JPH101786A - Galvanized steel sheet excellent in corrosion resistance and lubricity - Google Patents
Galvanized steel sheet excellent in corrosion resistance and lubricityInfo
- Publication number
- JPH101786A JPH101786A JP17305096A JP17305096A JPH101786A JP H101786 A JPH101786 A JP H101786A JP 17305096 A JP17305096 A JP 17305096A JP 17305096 A JP17305096 A JP 17305096A JP H101786 A JPH101786 A JP H101786A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- steel sheet
- chemical conversion
- galvanized steel
- corrosion resistance
- 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
Landscapes
- Lubricants (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】この発明は耐食性と潤滑性に
優れた亜鉛系めっき鋼板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a galvanized steel sheet having excellent corrosion resistance and lubricity.
【０００２】[0002]
【従来の技術】亜鉛系めっき鋼板は、めっき皮膜の犠牲
防食能により地鉄の腐食を大きく抑制することができる
ため、従来から各種用途の素材鋼板として広く用いられ
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発生し、外観品質が大きく低下する
という難点がある。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
メート処理を施して使用するのが通例である。しかし、
このクロメート処理は優れた耐食性が得られ、しかも比
較的簡単に行うことができる経済的な処理方法である反
面、６価クロムを使用するため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 galvanized steel sheets have been widely used as steel sheets for various applications since the corrosion of ground iron can be greatly suppressed by the sacrificial corrosion protection of the plating film. However, zinc-plated steel sheets have the disadvantage that white zinc rust is generated during the corrosion process, and the appearance quality is greatly reduced. Therefore, in order to suppress the white rust, it is customary to use a chromate treatment mainly using chromic acid, dichromic acid or salts thereof. But,
This chromate treatment provides an excellent corrosion resistance and is an economical treatment method that can be performed relatively easily. On the other hand, since hexavalent chromium is used, a large amount of equipment and cost is required for the management of a chromate treatment plant and wastewater treatment. Is necessary.
【０００３】このようなことから、クロメート処理を施
すことなく亜鉛系めっき鋼板の白錆発生を防止するため
の方法が数多く提案されており、その中に例えば次のよ
うな方法がある。 (1) モリブデンやタングステン等のポリ金属の酸化物を
被覆する方法（特開昭５７−５８７５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４８−４３４０６号公報） (3) タンニン酸を用いる方法（特公昭５１−２９０２号
公報）[0003] In view of the above, a number of methods have been proposed for preventing the generation of white rust on a zinc-based plated steel sheet without performing a chromate treatment, and the following methods are among them. (1) A method of coating a polymetal oxide such as molybdenum or tungsten (Japanese Patent Application Laid-Open No. 57-5875, etc.) (2) A method of using a processing solution containing phytic acid as a main component (Japanese Patent Publication No. 48-43406) (3) Method using tannic acid (Japanese Patent Publication No. 51-2902)
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記(1)の方
法は、モリブデン、タングステン等のポリ金属の酸化物
の腐食に対する安定領域がクロムのそれよりも狭いた
め、クロメート皮膜並の耐食性を得ることは不可能であ
る。また、上記(2)や(3)の方法も耐食性がクロメート皮
膜に較べてかなり劣る上、処理によってめっき面が着色
し外観が劣ったものとなる、処理液コストが高い等の問
題がある。したがって、クロメート処理の代替となり得
るような亜鉛系めっき鋼板の白錆防止方法は未だ開発さ
れていないのが現状である。However, in the above method (1), the stable area against corrosion of polymetal oxides such as molybdenum and tungsten is narrower than that of chromium, so that the corrosion resistance is equivalent to that of a chromate film. It is impossible. In addition, the methods (2) and (3) also have problems such that the corrosion resistance is considerably inferior to that of the chromate film, the plating surface is colored by the treatment, the appearance is inferior, and the cost of the treatment solution is high. Therefore, at present, a method for preventing white rust of galvanized steel sheet, which can be an alternative to the chromate treatment, has not yet been developed.
