JP4053683B2 - Anti-corrosion treatment agent for aluminum with high corrosion resistance - Google Patents
Anti-corrosion treatment agent for aluminum with high corrosion resistance Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、アルミニウム(本発明においては、アルミニウム並びにアルミニウム合金を総称して単に「アルミニウム」という。)の耐食性改良のための表面処理用のノンクロメートタイプ処理剤、並びに該処理剤を用いての表面処理方法に関し、表面の直接改質のほか、続くペイント塗布後や有機保護膜による同様な被覆後の表面の改質が達成できる。本発明は、主としてアルミニウムより成るどんな表面にも適用でき、特に多くの市販アルミニウム合金、例えば３００３、３００４、３１０５、５１８２、５０５０、および５３５２合金に適しているが、これら特定の合金に限定されるわけではない。本発明の表面処理剤には、クロムは実質的にまたは全く含有されないので、従って、現在同じ目的のために通常商業的に行われているクロム酸塩処理に較べて公害程度が小さいものである。
【０００２】
【従来の技術】
現在、アルミニウム質表面を処理するための多くの表面処理剤および表面処理方法が、技術に既知となっている。アルミニウム質表面の腐食防止を最大限に行うことが所望の場合は、クロム含有表面処理剤を用いるが、クロムの使用は環境汚染に危険性が付きまとっている。クロム含有処理剤に代わって、ノンクロム系の表面処理が広く使用されている。
【０００３】
ノンクロム系のアルミニウム用防錆処理剤はたくさん提案されている。例えば、特開平４−２６３０８３号公報には、ヘキサフルオロジルコネートと水溶性または水分散性ポリマーとを基本として含有するノンクロメート表面処理剤が開示されている。この種のジルコニウムを含有する化合物を含む処理剤は、クロムが含まれていない点で非常に優れており、それなりの性能を有するが、クロム含有処理剤と比較して耐食性が得られず少し劣っていることは否めない。
【０００４】
【発明が解決しようとする課題】
本発明は、上記ジルコニウムを含有する化合物を用いたアルミニウム用表面処理剤において、その耐食性を向上することにある。
【０００５】
【課題を解決するための手段】
すなわち、本発明はジルコニウムの酸化物、酸素酸塩、有機酸塩、フルオロ錯塩およびそれらの混合物から成る群から選択されるジルコニウム化合物を含むアルミニウム用防錆処理剤に亜鉛化合物を亜鉛／ジルコニウムの重量比０．０１〜１の量で配合することを特徴するアルミニウム用ノンクロム防錆処理剤に存する。
【０００６】
発明者らはジルコニウム化合物を含有するアルミニウム用防錆処理剤に亜鉛を含有する化合物を亜鉛／ジルコニウムの重量比で０．０１〜１の量で含有する耐食性が極めて向上することを発見した。
本発明で使用するアルミニウム用防錆処理剤はジルコニウムの酸化物、酸素酸塩、有機酸塩、フルオロ錯塩およびそれらの混合物から成る群から選択されるジルコニウム化合物を含むものである。ジルコニウム酸化物の例としては、ＺｒＯ2、ＺｒＯ3２Ｈ2ＯまたはＫ4ＺｒＯ4・４Ｈ2Ｏ2・２Ｈ2Ｏが挙げられる。ジルコニウムの酸素酸塩としては、Ｚｒ(ＮＯ3)4、Ｚｒ(ＮＯ3)2、Ｚｒ(ＳＯ4)2、Ｚｒ(Ｈ2ＰＯ4)2、ＺｒＰ2Ｏ7またはＺｒＳｉＯ4が挙げられる。ジルコニウムの有機酸塩としては、Ｚｒ(ＣＨ3ＣＯ2)4またはＺｒＯ(ＣＨ3ＣＯ2)2が挙げられる。ジルコニウムのフルオロ錯塩の例としては、ヘキサフルオロジルコニウム酸塩またはオクタフルオロジルコニウム酸塩が挙げられる。ジルコニウム化合物は処理剤中にジルコニウムの量として０．０１〜５重量％、好ましくは０．１〜２重量％の量で存在する。
【０００７】
本発明ではジルコニウム化合物を含有するアルミニウム用防錆処理剤において、亜鉛化合物を亜鉛／ジルコニウムの重量比で０．０１〜１、好ましくは０．１〜０．７の量で含むことを特徴とする。使用し得る亜鉛化合物としては硝酸亜鉛、硫酸亜鉛、炭酸亜鉛、酸化亜鉛などの亜鉛化合物である。亜鉛化合物は、亜鉛の量で処理剤中に１０〜１０,０００ppm、好ましくは１００〜５，０００ppmの量で配合し得る。亜鉛の添加量が少ないと、前述の耐食性が発揮されず、亜鉛の添加量が多すぎると、配合の添加量の割りに耐食性の向上が見られず、逆に被膜物性が悪くなる。
【０００８】
防錆処理剤中には上記成分の他に水溶性樹脂、酸、塩基、界面活性剤、抗菌剤などを含んでもよい。
【０００９】
水溶性樹脂は親水基として水酸基、またはカルボキシル基またはアミド基を有するものである。水溶性樹脂はジルコニウムと亜鉛との被膜の架橋による耐食性向上および被膜表面に親水性を付与する効果がある。水溶性樹脂は、より具体的には、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンオキシド、ポリアミド、セルロースなどが挙げられる。
