JPS6013078A - Double-chromated steel sheet - Google Patents
Double-chromated steel sheetInfo
- Publication number
- JPS6013078A JPS6013078A JP12025683A JP12025683A JPS6013078A JP S6013078 A JPS6013078 A JP S6013078A JP 12025683 A JP12025683 A JP 12025683A JP 12025683 A JP12025683 A JP 12025683A JP S6013078 A JPS6013078 A JP S6013078A
- Authority
- JP
- Japan
- Prior art keywords
- chromate
- film
- chromate film
- steel sheet
- layer
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Abstract
Description
【発明の詳細な説明】
本発明は猟妬又は亜鉛合金めっき鋼板（以下単に亜鉛め
っき鋼板という。）の表面にクロメート処理を行った表
面処理鋼板に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface-treated steel sheet in which the surface of a galvanized or zinc alloy coated steel sheet (hereinafter simply referred to as a galvanized steel sheet) is subjected to chromate treatment.
本発明の表面処理鋼板は優れた耐食性、スポット溶接性
及び上塗塗装性が同時に要求される例えば家電及び自動
車用鋼板として利用するものである。The surface-treated steel sheet of the present invention is used, for example, as a steel sheet for home appliances and automobiles, which requires excellent corrosion resistance, spot weldability, and finish coatability.
亜鉛めっき鋼板の防錆を目的とした化成処理鋼板として
クロメート処理鋼板が多用されている。Chromate-treated steel sheets are often used as chemically treated steel sheets for the purpose of rust-preventing galvanized steel sheets.
しかしながら、その目的の多くは、鋼板の製造後から需
要家が使用する迄の一時防錆効果を狙ったものであり、
その耐食性は例えば塩水噴霧試験（ＪＩＳ Ｚ−２３７
１）で高々２４〜４８時間程度で発゛錆に至るなど低レ
ベルの耐食性でしかなかった。However, most of the purposes are to temporarily prevent rust from the time the steel plate is manufactured until it is used by the customer.
Its corrosion resistance can be determined by, for example, the salt spray test (JIS Z-237
1), the corrosion resistance was only at a low level, with rust forming in about 24 to 48 hours at most.
そのため、厳しい腐食環境の下では、加工製品に対し５
μｍ以上の塗装を施すなど腐食の防止を必要としている
。しかしこのような方法は経済性の点から好・ましくな
く、近年では塗装せずに、単に化成処理を施しただけで
、優れた耐食性をもつクロメート処理鋼板の開発が望ま
れるようになった。Therefore, under severe corrosive environments, processed products
It is necessary to prevent corrosion by applying a coating with a thickness of μm or more. However, this method is unfavorable from an economic point of view, and in recent years there has been a desire to develop chromate-treated steel sheets that have excellent corrosion resistance by simply applying chemical conversion treatment without painting. .
一般に、化成処理方法には大別してクロメート処理と、
リン酸塩処理の２つがあるが、高耐食性で且つ加工性の
観点からクロメート処理の方が有効と考えられる。Generally, chemical conversion treatment methods are broadly divided into chromate treatment,
There are two types of phosphate treatment, but chromate treatment is considered to be more effective in terms of high corrosion resistance and workability.
従来のクロメート処理はその処理方法から電解型、反応
型及び塗布型の３つに大別され、生成したクロメート皮
膜は以下に述べる如くそれぞれに特徴がある。すなわち
、電解型クロメート法は、クロム酸又はその塩を溶解さ
せてなる水溶液を基本浴とし、それに適量の硫酸などを
添加し陰極電解することによって素地亜鉛めっき鋼板の
表面にゲル状のｃｒ よりなるクロメート皮膜を生成さ
せる方法で、このクロメート皮膜はｃｒ６＋／ｃｒ３＋
の比を小さくすることが可能なため、塗装下地として優
れたアンカー効果を発揮し且つ水に難溶の特長をもつ。Conventional chromate treatments are broadly classified into three types based on their treatment methods: electrolytic, reactive, and coating, and the chromate films produced each have their own characteristics as described below. In other words, the electrolytic chromate method uses an aqueous solution prepared by dissolving chromic acid or its salt as a basic bath, adds an appropriate amount of sulfuric acid, etc., and performs cathodic electrolysis to form a gel-like Cr on the surface of a base galvanized steel sheet. This method produces a chromate film, and this chromate film is cr6+/cr3+
Because it is possible to reduce the ratio of
しかしＣｒ ／Ｃｒ の比が小さすぎると防錆性は低下
する。また２反応型クロメート法は上記のクロム酸基本
格に対し、硫酸、硝酸などの鉱酸と必要に応じて用いる
弗酸、リン酸などを適量添加してなる処理液に亜鉛めっ
き鋼板を浸漬し、亜鉛めっき界面での化学反応によって
、めっき表面にクロメート皮膜を還元析出させる方法で
ある。However, if the ratio of Cr /Cr is too small, the rust prevention properties will be reduced. In the two-reaction chromate method, a galvanized steel sheet is immersed in a treatment solution made by adding appropriate amounts of mineral acids such as sulfuric acid and nitric acid and, if necessary, hydrofluoric acid and phosphoric acid to the basic chromic acid mentioned above. This is a method in which a chromate film is reduced and precipitated on the galvanized surface through a chemical reaction at the galvanized surface.
この方法によって得られるクロメート皮膜は比較的厚膜
であるが電解型と同様ｃｒ６＋の少ないｃｒ３＋主体の
皮膜なので水に難溶で且つ塗装下地としては優れたアン
カー効果を示すが、ｃｒ６＋にょる自己修復作用に乏し
く高クロム付着量の割には耐食性は高くない。The chromate film obtained by this method is relatively thick, but like the electrolytic type, it is a film mainly composed of cr3+ with little cr6+, so it is poorly soluble in water and has an excellent anchoring effect as a paint base. It has poor action and corrosion resistance is not high considering the high amount of chromium deposited.
次に塗布型クロメート法については無水クロム酸を用い
た水溶液を基本浴に、これにシリカゾル等の無機系高分
子を添加した処理液の所定量を亜鉛めっき鋼板に塗布し
乾燥してなるもので、この処理法によって得られるクロ
メート皮膜は自己修復作用をもつＣｒ が多く含まれる
ため上述したタイプの異なるクロメート皮膜を含め３者
の中で最も優れた防錆力を有しており、クロム付着量に
応じて高耐食性を示す。Next, regarding the coating type chromate method, a predetermined amount of a treatment solution made by adding an inorganic polymer such as silica sol to a basic bath of an aqueous solution using chromic anhydride is applied onto a galvanized steel sheet and dried. Since the chromate film obtained by this treatment method contains a large amount of Cr, which has a self-repairing effect, it has the best rust prevention ability among the three types, including the different types of chromate films mentioned above, and the amount of chromium deposited is Shows high corrosion resistance according to
しかじなか１ｐｃｒ は水に可溶な性質があり。Shikajinaka 1pcr has the property of being soluble in water.
