JPH05295562A - Method for chromate-treating galvanized steel sheet - Google Patents
Method for chromate-treating galvanized steel sheetInfo
- Publication number
- JPH05295562A JPH05295562A JP12286492A JP12286492A JPH05295562A JP H05295562 A JPH05295562 A JP H05295562A JP 12286492 A JP12286492 A JP 12286492A JP 12286492 A JP12286492 A JP 12286492A JP H05295562 A JPH05295562 A JP H05295562A
- Authority
- JP
- Japan
- Prior art keywords
- chromate
- steel sheet
- chromium
- zinc
- soln
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—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
- C23C22/34—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 containing fluorides or complex fluorides
- C23C22/37—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 containing fluorides or complex fluorides containing also hexavalent chromium compounds
- C23C22/38—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 containing fluorides or complex fluorides containing also hexavalent chromium compounds containing also phosphates
-
- 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
- C23C22/40—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 containing molybdates, tungstates or vanadates
- C23C22/43—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 containing molybdates, tungstates or vanadates containing also hexavalent chromium compounds
-
- 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 & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、亜鉛系めっき鋼板のク
ロメート処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chromate treatment method for zinc-based plated steel sheet.
【０００２】[0002]
【従来の技術】近年、自動車や家電など亜鉛系めっき鋼
板の高防錆性をはじめとする高機能化ならびに低コスト
化に対する市場ニーズはますます高まり、これに呼応し
た新製品の開発研究も最近盛んに行われている。この中
で、亜鉛系めっき鋼板のクロメート処理に対し、より一
層の防錆機能付与と無公害化の観点から、他の性能を低
下させることなく耐クロム溶出性を高めたクロメート処
理鋼板の開発要求が強い。2. Description of the Related Art In recent years, the market needs for high functionality such as high corrosion resistance of zinc-based plated steel sheets for automobiles and home appliances and cost reduction have been increasing, and the research and development of new products in response to this has been recently It is being actively conducted. Among these, from the viewpoint of providing a further anticorrosion function and pollution-free with respect to the chromate treatment of zinc-based plated steel sheets, there is a demand for the development of chromate treated steel sheets with improved chromium elution resistance without degrading other performance. Is strong.
【０００３】クロメート処理液は従来クロム酸または重
クロム酸水溶液からなるものであって、その耐食性確保
のため、クロメート皮膜形成後、酸またはアルカリで処
理された場合に難溶性である皮膜を形成する方法が種々
提案されている。以下、これらの従来技術について説明
する。The chromate treatment liquid has conventionally been composed of an aqueous solution of chromic acid or dichromic acid, and in order to ensure its corrosion resistance, it forms a film which is hardly soluble when treated with an acid or an alkali after forming a chromate film. Various methods have been proposed. Hereinafter, these conventional techniques will be described.
【０００４】亜鉛系めっき鋼板の表面に難溶性クロメー
ト皮膜を形成させる方法として、（Ａ）無水クロム酸−
リン酸−水溶性または水分散性高分子化合物系のクロメ
ート液であって、その処理液中のＣｒ6+がエチレングリ
コールなどの還元剤で７０％以上Ｃｒ3+に還元されたも
のを使用する方法が特開昭５０−１５８５３５号公報
に、（Ｂ）クロメート液成分をクロム酸−クロム酸還元
生成物−シリカゾル系に特定した処理方法が特公昭６１
−５８５２２号公報に、（Ｃ）クロメート処理液中の６
価クロム還元剤としてシランカップリング剤を使用する
ものが特開昭５８−２２３８３号公報ならびに特開昭６
２−８３４７８号公報に示されている。As a method for forming a poorly soluble chromate film on the surface of a zinc-based plated steel sheet, (A) chromic anhydride-
Phosphoric acid - a water-soluble or water-dispersible polymer compounds based chromate solution is used which Cr 6+ in the processing solution is reduced to Cr 3+ 70% or more with a reducing agent such as ethylene glycol The method is disclosed in JP-A-50-158535, and the treatment method in which the chromate solution component (B) is specified as a chromic acid-chromic acid reduction product-silica sol system is disclosed in JP-B-61-61.
