JP2001098384A - Chromate treating solution and treating method - Google Patents
Chromate treating solution and treating methodInfo
- Publication number
- JP2001098384A JP2001098384A JP27584299A JP27584299A JP2001098384A JP 2001098384 A JP2001098384 A JP 2001098384A JP 27584299 A JP27584299 A JP 27584299A JP 27584299 A JP27584299 A JP 27584299A JP 2001098384 A JP2001098384 A JP 2001098384A
- Authority
- JP
- Japan
- Prior art keywords
- coupling agent
- silane coupling
- silica sol
- chromate
- added
- 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
- 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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、保管安定性に優れ、耐
指紋性、塗膜密着性に優れたクロメ−ト皮膜を形成でき
るクロメ−ト処理液および処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chromate treating solution and a treating method capable of forming a chromate film having excellent storage stability, fingerprint resistance and coating film adhesion.
【０００２】[0002]
【従来技術】近年、亜鉛やアルミニウムまたはこれらの
合金等のめっき鋼板、銅めっき鋼板、アルミニウム板等
のクロメ−ト処理液は、クロム酸、クロム酸塩、重クロ
ム酸塩のような水溶性クロム化合物の水溶液またはこれ
に水溶性もしくは水分散性有機樹脂を添加して、被処理
材に塗布後水洗することなく乾燥する塗布型のものが主
流になっている。一方、クロメ−ト処理材の塗装は従来
クロメ−ト皮膜を除去して、新たに塗装前処理を施して
行っていたが、近年はそのまま塗装するようになってき
ている。このため、クロメ−ト処理液としては、耐食性
のほかに取り扱いの際に指紋などの汚染物が付着しにく
い耐指紋性や塗膜密着性の優れたクロメ−ト皮膜の形成
可能なものが要求されている。2. Description of the Related Art In recent years, chromate treatment solutions for plated steel sheets such as zinc and aluminum or alloys thereof, copper-plated steel sheets, aluminum sheets, etc. are made of water-soluble chromium such as chromate, chromate and dichromate. The mainstream is an application type in which an aqueous solution of a compound or a water-soluble or water-dispersible organic resin is added thereto, and the applied material is applied to a material to be treated and then dried without washing. On the other hand, the coating of a chromate treatment material has conventionally been carried out by removing a chromate film and performing a new pre-coating treatment. However, in recent years, it has been applied as it is. For this reason, it is required that the chromate treatment liquid be capable of forming a chromate film which is excellent in fingerprint resistance and coating film adhesion which is hard to adhere to contaminants such as fingerprints in handling, in addition to corrosion resistance. Have been.
【０００３】クロメ−ト皮膜の耐指紋性を高める方法と
しては、クロメ−ト処理液にシリカゾルを添加する方法
が知られているが、シリカゾルを多量に添加すると、ク
ロメ−ト皮膜の塗膜密着性が低下してしまう。特に、ク
ロメ−ト皮膜の耐湿性を改善するため、還元剤として、
オキシカルボン酸化合物などを用いて、６価クロムイオ
ンを３価クロムイオンに還元して、６価クロムイオンが
Ｃｒ6+／全Ｃｒの比率で０.１以下になるようにしたク
ロメ−ト処理液の場合、シリカゾル添加によるクロメ−
ト皮膜の塗膜密着性低下が著しい。As a method for improving the fingerprint resistance of a chromate film, a method of adding silica sol to a chromate treatment solution is known. However, when a large amount of silica sol is added, the adhesion of the chromate film to the coating film is increased. Performance is reduced. In particular, as a reducing agent, to improve the moisture resistance of the chromate film,
Chromate treatment in which hexavalent chromium ions are reduced to trivalent chromium ions using an oxycarboxylic acid compound or the like so that the ratio of hexavalent chromium ions becomes 0.1 or less in the ratio of Cr 6+ / total Cr. In the case of liquid, the chroma
The coating film adhesion of the film is significantly reduced.