【００１０】
処理浴は、pＨを１〜５、望ましくは２〜４に調整する。pＨの調整は酸、例えば硝酸、フッ酸、硫酸などまたは塩基、例えばアンモニア、トリエタノールアミン、グアニジンなどが用いられる。pＨが５より高いと浴の安定性が悪くなり、逆に１より低いと浴老化が早過ぎて、実用性に乏しい。
【００１１】
界面活性剤は一般的な界面活性剤あるいは消泡作用を有する界面活性剤が好ましく用いられる。一般的には非イオン性界面活性剤、例えばプロピレングリコール−エチレンオキサイド付加反応生成物、ポリアルキレンアルコールエーテル類およびポリアルキレンアルキルフェニルエーテル類などが考えられる。
【００１２】
本発明に用いる抗菌剤は一般的に抗菌作用を有する化合物、例えば２,２'−ジチオ−ビス(ピリジン−１−オキサイド)、亜鉛ピリチオン、１,２−ジブロモ−２,４−ジシアノブタン、２−メチル−４−イソチアゾリン−３−オン、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、１,２−ベンズイソチアゾリン−３−オン、２−チオシアノメチル−ベンゾチアゾール、および２−ピリジン−チオール−１−オキサイドナトリウムなどが挙げられる。抗菌剤は、処理剤の固形分に対し０．５〜３０重量％の量で用いられるのが好ましい。抗菌剤は、上記処理剤の膜中に保持され、バクテリア、カビおよび酵母の繁殖を長期化にわたって有効に防止することができる。
【００１３】
上記処理剤中にアルミニウム基材を浸漬あるいは塗布などの方法で付着すればよいのであるが、具体的な手順としてはアルミニウム合金の脱脂→水洗→防錆・親水化処理→焼き付けの順序に従って行われる。
【００１４】
脱脂は基本的にはアルミニウム合金の表面の油分と汚れが落ちればどのような方法で行ってもよい。アルミニウムの表面に油分、汚れが無いときには基本的には脱脂は行わなくてもよい。脱脂と次の防錆・親水化処理の間に、表面調整を行うこともある。表面調整には、具体的に一般的なものが用いられるが、クロメート処理、酸による洗浄、ベーマイト処理、アルマイト処理などが挙げられるが、要するに塗装のようにアルミの素地を完全に覆わなければなんでもよい。これらの脱脂あるいは表面調整はアルミニウム合金の種類によって変化するが、例えば純アルミニウム板１１００番やアルミニウム合金３００３番のときにはサーフクリーナー３２２Ｎ−８(リン酸ナトリウムを主成分とする)と混酸(硝酸＋硫酸)が一番耐食性がよくなる。
【００１５】
防錆・親水化処理は前述のように浸漬、塗布、スプレーなどのいずれの方法であっても、アルミニウム合金基材の表面に付着させればよい。望ましい方法は浸漬であり、処理温度は２０〜７０℃、好ましくは４０〜６０℃、より具体的には約５０℃前後で行われる。処理温度が７０℃より高すぎると、反応性が高くなって、浴老化が速く実用性が乏しくなる。逆に２０℃より処理温度が低いと処理時間が長くなる程度で、より低くする必要性は特にない。処理時間は５〜９０秒、望ましくは１０〜９０秒、より好ましくは１０〜６０秒、最も好適には約３０秒前後である。処理時間が非常に長くなると浴老化が速くなって、実用性がなくなる。処理時間は処理剤が基材に付着すれば短くてもよい。
【００１６】
上記防錆・親水化処理の後、焼き付けを行って架橋的結合を完結させる。焼き付けは１００〜２００℃の温度で３〜６０分行われる。好ましくは焼き付けは１３０〜１８０℃で１０〜４０分、より好ましくは１５０〜１７０℃で１０〜３０分で行われる。ここで焼き付け温度とは被塗物到達温度を意味する。焼き付け温度が２００℃より高いと、焦げ臭くなり、１００℃より低いと十分な耐食性が出ない。焼き付け時間が長いと、表面の親水性が低下し、逆に短いと十分な耐食性が得られない。
【００１７】
【発明の効果】
本発明では、特定のジルコニウム化合物を用いるノンクロム型のアルミニウム用防錆処理剤において、亜鉛化合物を所定量配合することによりその耐食性が非常に高くなり、アルミニウムの防錆処理剤としての効能が著しく上昇するものである。
【００１８】
【実施例】
本発明を実施例によりさらに詳細に説明する。本発明はこれら実施例に限定するものと解してははならない。
【００１９】
実施例１
コイル用の表面処理剤の作製
４０％ジルコンフッ化水素酸水溶液５６．７５g(ジルコンフッ化水素酸２２．７g)に炭酸亜鉛０．１９gを少しずつ添加した。全部溶けたら純水を５００g加え、ポリアクリル酸系共重合樹脂０．２４gを添加する。次いでポリビニルアルコールの１０％水溶液２００g(ポリビニルアルコール２０g)を加え、残りの水を加えて全量１０００gに調整した。
【００２０】
コイルの表面処理
熱交換機用コイル材をサーフクリーナー３２２Ｎ−８(日本ペイント社製)３％溶液中に浸漬した後、７０℃で３０秒間保持した。得られたコイルを上記処理浴中に浸漬した。処理剤の浴温度は５０℃であり、処理時間は３０秒間であった。処理した後パネルを取り出して１６０℃で焼き付けた。得られた処理パネルについて、塩水噴霧試験および湿潤試験の実験を行い、その結果を表２に示す。
