JPH11350161A - Conversion treatment agent for zinc or zinc alloy plating and conversion treatment - Google Patents
Conversion treatment agent for zinc or zinc alloy plating and conversion treatmentInfo
- Publication number
- JPH11350161A JPH11350161A JP15766198A JP15766198A JPH11350161A JP H11350161 A JPH11350161 A JP H11350161A JP 15766198 A JP15766198 A JP 15766198A JP 15766198 A JP15766198 A JP 15766198A JP H11350161 A JPH11350161 A JP H11350161A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- conversion treatment
- chemical conversion
- aluminum
- water
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、亜鉛または亜鉛合金用
の化成処理剤と化成処理方法、特にクロムおよびフッ素
を含まない化成処理剤と化成処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical conversion treatment agent and a chemical conversion treatment method for zinc or a zinc alloy, and more particularly to a chemical conversion treatment agent and a chemical conversion treatment method containing no chromium and fluorine.
【０００２】[0002]
【従来の技術】従来より、金属表面の防食方法として亜
鉛めっきまたは亜鉛合金めっき (以下、単に亜鉛めっき
と称することもある) を行う方法が比較的多く使用され
ているが、亜鉛めっき後めっき面の耐食性をさらに向上
させるために、クロメート処理を行うのが一般的であ
る。このクロメート皮膜により耐食性をさらに向上させ
るのである。2. Description of the Related Art Conventionally, zinc plating or zinc alloy plating (hereinafter sometimes simply referred to as zinc plating) has been used relatively frequently as a method for preventing corrosion of metal surfaces. In order to further improve the corrosion resistance of the steel, a chromate treatment is generally performed. This chromate film further improves the corrosion resistance.
【０００３】従来、クロメート処理は殆どが光沢クロメ
ート処理であったが、最近は、外観上から黒色クロメー
ト処理、また耐食性の面からは緑色クロメート処理とい
うように有色クロメート処理が比較的多く用いられてい
る。Conventionally, most chromate treatments are gloss chromate treatments. Recently, however, colored chromate treatments such as black chromate treatment from the appearance and green chromate treatment from the viewpoint of corrosion resistance have been used relatively frequently. I have.
【０００４】このように広く用いられているクロメート
処理は、基本浴組成が、無水クロム酸と鉱酸(H2SO4、HN
O3、HF、H2SiF6、H3PO4 、HCl を含む) の水溶液であっ
て、通常、塗布型と反応型と電解型とに分類されるが、
無水クロム酸含有液における６価のクロムを３価のクロ
ムに変換することで皮膜を生成させるのである。例え
ば、このときの皮膜組成は、xCr2O3・yCrO3 ・zH2Oとな
り、塗布型、反応型、電解型のいずれにおいても、生成
皮膜の中には未還元の６価のクロムの残留は避けられな
い。[0004] In such a chromate treatment widely used, the basic bath composition is composed of chromic anhydride and mineral acid (H 2 SO 4 , HN
O 3 , HF, H 2 SiF 6 , H 3 PO 4 , HCl) aqueous solution, which is generally classified into a coating type, a reaction type, and an electrolytic type,
By converting hexavalent chromium in the chromic anhydride-containing liquid into trivalent chromium, a film is formed. For example, the coating composition of this time, xCr 2 O 3 · yCrO 3 · zH 2 O , and the coating type, reaction type, in any of the electrolytic also residual hexavalent chromium unreduced Some generation film Is inevitable.
【０００５】このように、亜鉛めっき皮膜に対するクロ
メート処理の目的は、化学研摩と化成皮膜形成とであ
り、前者の化学研摩に対しては、フッ素化合物を添加す
ることで、また皮膜形成には６価クロムの還元で対処し
ている。[0005] As described above, the purpose of the chromate treatment for the galvanized film is chemical polishing and chemical conversion film formation. For the former chemical polishing, a fluorine compound is added, and for the film formation, 6 times. It deals with reduction of chromium (VI).
【０００６】しかしながら、近年この６価クロムがクロ
メート処理した皮膜、つまりクロメート皮膜中に含まれ
るため、人体の皮膚への悪影響が心配され、またその処
理物が廃棄された後、６価クロムがその皮膜から溶出さ
れ自然界に残留することが問題となっている。従来にあ
っても、このような問題点を解決するため、種々の処理
方法が検討されてきたが、十分な解決策は未だ見出され
ていない。However, in recent years, since hexavalent chromium is contained in a chromate-treated film, that is, a chromate film, there is a concern that the hexavalent chromium may have an adverse effect on the skin of the human body. There is a problem that it is eluted from the film and remains in the natural world. Conventionally, various processing methods have been studied in order to solve such a problem, but a sufficient solution has not been found yet.
