JP2000192251A - Chromate treating solution and treatment - Google Patents
Chromate treating solution and treatmentInfo
- Publication number
- JP2000192251A JP2000192251A JP10367477A JP36747798A JP2000192251A JP 2000192251 A JP2000192251 A JP 2000192251A JP 10367477 A JP10367477 A JP 10367477A JP 36747798 A JP36747798 A JP 36747798A JP 2000192251 A JP2000192251 A JP 2000192251A
- Authority
- JP
- Japan
- Prior art keywords
- ratio
- chromate
- chromate treatment
- total
- chromium ions
- 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、塗膜密着性に優れた耐
クロム溶出性のクロメ−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 treatment solution and a treatment method capable of forming a chromium-resistant elution chromate film having excellent 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。この処理液では含有クロムイオンがす
べて６価クロムイオンであると、クロムイオンが溶出し
易く、また、吸湿性になる。このため、通常、６価クロ
ムイオンの一部を還元剤で不溶性の３価クロムイオンに
還元して、クロメ−ト皮膜の耐クロムイオン溶出性、耐
湿性を高めている。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. If all chromium ions contained in this treatment liquid are hexavalent chromium ions, the chromium ions are easily eluted and become hygroscopic. For this reason, usually, a part of hexavalent chromium ions is reduced to insoluble trivalent chromium ions with a reducing agent to improve the chromium ion elution resistance and moisture resistance of the chromate film.
【０００３】６価クロムイオンの３価クロムイオンへの
還元は、還元剤として、澱粉、ポリビニルアルコ−ル、
ホルマリンのような有機化合物や過酸化水素のような無
機化合物を用いて還元率５０％以上に還元すると、還元
率の上昇に伴ってｐＨも上昇するため、３価クロムイオ
ンが水酸化クロム化合物等に変化して、処理液のゲル化
や沈降が生じ、被処理材への塗布が困難になる。このた
め、従来、６価クロムイオンの還元率を５０％以上にす
るのは困難であったが、近年、還元剤にオキシカルボン
酸化合物またはこれとリン酸もしくはリン酸化合物を使
用すると、還元率を５０％以上にしても処理液はゲル化
しないことが判明した（特開平１０−８１９７６号公
報、同１０−８１９７７号公報）。ここで、オキシカル
ボン酸化合物とは、例えば、酒石酸、マロン酸、クエン
酸、乳酸、グルコ−ル酸、グリセリン酸、トロパ酸、ベ
ンジル酸、ヒドロキシ吉草酸等である。[0003] The reduction of hexavalent chromium ions to trivalent chromium ions is carried out by using starch, polyvinyl alcohol,
When the reduction rate is reduced to 50% or more using an organic compound such as formalin or an inorganic compound such as hydrogen peroxide, the pH increases with an increase in the reduction rate. , The treatment liquid is gelled or settled, and it becomes difficult to apply the treatment liquid to the material to be treated. For this reason, it has conventionally been difficult to reduce the reduction rate of hexavalent chromium ions to 50% or more. However, in recent years, when an oxycarboxylic acid compound or a phosphoric acid or a phosphoric acid compound is used as a reducing agent, the reduction rate is reduced. It has been found that the treatment liquid does not gel even when the concentration is 50% or more (Japanese Patent Application Laid-Open Nos. 10-81976 and 10-81977). Here, the oxycarboxylic acid compound is, for example, tartaric acid, malonic acid, citric acid, lactic acid, gluconic acid, glyceric acid, tropic acid, benzylic acid, hydroxyvaleric acid and the like.
【０００４】しかし、クロメ−ト処理液の６価クロムイ
オンをオキシカルボン酸化合物により３価クロムに還元
して、６価クロムイオンがＣｒ6+／全Ｃｒの比率で０.
１以下になるようにすると、クロメ−ト皮膜の塗膜密着
性が塗料の種類により不十分となる場合があった。これ
はクロメ−ト処理液が水溶性もしくは水分散性有機樹脂
とを含有する場合も同じであった。However, hexavalent chromium ions in the chromatized solution are reduced to trivalent chromium by an oxycarboxylic acid compound, and the hexavalent chromium ions are reduced to a ratio of Cr 6+ / total Cr of 0.1 .
