JPS5822383A - Chromate treatment of plated steel plate - Google Patents
Chromate treatment of plated steel plateInfo
- Publication number
- JPS5822383A JPS5822383A JP12068781A JP12068781A JPS5822383A JP S5822383 A JPS5822383 A JP S5822383A JP 12068781 A JP12068781 A JP 12068781A JP 12068781 A JP12068781 A JP 12068781A JP S5822383 A JPS5822383 A JP S5822383A
- Authority
- JP
- Japan
- Prior art keywords
- plated steel
- steel sheet
- treatment
- chromate
- steel plate
- 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
- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
-
- 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)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はメッキ鋼板の表面に耐食性、加工性、塗装密着
性を有するクロメート皮膜を形成させるためのメッキ鋼
板のクロメート処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for chromate treatment of a plated steel plate for forming a chromate film having corrosion resistance, workability, and paint adhesion on the surface of the plated steel plate.
従来から亜鉛或いはアｎ・ミニラム表どのメッキが施さ
れたメッキ鋼板は、未塗装のまま滅すは塗装して更には
之等の両者が組み合わされて使用されている。そこで之
等の用途に応じて防錆及び塗装後の塗膜の密着性、耐食
性の向上を目的として。Conventionally, plated steel sheets plated with zinc or annealed aluminum have been used either unpainted, painted, or in combination. Therefore, the purpose of this product is to prevent rust and improve the adhesion and corrosion resistance of the paint film after painting.
主としてクロム酸系処理またはリン酸塩系処理が行なわ
れている。クロメート皮膜を形成させるだめのクロム酸
系処理としては、鋼板表面と処理液とのエツチング反応
を伴う化学反応によるもの、６価クロムの一部を還元剤
により６価クロムに還元させて６価クロム及び６価クロ
ムが共存する処理液を鋼板表面に塗布するもの、及び電
解処理法によるものなどに区分出来る。この中で金属表
面との化学反応によってクロメート皮膜を形成させる方
法では、母材表面の金属（Ｚｎ、ＡＪなど）が金属イオ
ンとガリ同時に処理液中の水素イオンガ消費される。そ
の結果、被処理母材の処理量に応じて液中の遊離酸濃度
が減少し、遂には適正なりロメート皮膜が形成されなく
なり、その処理液は廃液処分にして新しい処理液に更新
しなければならな込。Chromic acid treatment or phosphate treatment is mainly used. Chromate-based treatments to form a chromate film include chemical reactions involving etching reactions between the steel plate surface and the treatment solution, and hexavalent chromium by reducing a portion of hexavalent chromium to hexavalent chromium with a reducing agent. It can be divided into two types: one in which a treatment solution containing hexavalent chromium is applied to the surface of the steel plate, and one in which electrolytic treatment is used. Among these methods, in the method of forming a chromate film by a chemical reaction with the metal surface, the metal (Zn, AJ, etc.) on the surface of the base material is consumed by the hydrogen ions in the treatment solution at the same time as the metal ions. As a result, the free acid concentration in the solution decreases in proportion to the amount of treated base material, and eventually it reaches an appropriate level and no longer forms a romate film, and the treatment solution must be disposed of as waste and replaced with a new treatment solution. Naranakomi.
ト処理液中には公害規制物質である多量の６価クロム及
び６価クロムを含んでいるので何郷かの方法でクロムを
除去する無公害化の処理を行にわｋければガらｋいが、
この廃液処理は非常に厄介であるばかりでなく多額の処
理費を要する。The treatment solution contains a large amount of hexavalent chromium and hexavalent chromium, which are pollution control substances, so if you do a non-pollution treatment to remove chromium using some method, it will be a waste. Yes, but
This waste liquid treatment is not only very troublesome but also requires a large amount of treatment cost.
こうした廃液処理上の問題から最近では廃クロム酸を生
じない塗布型クロメート処理液の開発が盛んに行なわれ
ている。塗布型クロメート処理液は６価クロムと還元剤
によって６価クロムが還元された結果生ずる６価クロム
を含み、或いは更に造膜剤としてシリカシ１１アルミナ
ゾル、アルキルシリケートなどの無機高分子またはポリ
ビニルアルコール、ポリアクリル酸、ポリアクリル酸エ
ステル々どの水溶性高分子を添加したものを用いて耐食
性の向上を図っているのが一般的である。Due to these problems in waste liquid treatment, there has recently been much effort to develop coating-type chromate treatment liquids that do not generate waste chromic acid. The coating type chromate treatment solution contains hexavalent chromium and hexavalent chromium produced as a result of reduction of hexavalent chromium by a reducing agent, or it may further contain inorganic polymers such as silica 11 alumina sol, alkyl silicate, polyvinyl alcohol, polyvinyl alcohol, etc. as a film forming agent. It is common to use water-soluble polymers such as acrylic acid and polyacrylic esters to improve corrosion resistance.
