JPH09195063A - White chromate treated steel sheet excellent in corrosion resistance and appearance - Google Patents
White chromate treated steel sheet excellent in corrosion resistance and appearanceInfo
- Publication number
- JPH09195063A JPH09195063A JP432696A JP432696A JPH09195063A JP H09195063 A JPH09195063 A JP H09195063A JP 432696 A JP432696 A JP 432696A JP 432696 A JP432696 A JP 432696A JP H09195063 A JPH09195063 A JP H09195063A
- Authority
- JP
- Japan
- Prior art keywords
- chromate
- steel sheet
- treated steel
- white
- coating
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、亜鉛または亜鉛合
金めっき鋼板表面に、耐食性に優れ、かつ美麗な白色外
観を呈するクロメート皮膜が形成されているクロメート
処理鋼板に関し、無塗装でそのまま自動車や家庭電器製
品の内装・外装部材、あるいは鋼製家具等の外板材等に
使用することのできるクロメート処理鋼板に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chromate-treated steel sheet on which a zinc or zinc alloy-plated steel sheet surface has a chromate film excellent in corrosion resistance and which has a beautiful white appearance. The present invention relates to a chromate-treated steel plate that can be used as an interior / exterior member of an electric appliance or an outer plate material such as steel furniture.
【０００２】[0002]
【従来の技術】従来、自動車、家庭電器製品、建築材料
等には亜鉛または亜鉛合金（以下両者を合わせて亜鉛系
という）めっき鋼板が広く用いられている。これらの亜
鉛系めっき鋼板は、そのままでは耐食性に劣り、また外
観調整のために形成される樹脂塗膜との密着性が不充分
であるため、めっき層上にクロメート処理が施されるこ
とが多い。しかし最近では、樹脂塗膜が施されることな
く無塗装で使用される、いわゆる「裸使用」の機会が増
加している。このため、従来は一次防錆的な役割を果た
すだけで良かったクロメート処理皮膜に対して、耐食性
をさらに向上させる必要があり、例えば、特公昭４２−
１４０５０号や特公昭５２−２８５１号には、クロメー
ト処理液中にシリカゾルや３価のクロムイオンを添加し
て、耐食性を向上させる技術が提案された。2. Description of the Related Art Conventionally, zinc or zinc alloy (hereinafter, both are collectively referred to as zinc-based) plated steel sheets have been widely used for automobiles, household electric appliances, building materials and the like. These zinc-based plated steel sheets are inferior in corrosion resistance as they are, and have insufficient adhesion to the resin coating film formed for appearance adjustment, so that the plating layer is often subjected to chromate treatment. . However, recently, there is an increasing number of opportunities for so-called "naked use" in which a resin coating film is not applied and used without coating. For this reason, it is necessary to further improve the corrosion resistance of the chromate-treated film, which was conventionally good only to play a role of primary rust prevention.
No. 14050 and Japanese Examined Patent Publication No. 52-2851 propose a technique for improving corrosion resistance by adding silica sol or trivalent chromium ions to a chromate treatment liquid.
【０００３】しかし、上記技術を適用したクロメート処
理鋼板では、色調に黄色味が多く、また外観にむらがあ
るため、裸使用でのクロメート処理鋼板の需要の増加に
伴って厳しくなっていくユーザーの要求、すなわち耐食
性向上と外観品質の高級化の両立を満足させることはで
きない。However, since the chromate-treated steel sheet to which the above technique is applied has a lot of yellowish color tone and has an uneven appearance, the demand for the chromate-treated steel sheet for naked use increases with the demand of users. It is not possible to satisfy the requirement, that is, the improvement of corrosion resistance and the enhancement of appearance quality at the same time.
【０００４】そこで、色調や塗装むらの問題点を改善し
た白色外観を呈するクロメート処理鋼板の製造方法が提
案された。例えば、特公平３−６８１１５号には、クロ
ム酸、シリカゾル、りん酸の配合比を特定したクロメー
ト処理液を利用する方法が、また特公平７−３３５８３
号には、クロム酸、シリカゾルと共にカルボン酸および
／またはカルボン酸の誘導体を含有させたクロメート処
理液を用い、１５０℃以上の温度で焼き付け処理を行う
方法が開示されている。Therefore, a method for producing a chromate-treated steel sheet having a white appearance, in which the problems of color tone and coating unevenness are improved, has been proposed. For example, in Japanese Examined Patent Publication No. 3-68115, there is disclosed a method of using a chromate treatment liquid in which the compounding ratio of chromic acid, silica sol and phosphoric acid is specified.