【００２１】
塩水噴霧試験の試験方法と評価基準
試験方法：ＪＩＳ規格 ＪＩＳ Ｚ ２３７１
評価基準：評価は１０点満点で、下記表１に従って評価する。１０は全く錆がない状態を示し、０は全面錆が発生した状態を示す。
【００２２】
湿潤試験の試験方法と評価基準
試験方法：湿潤試験機(５０℃、湿度９９％)中にコイルを放置した後、２４０時間経過後錆発生状況を観察する。
評価基準：塩水噴霧試験と同じ表１の評価基準に従った。
【００２３】
【表１】
実施例２
防錆処理剤中に添加する炭酸亜鉛を１．９gにする以外は、実施例１と同様に処理した。塩水噴霧試験および湿潤試験の結果を表２に示す。
【００２５】
実施例３
実施例１において炭酸亜鉛の炭化量を１９．２gにする以外は実施例１と同様に処理した。塩水噴霧試験および湿潤試験の結果を表２に示す。
【００２６】
実施例４
炭酸亜鉛の添加量を３９．２gにする以外は実施例１と同様に処理した。塩水噴霧試験および湿潤試験の結果を表２に示す。
【００２７】
比較例１
炭酸亜鉛を添加しない以外は実施例１と全く同様に処理した。塩水噴霧試験および湿潤試験の結果を表２に示す。
【００２８】
比較例２
炭酸亜鉛の添加量を１９２gにする以外は実施例１と同様に処理した。塩水噴霧試験および湿潤試験の結果を表２に示す。
【００２９】
【表２】
実施例５
カーエバポレーター用処理剤の調整
フッ化ジルコニウムアンモニウム２６．２６gを３００gの水に溶解し、そこに浴安定としてポリアクリル酸共重合体０．２４gを添加した。予め別に架橋性樹脂としてポリビニルアルコール２０gを４００gの水に溶かしたものをその中に加え、さらにポリビニルピロリドン１０gを水１０gに溶かしたものとポリエチレンオキサイド２gを水８gに溶かしたものを加えた。ポリビニルピロリドンとポリエチレンオキサイドはいずれも親水性樹脂として作用した。その中へノニオン性界面活性剤０．２５g(旭電化工業(株)から市販のアデカノールＳＯ−１４５)、消泡剤０．２５g(旭電化工業(株)から入手したアデカネートＢ−９４０)を加え、次いで操作時のアルミニウムイオンの量を考慮して硝酸アルミニウム適当量を水１００gに溶かしたものを加えた。硝酸亜鉛２．９０ｇを純水１００ｇに溶かした後、溶液中に加え、また抗菌剤３g（武田薬品工業(株)から入手したスラオフ９５）も加えた。水で全量を９５０gにし、１０％硝酸と１０％アンモニア水でpＨを３に調整した。最後に水を加えて全量を１０００gにした。
【００３１】
アルミ素材の処理
素材Ａ３００３Ｐアルミニウム合金パネル(日本テストパネル社製)にサーフクリーナ３２２Ｎ−８(日本ペイント社製)３％溶液中にパネルを浸漬し、７０℃で３０秒間保持した。
【００３２】
得られたパネルを用いて上記処理剤中に浸漬した。処理剤の浴温度は５０℃であり、処理時間は３０秒であった。処理した後パネルを取り出して１６０℃で焼き付けた。得られた処理パネルについて、前記同様の塩水噴霧試験を行った。結果を表３に示す。
【００３３】
比較例３
硝酸亜鉛の量を０にする以外は実施例５と同様に処理した。塩水噴霧試験の結果について表３に示す。
【００３４】
比較例４
硝酸亜鉛の量を２９０gにする以外は実施例５と同様に処理した。塩水噴霧試験について結果を表３に示す。
【００３５】
【表３】
BACKGROUND OF THE INVENTION
The present invention relates to a non-chromate type treatment agent for surface treatment for improving the corrosion resistance of aluminum (in the present invention, aluminum and aluminum alloys are collectively referred to simply as “aluminum”), and the use of the treatment agent. Regarding the surface treatment method, in addition to direct modification of the surface, it is possible to achieve modification of the surface after subsequent coating or similar coating with an organic protective film. The present invention is applicable to any surface consisting primarily of aluminum and is particularly suitable for many