また、６価クロムを３価クロムに還元させる還元剤とし
ては、一般に有機系還元剤として、エチレングリコール
、プロピレングリコール、ポリプロピレングリコールな
どのグリコール類；メタノール、エタノールなどの１価
アルコール類；及びピロガロール、ブドウ糖、サッカロ
ース、メチルセルロース、マンニトールなどの多価アル
コール類；無機系還元剤として過酸化水素などがある。In addition, as reducing agents for reducing hexavalent chromium to trivalent chromium, organic reducing agents generally include glycols such as ethylene glycol, propylene glycol, and polypropylene glycol; monohydric alcohols such as methanol and ethanol; and pyrogallol, Polyhydric alcohols such as glucose, saccharose, methylcellulose, and mannitol; hydrogen peroxide as an inorganic reducing agent.
こうした従来の還元剤では処理液の６価クロムと６価ク
ロムが一定の比率を保ち且つ水酸化クロムなどの沈殿或
いは液のゲル化などを生ずることなく安定外処理浴とし
て維持するのが困難であった抄、或いは処理浴が成る程
度維持出来てもその反面被処理板の耐食性、加工性、塗
膜密着性などの性能の点で充分でなかったことなどが挙
げられる。With these conventional reducing agents, it is difficult to maintain a constant ratio of hexavalent chromium to hexavalent chromium in the treatment solution and maintain it as a stable external treatment bath without precipitation of chromium hydroxide or gelation of the solution. Even if the paper or treatment bath could be maintained to a certain degree, on the other hand, the performance of the plate to be treated, such as corrosion resistance, workability, and coating adhesion, was insufficient.
本発明者等は上記問題点を解決すべく鋭意研究の結果、
シランカップリング剤を還元剤として用いることにより
従来の公知技術では得られない優れた処理浴の安定性、
耐食性、加工性、塗膜密着性を示すこと、及び亜鉛メッ
キ鋼板のみならず。As a result of intensive research to solve the above problems, the inventors of the present invention found that
By using a silane coupling agent as a reducing agent, excellent stability of the processing bath, which cannot be obtained with conventional known techniques, can be achieved.
Showing corrosion resistance, workability, coating adhesion, and not only galvanized steel sheets.
アルミニウムなど他の金属をメッキ金属として用いたメ
ッキ鋼板にも適用可能であることを見出し本発明を完成
するに到った。The present invention was completed by discovering that the present invention can also be applied to plated steel plates using other metals such as aluminum as the plated metal.
即ち１本発明は無水クロム酸（Ｃ，０３）溶液にシラン
カップリング剤を添加して無水クロム酸の一部を還元さ
せて得られた液の組成を無水クロム酸０．１〜１ ｍｏ
ｌ／ｌ 、 ３価クロムと６価クロムとのモル比（Ｃｒ
”／ｃｒ” ）を０．０５〜０．７とした処理液でメッ
キ鋼板を表面処理することを特徴とするメッキ鋼板のク
ロメート処理方法に関するものである。That is, 1. In the present invention, a silane coupling agent is added to a chromic anhydride (C,03) solution to reduce a part of the chromic anhydride, and the composition of the obtained solution is changed to 0.1 to 1 mo of chromic anhydride.
l/l, molar ratio of trivalent chromium to hexavalent chromium (Cr
The present invention relates to a method for chromate treatment of a plated steel sheet, characterized in that the surface of the plated steel sheet is treated with a treatment liquid having a ratio of 0.05 to 0.7.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明に用いる無水クロム酸は従来鋼板の表面処理に用
いられているもので充分である。As the chromic anhydride used in the present invention, those conventionally used for surface treatment of steel plates are sufficient.
またシランカップリング剤は一般式ＹＲ８ｉ Ｘ３で表
わされ、Ｘはケイ素原子に結合している加水分解性の基
を表わし、アルコキシ基及びアセトキシ基などがある。The silane coupling agent is represented by the general formula YR8i X3, where X represents a hydrolyzable group bonded to a silicon atom, such as an alkoxy group and an acetoxy group.