【０００４】このような場合の対策として、シランカッ
プリング剤を添加して、塗膜密着性を高める方法が知ら
れているが、シランカップリング剤はクロメ−ト処理液
のような酸性水溶液に添加すると、加水分解して化学的
に不安定なシラノ−ル濃度が高くなるため、脱水縮合を
起こし易く、処理液は調製後保管しておくと、シランカ
ップリング剤の脱水縮合が次第に進行して、増粘、ゲル
化が生じ、塗布が困難になる場合がある。このため、シ
リカゾル添加による塗膜密着性低下を回復させるのにシ
ランカップリング剤は無制限に添加できず、シランカッ
プリング剤はシラノ−ルの脱水縮合が進行する程添加し
なくてよいようにシリカゾル添加量を制限する必要があ
った。そこで、予めシランカップリング剤とシリカゾル
を混合し、シランカップリング剤をシリカゾルに反応さ
せることでシラノ−ル濃度を低減する方法が知られてい
る。しかし、その反応程度を把握し管理する手段がない
ので、目的の品質性能を満足できるか否かは、それらを
クロメ−ト処理液に添加して全ての性能試験を行って確
認するしかなかった。As a countermeasure for such a case, a method of adding a silane coupling agent to enhance the adhesion of the coating film is known, but the silane coupling agent is added to an acidic aqueous solution such as a chromate treatment solution. When added, the concentration of the chemically unstable silanol increases due to hydrolysis, so that dehydration condensation is liable to occur.If the treatment liquid is stored after preparation, the dehydration condensation of the silane coupling agent gradually proceeds. As a result, thickening and gelation may occur, making application difficult. For this reason, the silane coupling agent cannot be added indefinitely in order to recover the decrease in coating film adhesion due to the addition of the silica sol, and the silane coupling agent does not need to be added as the dehydration condensation of the silanol progresses. It was necessary to limit the amount added. Therefore, a method has been known in which a silane coupling agent and a silica sol are mixed in advance, and the silane coupling agent is reacted with the silica sol to reduce the silanol concentration. However, since there is no means for grasping and managing the degree of the reaction, it was only possible to confirm whether or not the desired quality performance could be satisfied by adding them to the chromate treatment solution and conducting all performance tests. .
【０００５】[0005]
【発明が解決しようとする課題】本発明は、シリカゾル
添加による耐指紋性とシランカップリング剤添加による
塗膜密着性を改善したクロメ−ト処理液において、保管
安定性とクロメ−ト皮膜の耐指紋性との調和したクロメ
−ト処理液および処理方法を提供するものである。SUMMARY OF THE INVENTION The present invention relates to a chromate treatment solution having improved fingerprint resistance by adding silica sol and improved coating adhesion by adding a silane coupling agent. An object of the present invention is to provide a chromate processing solution and a processing method that are in harmony with fingerprints.
【０００６】[0006]
【課題を解決するための手段】本発明は、シリカゾルと
シランカップリング剤を添加したクロメ−ト処理液にお
いて、シリカゾルとシランカップリング剤のクロメ−ト
処理液への添加は添加前に予め両者を混合して、シラン
カップリング剤の一部をシリカゾルのシリカ表面に結合
させ、シリカゾルに反応してないシランカップリング剤
に起因した29Ｓｉ（−Ｏ−）3とシリカゾルに起因した
29Ｓｉ（−Ｏ−）4の核磁気共鳴分析（ＮＭＲ）ピ−ク
強度比Ｒ＝29Ｓｉ（−Ｏ−）3／29Ｓｉ（−Ｏ−）4を
０.１６〜１.８５の範囲に調整して添加する方法で行
い、シランカップリング剤添加量Ｓは全Ｃｒに対してモ
ル比でＳ／全Ｃｒ＝０.００２〜２.０の範囲にすること
を特徴としている。クロメ−ト処理液はオキシカルボン
酸化合物により６価クロムイオンを３価クロムイオンに
還元して、６価クロムイオンをＣｒ6+／全Ｃｒの比率で
０.１以下にしたものにするのが好ましい。処理液には
リン酸またはリン酸化合物をＰ／全Ｃｒ＝０.１〜４.０
の比率で添加することも可能である。クロメ−ト処理液
は被処理材に塗布した後、水洗することなく乾燥する。SUMMARY OF THE INVENTION The present invention relates to a chromat treatment solution to which a silica sol and a silane coupling agent are added, wherein the silica sol and the silane coupling agent are added to the chromat treatment solution before the addition. And a part of the silane coupling agent is bonded to the silica surface of the silica sol, and 29 Si (—O—) 3 and the silica sol caused by the silane coupling agent not reacting with the silica sol.
