JP2003073851A - Galvanized steel sheet superior in heat resistance and corrosion resistance - Google Patents
Galvanized steel sheet superior in heat resistance and corrosion resistanceInfo
- Publication number
- JP2003073851A JP2003073851A JP2001264728A JP2001264728A JP2003073851A JP 2003073851 A JP2003073851 A JP 2003073851A JP 2001264728 A JP2001264728 A JP 2001264728A JP 2001264728 A JP2001264728 A JP 2001264728A JP 2003073851 A JP2003073851 A JP 2003073851A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- component
- heat resistance
- galvanized 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.)
- Withdrawn
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、６価クロムを含ま
ないことで環境負荷を軽減し、かつ無機系成分を主体と
することにより耐熱用途にも使用できる化成皮膜を被覆
したＺｎ系めっき鋼板に関するものである。TECHNICAL FIELD The present invention relates to a Zn-based plated steel sheet coated with a chemical conversion coating which contains no hexavalent chromium to reduce the environmental load, and is mainly composed of an inorganic component and can be used for heat resistant applications. It is about.
【０００２】[0002]
【従来の技術】亜鉛系めっき鋼板は、海水等の塩分を含
む雰囲気または高温多湿の雰囲気では、表面に白錆が発
生し外観を著しく損ねたり、素地鉄面に対する防錆力が
低下したりする。白錆発生防止には、従来よりクロメー
ト系の防錆処理が多用されており、例えば特開平３−１
３１３７０号公報には、オレフィン−α，β−エチレン
性不飽和カルボン酸共重合体樹脂ディスパージョンに水
分散性クロム化合物と水分散性シリカを含有させた樹脂
系処理が開示されている。2. Description of the Related Art Zinc-based galvanized steel sheets have white rust on the surface and significantly impair their appearance in an atmosphere containing salt such as seawater or in an atmosphere of high temperature and high humidity, and the rust preventive power against the base iron surface is lowered. . To prevent the occurrence of white rust, a chromate-based rust preventive treatment has been frequently used, for example, Japanese Patent Laid-Open No. 3-1.
Japanese Patent No. 31370 discloses a resin-based treatment in which an olefin-α, β-ethylenically unsaturated carboxylic acid copolymer resin dispersion contains a water-dispersible chromium compound and water-dispersible silica.
【０００３】しかしながら、上記のようなクロム含有樹
脂系処理といえども、その耐食性は、必ずしも十分では
なく、塩水や高温多湿の雰囲気に長時間晒されると白錆
が発生する。近年では６価クロムを含まない環境汚染の
ない処理剤の要望も高まっている。一方、特開平３−１
３１３７０号公報、特開平８−２３９７７６号公報等の
クロムを使用しない処理皮膜が報告されている。本発明
者らも特願平１１−１０４８９２号公報でＺｎ系めっき
を対象としたものではないが、クロムを使用しない皮膜
を得ている。しかし、大概、有機樹脂との複合処理であ
り、耐熱用途には使用しづらい課題があった。However, even with the above chromium-containing resin-based treatment, its corrosion resistance is not always sufficient, and white rust occurs when it is exposed to salt water or a hot and humid atmosphere for a long time. In recent years, there has been an increasing demand for a treatment agent containing no hexavalent chromium and having no environmental pollution. On the other hand, Japanese Patent Laid-Open No. 3-1
There are reports of treatment films that do not use chromium, such as Japanese Patent No. 31370 and Japanese Patent Laid-Open No. 8-239776. The present inventors have also obtained a coating that does not use chromium, although it is not intended for Zn-based plating in Japanese Patent Application No. 11-104892. However, it is a composite treatment with an organic resin in most cases, and there is a problem that it is difficult to use for heat resistant applications.
【０００４】[0004]
【発明が解決しようとする課題】耐熱用途に使用する、
および最近の家電業界で指向されている無塗油プレス用
途までの適用を考えると、耐熱性がある無機系皮膜であ
りながら潤滑性に優れ、かつ、耐食性も従来のクロメー
トと同等の特性を有する化成皮膜を被覆したＺｎ系めっ
き鋼板であることが要求される。To be used for heat resistance,
Considering the application to oilless presses, which is being aimed at in the home electric appliances industry recently, it is an inorganic film with heat resistance, yet it has excellent lubricity and corrosion resistance equivalent to that of conventional chromate. It is required to be a Zn-based plated steel sheet coated with a chemical conversion film.