【０００５】一方、クロメート処理した亜鉛系めっき鋼
板は潤滑性が劣るため、従来ではプレス加工する際に防
錆潤滑油が使用されてきたが、防錆潤滑油を使用した場
合、加工後の脱脂工程においてクロムを含有する脱脂液
が排出されるため、この脱脂液の脱クロム処理が不可欠
になる。このため、プレス加工後に塗布した油が自然乾
燥する速乾油の使用が一般的になっているが、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、従来の速乾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。した
がって本発明の目的は、上記のような従来技術の問題点
を解決し、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ともに、高度の潤滑特性をも兼
ね備えた亜鉛系めっき鋼板を提供することにある。[0005] On the other hand, zinc-plated steel sheets subjected to chromate treatment have inferior lubricity, so that rust-preventive lubricating oils have conventionally been used in press working. Since the degreasing solution containing chromium is discharged in the process, the dechroming treatment of the degreasing solution is indispensable. For this reason, the use of quick-drying oil, in which the oil applied after press working is naturally dried, has become common, but recently more advanced press formability has been required for press working materials. It is becoming difficult for quick-drying oils to meet such demands. Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and provide a galvanized steel sheet having excellent corrosion resistance comparable to a chromate-treated galvanized steel sheet and also having a high level of lubrication properties. Is to do.
【０００６】[0006]
【課題を解決するための手段】このような目的を達成す
るための本発明の構成は以下の通りである。 (1) 亜鉛系めっき鋼板の表面に、ケイ酸エステルとアル
ミニウムの無機塩とを、ケイ酸エステル中のＳｉ及びア
ルミニウムの無機塩中のＡｌ換算でのＡｌ／（Ａｌ＋Ｓ
ｉ）のモル比で０．１０〜０．７５の範囲で含有する溶
液を塗布し、加熱乾燥させて形成された化成処理皮膜を
有し、その上層に、チオール化合物と前記化成処理皮膜
の一部との反応生成物であるメルカプチド化合物からな
る皮膜、またはチオール化合物及び該チオール化合物と
前記化成処理皮膜の一部との反応生成物であるメルカプ
チド化合物からなる皮膜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。The structure of the present invention for achieving the above object is as follows. (1) A silicate ester and an inorganic salt of aluminum are coated on the surface of a zinc-based plated steel sheet with Al / (Al + S in terms of Al in the inorganic salts of Si and aluminum in the silicate ester.
a chemical conversion coating formed by applying and heating and drying a solution containing the solution in the range of 0.10 to 0.75 in a molar ratio of i), and a thiol compound and one of the chemical conversion coatings formed thereon And a coating comprising a mercaptide compound which is a reaction product of a part and a thiol compound and a coating comprising a mercaptide compound which is a reaction product of the thiol compound and a part of the chemical conversion coating. Galvanized steel sheet with excellent lubricity.
【０００７】(2) 上記(1)の亜鉛系めっき鋼板におい
て、メルカプチド化合物が、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
オール化合物と化成処理皮膜の一部との反応生成物であ
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。(2) In the galvanized steel sheet of the above (1), the mercaptide compound comprises an alkylthiol compound having a thiol group at the terminal or both ends of a linear alkyl group having 8 or more carbon atoms and a part of the chemical conversion coating. A galvanized steel sheet with excellent corrosion resistance and lubricity, characterized by being a reaction product of:
【０００８】[0008]
【発明の実施の形態】本発明の特徴は、亜鉛系めっき鋼
板の表面に、耐食性向上のために特定のＡｌ−Ｓｉ系化
成処理皮膜を形成し、その上層に、チオール化合物と上
記Ａｌ−Ｓｉ系化成処理皮膜の一部との反応生成物であ
るメルカプチド化合物を含有する皮膜（潤滑層）を形成
したことにある。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を挙げることができ
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is characterized in that a specific Al-Si-based chemical conversion coating is formed on the surface of a galvanized steel sheet to improve corrosion resistance, and a thiol compound and the above-mentioned Al-Si This is to form a film (lubricating layer) containing a mercaptide compound which is a reaction product with a part of the system chemical conversion treatment film. Galvanized steel sheets that are the subject of the present invention include hot-dip galvanized steel sheets, electrogalvanized steel sheets,
Examples include an alloyed hot-dip galvanized steel sheet, a Zn-Al-based alloy-coated steel sheet, and an Al-Zn-based alloy-coated steel sheet.