If the ratio is set to 1 or less, the adhesion of the chromate coating film may be insufficient depending on the type of the coating material. This was the same when the chromate treatment liquid contained a water-soluble or water-dispersible organic resin.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、６価クロム
イオンをＣｒ6+／全Ｃｒの比率で０.１以下になるよう
に還元しても、塗膜密着性の優れたクロメ−ト皮膜を形
成できるクロメ−ト処理液および処理方法を提供するも
のである。SUMMARY OF THE INVENTION The present invention provides a chromate having excellent coating film adhesion even if the hexavalent chromium ion is reduced so that the ratio of Cr 6+ / total Cr becomes 0.1 or less. An object of the present invention is to provide a chromate treatment solution and a treatment method capable of forming a film.
【０００６】[0006]
【課題を解決するための手段】本発明は、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、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−ト処理液において、シランカ
ップリング剤を添加して、添加量Ｓを全Ｃｒに対するモ
ル比でＳ／全Ｃｒ＝０.０１〜３.０にしたことを特徴と
するクロメ−ト処理液にするか、またはこの処理液にリ
ン酸またはリン酸化合物をＰ／全Ｃｒ＝０.１〜４.０の
比率あるいはシリカゾルをＳｉ／全Ｃｒ＝０.５〜３.０
の比率で添加した処理液にする。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。According to the present invention, hexavalent chromium ions are reduced to trivalent chromium ions by an oxycarboxylic acid compound, and the hexavalent chromium ions are reduced to a Cr 6+ / total Cr ratio of 0.1 or less. A chromate treatment solution characterized in that a silane coupling agent is added to the chromate treatment solution thus prepared, and the added amount S is set to a molar ratio of S / total Cr = 0.01-3.0. Or a phosphoric acid or a phosphoric acid compound in a ratio of P / total Cr = 0.1 to 4.0 or a silica sol to Si / total Cr = 0.5 to 3.0.
To make the processing solution added at the ratio of After the chromate treatment liquid is applied to the material to be treated, it is dried without washing.
【０００７】[0007]
【作用】本発明のクロメ−ト処理液で被処理材を処理し
た場合、クロメ−ト皮膜にシランカップリング剤が含有
されるので、処理材に塗装を施した場合、塗膜密着性は
向上する。シランカップリング剤は全Ｃｒに対する添加
量Ｓがモル比でＳ／全Ｃｒ＝０.０１より少ないと、塗
膜密着性向上効果が小さく、Ｓ／全Ｃｒ＝３.０より多
いと、シランカップリング剤同士が凝集反応を起こし易
くなるため、処理液の安定性が低下する。このため、Ｓ
／全Ｃｒ＝０.０１〜３.０にする。When the material to be treated is treated with the chromate treatment liquid of the present invention, the chromium film contains a silane coupling agent, so that when the treated material is coated, the coating film adhesion is improved. I do. When the addition amount S of the silane coupling agent to the total Cr is less than S / total Cr = 0.01 in molar ratio, the effect of improving the coating film adhesion is small. Since the ringing agents tend to cause an agglutination reaction, the stability of the treatment liquid is reduced. Therefore, S
/ Set all Cr = 0.01 to 3.0.
【０００８】シランカップリング剤の種類としては、と
くに制限はなく、例えば、アミノ系、ウレイド系、ビニ
ル系、メタクリル系、エポキシ系、メルカプト系、イソ
シアネ−ト系などの１種または２種以上を使用すればよ
い。具体的には、アミノ系として、γ−アミノプロピル
トリエトキシシラン、γ−アミノ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−フェニルアミノプロピルト
リメトキシシランなどが挙げられ、ウレイド系として
は、ウレイドプロピルトリエトキシシラン、ビニル系と
しては、ビニルトリエトキシシラン、ビニルトリメトキ
シシラン、ビニルトリス（β−メトキシエトキシ）シラ
ンなどが挙げられる。また、メタクリル系としては、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が、エポ
キシ系としては、β−（３,４−エポキシシクロヘキシ
ル）エチルトリメトキシシランが挙げられる。さらに、
メルカプト系としては、γ−メルカプトプロピルトリメ
トキシシランが、イソシアネ−ト系としては、γ−イソ
シアネ−トプロピルトリエトキシシラン、γ−グリシド
キシプロピルトリメトキシシランなどが挙げられる。The type of the silane coupling agent is not particularly limited. For example, one or two or more of amino, ureide, vinyl, methacryl, epoxy, mercapto, isocyanate, etc. may be used. Just use it. Specifically, as the amino group, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane Examples of the ureide type include ureidopropyltriethoxysilane, and examples of the vinyl type include vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β-methoxyethoxy) silane. As methacrylic compounds, γ
-Methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane, and epoxy-based resins include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. further,
Examples of the mercapto type include γ-mercaptopropyltrimethoxysilane, and examples of the isocyanate type include γ-isocyanatopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane.
