-A-57-5875, etc.) (2) A method of using a treatment liquid containing phytic acid as a main component (JP-B-48-43406) (3) Method using tannic acid (Japanese Patent Publication No. 51-2902)
However, according to the method (1), the stable region against corrosion of polymetal oxides such as molybdenum and tungsten is narrower than that of chromium, and it is impossible to obtain corrosion resistance comparable to that of a chromate film. In addition, the methods (2) and (3) have considerably poorer corrosion resistance than the chromate film, and there are problems that the plating surface is colored due to the treatment and the appearance is inferior, and the cost of the treatment liquid is high. A possible method of preventing white rust on zinc-based plated steel sheet has not yet been developed.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記のような
問題点の解決を図るために、クロメート処理亜鉛系めっ
き鋼板に匹敵する優れた耐食性を有すると共に、高度の
潤滑特性をも備えた亜鉛系めっき鋼板及びその製造方法
を提供することを目的とする。In order to solve the above problems, the present invention has excellent corrosion resistance comparable to that of a chromate-treated zinc-plated steel sheet, and zinc having a high degree of lubricating property. An object is to provide a system-plated steel sheet and a method for manufacturing the same.
【０００８】[0008]
【課題を解決するための手段】請求項１に係る発明は、
亜鉛系めっき鋼板の表面に、ケイ酸エステルと硝酸アル
ミニウムをＡｌ／（Ａｌ＋Ｓｉ）のモル比で０．１〜
０．７５の範囲で含有する溶液を塗布、加熱乾燥して形
成された皮膜を有し、その上に、該皮膜とチオール化合
物との反応生成物であるメルカプチド化合物と潤滑剤と
を含有する潤滑層を有することを特徴とする耐食性と潤
滑性に優れた亜鉛系めっき鋼板である。The invention according to claim 1 is
On the surface of the zinc-based plated steel sheet, silicate ester and aluminum nitrate are added in an Al / (Al + Si) molar ratio of 0.1 to 0.1.
Lubrication comprising a film formed by applying a solution containing in the range of 0.75 and heating and drying, and further containing a mercaptide compound, which is a reaction product of the film and a thiol compound, and a lubricant. It is a zinc-based plated steel sheet excellent in corrosion resistance and lubricity characterized by having a layer.
【０００９】請求項２に係る発明は、請求項１に係る発
明においてチオール化合物が、炭素数８以上の直鎖アル
キル基の末端または両端にチオール基を有するアルキル
チオールであることを特徴とする耐食性と潤滑性に優れ
た亜鉛系めっき鋼板である。The invention according to claim 2 is characterized in that, in the invention according to claim 1, the thiol compound is an alkylthiol having a thiol group at a terminal or both ends of a linear alkyl group having 8 or more carbon atoms. And a zinc-based plated steel sheet with excellent lubricity.
【００１０】請求項３に係る発明は、亜鉛系めっき鋼板
の表面に、ケイ酸エステルと硝酸アルミニウムをＡｌ／
（Ａｌ＋Ｓｉ）のモル比で０．１〜０．７５の範囲で含
有する溶液を塗布後、加熱乾燥し、次いでチオール化合
物を含む溶液と潤滑剤を順次塗布することを特徴とする
耐食性と潤滑性に優れた亜鉛系めっき鋼板の製造方法で
ある。According to a third aspect of the invention, the surface of the zinc-plated steel sheet is coated with Al /
Corrosion resistance and lubricity characterized by applying a solution containing (Al + Si) in a molar ratio of 0.1 to 0.75, heating and drying, and then sequentially applying a solution containing a thiol compound and a lubricant. It is a manufacturing method of a zinc-based plated steel sheet excellent in heat resistance.
【００１１】請求項４に係る発明は、亜鉛系めっき鋼板
の表面に、ケイ酸エステルと硝酸アルミニウムをＡｌ／
（Ａｌ＋Ｓｉ）のモル比で０．１〜０．７５の範囲で含
有する溶液を塗布後、加熱乾燥し、次いでチオール化合
物を含む潤滑剤を塗布することを特徴とする耐食性と潤
滑性に優れた亜鉛系めっき鋼板の製造方法である。According to a fourth aspect of the present invention, the surface of the zinc-based plated steel sheet is coated with Al / silicic acid ester and aluminum nitrate.