【０００９】前記Ａｌ−Ｓｉ系化成処理皮膜はケイ酸エ
ステルとアルミニウムの無機塩を混合した溶液を塗布
し、加熱乾燥させることにより形成させる。この化成処
理皮膜による耐食性改善のメカニズムは必ずしも明らか
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、シロキサン結合形成により白錆抑制能が得られ、
さらに無機塩中のアルミニウムにより皮膜の緻密化が増
し、耐食性が向上するものと考えられる。ケイ酸エステ
ルとしては、The Al-Si-based chemical conversion treatment film is formed by applying a solution obtained by mixing a silicate ester and an inorganic salt of aluminum, followed by drying by heating. Although the mechanism of the corrosion resistance improvement by this chemical conversion treatment film is not necessarily clear, in the hydrolysis / condensation process of the silicate ester, the ability to suppress white rust is obtained by forming a siloxane bond,
Further, it is considered that the aluminum in the inorganic salt increases the densification of the film and improves the corrosion resistance. As silicate esters,
【化１】 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。アルミニウムの無機塩としては、例
えば、硝酸アルミニウム、硫酸アルミニウム、塩化アル
ミニウム等が挙げられる。Embedded image Can be used, for example, methyl silicate, ethyl silicate, n-butyl silicate and the like. Examples of the inorganic salt of aluminum include aluminum nitrate, aluminum sulfate, and aluminum chloride.
【００１０】ケイ酸エステルとアルミニウムの無機塩の
混合比は、ケイ酸エステル中のＳｉ及びアルミニウムの
無機塩中のＡｌ換算でのＡｌ／（Ａｌ＋Ｓｉ）のモル比
で０．１０〜０．７５とする。この混合比（モル比）の
下限は耐食性の観点だけからすれば０．０２５まで許容
できるが、混合比（モル比）が０．１０未満ではチオー
ル化合物と化成処理皮膜中のＡｌまたはＡｌ酸化物との
反応生成物であるメルカプチド化合物が十分に生成でき
ないため、潤滑性が著しく低下する。一方、混合比（モ
ル比）が０．７５を超えると白錆抑制に効果があるシロ
キサン結合が十分に形成されず、優れた耐食性が得られ
ない。以上の理由から、ケイ酸エステルとアルミニウム
の無機塩の混合比はＡｌ／（Ａｌ＋Ｓｉ）のモル比で
０．１０〜０．７５とする必要がある。The mixing ratio between the silicate ester and the inorganic salt of aluminum is 0.10 to 0.75 as a molar ratio of Al / (Al + Si) in terms of Al in the inorganic salt of Si and aluminum in the silicate ester. I do. The lower limit of the mixing ratio (molar ratio) can be tolerated up to 0.025 from the viewpoint of corrosion resistance alone. However, if the mixing ratio (molar ratio) is less than 0.10, the thiol compound and Al or Al oxide in the chemical conversion coating film may be used. Since the mercaptide compound, which is a reaction product of the above, cannot be produced sufficiently, lubricity is significantly reduced. On the other hand, when the mixing ratio (molar ratio) exceeds 0.75, a siloxane bond effective for suppressing white rust is not sufficiently formed, and excellent corrosion resistance cannot be obtained. For the above reasons, the mixing ratio between the silicate ester and the inorganic salt of aluminum needs to be 0.10 to 0.75 in a molar ratio of Al / (Al + Si).
【００１１】また、上記化成処理皮膜を形成するための
溶液には、皮膜欠陥部での耐食性向上を目的としてＮ
ｉ、ＣｏまたはＭｇの無機塩の１種または２種以上を添
加することもできる。Ｎｉ、Ｃｏ、Ｍｇの無機塩として
は、硝酸塩、硫酸塩、塩化物等が挙げられるが、これら
に限定されるものではない。上記溶液に用いる溶媒に特
別な制約はなく、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等のようにケイ酸
エステルとアルミニウムの無機塩を溶解可能なものを使
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組み合わせることにより
使用することができる。また、水もアルコール等の組み
合わせにより使用することができる。The solution for forming the chemical conversion treatment film contains N for the purpose of improving the corrosion resistance at the film defect.
One or more inorganic salts of i, Co or Mg may be added. Examples of the inorganic salts of Ni, Co, and Mg include, but are not limited to, nitrates, sulfates, and chlorides. There is no particular limitation on the solvent used in the above solution, for example, silicate esters such as methanol, ethanol, butanol, propanol, methylcellosolve, ethylcellosolve, butylcellosolve, ethylene glycol, diformaldehyde metaxyethanol and the like. A solvent capable of dissolving an inorganic salt of aluminum can be used, and a non-polar solvent such as 1,4-dioxane can be used in combination with a polar solvent such as alcohol. Water can also be used in combination with alcohol and the like.