またＹは有機官能基を示し、ビニル基、メタクリロキシ
基、ランイド基、環状エポキシ基、グリシドキシ基、メ
ルカプト基、アミノ基、ジアミノ基などが挙げられる。Further, Y represents an organic functional group, and examples thereof include a vinyl group, a methacryloxy group, a ranide group, a cyclic epoxy group, a glycidoxy group, a mercapto group, an amino group, and a diamino group.
シランカップリング剤による６価クロムの還元機構は次
の通りである。The mechanism of reduction of hexavalent chromium by the silane coupling agent is as follows.
シランカップリング剤をクロム酸水溶液中に添加すると
之等の基または原子は加水分解を受けて下式の様にシラ
ノール及びＨＸを生ずる。When a silane coupling agent is added to an aqueous chromic acid solution, these groups or atoms undergo hydrolysis to produce silanol and HX as shown in the following formula.
ＹＲ８ｉＸ３＋ Ｈ２Ｏ−＋ ＹＲ８ｉ （ＯＨ）３
＋３ ＨＸ例えばＸがメトキシ基及びエトキシ基の時、
ＨＸはそれぞれメタノール、エタノールとなり、この
副生されたアルコールによって６価クロムは３価クロム
に還元される。YR8iX3+ H2O-+ YR8i (OH)3
+3 HX For example, when X is a methoxy group or an ethoxy group,
HX becomes methanol and ethanol, respectively, and the by-produced alcohol reduces hexavalent chromium to trivalent chromium.
本発明に用いる処理液は処理液１ｔ”ｈｔ：を無水クロ
ム酸０．１〜１ ｍａｔ／ｌを含み且つシランカップリ
ング剤によって還元された３価クロムを６価クロムと６
価クロムのモル比（Ｃ「＋５／ｃｒ＋６）で０．０５〜
０．７含む様に調整する。処理液の組成をこの様に限定
するのは次の理由による。即ち、無水クロム酸の濃度−
ＡＥｏ、１ ｍ０１７１未満では工業的生産工程で行な
われている６〜７秒間程度の短時間処理では耐食性の優
れた皮膜が形成されず、１Ｗｒｏ１７１を超えると皮膜
が黄味を呈し外観が損われるので好ましくない。The processing solution used in the present invention contains 1 t"h of chromic anhydride and 0.1 to 1 mat/l of chromic anhydride, and converts trivalent chromium reduced by a silane coupling agent into hexavalent chromium and 6 valent chromium.
The molar ratio of valent chromium (C'+5/cr+6) is 0.05~
Adjust to include 0.7. The reason why the composition of the processing liquid is limited in this way is as follows. That is, the concentration of chromic anhydride -
If AEo is less than 1 m0171, a film with excellent corrosion resistance will not be formed in the short-time treatment of about 6 to 7 seconds that is carried out in industrial production processes, and if it exceeds 1 Wro171, the film will take on a yellowish tinge and the appearance will be impaired. Undesirable.
また６価クロムと６価クロムのモル比が０．０５未満で
は耐食性、加工性々どの性能向上が期待されず、０．７
を超えると３価クロムの含有率が非常に高く々るので逆
に耐食性が却って低下するからである。Furthermore, if the molar ratio of hexavalent chromium to hexavalent chromium is less than 0.05, no improvement in performance such as corrosion resistance or workability is expected;
This is because if the content exceeds 100%, the content of trivalent chromium becomes very high, and the corrosion resistance actually decreases.
本発明において処理対象とするメッキ鋼板としては亜鉛
アルミニウムなどの溶融メッキまたは電気メッキを鋼板
に施したメッキ鋼板が用いられ、ｔ、を亜鉛メッキ鋼板
とじでは単に亜鉛をメッキしただけのメッキ鋼板の他に
、亜胎メッキ後更に高温加熱して合金化処理を施したメ
ッキ鋼板も用いられる（本発明においては上記処理対象
の各鋼板をメッキ鋼板と総称する）。The plated steel sheet to be treated in the present invention is a plated steel sheet that is hot-dip plated or electroplated with zinc-aluminum or the like. Also used is a plated steel plate that is subjected to alloying treatment by further heating at a high temperature after subplating (in the present invention, each steel plate to be treated is collectively referred to as a plated steel plate).