The publication discloses a method of performing a baking treatment at a temperature of 150 ° C. or higher using a chromate treatment liquid containing a carboxylic acid and / or a derivative of a carboxylic acid together with chromic acid and silica sol.
【０００５】しかし、これらの公報に開示された方法で
得られる白色クロメート処理皮膜も厳しくなる一方であ
るユーザー要求を満足する色調は得られておらず、また
製造時の焼き付け温度が高い後者の方法では高温乾燥の
設備が必要なため生産能率が悪くコスト負担が大きいと
いう問題があった。However, the white chromate-treated coatings obtained by the methods disclosed in these publications are becoming stricter, but the color tone satisfying some user's requirements is not obtained, and the baking method at the time of production is high. However, there was a problem that the production efficiency was poor and the cost burden was large because high temperature drying equipment was required.
【０００６】[0006]
【発明が解決しようとする課題】そこで本発明では、耐
食性に優れ、かつ美麗で高級感のある白色外観を呈する
クロメート処理鋼板の提供を課題とするものである。SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a chromate-treated steel sheet which is excellent in corrosion resistance and has a beautiful and high-quality white appearance.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決し得た本
発明の耐食性および外観に優れた白色クロメート処理鋼
板は、亜鉛または亜鉛合金めっき鋼板の表面にクロメー
ト皮膜が形成されているクロメート処理鋼板であって、
クロメート皮膜は、コロイダルシリカと、３個のメトキ
シ基を有するシランカップリング剤が含まれたクロメー
ト処理液を亜鉛または亜鉛合金めっき鋼板表面に塗布し
て乾燥することによって該皮膜の付着量が金属Ｃｒ換算
で片面当たり５〜１００ｍｇ／ｍ2 になる様に形成され
ており、クロメート処理前の亜鉛または亜鉛合金めっき
鋼板の６０°鏡面光沢度をＧ0、クロメート処理後の鋼
板の６０°鏡面光沢度をＧ1 としたとき、Ｇ0 、Ｇ1 が
下記式（１）および（２）を満足するところに要旨を有
するものである。 ４０．０≦Ｇ0 ≦１５０．０ …（１） ０．４Ｇ0 ≦Ｇ1 …（２）The white chromate-treated steel sheet excellent in corrosion resistance and appearance according to the present invention which can solve the above-mentioned problems is a chromate-treated steel sheet in which a chromate film is formed on the surface of a zinc or zinc alloy plated steel sheet. And
The chromate film is formed by applying a chromate treatment liquid containing colloidal silica and a silane coupling agent having three methoxy groups to the surface of a zinc or zinc alloy plated steel sheet and drying it so that the amount of adhesion of the film is metal Cr. It is formed so that it will be 5 to 100 mg / m 2 per one side, and the 60 ° specular gloss of the zinc or zinc alloy plated steel sheet before chromate treatment is G 0 , and the 60 ° specular gloss of the steel sheet after chromate treatment is the when the G 1, and has a gist where the G 0, G 1 satisfies the following formula (1) and (2). 40.0 ≦ G 0 ≦ 150.0 (1) 0.4G 0 ≦ G 1 (2)
【０００８】本発明において、コロイダルシリカの平均
粒径が１０〜５０ｎｍであること、クロメート処理液中
のコロイダルシリカおよびシランカップリング剤が、ク
ロム酸換算値１に対して、コロイダルシリカは１．０〜
１０．０、シランカップリング剤は０．５〜５．０含ま
れていること、クロメート処理液中のクロムの還元率：
Ｃｒ3+／（Ｃｒ3+＋Ｃｒ6+）が０．１〜０．５であるこ
と、クロメート処理液が、さらに、クロム酸換算値１に
対して０．０５〜０．５０のりん酸化合物を含有するこ
と、はいずれも好ましい実施態様である。In the present invention, the average particle size of the colloidal silica is 10 to 50 nm, and the colloidal silica and the silane coupling agent in the chromate treatment liquid have a chromic acid conversion value of 1 and a colloidal silica content of 1.0. ~
10.0, the silane coupling agent is contained in 0.5 to 5.0, and the reduction rate of chromium in the chromate treatment liquid:
Cr 3+ / (Cr 3+ + Cr 6+ ) is 0.1 to 0.5, and the chromate treatment liquid is a phosphoric acid compound of 0.05 to 0.50 with respect to a chromic acid conversion value of 1. Containing all is a preferred embodiment.