A solution containing a molar ratio of (Al + Si) in the range of 0.1 to 0.75 is applied, heated and dried, and then a lubricant containing a thiol compound is applied, which is excellent in corrosion resistance and lubricity. It is a manufacturing method of a galvanized steel sheet.
【００１２】[0012]
【発明の実施の形態】本発明の特徴は亜鉛めっき鋼板表
面に、耐食性向上のためにＡｌ−Ｓｉ系皮膜を形成し、
その皮膜表面に、Ａｌ−Ｓｉ系皮膜とチオール化合物と
の反応生成物であるメルカプチド化合物を含有する潤滑
層を設けることにある。BEST MODE FOR CARRYING OUT THE INVENTION The feature of the present invention is to form an Al-Si-based coating on the surface of a galvanized steel sheet to improve corrosion resistance.
A lubricating layer containing a mercaptide compound which is a reaction product of an Al-Si based film and a thiol compound is provided on the surface of the film.
【００１３】Ａｌ−Ｓｉ系皮膜はケイ酸エステルと硝酸
アルミニウムを混合した溶液を塗布することにより形成
することができる。The Al-Si type coating can be formed by applying a solution in which a silicate ester and aluminum nitrate are mixed.
【００１４】この皮膜の耐食性発現メカニズムについて
は明らかではないが、ケイ酸エステルの加水分解・縮合
過程において、シロキサン結合の形成により白錆抑制能
が得られ、さらに、硝酸アルミニウム中のアルミニウム
により膜の緻密化が進行し、耐食性が向上すると考えら
れる。Although the mechanism of developing corrosion resistance of this film is not clear, white rust inhibiting ability can be obtained by the formation of siloxane bond during the hydrolysis / condensation process of silicate ester, and further, aluminum in aluminum nitrate can form a film. It is considered that densification progresses and corrosion resistance improves.
【００１５】ケイ酸エステルとしては、Ｓｉ（ＯＣn Ｈ
2n+1）4 で示される化合物を使用することができ、例え
ば、メチルシリケート、エチルシリケート、ｎ−ブチル
シリケート等が挙げられる。As the silicate ester, Si (OC n H
The compound represented by 2n + 1 ) 4 can be used, and examples thereof include methyl silicate, ethyl silicate, and n-butyl silicate.
【００１６】ケイ酸エステルと硝酸アルミニウムの混合
比はＡｌ／（Ａｌ＋Ｓｉ）のモル比で耐食性の観点から
は０．０２５〜０．７５にするのが好ましい。The mixing ratio of silicic acid ester and aluminum nitrate is a molar ratio of Al / (Al + Si), and is preferably 0.025 to 0.75 from the viewpoint of corrosion resistance.
【００１７】しかし、混合比が０．１未満ではチオール
とＡｌまたはＡｌ酸化物との生成反応物であるメルカプ
チドが十分に生成出来ないため、著しく潤滑性が低下す
る。However, if the mixing ratio is less than 0.1, the mercaptide, which is a reaction product of thiol and Al or Al oxide, cannot be sufficiently formed, so that the lubricity is remarkably lowered.
【００１８】従って、ケイ酸エステルと硝酸アルミニウ
ムの混合比はＡｌ／（Ａｌ＋Ｓｉ）モル比で０．１〜
０．７５にする必要がある。Therefore, the mixing ratio of silicate ester and aluminum nitrate is 0.1 / (Al + Si) molar ratio.
It should be 0.75.