水溶性塗料の使用や優れた塗料密着性を維持するために
はクロム付着量に限界がある。以上述べたような無機系
クロメート処理は従来では単独で用いる場合が多く、こ
の場合皮膜の特性からいって高い耐食性を期待すること
は難しい。さらに一般にクロメート処理鋼板は需要家に
おいて次の工程で使用されることが多い。すなわちブラ
ンキング−プレス成形加工→溶接９組立て→脱脂→塗装
などの処理工程である。There is a limit to the amount of chromium deposited in order to use water-soluble paints and maintain excellent paint adhesion. Conventionally, inorganic chromate treatment as described above is often used alone, and in this case, it is difficult to expect high corrosion resistance from the characteristics of the film. Furthermore, generally, chromate-treated steel sheets are often used by consumers in the following process. That is, the processing steps include blanking - press forming - welding 9 assembly - degreasing - painting.
この工程におけるクロメート処理鋼板の品質上の問題点
は■脱脂後、製品の取り扱い中に付着する指紋部からの
発錆、■プレス加工の際の型カジリによるクロメート皮
膜の脱落、■脱脂時のクロメート皮膜の溶出などである
。The quality problems of chromate-treated steel sheets in this process are: ■ After degreasing, rust develops from fingerprints that adhere during handling of the product, ■ Falling off of the chromate film due to mold galling during press processing, ■ Chromate during degreasing This includes elution of the film.
そこで、これらの問題点を解決する技術としては最近ク
リアー樹脂を活用した例がある。例えば特公昭５２−３
５６２０号に示されるように、２層の化成処理皮膜から
なり、下層にクロメート皮膜を、上層に水溶性樹脂を形
成せしめたものである。Therefore, as a technique to solve these problems, there is a recent example of using clear resin. For example, special public relations
As shown in No. 5620, it consists of two layers of chemical conversion coatings, with a chromate coating formed in the lower layer and a water-soluble resin formed in the upper layer.
しかしながら、′この化成処理皮膜は上層の水溶性樹脂
皮膜が、樹脂構造として低分子量で且つガラス転移点（
ＴＶ）が低く、更には該樹脂中の官能基が親水性である
ため、厳しいプレス加工においては下地金属との密着性
に乏しく、加工部の樹脂皮膜は脱膜し易い傾向にある。However, in this chemical conversion coating, the upper water-soluble resin coating has a low molecular weight as a resin structure and a glass transition point (
TV) is low, and furthermore, the functional groups in the resin are hydrophilic, so during severe press working, there is poor adhesion to the base metal, and the resin film in the processed area tends to peel off easily.
また、この樹脂皮膜は水に対して膨潤し易いため、下層
にあるクロメート皮膜の溶出防止に対するバリアー効果
は小さい。Furthermore, since this resin film is easily swollen by water, its barrier effect on preventing elution of the underlying chromate film is small.
従って、指紋の付着防止効果は優れるものの耐食性の向
上に対する水溶性樹脂の採用効果は必らずしも十分とは
言い難い。同様の例として、特公昭４９−３６１００号
、特公昭５０−１８４５５号により提案されている。し
かしながら、これらはいづれも上層樹脂皮膜中の官能基
が親水性であるという共通点があり、このため、高度の
耐食性及びプレス加工゛性を期待することは難しい。こ
れらはむしろ官能基を活用した塗装下地としてのみ有効
であると考えられる。Therefore, although the effect of preventing the adhesion of fingerprints is excellent, the effect of using a water-soluble resin in improving corrosion resistance cannot necessarily be said to be sufficient. Similar examples are proposed in Japanese Patent Publication No. 49-36100 and Japanese Patent Publication No. 50-18455. However, all of these have in common that the functional groups in the upper resin film are hydrophilic, and for this reason, it is difficult to expect high corrosion resistance and press workability. Rather, these are considered to be effective only as paint bases that utilize functional groups.
他方、これらの改良技術として、上記水溶性樹脂の欠点
を成分的に強化することで解決した塗装下地であって且
つ、高耐食性を有する複合鋼板として特公昭５７−１０
８２９２号が提案されている。On the other hand, as an improvement technique for these, a composite steel plate that is a coating base that solves the drawbacks of the above-mentioned water-soluble resin by strengthening its composition and has high corrosion resistance was developed in Japanese Patent Publication No. 57-10.
No. 8292 has been proposed.
すなわち、上層皮膜を形成する樹脂として、従来の水溶
性から水分散性のエマルション樹脂を採用し、基本的に
樹脂を高分子化すると共に、更にキレート化合物とシリ
カゾル等の無機系高分子化合物を添加して、架橋密度を
上げ、樹脂皮膜の高分子樹脂化を図ったもので、この樹
脂皮膜を上層に、下層に反応型クロメート皮膜を設け、
２層皮膜としての相乗効果から、耐食性の飛躍的な向上
を図ったものである。In other words, we use a water-dispersible emulsion resin instead of the conventional water-soluble one as the resin that forms the upper layer film, basically polymerize the resin, and then add a chelate compound and an inorganic polymer compound such as silica sol. The crosslinking density was increased and the resin film was made into a polymer resin.This resin film was used as the upper layer, and a reactive chromate film was provided as the lower layer.
Due to the synergistic effect of the two-layer coating, corrosion resistance is dramatically improved.
しかしながら、この複合鋼板で優れた耐食性を得るため
にはスポツｈｉ接性を犠牲にしなければならない欠点が
あり、これは上述した需要家での製品処理工程において
溶接組立て作業の繁雑化を招き好ましくない。従って逆
にスポット溶接性を阻害しない複合樹脂皮膜の膜厚下で
は高度の耐食性は期待できない。However, in order to obtain excellent corrosion resistance with this composite steel plate, there is a drawback that the spot weldability must be sacrificed, which is undesirable because it complicates the welding and assembly work in the product processing process at the customer mentioned above. . Therefore, a high degree of corrosion resistance cannot be expected if the thickness of the composite resin film does not inhibit spot weldability.
更には、架橋密度の高い樹脂皮膜のため、素地に対する
密着性には優れるが、厳しいプレス加工の際は樹脂皮膜
の加工伸び性ζこ欠け、加工部の型カジリ又は脱膜を生
じる欠点もある。Furthermore, because the resin film has a high cross-linking density, it has excellent adhesion to the substrate, but during severe press processing, the resin film has the disadvantage of chipping in the processing elongation, mold galling at the processed part, or peeling off the film. .