【０００７】[0007]
【発明が解決しようとする課題】よって、本発明の一般
的な課題は、亜鉛または亜鉛合金めっき皮膜のさらなる
耐食性を確保するための化成処理剤とそれを使った化成
処理方法を開発することである。SUMMARY OF THE INVENTION Accordingly, a general object of the present invention is to develop a chemical conversion treatment agent and a chemical conversion treatment method using the same to ensure further corrosion resistance of a zinc or zinc alloy plating film. is there.
【０００８】従来は、そのような目的にクロメート処理
が行われてきたが、それには上述のような６価クロムの
溶出という問題があり、その解決が求められている。し
たがって、本発明の具体的な課題は、クロメート皮膜に
残留する６価クロムの溶出の問題を解決する技術を開発
することである。Conventionally, chromate treatment has been performed for such a purpose, but there is a problem of elution of hexavalent chromium as described above, and there is a need for a solution. Therefore, a specific object of the present invention is to develop a technique for solving the problem of elution of hexavalent chromium remaining in a chromate film.
【０００９】ところで、そのような目的達成には、現在
のところ、最初よりクロメート処理液に３価のクロムだ
けを含有させておく、３価のクロムを使用した処理法が
有望であるが、６価クロムから３価クロムへ還元するこ
とにより皮膜形成を促進させる従来法と比較して当初よ
り３価クロムを使用する方法では皮膜の形成が十分でな
く耐食性がかなり劣ることが判明している。In order to achieve such an object, a treatment method using trivalent chromium, in which only a trivalent chromium is initially contained in a chromate treatment solution, is promising. From the beginning, it has been found that the method using trivalent chromium does not form a sufficient film and the corrosion resistance is considerably inferior to the conventional method in which the film formation is promoted by reducing the trivalent chromium to trivalent chromium.
【００１０】したがって、本発明の別の課題は、クロム
を含まない処理液を使った表面処理により耐食性に優れ
た化成皮膜を形成する技術を開発することである。ま
た、前述のように、クロメート処理液にはフッ素化合物
が含有されることがあり、フッ素化合物の存在は被処理
物品の表面の化学研摩に効果があり、優れた皮膜密着
性、耐食性を得るためには、フッ化物の使用は望まし
い。しかし、フッ化物は人体の骨に悪影響を及ぼし、ま
た、環境規制物質であるため、使用することは好ましく
ない。Therefore, another object of the present invention is to develop a technique for forming a chemical conversion film having excellent corrosion resistance by surface treatment using a treatment solution containing no chromium. In addition, as described above, the chromate treatment liquid may contain a fluorine compound, and the presence of the fluorine compound is effective for chemical polishing of the surface of the article to be treated, and to obtain excellent film adhesion and corrosion resistance. The use of fluoride is desirable. However, the use of fluoride is not preferable because it has an adverse effect on human bones and is an environmentally regulated substance.
【００１１】したがって、本発明のさらに別の課題は、
クロム・フッ化物を使用しない表面処理液を用いて行う
化成処理により、さらに耐食性に優れた化成処理皮膜を
形成する技術を開発することである。Therefore, still another object of the present invention is to provide:
It is an object of the present invention to develop a technology for forming a chemical conversion coating film having more excellent corrosion resistance by performing a chemical conversion treatment using a surface treatment solution that does not use chromium and fluoride.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、従来のク
ロメート処理にこだわることなく、全く発想を変え、こ
れまで化成皮膜形成に用いられることのなかったポリ塩
化アルミニウムのような塩基性アルミニウムを含む溶液
による一種の化成処理によって、亜鉛または亜鉛合金め
っき皮膜上にこれまでのクロメート皮膜に匹敵する化成
処理皮膜が形成されることを知り、本発明を完成した。Means for Solving the Problems The present inventors have completely changed the idea without sticking to the conventional chromate treatment, and have made basic aluminum such as polyaluminum chloride which has not been used for the formation of a chemical conversion film. It has been found that a kind of chemical conversion treatment with a solution containing a zinc or zinc alloy plating film forms a chemical conversion coating film comparable to the conventional chromate coating film, and completed the present invention.
【００１３】ここに、本発明は次の通りである。 (1) 塩基性アルミニウムを含有することを特徴とする亜
鉛または亜鉛合金めっき用化成処理剤。 (2) クロム化合物およびフッ素化合物を含まない上記
(1) 記載の亜鉛または亜鉛合金めっき用化成処理剤。Here, the present invention is as follows. (1) A chemical conversion treating agent for zinc or zinc alloy plating, comprising basic aluminum. (2) Above that does not contain chromium compounds and fluorine compounds
The chemical conversion treating agent for zinc or zinc alloy plating according to (1).
【００１４】(3) 上記(1) または(2) 記載の化成処理剤
を亜鉛または亜鉛合金めっき皮膜に適用して化成処理皮
膜を形成することを特徴とする亜鉛または亜鉛合金の化
成処理方法。 (4) 前記化成処理剤を適用した後、水洗を行うことなく
化成処理皮膜を形成する上記(3) 記載の化成処理方法。(3) A chemical conversion treatment method for zinc or a zinc alloy, wherein the chemical conversion treatment agent according to the above (1) or (2) is applied to a zinc or zinc alloy plating film to form a chemical conversion treatment film. (4) The chemical conversion treatment method according to the above (3), wherein the chemical conversion treatment film is formed without performing water washing after applying the chemical conversion treatment agent.