【０００９】シランカップリング剤の添加量Ｓは、全Ｃ
ｒに対するモル比でＳ／全Ｃｒ＝３.０以下にすれば、
処理液の安定性が得られるのであるが、この安定性はシ
ランカップリング剤にオルガノアルコキシシランを使用
する場合、その加水分解物であるオルガノシラノ−ルを
一部混合しておくと、処理液が長期間安定するようにな
る。この理由は明らかでないが、オルガノアルコキシシ
ランのアルコキシ基が水酸基に加水分解される過程で、
オキシカルボン酸化合物と錯体を形成している３価クロ
ムに影響を及ぼし、処理液の安定性を高めるものと推定
される。オルガノシラノ−ルの混合量は前者の29Ｓｉ−
ＯＲと後者の29Ｓｉ−ＯＨの核磁気共鳴分析（ＮＭＲ）
ピ−ク強度比29Ｓｉ−ＯＲ／29Ｓｉ−ＯＨが３.０以下
になるようにするのが好ましい。The addition amount S of the silane coupling agent is
If S / total Cr = 3.0 or less in a molar ratio to r,
The stability of the processing solution can be obtained. However, when organoalkoxysilane is used as a silane coupling agent, the stability of the processing solution can be improved by partially mixing the organosilanol as its hydrolyzate. Becomes stable for a long time. Although the reason for this is not clear, in the process where the alkoxy group of the organoalkoxysilane is hydrolyzed to a hydroxyl group,
It is presumed that it affects trivalent chromium which forms a complex with the oxycarboxylic acid compound, and enhances the stability of the treatment liquid. The amount of organosilanol mixed was the same as that of the former 29 Si-
Nuclear magnetic resonance analysis (NMR) of OR and the latter 29 Si-OH
It is preferable that the peak intensity ratio 29 Si-OR / 29 Si-OH be 3.0 or less.
【００１０】オキシカルボン酸化合物による６価クロム
イオンの３価クロムイオンへの還元は、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、これはシランカップリング
剤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、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。The reduction of hexavalent chromium ions to trivalent chromium ions by an oxycarboxylic acid compound can be accelerated by adding a small amount of phosphoric acid or a phosphoric acid compound to the treatment solution. It is also applicable when a silane coupling agent is added. However, the added amount is P
/ All Cr = 0.1 to 4.0. If it is less than 0.1, the improvement in corrosion resistance due to the insolubility of the film is small,
If it exceeds 4.0, the stability of the processing solution will decrease.
【００１１】また、クロメ−ト処理液には、シリカゾル
を添加して、クロメ−ト皮膜の耐食性や耐湿性を高める
ことが従来より行われているが、このクロメ−ト処理液
の場合にもシリカゾルを添加することは可能である。こ
の場合、Ｓｉ／全Ｃｒ＝０.５〜３.０の比率で添加する
のが好ましい。０.５より少ないと、耐食性向上効果が
小さく、３.０より多いと、耐水２次密着性が低下す
る。また、水溶性もしくは水分散性の有機樹脂を添加し
て、塗膜密着性を高めることも行われているが、このク
ロメ−ト処理液の場合もそのような有機樹脂の添加は可
能である。It has been conventionally practiced to add a silica sol to a chromate treatment liquid to enhance the corrosion resistance and moisture resistance of the chromate film. It is possible to add silica sol. In this case, it is preferable to add Si / total Cr at a ratio of 0.5 to 3.0. If it is less than 0.5, the effect of improving the corrosion resistance is small, and if it is more than 3.0, the water-resistant secondary adhesion decreases. It has also been practiced to add a water-soluble or water-dispersible organic resin to increase the coating film adhesion. However, in the case of this chromatized solution, such an organic resin can be added. .
【００１２】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.