【０００５】[0005]
【課題を解決するための手段】環境負荷物質として問題
視されているのは６価クロムであり、３価クロムの弊害
はないことは従来から知られている。そこで、６価クロ
ムには劣るが防食性を有する３価クロムを主成分とし、
６価クロムに比較して低下する防食性を補完するために
水分散性シリカや一部の硝酸金属塩を併用添加する。ま
た、無機皮膜は潤滑性に乏しく、そのため無塗油プレス
には適応できない場合が多いが、本発明ではワックスを
潤滑付与成分として皮膜に含有させることを検討した。
その結果、無機系皮膜で耐熱性があり、かつ、従来クロ
メート並の耐食性と無塗油プレス可能な化成皮膜を処理
したＺｎ系めっき鋼板を得た。Hexavalent chromium has been regarded as a problem as an environmentally hazardous substance, and it has been conventionally known that trivalent chromium does not have a harmful effect. Therefore, the main component is trivalent chromium, which is inferior to hexavalent chromium but has corrosion resistance,
Water-dispersible silica and some metal nitrate salts are added together in order to complement the anticorrosion property, which is lower than that of hexavalent chromium. Further, although the inorganic film has poor lubricity and is often not applicable to the oilless press, in the present invention, inclusion of wax as a lubrication-imparting component in the film was examined.
As a result, a Zn-plated steel sheet having an inorganic coating, heat resistance, and corrosion resistance comparable to that of conventional chromate, and a non-oil pressable chemical conversion coating, was obtained.
【０００６】即ち、本発明は、３価クロム化合物（Ａ）
と、水分散性シリカ（Ｂ）と、潤滑性付与剤（Ｃ）と、
水とを含有する化成皮膜を被覆したことを特徴とするＺ
ｎ系めっき鋼板に関するものである。化成皮膜処理液の
全固形分１００重量％に対する成分（Ｂ）の固形分の割
合が１０〜９０重量％である事が好ましい。追加成分と
してアルカリ土類金属、Ｃｏ、Ｎｉ、Ｆｅ、Ｚｒおよび
Ｔｉからなる群から選ばれる少なくとも１種の硝酸金属
塩（Ｄ）を含むことが好ましい。また、追加成分として
ホスホン酸またはホスホン酸化合物（Ｅ）を含むことが
好ましい。また、本発明の表面処理皮膜をＺｎめっきお
よびＺｎ合金めっきからなる所謂Ｚｎ系めっき鋼板表面
に塗布後乾燥させ、乾燥皮膜重量で５〜１００ｍｇ／ｍ
2の皮膜を有するＺｎ系めっき鋼板に関するものであ
る。That is, the present invention is a trivalent chromium compound (A)
A water-dispersible silica (B), a lubricity imparting agent (C),
Z characterized by being coated with a chemical conversion film containing water
The present invention relates to an n-based plated steel sheet. The ratio of the solid content of the component (B) to the total solid content of 100% by weight of the chemical conversion coating solution is preferably 10 to 90% by weight. As an additional component, it is preferable to contain at least one nitrate metal salt (D) selected from the group consisting of alkaline earth metals, Co, Ni, Fe, Zr and Ti. Further, it is preferable to include phosphonic acid or the phosphonic acid compound (E) as an additional component. Further, the surface-treated film of the present invention is applied to a so-called Zn-based plated steel plate surface made of Zn plating and Zn alloy plating and then dried, and the dry film weight is 5 to 100 mg / m 2.
The present invention relates to a Zn-based plated steel sheet having a film of 2 .