【００１５】このように、本発明は、塩基性アルミニウ
ムを含む化成処理液を適用する処理(以下、「塩基性ア
ルミニウム処理」とも言う) をすることにより、優れた
耐食性が得られることを見出して完成されたものであっ
て、pH調整剤、錯化剤等のその他の添加成分については
任意である。As described above, the present invention has been found to provide excellent corrosion resistance by performing a treatment using a chemical conversion treatment solution containing basic aluminum (hereinafter, also referred to as "basic aluminum treatment"). It is a completed product, and other additional components such as a pH adjuster and a complexing agent are optional.
【００１６】本発明の好適態様にあっては、上記化成処
理剤は本質的にクロム、フッ素を含有することがない。
また、化成皮膜の形成に際しても、水洗を行うことな
く、乾燥するだけで良いため、排水処理の負荷の軽減が
可能となる。In a preferred embodiment of the present invention, the chemical conversion treating agent contains essentially no chromium or fluorine.
Also, when forming the chemical conversion film, it is only necessary to dry without performing washing with water, so that the load of wastewater treatment can be reduced.
【００１７】[0017]
【発明の実施の形態】次に、添付図面を参照して本発明
をさらに具体的に説明する。図１は、亜鉛めっきまたは
亜鉛合金めっき物品に対して本発明を適用する場合の工
程図である。Next, the present invention will be described more specifically with reference to the accompanying drawings. FIG. 1 is a process chart when the present invention is applied to a galvanized or zinc alloy-plated article.
【００１８】図中、本発明において対象とされる物品
は、本発明にかかる化成処理剤が従来のクロメート処理
剤に代えて開発されたものであり、従来よりクロメート
処理を行っている物品一般に適用可能である。しかし、
実際上の観点からは、いわゆる二次成形品の電気めっき
等で予めめっき処理された亜鉛めっきまたは亜鉛合金め
っき物品であって、例えば、家電製品部品、自動車部品
などである。In the figure, the articles targeted in the present invention are those in which the chemical conversion treating agent according to the present invention has been developed in place of the conventional chromate treating agent, and is generally applied to articles which have been conventionally subjected to chromate treatment. It is possible. But,
From a practical point of view, it is a zinc-plated or zinc-alloy-plated article that has been pre-plated by electroplating of a so-called secondary molded product, for example, a home appliance part, an automobile part, and the like.
【００１９】このような物品を水洗した後、一般には硝
酸溶液、要すれば硫酸あるいは塩酸溶液に上記物品を浸
漬することで酸活性処理を行い水洗する。このように、
酸活性処理を行ってから本発明にかかる化成処理剤を用
いて化成処理、つまり塩基性アルミニウム処理を行う
が、そのときの処理条件は次の通りである。After such an article is washed with water, the article is generally immersed in a nitric acid solution, if necessary, a sulfuric acid or hydrochloric acid solution, subjected to an acid activation treatment, and washed with water. in this way,
After performing the acid activation treatment, the chemical conversion treatment, that is, the basic aluminum treatment is performed using the chemical conversion treatment agent according to the present invention. The treatment conditions at that time are as follows.
【００２０】化成処理の処理条件の範囲 ｐＨ範囲：1.0 〜3.4 、好ましくは、1.5 〜3.4 温度範囲：10〜60℃、好ましくは、15〜25℃ 時間範囲：５〜180 秒、好ましくは、15〜90秒 本発明にかかる化成処理剤の好適組成例は次の通りであ
る。 Range of treatment conditions for chemical conversion treatment pH range: 1.0 to 3.4, preferably 1.5 to 3.4 Temperature range: 10 to 60 ° C, preferably 15 to 25 ° C Time range: 5 to 180 seconds, preferably 15 to 180 seconds Preferred composition examples of the chemical conversion treating agent according to the present invention are as follows.
【００２１】 塩基性アルミニウム : 0.1 〜 5 g/L pH調整剤、錯化剤 : 適宜量 水 : 残り なお、pH調整剤として例えば塩酸、硫酸、硝酸があり、
錯化剤としては乳酸が例示される。Basic aluminum: 0.1 to 5 g / L pH adjuster, complexing agent: Appropriate amount Water: Remaining Examples of the pH adjuster include hydrochloric acid, sulfuric acid, and nitric acid.
Lactic acid is exemplified as a complexing agent.