【００１３】[0013]
【実施例】無水クロム酸水溶液に乳酸と酒石酸とを添加
して、Ｃｒ6+／全Ｃｒの比率を０.１にした後、シラン
カップリング剤を添加する方法で種々のクロメ−ト処理
液を調製した。そして、この処理液を電気亜鉛めっき鋼
板（板厚０.８ｍｍ、片面Ｚｎ付着量２０ｇ／ｍ2）にロ
−ルコ−ト法で塗布し、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。EXAMPLES Various chromate treatment solutions were prepared by adding lactic acid and tartaric acid to an aqueous solution of chromic anhydride to adjust the ratio of Cr 6+ / total Cr to 0.1 and then adding a silane coupling agent. Was prepared. Then, this treatment solution was applied to an electrogalvanized steel sheet (sheet thickness: 0.8 mm, one-side Zn adhesion amount: 20 g / m 2 ) by a roll coating method, and dried at 120 ° C. Table 1 shows the composition of the chromate treatment solution and the amount of chromium adhering to the chromate film.
【００１４】[0014]
【表１】 （注）シランカップリング剤の種類 Ａ：γ−アミノプロピルトリエトキシシラン Ｂ：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) Kind of silane coupling agent A: γ-aminopropyltriethoxysilane B: γ-glycidoxypropyltrimethoxysilane C: A mixture of A and B in a 1: 1 molar ratio
【００１５】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 ４０℃の処理液をロ−ルコ−タ−にセットして、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、４８時間経過しても増粘やゲル化の認められない
ものを記号◎で、２４時間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、２４時間経過前に増粘や
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 有機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］
またはエポキシ系塗料［東洋インキ（株）製、ＳＳ−２
５−９１１、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８
０％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 A treatment liquid at 40 ° C was set on a roll coater, and the time until thickening or gelation was observed in the treatment liquid was measured. A mark ４８ indicates that no thickening or gelation was observed even after 48 hours, and a sign ○ indicates that no thickening or gelation was observed until 24 hours had passed. And those in which gelation was observed were evaluated with the symbol x. (2) Coating film adhesion test Organic solvent-based amino alkyd paint [Kansai Paint Co., Ltd., Amirac 1531, dry coating thickness 30 μm]
Or epoxy paint [Toyo Ink Co., Ltd., SS-2
5-911, dried film thickness 5 μm], and then applied at 90 ° C.
And immersed in hot water for 2 hours to conduct a coating adhesion test in accordance with the grid method of JIS K 5400.
Those with 0% or more were evaluated with the symbol 、, those with 60% or more and less than 80% were evaluated with the symbol 、, and those with less than 60% were evaluated with the symbol x.
【００１６】（３）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。 （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。(3) 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, 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. (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.
【００１７】[0017]
【表２】 [Table 2]
【００１８】実施例２ 全Ｃｒ濃度が１５ｇ／Ｌである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にした後、まずシランカップリン
グ剤を添加し、次に、リン酸および／またはシリカゾル
を添加する方法で種々のクロメ−ト処理液を調製した。
そして、この処理液を溶融亜鉛めっき鋼板（板厚０.５
ｍｍ、片面Ｚｎ付着量６０ｇ／ｍ2）にロ−ルコ−ト法
でクロメ−ト皮膜のＣｒ付着量が４０ｍｇ／ｍ2一定と
なるように塗布し、１５０℃で乾燥した。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 Glycolic acid and tartaric acid were added to an aqueous solution of ammonium chromate having a total Cr concentration of 15 g / L to make the ratio of Cr 6+ / total Cr 0.05, and then silane was added. Various chromate treatment solutions were prepared by adding a coupling agent and then adding phosphoric acid and / or silica sol.
Then, this treatment solution is applied to a hot-dip galvanized steel sheet (sheet thickness 0.5).
mm, the amount of Zn deposited on one side was 60 g / m 2 ), and the coating was applied by a roll coating method so that the Cr adhesion of the chromate film was constant at 40 mg / m 2 and dried at 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.