かかるメッキ鋼板を本発明において用いる処理液によっ
て表面処理する方法は通常実施されている方法に従い、
メッキ鋼板を必要に応じて脱脂後、水洗して表面を清浄
にした後に、浸漬法、スプレー法、ロールコータ−法、
ロール絞す法、エアーナイフ絞り法などの方法により処
理液を鋼板表面に塗布する。The method for surface treating such a plated steel plate with the treatment liquid used in the present invention is according to a commonly practiced method.
After degreasing the plated steel plate as necessary and cleaning the surface by washing with water, the plated steel plate is subjected to dipping, spraying, roll coating,
The treatment liquid is applied to the surface of the steel plate by a method such as a roll drawing method or an air knife drawing method.
乾燥は水分を蒸発する程度で良く、望ましくは板温とし
て７０〜１００℃が好ましい。Drying may be carried out to the extent that moisture is evaporated, and the board temperature is preferably 70 to 100°C.
シランカップリング剤を還元剤として用いると従来の還
元剤では得られない数々の優れた性能を得ることが出来
る。When a silane coupling agent is used as a reducing agent, it is possible to obtain a number of excellent performances that cannot be obtained with conventional reducing agents.
之等の性能としては先ず第一に処理浴の安定性が挙げら
れる。一般に６価クロムを含有するクロメート処理液は
ｐＨが３を超えると沈殿物が生じたりゲル化する傾向が
ある。しかし、シラ／カップリング剤を還元剤として使
用した場合にはｐＨは５．０程度でも何等液の安定性に
問題はない。The first consideration of such performance is the stability of the processing bath. In general, a chromate treatment solution containing hexavalent chromium tends to form a precipitate or gel when the pH exceeds 3. However, when a silica/coupling agent is used as a reducing agent, there is no problem with the stability of the liquid even if the pH is about 5.0.
次に第二の特徴として、メッキ鋼板の耐食性、加工性も
極めて優れている。これはシラ／カップリング剤の本来
の機能である加水分解によって生成されるシラノール基
が金属表面に吸着されると共にＣ「０４″″・ Ｃｒ
（ＯＨ） ３ などとの間で架橋反応々どの化学反応
を起こして強固カクロメート皮膜を形成することが考え
られる。また一方、シランカップリング剤は有機官能基
をも有しているのでアルキド、アクリル、エポキシ塗料
々どの塗膜密着性にも優れている。The second feature is that the plated steel sheet has excellent corrosion resistance and workability. This is because the silanol groups generated by hydrolysis, which is the original function of the sila/coupling agent, are adsorbed onto the metal surface and C
It is conceivable that a chemical reaction such as a crosslinking reaction occurs with (OH) 3 or the like to form a strong cachromate film. On the other hand, since the silane coupling agent also has an organic functional group, it has excellent adhesion to alkyd, acrylic, and epoxy paints.
本発明のクロメート処理方法は、それによって処理され
たメッキ鋼板の耐食性、加工性、塗膜密着性を大幅に向
上させるものであり、また本発明のクロメート処理方法
は塗布型であるため処理液の老化もなく、従って廃液処
理の必要性もないことと相俟って産業上非常に価値の高
いものである。The chromate treatment method of the present invention significantly improves the corrosion resistance, workability, and coating adhesion of the plated steel sheet treated with it, and since the chromate treatment method of the present invention is a coating type, it requires no treatment solution. Coupled with the fact that it does not age and therefore does not require waste liquid treatment, it is extremely valuable industrially.
以下、実施例、比較例によって本発明を更に説明する。The present invention will be further explained below with reference to Examples and Comparative Examples.
実施例
各種金属メッキ鋼板の表直に本発明方法によるハ
方法及びその組成、ｐＨ１塗布方法、処理方法、皮膜量
（クロム付着量）、乾燥温度（板温）などの詳細表条件
を第１表に示す。Examples Table 1 shows detailed conditions such as the method of the present invention, its composition, pH 1 coating method, treatment method, film amount (chromium adhesion amount), drying temperature (plate temperature), etc. on the surface of various metal-plated steel sheets. Shown below.