本発明は以上のような従来のクロメート処理鋼板及び樹
脂を活用したクロメータ処理鋼板が有する種々の欠点を
解消し、更には塗装省略と言った高度の品質要求ζこ対
しても十分答え得るものとして耐食性、プレス加工性或
いはスボツｊ・溶接性〈・こ憂れた２層クロメート処理
鋼板を提供する点にある。The present invention eliminates the various drawbacks of conventional chromate-treated steel sheets and chromate-treated steel sheets using resins as described above, and is also capable of satisfying high quality demands such as omitting painting. The purpose is to provide a double-layer chromate-treated steel sheet that has poor corrosion resistance, press workability, and poor weldability.
本発明の要旨は亜鉛めっき鋼板の表面にクロメート皮膜
を形成させるにあたり、第１層皮膜としてＣｒ ／Ｃｒ
の比が３／１０−３／ｌで且つ、クロム付着量か３０
〜１５０７ｎＷ／ ｍ’ （片面）のクロメート皮膜を
形成させその上層に第２皮膜としてアミンをポリマー末
端にもつエポキシ樹脂をウレタン変性してなる熱硬化性
樹脂をバインダーとし、これにアルカリ金属もしくはア
ルカリ土類金属てその酸基を固定した粒径１μｍ以下の
粉末状クロム化合物を１０〜８０重量％含才せてなる複
合クロメート皮膜を０５〜５２／Ｉの範囲で形成させた
ことを特徴とする２層クロメート処理鋼板であり、その
内容について以下に述べる。The gist of the present invention is that in forming a chromate film on the surface of a galvanized steel sheet, Cr/Cr is used as the first layer film.
The ratio of 3/10-3/l and the amount of chromium deposited is 30
A chromate film of ~1507 nW/m' (one side) is formed, and a second film is formed on top of the thermosetting resin, which is made by urethane-modifying an epoxy resin with an amine at the polymer end, as a binder, and an alkali metal or alkaline earth 2, characterized in that a composite chromate film containing 10 to 80% by weight of a powdered chromium compound having a particle size of 1 μm or less and fixing acid groups of similar metals is formed in the range of 05 to 52/I. This is a layered chromate-treated steel sheet, and its contents are described below.
まず第１層クロメート皮膜においては、水に対する膨潤
溶出性を抑制して高耐食性を付与させ且つ下地めっきき
第２層の複合クロメート皮膜♂の密着性を向上させるに
あたり、該クロメート皮膜中のＣｒ ／Ｃｒ に適正な
比を設けた点にある。First, in the first layer chromate film, in order to suppress swelling and elution with water to impart high corrosion resistance and to improve the adhesion of the composite chromate film ♂ of the second base plating layer, Cr/Cr in the chromate film is The point is that an appropriate ratio is set for Cr.
次に、その上層の第２層複合クロメート皮膜においては
５該りロム化合物による更に高耐食化とプレス加工性或
いは塗装下地として優れた密着性を付与させるにあたり
、ウレタン変性した熱硬化性樹脂を該クロム化合物のバ
インダーとして用いた点にあり、本発明の構成にあたっ
て最も重要な技術を占める。Next, in the second layer composite chromate film on top of the chromate film, a urethane-modified thermosetting resin was added to provide even higher corrosion resistance and press workability, as well as excellent adhesion as a coating base. It is used as a binder for chromium compounds, and is the most important technology in the construction of the present invention.
第１層クロメート皮膜においてＣｒ”／Ｃｒ３”（７）
比が３／ｌＯ未満では ｃ 、 ６＋のセルフヒーリン
グ作用に乏しく、プレス加工後の耐食性を著るしく阻害
しまた、その比力１３／１超では耐食性は更に向上する
が、過剰のＣｒ は該クロメート皮膜の水に対する耐膨
潤性低下させ、且つ、これが下地めっきと上層の第２層
複合クロメート皮膜との密着性低下を招くなど、コスト
面からも不利である。Cr”/Cr3” (7) in the first layer chromate film
If the ratio is less than 3/lO, the self-healing effect of c, 6+ is poor, and the corrosion resistance after pressing is significantly inhibited.If the specific force exceeds 13/1, the corrosion resistance is further improved, but excessive Cr This is also disadvantageous from a cost perspective, as it reduces the swelling resistance of the chromate film to water, and this also leads to a decrease in the adhesion between the base plating and the upper second layer composite chromate film.
以上から上層に該複合クロメート皮膜を設ける場合、下
層の第１層クロメート皮膜のＣｒ６ｙＣｒ３＋の比は３
／１０−３／１ カよく好ましくは５／１０〜２／１が
よい。From the above, when the composite chromate film is provided in the upper layer, the Cr6yCr3+ ratio of the first layer chromate film in the lower layer is 3.
/10-3/1, preferably 5/10 to 2/1.
またクロム付着量が３０πｙ／ｒｒ１未満ではプレス加
工後の耐食性ζこおいて高い性能を期待することは難し
く、一方、１５０■／Ｉ超では高耐食性を得る点では支
障はないが、上層の第２層複合クロメート皮膜或いは上
塗塗料密着性に支障を招き好ましくない。好才しくは５
ｏ〜１２０〜／ばかよい。Furthermore, if the amount of chromium deposited is less than 30πy/rr1, it is difficult to expect high performance in terms of corrosion resistance ζ after press working, while if it exceeds 150πy/I, there is no problem in obtaining high corrosion resistance, but the This is undesirable because it impedes the adhesion of the two-layer composite chromate film or the top coat. Good talent is 5
o~120~/Bakayoi.
第１層クロメート皮膜のｃｒ６＋／ｃｒ３＋の適正比を
得る方法にあたっては、上述した従来型クロメート処理
法の１種又は２種以上の組み合せのいづれであってもよ
いが、耐食性、経済性の点がら好才しくは塗布型クロメ
ート処理がよい。The method for obtaining an appropriate ratio of cr6+/cr3+ in the first layer chromate film may be one of the above-mentioned conventional chromate treatment methods or a combination of two or more, but from the viewpoint of corrosion resistance and economic efficiency, A coating type chromate treatment is preferable.
なお、塗布型クロメート処理におけるＣｒ の生成は過
酸化水素、アルコール等の還元剤を用いてもよい。Note that a reducing agent such as hydrogen peroxide or alcohol may be used to generate Cr in the coating type chromate treatment.
