JPH11181578A - Metallic surface treating agent and treatment - Google Patents
Metallic surface treating agent and treatmentInfo
- Publication number
- JPH11181578A JPH11181578A JP36383697A JP36383697A JPH11181578A JP H11181578 A JPH11181578 A JP H11181578A JP 36383697 A JP36383697 A JP 36383697A JP 36383697 A JP36383697 A JP 36383697A JP H11181578 A JPH11181578 A JP H11181578A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- inorganic
- treating agent
- film
- treatment
- 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
Landscapes
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、亜鉛又は亜鉛合
金ならびにこれらのめっきを施した金属材料に関する、
特に亜鉛および亜鉛系合金めっきを施した鉄部品に関す
る。The present invention relates to a zinc or zinc alloy and a metal material plated with the same.
More particularly, the present invention relates to an iron component plated with zinc and a zinc-based alloy.
【０００２】[0002]
【従来の技術】一般的に鉄系材料・部品の防錆方法とし
て亜鉛あるいは亜鉛系合金めっき（以下亜鉛めっきと称
す）は最も広く一般的に利用されている。しかし、亜鉛
めっきされた鉄系材料・部品は、そのまま使用すると亜
鉛の錆である白錆がすぐに発生してしまうため、通常は
さらに保護皮膜を形成させる事が一般的である。亜鉛め
っきに通常施される保護皮膜としてクロメ−ト皮膜処理
は一般的であり、クロメ−ト皮膜処理はさらに電解クロ
メ−ト処理、塗布型クロメ−ト処理、反応型クロメ−ト
処理の３種類に分類される。クロメート処理は亜鉛に限
らずアルミニウムやカドミニウム、マグネシウムなどに
も施される。2. Description of the Related Art In general, zinc or zinc-based alloy plating (hereinafter referred to as zinc plating) is most widely used as a method for preventing rust on iron-based materials and parts. However, when zinc-plated iron-based materials and components are used as they are, white rust, which is the rust of zinc, is immediately generated, so that it is common practice to further form a protective film. A chromate film treatment is generally used as a protective film usually applied to zinc plating, and the chromate film treatment is further divided into three types: electrolytic chromate treatment, coating type chromate treatment, and reactive type chromate treatment. are categorized. The chromate treatment is applied not only to zinc but also to aluminum, cadmium, magnesium and the like.
【０００３】クロメ−ト皮膜は安価で容易に実用的な耐
食性を得られるため広く利用されているが、クロメ−ト
処理はいずれも有害な六価クロムを使用するため処理液
のみならず、処理品から溶出する六価クロムが人体や環
境へ悪影響があるとして近年、大きな問題となってい
る。これは、クロメート皮膜が皮膜中の六価クロムによ
り、耐食性を発揮する皮膜である以上、如何ともしがた
い問題である。[0003] Chromate films are widely used because they are inexpensive and can easily obtain practical corrosion resistance. However, all chromate treatments use harmful hexavalent chromium. In recent years, hexavalent chromium eluted from products has a serious problem because it has an adverse effect on human bodies and the environment. This is a difficult problem since the chromate film is a film exhibiting corrosion resistance due to hexavalent chromium in the film.
【０００４】六価クロムの公害上の問題解決のためこれ
まで種々の発明が出願されており、例えば、亜鉛上にチ
タンとリン酸、フィチン酸、タンニン酸、過酸化水素の
一種を組み合わせた処理液による皮膜生成が記載されて
いる特開昭５２−９２８３６、酸化性物質とケイ素化合
物とＴｉ、Ｚｒ、Ｃｅ、Ｓｒ、Ｖ、Ｗ、Ｍｏの一種を組
み合わせた処理液による皮膜生成が記載されている特開
平９−５３１９２、Ｍｏとアルミニウムの燐酸塩と有機
又は無機酸を含有するｐＨ１〜６の処理液による処理を
記載した特開昭５７ー５８７５、リン酸とＺｒ又はＴｉ
とフッ素と亜リン酸又は次亜リン酸の処理液による処理
を記載した特開平９ー１４３７５２などがある。Various inventions have been filed for solving the pollution problem of hexavalent chromium. For example, a treatment in which titanium is combined with titanium and one of phosphoric acid, phytic acid, tannic acid and hydrogen peroxide is applied. Japanese Patent Application Laid-Open No. 52-92836 describes the formation of a film by a liquid, and describes the formation of a film by a treatment solution combining an oxidizing substance, a silicon compound, and one of Ti, Zr, Ce, Sr, V, W, and Mo. Japanese Patent Application Laid-Open No. 9-53192, JP-A-57-5875, which describes a treatment with a treatment solution having a pH of 1 to 6 containing a phosphate of Mo and aluminum and an organic or inorganic acid, and phosphoric acid and Zr or Ti.
Japanese Patent Application Laid-Open No. 9-143752 which describes a treatment with a treating solution of fluorinated and phosphorous or hypophosphorous acid.