以下余白
この第１表に示す条件によって得られたクロメート処理
鋼板より試験片を採取し、性能評価として平面部、加工
部としてエリクセン部、折曲部の各部についての耐塩水
噴霧性を、また塗膜密着性としてはゴバン目試験、デュ
ポン衝撃試験、エリクセン押出試験による試験を行なっ
た。その試験結果を第２表に示す。Test pieces were taken from the chromate-treated steel plates obtained under the conditions shown in Table 1, and the salt spray resistance of the flat part, the Erichsen part as the processed part, and the bent part was evaluated for performance evaluation. As for film adhesion, tests were conducted using a cross-cut test, a DuPont impact test, and an Erichsen extrusion test. The test results are shown in Table 2.
第 ２ 表 性能評価 各試験の試験方法は次の通りである。Table 2 Performance evaluation The test method for each test is as follows.
耐塩水噴霧性の試験はＪＩＳ Ｚ ２３７１． （塩水
噴霧試験方法）に準拠し塩水噴霧試験後に白錆発生しな
いものを◎印、１０チ未満の発生は○印、１０チ以上３
０チ未満のものをΔ印、６０チ以上のものをＸ印とした
。Salt spray resistance test is based on JIS Z 2371. (Salt water spray test method), those that do not develop white rust after the salt water spray test are marked with ◎, those with less than 10 inches are marked with ○, and those with 10 or more rust are marked with 3
Those less than 0 inches were marked with Δ, and those with 60 inches or more were marked with X.
即ちシランカップリング剤を用いない比較例１〜５．無
水クロム酸濃度が高過ぎる比較例６゜Ｃｒ”／ｃｒ＋
６の比が本発明の規定範囲外である比較例７〜１２は何
れも本発明の実施例に比し劣っていることが判る。That is, Comparative Examples 1 to 5 in which no silane coupling agent was used. Comparative example 6°Cr”/cr+ where the concentration of chromic acid anhydride is too high
It can be seen that Comparative Examples 7 to 12, in which the ratio of 6 is outside the specified range of the present invention, are inferior to the Examples of the present invention.
平 面部：平板な試験片をその侠試験に供し。Flat part: A flat test piece is used for the chisel test.
塩水噴霧試験１６０時間後で評価した。Evaluation was made after 160 hours of salt spray test.
鴫押出したものを試験に供し、塩水 噴霧試験１２０時間後で評価した。The extruded product was tested and soaked in salt water. Evaluation was made after 120 hours of the spray test.
折 曲 部＝１８０°折曲げた試験片を試験に供し、塩
水噴霧試験４８時間後で評価した。A test piece with a bent portion of 180° was subjected to a test and evaluated after 48 hours of a salt spray test.
塗膜密着性の試験はアクリル系塗料を使用し２００℃で
約２分間乾燥した塗装試験片について次の様に各項目の
試験を行Δつた。The paint film adhesion test was conducted using an acrylic paint and using a painted test piece that had been dried at 200° C. for about 2 minutes, and was tested for each item as follows.
ゴバン目試験：塗装試験片に対し１ｍｍ平方のマス目を
鋼素地に達する様にカッターで
切り込み、セロハンテープを貼り付
けて急速に引き剥がし、塗装面の異
Ｋｆの重錘を５０眞の高さから落下さ
せ、セロハンテープを貼り付は急速
に剥が・し、塗装面の異常の程度を観
察した。Goban test: Cut 1 mm square squares into the painted test piece with a cutter so that it reaches the steel base, apply cellophane tape and quickly peel it off, and place a weight of a different Kf on the painted surface at a height of 50 mm. The cellophane tape was quickly peeled off and the degree of abnormality on the painted surface was observed.
エリクセン
押出試験 ： エリクセン押出機により塗装試験片を６
ｍｍ押出し、セロハンテープを
貼り付は急速に剥がし、塗装面の異
常の程度を観察した。Erichsen extrusion test: 6 coated test pieces were prepared using an Erichsen extruder.
mm extrusion, the applied cellophane tape was quickly peeled off, and the degree of abnormality on the painted surface was observed.
上記各項目の塗膜密着性は塗膜の剥離程度によって次の
４段階に分けて表示した。The coating adhesion of each of the above items was classified into the following four levels depending on the degree of peeling of the coating.