29 Si (-O-) 4 nuclear magnetic resonance analysis (NMR) peak - click intensity ratio R = 29 Si (-O-) 3 /29 Si (-O-) 4 of from 0.16 to 1.85 range The amount S of the silane coupling agent added is in the range of S / total Cr = 0.002 to 2.0 in molar ratio with respect to total Cr. The chromate treatment liquid is preferably prepared by reducing hexavalent chromium ions to trivalent chromium ions with an oxycarboxylic acid compound so that the ratio of hexavalent chromium ions to Cr 6+ / total Cr is 0.1 or less. preferable. The processing solution contains phosphoric acid or a phosphoric acid compound in a ratio of P / total Cr = 0.1 to 4.0.
It is also possible to add at a ratio of After the chromate treatment liquid is applied to the material to be treated, it is dried without washing.
【０００７】[0007]
【作用】クロメ−ト処理液にシリカゾルとシランカップ
リング剤とをそれぞれ耐指紋性、塗膜密着性を改善する
程度に直接添加したのでは、濃度が薄いため、両者は反
応しないが、両者を直接混合すると、反応する。ここ
で、シランカップリング剤として、オルガノトリアルコ
キシシランＲ1Ｓｉ（ＯＲ2）3［Ｒ1はアルキル基、エポ
キシ基、ビニル基、（メタ）アクリル基、アミノ基、Ｒ
2は水素またはアルキル基など］を使用すると、シラノ
−ルの構造はＲ1Ｓｉ（ＯＨ）3となる。そして、シリカ
ゾル表面へのシラノ−ルの反応程度は核磁気共鳴分析
（ＮＭＲ）でシリカゾルに起因する29Ｓｉ（−Ｏ−）4
のピ−クとシリカゾルに反応していないシランカップリ
ング剤に起因する29Ｓｉ（−Ｏ−）3のピ−クを測定
し、それらのピ−ク強度比から把握できる。そのため、
それらのピ−ク強度比を測定できれば、処理液保管安定
性とクロメ−ト皮膜の耐指紋性の管理が可能になる。If the silica sol and the silane coupling agent are directly added to the chromate treatment solution to the extent that the fingerprint resistance and the coating film adhesion are improved, respectively, the two do not react because the concentration is low. Reacts when mixed directly. Here, as the silane coupling agent, an organotrialkoxysilane R 1 Si (OR 2 ) 3 [R 1 is an alkyl group, an epoxy group, a vinyl group, a (meth) acryl group, an amino group,
When 2 is hydrogen or an alkyl group, the structure of silanol becomes R 1 Si (OH) 3 . The silanol to the silica sol surface - reaction about Le 29 due to the silica sol in the nuclear magnetic resonance analysis (NMR) Si (-O-) 4
The peak - click silica sol 29 due to unreacted silane coupling agent Si of (-O-) 3 peak - a click measure their peak - can be understood from the click intensity ratio. for that reason,
If these peak intensity ratios can be measured, it becomes possible to control the storage stability of the processing solution and the fingerprint resistance of the chromate film.
【０００８】そこで、シリカゾルとシランカップリング
剤とは、クロメ−ト処理液に添加する前予め混合して、
シリカゾルにシランカップリング剤を反応させた後、反
応していないシランカップリング剤濃度を確認し、クロ
メ−ト処理液に添加するようにすれば、クロメ−ト皮膜
の耐指紋性とクロメ−ト処理液の保管安定性とを調和さ
せることができる。シリカゾルに反応していないシラン
カップリング剤濃度の確認は核磁気共鳴分析による29Ｓ
ｉ（−Ｏ−）3と29Ｓｉ（−Ｏ−）4のピ−ク強度比Ｒ＝
29Ｓｉ（−Ｏ−）3／29Ｓｉ（−Ｏ−）4によればよい。
実験の結果、Ｒが０.１６より小さいと、クロメ−ト皮
膜の耐指紋性が不十分で、１.８５より大きくなると、
処理液に添加した場合、保管安定性が低下することが判
明した。このため、ピ−ク強度比Ｒは０.１６〜１.８５
にする必要があった。Therefore, the silica sol and the silane coupling agent are mixed in advance before being added to the chromatizing solution,
After reacting the silane coupling agent with the silica sol, the concentration of the unreacted silane coupling agent is checked, and if it is added to the chromate treatment solution, the fingerprint resistance of the chromate film and the chromate The storage stability of the processing solution can be harmonized. 29 S confirmation of the silane coupling agent concentration which does not react to silica sol by nuclear magnetic resonance analysis
i (-O-) 3 and 29 Si (-O-) 4 of peak - click intensity ratio R =
29 Si (-O-) 3/29 Si (-O-) or according to 4.
As a result of the experiment, if R is smaller than 0.16, the fingerprint resistance of the chromate film is insufficient, and if R is larger than 1.85,
It was found that when added to the processing solution, the storage stability was reduced. Therefore, the peak intensity ratio R is 0.16 to 1.85.