【０００５】これらの発明は六価クロムを使用していな
い点で注目できるが、これらの処理方法は、必ずしも実
用レベルに達した十分な耐食性を金属表面に付与してい
るとは言えず、六価のクロムを含有したクロメート処理
の代替え処理としては満足できる物ではない。例えばＪ
ＩＳ Ｈ ２７３１に規定される塩水噴霧試験におい
て、安定して発揮される耐食性は特開昭５２ー９２８３
６、特開昭５７ー５８７５、特開平９ー１４３７５２な
どで１２〜４８時間前後であり、特開平９ー５３１９２
でも４８〜６０時間前後である。この耐食性は一般に用
いられている有色クロメートや黒色クロメートの１／１
０〜１／２でしかない。更に大きな問題としてこれらの
コストが従来の有色クロメートの５〜１０倍にもなるた
め、クロメートの特徴の一つであるコストパフォーマン
スの素晴らしさを失うことが挙げられる。廉価な処理で
あるクロメートに取ってコストが一桁上がることはその
魅力を半減する物であり、クロメート処理業者にとって
代替え技術への移行を検討する際の最初で障害となる点
であった。Although these inventions can be noted in that they do not use hexavalent chromium, these treatment methods do not necessarily impart sufficient corrosion resistance to the metal surface to a practical level. It is not satisfactory as an alternative treatment to chromate treatment containing chromium. For example, J
In the salt spray test specified in ISH 2731, the stable corrosion resistance is as described in JP-A-52-9283.
6, about 12 to 48 hours according to JP-A-57-5875 and JP-A-9-143752.
But it is around 48-60 hours. This corrosion resistance is 1/1 of that of commonly used colored chromate or black chromate.
Only 0-1 / 2. An even greater problem is that the cost is 5 to 10 times that of the conventional colored chromate, so that one of the features of the chromate is to lose the splendid cost performance. The cost increase of an order of magnitude for the inexpensive process, chromate, halved its appeal and was the first obstacle to the transition to alternative technologies for chromate processors.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、亜鉛
又は亜鉛合金表面に保護皮膜を形成させるに当たり、有
害な六価クロムを使用せず、均一で良好な外観と耐食性
を兼ね備えた皮膜を生成させることにある。特に、これ
まで発明されてきた代替え技術の実用化の障害となって
いる優れたコストパフォーマンスを得ることにある。SUMMARY OF THE INVENTION An object of the present invention is to form a protective film on the surface of zinc or a zinc alloy without using harmful hexavalent chromium and providing a film having a uniform and good appearance and corrosion resistance. To generate. In particular, it is to obtain excellent cost performance which is an obstacle to the practical application of the alternative technology that has been invented so far.
【０００７】[0007]
【課題を解決するための手段】従来技術における問題を
解決するため、本発明者らが鋭意研究した結果、アルミ
ニウムとケイ素と有機又は無機の酸を含む液体組成物に
より防錆皮膜を生成させることによりこれらの問題を解
決できることを見出した。Means for Solving the Problems In order to solve the problems in the prior art, the inventors of the present invention have made intensive studies and found that a rust preventive film can be formed by a liquid composition containing aluminum, silicon and an organic or inorganic acid. Have found that these problems can be solved.
【０００８】[0008]
【発明の実施の形態】すなわち０．０１〜２００ｇ／Ｌ
好ましくは０．１〜２０ｇ／Ｌのアルミニウムと０．０
１〜２５０ｇ／Ｌ好ましくは１〜５０ｇ／Ｌのケイ酸ア
ルカリ又はコロイダルシリカと、添加する場合は０．１
〜１５０ｇ／Ｌ好ましくは１〜２５ｇ／Ｌのフッ素化合
物と０．１〜１００ｇ／Ｌ好ましくは１〜２０ｇ／Ｌの
無機酸として塩酸、硫酸、硝酸、過酸化水素若しくはリ
ン酸、又は有機酸として蟻酸、酢酸、琥珀酸若しくはジ
グリコール酸などのカルボン酸のいずれか１種以上を含
有するｐＨ６．５以下の金属表面処理剤により保護皮膜
を形成することにより従来の有色クロメートに匹敵する
耐食性を得られることが判明した。DESCRIPTION OF THE PREFERRED EMBODIMENTS That is, 0.01 to 200 g / L
Preferably 0.1 to 20 g / L of aluminum and 0.0
1 to 250 g / L, preferably 1 to 50 g / L of alkali silicate or colloidal silica;
Hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide or phosphoric acid, or an organic acid as an inorganic acid of from 150 to 150 g / L, preferably from 1 to 25 g / L, and from 0.1 to 100 g / L, preferably from 1 to 20 g / L. By forming a protective film with a metal surface treating agent having a pH of 6.5 or less containing at least one of carboxylic acids such as formic acid, acetic acid, succinic acid and diglycolic acid, corrosion resistance comparable to conventional colored chromate is obtained. Turned out to be.