【０００７】[0007]
【発明の実施の形態】以下に本発明の構成を詳細に説明
する。本発明の第１の特徴は、成分（Ａ）３価クロム化
合物を含有することにある。３価クロムの化合物として
は特に限定するものではないが、硫酸クロム（ＩＩ
Ｉ）、硝酸クロム（ＩＩＩ）、重リン酸クロム（ＩＩ
Ｉ）、フッ化クロム（ＩＩＩ）、ハロゲン化クロム（Ｉ
ＩＩ）、などが挙げられる。また、成分（Ａ）の本発明
水系金属表面処理剤中への配合量は特に限定されない。BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below. A first feature of the present invention is that it contains a trivalent chromium compound as the component (A). Although the compound of trivalent chromium is not particularly limited, chromium sulfate (II
I), chromium (III) nitrate, chromium diphosphate (II
I), chromium (III) fluoride, chromium halide (I
II), and the like. The amount of component (A) to be added to the water-based metal surface treatment agent of the present invention is not particularly limited.
【０００８】本発明で使用される成分（Ｂ）水分散性シ
リカとしては、コロイダルシリカ、気相シリカがある。
コロイダルシリカとしては、特に限定するものではない
が、スノーテックスＣ、スノーテックスＯ、スノーテッ
クスＮ、スノーテックスＳ、スノーテックスＵＰ、スノ
ーテックスＰＳ−Ｍ、スノーテックスＰＳ−Ｌ、スノー
テックス２０、スノーテックス３０、スノーテックス４
０（何れも日産化学工業製）、などが挙げられる。気相
シリカとしては、特に限定するものではないが、アエロ
ジル５０、アエロジル１３０、アエロジル２００、アエ
ロジル３００、アエロジル３８０、アエロジルＴＴ６０
０、アエロジルＭＯＸ８０、アエロジルＭＯＸ１７０
（何れも日本アエロジル製）、などが挙げられる。The component (B) water-dispersible silica used in the present invention includes colloidal silica and vapor phase silica.
The colloidal silica is not particularly limited, but it is Snowtex C, Snowtex O, Snowtex N, Snowtex S, Snowtex UP, Snowtex PS-M, Snowtex PS-L, Snowtex 20, Snowtex. Tex 30, Snowtex 4
0 (both manufactured by Nissan Chemical Industries, Ltd.) and the like. The vapor phase silica is not particularly limited, but is Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT60.
0, Aerosil MOX80, Aerosil MOX170
(All manufactured by Nippon Aerosil), and the like.
【０００９】本発明で使用される成分（Ｃ）潤滑性付与
剤としては、ポリオレフィン系ワックス、フッ素系ワッ
クス、パラフィン系ワックスのうちの１種または２種以
上を使用することにより表面の摩擦係数を低減すること
により潤滑性を付与し、かじり等を防止して無塗油プレ
ス加工性、しごき加工性を向上させる作用を有してい
る。このような潤滑性付与剤としては得られる皮膜に潤
滑性を付与できるものであればよいが、ポリエチレン、
ポリプロピレンなどのポリオレフィン系、ポリテトラフ
ルオロエチレン、ポリクロロトリフルオロエチレン、ポ
リフッ化ビニリデン、ポリフッ化ビニルなどのフッ素
系、パラフィン系のうち１種または２種以上からなるも
のが好ましい。As the component (C) lubricity imparting agent used in the present invention, one or more of polyolefin wax, fluorine wax and paraffin wax are used to improve the friction coefficient of the surface. By reducing the amount, lubricity is imparted to prevent galling and the like, and has an effect of improving oilless press workability and ironing workability. As such a lubricity-imparting agent, any agent can be used as long as it can impart lubricity to the obtained film.
It is preferable to use one or two or more selected from polyolefin-based materials such as polypropylene, fluorine-based materials such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride, and paraffin-based materials.