I needed to.
【０００９】シリカゾルとシランカップリング剤の混合
物のクロメ−ト処理液への添加は、シランカップリング
剤の全Ｃｒに対する添加量Ｓがモル比でＳ／全Ｃｒ＝
０.００２〜２.０になるように行う。Ｓ／全Ｃｒ＝０.
００２より少ないと、クロメ−ト皮膜の塗膜密着性向上
効果が小さく、Ｓ／全Ｃｒ＝２.０より多いと、シラン
カップリング剤同士が脱水縮合反応を起こし易くなるた
め、処理液の安定性が低下する。The addition of the mixture of the silica sol and the silane coupling agent to the chromatizing solution is performed by adding the silane coupling agent to the total Cr in a molar ratio of S / total Cr = S / total Cr =
It is performed so as to be 0.002 to 2.0. S / All Cr = 0.
If it is less than 002, the effect of improving the adhesion of the chromate film to the coating film is small, and if it is more than S / total Cr = 2.0, the silane coupling agents tend to undergo a dehydration-condensation reaction. Is reduced.
【００１０】クロメ−ト処理液でオキシカルボン酸化合
物により６価クロムイオンを３価クロムイオンに還元す
る場合、処理液にリン酸またはリン酸化合物を添加する
と、少ない添加量で還元を促進することができるが、こ
れはシリカゾルとシランカップリング剤とを添加した場
合にも適用できる。しかし、添加量はＰ／全Ｃｒ＝０.
１〜４.０になるようにする。０.１未満であると、クロ
メ−ト皮膜難溶化による耐食性の向上が小さく、４.０
を超えると、処理液の安定性が低下するようになる。In the case where hexavalent chromium ions are reduced to trivalent chromium ions by an oxycarboxylic acid compound in a chromate treatment solution, the addition of phosphoric acid or a phosphate compound to the treatment solution promotes the reduction with a small amount of addition. However, this can be applied to the case where a silica sol and a silane coupling agent are added. However, the added amount was P / total Cr = 0.
It should be 1 to 4.0. When it is less than 0.1, the improvement in corrosion resistance due to the insolubilization of the chromate film is small, and it is less than 4.0.
If it exceeds, the stability of the processing solution will decrease.
【００１１】被処理材への処理液塗布は、従来の塗布型
クロメ−ト処理の場合と同様に公知方法、例えば、ロ−
ルコ−ト法、エア−カ−テン法、静電霧化法、スクイズ
ロ−ルコ−ト法などにより行い、水洗せずに乾燥する方
法で行う。The treatment liquid is applied to the material to be treated in the same manner as in the case of the conventional coating type chromate treatment.
It is carried out by a coating method, an air curtain method, an electrostatic atomization method, a squeeze roll coating method, etc., and a method of drying without washing with water.
【００１２】[0012]
【実施例】シリカゾルとシランカップリング剤とを種々
の割合に混合して、シランカップリング剤の一部をシリ
カゾルのシリカ表面に反応させた後、核磁気共鳴分析で
シリカゾルに反応してないシランカップリング剤に起因
した29Ｓｉ（−Ｏ−）3とシリカゾルに起因した29Ｓｉ
（−Ｏ−）4のピ−ク強度比Ｒ＝29Ｓｉ（−Ｏ−）3／29
Ｓｉ（−Ｏ−）4を求め、シリカゾルに反応していない
シランカップリング剤濃度を確認する方法で添加液を調
製した。一方、これとは別に、無水クロム酸水溶液にポ
リビニルアルコ−ルを添加して、Ｃｒ6+／全Ｃｒの比率
を０.６にしたクロメ−ト処理液を調製した。そして、
このクロメ−ト処理液に前記添加液を加えて、溶融亜鉛
めっき鋼板（板厚０.５ｍｍ、片面Ｚｎ付着量６０ｇ／
ｍ2）にロ−ルコ−ト法で塗布し、到達板温１２０℃で
乾燥した。表１にクロメ−ト処理液組成、クロメ−ト皮
膜のクロム付着量を示す。EXAMPLE A silica sol and a silane coupling agent were mixed in various ratios, and a part of the silane coupling agent was allowed to react on the silica surface of the silica sol. 29 Si (-O-) 3 and silica sol 29 due to Si due to the coupling agent
(-O-) 4 of peak - click intensity ratio R = 29 Si (-O-) 3 /29
Si (-O-) 4 was determined, and an additive solution was prepared by a method of confirming the concentration of the silane coupling agent not reacting with the silica sol. Separately, polyvinyl alcohol was added to an aqueous solution of chromic anhydride to prepare a chromate treatment solution in which the ratio of Cr 6+ / total Cr was 0.6. And
The above-mentioned additive solution was added to this chromate treatment solution, and a hot-dip galvanized steel sheet (sheet thickness: 0.5 mm, Zn adhesion amount on one side: 60 g /
m 2 ) was applied by a roll coating method and dried at an ultimate plate temperature of 120 ° C. Table 1 shows the composition of the chromate treatment solution and the amount of chromium adhering to the chromate film.