JP-A-58522 discloses that (C) 6 in the chromate treatment liquid.
Those using a silane coupling agent as a valent chromium reducing agent are disclosed in JP-A-58-22383 and JP-A-6-62.
No. 2-83478.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、（Ａ）
においては、その実施によって形成されるクロメート皮
膜は高分子を含有するので、難溶性、耐食性、塗装性に
おいて優れているが、処理浴としての寿命が短く、生産
性の高い製造ラインでは安定した性能が得にくいという
安定製造上の欠点があり、（Ｂ）においては、得られた
クロメート皮膜は塗装前のアルカリ洗浄や水洗等で６価
クロムが溶出しやすく、耐食性の低下や排水処理等製造
上の煩雑作業を要するなど問題を有しており、（Ｃ）に
おいては、形成されるクロメート皮膜は何れも塗料密着
性に優れるものの、皮膜にはリン酸を含まないので耐ア
ルカリ性が良くないといった難点を有している。[Problems to be Solved by the Invention] However, (A)
In that, since the chromate film formed by the implementation contains a polymer, it is excellent in poor solubility, corrosion resistance, and paintability, but it has a short life as a treatment bath and stable performance in a production line with high productivity. However, in (B), the chromate film obtained in (B) is prone to the elution of hexavalent chromium by alkali washing or water washing before coating, resulting in reduced corrosion resistance or wastewater treatment. However, in (C), all of the chromate coatings formed have excellent paint adhesion, but the coating does not contain phosphoric acid, so the alkali resistance is poor. have.
【０００６】本発明は、これらの難点を有利に解決する
ためになされたものである。The present invention has been made in order to advantageously solve these problems.
【０００７】[0007]
【課題を解決するための手段】本発明の要旨は、総クロ
ム濃度が５〜３０ｇ／ｌで、かつクロム還元率が４０〜
８０％であり、リン酸１０〜２００ｇ／ｌとフッ酸０．
１〜１．０ｇ／ｌを含有する水系クロメート液を亜鉛系
めっき鋼板表面に塗布し、ついで、乾燥板温が最高到達
板温として５０〜２００℃になるよう乾燥し、直ちに、
冷却媒体として濃度０．５％以上のシランカップリング
剤溶液を用いて冷却し、その表面に片面当たり総クロム
量で５〜１５０ｍｇ／ｍ2 のクロメート皮膜を形成させ
ることを特徴とする亜鉛系めっき鋼板のクロメート処理
方法である。The gist of the present invention is that the total chromium concentration is 5 to 30 g / l, and the chromium reduction rate is 40 to.
80%, phosphoric acid 10-200 g / l and hydrofluoric acid 0.
An aqueous chromate solution containing 1 to 1.0 g / l was applied to the surface of the zinc-based plated steel sheet, and then dried so that the maximum temperature reached was 50 to 200 ° C.
A zinc-based plating characterized in that a silane coupling agent solution having a concentration of 0.5% or more is used as a cooling medium, and a chromate film having a total amount of chromium per surface of 5 to 150 mg / m 2 is formed on the surface thereof by cooling. This is a chromate treatment method for steel sheets.