【０００９】[0009]
【発明の実施の形態】本発明者等は、厳格化するユーザ
ー要求に応えるために鋭意研究した結果、クロメート処
理鋼板の外観が原板（亜鉛系めっき鋼板）の光沢度と密
接に関係していることを見出した。そして、特定の光沢
度を有する原板を用い、クロメート処理後に原板の光沢
度の少なくとも４０％の光沢度を保持すればクロメート
処理後の鋼板の外観が優れたものになること、およびク
ロメート処理液中におけるコロイダルシリカとシランカ
ップリング剤の併用が、耐食性に優れ、しかも美しい外
観の白色皮膜の形成に効果的であることを知見して、本
発明を完成させたものである。以下、本発明を詳細に説
明する。DETAILED DESCRIPTION OF THE INVENTION As a result of intensive studies conducted by the present inventors in order to meet stricter user requirements, the appearance of a chromate-treated steel sheet is closely related to the glossiness of a base sheet (zinc-based plated steel sheet). I found that. Then, if a master plate having a specific glossiness is used and a glossiness of at least 40% of the glossiness of the master plate is maintained after the chromate treatment, the appearance of the steel sheet after the chromate treatment will be excellent, and in the chromate treatment liquid. The present inventors have completed the present invention by finding that the combined use of colloidal silica and a silane coupling agent in 1) is effective in forming a white film having excellent corrosion resistance and a beautiful appearance. Hereinafter, the present invention will be described in detail.
【００１０】まず、本発明において原板として用いられ
る亜鉛または亜鉛合金めっき鋼板は、その６０°鏡面光
沢度Ｇ0 が下記式（１）を満足しなければならない。 ４０．０≦Ｇ0 ≦１５０．０ …（１） コロイダルシリカがクロメート処理鋼板表面に入射する
光を拡散反射させて皮膜を白色化するのであるが、この
とき原板の光沢度Ｇ0 が１５０．０を超えていると、原
板自体は黒っぽく見えるため、白色を呈するクロメート
皮膜を原板上に形成しても、白色化の効果が相殺されて
しまって、高級感のある白色外観を得ることができな
い。また光沢度Ｇ0 が４０．０より低い場合には、クロ
メート皮膜の塗布むらが目立ちやすく、コロイダルシリ
カの添加量を増加しても塗布むらを防止することができ
ない。上記範囲の光沢度の原板を用いれば、クロメート
皮膜の白色が生かされ、しかも塗布むらの低減作用が有
効に発揮できるため、上記要件を必須要件として定め
た。First, the 60 ° specular gloss G 0 of the zinc or zinc alloy-plated steel sheet used as the original plate in the present invention must satisfy the following formula (1). 40.0 ≦ G 0 ≦ 150.0 (1) The colloidal silica diffuses and reflects the light incident on the surface of the chromate-treated steel sheet to whiten the coating film. At this time, the gloss G 0 of the original plate is 150. If it exceeds 0, the original plate looks blackish, so even if a white chromate film is formed on the original plate, the whitening effect is canceled out, and a high-quality white appearance cannot be obtained. . When the glossiness G 0 is lower than 40.0, uneven coating of the chromate film is conspicuous, and uneven coating cannot be prevented even if the amount of colloidal silica added is increased. The use of the original plate having the glossiness in the above range makes the white color of the chromate film effective, and moreover, the effect of reducing the coating unevenness can be effectively exhibited.
【００１１】なお亜鉛または亜鉛めっき鋼板としては上
記光沢度の条件を満足するものであれば特に限定されず
使用することができ、溶融めっき法、電気めっき法、蒸
着めっき法等の製造方法によって、純亜鉛めっき、亜鉛
−ニッケル合金めっき、亜鉛−鉄合金めっき、亜鉛−ク
ロム合金めっき等が鋼板上に施されたものを適宜用いれ
ばよい。The zinc or galvanized steel sheet can be used without particular limitation as long as it satisfies the above-mentioned conditions of glossiness, and can be used according to a manufacturing method such as a hot dip plating method, an electroplating method and a vapor deposition plating method. It is appropriate to use pure zinc plating, zinc-nickel alloy plating, zinc-iron alloy plating, zinc-chromium alloy plating, etc., applied to the steel sheet.
【００１２】クロメート処理後の光沢度は、原板の６０
°鏡面光沢度をＧ0 、クロメート処理後の鋼板の６０°
鏡面光沢度をＧ1 としたときに、以下の（２）式を満足
しなければならない。 ０．４Ｇ0 ≦Ｇ1 …（２） クロメート処理鋼板の耐食性向上を意識して皮膜の付着
量を多くしたり、コロイダルシリカの量をあまりに増や
し過ぎると、処理後の光沢度Ｇ1 が原板の光沢度Ｇ0 の
４０％未満となってしまうが、この場合、クロメート処
理鋼板の外観の塗布むらが目立ち高級感が失われてしま
うため、クロメート皮膜形成後の光沢度は原板の少なく
とも４０％維持することが必要である。The glossiness after chromate treatment is 60% of that of the original plate.