【００１３】[0013]
【表１】 （注）シランカップリング剤の種類 Ａ：アミノ系（γ−アミノプロピルトリエトキシシラ
ン） Ｂ：エポキシ系（γ−グリシドキシプロピルトリメトキ
シシラン） Ｃ：ＡとＢとを１：１のモル比で混合したもの[Table 1] (Note) Type of silane coupling agent A: Amino-based (γ-aminopropyltriethoxysilane) B: Epoxy-based (γ-glycidoxypropyltrimethoxysilane) C: A: B molar ratio of 1: 1 Mixed with
【００１４】次に、クロメ−ト処理鋼板に以下のような
性能試験を実施した。この結果を表２に示す。 （１）処理液の安定性試験 処理液を容器中に密封して、４０℃の雰囲気中に放置
し、処理液に増粘やゲル化が認められるまでの時間を測
定した。そして、３カ月経過しても増粘やゲル化の認め
られないものを記号◎で、１カ月経過するまで増粘やゲ
ル化が認められないものを記号○で、１カ月経過前に増
粘やゲル化が認められたものを記号×で評価した。 （２）塗膜密着性試験 溶剤系のアミノアルキッド塗料［関西ペイント（株）
製、アミラック１５３１、乾燥塗膜厚３０μｍ］または
エポキシ塗料［東洋インキ（株）製、ＳＳ−２５−９１
１、乾燥塗膜厚５μｍ］を塗装した後、９０℃の熱水に
２時間浸漬して、ＪＩＳ Ｋ ５４００の碁盤目法に準
拠した塗膜密着性試験を行い、塗膜残存率が８０％以上
のものを記号○で、６０％以上、８０％未満のものを記
号△で、６０％未満のものを記号×で評価した。Next, the following performance tests were performed on the chromate-treated steel sheet. Table 2 shows the results. (1) Stability test of treatment liquid The treatment liquid was sealed in a container, left in an atmosphere of 40 ° C, and the time until thickening or gelation was observed in the treatment liquid was measured. If no thickening or gelling was observed even after 3 months, the symbol ◎ indicates that no thickening or gelling was observed until 1 month. And those in which gelation was observed were evaluated with the symbol x. (2) Paint adhesion test Solvent-based amino alkyd paint [Kansai Paint Co., Ltd.
Amirac 1531, dry film thickness 30 μm] or epoxy paint [SS-25-91, manufactured by Toyo Ink Co., Ltd.]
1, dried coating thickness 5 μm], immersed in hot water at 90 ° C. for 2 hours, and performed a coating adhesion test in accordance with the cross-cut method of JIS K 5400. The coating residual ratio was 80%. The above items were evaluated by the symbol 、, those of 60% or more and less than 80% were evaluated by the symbol 、, and those of less than 60% were evaluated by the symbol ×.