【０００９】アルミニウムの供給方法に特に指定はな
く、硫酸アルミニウムや硝酸アルミニウムなどの塩で供
給すればアルミニウム以外に無機酸の成分も供給できる
ため都合がよい。ケイ素の供給源としてはケイ酸ナトリ
ウム、ケイ酸カリウム、ケイ酸リチウム、あるいは粒径
５０ｎｍ以下のコロイダルシリカが好ましく、例えば三
号ケイ酸ソーダなどが使用できる。これらの組成物に更
にフッ素を添加すると外観が明るくなり良好な外観が得
られる。フッ素の供給源としてはフッ化水素酸、フッ化
アンモニウム、ホウフッ化水素酸、フッ化ナトリウムな
どが挙げられる。また、有機又は無機酸を含有すること
により処理が安定し、特に硫酸などは均一な外観を得る
ために有効である。ｐＨとしては６．５以下、好ましく
はｐＨ３以下が望ましく、ｐＨの調整には既に添加して
いる酸種又は水酸化アルカリやアンモニアなどのアルカ
リ成分が用いられる。The method of supplying aluminum is not particularly specified, and if it is supplied with a salt such as aluminum sulfate or aluminum nitrate, a component of an inorganic acid other than aluminum can be supplied, which is convenient. As a source of silicon, sodium silicate, potassium silicate, lithium silicate, or colloidal silica having a particle size of 50 nm or less is preferable. For example, sodium silicate No. 3 can be used. When fluorine is further added to these compositions, the appearance becomes bright and a good appearance is obtained. Examples of the source of fluorine include hydrofluoric acid, ammonium fluoride, borofluoric acid, and sodium fluoride. Further, by containing an organic or inorganic acid, the treatment is stable, and sulfuric acid is particularly effective for obtaining a uniform appearance. The pH is preferably 6.5 or less, more preferably pH 3 or less. For adjusting the pH, an acid species already added or an alkali component such as alkali hydroxide or ammonia is used.
【００１０】各成分の働きは明らかではないが、アルミ
ニウムおよびケイ素化合物が皮膜の骨格を形成する物と
推定されフッ素並びに他の酸は基材のエッチングや皮膜
の均一な形成に関与していると推定される。また、リン
酸や他の有機酸は皮膜の厚膜化剤としての効果も期待で
きる。Although the function of each component is not clear, it is presumed that aluminum and silicon compounds form the skeleton of the film, and that fluorine and other acids are involved in etching of the substrate and uniform formation of the film. Presumed. Further, phosphoric acid and other organic acids can also be expected to have an effect as a thickening agent for the film.
【００１１】本発明の処理は従来のクロメートと同様の
条件で処理可能であり、例えば処理温度は２０〜７０℃
と広い管理幅を持っており、処理時間は３０〜１２０秒
で処理可能であり、処理設備も従来の光沢クロメートな
どに使用していた設備が使用可能であり、従来の感覚で
導入可能である。The treatment of the present invention can be carried out under the same conditions as conventional chromate. For example, the treatment temperature is 20 to 70 ° C.
The processing time is 30 to 120 seconds, and the processing equipment can be the same as the one used for conventional gloss chromate, etc., and can be introduced with the conventional feeling. .
【００１２】本発明の組成物は従来の代替え技術に示さ
れる種々の物質を含むことも可能である。例えば、Ｔ
ｉ、Ｚｒ、Ｃｅ、Ｓｒ、Ｖ，Ｗ，又はＭｏなどの金属や
フィチン酸、タンニン酸、シアヌル酸、チオール化合
物、又はチオグリコレートなどの有機物あるいはシラン
カップリング剤が挙げられる。これらの添加の目的とし
て耐食性などの他に外観の変化が挙げられ、例えば金属
の添加による濃色化や有機物の添加による新たな色の提
供なども可能である。これらの物質を添加する際は添加
によるコスト上昇を考え、本発明の特徴の一つであるコ
ストパフォーマンスの良さに十分注意する必要がある。[0012] The compositions of the present invention can also include various materials as set forth in conventional alternative techniques. For example, T
Examples include metals such as i, Zr, Ce, Sr, V, W, and Mo; organic substances such as phytic acid, tannic acid, cyanuric acid, thiol compounds, and thioglycolate; and silane coupling agents. The purpose of these additions is to change the appearance in addition to corrosion resistance and the like. For example, it is possible to increase the color by adding a metal or to provide a new color by adding an organic substance. When adding these substances, it is necessary to pay attention to the cost performance, which is one of the features of the present invention, in consideration of the cost increase due to the addition.