° specular gloss of G 0, 60 ° of the steel sheet after the chromate treatment
When the specular gloss is G 1 , the following expression (2) must be satisfied. 0.4G 0 ≦ G 1 (2) If the amount of coating film is increased or the amount of colloidal silica is increased too much in consideration of improving the corrosion resistance of the chromate-treated steel sheet, the gloss G 1 after the treatment will be the same as that of the original plate. The gloss becomes less than 40% of the gloss G 0 , but in this case, the uneven coating on the appearance of the chromate-treated steel sheet is conspicuous and the high-grade feeling is lost. Therefore, the gloss after the chromate film is formed is maintained at least 40% of that of the original plate. It is necessary to.
【００１３】上記クロメート処理後の光沢度保持度合い
と、耐食性のバランスをとるためには、クロメート処理
皮膜の付着量は、鋼板片面当たり５〜１００ｍｇ／ｍ2
（金属Ｃｒ換算）とすべきである。５ｍｇ／ｍ2 より少
ないと、耐食性が発現せず、１００ｍｇ／ｍ2 を超える
と、上記（２）の要件を満足できず、塗布むらが目立ち
しかも黄色味の強い劣った外観の鋼板しか得られないた
めである。In order to balance the degree of gloss retention after the chromate treatment and the corrosion resistance, the amount of the chromate-treated film attached is 5 to 100 mg / m 2 per one side of the steel sheet.
It should be (corresponding to metallic Cr). If it is less than 5 mg / m 2 , corrosion resistance will not be expressed, and if it exceeds 100 mg / m 2 , the requirement of (2) above cannot be satisfied, and only a steel sheet with inconspicuous coating unevenness and a strong yellow tint is obtained. Because there is no.
【００１４】次にクロメート処理液の組成について説明
する。クロメート処理液は、通常無水クロム酸を主体と
した水溶液であるが、本発明では、クロメート処理液中
にコロイダルシリカとシランカップリング剤を共存させ
なければならない。クロメート皮膜中に含まれるコロイ
ダルシリカがクロメート皮膜の耐食性を向上させること
は公知であるが、本発明では、クロメート中に含まれる
コロイダルシリカが、クロメート処理鋼板表面に入射す
る光を拡散反射させ、外観の色調を白色化させると共
に、色調むらを目立ちにくくする効果があることが見出
されたため必須的に用いられる。コロイダルシリカの処
理液中の量は、クロム酸換算値１に対し、１．０〜１
０．０とすることが好ましい。少な過ぎると、白色化効
果や、色調むらを目立たなくさせる効果が発現しない。
しかし１０．０を超えて加えると、得られる皮膜の耐ア
ルカリ性が低下して、耐食性に悪影響を及ぼすことがあ
る。またコロイダルシリカの平均粒径は１０〜５０ｎｍ
であることが好ましい。この範囲の粒径のコロイダルシ
リカを用いると、皮膜の白色化効果と耐食性の両特性が
最も良好になるためである。Next, the composition of the chromate treatment liquid will be described. The chromate treatment liquid is usually an aqueous solution containing chromic anhydride as a main component, but in the present invention, colloidal silica and a silane coupling agent must coexist in the chromate treatment liquid. It is known that the colloidal silica contained in the chromate film improves the corrosion resistance of the chromate film, but in the present invention, the colloidal silica contained in the chromate diffusely reflects the light incident on the surface of the chromate-treated steel plate to give an appearance. It has been found that it has an effect of making the color tone of the white color white and making the color tone unevenness inconspicuous. The amount of colloidal silica in the treatment liquid is 1.0 to 1 with respect to a chromic acid conversion value of 1.
It is preferably 0.0. If the amount is too small, the whitening effect and the effect of making the color unevenness inconspicuous do not appear.
However, if it is added in excess of 10.0, the alkali resistance of the resulting coating may be deteriorated, which may adversely affect the corrosion resistance. The average particle size of colloidal silica is 10 to 50 nm.
It is preferred that This is because when colloidal silica having a particle size in this range is used, both the whitening effect of the film and the corrosion resistance are the best.