【０００８】[0008]
【作用】本発明は亜鉛系めっき鋼板表面への水系クロメ
ート液塗布、乾燥、シランカップリング剤溶液を冷却媒
体とした冷却の３工程を連続して行うクロメート処理で
ある。このように処理することにより、亜鉛系めっき鋼
板の表面に難溶性クロメート皮膜を形成させることがで
き、優れた耐食性、塗膜密着性ならびに塗装後耐食性が
発現する。この効果の発現理由は必ずしも明確ではない
が、本発明者等は種々実験検討の結果、亜鉛系めっき鋼
板表面へのクロメート処理に際して、水系クロメート液
の塗布、乾燥後にシランカップリング剤溶液を冷却媒体
として冷却することにより、水系クロメート液の塗布、
乾燥後、空冷もしくは水冷を行う従来の処理方法に比較
し、格段にクロメート皮膜の難溶性が向上することを見
出した。The present invention is a chromate treatment in which three steps of coating an aqueous chromate solution on the surface of a galvanized steel sheet, drying and cooling with a silane coupling agent solution as a cooling medium are continuously performed. By such treatment, a poorly soluble chromate film can be formed on the surface of the zinc-plated steel sheet, and excellent corrosion resistance, coating adhesion and post-coating corrosion resistance are exhibited. Although the reason for the appearance of this effect is not always clear, as a result of various experimental studies, the present inventors have shown that when chromate treatment is applied to the surface of a zinc-based plated steel sheet, application of an aqueous chromate solution, and a silane coupling agent solution as a cooling medium after drying. By cooling as, application of water-based chromate solution,
It was found that the refractory solubility of the chromate film is remarkably improved as compared with the conventional treatment method in which air cooling or water cooling is performed after drying.
【０００９】なお、本発明に適用されるめっき系として
は、電気めっき系において、Ｚｎめっき、ＺｎにＮｉ、
Ｃｒ、Ｆｅからなる合金元素群のうち少なくとも１種を
含むＺｎ系合金めっき鋼板を用いることができる。ま
た、溶融めっき系においては、亜鉛鉄板、Ｚｎ−Ａｌ系
合金めっき鋼板、およびそれらの合金化処理亜鉛めっき
鋼板を適用できる。As the plating system applied to the present invention, in the electroplating system, Zn plating, Zn to Ni,
It is possible to use a Zn-based alloy-plated steel sheet containing at least one kind of alloy element group consisting of Cr and Fe. Further, in the hot-dip galvanizing system, a zinc iron plate, a Zn-Al alloy-plated steel plate, and an alloyed zinc-plated steel plate thereof can be applied.
【００１０】本発明の方法に使用する水系クロメート液
の構成についてまず説明する。First, the constitution of the aqueous chromate solution used in the method of the present invention will be described.
【００１１】水系クロメート液は水を溶媒とするもので
あって、亜鉛系めっき鋼板の耐食性等諸性能を安定して
維持するため総クロム濃度５〜３０ｇ／ｌ、クロム還元
率４０〜８０％とすることが必要である。The aqueous chromate solution uses water as a solvent, and in order to stably maintain various performances such as corrosion resistance of the galvanized steel sheet, the total chromium concentration is 5 to 30 g / l and the chromium reduction rate is 40 to 80%. It is necessary to.
【００１２】総クロム濃度が５ｇ／ｌ未満あるいはクロ
ム還元率が４０％未満では、可溶性の６価クロムが主体
のクロメート皮膜となるため、高耐食性に必要なクロム
が水に抽出されやすくなり、亜鉛系めっき鋼板としての
裸耐食性および塗装後の耐食性寿命の低下を招くととも
に、溶出クロムにより排水処理が必要となるなど品質向
上および生産性の上で効果が小さい。また、総クロム濃
度が３０ｇ／ｌあるいはクロム還元率が８０％を超えて
はクロメート液の粘性が高くなり、かつ、クロメート液
としての安定性が低下するため、クロメート付着量の制
御も困難になる。If the total chromium concentration is less than 5 g / l or the chromium reduction rate is less than 40%, the soluble hexavalent chromium is the main component of the chromate film, so that the chromium required for high corrosion resistance is easily extracted into water, and zinc The bare corrosion resistance as a system-plated steel sheet and the corrosion resistance after coating are shortened, and the wastewater treatment is required due to the eluted chromium, so that the effect on quality improvement and productivity is small. Further, when the total chromium concentration is 30 g / l or the chromium reduction rate exceeds 80%, the viscosity of the chromate solution becomes high and the stability as a chromate solution decreases, so that it becomes difficult to control the chromate adhesion amount. ..
【００１３】なお、クロムの還元については、アルコー
ルや過酸化水素等による方法など公知の方法のいずれで
あってもよい。The reduction of chromium may be performed by any known method such as a method using alcohol or hydrogen peroxide.