【００１５】（３）耐指紋性試験 試験片に対して人工指紋液に浸漬したゴム栓を押し付け
て、試験前後の明度差をＪＩＳ Ｚ ８７３０に準じた
Ｌａｂ法によるＬ値から測定し、ΔＬが２未満のものを
記号○で、２以上、４未満のものを記号△で、４以上の
ものを記号×で評価した。 （４）耐食性試験 塩水噴霧試験（ＪＩＳ Ｚ ２３７１）を１２０時間実
施して、白錆発生率が全面積の３％未満のものを記号◎
で、３％以上、２０％未満のものを記号○で、２０％以
上、５０％未満のものを記号△で、５０％以上のものを
記号×で評価した。 （５）耐Ｃｒ6+溶出性試験 クロメ−ト処理鋼板の試験片を９０℃の熱水に３分間浸
漬して、Ｃｒ6+溶出量を測定し、溶出量が１ｍｇ／ｍ2
未満のものを記号○で、１ｍｇ／ｍ2以上、５ｍｇ／ｍ2
未満のものを記号△で、５ｍｇ／ｍ2以上のものを記号
×で評価した。(3) Fingerprint resistance test A rubber stopper immersed in an artificial fingerprint solution was pressed against the test piece, and the difference in lightness before and after the test was measured from the L value by the Lab method according to JIS Z 8730, and ΔL was determined. Those with less than 2 were evaluated with the symbol で, those with 2 or more and less than 4 were evaluated with the symbol △, and those with 4 or more were evaluated with the symbol x. (4) Corrosion resistance test A salt spray test (JIS Z 2371) was performed for 120 hours.
And 3% or more and less than 20% were evaluated with the symbol 、, 20% or more and less than 50% were evaluated with the symbol 、, and 50% or more were evaluated with the symbol x. (5) Cr 6+ elution resistance test A test piece of a chromate treated steel sheet was immersed in hot water at 90 ° C. for 3 minutes, and the amount of Cr 6+ eluted was measured, and the elution amount was 1 mg / m 2.
Less than 1 mg / m 2 and 5 mg / m 2
Those with less than 5 mg / m 2 were evaluated with the symbol x and those with 5 mg / m 2 or more were evaluated with the symbol x.
【００１６】[0016]
【表２】 [Table 2]
【００１７】実施例２ 実施例１において、クロメ−ト処理液として、クロム酸
アンモニウム水溶液にグリコ−ル酸と酒石酸とを添加し
て、Ｃｒ6+／全Ｃｒの比率を０.０５にしたものを用い
た。また、処理液を塗布する鋼板を電気亜鉛めっき鋼板
（板厚０.８ｍｍ、片面Ｚｎ付着量２０ｇ／ｍ2）を用
い、乾燥温度を１５０℃に変更した。この処理液組成を
表３に示す。また、実施例１と同様の性能試験を実施し
た結果を表４に示す。Example 2 In Example 1, a chromate treatment solution was prepared by adding glycolic acid and tartaric acid to an aqueous solution of ammonium chromate to adjust the ratio of Cr 6+ / total Cr to 0.05. Was used. The steel sheet to which the treatment liquid was applied was an electrogalvanized steel sheet (0.8 mm in thickness, 20 g / m 2 on one side of Zn), and the drying temperature was changed to 150 ° C. Table 3 shows the composition of the treatment liquid. Table 4 shows the results of performance tests performed in the same manner as in Example 1.
【００１８】[0018]
【表３】 （注）シランカップリング剤の種類 Ａ：アミノ系（γ−アミノプロピルトリエトキシシラ
ン） Ｂ：エポキシ系（γ−グリシドキシプロピルトリメトキ
シシラン） Ｃ：ＡとＢとを１：１のモル比で混合したもの[Table 3] (Note) Type of silane coupling agent A: Amino-based (γ-aminopropyltriethoxysilane) B: Epoxy-based (γ-glycidoxypropyltrimethoxysilane) C: A: B molar ratio of 1: 1 Mixed with
【００１９】[0019]
【表４】 [Table 4]
【００２０】実施例３ 実施例２において、処理液として、実施例Ｎｏ.２４、
２６、２７、２９、３０、３１にリン酸を添加したもの
を用いた。また、塗布はクロム付着量が４０ｍｇ／ｍ2
一定となるように行った。表５にクロメ−ト処理液組成
と実施例１と同様の性能試験を実施した結果を示す。Example 3 In Example 2, the treatment liquid used in Example No. 24,
Those obtained by adding phosphoric acid to 26, 27, 29, 30, and 31 were used. In addition, the amount of chromium applied was 40 mg / m 2.
Performed to be constant. Table 5 shows the composition of the chromate treatment solution and the results of the same performance test as in Example 1.