【００２２】化成処理は上記化成処理剤を亜鉛または亜
鉛合金めっき皮膜に適用して行うが、その具体的態様と
しては化成処理剤を含む水溶液への浸漬、該水溶液の塗
布、吹付け等がある。かかる化成処理を行ってから乾燥
すると、物品の表面には、耐食性の化成皮膜が形成され
る。The chemical conversion treatment is carried out by applying the chemical conversion treatment agent to a zinc or zinc alloy plating film, and specific examples thereof include immersion in an aqueous solution containing the chemical conversion treatment agent, application and spraying of the aqueous solution. . When the chemical conversion treatment is performed and then dried, a corrosion-resistant chemical conversion film is formed on the surface of the article.
【００２３】次いで、所望により、水溶性または水分散
性のアクリル、ウレタン、シリコーン、メラミン、など
の樹脂をコーティングして更なる耐食性の確保を図るこ
とができる。Then, if desired, a resin such as water-soluble or water-dispersible acrylic, urethane, silicone, melamine or the like can be coated to further secure corrosion resistance.
【００２４】ここに、本発明において使用される塩基性
アルミニウムは、[Al(H2O)6]3+を形成するアルミニウム
を言い、具体的には、塩化アルミニウム、硝酸アルミニ
ウム、硫酸アルミニウム、乳酸アルミニウム、それらの
複塩、例えば、ミョウバンとしてのアルミニウムであ
る。Here, the basic aluminum used in the present invention refers to aluminum forming [Al (H 2 O) 6 ] 3+ , and specifically, aluminum chloride, aluminum nitrate, aluminum sulfate, lactic acid Aluminum, their double salts, for example, aluminum as alum.
【００２５】さらに、上記のようなアルミニウム化合物
あるいはその複塩を水に溶解すると、ポリマー化して下
記の組成式の多核錯体を生じ、これらはポリ塩化アルミ
ニウム、ポリ硝酸アルミニウム、ポリ硫酸アルミニウム
等と呼ばれるがこれらも本発明に言う「塩基性アルミニ
ウム」に含まれることは明らかである。 [Al(OH)n Ａ(6-n)/a ]m ただし、Ａは塩素原子、硝酸基、硫酸基等を示し、a 、
n 、m は整数である。Further, when the above-mentioned aluminum compound or its double salt is dissolved in water, it is polymerized to form a polynuclear complex having the following composition formula, and these are called polyaluminum chloride, polyaluminum nitrate, polyaluminum sulfate and the like. However, it is apparent that these are also included in the “basic aluminum” referred to in the present invention. [Al (OH) n A (6-n) / a ] m where A represents a chlorine atom, a nitrate group, a sulfate group, etc.
n and m are integers.
【００２６】本発明において使用する塩基性アルミニウ
ムは、好ましくは、塩化アルミニウム、ポリ塩化アルミ
ニウムとしてのアルミニウムである。本発明における塩
基性アルミニウムの濃度範囲は、好ましくは、処理液中
にアルミニウムとして0.5 〜５g/L 、さらに好ましくは
1.5 〜3.0g/Lである。The basic aluminum used in the present invention is preferably aluminum as aluminum chloride or polyaluminum chloride. The concentration range of the basic aluminum in the present invention is preferably 0.5 to 5 g / L as aluminum in the treatment liquid, and more preferably.
1.5 to 3.0 g / L.
【００２７】本発明にかかる化成処理剤を用いて行う化
成皮膜の形成機構は、まだ、不明な点が多いが、現在ま
でのところ、次のように推測される。亜鉛または亜鉛合
金めっき表面は、酸性溶液中において局部電池の作用に
より下記(1) 式に示すように、亜鉛の溶解が起こると同
時に、溶媒としての水および溶存酸素の存在下で、(1)
式にて放出された電子を受け取り、(2) 式により、水酸
イオンを形成する。The formation mechanism of the chemical conversion film formed by using the chemical conversion treating agent according to the present invention is still largely unknown, but up to now, it is presumed as follows. As shown in the following formula (1) by the action of a local battery in an acidic solution, the zinc or zinc alloy-plated surface is simultaneously dissolved in zinc and simultaneously in the presence of water and dissolved oxygen as a solvent, (1)
Receiving the emitted electrons by the formula, forms a hydroxyl ion by the formula (2).
【００２８】 アノード反応 (陽極) ： Zn → Zn2+＋2e- ・・・ (1) カソード反応 (陰極) ： H2O ＋1/2 O2＋2e- →2 OH- ・・ (2) 酸化還元反応が起こることによって生成された水酸基
は、塩基性アルミニウムに由来するアルミニウムアコイ
オンの配位子解離によって生成するプロトンと作用し、
OH基を配位したヒドロキソアコイオンの生成を促す。[0028] The anode reaction (anode): Zn → Zn 2+ + 2e - ··· (1) cathode reaction (cathode): H 2 O +1/2 O 2 + 2e - → 2 OH - ·· (2) an oxidation-reduction reaction The hydroxyl group generated by the occurrence of, acts on the proton generated by the ligand dissociation of aluminum aquo ion derived from basic aluminum,
Promotes the formation of hydroxo aquo ions coordinated with OH groups.