次に、第２層の複合クロメート皮膜を形成させるにあた
り、該クロム化合物のバインダーとして用いる樹脂は構
造式として
〔式中、−Ｒは−Ｈ又は−ＣＨ３，−ＡはンＣ（ＣＨ３
）ＩＩ−ＣＩ−ｂ、−〇−又は−８−およびｎは０又は
１〜１４の整数である。〕
で示されるエポキシ樹脂５０〜１００重量％及びその他
のエポキシ樹脂５０〜Ｏ重量％からなるエポキシ樹脂成
分（ａ、）とジカルボン酸（ａ２）と少なくとも１個の
第１級ヒドロキシル基を有する第２級アミン（ａ、）と
を反応させて得られる生成物（Ａ）とポリイソシアナー
ト化合物（ｂｔ）とインシアナート保護剤（ｂ２）とを
（ｂｔ ）のインシアナート基の数／ （ｂｔ ）の活
性水素基の数の比が７／１〜７／６となるように反応さ
せて得られる生成物（１３）とを生成物（Ａ）に含まれ
る第１級ヒドロキシル基の数／生成物ＣＢ）に含まれる
活性インシアナート基の数の比が２０／１−１／１とな
るように反応させて得られる熱硬化性樹脂である。Next, in forming the second layer of composite chromate film, the resin used as a binder for the chromium compound has the structural formula [wherein -R is -H or -CH3, -A is C (CH3
) II-CI-b, -0- or -8- and n are 0 or an integer from 1 to 14. ] An epoxy resin component (a,) consisting of 50 to 100% by weight of the epoxy resin represented by and 50 to 0% by weight of other epoxy resins, a dicarboxylic acid (a2), and a secondary compound having at least one primary hydroxyl group. The product (A) obtained by reacting the class amine (a,), the polyisocyanate compound (bt), and the inocyanate protecting agent (b2), the number of inocyanate groups in (bt)/the active hydrogen in (bt) The product (13) obtained by reacting so that the ratio of the number of groups is 7/1 to 7/6 to the number of primary hydroxyl groups contained in the product (A)/product CB). It is a thermosetting resin obtained by reacting so that the ratio of the number of active incyanato groups contained is 20/1 to 1/1.
この樹脂は才ず構造式として、
〔式中、−■は−Ｈ又は−ＣＨ，、−人は、＞Ｃ（ＣＩ
Ｉ３）２ 、 ｎは０又は１〜１４の整数である。〕で
示される一般のエポキシ樹脂に加工時の皮膜の伸び性を
付与させるに当りジカルボン酸で上記樹脂を鎖延長する
と共に、その末端に第１級ヒドロキシル基をもつ第２級
アミンを付加せしめて得られる。This resin has the structural formula: [In the formula, -■ is -H or -CH, - is >C (CI
I3) 2 and n are 0 or an integer of 1 to 14. ] In order to impart film elongation to the general epoxy resin shown in the figure above, the resin is chain-extended with a dicarboxylic acid, and a secondary amine having a primary hydroxyl group is added to the end of the resin. can get.
更に、この得られた樹脂にポリイソシアナート化合物の
部分保護を付加させ、該クロム化合物のバインダー効果
を発揮せしめる。Furthermore, partial protection of a polyisocyanate compound is added to this obtained resin, so that the binder effect of the chromium compound is exerted.
本発明において、上記エポキシ樹脂成分（、、）として
は上記構造式で示されるエポキシ樹脂が使用されてよく
、例えば東部化成社製商品名［エポト − ト ＹＤ−
０１７Ｊ ［同 ＹＤ−０１４Ｊ ｒ 同 ＹＤ−０１
１Ｊ「同ＹＤ−１２８Ｊ、大日本インキ化学工業社製［
エピクロン４０５０Ｊ等の市販品が挙げられ、これらを
単独又はこれらの５０重量％以下を、その他のエポキシ
樹脂（例えばポリアルキレングリコールジグリシジルエ
ーテル等）で置換した系で構成される。In the present invention, as the epoxy resin component (,,), an epoxy resin represented by the above structural formula may be used, for example, the product name [Epoto YD-
017J [same YD-014J r same YD-01
1J "YD-128J, manufactured by Dainippon Ink and Chemicals Co., Ltd. [
Commercially available products such as Epiclon 4050J are listed, and the system is constructed by replacing these alone or up to 50% by weight with other epoxy resins (eg, polyalkylene glycol diglycidyl ether, etc.).
上記置換率が５０重量％を越えると該クロム化合物の被
覆性が低下し耐食性、耐水性、密着性。When the above substitution rate exceeds 50% by weight, the coating properties of the chromium compound deteriorate, resulting in poor corrosion resistance, water resistance, and adhesion.
耐薬品性、硬化性等が低下する。Chemical resistance, hardenability, etc. decrease.
本発明において上記ジカルボン酸（ａ２）としては１例
えば、ポリメチレンジカルボン酸（アジピン酸、アゼラ
イン酸、セパチン酸など）、芳香族ジカルボン酸（無水
フタル酸、フタル酸、イソフタル酸、テレフタル酸など
）、ダイマー酸、ポリブタジェンカルボン酸、ポリエス
テルジカルボン酸等が挙げられ、これらの１種又は２種
以上を使用に供する。特ζこ、ポリメチレンジカルボン
酸が該クロム化合物の被覆性およびプレス加工性の点で
優れ、中でもアゼライン酸が最も好ましい。In the present invention, the dicarboxylic acids (a2) include 1, for example, polymethylene dicarboxylic acids (adipic acid, azelaic acid, cepatic acid, etc.), aromatic dicarboxylic acids (phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, etc.), Examples include dimer acid, polybutadienecarboxylic acid, polyester dicarboxylic acid, etc., and one or more of these may be used. In particular, polymethylenedicarboxylic acid is excellent in terms of coverage and press workability of the chromium compound, and azelaic acid is the most preferred among them.
本発明において、上記第２級アミン（ａ３）は、ａＩ成
分と３２成分の反応すなわち、グリシジル基とカルボキ
シル基の付加反応を低温で且つ迅速ｌこ進行させる触媒
としての役割をもち、しかも、その−ＮＨ基がグリシジ
ル基に付加して樹脂に第１級ヒドロキシル基を導入して
、皮膜化時の架橋反応を容易にし、該複合クロメート皮
膜からのＣｒ６＋の耐温水抽出性を抑制する点で重要で
ある。また、骨格中に導入された窒素は触媒作用として
有効に作用するので、硬化反応が促進される。In the present invention, the secondary amine (a3) has the role of a catalyst that allows the reaction between the aI component and the 32 components, that is, the addition reaction between the glycidyl group and the carboxyl group, to proceed rapidly at a low temperature. The -NH group is added to the glycidyl group to introduce a primary hydroxyl group into the resin, which is important in that it facilitates the crosslinking reaction during film formation and suppresses the hot water extraction resistance of Cr6+ from the composite chromate film. It is. Further, since the nitrogen introduced into the skeleton acts effectively as a catalyst, the curing reaction is promoted.
かかる第２級アミンとしては１例えば、ジアルカノール
アミン（ジェタノールアミン、ジプロパノールアミン、
ジェタノールアミンなど）、アルキルアルカノールアミ
ン（エチルエタノールアミンなど）が挙げられ、これら
の１種または２種以上を使用ｌこ供する。特ζこ、ジア
ルカノールアミンが好ましく、中でもジェタノールアミ
ンが最適テある。Examples of such secondary amines include dialkanolamines (jetanolamine, dipropanolamine,
(e.g., jetanolamine), alkylalkanolamines (e.g., ethylethanolamine), and one or more of these may be used. Particularly, dialkanolamines are preferred, and among them, jetanolamine is most suitable.