【００１４】リン酸は１０〜２００ｇ／ｌとする。リン
酸が１０ｇ／ｌ未満ではクロメート皮膜の耐食性、耐ア
ルカリ性が低下する。また、２００ｇ／ｌを超えるとク
ロメート皮膜の乾燥性が低下するため吸湿しやすくな
り、塗装後の耐食性が低下する。Phosphoric acid is 10 to 200 g / l. If the phosphoric acid content is less than 10 g / l, the corrosion resistance and alkali resistance of the chromate film will deteriorate. On the other hand, if it exceeds 200 g / l, the drying property of the chromate film is lowered, so that it tends to absorb moisture and the corrosion resistance after coating is lowered.
【００１５】フッ酸濃度は０．１〜１．０ｇ／ｌとす
る。このフッ酸の機能は、下地めっき鋼板のめっき表面
に生成してクロメート処理液の均一濡れ性を阻害する酸
化亜鉛や水酸化亜鉛を過不足なく除去してめっき表面と
クロメート処理液との界面反応を適宜に促進し、これに
よって密着性に富む塗布クロメート皮膜を安定して得る
ことにある。The concentration of hydrofluoric acid is 0.1 to 1.0 g / l. The function of this hydrofluoric acid is to remove the zinc oxide and zinc hydroxide, which are generated on the plating surface of the base plated steel sheet and impede the uniform wettability of the chromate treatment solution, in just the right amount and remove the interfacial reaction between the plating surface and the chromate treatment solution. In order to obtain a coated chromate film having a high adhesiveness in a stable manner.
【００１６】フッ酸濃度が０．１ｇ／ｌ未満では、めっ
き表面の酸化亜鉛や水酸化亜鉛を除去することが難し
く、クロメート皮膜としての密着性低下を招いたり、液
はじきが生じてクロメート皮膜の均一形成が難しいな
ど、安定した性能のクロメート処理は難しくなる。ま
た、フッ酸が１．０ｇ／ｌを超えては、過剰なエッチン
グによって下地めっき表面が劣化するのに加え、溶出し
た下地めっき成分がクロメート処理液へ混入し、これが
亜鉛系めっき鋼板としての耐食性低下を招いたり、さら
にはクロメート処理液の寿命を短くするため、処理液の
更新を余儀なくされる等、高生産性ライン下で安定した
性能を得るためにはコストの高騰を招く。When the concentration of hydrofluoric acid is less than 0.1 g / l, it is difficult to remove zinc oxide and zinc hydroxide on the plating surface, which leads to a decrease in adhesion as a chromate film and liquid repellency, resulting in the formation of a chromate film. Chromate treatment with stable performance is difficult due to difficulty in uniform formation. Further, when the hydrofluoric acid exceeds 1.0 g / l, the underlying plating surface is deteriorated by excessive etching, and the eluted underlying plating components are mixed in the chromate treatment liquid, which results in corrosion resistance as a zinc-based plated steel sheet. This leads to a decrease in the working life of the chromate treatment liquid, which necessitates a renewal of the treatment liquid, which leads to an increase in cost in order to obtain stable performance under a high productivity line.
【００１７】前述のごとく調製したクロメート液は、例
えばロールコーターなどで亜鉛系めっき鋼板表面に塗布
すればよい。The chromate solution prepared as described above may be applied to the surface of the zinc-based plated steel sheet with, for example, a roll coater.
【００１８】亜鉛系めっき鋼板表面に水系クロメート液
を所定量塗布した後の乾燥温度は、最高板温として５０
〜２００℃とする。５０℃未満では、クロメート皮膜に
含まれる過剰水分の蒸発乾燥にとどまり、高耐食性化に
必要な空気酸化によるクロメート皮膜の酸化重合を促進
して適宜な網目構造を持つクロメート皮膜は得られ難
く、そのため、密着性、耐クロム溶出性に優れたクロメ
ート皮膜の生成は難しい。また、２００℃を超えては、
クロメート皮膜が持つ結晶水の脱水反応から皮膜が脆化
し、密着性が大きく阻害されるため、耐食性の低下が著
しい。The drying temperature after applying a predetermined amount of the aqueous chromate solution to the surface of the zinc-based plated steel sheet is 50 as the maximum plate temperature.