【００２１】[0021]
【表５】 [Table 5]
【００２２】[0022]
【発明の効果】以上のように、シリカゾルとシランカッ
プリング剤のクロメ−ト処理液への添加を、添加前に予
め両者を混合して、シランカップリング剤の一部をシリ
カゾルのシリカ表面に結合させ、シリカゾルに反応しな
いシランカップリング剤に起因した29Ｓｉ（−Ｏ−）3
とシリカゾルに起因した29Ｓｉ（−Ｏ−）4の核磁気共
鳴分析（ＮＭＲ）ピ−ク強度比Ｒ＝29Ｓｉ（−Ｏ−）3
／29Ｓｉ（−Ｏ−）4を０.１６〜１.８５の範囲に調整
して添加する方法で行い、かつ、シランカップリング剤
添加量Ｓは全Ｃｒに対してモル比でＳ／全Ｃｒ＝０.０
０２〜２.０の範囲にすると、クロメ−ト処理液の保管
安定性とクロメ−ト皮膜の耐指紋性とを調和させること
ができる。この調和はオキシカルボン酸化合物により６
価クロムイオンを３価クロムイオンに還元して、６価ク
ロムイオンをＣｒ6+／全Ｃｒの比率で０.１以下にした
クロメ−ト処理液にも適用でき、リン酸またはリン酸化
合物をＰ／全Ｃｒ＝０.１〜４.０の比率になるように添
加して還元を促進したりすることもできる。さらに、ク
ロメ−ト処理液を被処理材に塗布した後、水洗すること
なく乾燥すれば、塗膜密着性に優れたクロメ−ト皮膜を
形成できる。As described above, the addition of the silica sol and the silane coupling agent to the chromatizing treatment solution is carried out by mixing the two beforehand and adding a part of the silane coupling agent to the silica surface of the silica sol. 29 Si (-O-) 3 due to the silane coupling agent that is bound and does not react with the silica sol
29 due to the silica sol and Si (-O-) 4 nuclear magnetic resonance analysis (NMR) peak - click intensity ratio R = 29 Si (-O-) 3
/ 29 Si (-O-) 4 was carried out in a manner that is added to adjust the range of 0.16 to 1.85, and a silane coupling agent amount S is S / total molar ratio relative to total Cr Cr = 0.0
When it is in the range of 02 to 2.0, the storage stability of the chromate treatment solution and the fingerprint resistance of the chromate film can be harmonized. This harmony is achieved by the oxycarboxylic acid compound.
It can also be applied to a chromate treatment solution in which hexavalent chromium ions are reduced to trivalent chromium ions and hexavalent chromium ions are reduced to 0.1 or less in the ratio of Cr 6+ / total Cr. P / total Cr = 0.1 to 4.0 may be added to promote reduction. Further, if the chromate treatment liquid is applied to the material to be treated and then dried without washing with water, a chromate film having excellent coating film adhesion can be formed.
フロントページの続き (72)発明者 武津 博文 大阪府堺市石津西町５番地 日新製鋼株式 会社技術研究所表面処理研究部内 Ｆターム(参考） 4K026 AA02 AA07 AA12 AA13 AA22 BA06 BA07 BB06 BB08 BB10 CA16 CA19 CA20 CA21 CA37 CA38 CA39 DA02 DA11 Continued on the front page (72) Inventor Hirofumi Takezu 5th Ishizu Nishimachi, Sakai City, Osaka Pref. CA20 CA21 CA37 CA38 CA39 DA02 DA11
Claims (4)
添加したクロメ−ト処理液において、シリカゾルとシラ
ンカップリング剤のクロメ−ト処理液への添加は添加前
に予め両者を混合して、シランカップリング剤の一部を
シリカゾルのシリカ表面に結合させ、シリカゾルに反応
してないシランカップリング剤に起因した29Ｓｉ（−Ｏ
−）3とシリカゾルに起因した29Ｓｉ（−Ｏ−）4の核磁
気共鳴分析（ＮＭＲ）ピ−ク強度比Ｒ＝29Ｓｉ（−Ｏ
−）3／29Ｓｉ（−Ｏ−）4を０.１６〜１.８５の範囲に
調整して添加する方法で行い、シランカップリング剤添
加量Ｓは全Ｃｒに対してモル比でＳ／全Ｃｒ＝０.００
２〜２.０の範囲にすることを特徴とするクロメ−ト処
理液。1. In a chromat treatment solution to which a silica sol and a silane coupling agent are added, the silica sol and the silane coupling agent are added to the chromat treatment solution in advance by mixing the two before addition. A part of the agent is bonded to the silica surface of the silica sol, and 29 Si (—O
-) 3 and silica sol 29 Si due to (-O-) 4 nuclear magnetic resonance analysis (NMR) peak - click intensity ratio R = 29 Si (-O
-) 3/29 Si (-O- ) 4 was carried out in a manner that is added to adjust the range of 0.16 to 1.85, the amount added silane coupling agent S is S in a molar ratio to the total Cr / Total Cr = 0.00
A chromate treatment solution characterized by being in the range of 2 to 2.0.