【００１３】本発明の処理液にて処理後、更に無機若し
くは有機のコート剤又は無機−有機複合コート剤等の処
理剤による二段処理による保護皮膜形成が可能である。
これらの処理剤についてはコロイダルシリカ、シリコン
化合物、アクリル樹脂、エポキシ樹脂、メラミン樹脂、
アルキド樹脂、フッ素樹脂、フェノール樹脂、ポリアミ
ド樹脂、ウレタン樹脂及びこれらの混合物が挙げられ
る。本発明を塗装下地として使用し、更にアニオン電着
塗装、カチオン電着塗装、静電塗装などの塗装を施すこ
とにより更に耐食性は向上する。After the treatment with the treatment liquid of the present invention, a protective film can be formed by two-step treatment with a treatment agent such as an inorganic or organic coating agent or an inorganic-organic composite coating agent.
Colloidal silica, silicone compounds, acrylic resins, epoxy resins, melamine resins,
Alkyd resins, fluororesins, phenolic resins, polyamide resins, urethane resins and mixtures thereof. The corrosion resistance is further improved by using the present invention as a coating base and applying a coating such as anionic electrodeposition coating, cationic electrodeposition coating, or electrostatic coating.
【００１４】従来の技術では性能の他にコストの問題が
未解決であったが、本発明においてはこの問題もほぼク
リヤーできる。すなわち従来の代替え皮膜に使用されて
いる薬品は例えば三塩化チタンの場合１６００〜１７０
０円／ｋｇ、バナジン酸アンモニウム２５００〜３００
０円／ｋｇ、タングステン酸ナトリウムは２５００〜３
０００円／ｋｇ、タングステン酸アンモニウム３０００
〜４０００円／ｋｇ、モリブデン酸ナトリウム３０００
〜３５００円／ｋｇ、モリブデン酸アンモニウム３５０
０〜４０００円／ｋｇとクロメートに使用されるクロム
酸の４９０〜５００円／ｋｇと比較し非常に高価である
が、本発明に依れば硫酸アルミニウム３８２〜４１２円
／ｋｇ、塩化アルミニウム３８０〜４００円／ｋｇ、ケ
イ酸ナトリウム３７円／ｋｇ（以上" １２９６６の化学
商品" 化学工業日報社刊による）と従来のクロメートよ
り安価である。Although the prior art has not solved the problem of cost in addition to the performance, this problem can be almost completely cleared in the present invention. That is, the chemical used for the conventional substitute film is, for example, 1600 to 170 in the case of titanium trichloride.
0 yen / kg, ammonium vanadate 2500-300
0 yen / kg, sodium tungstate 2,500-3
000 yen / kg, ammonium tungstate 3000
4,000 yen / kg, sodium molybdate 3000
~ 3500 yen / kg, ammonium molybdate 350
Although it is very expensive compared with 0 to 4000 yen / kg and 490 to 500 yen / kg of chromic acid used for chromate, according to the present invention, aluminum sulfate 382 to 412 yen / kg, aluminum chloride 380 to 380 400 yen / kg, sodium silicate 37 yen / kg (above "12966 chemical products" published by Kagaku Kogyo Nippo), which is cheaper than conventional chromate.
【００１５】また、従来の発明では供給薬品自体がクロ
メートより高価なだけでなく、これらの処理液自体の安
定性に乏しく液寿命が短いと言う欠点を持ち合わせる処
理液もあった。非常に短い物では毎日〜数日で更新する
ほどであり、ランニングによるトータルコストの低下が
期待できないため非常に高価な処理となってしまう。ま
た、頻繁な建浴のための労力や人件費、時間も無視でき
ないが、本発明においてはクロメートと同等以上の液寿
命持つため、ランニングコストまで含めたトータルコス
トでも従来のクロメート並を維持できる。Further, in the conventional invention, not only the supply chemical itself is more expensive than chromate, but also some processing liquids have a drawback that these processing liquids themselves are poor in stability and have a short liquid life. In the case of a very short object, it is updated almost every day to several days, and a reduction in the total cost due to running cannot be expected, resulting in a very expensive process. In addition, the labor, labor costs and time for frequent bathing cannot be ignored, but the present invention has a liquid life equal to or longer than that of chromate, so that the total cost including running costs can be maintained at the same level as conventional chromate.
【００１６】[0016]
【実施例】以下、実施例により本発明を説明する。試験
は試験片を脱脂、硝酸浸漬などの適当な前処理を行った
後、以下に示すそれぞれの実施例に従い処理を行った。
作製した試験片は塩水噴霧試験器に投入した。試験片は
記載のない限り５０×１００×１ｍｍの鉄板を用いた。
各試験における白錆発生時間を表１に示す。The present invention will be described below with reference to examples. In the test, the test piece was subjected to an appropriate pretreatment such as degreasing and immersion in nitric acid, and then subjected to the treatment according to each of the following examples.
The prepared test piece was put into a salt spray tester. Unless otherwise stated, a test piece was a 50 × 100 × 1 mm iron plate.
Table 1 shows the white rust occurrence time in each test.