【００２９】 [Al(H2O)6]3+ ←→ [Al(OH)(H2O)6]2+ ＋ H+ ・・・ (3) [Al(OH)(H2O)6]2+←→ [Al(OH)2(H2O)4]+ ＋ H+ ・・・ (4) 式(3) および(4) において生成する水素イオン H+ は前
述の式(2) の水酸イオンOH- と中和する。[Al (H 2 O) 6 ] 3+ ← → [Al (OH) (H 2 O) 6 ] 2+ + H + ... (3) [Al (OH) (H 2 O) 6 ] 2+ ← → [Al (OH) 2 (H 2 O) 4 ] + + H + ... (4) The hydrogen ions H + generated in formulas (3) and (4) are calculated by the formula (2) of hydroxide ion OH - and neutralize.
【００３０】OH基の配位したヒドロキソアコイオンは、
互いに水素結合によってμヒドロキソ多核錯体を形成す
る。これは上記(3) 、(4) 式にて生成するヒドロキソア
コイオンの増大により促進され、高分子化することが予
想される。The hydroxo aquo ion coordinated with an OH group is
Hydrogen bond to each other to form a mu-hydroxo polynuclear complex. This is expected to be promoted by an increase in the hydroxoacion generated in the above formulas (3) and (4), and to be polymerized.
【００３１】このようにして高分子化が進み、分子径と
して0.001 〜0.1 μｍとなった状態では、高い陽電子価
を有し吸着性の高い疎水コロイドとして液中に存在す
る。この疎水コロイドはその吸着活性の高さから、亜鉛
めっき皮膜上に吸着すると考えられる。これは乾燥によ
りアルミニウムを主成分とする防錆皮膜を形成するので
ある。In this way, when the polymerization proceeds and the molecular diameter becomes 0.001 to 0.1 μm, it exists in the liquid as a hydrophobic colloid having a high positron valence and a high adsorptivity. This hydrophobic colloid is considered to be adsorbed on the galvanized film because of its high adsorption activity. This forms a rust preventive film containing aluminum as a main component by drying.
【００３２】このような化成処理によりアルミニウムを
主体とする化成皮膜が物品表面に形成されるが、用途に
よっては、耐食性が不足する場合が考えられ、そのとき
には、慣用手段によりさらに有機樹脂皮膜のコーティン
グ処理を行う。A chemical conversion film mainly composed of aluminum is formed on the surface of the article by such a chemical conversion treatment. However, depending on the use, corrosion resistance may be insufficient. In such a case, the organic resin film may be further coated by conventional means. Perform processing.
【００３３】つまり、上述の化成皮膜が形成され、水
洗、乾燥を行った物品は、適宜コーティング剤の浴に浸
漬する。このときのコーティング剤としては、前述のよ
うに、水溶性または水分散性のアクリル、ウレタン、シ
リコーン、メラミンなどの樹脂が例示される。コーティ
ング後は乾燥して製品とする。かくして、本発明によれ
ば、クロム、フッ素( ふっ化物) を含有することなく、
耐食性皮膜が形成され耐食性の向上が可能となる。That is, the article on which the above-mentioned chemical conversion film is formed, washed and dried is immersed in a bath of a coating agent as appropriate. As described above, examples of the coating agent include water-soluble or water-dispersible resins such as acrylic, urethane, silicone, and melamine. After coating, dry the product. Thus, according to the present invention, without containing chromium, fluorine (fluoride),
A corrosion resistant film is formed, and the corrosion resistance can be improved.
【００３４】特公昭59−13595 号公報には、水と接触す
る鉄または鉄合金の部位を腐食から保護するために、そ
の水の中に添加する腐食抑制剤として塩化アルミニウム
等を使用することを開示している。この場合にも、不溶
性で密着性のよい水酸化アルミニウムの薄い皮膜が形成
され、防食効果が発揮されるが、その条件が、pH3.5〜
5.5 、アルミニウム配合量が5 〜50ppm という極く微量
であるから、特に亜鉛または亜鉛合金めっき皮膜への上
述のような化成皮膜形成が予測されることはない。Japanese Patent Publication No. 59-13595 discloses the use of aluminum chloride or the like as a corrosion inhibitor to be added to water in order to protect portions of iron or iron alloy that come into contact with water from corrosion. Has been disclosed. In this case, too, a thin film of aluminum hydroxide having good adhesion and insolubility is formed, and the anticorrosion effect is exhibited.
5.5 Since the aluminum content is as small as 5 to 50 ppm, the formation of the above-mentioned chemical conversion film on the zinc or zinc alloy plating film is not expected.