【００１０】また、成分（Ｂ）と（Ｃ）中の重量比
（Ｂ）／（Ｃ）は、５／９５〜９５／５の範囲であるこ
とが好ましい。更に、好ましくは７０／３０〜９０／１
０の範囲である。（Ｂ）／（Ｃ）の比が５／９５未満も
しくは９５／５を超える場合には、プレス加工性、しご
き加工性のレベルが不十分であるため好ましくない。成
分（Ａ）〜（Ｃ）の全固形分１００重量％に対する成分
（Ｂ）の固形分の割合は、１０〜９０重量％に制御する
ことが必要で、好ましくは２０〜８０重量％である。成
分（Ａ）〜（Ｃ）の全固形分１００重量％に対する成分
（Ｂ）の固形分の割合が１０重量％未満の場合は、得ら
れる皮膜の耐食性および塗装性が劣るため好ましくな
い。The weight ratio (B) / (C) in the components (B) and (C) is preferably in the range of 5/95 to 95/5. Furthermore, preferably 70/30 to 90/1
The range is 0. When the ratio of (B) / (C) is less than 5/95 or exceeds 95/5, the press workability and the ironing workability are insufficient, which is not preferable. The ratio of the solid content of the component (B) to 100% by weight of the total solid content of the components (A) to (C) needs to be controlled to 10 to 90% by weight, and preferably 20 to 80% by weight. When the ratio of the solid content of the component (B) is less than 10% by weight based on 100% by weight of the total solid content of the components (A) to (C), the resulting film has poor corrosion resistance and coatability, which is not preferable.
【００１１】一方、成分（Ａ）〜（Ｃ）の全固形分１０
０重量％に対する成分（Ｂ）の固形分の割合が９０重量
％を超える場合は、耐食性に効果のある成分（Ａ）の絶
対量が少なくなるため耐食性が低下すること、およびプ
レス性低下に繋がるので好ましくない。本発明で更に耐
食性を向上させる目的で使用される成分（Ｄ）の硝酸金
属塩としては特に限定はしないが、Ｍｇ、Ｃａ、Ｂａの
ようなアルカリ土類金属、Ｃｏ、Ｎｉ、Ｆｅ、Ｚｒおよ
びＴｉからなる群から選ばれる少なくとも１種を用いる
のが好ましい。On the other hand, the total solid content of the components (A) to (C) is 10
When the ratio of the solid content of the component (B) to 0% by weight is more than 90% by weight, the absolute amount of the component (A), which has an effect on the corrosion resistance, decreases so that the corrosion resistance decreases and the pressability decreases. It is not preferable. The nitrate metal salt of component (D) used for the purpose of further improving the corrosion resistance in the present invention is not particularly limited, but alkaline earth metals such as Mg, Ca and Ba, Co, Ni, Fe, Zr and It is preferable to use at least one selected from the group consisting of Ti.
【００１２】また、追加成分としてホスホン酸またはホ
スホン酸化合物（Ｅ）を配合することにより、更なる耐
食性、塗装性の向上が可能である。ホスホン酸化合物と
しては特に限定はないが、例えば、メチルジホスホン
酸、アミノトリス（メチレンホスホン酸）、エチリデン
ジホスホン酸、１−ヒドロキシエチリデン−１，１−ジ
ホスホン酸、１−ヒドロキシプロピリデン−１，１−ジ
ホスホン酸、１−ヒドロキシブチリデン−１，１−ジホ
スホン酸、エチルアミノビス（メチレンホスホン酸）、
ドデシルアミノビス（メチレンホスホン酸）、ニトリロ
トリス（メチレンホスホン酸）、エチレンジアミンビス
（メチレンホスホン酸）、エチレンジアミンテトラキス
（メチレンホスホン酸）、ヘキセンジアミンテトラキス
（メチレンホスホン酸）、ジエチレントリアミンペンタ
（メチレンホスホン酸）、或はこれらのアンモニウム
塩、アルカリ金属塩（Ｎａ塩は除く）等、分子中にホス
ホン酸基又はその塩を１以上有するキレート剤が挙げら
れ、それらの酸化体としては、これらホスホン酸系キレ
ート剤の内、その分子中に窒素原子を有するものが酸化
されてＮ−オキシド体となっているものが挙げられる。Further, by adding a phosphonic acid or a phosphonic acid compound (E) as an additional component, it is possible to further improve corrosion resistance and paintability. The phosphonic acid compound is not particularly limited, and examples thereof include methyldiphosphonic acid, aminotris (methylenephosphonic acid), ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1. , 1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid),
Dodecylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), hexenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), Alternatively, chelating agents having one or more phosphonic acid groups or salts thereof in the molecule such as ammonium salts, alkali metal salts (excluding Na salts) thereof, etc. may be mentioned, and their oxidants may be phosphonic acid type chelating agents. Among them, those having a nitrogen atom in the molecule are oxidized to form an N-oxide.