【００１７】[0017]
【表１】 [Table 1]
【００１８】実施例１ 亜鉛めっきした鉄板を硫酸アルミニウム７．５ｇ／Ｌ、
三号ケイ酸ソーダ７０ｇ／Ｌ、６７．５％硝酸４．５ｇ
／Ｌを含むｐＨ３．０の水溶液に４０秒間浸漬し皮膜生
成した。実施例２ 亜鉛めっきした鉄板を硝酸アルミニウム８．５ｇ／Ｌ、
三号ケイ酸ソーダ９０ｇ／Ｌ、６２．５％硝酸５．５ｇ
／Ｌを含むｐＨ２．６の水溶液に５０秒間浸漬し皮膜生
成した。 Example 1 A galvanized iron sheet was prepared by adding 7.5 g / L of aluminum sulfate.
No.3 sodium silicate 70g / L, 4.5g 67.5% nitric acid
/ L for 30 seconds in an aqueous solution of pH 3.0 containing / L to form a film. Example 2 A zinc-plated iron plate was coated with 8.5 g / L of aluminum nitrate,
No. 3 sodium silicate 90g / L, 62.5% nitric acid 5.5g
/ L for 50 seconds in an aqueous solution of pH 2.6 containing / L to form a film.
【００１９】実施例３ 亜鉛めっきした鉄板を硫酸アルミニウム５ｇ／Ｌ、三号
ケイ酸ソーダ５０ｇ／Ｌ、フッ化アンモニウム２５ｇ／
Ｌ、６７．５％硝酸３ｇ／Ｌを含むｐＨ２．８の水溶液
に４０秒間浸漬し皮膜生成した。実施例４ 亜鉛めっきした鉄板を硝酸アルミニウム１０ｇ／Ｌ、カ
タロイドＳＩ−３０３５ｇ／Ｌ、フッ化ナトリウム１２
ｇ／Ｌ、７５％硫酸９ｇ／Ｌ、３５％塩酸２ｇ／Ｌを含
むｐＨ３．０に調整した処理液に１分間浸漬し皮膜生成
して試験片を作製した。 EXAMPLE 3 A zinc-plated iron plate was prepared by using aluminum sulfate 5 g / L, No. 3 sodium silicate 50 g / L, and ammonium fluoride 25 g / L.
L, and dipped in an aqueous solution of pH 2.8 containing 3 g / L of 67.5% nitric acid for 40 seconds to form a film. Example 4 A zinc-plated iron plate was coated with aluminum nitrate 10 g / L, cataloid SI-3035 g / L, sodium fluoride 12
g / L, 9% g / L of 75% sulfuric acid, 2% g / L of 35% hydrochloric acid, and immersed for 1 minute in a treatment solution adjusted to pH 3.0 to form a film and produce a test piece.
【００２０】実施例５ 亜鉛めっきした鉄板をｐＨ１．６の硝酸アルミニウム６
ｇ／Ｌ、三号ケイ酸ソーダ２０ｇ／Ｌ、フッ酸５ｇ／
Ｌ、リン酸１ｇ／Ｌ、硫酸２ｇ／Ｌを含む処理液に２分
間浸漬し皮膜生成した。実施例６ 亜鉛めっきした鉄板を硫酸アルミニウム９ｇ／Ｌ、ケイ
酸ソーダ１３ｇ／Ｌ、酸性フッ化アンモニウム１２ｇ／
Ｌ、６０％硝酸１０ｇ／Ｌ、７５％硫酸１１ｇ／Ｌを含
むｐＨ２．３に調整した処理液に１分間浸漬し皮膜生成
した。 Example 5 A zinc-plated iron plate was treated with aluminum nitrate 6 having a pH of 1.6.
g / L, No. 3 sodium silicate 20 g / L, hydrofluoric acid 5 g /
L, 1 g / L of phosphoric acid, and 2 g / L of sulfuric acid were immersed for 2 minutes to form a film. Example 6 A zinc-plated iron plate was coated with aluminum sulfate 9 g / L, sodium silicate 13 g / L, and acidic ammonium fluoride 12 g / L.
L, a treatment solution adjusted to pH 2.3 containing 10 g / L of 60% nitric acid and 11 g / L of 75% sulfuric acid for 1 minute to form a film.