-200 degreeC. If the temperature is lower than 50 ° C, the excess water contained in the chromate film is limited to evaporation and drying, and it is difficult to obtain a chromate film having an appropriate network structure by accelerating the oxidative polymerization of the chromate film by air oxidation, which is required for high corrosion resistance. , It is difficult to form a chromate film with excellent adhesion and chromium elution resistance. In addition, above 200 ℃,
Due to the dehydration reaction of the water of crystallization that the chromate film has, the film becomes brittle and adhesion is greatly impaired, resulting in a significant decrease in corrosion resistance.
【００１９】なお、本発明にあって、加熱時間について
は特に限定するものではない。In the present invention, the heating time is not particularly limited.
【００２０】本発明の特徴の一つに、水系クロメート液
を塗布、乾燥後の冷却媒体に濃度０．５％以上のシラン
カップリング剤溶液を用いる点が挙げられる。シランカ
ップリング剤として特定はしないが、ビニルトリメトキ
シシラン、γ−シメルカプト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、γ
−グリシドキシプロピルメチルジメトキシシラン、γ−
メタクリロキシプロピルトリメトキシシラン、γ−メタ
クリロキシプロピルメチルジメトキシシランなどが挙げ
られる。これらの１種または２種以上の混合でも良い
が、濃度としては０．５％以上であることが必須であ
る。０．５％未満では難溶性のクロメート皮膜を形成し
ない。シランカップリング剤溶液濃度の上限については
特に定めない。One of the characteristics of the present invention is that a silane coupling agent solution having a concentration of 0.5% or more is used as a cooling medium after coating and drying an aqueous chromate solution. Although not specified as a silane coupling agent, vinyltrimethoxysilane, γ-cymercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like can be mentioned. One kind or a mixture of two or more kinds thereof may be used, but it is essential that the concentration is 0.5% or more. If it is less than 0.5%, a poorly soluble chromate film is not formed. The upper limit of the silane coupling agent solution concentration is not specified.
【００２１】亜鉛系めっき鋼板の表面に形成させるクロ
メート皮膜の付着量は、片面当たり総クロム量で５〜１
５０ｍｇ／ｍ2 とする。クロメート皮膜の付着量が５ｍ
ｇ／ｍ2 未満では、亜鉛系めっき鋼板としての裸および
塗装後の耐食性が不十分であり、また１５０ｍｇ／ｍ2
を超えては、クロメート皮膜の均一塗布制御が難しくな
り、耐食性の面でも飽和状態であって、かつ、クロメー
ト皮膜の一部が外力により除去され易くなるので塗膜付
着性低下の原因となるなど、性能面および製造技術の面
で問題がある。The amount of the chromate film formed on the surface of the galvanized steel sheet is 5 to 1 in terms of the total amount of chromium on one side.
50 mg / m 2 . Chromate coating amount is 5m
If it is less than g / m 2 , the corrosion resistance after coating bare and as a zinc-based plated steel sheet is insufficient, and also 150 mg / m 2
Beyond the above, it becomes difficult to control the uniform coating of the chromate film, and it is saturated in terms of corrosion resistance, and part of the chromate film is easily removed by external force, which causes a decrease in coating film adhesion. However, there are problems in terms of performance and manufacturing technology.
【００２２】[0022]
【実施例】次に、本発明の実施例を比較例と共に挙げ
る。EXAMPLES Next, examples of the present invention will be given together with comparative examples.