【００１９】上記の溶液に用いる有機溶媒は、特に限定
されるものではないが、例えば、メタノール、エタノー
ル、ブタノール、プロパノール、メチルセルソルブ、エ
チルセルソルブ、ブチルセルソルブ、エチレングリコー
ル、ジホルムアルデヒドメタキシエタノールなどケイ酸
エステル、硝酸アルミニウムを溶解可能なものが使用で
き、また、１、４ジオキサンのような非極性溶媒でもア
ルコール等の極性溶媒との組み合わせにより使用でき
る。The organic solvent used in the above-mentioned solution is not particularly limited, but for example, methanol, ethanol, butanol, propanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol, diformaldehyde metaxy. Those capable of dissolving silicate ester and aluminum nitrate such as ethanol can be used, and nonpolar solvents such as 1,4 dioxane can be used in combination with polar solvents such as alcohol.
【００２０】上記の溶液を塗布する方法としては、特に
限定されるものではないが、例えばロールコータを用い
る方法、処理液に浸漬する方法、スプレーする方法など
を挙げることができる。The method of applying the above-mentioned solution is not particularly limited, but examples thereof include a method using a roll coater, a method of immersing in a treatment solution, and a method of spraying.
【００２１】上記の溶液を塗布後、加熱乾燥し皮膜を形
成する。この際の加熱温度は特に限定されるものではな
いが、高温下で乾燥させると皮膜にクラックを生じ、耐
食性が低下する傾向があるため、２００℃未満が好まし
い。After the above solution is applied, it is heated and dried to form a film. The heating temperature at this time is not particularly limited, but if it is dried at a high temperature, cracks are likely to occur in the film, and the corrosion resistance tends to decrease, so less than 200 ° C. is preferable.
【００２２】次に上層の潤滑層について述べる。チオー
ル化合物をＡｌ−Ｓｉ系皮膜に塗布した場合、チオール
化合物はＡｌ−Ｓｉ系皮膜表面のＡｌまたはＡｌ酸化物
と反応してメルカプチド化合物を生成し、Ａｌ−Ｓｉ系
皮膜面はメルカプチド化合物により被覆された状態にな
る。Next, the upper lubricating layer will be described. When the thiol compound is applied to the Al-Si based coating, the thiol compound reacts with Al or Al oxide on the surface of the Al-Si based coating to generate a mercaptide compound, and the Al-Si based coating surface is coated with the mercaptide compound. It will be in a state of being.
【００２３】本発明者はこのようなメルカプチド化合物
を潤滑剤と共にＡｌ−Ｓｉ系皮膜表面に共存させること
により、極めて優れた潤滑特性が得られることを見出し
た。The present inventor has found that coexistence of such a mercaptide compound together with a lubricant on the surface of the Al-Si type coating makes it possible to obtain extremely excellent lubricating characteristics.
【００２４】本発明の対象となる亜鉛系めっき鋼板とし
ては、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、合金
化溶融亜鉛めっき鋼板、Ｚｎ−Ａｌ系合金めっき鋼板、
Ａｌ−Ｚｎ系合金めっき鋼板等各種亜鉛系めっき鋼板が
挙げられる。The galvanized steel sheet which is the subject of the present invention includes hot-dip galvanized steel sheet, electrogalvanized steel sheet, galvannealed steel sheet, Zn-Al alloy-plated steel sheet,
Examples include various zinc-based plated steel sheets such as Al-Zn-based alloy plated steel sheets.
【００２５】潤滑層中のメルカブチド化合物の含有量
（Ａｌ−Ｓｉ系亜鉛めっき鋼板表面に対するチオールの
反応量）は微量であるため、これを定量的に限定するこ
とは困難であるが、例えば、Ｘ線電子分光装置（ＸＰ
Ｓ）等の分析手段を用いてＣ、Ｓ、Ｏ及びＡｌの状態を
調べることによりチオール化合物吸着の有無を確認する
ことができ、このような手段で確認できる程度の含有量
があれば、所望の潤滑性向上効果が得られる。Since the content of the merkabutide compound in the lubricating layer (the reaction amount of thiol with respect to the surface of the Al-Si-based galvanized steel sheet) is very small, it is difficult to quantitatively limit it. X-ray electron spectrometer (XP
The presence or absence of thiol compound adsorption can be confirmed by examining the states of C, S, O, and Al using an analyzing means such as S), and if the content can be confirmed by such means, it is desired. The effect of improving the lubricity can be obtained.