【００２１】実施例７ 亜鉛めっきしたボルト（Ｍ５ 首下３０ｍｍ）を硫酸ア
ルミニウム１０ｇ／Ｌ、三号ケイ酸ソーダ２５ｇ／Ｌ、
ホウフッ化水素酸５ｇ／Ｌ、６０％硝酸８ｇ／Ｌを含む
ｐＨ２．８の処理液に１分間浸漬し皮膜生成後した。実施例８ 亜鉛ー鉄合金めっきした鉄板をｐＨ２．５の硝酸アルミ
ニウム１０ｇ／Ｌ、三号ケイ酸ソーダ２５ｇ／Ｌ、酸性
フッ化アンモニウム１０ｇ／Ｌ、塩酸１．５ｇ／Ｌ、６
０％硝酸６ｇ／Ｌ、７５％硫酸４ｇ／Ｌを含む処理液に
７０秒間浸漬し皮膜生成した。 Example 7 A zinc-plated bolt (M5, 30 mm below neck) was treated with aluminum sulfate 10 g / L, No. 3 sodium silicate 25 g / L,
The film was immersed in a treatment solution having a pH of 2.8 containing 5 g / L of borofluoric acid and 8 g / L of 60% nitric acid for 1 minute to form a film. Example 8 An iron plate plated with a zinc-iron alloy was coated with 10 g / L of aluminum nitrate having a pH of 2.5, 25 g / L of sodium silicate No. 3, 10 g / L of ammonium ammonium fluoride, 1.5 g / L of hydrochloric acid, 6
The film was immersed in a treatment solution containing 6 g / L of 0% nitric acid and 4 g / L of 75% sulfuric acid for 70 seconds to form a film.
【００２２】実施例９ 亜鉛めっきした鉄板をｐＨ３．０の硫酸アルミニウム１
５ｇ／Ｌ、三号ケイ酸ソーダ２０ｇ／Ｌ、フッ酸８ｇ／
Ｌ、リン酸２ｇ／Ｌ、酢酸２ｇ／Ｌ、６７．５％硝酸５
ｇ／Ｌを含む処理液に７５秒間浸漬し、皮膜生成後、ケ
イ酸カリウム８０ｇ／Ｌ、カ性カリ７ｇ／Ｌを含む処理
液に５０℃−３０秒浸漬して試験片を作製した。実施例１０ 亜鉛めっきした鉄板をｐＨ２．６の硝酸アルミニウム１
５ｇ／Ｌ、三号ケイ酸ソーダ３０ｇ／Ｌ、フッ酸１０ｇ
／Ｌ、リン酸３ｇ／Ｌ、酢酸１ｇ／Ｌ、７５％硫酸５ｇ
／Ｌを含む処理液に８５秒間浸漬し、皮膜生成後したも
のをコスマーコートＮｏ９００１（関西ペイント製）に
浸漬しコーティングし試験片を作製した。 Example 9 A zinc-plated iron plate was treated with aluminum sulfate 1 having a pH of 3.0.
5 g / L, No. 3 sodium silicate 20 g / L, hydrofluoric acid 8 g /
L, phosphoric acid 2 g / L, acetic acid 2 g / L, 67.5% nitric acid 5
After immersion in a treatment solution containing g / L for 75 seconds and forming a film, a test piece was prepared by immersion in a treatment solution containing 80 g / L of potassium silicate and 7 g / L of potassium hydroxide for 30 seconds. Example 10 A zinc-plated iron plate was treated with aluminum nitrate 1 having a pH of 2.6.
5 g / L, No. 3 sodium silicate 30 g / L, hydrofluoric acid 10 g
/ L, phosphoric acid 3g / L, acetic acid 1g / L, 75% sulfuric acid 5g
/ L was immersed in a treatment solution containing 85 L for 85 seconds, and the film after the film was formed was immersed in Cosmercoat No. 9001 (manufactured by Kansai Paint) and coated to prepare a test piece.
【００２３】比較例１ 表面に何の処理もしていない亜鉛めっきした鉄板を試験
片とし、塩水噴霧試験（ＪＩＳ Ｚ ２３７１）におけ
る白錆発生までの時間を調査した。比較例２ ３５％過酸化水素２０ｇ／Ｌ、６２％硝酸を１０ｇ／
Ｌ、硫酸チタン１．０ｇ／Ｌを含有するｐＨ１．３の処
理液で亜鉛めっきした鉄板を液温２０℃で４５秒の化成
処理を施した。COMPARATIVE EXAMPLE 1 A test piece was a zinc-plated iron sheet whose surface had not been subjected to any treatment, and the time until the occurrence of white rust in a salt spray test (JIS Z 2371) was examined. Comparative Example 2 20 g / L of 35% hydrogen peroxide and 10 g / 62% of nitric acid
L, an iron plate galvanized with a pH 1.3 treatment liquid containing 1.0 g / L of titanium sulfate was subjected to a chemical conversion treatment at a liquid temperature of 20 ° C. for 45 seconds.