【００１５】またシランカップリング剤は、クロメート
処理皮膜の上にさらに施される樹脂皮膜との間の密着性
を改善することを目的として添加されてきたが、無塗装
で使用される機会が増加するに伴い、不必要であると考
えられる。しかしながら、シランカップリング剤は処理
液中のＣｒ6+をＣｒ3+に還元して黄色味を減少させる作
用があること、また、シランカップリング剤とコロイダ
ルシリカとの相互作用によって緻密で強固なクロメート
処理皮膜が形成し、耐食性の向上に寄与することが本発
明者らによって見出されたため、必須成分とした。Further, the silane coupling agent has been added for the purpose of improving the adhesion between the chromate-treated film and the resin film further applied, but the chance of being used without coating increases. Therefore, it is considered unnecessary. However, the silane coupling agent has the effect of reducing Cr 6+ in the treatment liquid to Cr 3+ to reduce the yellowish tint, and the interaction between the silane coupling agent and colloidal silica makes it dense and strong. It was found by the present inventors that a chromate-treated film is formed and contributes to the improvement of corrosion resistance, so it was made an essential component.
【００１６】シランカップリング剤は、メトキシ基また
はエトキシ基と、ビニル基、グリシドキシ基、メタクリ
ロキシ基、アミノ基、メルカプト基等の官能基がアルキ
ル基を介してまたは介さずにＳｉに結合したものであ
る。本発明では、特に、３個のメトキシ基を有するシラ
ンカップリング剤を用いた場合に、黄色味の改善効果と
耐食性の向上効果の両者をバランス良く形成させること
ができるため、公知の種々のシランカップリング剤の中
でも、Ｓｉに３個のメトキシ基が結合したシランカップ
リング剤を用いる。具体例としては、ビニルトリメトキ
シシラン、γ−（メタクリロキシプロピル）トリメトキ
シシラン、γ−グリシドキシプロピルトリメトキシシラ
ン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメ
トキシシラン、γ−メルカプトプロピルトリメトキシシ
ラン等が挙げられ、これらの１種または２種以上を組合
せて用いることができる。The silane coupling agent is a compound in which a methoxy group or an ethoxy group and a functional group such as a vinyl group, a glycidoxy group, a methacryloxy group, an amino group or a mercapto group are bonded to Si with or without an alkyl group. is there. In the present invention, in particular, when a silane coupling agent having three methoxy groups is used, it is possible to form both a yellow tint improving effect and a corrosion resistance improving effect in a well-balanced manner. Among the coupling agents, a silane coupling agent in which 3 methoxy groups are bonded to Si is used. Specific examples include vinyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-mercaptopropyl. Examples thereof include trimethoxysilane, and these can be used alone or in combination of two or more.
【００１７】シランカップリング剤は、クロメート処理
液中、クロム酸換算値１に対して０．５〜５．０の範囲
で用いることが好ましい。少な過ぎると、黄色味の低減
効果と耐食性の向上効果が発現しない。また、５．０を
超えて添加してもこれらの作用効果が飽和してしまうた
め、経済面から考えると５．０以下とすることが好まし
い。The silane coupling agent is preferably used in the chromate treatment liquid in a range of 0.5 to 5.0 with respect to a chromic acid conversion value of 1. If it is too small, the effect of reducing the yellow tint and the effect of improving the corrosion resistance do not appear. Further, even if added in excess of 5.0, these functions and effects are saturated, so from the economical point of view, it is preferable to set it to 5.0 or less.
【００１８】上記の様にシランカップリング剤とコロイ
ダルシリカを併用することによって、耐食性に優れ、し
かも高級感のある美麗な白色外観のクロメート処理鋼板
が得られるが、安定性良く、しかも黄色味のない皮膜を
得るためには、クロメート処理液中のクロムの還元率：
Ｃｒ3+／（Ｃｒ3+＋Ｃｒ6+）を０．１〜０．５に調整す
ることが好ましい。Ｃｒ3+が０．１より少ないと、シラ
ンカップリング剤によるＣｒ6+→Ｃｒ3+の還元効果を加
味したとしても、Ｃｒ3+が少ないため、皮膜の黄色味を
低減させることが難しい。しかしＣｒ3+が０．５を超え
ると、処理液の安定性が低下していくため、上記範囲に
調整することが望まれる。Ｃｒ3+を上記範囲に調整する
方法は、特に限定されないが、エタノール、メタノー
ル、しゅう酸、澱粉、蔗糖等の公知の還元剤を加えて行
えば良い。By using a silane coupling agent and colloidal silica in combination as described above, a chromate-treated steel sheet having a beautiful white appearance with excellent corrosion resistance and high quality can be obtained, but it is stable and has a yellowish tint. The reduction rate of chromium in the chromate treatment solution is:
It is preferable to adjust Cr 3+ / (Cr 3+ + Cr 6+ ) to 0.1 to 0.5. When the content of Cr 3+ is less than 0.1, it is difficult to reduce the yellow tint of the film because the content of Cr 3+ is small even if the reduction effect of Cr 6+ → Cr 3+ by the silane coupling agent is added. However, when Cr 3+ exceeds 0.5, the stability of the treatment liquid decreases, so it is desirable to adjust the content within the above range. The method of adjusting Cr 3+ to the above range is not particularly limited, but it may be carried out by adding a known reducing agent such as ethanol, methanol, oxalic acid, starch, sucrose and the like.