本発明における生成物（Ａ）は上記エポキシ樹脂成分（
ａｌ）とジカルボン酸（ａｌ）と第２級アミン（ａ、）
、！：を反応させることにより得られるが、この場合、
該クロム化合物の被覆性の観点から。The product (A) in the present invention is the epoxy resin component (
al), dicarboxylic acid (al), and secondary amine (a,)
,! : can be obtained by reacting, but in this case,
From the viewpoint of coverage of the chromium compound.
［（ａ、）のグリシジル基の１当量−（ａｌ）のカルボ
キシル基の２当量） ／ （（ａ＋）＋（ａｌ）＋Ｃａ
５）の合計型骨（ｙ）〕の値が７×１０１７当量力以下
好ましくは４Ｘ］、０’〜０．３ＸＩＯ−’ｇ当量／ｙ
で且っＣ（，２）のカルボキシル基の２当量＋（ａ３）
のアミン基のＶ当量） ／ （（ａ、）のグリシジル基
の７当量〕の比が４／５〜６／５好才しくは９／１０〜
２３／２０となるような範囲で設定する必要がある。[1 equivalent of glycidyl group in (a,) - 2 equivalents of carboxyl group in (al)) / ((a+) + (al) + Ca
5) total type bone (y)] value is 7×1017 equivalent force or less, preferably 4X], 0' to 0.3XIO-'g equivalent/y
and 2 equivalents of carboxyl group of C(,2) + (a3)
The ratio of (V equivalent of the amine group in (a,)) / (7 equivalents of the glycidyl group in (a,
It is necessary to set the value within a range of 23/20.
上記の値が７×１０→り当量／りを越えると、該クロム
化合物の被覆性が劣化し、十分な加工性が得られない。If the above value exceeds 7×10 → equivalent weight/liter, the coating properties of the chromium compound will deteriorate and sufficient workability will not be obtained.
また上記の比が４７５未満では十分な熱硬化性が得られ
ず、また６１５を越えると未反応のジカルボン酸或いは
第２級アミンが残存して、該複合クロメート皮膜の耐水
性や耐薬品性を阻害する。In addition, if the above ratio is less than 475, sufficient thermosetting properties cannot be obtained, and if it exceeds 615, unreacted dicarboxylic acid or secondary amine remains, impairing the water resistance and chemical resistance of the composite chromate film. inhibit.
本発明における生成物ＣＢ）は、ポリイソシアナート化
合物（ｂ、）とイソシアナート保護剤（ｂ２）とを（ｂ
、）のイソシアナート基の数／（ｂ２）の活性水素基の
数の比が７／１〜７／６となるよう反応させて得られる
が、この系には、通常、インシアナート基の全部が保護
された全ブロック体、一部が保護され残りのインシアナ
ート基は保護されていない部分ブロック体および全部の
インシアナート基が保護されないま才の未ブロック体が
混在する。The product CB) according to the invention comprises a polyisocyanate compound (b,) and an isocyanate protecting agent (b2) (b).
,) is obtained by reacting so that the ratio of the number of isocyanate groups in (b2) to the number of active hydrogen groups in (b2) is 7/1 to 7/6. There is a mixture of protected fully blocked forms, partially blocked forms where part of the incyanato groups are unprotected, and unblocked forms where all of the incyanato groups are not protected.
かかる生成物ＣＢ）にあって、全ブロック体は熱硬化性
樹脂を皮膜化する際の架橋剤として機能する。In such product CB), the whole block functions as a crosslinking agent when forming a film from a thermosetting resin.
部分ブロック体のうち、１個の活性インシアナート基と
１個以上のブロックイソシアナート基を有するものは、
生成物（、Ａ）に付加し、皮膜化時の架橋性官能基とし
ての役目を有し、また２個以上の活性イソシアナート基
と１個以上のブロックイソシアナート基を有するものは
、生成物Ｃ人〕＠鎖延長して分子量を大きくし、且つ、
架橋性官能基を付加する役割を有する。Among the partially blocked bodies, those having one active incyanato group and one or more blocked isocyanate groups are:
Those that are added to the product (A) and have a role as a crosslinking functional group during film formation, and have two or more active isocyanate groups and one or more blocked isocyanate groups are Person C] @Extend the chain to increase the molecular weight, and
It has the role of adding a crosslinkable functional group.
未ブロック体は生成物（Ａ）を鎖延長して分子量を大き
くし、主鎖中にウレタン結合を導入する役目を有する。The unblocked product has the role of extending the chain of the product (A) to increase its molecular weight and introducing a urethane bond into the main chain.
以上のようにして成る熱硬化性樹脂は、耐水膨潤性、プ
レス加工性、上塗塗料密着性に優れた性能を示すと共に
１本発明の第２層複合クロメート皮膜にあっては、樹脂
のバインダー効果による該クロム化合物の難溶化及び撥
水性の向上によって。The thermosetting resin formed as described above exhibits excellent performance in water swelling resistance, press workability, and top coat adhesion.1 In the second layer composite chromate film of the present invention, the binder effect of the resin By making the chromium compound less soluble and improving water repellency.
厳しい腐食環境にも十分耐え得る高耐食性が得られる。Provides high corrosion resistance that can withstand severe corrosive environments.
次に該複合クロメート皮膜を構成するクロム化合物とし
ては、それ自体水に難溶で解離度の小さいものが高耐食
性へと導く上で重要であり、更ζこ、その酸基を固定す
るアルカリ金属としてはＬｉ。Next, as the chromium compound constituting the composite chromate film, it is important to have a chromium compound that is hardly soluble in water and has a low degree of dissociation in order to achieve high corrosion resistance. As for Li.
Ｎａ 、 Ｋ 、 ＡＪ、アルカリ土類金属としてはＳ
ｒ。Na, K, AJ, S as alkaline earth metal
r.
Ｃａ、Ｚｎ、Ｂａのいづれか１種又は２種以上を使用に
、供するが、好ましくはアルカリ土類金属がよく中でも
Ｓｒが最適である。One or more of Ca, Zn, and Ba may be used, and alkaline earth metals are preferred, with Sr being most suitable.
また、粉末状クロム化合物を該熱硬化性樹脂によって被
覆する場合、粒径と配合割合に留意する必要がある。中
でも粒径は該複合クロメート皮膜の高耐食性、プレス加
工性、上塗塗料密着性および仕上り外観の均一性などの
諸性能を高レベルに維持する点で適正なものを選ぶこと
が肝要である。Furthermore, when covering a powdered chromium compound with the thermosetting resin, it is necessary to pay attention to the particle size and blending ratio. Among these, it is important to select an appropriate particle size in order to maintain the composite chromate film at a high level of various performances such as high corrosion resistance, press workability, top coat adhesion, and uniformity of finished appearance.