【００２４】比較例３ ３５％過酸化水素３０ｇ／Ｌ、６２％硝酸を１５ｇ／
Ｌ、コロイダルシリカ７０ｇ／Ｌ、硫酸チタン０．３ｇ
／Ｌを含有するｐＨ１．６処理液で亜鉛めっきした鉄板
を液温２０℃で４５秒の化成処理を施した。比較例４ ３５％過酸化水素５０ｇ／Ｌ、６２％硝酸を５ｇ／Ｌ、
コロイダルシリカ１００ｇ／Ｌ、硫酸チタン０．３ｇ／
Ｌ、７５％リン酸１５ｇ／Ｌを含有するｐＨ１．５の処
理液で亜鉛めっきした鉄板を４５秒の化成処理を施し
た。 Comparative Example 3 30 g / L of 35% hydrogen peroxide and 15 g / L of 62% nitric acid
L, colloidal silica 70 g / L, titanium sulfate 0.3 g
An iron plate galvanized with a pH 1.6 treatment solution containing / L was subjected to a chemical conversion treatment at a solution temperature of 20 ° C. for 45 seconds. Comparative Example 4 50 g / L of 35% hydrogen peroxide, 5 g / L of 62% nitric acid,
Colloidal silica 100 g / L, titanium sulfate 0.3 g /
L, a galvanized iron plate was treated with a treatment solution of pH 1.5 containing 15 g / L of 75% phosphoric acid for 45 seconds.
【００２５】比較例５ ３５％過酸化水素３０ｇ／Ｌ、酸性フッ化アンモン５ｇ
／Ｌ、硫酸チタン２．３ｇ／Ｌ、７５％リン酸１５ｇ／
Ｌ、次亜リン酸２ｇ／Ｌを含有する処理液で亜鉛めっき
した鉄板を４５秒の化成処理を施した。比較例６ モリブデン酸ナトリウム１２．１ｇ／Ｌ、７５％リン酸
１４．７ｇ／Ｌを含有する処理液に亜鉛めっきした鉄板
を浸漬して試験片を作製した。 Comparative Example 5 30 g / L of 35% hydrogen peroxide, 5 g of ammonium fluoride acid
/ L, titanium sulfate 2.3 g / L, 75% phosphoric acid 15 g /
L, a galvanized iron plate with a treatment solution containing 2 g / L of hypophosphorous acid was subjected to a chemical conversion treatment for 45 seconds. Comparative Example 6 A test piece was prepared by immersing a galvanized iron plate in a treatment solution containing 12.1 g / L of sodium molybdate and 14.7 g / L of 75% phosphoric acid.
【００２６】比較例７ モリブデン酸ナトリウム１２．１ｇ／Ｌ、７５％リン酸
１４．７ｇ／Ｌを含有する処理液に亜鉛めっきした鉄板
を２分間浸漬して試験片を作製した。比較例８ モリブデン酸ナトリウム０．１ｍｏｌ／Ｌ、リン酸０．
１５ｍｏｌ／Ｌを含有する処理液に亜鉛めっきした鉄板
を６０℃−２分浸漬して試験片を作製した。 Comparative Example 7 A test piece was prepared by immersing a galvanized iron plate in a treatment solution containing 12.1 g / L of sodium molybdate and 14.7 g / L of 75% phosphoric acid for 2 minutes. Comparative Example 8 Sodium molybdate 0.1 mol / L, phosphoric acid 0.1 mol / L
A test piece was prepared by immersing a galvanized iron plate in a treatment solution containing 15 mol / L at 60 ° C. for 2 minutes.
【００２７】比較例９ モリブデン酸ナトリウム２２ｇ／Ｌ、第一リン酸アルミ
ニウム１５．７ｇ／Ｌを含有する処理液に亜鉛めっきし
た鉄板を２分間浸漬して試験片を作製した。比較例１０ バナジン酸ナトリウム１５ｇ／Ｌ、７５％リン酸２０ｇ
／Ｌ、硝酸ナトリウム３５ｇ／Ｌを含有するｐＨ２の処
理液に２亜鉛めっきした鉄板を２分間浸漬して試験片を
作製した。 Comparative Example 9 A test piece was prepared by immersing a galvanized iron plate in a treatment solution containing 22 g / L of sodium molybdate and 15.7 g / L of aluminum monophosphate for 2 minutes. Comparative Example 10 Sodium vanadate 15 g / L, 75% phosphoric acid 20 g
/ L, a zinc-plated iron plate was immersed in a treatment solution of pH 2 containing 35 g / L of sodium nitrate for 2 minutes to prepare a test piece.
【００２８】[0028]
【発明の効果】本発明に規定する水溶液を用いることに
より、有害な六価クロムを使用せず、従来の反応型クロ
メートと同一処理設備、処理条件、処理方法で金属表面
に不溶性の強固な皮膜を生成することが可能である。こ
れにより処理物からの六価クロム溶出を心配する一般ユ
ーザーのみならず、従来クロム酸の有害性にさらされて
いたクロメート製造者やクロメート処理業者の健康面で
の影響や野生動物への影響に関する問題を解決すること
が可能となる。By using the aqueous solution specified in the present invention, a harmful hexavalent chromium is not used, and a strong film which is insoluble on the metal surface by the same processing equipment, processing conditions and processing method as conventional reactive chromate. Can be generated. As a result, not only general users who are concerned about elution of hexavalent chromium from processed products, but also the health effects of chromate manufacturers and chromate processors who have been exposed to the hazards of chromate and the effects on wild animals The problem can be solved.