◎：塗膜剥離なし
○ｇ塗膜剥離１０チ未満
Δ：塗膜剥離１０チ以上３０チ未満
×：塗膜剥離６０チ以上
第２表に示す様にシランカップリング剤で還元さ肛奔ク
ロメート処理液で表面処理を行なう本発明の実施例１〜
８のクロメート処理方法による場合は、比較例１〜１０
のクロメート処理液を用いる場合に較べて形成されるク
ロメート皮膜は平面部における耐食性が優れていること
は勿論の事。◎: No paint film peeling ○g Paint film peeling less than 10 inches Δ: Paint film peeling 10 inches or more and less than 30 inches ×: Paint film peeling 60 inches or more Anal chromate reduced with a silane coupling agent as shown in Table 2 Embodiment 1 of the present invention in which surface treatment is performed with a treatment liquid
Comparative Examples 1 to 10 when using the chromate treatment method of 8.
It goes without saying that the chromate film formed has superior corrosion resistance on flat surfaces compared to when using a chromate treatment solution.
エリクセン押出部や折曲部における耐食性も優れており
、クロメート皮膜が被処理板に極めて強固に密着してい
るものであり、従ってまた加工性が優れていることが判
った。また塗料の密着性についてもゴバン目、デュポン
＠寧、工Ｖクセン押出各試験共に本発明例は比較例に較
べて優れていることが判った。It was found that the corrosion resistance at the Erichsen extrusion part and the bent part was excellent, and the chromate film adhered extremely firmly to the plate to be treated, and therefore the workability was also excellent. It was also found that the inventive examples were superior to the comparative examples in terms of paint adhesion in the Goban, DuPont@Ning, and Kou V Kusen extrusion tests.
またシランカップリング剤で還元されたクロメート処理
液はｐＨ５，０程度でも伺等液の安定性に問題なく、従
来のクロメート処理浴の管理に比べて非常に管理し易い
浴に改善されている。In addition, the chromate treatment solution reduced with a silane coupling agent has no problem in stability even at a pH of about 5.0, and is much easier to manage than conventional chromate treatment baths.
Claims (1)
グ剤を添加して無水クロム酸の一部を還元させて得られ
た液の組成を無水クロム酸０．１〜１Ｆｌ！Ｏ／／／
、 ３価クロムと６価クロムとｏモル比（Ｃｒ”／Ｃ「
＋６ ） ヲ０．０５〜０．７ トシタ処理液でメッキ
鋼板を表面処理することを特徴とするメッキ鋼板のクロ
メート処理方法。 ２ 表面処理を施すメッキ鋼板として亜鉛メッキを施し
た亜鉛メッキ鋼板を用いる特許請求の範囲第１項に記載
のメッキ鋼板のクロメート処理方法。 ３ 表面処理を施すメッキ鋼板として亜鉛メッキを施し
た後に更に高温加熱して合金化処理を施した亜鉛メッキ
鋼板を用いる特許請求の範囲第」項に記載のメッキ鋼板
のクロメート処理方法。 ４ 表面処理を施すメッキ鋼板としてアルミニウムメッ
キを施したアルミニウムメッキ鋼板を用いる特許請求の
範囲第１項に記載のメッキ鋼板のクロメート処理方法。 ５ 表面処理を施されるメッキ鋼板がそのメッキを溶融
メッキによりなされたものである特許請求の範囲第１項
力いし第４項のうちの何れか１項に記載のメッキ鋼板の
クロメート処理方法０ ６ 表面処理を施されるメッキ鋼板がそのメッキを電気
メッキによりなされたものである特許請求の範囲第１項
ないしは第４項のうちの倒れか１項に記載のメッキ鋼板
のクロメート処理方法。[Claims] 1. The composition of the liquid obtained by adding silica/coupling agent to a chromic anhydride (CrOs) solution and reducing a part of the chromic anhydride is 0.1 to 1 Fl! of chromic anhydride! O／／／
, trivalent chromium, hexavalent chromium and o molar ratio (Cr"/C"
+6) 0.05 to 0.7 A method for chromate treatment of a plated steel sheet, characterized by surface treating the plated steel sheet with a Toshita treatment liquid. 2. The method for chromate treatment of a plated steel sheet according to claim 1, which uses a galvanized steel sheet that has been subjected to galvanization as the plated steel sheet to which the surface treatment is applied. 3. The method for chromate treatment of a plated steel sheet according to claim 1, which uses a galvanized steel sheet that has been subjected to galvanization and then further heated at a high temperature to undergo alloying treatment as the plated steel sheet to be subjected to surface treatment. 4. The method for chromate treatment of a plated steel plate according to claim 1, which uses an aluminum plated steel plate that has been subjected to aluminum plating as the plated steel plate to which the surface treatment is applied. 5. The method for chromate treatment of a plated steel sheet according to any one of claims 1 to 4, wherein the plated steel sheet to be surface-treated is plated by hot-dip plating. 6. The method for chromate treatment of a plated steel sheet according to claim 1 or 4, wherein the plated steel sheet to be surface-treated is plated by electroplating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12068781A JPS5822383A (en) | 1981-08-03 | 1981-08-03 | Chromate treatment of plated steel plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12068781A JPS5822383A (en) | 1981-08-03 | 1981-08-03 | Chromate treatment of plated steel plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5822383A true JPS5822383A (en) | 1983-02-09 |