【００１２】上記溶液を塗布する方法にも特別な制約は
なく、例えば、ロールコーター法、浸漬法、スプレー法
等を適用することができる。上記Ａｌ−Ｓｉ系化成処理
皮膜の付着量は特に限定しないが、Ａｌ＋Ｓｉ換算の付
着量が５０ｍｇ／ｍ2未満では耐食性が著しく低下し、
一方、３００ｍｇ／ｍ2を超えて付着させても付着量に
見合う耐食性向上効果が得られず、却って生産性や経済
性を損うことになる。上記溶液の塗布後、加熱乾燥させ
ることによりＡｌ−Ｓｉ系化成処理皮膜を形成する。こ
の際の加熱温度に特別な制約はないが、過度の高温下で
乾燥させると皮膜にクラックが生じ、耐食性が低下する
傾向があるため、加熱温度は２００℃未満とすることが
好ましい。There is no particular limitation on the method of applying the solution, and for example, a roll coater method, a dipping method, a spray method, etc. can be applied. The adhesion amount of the Al-Si-based chemical conversion coating is not particularly limited, but if the adhesion amount in terms of Al + Si is less than 50 mg / m 2 , the corrosion resistance is significantly reduced,
On the other hand, if the amount exceeds 300 mg / m 2 , the effect of improving the corrosion resistance corresponding to the amount of adhesion cannot be obtained, and the productivity and the economic efficiency will be impaired. After the application of the solution, the coating is dried by heating to form an Al-Si-based chemical conversion coating. There is no particular restriction on the heating temperature at this time, but if the film is dried at an excessively high temperature, cracks are generated in the film, and the corrosion resistance tends to decrease. Therefore, the heating temperature is preferably less than 200 ° C.
【００１３】上記Ａｌ−Ｓｉ系化成処理皮膜の上層に
は、メルカプチド化合物を含有する皮膜（潤滑層）が形
成される。チオール化合物を含む溶液を上記Ａｌ−Ｓｉ
系化成処理皮膜面に塗布した場合、チオール化合物はＡ
ｌ−Ｓｉ系化成処理皮膜のＡｌまたはＡｌ酸化物と反応
してメルカプチド化合物を形成し、Ａｌ−Ｓｉ系化成処
理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。本発明者はこのようなメルカプチド化合物をＡｌ
−Ｓｉ系化成処理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い出した。A film (lubricating layer) containing a mercaptide compound is formed as an upper layer of the Al-Si-based chemical conversion treatment film. The solution containing a thiol compound is mixed with the Al-Si
When applied to the surface of a chemical conversion coating, the thiol compound is A
It reacts with Al or Al oxide in the l-Si chemical conversion treatment film to form a mercaptide compound, and the surface of the Al-Si chemical conversion treatment film is in a state of being covered with the mercaptide compound. The present inventors have proposed such a mercaptide compound as Al
It has been found that extremely excellent lubrication properties can be obtained by coexisting on the surface of a Si-based chemical conversion coating.
【００１４】皮膜中のメルカプチド化合物の含有量（Ａ
ｌ−Ｓｉ系化成処理皮膜表面に対するチオールの吸着
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（ＸＰＳ）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吸着の有無を確認することができ、
このような手段でチオール吸着が確認できる程度の含有
量があれば、所望の潤滑性が得られる。本発明では皮膜
中に未反応のチオール化合物が存在することを妨げず、
このような未反応のチオール化合物が存在しても、上記
メルカプチド化合物が生成されていれば所望の潤滑性が
得られる。上記の皮膜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・稀釈したチオ
ール化合物をＡｌ−Ｓｉ系化成処理皮膜表面に塗布する
方法が一般的である。Ａｌ−Ｓｉ系化成処理皮膜表面に
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
る。The content of the mercaptide compound in the film (A
Since the amount of thiol adsorbed on the surface of the l-Si chemical conversion treatment film is very small, it is difficult to quantitatively limit the amount. However, for example, an analysis means such as an X-ray electron spectrometer (XPS) is used. The presence or absence of thiol adsorption can be confirmed by examining the state of C, S, O and Al,
If the content is such that thiol adsorption can be confirmed by such means, desired lubricity can be obtained. In the present invention, does not prevent the presence of unreacted thiol compound in the film,
Even if such an unreacted thiol compound is present, desired lubricity can be obtained as long as the mercaptide compound is formed. As a method for forming the above-mentioned film,
A general method is to apply a thiol compound dissolved / diluted with ether, alcohol, water or the like to the surface of the Al-Si-based chemical conversion treatment film. The adhesion amount of the thiol compound when applied to the surface of the Al—Si-based chemical conversion treatment film is not particularly limited, but even if it is excessively adhered, the lubricity improving effect is limited.