この場合、あまり微粒化し過ぎると該複合クロメート皮
膜の下地めっき面に対する密着性やｃｒ６＋のセルフヒ
ーリング作用を効率的に発揮させ難くなり、耐食寿命は
期待できない。一方、逆に粗粒化し過ぎると、該複合ク
ロメート皮膜の表面平滑さが失なわれ仕上り外観の不拘
−或いはまた。プレス加工時の型カジリの発生を招くな
ど商品価値を大きく損なう。In this case, if the particles are too atomized, it becomes difficult to efficiently exhibit the adhesion of the composite chromate coating to the underlying plating surface and the self-healing action of cr6+, and a long corrosion-resistant life cannot be expected. On the other hand, if the grains are made too coarse, the surface smoothness of the composite chromate film will be lost, and the finished appearance will be unreliable. This greatly reduces product value, such as causing mold galling during press processing.
かくして該クロム化合物の粒径は０．１〜１μｍがよい
。また、該クロム化合物の該熱硬化性樹脂に対する配合
割合は、高耐食化ζこ必要なＣｒ による自己修復作用
の持続性及びプレス加工後の該複合クロメ−ト皮膜の下
地めっき面に対する密着性、上塗塗料密着性からみて１
０〜８０％がよく、奸才しくは２０〜６０％がよい。才
た、このようζこ該複合クロメート皮膜は樹脂で被覆さ
れたクロム化合物より成るため、その電気抵抗は比較的
大きく、その付着量によっては当然スポット溶接性に支
障を招く。そこで、耐食性を犠牲をこすることなくスポ
ット溶接性を維持するためには片面で０５〜５ｆ／、、
ｆの付着量範囲がよく、好ましくは０．８〜３．５ｆ／
ｄがよい。Thus, the particle size of the chromium compound is preferably 0.1 to 1 μm. In addition, the blending ratio of the chromium compound to the thermosetting resin is determined by the sustainability of the self-repairing action of Cr necessary for high corrosion resistance, and the adhesion of the composite chromate film to the underlying plating surface after press working. From the viewpoint of top coat adhesion 1
0 to 80% is good, and 20 to 60% is good for skillfulness. Since the composite chromate film is made of a chromium compound coated with a resin, its electrical resistance is relatively high, and depending on the amount of the coating, spot weldability may be impaired. Therefore, in order to maintain spot weldability without sacrificing corrosion resistance, it is necessary to
The adhesion amount range of f is good, preferably 0.8 to 3.5 f/
d is good.
以上のような２層クロメート皮膜構成からなる本発明に
よれば従来クロメート処理鋼板の有する欠点が解消でき
、更にはスポット溶接性を阻害することなく耐食性、上
塗塗料密着性、プレス加工性等の諸性能を格段に飛躍さ
せることができる。According to the present invention, which has a two-layer chromate film structure as described above, the drawbacks of conventional chromate-treated steel sheets can be overcome, and various improvements such as corrosion resistance, top coat adhesion, and press workability can be achieved without impeding spot weldability. Performance can be dramatically improved.
なお、本発明に用いる亜鉛めっき鋼板としてはめつき層
が亜鉛若しくは亜鉛系合金でなり５合金系としてはＮｉ
、Ｃｏ、Ｆｅ、Ｃｒの１種又は２種以上含んでもよい。The galvanized steel sheet used in the present invention has a plating layer made of zinc or a zinc-based alloy, and the galvanized steel sheet used in the present invention is made of zinc or a zinc-based alloy.
, Co, Fe, and Cr.
才た、これらの亜鉛めっき層を得る方法とじては電気め
っき、溶融めっき或いは蒸着めっきのいづれでもよく、
単層又は多層めっきのいづれであってもよい。The method of obtaining these galvanized layers may be electroplating, hot-dip plating or vapor deposition plating.
Either single layer or multilayer plating may be used.
以下に実施例、比較例及び従来例を挙げて本発明を具体
的に説明する。The present invention will be specifically explained below by giving examples, comparative examples, and conventional examples.
下表に示すように種々の異なる第１層クロメート皮膜の
Ｃｒ ／Ｃｒ の比およびクロム付着量と第２層の複合
クロメート皮膜の有機樹脂のタイプ、クロム化合物のタ
イプと配合比及び所定付着量とでなる本発明の実施例Ｎ
α１〜Ｎα３１につき、耐食性、プレス加工性、連続ス
ポット溶接性及び上塗塗料密着性の各種性能試験を行な
った。As shown in the table below, the Cr/Cr ratio and amount of chromium deposited in various different first layer chromate films, the type of organic resin, type and blending ratio of chromium compound, and predetermined amount of deposited in the second layer composite chromate film. Example N of the present invention consisting of
Various performance tests of corrosion resistance, press workability, continuous spot weldability, and top coat adhesion were conducted for α1 to Nα31.
その結果を参考例Ｎα３２〜Ｎα４１および従来比較例
のＮα４２〜尚４７との対比て示ず。The results are not shown in comparison with reference examples Nα32 to Nα41 and conventional comparative examples Nα42 to 47.
なお、第１層クロメート皮膜を得る方法としては次によ
った。The method for obtaining the first layer chromate film was as follows.
Ｄ；処理液ＣｒＯａ ／Ｈ２Ｓ ０４ ＝１５１０．２
（ｆ／ｚ ） 。D; Processing liquid CrOa /H2S 04 =1510.2
(f/z).
浴温４５℃、陰極電流密度１０Ａ／ｄＪで処理する電解
クロメート処理。Electrolytic chromate treatment at a bath temperature of 45°C and a cathode current density of 10 A/dJ.
■（；処理液Ｂｔ３３６７／日本パーカーライジング製
使ＪｐＨ２，０浴ｆｍ４０’ｃ、スプレー処理後水洗し
て得られる反応型クロメート処理。(2) Treatment liquid Bt3367/Nippon Parkerizing Co., Ltd. JpH2.0 bath fm40'c, reactive chromate treatment obtained by washing with water after spray treatment.
Ｔ；処理液ＣｒＯ３／ＳｉＯ２ゾル＝ １０／２０ Ｃ
ｆ／ｌ、〕但し必要に応じ、 Ｈ２Ｏ２で所定量のｃｒ
３＋を得る。浴温４０℃、スプレー処理後ガスワイピン
グして所定クロム付着量を得る塗布型クロメート処理。T; Treatment liquid CrO3/SiO2 sol = 10/20 C
f/l,] However, if necessary, add a predetermined amount of cr with H2O2.
Get a 3+. Spray-on chromate treatment in which the bath temperature is 40°C and gas wiping is performed after spraying to obtain a predetermined amount of chromium deposit.