| JPS6335712B2 JPS6335712B2 (en) | 1988-07-15 |
Family
ID=14792462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12068781A Granted JPS5822383A (en) | 1981-08-03 | 1981-08-03 | Chromate treatment of plated steel plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5822383A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62202084A (en) * | 1986-02-28 | 1987-09-05 | Nippon Parkerizing Co Ltd | Treatment of surface of metal |
| JPS62202083A (en) * | 1986-02-28 | 1987-09-05 | Nippon Parkerizing Co Ltd | Method for chromating metal |
| JPH0219477A (en) * | 1988-07-08 | 1990-01-23 | Nippon Dakuro Shamrock:Kk | Surface treatment of metal |
| JPH03243796A (en) * | 1990-02-22 | 1991-10-30 | Nippon Steel Corp | Production of organic compositely plated steel sheet having high corrosion resistance |
| US5230750A (en) * | 1990-10-05 | 1993-07-27 | Nihon Parkerizing Co., Ltd. | Chromating method of zinc-based plated steel sheet |
| US5304401A (en) * | 1990-11-14 | 1994-04-19 | Nippon Steel Corporation | Method of producing organic composite-plated steel sheet |
| US5366567A (en) * | 1990-10-08 | 1994-11-22 | Henkel Corporation | Method for chromating treatment of zinc coated steel |
| US5507884A (en) * | 1993-10-21 | 1996-04-16 | Henkel Corporation | Process for forming a sparingly soluble chromate coating on zinciferous metal coated steel |
| US6149735A (en) * | 1995-11-30 | 2000-11-21 | Henkel Corporation | Chromate treatment bath composition and process for application to metals |
| JP2011021279A (en) * | 2004-03-10 | 2011-02-03 | Jfe Steel Corp | Steel sheet for fuel tank and method for manufacturing the same |
-
1981
- 1981-08-03 JP JP12068781A patent/JPS5822383A/en active Granted
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62202084A (en) * | 1986-02-28 | 1987-09-05 | Nippon Parkerizing Co Ltd | Treatment of surface of metal |
| JPS62202083A (en) * | 1986-02-28 | 1987-09-05 | Nippon Parkerizing Co Ltd | Method for chromating metal |
| JPS6366906B2 (en) * | 1986-02-28 | 1988-12-22 | Nippon Packaging Kk | |
| JPH08982B2 (en) * | 1986-02-28 | 1996-01-10 | 日本パ−カライジング株式会社 | Metal chromating method |
| JPH0219477A (en) * | 1988-07-08 | 1990-01-23 | Nippon Dakuro Shamrock:Kk | Surface treatment of metal |
| JPH03243796A (en) * | 1990-02-22 | 1991-10-30 | Nippon Steel Corp | Production of organic compositely plated steel sheet having high corrosion resistance |
| US5230750A (en) * | 1990-10-05 | 1993-07-27 | Nihon Parkerizing Co., Ltd. | Chromating method of zinc-based plated steel sheet |
| US5366567A (en) * | 1990-10-08 | 1994-11-22 | Henkel Corporation | Method for chromating treatment of zinc coated steel |
| US5304401A (en) * | 1990-11-14 | 1994-04-19 | Nippon Steel Corporation | Method of producing organic composite-plated steel sheet |
| US5507884A (en) * | 1993-10-21 | 1996-04-16 | Henkel Corporation | Process for forming a sparingly soluble chromate coating on zinciferous metal coated steel |
| US6149735A (en) * | 1995-11-30 | 2000-11-21 | Henkel Corporation | Chromate treatment bath composition and process for application to metals |
| JP2011021279A (en) * | 2004-03-10 | 2011-02-03 | Jfe Steel Corp | Steel sheet for fuel tank and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6335712B2 (en) | 1988-07-15 |
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