【００１５】また、メルカプチド化合物を形成するため
に用いるチオール化合物の種類や化学構造等は特に限定
しないが、特に好適なチオール化合物として、アルキル
基が炭素数８以上の直鎖となっており、その末端または
両端にチオール基を有するアルキルチオール化合物を挙
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化合物としては、例えば
１−オクタデカンチオール、１−ヘキサデカンチオー
ル、１−ドデカンチオール、１−オクタチオール等のア
ルキルチオー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化合物
としては、ｎ−デカンジチオール（Ｃ10Ｈ20（Ｓ
Ｈ）2）等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る。The type and chemical structure of the thiol compound used to form the mercaptide compound are not particularly limited, but as a particularly preferred thiol compound, the alkyl group is a straight chain having 8 or more carbon atoms. An alkylthiol compound having a thiol group at the terminal or at both ends can be mentioned. Examples of the alkylthiol compound having a thiol group at the terminal of the alkyl group include alkylthiols such as 1-octadecanethiol, 1-hexadecanethiol, 1-dodecanethiol, and 1-octathiol. Examples of the alkyl thiol compound having thiol groups at both ends of the alkyl group include n-decanedithiol (C 10 H 20 (S
H) 2 ) and the like. These thiol compounds have a particularly excellent lubricity improving effect.
【００１６】なお、チオールの酸性度が過剰に高くなる
とＡｌ−Ｓｉ系化成処理皮膜表面をエッチングする作用
が大きくなるため好ましくない。一般的にチオールの酸
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
ルは一級＞二級＞三級の順で酸性度が小さくなるため、
チオールの構造を選択する上で有効な目安となる。した
がって、素材に応じてチオールの構造を選択することが
好ましい。If the acidity of the thiol is excessively high, the action of etching the surface of the Al—Si-based chemical conversion coating film is undesirably increased. Generally, the acidity of a thiol is affected by the size of the alkyl group, and the larger the alkyl group, the lower the acidity. In addition, the acidity of thiol decreases in the order of primary>secondary> tertiary,
This is an effective guide for selecting the structure of thiol. Therefore, it is preferable to select the thiol structure according to the material.
【００１７】[0017]
【実施例】電気亜鉛めっき鋼板（片面当りのめっき付着
量２０ｇ／ｍ2）を素材めっき鋼板とし、その表面に表
１に示す組成のケイ酸エチルとアルミニウムの無機塩を
溶解させたエタノール溶液をロールコーターによって塗
布し、熱風乾燥炉により加熱温度１００℃で加熱処理を
施し、Ａｌ−Ｓｉ系化成処理皮膜を形成した。この皮膜
の付着量は処理液の稀釈率で調整し、いずれもＳｉ及び
Ａｌ換算の合計量で１００ｍｇ／ｍ2とした。次いで、
上記Ａｌ−Ｓｉ系化成処理皮膜の上層に以下の４種類の
方法で潤滑層を形成し、供試材を作成した。各供給材に
ついて潤滑性（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。EXAMPLE An electrogalvanized steel sheet (coating weight per side: 20 g / m 2 ) was used as a material-coated steel sheet, and an ethanol solution in which an inorganic salt of ethyl silicate and aluminum having the composition shown in Table 1 was dissolved was used. The composition was applied by a roll coater and subjected to a heat treatment at a heating temperature of 100 ° C. by a hot-air drying furnace to form an Al—Si-based chemical conversion treatment film. The adhesion amount of this film was adjusted by the dilution ratio of the processing solution, and the total amount was 100 mg / m 2 in terms of Si and Al. Then
A lubricating layer was formed on the Al-Si-based chemical conversion coating film by the following four methods to prepare test materials. The lubricating properties (coefficient of friction) and corrosion resistance of each of the supplied materials were measured and evaluated.