【００１９】[0019]
【表３】 （注）シランカップリング剤の種類 Ａ：γ−アミノプロピルトリエトキシシラン Ｂ：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) Kind of silane coupling agent A: γ-aminopropyltriethoxysilane B: γ-glycidoxypropyltrimethoxysilane C: A mixture of A and B in a 1: 1 molar ratio
【００２０】[0020]
【表４】 （注）実施例２９は処理液ゲル化のため、性能評価は困
難であった。[Table 4] (Note) In Example 29, performance evaluation was difficult due to gelation of the treatment liquid.
【００２１】[0021]
【発明の効果】以上のように、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、
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−ト処理液において、シランカップリング
剤を添加して、添加量Ｓを全Ｃｒに対するモル比でＳ／
全Ｃｒ＝０.０１〜３.０にすると、塗膜密着性の優れた
クロメ−ト皮膜を形成できる。また、このクロメ−ト処
理液に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、シリカゾルを添加して塗膜密着性を高めたりするこ
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, hexavalent chromium ions are reduced to trivalent chromium ions by an oxycarboxylic acid compound,
In a chromate treatment solution in which hexavalent chromium ions are reduced to 0.1 or less in the ratio of Cr 6+ / total Cr, a silane coupling agent is added, and the added amount S is S / molar to the total Cr.
When the total Cr is 0.01 to 3.0, a chromate film having excellent coating film adhesion can be formed. Further, phosphoric acid or a phosphoric acid compound was added to the chromatized solution with P / total Cr = 0.1.
It can be added so as to have a ratio of up to 4.0 to promote reduction, or silica sol can be added to enhance coating film adhesion. Furthermore, 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 (72)発明者 和泉 圭二 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 AA22 BA06 BB06 BB08 BB10 CA16 CA19 CA20 CA23 CA26 CA37 CA38 CA41 DA02 DA11 DA15 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hirofumi Takezu 5th Ishizu Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd., Surface Treatment Research Laboratory (72) Inventor Keiji Izumi 5th Ishizu Nishimachi, Sakai City, Osaka Prefecture F-term (Reference) 4N026 AA02 AA07 AA12 AA22 BA06 BB06 BB08 BB10 CA16 CA19 CA20 CA23 CA26 CA37 CA38 CA41 DA02 DA11 DA15
Claims (5)
ロムイオンを３価クロムイオンに還元し、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
−ト処理液において、シランカップリング剤を添加し
て、添加量Ｓを全Ｃｒに対するモル比でＳ／全Ｃｒ＝
０.０１〜３.０にしたことを特徴とするクロメ−ト処理
液。1. A chromate treatment solution in which hexavalent chromium ions are reduced to trivalent chromium ions by an oxycarboxylic acid compound and the ratio of hexavalent chromium ions is reduced to 0.1 or less in a ratio of Cr 6+ / total Cr, A silane coupling agent was added, and the added amount S was expressed as a molar ratio of S / total Cr = total Cr =
A chromate treatment solution characterized in that the chromate treatment solution is adjusted to 0.01 to 3.0.
コキシシランとオルガノシラノ−ルとの混合物で、前者
の29Ｓｉ−ＯＲと後者の29Ｓｉ−ＯＨの核磁気共鳴分析
（ＮＭＲ）ピ−ク強度比29Ｓｉ−ＯＲ／29Ｓｉ−ＯＨが
３.０以下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. A silane coupling agent comprising a mixture of an organoalkoxysilane and an organosilanol, wherein the former 29 Si-OR and the latter 29 Si-OH have a nuclear magnetic resonance (NMR) peak intensity ratio of 29. chromate according to claim 1, Si-OR / 29 Si-OH is equal to or more than 3.0 - DOO treatment liquid.
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.
処理液にシリカゾルをＳｉ／全Ｃｒ＝０.５〜３.０の比
率で添加したことを特徴とするクロメ−ト処理液。4. A chromate treatment solution according to claim 1, wherein silica sol is added to the chromate treatment solution according to claim 1 in a ratio of Si / total Cr = 0.5 to 3.0.
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。5. A chromate treatment method comprising applying the chromate treatment liquid according to any one of claims 1 to 4 to a material to be treated, followed by drying without washing with water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012531527A (en) * | 2009-07-03 | 2012-12-10 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Anticorrosion treatment for zinc and zinc alloy surfaces |
-
1998
- 1998-12-24 JP JP10367477A patent/JP2000192251A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012531527A (en) * | 2009-07-03 | 2012-12-10 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Anticorrosion treatment for zinc and zinc alloy surfaces |
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