【００２６】また、本発明では潤滑層に未反応のチオー
ル化合物が存在することを妨げない。メルカブチド化合
物が生成されていれば、未反応のチオール化合物が存在
しても、所望の潤滑性が得られる。The present invention does not prevent the presence of unreacted thiol compound in the lubricating layer. If the mercaptide compound is produced, the desired lubricity can be obtained even if there is an unreacted thiol compound.
【００２７】潤滑層を構成する潤滑剤の種類や組成には
特別の制約はない。従って潤滑油の場合には、ベースオ
イル（動植物油、鉱物油、合成油等）のみからなるも
の、ベースオイルに耐食性向上を目的とした防錆添加剤
を添加したもの、ベースオイルに潤滑性、耐食性等の向
上を目的とした２種以上添加剤を添加したもの等、任意
の種類、組成の潤滑油を使用することができ、いずれの
場合も良好な潤滑性向上効果が得られる。There are no particular restrictions on the type or composition of the lubricant constituting the lubricating layer. Therefore, in the case of lubricating oils, those consisting only of base oil (animal and vegetable oils, mineral oils, synthetic oils, etc.), those with a rust-preventive additive for the purpose of improving corrosion resistance added to the base oil, lubricity, corrosion resistance, etc. Lubricating oils of any kind and composition, such as those to which two or more additives are added for the purpose of improvement, can be used, and in any case, a good lubricating property improving effect can be obtained.
【００２８】但し、鋼板の脱脂性は主として潤滑油自体
の脱脂性能に依存するため、潤滑油は脱脂性が良好なも
のを用いることが好ましい。However, since the degreasing property of the steel sheet mainly depends on the degreasing performance of the lubricating oil itself, it is preferable to use a lubricating oil having a good degreasing property.
【００２９】また、これ以外にも、いわゆる固形潤滑剤
であるフッ素系ワックス、ポリオレフィン系ワックス、
二硫化モリブテン等を使用することができる。Other than this, so-called solid lubricants such as fluorine-based wax, polyolefin-based wax,
Molybdenum disulfide and the like can be used.
【００３０】なお、チオール化合物は酸化しやすい性質
があるため、潤滑油中への酸化剤成分の含有は極力避け
ることが好ましく、場合によっては酸化防止剤を添加す
ることが望ましい。Since the thiol compound has a property of being easily oxidized, it is preferable to avoid inclusion of the oxidizer component in the lubricating oil as much as possible, and it is desirable to add an antioxidant in some cases.
【００３１】上記の潤滑層を形成するための方法として
は、エーテル、アルコールまたは水等で溶解、希釈した
チオール化合物をＡｌ−Ｓｉ系皮膜表面に塗布した後、
潤滑剤を塗布する方法が一般的であるが、この他にチオ
ール化合物を潤滑剤に混合し、これをＡｌ−Ｓｉ系皮膜
表面に塗布することによっても潤滑層を形成することが
できる。As a method for forming the above-mentioned lubricating layer, a thiol compound dissolved and diluted with ether, alcohol, water or the like is applied to the surface of the Al-Si type coating,
Although a method of applying a lubricant is generally used, the lubricant layer can also be formed by mixing a thiol compound with a lubricant and applying the mixture to the surface of the Al-Si-based film.
【００３２】このような方法によっても目的とする潤滑
層が得られるのは、潤滑剤中に混合されたチオール化合
物が選択的にＡｌ−Ｓｉ系皮膜表面に吸着し反応するた
めであると考えられる。The reason why the intended lubricating layer can be obtained by such a method is considered to be that the thiol compound mixed in the lubricant selectively adsorbs on the surface of the Al--Si based coating and reacts therewith. .
【００３３】また、上記の両方法を併用すること、即
ち、チオール化合物を含む溶液を塗布した後、さらにチ
オール化合物を混合した潤滑剤を塗布する方法を採るこ
とも可能である。It is also possible to use both of the above methods in combination, that is, to apply a solution containing a thiol compound and then apply a lubricant containing a thiol compound.