Table 1 shows the results.
【００１８】［潤滑層］ （本発明条件）；ブチルセルソルブ中に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
系化成処理皮膜を形成させた亜鉛めっき鋼板を浸漬し、
乾燥した。 （本発明条件）；ブチルセルソルブ中に１−ドデカン
チオール：５ミリモルを加えた溶液中にＡｌ−Ｓｉ系化
成処理皮膜を形成させた亜鉛めっき鋼板を浸漬し、乾燥
した。 （本発明条件）；１，３，５−トリアジン−２，４，
６−トリチオール：５ミリモルを加えた水溶液中にＡｌ
−Ｓｉ系化成処理皮膜を形成させた亜鉛めっき鋼板を浸
漬し、乾燥した。 （比較条件）；市販の速乾油Ｇ６２１１（日本工作油
製）をＡｌ−Ｓｉ系化成処理皮膜を形成させた亜鉛めっ
き鋼板に塗布した。[Lubrication layer] (Conditions of the present invention); Al-Si in a solution obtained by adding 5 mmol of 1-octadecanethiol to butyl cellosolve
Dipped galvanized steel sheet with a chemical conversion coating
Dried. (Conditions of the present invention); A galvanized steel sheet on which an Al-Si-based chemical conversion coating was formed was immersed in a solution obtained by adding 5 mmol of 1-dodecanethiol to butyl cellosolve, and dried. (Conditions of the invention); 1,3,5-triazine-2,4
6-trithiol: Al in an aqueous solution containing 5 mmol
A galvanized steel sheet on which a Si-based chemical conversion coating was formed was immersed and dried. (Comparative conditions); Commercially available quick-drying oil G6211 (manufactured by Nippon Kogyo Oil Co., Ltd.) was applied to a galvanized steel sheet on which an Al-Si-based chemical conversion coating was formed.
【００１９】潤滑性は、測定サンプルをＳＫＤ１１で作
製した治具の間に挾み、押さえ荷重Ｗ＝０．８ｋｇｆ／
ｍｍ2（引き抜き速度：２００ｍｍ／ｍｉｎ）で平面摺
動試験を行った際の引き抜き荷重Ｐを測定し、これを動
摩擦係数（＝Ｐ／（Ｗ×２））に換算し、潤滑性の評価
とした。耐食性は、速乾油を塗布した比較例の速乾油が
自然乾燥した後の耐食性と比較するため、上記各供試材
とも作製してから７日間エージングを行ってから塩水噴
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。The lubricating property was measured by sandwiching the measurement sample between jigs made of SKD11, and pressing force W = 0.8 kgf /
mm 2 (drawing speed: 200 mm / min), a pulling load P was measured when a plane sliding test was performed, and this was converted into a kinetic friction coefficient (= P / (W × 2)) to evaluate the lubricity. did. In order to compare the corrosion resistance of the quick drying oil of the comparative example to which the quick drying oil was applied after the natural drying, the specimens were aged for 7 days after being made with each of the test materials, and then subjected to a salt spray test (JIS Z 2371) and the area ratio of white rust was 10
% Was evaluated by the test time which was suppressed to less than%.
【００２０】表１によれば、本発明例である実施例３〜
実施例７、実施例９〜１２はいずれも優れた耐食性と潤
滑性を示している。これに対してＡｌ−Ｓｉ系化成処理
皮膜のＡｌ／（Ａｌ＋Ｓｉ）のモル比が０．１０未満で
ある実施例１、実施例２は耐食性、潤滑性がともに著し
く劣り、また、Ａｌ／（Ａｌ＋Ｓｉ）のモル比が０．１
０〜０．７５であっても本発明の上層皮膜の代りに速乾
油を塗布した実施例８、実施例１３は潤滑性が著しく劣
っている。According to Table 1, Examples 3 to 5 of the present invention are shown.