化合物により６価クロムイオンを３価クロムイオンに還
元して、６価クロムイオンをＣｒ6+／全Ｃｒの比率で
０.１以下にしたものであることを特徴とする請求項１
に記載のクロメ−ト処理液。2. The chromate treatment liquid reduces hexavalent chromium ions to trivalent chromium ions with an oxycarboxylic acid compound to reduce the hexavalent chromium ions to a ratio of Cr 6+ / total Cr of 0.1 or less. 2. The method according to claim 1, wherein
The chromate treatment liquid described in 1.
またはリン酸化合物をＰ／全Ｃｒ＝０.１〜４.０の比率
で添加したことを特徴とするクロメ−ト処理液。3. A chromate treatment liquid, wherein phosphoric acid or a phosphoric acid compound is added to the chromate treatment liquid according to claim 1 in a ratio of P / total Cr = 0.1 to 4.0.
メ−ト処理液を被処理材に塗布した後、水洗することな
く乾燥することを特徴とするクロメ−ト処理方法。4. A method for chromate treatment, comprising applying the chromate treatment liquid according to any one of claims 1 to 3 to a material to be treated and drying without washing with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27584299A JP2001098384A (en) | 1999-09-29 | 1999-09-29 | Chromate treating solution and treating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27584299A JP2001098384A (en) | 1999-09-29 | 1999-09-29 | Chromate treating solution and treating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001098384A true JP2001098384A (en) | 2001-04-10 |
Family
ID=17561205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27584299A Pending JP2001098384A (en) | 1999-09-29 | 1999-09-29 | Chromate treating solution and treating method |
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| Country | Link |
|---|---|
| JP (1) | JP2001098384A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001170557A (en) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | Surface treatment liquid for plated steel plate and treating method therefor |
| JP2021507991A (en) * | 2017-12-22 | 2021-02-25 | ポスコＰｏｓｃｏ | Solution composition for surface treatment of steel sheet and steel sheet surface-treated using it |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6283478A (en) * | 1985-10-09 | 1987-04-16 | Sumitomo Metal Ind Ltd | Chromated steel material having superior adhesion to coating |
| JPH03234527A (en) * | 1990-02-09 | 1991-10-18 | Nippon Steel Corp | Polyolefin coated steel material |
| JPH09195063A (en) * | 1996-01-12 | 1997-07-29 | Kobe Steel Ltd | White chromate treated steel sheet excellent in corrosion resistance and appearance |
| JPH1081976A (en) * | 1996-09-05 | 1998-03-31 | Nisshin Steel Co Ltd | Chromate treating solution and treatment |
| JPH1088010A (en) * | 1996-09-17 | 1998-04-07 | Nippon Paint Co Ltd | Curable resin composition |
-
1999
- 1999-09-29 JP JP27584299A patent/JP2001098384A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6283478A (en) * | 1985-10-09 | 1987-04-16 | Sumitomo Metal Ind Ltd | Chromated steel material having superior adhesion to coating |
| JPH03234527A (en) * | 1990-02-09 | 1991-10-18 | Nippon Steel Corp | Polyolefin coated steel material |
| JPH09195063A (en) * | 1996-01-12 | 1997-07-29 | Kobe Steel Ltd | White chromate treated steel sheet excellent in corrosion resistance and appearance |
| JPH1081976A (en) * | 1996-09-05 | 1998-03-31 | Nisshin Steel Co Ltd | Chromate treating solution and treatment |
| JPH1088010A (en) * | 1996-09-17 | 1998-04-07 | Nippon Paint Co Ltd | Curable resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001170557A (en) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | Surface treatment liquid for plated steel plate and treating method therefor |
| JP2021507991A (en) * | 2017-12-22 | 2021-02-25 | ポスコＰｏｓｃｏ | Solution composition for surface treatment of steel sheet and steel sheet surface-treated using it |
| JP7281467B2 (en) | 2017-12-22 | 2023-05-25 | ポスコ カンパニー リミテッド | surface treated steel plate |
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