【００３４】Ａｌ−Ｓｉ系皮膜表面に塗布する際のチオ
ール化合物の付着量は特に限定しないが、過剰に付着さ
せても潤滑性改善効果には限界があり、また、過剰に付
着させるといわゆる油やけと称される外観異常が生じる
ことがあるため好ましくない。The amount of the thiol compound deposited on the surface of the Al-Si type coating is not particularly limited, but even if it is excessively deposited, the effect of improving lubricity is limited. It is not preferable because an abnormal appearance called burn may occur.
【００３５】メルカプチド化合物を生成するために用い
るチオール化合物の種類や化学構造等に特に限定はない
が、好適なチオール化合物としては、炭素数８以上の直
鎖アルキル基の末端または両端にチオール基を有するア
ルキルチオールを挙げることができる。このうち、アル
キル基の末端にチオール基を有するアルキルチオールと
しては、例えば１−オクタデカンチオ−ル、１−ヘキサ
デカンチオ−ル、１−ドデカンチオ−ル、１−オクタチ
オ−ル等のアルキルチオ−ル類を挙げることができ、ま
た、アルキル基の両端にチオール基を有するアルキルチ
オールとしては、ｎ−デカンジチオ−ル（Ｃ10Ｈ20（Ｓ
Ｈ）2 ）を挙げることができる。これらのチオール化合
物には特に優れた潤滑性改善効果があり、また、いわゆ
る油やけによる外観異常も生じることがない。The type and chemical structure of the thiol compound used for producing the mercaptide compound are not particularly limited, but a suitable thiol compound is a thiol group at the end or both ends of a linear alkyl group having 8 or more carbon atoms. The alkyl thiol which it has can be mentioned. Among these, examples of the alkylthiol having a thiol group at the end of the alkyl group include alkylthiols such as 1-octadecanethiol, 1-hexadecanethiol, 1-dodecanethiol and 1-octathiol. Examples of the alkyl thiol having a thiol group at both ends of the alkyl group include n-decanedithiol (C 10 H 20 (S
H) 2 ) can be mentioned. These thiol compounds have a particularly excellent lubricity-improving effect and do not cause abnormal appearance due to so-called oil burn.
【００３６】なお、一般的にチオール化合物の酸性度は
アルキル基の大きさにより影響を受け、アルキル基が大
きくなるほど酸性度が小さくなる。また、チオール化合
物は一級＞二級＞三級の順で酸性度が小さくなる傾向が
ある。チオール化合物の酸性度が過剰に高くなると、Ａ
ｌ−Ｓｉ系皮膜表面をエッチングする作用が大きくなる
ために好ましくない。従って、このようなことを考慮
し、素材に応じてチオール化合物の構造を選択すること
が好ましい。Generally, the acidity of the thiol compound is affected by the size of the alkyl group, and the larger the alkyl group, the smaller the acidity. The thiol compound tends to have a lower acidity in the order of primary>secondary> tertiary. If the acidity of the thiol compound becomes too high, A
It is not preferable because the action of etching the surface of the 1-Si-based coating becomes large. Therefore, in consideration of the above, it is preferable to select the structure of the thiol compound according to the material.
【００３７】[0037]
【実施例】電気亜鉛めっき鋼板（めっき量片面当たり２
０ｇ／ｍ2 ）を素材鋼板とし、その表面に表１に示す組
成のケイ酸エチル、硝酸アルミニウムを溶解させたエタ
ノール溶液をロールコータによって塗布し、熱風乾燥炉
により加熱温度１００℃にて加熱処理を施した。得られ
たＡｌ−Ｓｉ系皮膜の付着量は、処理液の希釈率で制御
し、Ｓｉ及びＡｌの合計量で換算して１００ｍｇ／ｍ2
になるようにした。[Example] Electrogalvanized steel sheet (plating amount: 2 per side)
0 g / m 2 ) is used as a material steel plate, the surface of which is coated with an ethanol solution in which ethyl silicate and aluminum nitrate are dissolved by a roll coater, and heat-treated at a heating temperature of 100 ° C. in a hot air drying oven. Was applied. The adhesion amount of the obtained Al-Si-based film was controlled by the dilution ratio of the treatment liquid, and converted into the total amount of Si and Al to be 100 mg / m 2.