【００１９】本発明では、クロメート処理液が、さら
に、クロム酸換算値１に対して０．０５〜０．５０のり
ん酸化合物を含有していることも好ましい実施態様であ
る。りん酸化合物は、クロメート処理皮膜の耐食性、特
に耐アルカリ性の向上に効果があるためである。０．０
５より少ないと耐食性向上効果が発現せず、０．５０を
超えて加えると、皮膜の吸湿性が増して耐食性に悪影響
を与えることがあるので、上記範囲内の量を添加するこ
とが推奨される。りん酸化合物としては、オルトりん酸
や各種の縮合りん酸、あるいはこれらのアンモニウム塩
やアルカリ土類金属塩を用いることができる。In the present invention, it is also a preferred embodiment that the chromate treatment liquid further contains 0.05 to 0.50 of a phosphoric acid compound with respect to a chromic acid conversion value of 1. This is because the phosphoric acid compound is effective in improving the corrosion resistance, especially the alkali resistance of the chromate-treated film. 0.0
If it is less than 5, the effect of improving corrosion resistance does not appear, and if it is added over 0.50, the hygroscopicity of the film may be increased and the corrosion resistance may be adversely affected. Therefore, it is recommended to add an amount within the above range. It As the phosphoric acid compound, orthophosphoric acid, various condensed phosphoric acids, their ammonium salts or alkaline earth metal salts can be used.
【００２０】本発明のクロメート処理鋼板は、これまで
説明した組成のクロメート処理液を亜鉛系めっき鋼板に
塗布し、乾燥することによって製造することができる。
塗布方法は、特に限定されず、公知のロールコーター
法、バーコーター法、エアーナイフ法、スプレーミスト
法、カーテンコーター法等適宜選択すれば良い。塗布後
の乾燥条件は、到達板温度で４０〜１５０℃が好まし
い。４０℃より低い場合には、皮膜の白色化が不充分に
なることがある。１５０℃を超えると、皮膜の耐食性が
劣化すると共に、製造コストが上昇するため好ましくな
い。The chromate-treated steel sheet of the present invention can be produced by applying the chromate-treating solution having the composition described above to a zinc-based plated steel sheet and drying it.
The coating method is not particularly limited and may be appropriately selected from known roll coater method, bar coater method, air knife method, spray mist method, curtain coater method and the like. The drying condition after coating is preferably 40 to 150 ° C. at the ultimate plate temperature. If the temperature is lower than 40 ° C, the whitening of the coating may be insufficient. When the temperature exceeds 150 ° C, the corrosion resistance of the film deteriorates and the manufacturing cost increases, which is not preferable.
【００２１】[0021]
【実施例】以下実施例によって本発明をさらに詳述する
が、下記実施例は本発明を制限するものではなく、前・
後記の趣旨を逸脱しない範囲で変更実施することは全て
本発明の技術範囲に包含される。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention.
【００２２】実施例 スキンパスの圧下条件を種々変更し、６０°鏡面光沢度
が３０．２〜１８０．３の範囲の溶融純亜鉛めっき鋼板
を作成し、原板として用いた。表１に示した組成の７種
類のクロメート処理液をロールコーターで塗布した後、
到達板温８０℃で乾燥・焼付を行った。得られたクロメ
ート処理鋼板は、下記の方法で性能を評価し、測定結果
を表２〜４に示した。Example A hot-dip galvanized steel sheet having a 60 ° specular gloss of 30.2 to 180.3 was prepared by variously changing the skin pass rolling conditions and used as a base sheet. After applying seven types of chromate treatment liquids having the compositions shown in Table 1 with a roll coater,
Drying and baking were carried out at the ultimate plate temperature of 80 ° C. The obtained chromate-treated steel sheet was evaluated for performance by the following method, and the measurement results are shown in Tables 2-4.