【００２３】表１、表２に示す組成の処理液、処理条件
（乾燥温度、冷却方法、クロム付着量）で電気亜鉛めっ
き鋼板（亜鉛めっき量：２０ｇ／ｍ2 、板厚：０．８ｍ
ｍ、パネルサイズ：２００×３００ｍｍ）を処理し、ク
ロメート皮膜を表面に形成した亜鉛めっき鋼板および各
種比較材を得た。Electrolytic galvanized steel sheets (galvanized amount: 20 g / m 2 , plate thickness: 0.8 m) with treatment liquids having the compositions shown in Tables 1 and 2 and treatment conditions (drying temperature, cooling method, chromium deposition amount)
m, panel size: 200 × 300 mm) to obtain a galvanized steel sheet having a chromate film formed on its surface and various comparative materials.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】得られたクロメート処理鋼板および比較材
より試験片を採取して、以下に述べる方法で耐アルカリ
性、耐食性、塗装板耐食性および塗膜密着性の各性能試
験を行った。Test pieces were taken from the obtained chromate-treated steel sheet and the comparative material, and performance tests of alkali resistance, corrosion resistance, coated board corrosion resistance and coating film adhesion were conducted by the following methods.
【００２７】（ａ）耐アルカリ性試験 クロメート処理鋼板を珪酸ソーダを主成分とするアルカ
リ脱脂剤（日本パーカライジング製・パルクリーン３６
４Ｓ）の２％水溶液で、温度６０℃、２分間スプレー処
理し、その前後におけるクロム付着量減少率で耐アルカ
リ性を評価した。(A) Alkali resistance test An alkali degreasing agent containing sodium silicate as a main component in a chromate-treated steel sheet (manufactured by Nippon Parkerizing Palclean 36
4S) was spray-treated with a 2% aqueous solution at a temperature of 60 ° C. for 2 minutes, and the alkali resistance was evaluated by the reduction rate of the amount of chromium deposited before and after the spray treatment.
【００２８】（ｂ）耐食性 サイズが７０×１５０ｍｍの試験片でＪＩＳ−Ｚ−２３
７１に規定された塩水噴霧試験を１５０時間行い、試験
片の全面積に対する白錆発生状態から耐食性を評価し
た。(B) Corrosion resistance JIS-Z-23 for test pieces of size 70 × 150 mm
The salt spray test prescribed in No. 71 was carried out for 150 hours, and the corrosion resistance was evaluated from the white rust generation state with respect to the entire area of the test piece.
【００２９】（ｃ）塗装板耐食性 サイズが７０×１５０ｍｍの試験片に焼付型メラミンア
ルキッド塗料（大日本塗料製・デリコン７００白）を塗
装し、１４０℃で２０分間焼付乾燥して、塗装板（塗膜
厚２５μｍ）を作製した。(C) Corrosion Resistance of Painted Plate A baking type melamine alkyd paint (Delicon 700 white manufactured by Dainippon Paint Co., Ltd.) is applied to a test piece having a size of 70 × 150 mm, and baked and dried at 140 ° C. for 20 minutes to obtain a coated plate ( A coating film thickness of 25 μm) was prepared.
【００３０】塗膜に素地金属まで達するキズをカッター
で入れ、塩水噴霧試験を２００時間実施後、接着テープ
（セロハンテープ）剥離を行い、キズからの最大片側剥
離幅で塗装板耐食性を評価した。A scratch reaching the base metal was put into the coating film with a cutter, a salt spray test was carried out for 200 hours, and then the adhesive tape (cellophane tape) was peeled off, and the corrosion resistance of the coated plate was evaluated by the maximum peeling width on one side from the scratch.
【００３１】（ｄ）塗膜密着性 塗料、乾燥条件および塗膜厚みが前項（ｃ）と同じ条件
で塗装されたサイズが７０×１５０ｍｍの試験片に対
し、エリクセン押し出し機により６ｍｍ押し出し、接着
テープ（セロハンテープ）を試験片面に貼り付けて急速
に剥がし、塗膜の剥離程度を観察した。塗膜密着性は塗
膜の剥離程度によって３段階に分けて評価した。(D) Adhesion of coating film A 6 mm-sized test piece extruded by an Erichsen extruder was applied to a test piece having a size of 70 × 150 mm, which had been coated under the same conditions as those in the above-mentioned item (c) in terms of coating material, drying conditions and coating film thickness, and an adhesive tape (Cellophane tape) was attached to the surface of the test piece and rapidly peeled off, and the degree of peeling of the coating film was observed. The coating film adhesion was evaluated by dividing it into three stages according to the degree of peeling of the coating film.