Claims (8)
酸又は無機酸の一種以上を含有する金属表面処理剤。1. A metal surface treating agent containing aluminum and silicon and further containing one or more organic acids or inorganic acids.
金属表面処理剤。2. The metal surface treating agent according to claim 1, further comprising fluorine.
水素及びリン酸から成る群から選択される少なくとも一
種であり、前記有機酸がカルボン酸である請求項１又は
２に記載の金属表面処理剤。3. The metal according to claim 1, wherein the inorganic acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide and phosphoric acid, and the organic acid is a carboxylic acid. Surface treatment agent.
カリウム、ケイ酸リチウム又は粒径５０ｎｍ以下のコロ
イダルシリカにより供給される請求項１〜３のいずれか
一の請求項に記載の金属表面処理剤。4. The metal surface treating agent according to claim 1, wherein the silicon is provided by sodium silicate, potassium silicate, lithium silicate, or colloidal silica having a particle size of 50 nm or less. .
／Ｌ、前記ケイ素が０．０１〜２５０ｇ／Ｌ及び前記有
機酸又は無機酸が０．１〜１００ｇ／Ｌ含有され、任意
に前記フッ素が０．１〜１００ｇ／Ｌ含有され、ｐＨ
６．５が以下である請求項１〜４のいずれか一の請求項
に記載の金属表面処理剤。5. The aluminum of 0.01 to 200 g
/ L, 0.01 to 250 g / L of the silicon and 0.1 to 100 g / L of the organic acid or inorganic acid, and optionally 0.1 to 100 g / L of the fluorine, pH
The metal surface treating agent according to any one of claims 1 to 4, wherein 6.5 is the following.
一の請求項に記載の金属表面処理剤に浸漬し、保護皮膜
が表面上に形成された金属基体を生成する方法。6. A method for immersing a metal substrate in the metal surface treating agent according to any one of claims 1 to 5 to produce a metal substrate having a protective film formed on the surface.
銀、鉄、カドミウム、マグネシウム、アルミニウム及び
それらの合金から成る群から選択される請求項６に記載
の方法。7. The method according to claim 1, wherein the metal substrate is zinc, nickel, copper,
7. The method of claim 6, wherein the method is selected from the group consisting of silver, iron, cadmium, magnesium, aluminum, and alloys thereof.
皮膜が表面上に形成された金属基体を生成した後、更に
無機若しくは有機のコート剤又は無機−有機複合コート
剤により処理することにより保護皮膜が表面上に形成さ
れた金属基体を生成する方法。8. After forming a metal substrate having a protective film formed on the surface by the method according to claim 6 or 7, further treating with a inorganic or organic coating agent or an inorganic-organic composite coating agent. A method for producing a metal substrate having a protective film formed on a surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36383697A JPH11181578A (en) | 1997-12-18 | 1997-12-18 | Metallic surface treating agent and treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36383697A JPH11181578A (en) | 1997-12-18 | 1997-12-18 | Metallic surface treating agent and treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11181578A true JPH11181578A (en) | 1999-07-06 |
Family
ID=18480317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36383697A Pending JPH11181578A (en) | 1997-12-18 | 1997-12-18 | Metallic surface treating agent and treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11181578A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006509106A (en) * | 2002-12-09 | 2006-03-16 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼーション | Aqueous coating solution and method for treating metal surface |
| KR100818668B1 (en) | 2004-07-19 | 2008-04-01 | 대윤계기산업 주식회사 | Extraction solution for extracting acid soluble chrolide and water soluble chrolide contained to concrete |
| WO2010116854A1 (en) | 2009-04-09 | 2010-10-14 | 株式会社ムラタ | Chemical conversion liquid, method for producing same, and method for forming chemical conversion coating film |
| JP2012514669A (en) * | 2009-05-18 | 2012-06-28 | パンガン グループ スチール バナジウム アンドチタニウム カンパニー リミテッド | Coating composition and passivated galvanized material |
-
1997
- 1997-12-18 JP JP36383697A patent/JPH11181578A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006509106A (en) * | 2002-12-09 | 2006-03-16 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼーション | Aqueous coating solution and method for treating metal surface |
| KR100818668B1 (en) | 2004-07-19 | 2008-04-01 | 대윤계기산업 주식회사 | Extraction solution for extracting acid soluble chrolide and water soluble chrolide contained to concrete |
| WO2010116854A1 (en) | 2009-04-09 | 2010-10-14 | 株式会社ムラタ | Chemical conversion liquid, method for producing same, and method for forming chemical conversion coating film |
| US8999077B2 (en) | 2009-04-09 | 2015-04-07 | Murata Co., Ltd. | Chemical conversion treatment liquid, method of producing the same, and method of forming conversion layer |
| JP2012514669A (en) * | 2009-05-18 | 2012-06-28 | パンガン グループ スチール バナジウム アンドチタニウム カンパニー リミテッド | Coating composition and passivated galvanized material |
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