【００１３】成分（Ａ）〜（Ｅ）の全固形分１００重量
％に対する成分（Ｅ）の固形分の割合は、０．１〜２０
重量％が好ましく、より好ましくは０．５〜１０重量％
である。成分（Ａ）〜（Ｅ）の全固形分１００重量％に
対する成分（Ｅ）の固形分の割合が０．１重量％未満の
場合は、耐食性の向上効果が乏しく、一方、２０重量％
を超える場合は耐食性向上効果が飽和するので経済的で
なかったり、塗装性が低下するので好ましくない。The proportion of the solid content of the component (E) relative to 100% by weight of the total solid content of the components (A) to (E) is 0.1 to 20.
Wt% is preferred, more preferably 0.5-10 wt%
Is. When the ratio of the solid content of the component (E) to the total solid content of 100% by weight of the components (A) to (E) is less than 0.1% by weight, the effect of improving the corrosion resistance is poor, while the content of 20% by weight is low.
If it exceeds the range, the corrosion resistance improving effect is saturated, which is not economical or the coating property is deteriorated, which is not preferable.
【００１４】また、本発明の化成処理液をＺｎ系めっき
鋼板表面に塗布後乾燥させ、乾燥皮膜重量で５〜１００
ｍｇ／ｍ2 の皮膜を形成させる。乾燥皮膜重量が５ｍｇ
／ｍ 2 未満の場合は、成型性、耐食性が不十分であるた
め好ましくない。一方 、皮膜重量が１００ｍｇ／ｍ2
を超える場合は、成型性、耐食性の向上効果が飽和する
ため経済的でなかったり、塗装性や溶接性が低下するた
め好ましくない。Further, the chemical conversion treatment liquid of the present invention is plated with Zn-based plating.
After coating on the steel plate surface and drying, the dry film weight is 5-100.
mg / m2 To form a film. Dry film weight is 5mg
/ M 2 If it is less than, moldability and corrosion resistance are insufficient.
Not preferable. On the other hand, the coating weight is 100 mg / m2
If it exceeds, the effect of improving moldability and corrosion resistance will be saturated.
Therefore, it is not economical, and the paintability and weldability deteriorate.
Not preferable.
【００１５】本発明で言うＺｎ系めっき鋼板とは、溶融
めっき、電気めっき、気相めっきなどの何れのめっき法
で得られても良く、Ｚｎめっき単独、あるいはＺｎとＮ
ｉ，Ｃｏ，Ｃｒ，Ａｌ，Ｆｅ，Ｍｇ，Ｍｎ，Ｓｎ，Ｔ
ｉ，Ｓｉの１種または２種以上からなる合金めっきであ
っても良い。これらめっき材料の表面をアルカリ脱脂、
酸洗などで清浄にした後に本発明の化成処理液を塗布乾
燥させるのが好ましい。処理液の塗布方法としては特に
限定するものではないが、ロールコーター法、浸漬法、
静電塗布法などを用いることができる。塗布後の乾燥
は、到達板温度として６０〜２００℃で乾燥させるのが
好ましい。The Zn-based plated steel sheet referred to in the present invention may be obtained by any plating method such as hot dipping, electroplating, vapor phase plating, etc. Zn plating alone or Zn and N.
i, Co, Cr, Al, Fe, Mg, Mn, Sn, T
It may be alloy plating composed of one or more of i and Si. Alkali degreasing on the surface of these plating materials,
It is preferable that the chemical conversion treatment liquid of the present invention is applied and dried after cleaning by pickling or the like. The method for applying the treatment liquid is not particularly limited, but a roll coater method, a dipping method,
An electrostatic coating method or the like can be used. Drying after coating is preferably performed at an ultimate plate temperature of 60 to 200 ° C.