【００３２】結果を表３、表４に示す。同表中×は不
良、△はやや良い、○は良好を示す。The results are shown in Tables 3 and 4. In the table, x indicates bad, Δ indicates a little good, and ○ indicates good.
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】これらの表に見られるように、本発明の亜
鉛系めっき鋼板のクロメート処理方法は、亜鉛系めっき
鋼板に優れた耐食性、耐アルカリ性ならびに塗装性（塗
膜付着性および塗装後の耐食性）を有するクロメート皮
膜を形成し得る方法であり、自動車、家電、建材などの
分野における亜鉛系めっき鋼板の高防錆処理として好適
である。As can be seen from these tables, the method for chromate treatment of zinc-based plated steel sheet of the present invention is excellent in corrosion resistance, alkali resistance and paintability (coating film adhesion and corrosion resistance after coating) of zinc-based plated steel sheet. It is a method capable of forming a chromate film having the following properties, and is suitable as a highly rustproof treatment for zinc-based plated steel sheets in the fields of automobiles, home appliances, building materials, etc.
【００３６】[0036]
【発明の効果】本発明によれば、亜鉛系めっき鋼板に優
れた耐食性、耐アルカリ性ならびに塗装性（塗膜付着性
および塗装後の耐食性）を有するクロメート皮膜を形成
することが可能となる。According to the present invention, it is possible to form a chromate film having excellent corrosion resistance, alkali resistance and paintability (coating adhesion and corrosion resistance after coating) on a zinc-based plated steel sheet.
Claims (1)
クロム還元率が４０〜８０％であり、リン酸１０〜２０
０ｇ／ｌとフッ酸０．１〜１．０ｇ／ｌを含有する水系
クロメート液を亜鉛系めっき鋼板表面に塗布し、つい
で、乾燥板温が最高到達板温として５０〜２００℃にな
るよう乾燥し、直ちに、冷却媒体として濃度０．５％以
上のシランカップリング剤溶液を用いて冷却し、その表
面に片面当たり総クロム量で５〜１５０ｍｇ／ｍ2 のク
ロメート皮膜を形成させることを特徴とする亜鉛系めっ
き鋼板のクロメート処理方法。1. A total chromium concentration of 5 to 30 g / l, a chromium reduction rate of 40 to 80%, and phosphoric acid of 10 to 20.
An aqueous chromate solution containing 0 g / l and 0.1-1.0 g / l hydrofluoric acid was applied to the surface of the zinc-plated steel sheet, and then dried so that the maximum temperature reached was 50-200 ° C. Then, immediately, using a silane coupling agent solution having a concentration of 0.5% or more as a cooling medium, cooling is performed to form a chromate film having a total amount of chromium of 5 to 150 mg / m 2 on one surface thereof. Chromate treatment method for zinc-based plated steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12286492A JPH05295562A (en) | 1992-04-17 | 1992-04-17 | Method for chromate-treating galvanized steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12286492A JPH05295562A (en) | 1992-04-17 | 1992-04-17 | Method for chromate-treating galvanized steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05295562A true JPH05295562A (en) | 1993-11-09 |
Family
ID=14846527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12286492A Pending JPH05295562A (en) | 1992-04-17 | 1992-04-17 | Method for chromate-treating galvanized steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05295562A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817027A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Low-temperature phosphating solution |
| CN102817023A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | High-temperature corrosion-resistant phosphating solution |
| CN102817024A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Low-temperature phosphating solution containing carboxymethyl cellulose sodium |
-
1992
- 1992-04-17 JP JP12286492A patent/JPH05295562A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817027A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Low-temperature phosphating solution |
| CN102817023A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | High-temperature corrosion-resistant phosphating solution |
| CN102817024A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Low-temperature phosphating solution containing carboxymethyl cellulose sodium |
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