I tried to be.
【００３８】さらに、上層に以下の４種類の方法で潤滑
層を形成し、潤滑性（摩擦係数）と耐食性を測定、評価
した。その結果を表１に示す。Further, a lubricating layer was formed on the upper layer by the following four methods, and the lubricity (friction coefficient) and corrosion resistance were measured and evaluated. Table 1 shows the results.
【００３９】[0039]
【表１】 [Table 1]
【００４０】（本発明例）；エタノールと水の混合溶
媒（４：１）１リットル当りに１−オクタデカンチオー
ル５ミリモルを加えた溶液中にＡｌ−Ｓｉ系皮膜が形成
された亜鉛めっき鋼板を浸漬し、次いで市販の防錆潤滑
油を塗布した。(Example of the present invention): A galvanized steel sheet on which an Al-Si-based coating was formed was immersed in a solution containing 5 mmol of 1-octadecanethiol per liter of a mixed solvent (4: 1) of ethanol and water. Then, a commercially available rust preventive lubricating oil was applied.
【００４１】（本発明例）；で用いたものと同じ防
錆潤滑油１リットル当りに１−オクタデカンチオール５
ミリモルを添加した防錆潤滑油をＡｌ−Ｓｉ系皮膜が形
成された亜鉛めっき鋼板に塗布した。(Inventive Example) 1-octadecanethiol 5 per liter of the same rust preventive lubricating oil as used in
The rust-preventive lubricating oil containing millimolar was applied to a galvanized steel sheet on which an Al-Si based film was formed.
【００４２】（本発明例）；で用いたものと同じ防
錆潤滑油１リットル当りに１、３、５トリアジン−２、
４、６−トリチオール５ミリモルを添加した防錆潤滑油
をＡｌ−Ｓｉ系皮膜が形成された亜鉛めっき鋼板に塗布
した。(Example of the present invention): 1, 3, 5 triazine-2, per liter of the same rust preventive lubricating oil as used in
A rust preventive lubricating oil containing 5 mmol of 4,6-trithiol was applied to a galvanized steel sheet on which an Al-Si based film was formed.
【００４３】（比較例）；Ａｌ−Ｓｉ系皮膜が形成さ
れた亜鉛めっき鋼板に、で用いたものと同じ防錆潤滑
油を塗布しただけの供試材を作製した。(Comparative Example): A test material was prepared by simply applying the same rust preventive lubricating oil as used in (1) to a galvanized steel sheet on which an Al-Si based film was formed.
【００４４】潤滑性は、ＳＫＤ１１で作製した工具の間
に供試材を挟み（工具と供試材の接触面積１０ｍ
ｍ2 ）、押し付け荷重Ｗ：１００ｋｇｆで平面引抜き試
験を行った際の引抜き荷重Ｐを測定し、これを摩擦係数
（＝Ｐ／（Ｗ×２））に換算し、潤滑性の評価とした。The lubricity is determined by sandwiching the test material between the tools made of SKD11 (contact area between the tool and the test material is 10 m).
m 2 ), the pressing load W: 100 kgf, the pulling load P was measured when the flat pulling test was performed, and this was converted into a friction coefficient (= P / (W × 2)) to evaluate the lubricity.