【００３５】[0035]
【実施例】[実施例１]冷間圧延鋼板に亜鉛めっき(8μm)
をして水洗後、67.5％硝酸２mL/Lの酸活性液にて室温で
５秒浸漬後水洗した。その後、下記配合水溶液に25℃で
60秒揺動浸漬し塩基性アルミニウム処理を行った後、水
洗せずに60℃にて15分乾燥し、化成皮膜を形成した。 塩基性アルミニウム処理液 ポリ塩化アルミニウム ：10ｇ/L (Al として0.5 g/L) 35％塩酸 (ｐＨ調整剤) ： 5ｇ/L 水 ：残り (注) ポリ塩化アルミニウム: 商品名タイパック [大明化学工業 (株) 社製] 以下、同じ。[Example] [Example 1] Galvanizing a cold-rolled steel sheet (8 μm)
After rinsing with water, the plate was immersed in an acid active solution of 67.5% nitric acid (2 mL / L) at room temperature for 5 seconds and then washed with water. Then, at 25 ° C in the following formulation aqueous solution
After subjecting to a basic aluminum treatment by rocking immersion for 60 seconds, it was dried at 60 ° C. for 15 minutes without washing with water to form a chemical conversion film. Basic aluminum treatment solution Polyaluminum chloride: 10 g / L (0.5 g / L as Al) 35% hydrochloric acid (pH adjuster): 5 g / L Water: Remaining The same applies hereinafter.
【００３６】[実施例２]冷間圧延鋼板に亜鉛めっき(8μ
m)をして水洗後、67.5％硝酸２mL/Lの酸活性液にて室温
で５秒浸漬後水洗した。その後、下記配合水溶液に25℃
で60秒揺動浸漬し塩基性アルミニウム処理を行った後、
60℃にて15分乾燥し、化成皮膜を形成した。 (注) ポリ乳酸アルミニウム: 商品名タキセラムG-17P
[多木化学 (株) 社製]以下、同じ。Example 2 Galvanizing (8 μm) was applied to a cold-rolled steel sheet.
m) and washed with water, immersed in a 67.5% nitric acid 2 mL / L acid activation solution at room temperature for 5 seconds, and then washed with water. Then, at 25 ℃
After shaking for 60 seconds to perform basic aluminum treatment,
The coating was dried at 60 ° C. for 15 minutes to form a chemical conversion film. (Note) Aluminum polylactate: Trade name TAXERAM G-17P
[Manufactured by Taki Chemical Co., Ltd.] The same applies hereinafter.
【００３７】[比較例１]冷間圧延鋼板に亜鉛めっき(8μ
m)をして水洗後、67.5％硝酸２mL/Lの酸活性液にて室温
で５秒浸漬後水洗した。その後、下記配合水溶液に25℃
で60秒揺動浸漬し塩基性アルミニウム処理を行った後、
水洗せずに60℃にて15分乾燥した。 塩基性アルミニウム処理液 ポリ塩化アルミニウム ：0.1 ｇ/L (Al として0.005 g/L) 35％塩酸 (ｐＨ調整剤) ： 5ｇ/L 水 ：残り。[Comparative Example 1] Galvanizing (8 μm)
m) and washed with water, immersed in a 67.5% nitric acid 2 mL / L acid activation solution at room temperature for 5 seconds, and then washed with water. Then, at 25 ℃
After shaking for 60 seconds to perform basic aluminum treatment,
It was dried at 60 ° C. for 15 minutes without washing with water. Basic aluminum treatment solution Polyaluminum chloride: 0.1 g / L (0.005 g / L as Al) 35% hydrochloric acid (pH adjuster): 5 g / L Water: The remainder.
【００３８】[比較例２]冷間圧延鋼板に亜鉛めっき(8μ
m)をして水洗後、67.5％硝酸２mL/Lの酸活性液にて室温
で５秒浸漬後水洗した。その後、下記配合水溶液に25℃
で60秒揺動浸漬し塩基性アルミニウム処理を行った後、
水洗せずに60℃にて15分乾燥した。 塩基性アルミニウム処理液 ポリ塩化アルミニウム ：1.0 ｇ/L (Al として0.050g/L) 35％塩酸 (ｐＨ調整剤) ： 5ｇ/L 水 ：残り。[Comparative Example 2] Galvanizing (8 μm)
m) and washed with water, immersed in a 67.5% nitric acid 2 mL / L acid activation solution at room temperature for 5 seconds, and then washed with water. Then, at 25 ℃
After shaking for 60 seconds to perform basic aluminum treatment,
It was dried at 60 ° C. for 15 minutes without washing with water. Basic aluminum treatment liquid Polyaluminum chloride: 1.0 g / L (0.050 g / L as Al) 35% hydrochloric acid (pH adjuster): 5 g / L Water: The remainder.
【００３９】[比較例３]冷間圧延鋼板に亜鉛めっき(8μ
m)をして水洗後、67.5％硝酸２mL/Lの酸活性液にて室
温、５秒浸漬後水洗した。その後、下記配合水溶液に25
℃で60秒揺動浸漬しリン酸亜鉛処理を行った後、60℃に
て15分乾燥した。 Comparative Example 3 Galvanizing (8 μm)
m) and washed with water, immersed in 67.5% nitric acid (2 mL / L) at room temperature for 5 seconds, and washed with water. Then, add 25
After immersing in rocking at 60 ° C for 60 seconds to perform zinc phosphate treatment, it was dried at 60 ° C for 15 minutes.