【００２３】［皮膜付着量］蛍光Ｘ線分析によってクロ
メート皮膜中のクロム付着量（ｍｇ／ｍ2 ）を求めた。 ［光沢度］ＪＩＳ Ｚ８７４１に準じて、６０°鏡面反
射角における光沢度を、原板（Ｇ 0 ）と、クロメート処
理後（Ｇ1 ）について、日本電色（株）製光沢度計を用
いて測定した。なお表中の光沢度保持率は、Ｇ1 ／Ｇ0
≧０．４のものを○、Ｇ1／Ｇ0 ＜０．４のものを×と
して示した。[Amount of coating film] Black by X-ray fluorescence analysis
Chromium adhesion in mate coating (mg / mTwo ). [Glossiness] In accordance with JIS Z8741, 60 ° mirror opposite
Gloss at the angle of incidence 0 ) And the chromate treatment
After reason (G1 ), Using a gloss meter manufactured by Nippon Denshoku Co., Ltd.
And measured. The gloss retention rate in the table is G1 / G0
≧ 0.4 ○, G1/ G0 <0.4 for x
Shown.
【００２４】［外観むら］クロメート処理鋼板の外観を
目視観察し、クロメート皮膜の塗布むらが目立つかどう
かを中心に評価した。評価基準は、以下の通りである。 ◎：極めて外観良好 ○：比較的外観良好 △：若干外観にむらが目立つ ×：外観むらが著しく目立つ[Appearance unevenness] The appearance of the chromate-treated steel sheet was visually observed to evaluate whether or not the coating unevenness of the chromate film was conspicuous. The evaluation criteria are as follows. ⊚: Extremely good appearance ○: Relatively good appearance Δ: Slightly uneven appearance is noticeable ×: Significantly uneven appearance is noticeable
【００２５】［外観色調］クロメート処理鋼板の外観を
目視観察し、クロメート皮膜の白色下の効果の程度を評
価した。評価基準は、以下の通りである。 ◎：極めて外観良好 ○：比較的外観良好 △：若干暗いかもしくは黒っぽい ×：著しく暗いかもしくは黒っぽい[Appearance Color Tone] The appearance of the chromate-treated steel sheet was visually observed to evaluate the degree of the whitening effect of the chromate film. The evaluation criteria are as follows. ◎: Very good appearance ○: Relatively good appearance △: Slightly dark or darkish ×: Remarkably dark or darkish
【００２６】［耐食性］ＪＩＳ Ｚ２３７１に準じて塩
水噴霧試験を実施し、７２時間後の白錆発生率を下記基
準で評価した。 ○：白錆発生率１％未満 △：白錆発生率１％以上５％未満 ×：白錆発生率５％以上[Corrosion resistance] A salt spray test was carried out according to JIS Z2371, and the white rust occurrence rate after 72 hours was evaluated according to the following criteria. ◯: White rust occurrence rate of less than 1% △: White rust occurrence rate of 1% or more and less than 5% ×: White rust occurrence rate of 5% or more
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【表３】 [Table 3]
【００３０】[0030]
【表４】 [Table 4]
【００３１】[0031]
【発明の効果】本発明のクロメート処理鋼板は、耐食性
に優れ、かつ美麗な白色外観を呈するので、無塗装でそ
のまま自動車や家庭電器製品の内装・外装部材、あるい
は鋼製家具等の外板材等に使用することができる。The chromate-treated steel sheet of the present invention is excellent in corrosion resistance and has a beautiful white appearance. Therefore, it is unpainted as it is as an interior / exterior member of automobiles and household electric appliances, or an outer panel material such as steel furniture. Can be used for
Claims (5)
クロメート皮膜が形成されているクロメート処理鋼板で
あって、 クロメート皮膜は、コロイダルシリカと、３個のメトキ
シ基を有するシランカップリング剤が含まれたクロメー
ト処理液を亜鉛または亜鉛合金めっき鋼板表面に塗布し
て乾燥することによって該皮膜の付着量が金属Ｃｒ換算
で片面当たり５〜１００ｍｇ／ｍ2 になる様に形成され
ており、 クロメート処理前の亜鉛または亜鉛合金めっき鋼板の６
０°鏡面光沢度をＧ0、クロメート処理後の鋼板の６０
°鏡面光沢度をＧ1 としたとき、Ｇ0 、Ｇ1 が下記式
（１）および（２）を満足することを特徴とする耐食性
および外観に優れた白色クロメート処理鋼板。 ４０．０≦Ｇ0 ≦１５０．０ …（１） ０．４Ｇ0 ≦Ｇ1 …（２）1. A chromate-treated steel sheet having a chromate coating formed on the surface of a zinc or zinc alloy plated steel sheet, wherein the chromate coating contains colloidal silica and a silane coupling agent having three methoxy groups. The chromate treatment liquid is applied to the surface of a zinc or zinc alloy plated steel sheet and dried so that the amount of the coating adhered is 5 to 100 mg / m 2 on one side in terms of metal Cr. 6 of zinc or zinc alloy plated steel sheet
0 ° specular gloss G 0 , 60 after chromate treatment
A white chromate-treated steel sheet excellent in corrosion resistance and appearance, characterized in that G 0 and G 1 satisfy the following formulas (1) and (2) when the specular gloss is G 1 . 40.0 ≦ G 0 ≦ 150.0 (1) 0.4G 0 ≦ G 1 (2)
０ｎｍである請求項１に記載の白色クロメート処理鋼
板。2. Colloidal silica having an average particle size of 10 to 5
The white chromate-treated steel sheet according to claim 1, which has a thickness of 0 nm.