【００１６】[0016]
（１） 供試材（めっき鋼板）
表１に示す成分の鋼を通常の転炉−真空脱ガス処理によ
り溶製し、鋼片とした後、通常の条件で熱間圧延、冷間
圧延、連続焼鈍工程を行い、焼鈍鋼板（０．８ｍｍ）を
得た。この鋼板に電気めっき法にてＺｎめっきを、めっ
き付着量２０ｇ／ｍ2 狙いで行った。また溶融めっき法
でＺｎ−５％Ａｌ，Ｚｎ−５５％Ａｌめっきを、めつき
付着量６０ｇ／ｍ2 行った。更には気相めっき法でＺｎ
−３５％Ｍｇ，Ｚｎ−５％Ｔｉめっきを、めっき付着量
２０ｇ／ｍ2 で行った。
（２） 脱脂処理
上記の各供試材をシリケート系アルカリ脱脂剤のファイ
ンクリーナー４３３６（登録商標；日本パーカライジン
グ（株）製）で脱脂処理（濃度２０ｇ／ｌ、温度６０
℃、２０秒間スプレー）した後、水道水で清浄した。(1) Specimen material (plated steel sheet) After the steel having the components shown in Table 1 was melted by a normal converter-vacuum degassing process to form a slab, hot rolling, cold rolling under normal conditions, A continuous annealing process was performed to obtain an annealed steel plate (0.8 mm). Zn plating was performed on this steel sheet by an electroplating method with the aim of depositing 20 g / m 2 . Zn-5% Al and Zn-55% Al plating was performed by hot dip plating to give a plating adhesion amount of 60 g / m 2 . Furthermore, Zn is vapor-phase plated.
-35% Mg, Zn-5% Ti plating was performed with a coating weight of 20 g / m 2 . (2) Degreasing treatment Each of the above test materials was subjected to a degreasing treatment (concentration 20 g / l, temperature 60 with Fine Cleaner 4336 (registered trademark; manufactured by Nihon Parkerizing Co., Ltd.)) which is a silicate alkaline degreasing agent.
After spraying at ℃ for 20 seconds), it was cleaned with tap water.
【００１７】[0017]
【表１】 [Table 1]
【００１８】（３） 化成処理液の調整
室温にて、表２の３価クロム化合物、表３の水分散性シ
リカ、表４の潤滑性付与剤、表５の硝酸金属塩、表６の
ホスホン酸、及びホスホン酸化合物を順に蒸留水に投入
し、プロペラ攪拌機を用いて攪拌しながら混合し化成処
理液を調整した。本発明例の化成処理液を表７、比較例
の化成処理液を表８に示す。
（４） 化成処理液の塗布
上記にて調整した各化成処理液をバーコーターにて上記
各試験板上に塗布し、２４０℃の雰囲気温度で乾燥し
た。尚、皮膜量（ｇ／ｍ2 ）の調整は化成処理液の固形
分濃度を適宜調整することにより行った。表９に本発明
例および比較例の試験水準および皮膜性能の結果を示
す。(3) Preparation of chemical conversion treatment liquid At room temperature, the trivalent chromium compound of Table 2, the water-dispersible silica of Table 3, the lubricity-imparting agent of Table 4, the nitrate metal salt of Table 5, and the phosphone of Table 6 are prepared. An acid and a phosphonic acid compound were sequentially added to distilled water and mixed with stirring using a propeller stirrer to prepare a chemical conversion treatment liquid. Table 7 shows the chemical conversion treatment solutions of the examples of the present invention, and Table 8 shows the chemical conversion treatment solutions of the comparative examples. (4) Application of chemical conversion treatment liquid Each chemical conversion treatment liquid prepared above was applied onto each of the above test plates by a bar coater and dried at an ambient temperature of 240 ° C. The coating amount (g / m 2 ) was adjusted by appropriately adjusting the solid content concentration of the chemical conversion treatment liquid. Table 9 shows the results of the test levels and coating performances of the examples of the present invention and the comparative examples.