【００４０】[実施例３]冷間圧延鋼板に亜鉛−鉄合金め
っき(8μｍ：鉄共析率0.4 ％) をして水洗後、67.5％硝
酸２mL/Lの酸活性液にて室温で５秒浸漬後水洗した。そ
の後、下記配合液に25℃で60秒揺動浸漬し塩基性アルミ
ニウム処理を行った後、水洗せずに60℃にて15分乾燥し
た。 塩基性アルミニウム処理液 ポリ塩化アルミニウム ：10g/L (Alとして0.5 g/L) 35％塩酸 (ｐＨ調整剤) ： 5ｇ/L 水 ：残り。Example 3 A cold-rolled steel sheet was zinc-iron alloy plated (8 μm: iron eutectoid rate 0.4%), washed with water, and then treated with an acid active solution of 67.5% nitric acid 2 mL / L at room temperature for 5 seconds. After immersion, it was washed with water. Thereafter, the substrate was subjected to a basic aluminum treatment by rocking and immersing in the following formulation at 25 ° C. for 60 seconds, and then dried at 60 ° C. for 15 minutes without washing with water. Basic aluminum treatment solution Polyaluminum chloride: 10 g / L (0.5 g / L as Al) 35% hydrochloric acid (pH adjuster): 5 g / L Water: The remainder.
【００４１】[実施例４]冷間圧延鋼板に亜鉛−鉄合金め
っき(8μｍ：鉄共析率0.4 ％) をして水洗後、67.5％硝
酸２mL/Lの酸活性液にて室温で５秒浸漬後水洗した。そ
の後、下記配合液に25℃で60秒揺動浸漬し塩基性アルミ
ニウム処理を行った後、水洗せずに60℃にて15分乾燥し
た。 Example 4 A cold-rolled steel sheet was zinc-iron alloy plated (8 μm: iron eutectoid rate 0.4%), washed with water, and then treated with a 67.5% nitric acid 2 mL / L acid active solution at room temperature for 5 seconds. After immersion, it was washed with water. Thereafter, the substrate was subjected to a basic aluminum treatment by rocking and immersing in the following formulation at 25 ° C. for 60 seconds, and then dried at 60 ° C. for 15 minutes without washing with water.
【００４２】[比較例４]冷間圧延鋼板に亜鉛−鉄合金め
っき(8μｍ：鉄共析率0.4 ％) をして水洗後、67.5％硝
酸２mL/Lの酸活性液にて室温で５秒浸漬後水洗した。そ
の後、下記配合液に25℃で60秒揺動浸漬し塩基性アルミ
ニウム処理を行った後、水洗せずに60℃にて15分乾燥し
た。 塩基性アルミニウム処理液 ポリ塩化アルミニウム ： 0.10g/L (Al として0.005 g/L) 35％塩酸 (ｐＨ調整剤) ： 5ｇ/L 水 ： 残り。[Comparative Example 4] A cold-rolled steel sheet was plated with zinc-iron alloy (8 µm: iron eutectoid rate 0.4%), washed with water, and then treated with a 67.5% nitric acid 2 mL / L acid active solution at room temperature for 5 seconds. After immersion, it was washed with water. Thereafter, the substrate was subjected to a basic aluminum treatment by rocking and immersing in the following formulation at 25 ° C. for 60 seconds, and then dried at 60 ° C. for 15 minutes without washing with water. Basic aluminum treatment solution Polyaluminum chloride: 0.10 g / L (0.005 g / L as Al) 35% hydrochloric acid (pH adjuster): 5 g / L Water: The remainder.
【００４３】[比較例５]冷間圧延鋼板に亜鉛−鉄合金め
っき(8μｍ：鉄共析率0.4 ％) をして水洗後、67.5％硝
酸２mL/Lの酸活性液にて室温で５秒浸漬後水洗した。そ
の後、下記配合液に25℃で60秒揺動浸漬し塩基性アルミ
ニウム処理を行った後、水洗せずに60℃にて15分乾燥し
た。 塩基性アルミニウム処理液 ポリ塩化アルミニウム ：1.0g/L (Al として0.050g/L) 35％塩酸 (ｐＨ調整剤) ： 5ｇ/L 水 ：残り。Comparative Example 5 A cold-rolled steel sheet was zinc-iron alloy plated (8 μm: iron eutectoid rate 0.4%), washed with water, and then treated with an acid active solution of 67.5% nitric acid 2 mL / L at room temperature for 5 seconds. After immersion, it was washed with water. Thereafter, the substrate was subjected to a basic aluminum treatment by rocking and immersing in the following formulation at 25 ° C. for 60 seconds, and then dried at 60 ° C. for 15 minutes without washing with water. Basic aluminum treatment liquid Polyaluminum chloride: 1.0 g / L (0.050 g / L as Al) 35% hydrochloric acid (pH adjuster): 5 g / L Water: The remainder.