Ｐ−２；
才た。第２層の複合クロメート皮膜を得るために用いた
有機樹脂のタイプとして次の樹脂を代表として用いた。P-2; Saitata. The following resin was used as a representative type of organic resin to obtain the second layer of composite chromate film.
ｐ−ｉ；エポキシ樹脂（エポト−トＹＤ−０１７／東部
化成製）７８４部（重量部以下同様）をキシｏ−ルア
８．４ 部及びセロアセ１９６部に溶解したのち、アゼ
ライン酸２５．１部、ジェタノールアミン１３．３部を
加えｈ Ｎ２ガス下１４０℃で４時間半反応させ、その
後キジロール３１．４．メチルエチルケトン２４５部加
えたもの１６５．５部に対して別途セロアセ３７５部に
−＼キサメチレンジイソシアナート２２４部及びε−カ
プロラクタム１５１部を加え１００℃で３時間反応させ
て得られるインシアナートを７５部及びキジロール２６
．３部を加え１００℃で３時間反応させたのち、メチル
エチルケトン１９．４部を加え才なる熱硬化性樹脂をク
ロム化合物として２５部に対し１６０部加えてなる樹脂
。p-i; 784 parts of epoxy resin (Epotote YD-017/manufactured by Tobu Kasei) (same parts by weight as below)
After dissolving in 8.4 parts and 196 parts of celloacetate, 25.1 parts of azelaic acid and 13.3 parts of jetanolamine were added and reacted for 4 and a half hours at 140°C under N2 gas. To 165.5 parts of 245 parts of methyl ethyl ketone, 224 parts of -\xamethylene diisocyanate and 151 parts of ε-caprolactam were added to 375 parts of celloacetate and reacted at 100°C for 3 hours to obtain 75 parts of incyanate. Kijiroll 26
．． After adding 3 parts and reacting at 100°C for 3 hours, 19.4 parts of methyl ethyl ketone was added, and 160 parts of a thermosetting resin was added to 25 parts as a chromium compound.
、エポトートＹＤ−０１７３９２部をキジロール２４７
部、セロアセ１２４部に溶解させたのち、セパチン酸１
３５部、ジェタノールアミン６．７部を加えて、Ｎ２ガ
ス下１４０℃で８時間反応させたものを２９０部に対し
。, Epototo YD-017392 parts to Kijiroll 247
After dissolving in 124 parts of celloacetate, 1 part of cepacic acid
35 parts and 6.7 parts of jetanolamine were added and reacted for 8 hours at 140°C under N2 gas to 290 parts.
別途セロアセ３７５部にヘキサメチレンジイソシアナー
ト２２４部およびε−カプロラクタム１５１部を加えて
１００℃で３時間反応させて得るインシアナート１４部
を加えｓ Ｎ２ガス下１００℃で４時間反応させたのち
、メチルイソブチルケトン９５部を加えてなる熱硬化性
樹脂をクロム化合物として２５部に対し１６０部加えて
なる樹脂。Separately, 14 parts of incyanate obtained by adding 224 parts of hexamethylene diisocyanate and 151 parts of ε-caprolactam to 375 parts of celloacetate and reacting at 100°C for 3 hours were added. A resin made by adding 160 parts to 25 parts of a thermosetting resin containing 95 parts of isobutyl ketone as a chromium compound.
なお、素材としては、電気めっき鋼板とし、めっき系を
亜鉛或いはＺｎ−１１Ｎｉ−ＩＦｅとして、めっき付着
量を２（１／ｎ？の単層めっきを代表に用いた。The material was an electroplated steel sheet, the plating system was zinc or Zn-11Ni-IFe, and a single layer plating with a coating weight of 2 (1/n?) was used as a representative.
下表から本発明の実施側限１〜権３１は従来の比較例歯
４２〜＆４７１こ較へ、格段の耐食性を有しており、更
に゛スポット溶接性及び塗装下地としても優れた性能を
有していることがわかる。From the table below, the teeth 1 to 31 of the implementation side of the present invention have much better corrosion resistance than the conventional comparative examples 42 to 471, and also have excellent spot weldability and excellent performance as a paint base. I know what you're doing.
以上のように２本発明の２層クロメート処理鋼板は従来
のクロメート処理鋼板が有する欠点を解消し、更ζこは
、必要に応じて着色顔料を用い処理外観の色調を自由に
得ることが可能な特徴をも有する高性能の２層クロメー
ト処理鋼板である。As described above, the two-layer chromate-treated steel sheet of the present invention eliminates the drawbacks of conventional chromate-treated steel sheets, and it is also possible to freely obtain the color tone of the treated appearance using coloring pigments as necessary. This is a high-performance double-layer chromate-treated steel sheet that also has the following characteristics.
＊１ 耐食性評価方法
（１） 試片
角筒プレス加工→弱アルカリ脱脂→水洗→乾燥４０Ｗｘ
４０Ｌｘ３０Ｈ（ｍ秒 ＦＣ４３３６（日本バーカーラ
イング製）Ｉ６２０塗油（日本工作油）６０℃×１２０
秒スプレー処理絞り比２．４
（２）腐食試験 ＊３
塩水噴霧試験（ＪＩＳＺ−２３７１） ５００時間後の
発錆性評価
◎白錆発生面積率 ５％以下 赤錆発生面積率 ０％０
５〜１０％ ０％
△ Ｉ １０〜３０％ ５％以下
× ３０％以上 １０％以上
＊２ プレス加工性
ｆｌ） 角筒プレス加工（４０ＷＸ４０ＬＸ３０Ｈ（ｍ
ｍ） ％＄６２０塗油／日塗油／日本工作比２．４）
プ剥離状況評価
（型カジリ性） （加工部脱膜性）
◎ 全く発生なし ◎全く脱膜せず
○ ごく催かに発生 ○ ごく僅かに脱膜Δ 部分的に
発生 Δ 部分的に脱膜
× 全面発生 × 全面脱膜
連続スポラ１−溶接性
５
溶接電流 適正電流値ｘ −１−ｏ ｏ （ＫＡ ）電
極径 ４５朋φ
電極圧下刃 ２００ Ｋｙ
通電時間 １０サイクル／ ５０ Ｔ−１ｙ。*1 Corrosion resistance evaluation method (1) Test piece square tube press processing → Weak alkaline degreasing → Water washing → Drying 40Wx
40L x 30H (ms FC4336 (made by Nippon Barker Lining) I620 oil (Nippon Craft Oil) 60℃ x 120
Second spray treatment aperture ratio 2.4 (2) Corrosion test *3 Salt spray test (JISZ-2371) Rust development evaluation after 500 hours ◎White rust area ratio: 5% or less Red rust area ratio: 0%0
5-10% 0% △ I 10-30% 5% or less
m) %$620 oil application/day oil application/Japanese work ratio 2.4) Evaluation of peeling status (mold galling) (film removal property of processed parts) ◎ No occurrence ◎ No film removal at all ○ Very unlikely Occurrence ○ Very slight film removal Δ Partial occurrence Δ Partial film removal × Full surface occurrence × Full film removal Continuous spora 1 - Weldability 5 Welding current Appropriate current value x -1-o o (KA) Electrode diameter 45 mm φ Electrode lowering blade 200 Ky Current application time 10 cycles/50 T-1y.