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【表３】 [Table 3]
【００２１】[0021]
【表４】 [Table 4]
【００２２】[0022]
【表５】 [Table 5]
【００２３】[0023]
【表６】 [Table 6]
【００２４】[0024]
【表７】 [Table 7]
【００２５】[0025]
【表８】 [Table 8]
【００２６】〔性能評価項目及び評価方法〕
（１）加工性試験
加工性の評価にはカップ成形試験を行った。絞り比を
２．０から０．０５刻みで変化させ、カップ成形を実施
した。この時には無塗油で行った。加工後のカップ側壁
の外観により評価した。
〔評価基準〕
〇：成形可能で、めっき層の欠陥無し
△：成形可能であるが、めっき層が損傷
×：成形不可能で、成形途中で割れ発生[Performance Evaluation Items and Evaluation Methods] (1) Workability Test A cup molding test was performed to evaluate workability. Cup forming was performed while changing the drawing ratio in increments of 2.0 to 0.05. At this time, no oil was applied. The appearance was evaluated on the side wall of the cup after processing. [Evaluation Criteria] ◯: Moldable, no defects in plating layer △: Moldable, damage to plating layer ×: Unmoldable, cracking occurred during molding
【００２７】（２）耐食性試験
平板（無加工）の状態で、加熱なしと５００℃で１０秒
間加熱処理した場合の２種について、ＪＩＳＺ２３７１
条件により、塩水噴霧試験１６８時間後の錆発生率を測
定した。
〔評価条件〕
試験期間：塩水噴霧１６８時間
〔評価基準〕
◎：白錆発生１０％未満
〇：白錆発生１０％以上５０％未満、または赤錆発生１
０未満
△：白錆発生率５０％以上、または赤錆発生１０％以上
３０％未満
×：赤錆発生率３０％以上(2) Corrosion resistance test JIS Z2371 was carried out on two types of a flat plate (unprocessed) without heating and with heat treatment at 500 ° C. for 10 seconds.
Depending on the conditions, the rust occurrence rate after 168 hours of the salt spray test was measured. [Evaluation conditions] Test period: Salt spray for 168 hours [Evaluation criteria] ⊚: White rust occurrence is less than 10% ◯: White rust occurrence is 10% or more and less than 50%, or red rust occurrence 1
Less than 0 △: White rust occurrence rate of 50% or more, or red rust occurrence of 10% or more and less than 30% ×: Red rust occurrence rate of 30% or more
【００２８】（３）塗装性
寸法７０×１５０ｍｍの試験片にスプレ−塗装を行っ
た。塗料は関西ペイント製白色塗料（アミラックＮｏ１
０００）を使用し、膜厚２０μｍ、焼き付け時間１２０
℃×２０分とした。次に沸騰水中に３０分間浸漬した
後、取出した、２ｍｍ碁盤目を１００マス切った後、テ
−ピングした。テ−ピング後の塗膜剥離状況で評価し
た。
〔評価基準〕
〇：塗膜剥離なし
△：塗膜剥離マス目が１０マス未満
×：塗膜剥離マス目が１０マス以上(3) Paintability A test piece having a dimension of 70 × 150 mm was spray-painted. The paint is white paint made by Kansai Paint (Amilac No. 1
000), film thickness 20 μm, baking time 120
℃ × 20 minutes. Next, after dipping in boiling water for 30 minutes, the 2 mm grids taken out were cut into 100 squares and then taped. Evaluation was made based on the state of peeling of the coating film after taping. [Evaluation Criteria] ◯: No peeling of coating film Δ: Less than 10 squares of peeling coating film ×: 10 or more squares of peeling coating film
【００２９】[0029]
【表９】 [Table 9]
【００３０】〔発明の効果〕以上説明したように、本発
明の化成処理液を塗布乾燥して得られたＺｎ系めっき鋼
板は、加工性、加熱前後の耐食性および塗装性に優れて
おり、かつ、人体および環境に有害な６価クロムを含ま
ないことから、産業上の利用価値は非常に大きい。[Effects of the Invention] As described above, the Zn-plated steel sheet obtained by applying and drying the chemical conversion treatment solution of the present invention is excellent in workability, corrosion resistance before and after heating, and paintability, and Since it does not contain hexavalent chromium, which is harmful to the human body and the environment, it has a great industrial utility value.