【００４５】耐食性は、プレス加工後の脱脂工程を想定
して、市販の脱脂剤（ＦＣ−Ｌ４４８０、日本パーカラ
イジング製）を用い、濃度１８ｇ／ｌ、４０℃にて２分
間浸漬させて脱脂を行った後、水洗、乾燥させてから、
塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）を実施し、白錆
発生面積率が１０％未満に抑制されている試験時間によ
り評価した。As for the corrosion resistance, assuming a degreasing step after press working, a commercially available degreasing agent (FC-L4480, manufactured by Nihon Parkerizing Co., Ltd.) was used to perform degreasing by immersing at a concentration of 18 g / l at 40 ° C. for 2 minutes. After rinsing, washing with water and drying,
A salt spray test (JIS-Z-2371) was carried out, and the white rust generation area ratio was evaluated by the test time during which it was suppressed to less than 10%.
【００４６】表１によれば、本発明例である実施例Ｎ
ｏ．１〜Ｎｏ．５の亜鉛めっき鋼板は、耐食性、潤滑性
ともに優れていることがわかる。According to Table 1, Example N which is an example of the present invention
o. 1 to No. It can be seen that the galvanized steel sheet of No. 5 is excellent in both corrosion resistance and lubricity.
【００４７】これに対して、Ａｌ／（Ａｌ＋Ｓｉ）比が
０．１未満の比較材（比較例Ｎｏ．６〜Ｎｏ．８）とＡ
ｌ／（Ａｌ＋Ｓｉ）比が０．１以上であっても潤滑層に
チオール化合物を含まない比較材（比較例Ｎｏ．９）は
潤滑性が劣っている。On the other hand, a comparative material (Comparative Examples No. 6 to No. 8) having an Al / (Al + Si) ratio of less than 0.1 and A
Even if the 1 / (Al + Si) ratio is 0.1 or more, the comparative material (Comparative Example No. 9) having no thiol compound in the lubricating layer has inferior lubricity.
【００４８】また、Ａｌ／（Ａｌ＋Ｓｉ）比が０．０２
５未満の比較材（比較例Ｎｏ．６）と０．７５超の比較
材（比較例Ｎｏ．１０）は、耐食性が劣っている。Further, the Al / (Al + Si) ratio is 0.02.
The comparative material of less than 5 (Comparative Example No. 6) and the comparative material of more than 0.75 (Comparative Example No. 10) are inferior in corrosion resistance.
【００４９】[0049]
【発明の効果】以上のように、本発明によれば、クロメ
ート処理を行うことなしに優れた耐食性と潤滑性を兼備
した亜鉛系めっき鋼板を製造することができる。As described above, according to the present invention, it is possible to produce a zinc-based plated steel sheet having both excellent corrosion resistance and lubricity without performing chromate treatment.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２５Ｄ 3/22 Ｃ２５Ｄ 3/22 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C25D 3/22 C25D 3/22
Claims (4)
テルと硝酸アルミニウムをＡｌ／（Ａｌ＋Ｓｉ）のモル
比で０．１〜０．７５の範囲で含有する溶液を塗布、加
熱乾燥して形成された皮膜を有し、その上に、該皮膜と
チオール化合物との反応生成物であるメルカプチド化合
物と潤滑剤とを含有する潤滑層を有することを特徴とす
る耐食性と潤滑性に優れた亜鉛系めっき鋼板。1. Formed by applying a solution containing a silicate ester and aluminum nitrate in a molar ratio of Al / (Al + Si) in the range of 0.1 to 0.75 to the surface of a zinc-based plated steel sheet, and drying by heating. Zinc system having excellent corrosion resistance and lubricity, characterized by having a lubricating layer containing a mercaptide compound, which is a reaction product of the coating and a thiol compound, and a lubricant. Plated steel sheet.
アルキル基の末端または両端にチオール基を有するアル
キルチオールであることを特徴とする請求項１記載の耐
食性と潤滑性に優れた亜鉛系めっき鋼板。2. The zinc-based compound having excellent corrosion resistance and lubricity according to claim 1, wherein the thiol compound is an alkylthiol having a thiol group at the terminal or both ends of a linear alkyl group having 8 or more carbon atoms. Plated steel sheet.