【００４４】[比較例６]冷間圧延鋼板に亜鉛−鉄合金め
っき(8μｍ：鉄共析率0.4 ％) をして水洗後、67.5％硝
酸２mL/Lの酸活性液にて室温、５秒浸漬後水洗した。そ
の後、下記配合液に25℃で60秒揺動浸漬しリン酸亜鉛処
理を行った後、60℃にて15分乾燥した。 [Comparative Example 6] A cold-rolled steel sheet was plated with zinc-iron alloy (8 µm: iron eutectoid rate 0.4%), washed with water, and then treated with an acid active solution of 67.5% nitric acid 2mL / L at room temperature for 5 seconds. After immersion, it was washed with water. Thereafter, the substrate was rock-immersed in the following formulation at 25 ° C. for 60 seconds to perform zinc phosphate treatment, and then dried at 60 ° C. for 15 minutes.
【００４５】これらの結果は、表１にまとめて示すが、
これらからも分かるように、本発明によれば、従来のリ
ン酸亜鉛化成処理と比較して著しい耐食性の改善効果が
見られる。The results are shown in Table 1 below.
As can be seen from these, according to the present invention, a remarkable effect of improving corrosion resistance is observed as compared with the conventional zinc phosphate chemical conversion treatment.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【発明の効果】以上説明してきたように、本発明によれ
ば、クロム、フッ素を含むことのない化成処理液でもっ
て処理することで、従来のクロメート皮膜と同等かそれ
以上のすぐれた耐食性を示す皮膜が得られ、今日問題と
なっている環境問題、健康問題に容易に対処できるので
あって、その実用上の意義は大きい。As described above, according to the present invention, by treating with a chemical conversion treatment solution containing neither chromium nor fluorine, excellent corrosion resistance equivalent to or higher than that of a conventional chromate film can be obtained. The obtained film can be obtained, and can easily deal with environmental problems and health problems that are a problem today, and its practical significance is great.
【図１】本発明にかかる化成処理剤を用いる場合の１実
施例の工程図である。FIG. 1 is a process chart of one embodiment when a chemical conversion treating agent according to the present invention is used.
Claims (4)
徴とする亜鉛または亜鉛合金めっき用化成処理剤。1. A chemical conversion treating agent for zinc or zinc alloy plating comprising basic aluminum.
ない請求項１記載の亜鉛または亜鉛合金めっき用化成処
理剤。2. The chemical conversion treating agent for zinc or zinc alloy plating according to claim 1, which does not contain a chromium compound and a fluorine compound.
鉛または亜鉛合金めっき皮膜に適用して化成処理皮膜を
形成することを特徴とする亜鉛または亜鉛合金の化成処
理方法。3. A chemical conversion treatment method for zinc or a zinc alloy, wherein the chemical conversion treatment agent according to claim 1 or 2 is applied to a zinc or zinc alloy plating film to form a chemical conversion treatment film.
うことなく化成処理皮膜を形成する請求項３記載の化成
処理方法。4. The chemical conversion treatment method according to claim 3, wherein after applying the chemical conversion treatment agent, the chemical conversion treatment film is formed without washing with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15766198A JP3772321B2 (en) | 1998-06-05 | 1998-06-05 | Chemical conversion treatment agent and chemical conversion treatment method for zinc or zinc alloy plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15766198A JP3772321B2 (en) | 1998-06-05 | 1998-06-05 | Chemical conversion treatment agent and chemical conversion treatment method for zinc or zinc alloy plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11350161A true JPH11350161A (en) | 1999-12-21 |
| JP3772321B2 JP3772321B2 (en) | 2006-05-10 |
Family
ID=15654622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15766198A Expired - Fee Related JP3772321B2 (en) | 1998-06-05 | 1998-06-05 | Chemical conversion treatment agent and chemical conversion treatment method for zinc or zinc alloy plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3772321B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007240083A (en) * | 2006-03-09 | 2007-09-20 | Kobe Steel Ltd | Heat exchanger aluminum material excellent in corrosion resistance and heat exchanger |
| CN103272749A (en) * | 2013-06-07 | 2013-09-04 | 山东国强五金科技有限公司 | Surface treatment method of zinc alloy die casting |
-
1998
- 1998-06-05 JP JP15766198A patent/JP3772321B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007240083A (en) * | 2006-03-09 | 2007-09-20 | Kobe Steel Ltd | Heat exchanger aluminum material excellent in corrosion resistance and heat exchanger |
| CN103272749A (en) * | 2013-06-07 | 2013-09-04 | 山东国强五金科技有限公司 | Surface treatment method of zinc alloy die casting |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3772321B2 (en) | 2006-05-10 |
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