Examples 7 and 9 to 12 all show excellent corrosion resistance and lubricity. On the other hand, in Examples 1 and 2 in which the Al / (Al + Si) molar ratio of the Al—Si-based chemical conversion treatment film was less than 0.10, both the corrosion resistance and the lubricity were extremely poor, and Al / (Al + Si). ) Is 0.1
Even in the case of 0 to 0.75, the lubricating properties of Examples 8 and 13 in which quick drying oil was applied instead of the upper layer film of the present invention were remarkably poor.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】以上述べた本発明の亜鉛系めっき鋼板
は、クロメート処理を施さなくても優れた耐食性を有
し、しかも従来の速乾油の潤滑性能を超える高度の潤滑
性を有している。The zinc-coated steel sheet of the present invention described above has excellent corrosion resistance even without being subjected to chromate treatment, and has a high degree of lubricity exceeding the lubricating performance of conventional quick-drying oil. I have.
Claims (2)
テルとアルミニウムの無機塩とを、ケイ酸エステル中の
Ｓｉ及びアルミニウムの無機塩中のＡｌ換算でのＡｌ／
（Ａｌ＋Ｓｉ）のモル比で０．１０〜０．７５の範囲で
含有する溶液を塗布し、加熱乾燥させて形成された化成
処理皮膜を有し、その上層に、チオール化合物と前記化
成処理皮膜の一部との反応生成物であるメルカプチド化
合物からなる皮膜、またはチオール化合物及び該チオー
ル化合物と前記化成処理皮膜の一部との反応生成物であ
るメルカプチド化合物からなる皮膜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. A method in which a silicate ester and an inorganic salt of aluminum are coated on the surface of a zinc-based plated steel sheet with Al / Si in terms of Al in inorganic salts of Si and aluminum in the silicate ester.
It has a chemical conversion coating formed by applying a solution containing a molar ratio of (Al + Si) in the range of 0.10 to 0.75 and drying by heating, and has a thiol compound and the chemical conversion coating on the upper layer. Corrosion resistance characterized by having a coating comprising a mercaptide compound which is a reaction product with a part, or a coating comprising a thiol compound and a mercaptide compound which is a reaction product of the thiol compound and a part of the chemical conversion coating. Galvanized steel sheet with excellent lubricity.
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
アルキルチオール化合物と化成処理皮膜の一部との反応
生成物であることを特徴とする請求項１に記載の耐食性
と潤滑性に優れた亜鉛系めっき鋼板。2. The mercaptide compound is a reaction product of an alkylthiol compound having a thiol group at the terminal or both ends of a linear alkyl group having 8 or more carbon atoms and a part of a chemical conversion coating. Item 4. A galvanized steel sheet excellent in corrosion resistance and lubricity according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17305096A JPH101786A (en) | 1996-06-12 | 1996-06-12 | Galvanized steel sheet excellent in corrosion resistance and lubricity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17305096A JPH101786A (en) | 1996-06-12 | 1996-06-12 | Galvanized steel sheet excellent in corrosion resistance and lubricity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH101786A true JPH101786A (en) | 1998-01-06 |
Family
ID=15953293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17305096A Pending JPH101786A (en) | 1996-06-12 | 1996-06-12 | Galvanized steel sheet excellent in corrosion resistance and lubricity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH101786A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1568800A1 (en) * | 2004-02-25 | 2005-08-31 | Posco | Method of protecting metals from corrosion using thiol compounds |
| JP2006086113A (en) * | 2004-08-18 | 2006-03-30 | Yazaki Corp | Low insertion-force connector terminal, its manufacturing method, and board for low insertion-force connector terminal |
| EP3656890A4 (en) * | 2017-07-19 | 2021-06-09 | Okuno Chemical Industries Co., Ltd. | Treatment solution for film formation |
-
1996
- 1996-06-12 JP JP17305096A patent/JPH101786A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1568800A1 (en) * | 2004-02-25 | 2005-08-31 | Posco | Method of protecting metals from corrosion using thiol compounds |
| US7524535B2 (en) * | 2004-02-25 | 2009-04-28 | Posco | Method of protecting metals from corrosion using thiol compounds |
| JP2006086113A (en) * | 2004-08-18 | 2006-03-30 | Yazaki Corp | Low insertion-force connector terminal, its manufacturing method, and board for low insertion-force connector terminal |
| JP4592532B2 (en) * | 2004-08-18 | 2010-12-01 | 矢崎総業株式会社 | Low insertion force connector terminal, manufacturing method thereof, and low insertion force connector terminal board |
| EP3656890A4 (en) * | 2017-07-19 | 2021-06-09 | Okuno Chemical Industries Co., Ltd. | Treatment solution for film formation |
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