テルと硝酸アルミニウムをＡｌ／（Ａｌ＋Ｓｉ）のモル
比で０．１〜０．７５の範囲で含有する溶液を塗布後、
加熱乾燥し、次いでチオール化合物を含む溶液と潤滑剤
を順次塗布することを特徴とする耐食性と潤滑性に優れ
た亜鉛系めっき鋼板の製造方法。3. After applying a solution containing a silicate ester and aluminum nitrate in a molar ratio of Al / (Al + Si) in the range of 0.1 to 0.75 to the surface of a zinc-based plated steel sheet,
A method for producing a zinc-based plated steel sheet having excellent corrosion resistance and lubricity, which comprises heating and drying, and then sequentially applying a solution containing a thiol compound and a lubricant.
テルと硝酸アルミニウムをＡｌ／（Ａｌ＋Ｓｉ）のモル
比で０．１〜０．７５の範囲で含有する溶液を塗布後、
加熱乾燥し、次いでチオール化合物を含む潤滑剤を塗布
することを特徴とする耐食性と潤滑性に優れた亜鉛系め
っき鋼板の製造方法。4. A solution containing a silicate ester and aluminum nitrate in a molar ratio of Al / (Al + Si) in the range of 0.1 to 0.75 is applied to the surface of a zinc-based plated steel sheet,
A method for producing a galvanized steel sheet having excellent corrosion resistance and lubricity, which comprises heating and drying, and then applying a lubricant containing a thiol compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28026695A JPH09118989A (en) | 1995-10-27 | 1995-10-27 | Galvanized steel sheet excellent in corrosion resistance and lubricity and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28026695A JPH09118989A (en) | 1995-10-27 | 1995-10-27 | Galvanized steel sheet excellent in corrosion resistance and lubricity and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09118989A true JPH09118989A (en) | 1997-05-06 |
Family
ID=17622608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28026695A Withdrawn JPH09118989A (en) | 1995-10-27 | 1995-10-27 | Galvanized steel sheet excellent in corrosion resistance and lubricity and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09118989A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001059149A (en) * | 1999-08-18 | 2001-03-06 | Nkk Corp | Galvannealed steel sheet excellent in press-formability |
| JP2005238230A (en) * | 2004-02-25 | 2005-09-08 | Posco | Method for improving performance of organic coating for corrosion resistance |
| WO2008029833A1 (en) * | 2006-09-06 | 2008-03-13 | Tsubakimoto Chain Co. | Waterborne antirust pigment, waterborne antirust paint and highly anticorrosive surface-treated chain |
| LU101954B1 (en) * | 2020-07-24 | 2022-01-24 | Phoenix Contact Gmbh & Co | Process for producing a friction-optimized zinc coating on a steel component |
-
1995
- 1995-10-27 JP JP28026695A patent/JPH09118989A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001059149A (en) * | 1999-08-18 | 2001-03-06 | Nkk Corp | Galvannealed steel sheet excellent in press-formability |
| JP2005238230A (en) * | 2004-02-25 | 2005-09-08 | Posco | Method for improving performance of organic coating for corrosion resistance |
| WO2008029833A1 (en) * | 2006-09-06 | 2008-03-13 | Tsubakimoto Chain Co. | Waterborne antirust pigment, waterborne antirust paint and highly anticorrosive surface-treated chain |
| JPWO2008029833A1 (en) * | 2006-09-06 | 2010-01-21 | 株式会社椿本チエイン | Water-based anti-corrosion pigments, water-based anti-corrosion paints and highly corrosion-resistant surface treatment chains |
| US8415026B2 (en) | 2006-09-06 | 2013-04-09 | Tsubakimoto Chain Co. | Water-based rust preventive pigment, water-based rust preventive paint, and highly corrosion resistant surface-treated chain |
| LU101954B1 (en) * | 2020-07-24 | 2022-01-24 | Phoenix Contact Gmbh & Co | Process for producing a friction-optimized zinc coating on a steel component |
| WO2022018225A1 (en) * | 2020-07-24 | 2022-01-27 | Phoenix Contact Gmbh & Co. Kg Intellectual Property Licenses & Standards | Method for producing a zinc coating optimized for coefficient of friction on a steel component |
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Legal Events
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