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Claims (5)
カ（Ｂ）の無機物成分を主成分とし、更に潤滑性付与成
分（Ｃ）と、水とを含有した化成処理液を被覆処理した
耐熱性と耐食性に優れるＺｎ系めっき鋼板。1. A chemical conversion treatment liquid containing an inorganic component of a trivalent chromium compound (A) and a water-dispersible silica (B) as main components, and further containing a lubricity imparting component (C) and water. Zn-based plated steel sheet with excellent heat resistance and corrosion resistance.
分１００重量％に対する成分（Ｂ）の固形分の割合が１
０〜９０重量％である処理液を被覆処理した耐熱性と耐
食性に優れるＺｎ系めっき鋼板。2. The ratio of the solid content of the component (B) to the total solid content of 100% by weight of the chemical conversion treatment solution according to claim 1 is 1.
A Zn-based plated steel sheet excellent in heat resistance and corrosion resistance, which is coated with a treatment liquid of 0 to 90% by weight.
み、かつその硝酸金属塩中の金属が、アルカリ土類金
属、Ｃｏ、Ｎｉ、Ｆｅ、ＺｒおよびＴｉからなる群から
選ばれる少なくとも１種である、請求項１、２の何れか
１項に記載の耐熱性と耐食性に優れるＺｎ系めっき鋼
板。3. A nitrate metal salt (D) as an additional component, wherein the metal in the nitrate metal salt is at least one selected from the group consisting of alkaline earth metals, Co, Ni, Fe, Zr and Ti. The Zn-based plated steel sheet having excellent heat resistance and corrosion resistance according to any one of claims 1 and 2.
ン酸化合物（Ｅ）を含むものである、請求項１〜３の何
れか１項に記載の耐熱性と耐食性に優れるＺｎ系めっき
鋼板。4. The Zn-plated steel sheet having excellent heat resistance and corrosion resistance according to claim 1, which contains phosphonic acid or a phosphonic acid compound (E) as an additional component.
処理された皮膜が、乾燥皮膜重量で５〜１００ｍｇ／ｍ
2 の皮膜を有することを特徴とする耐熱性と耐食性に優
れるＺｎ系めっき鋼板。5. The coating-treated film according to any one of claims 1 to 4 has a dry film weight of 5 to 100 mg / m 2.
A Zn-based plated steel sheet having excellent heat resistance and corrosion resistance, which is characterized by having the film of 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001264728A JP2003073851A (en) | 2001-08-31 | 2001-08-31 | Galvanized steel sheet superior in heat resistance and corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001264728A JP2003073851A (en) | 2001-08-31 | 2001-08-31 | Galvanized steel sheet superior in heat resistance and corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003073851A true JP2003073851A (en) | 2003-03-12 |
Family
ID=19091286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001264728A Withdrawn JP2003073851A (en) | 2001-08-31 | 2001-08-31 | Galvanized steel sheet superior in heat resistance and corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003073851A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013183644A1 (en) * | 2012-06-04 | 2013-12-12 | ディップソール株式会社 | Trivalent chromium-conversion processing solution containing aluminum-modified colloidal silica |
| JP2017226925A (en) * | 2017-10-05 | 2017-12-28 | ディップソール株式会社 | Trivalent chromium chemical conversion treatment liquid containing aluminum modified colloidal silica |
-
2001
- 2001-08-31 JP JP2001264728A patent/JP2003073851A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013183644A1 (en) * | 2012-06-04 | 2013-12-12 | ディップソール株式会社 | Trivalent chromium-conversion processing solution containing aluminum-modified colloidal silica |
| JP2013249528A (en) * | 2012-06-04 | 2013-12-12 | Dipsol Chemicals Co Ltd | Trivalent chromium-conversion processing solution containing aluminum-modified colloidal silica |
| CN104334770A (en) * | 2012-06-04 | 2015-02-04 | 迪普索尔化学株式会社 | Trivalent chromium-conversion processing solution containing aluminum-modified colloidal silica |
| US9206321B2 (en) | 2012-06-04 | 2015-12-08 | Dipsol Chemicals Co., Ltd. | Trivalent chromium-conversion processing solution containing aluminum-modified colloidal silica |
| JP2017226925A (en) * | 2017-10-05 | 2017-12-28 | ディップソール株式会社 | Trivalent chromium chemical conversion treatment liquid containing aluminum modified colloidal silica |
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