およびシランカップリング剤は、クロム酸換算値１に対
してコロイダルシリカが１．０〜１０．０、シランカッ
プリング剤が０．５〜５．０含まれているものである請
求項１または２に記載の白色クロメート処理鋼板。3. The colloidal silica and the silane coupling agent in the chromate treatment liquid are 1.0 to 10.0 for colloidal silica and 0.5 to 5.0 for the silane coupling agent with respect to a chromic acid conversion value of 1. The white chromate-treated steel sheet according to claim 1 or 2, which is included.
Ｃｒ3+／（Ｃｒ3+＋Ｃｒ6+）が０．１〜０．５である請
求項１〜３のいずれかに記載の白色クロメート処理鋼
板。4. The reduction rate of chromium in the chromate treatment liquid:
Cr 3+ / (Cr 3+ + Cr 6+ ) is 0.1-0.5, The white chromate-treated steel plate in any one of Claims 1-3.
換算値１に対して０．０５〜０．５０のりん酸化合物を
含有するものである請求項１〜４のいずれかに記載の白
色クロメート処理鋼板。5. The white chromate according to any one of claims 1 to 4, wherein the chromate treatment liquid further contains 0.05 to 0.50 of a phosphoric acid compound with respect to a chromic acid conversion value of 1. Treated steel plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8004326A JP2943681B2 (en) | 1996-01-12 | 1996-01-12 | White chromate treated steel sheet with excellent corrosion resistance and appearance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8004326A JP2943681B2 (en) | 1996-01-12 | 1996-01-12 | White chromate treated steel sheet with excellent corrosion resistance and appearance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09195063A true JPH09195063A (en) | 1997-07-29 |
| JP2943681B2 JP2943681B2 (en) | 1999-08-30 |
Family
ID=11581336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8004326A Expired - Fee Related JP2943681B2 (en) | 1996-01-12 | 1996-01-12 | White chromate treated steel sheet with excellent corrosion resistance and appearance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2943681B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098384A (en) * | 1999-09-29 | 2001-04-10 | Nisshin Steel Co Ltd | Chromate treating solution and treating method |
| JP2001170557A (en) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | Surface treatment liquid for plated steel plate and treating method therefor |
| JP2005290465A (en) * | 2004-03-31 | 2005-10-20 | Nippon Steel Corp | White chromate treatment method imparting excellent corrosion resistance, fingerprint resistance and weldability and steel sheet subjected to the white chromate treatment |
| JP2010163615A (en) * | 2008-12-31 | 2010-07-29 | Posco | Self-cleaning member, cohydrolysis condensate included therein, and method for producing the condensate |
| JP2012107300A (en) * | 2010-11-18 | 2012-06-07 | Motorashi Seisakusho Co Ltd | Metal surface protective agent, method of manufacturing the same and metal surface treatment method |
-
1996
- 1996-01-12 JP JP8004326A patent/JP2943681B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098384A (en) * | 1999-09-29 | 2001-04-10 | Nisshin Steel Co Ltd | Chromate treating solution and treating method |
| JP2001170557A (en) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | Surface treatment liquid for plated steel plate and treating method therefor |
| JP2005290465A (en) * | 2004-03-31 | 2005-10-20 | Nippon Steel Corp | White chromate treatment method imparting excellent corrosion resistance, fingerprint resistance and weldability and steel sheet subjected to the white chromate treatment |
| JP2010163615A (en) * | 2008-12-31 | 2010-07-29 | Posco | Self-cleaning member, cohydrolysis condensate included therein, and method for producing the condensate |
| JP2012107300A (en) * | 2010-11-18 | 2012-06-07 | Motorashi Seisakusho Co Ltd | Metal surface protective agent, method of manufacturing the same and metal surface treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2943681B2 (en) | 1999-08-30 |
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