◎ 連続打点５０００点以上
○ ’ ４０００ ＃
△ ＃ ３０００ ＃
Ｘ ＃ ３０００点未満
上塗塗料密着性
メラミンアルキッド樹脂塗装２５μｍ、９０℃×３０分
焼付、４Ｔ折曲加工部セロテープ剥離◎ 全く塗膜剥離
せず
○ ごく僅かζこ剥離
Δ 部分的に剥離
× ５０％以上剥離◎ 5000 consecutive points or more ○ ' 4000 # △ # 3000 # ○ Very slight peeling Δ Partial peeling × 50% or more peeling
Claims (1)
を形成させるにあたり、第１層皮膜としてＣｒ ／Ｃｒ
の比が３／１０〜３／１で且つクロム付着量が３０〜
１５０η／、？ （片面）でなるクロメート皮膜を有し
、更にその上層に第２層皮膜として、アミンをポリマー
末端にもつエポキシ樹脂をウレタン変性してなる熱硬化
性樹脂をバインダーとしこれにアルカリ金属もしくはア
ルカリ土類金属でその酸基を固定した粒径１μｍ以下の
粉末状クロム化合物を１０〜８０重量％含ませてなる複
合クロメート皮膜を０．５〜５２／Ｉの範囲で形成させ
てなることを特徴とした２層クロメート処理鋼板。When forming a chrome-1 film on the surface of a zinc or zinc alloy coated steel sheet, Cr/Cr is used as the first layer film.
The ratio of 3/10 to 3/1 and the amount of chromium deposited is 30 to
150η/? It has a chromate film (on one side), and a second layer film on top of the chromate film, with a thermosetting resin made by urethane modification of an epoxy resin with an amine at the polymer end as a binder, and an alkali metal or alkaline earth It is characterized by forming a composite chromate film containing 10 to 80% by weight of a powdered chromium compound with a particle size of 1 μm or less whose acid groups are fixed with metal, in a range of 0.5 to 52/I. Double layer chromate treated steel plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12025683A JPS6013078A (en) | 1983-07-04 | 1983-07-04 | Double-chromated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12025683A JPS6013078A (en) | 1983-07-04 | 1983-07-04 | Double-chromated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6013078A true JPS6013078A (en) | 1985-01-23 |
| JPS6155592B2 JPS6155592B2 (en) | 1986-11-28 |
Family
ID=14781692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12025683A Granted JPS6013078A (en) | 1983-07-04 | 1983-07-04 | Double-chromated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6013078A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6270596A (en) * | 1985-09-20 | 1987-04-01 | Toshiba Corp | Method for plating copper alloy substrate containing tin with silver |
| JPS62199795A (en) * | 1986-02-27 | 1987-09-03 | Nippon Mining Co Ltd | Parts for electronic and electrical appliances |
| JPS62199794A (en) * | 1986-02-27 | 1987-09-03 | Nippon Mining Co Ltd | Parts for electronic and electric appliances |
| FR2596420A1 (en) * | 1986-03-27 | 1987-10-02 | Nippon Kokan Kk | SURFACE TREATED STEEL SHEET WITH HIGH CORROSION RESISTANCE |
| FR2604729A1 (en) * | 1986-03-27 | 1988-04-08 | Nippon Kokan Kk | High corrosion-resistant surface-treated steel plate |
| US4767508A (en) * | 1986-02-27 | 1988-08-30 | Nippon Mining Co., Ltd. | Strike plating solution useful in applying primer plating to electronic parts |
| US4959277A (en) * | 1988-12-07 | 1990-09-25 | Nihon Parkerizing Co., Ltd. | Process for treating plated steel sheet |
| US6420205B1 (en) | 1999-03-24 | 2002-07-16 | Kyocera Corporation | Method for producing package for housing photosemiconductor element |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037216A (en) * | 1973-06-20 | 1975-04-07 | ||
| JPS526306A (en) * | 1975-07-07 | 1977-01-18 | Nippon Denko Kk | Pretreatment process for reclaiming useful metalfrom inorganic sludge |
| JPS57108292A (en) * | 1980-12-24 | 1982-07-06 | Nippon Kokan Kk <Nkk> | Conposite coated steel plate with superior corrosion resistance, coating adhesion and corrosion resistance after coating |
-
1983
- 1983-07-04 JP JP12025683A patent/JPS6013078A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037216A (en) * | 1973-06-20 | 1975-04-07 | ||
| JPS526306A (en) * | 1975-07-07 | 1977-01-18 | Nippon Denko Kk | Pretreatment process for reclaiming useful metalfrom inorganic sludge |
| JPS57108292A (en) * | 1980-12-24 | 1982-07-06 | Nippon Kokan Kk <Nkk> | Conposite coated steel plate with superior corrosion resistance, coating adhesion and corrosion resistance after coating |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6270596A (en) * | 1985-09-20 | 1987-04-01 | Toshiba Corp | Method for plating copper alloy substrate containing tin with silver |
| JPH0256436B2 (en) * | 1985-09-20 | 1990-11-30 | Tokyo Shibaura Electric Co | |
| JPS62199795A (en) * | 1986-02-27 | 1987-09-03 | Nippon Mining Co Ltd | Parts for electronic and electrical appliances |
| JPS62199794A (en) * | 1986-02-27 | 1987-09-03 | Nippon Mining Co Ltd | Parts for electronic and electric appliances |
| US4767508A (en) * | 1986-02-27 | 1988-08-30 | Nippon Mining Co., Ltd. | Strike plating solution useful in applying primer plating to electronic parts |
| JPH0244913B2 (en) * | 1986-02-27 | 1990-10-05 | Nippon Mining Co | |
| FR2596420A1 (en) * | 1986-03-27 | 1987-10-02 | Nippon Kokan Kk | SURFACE TREATED STEEL SHEET WITH HIGH CORROSION RESISTANCE |
| FR2604729A1 (en) * | 1986-03-27 | 1988-04-08 | Nippon Kokan Kk | High corrosion-resistant surface-treated steel plate |
| US4959277A (en) * | 1988-12-07 | 1990-09-25 | Nihon Parkerizing Co., Ltd. | Process for treating plated steel sheet |
| US6420205B1 (en) | 1999-03-24 | 2002-07-16 | Kyocera Corporation | Method for producing package for housing photosemiconductor element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6155592B2 (en) | 1986-11-28 |
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