commercially available aluminum alloys, such as 3003, 3004, 3105, 5182, 5050, and 5352 alloys, but is limited to these specific alloys. Do not mean. Since the surface treatment agent of the present invention contains substantially or no chromium, it is therefore less polluted than the chromate treatments currently performed commercially for the same purpose. .
[0002]
[Prior art]
Currently, many surface treatment agents and surface treatment methods for treating aluminum surfaces are known in the art. If it is desired to maximize the corrosion protection of the aluminum surface, a chromium-containing surface treatment agent is used. However, the use of chromium has a risk of environmental pollution. Instead of chromium-containing treatment agents, non-chromium surface treatments are widely used.
[0003]
Many anti-chromium aluminum rust preventives have been proposed. For example, Japanese Patent Laid-Open No. 4-263083 discloses a non-chromate surface treatment agent containing hexafluorozirconate and a water-soluble or water-dispersible polymer as a basis. The treatment agent containing this kind of zirconium-containing compound is very excellent in that it does not contain chromium, and has some performance, but it is a little inferior in corrosion resistance as compared with the chromium-containing treatment agent. I cannot deny that.
[0004]
[Problems to be solved by the invention]
This invention exists in improving the corrosion resistance in the surface treating agent for aluminum using the said compound containing a zirconium.
[0005]
[Means for Solving the Problems]
That is, the present invention relates to an aluminum rust preventive agent containing a zirconium compound selected from the group consisting of an oxide, an oxyacid salt, an organic acid salt, a fluoro complex salt, and a mixture thereof, and the zinc compound is added to the weight of zinc / zirconium. It exists in the chromium-free rust preventive agent for aluminum characterized by mix | blending with the quantity of 0.01-1.
[0006]
The inventors have found that the corrosion resistance of zinc containing a compound containing zinc in a rust preventive agent for aluminum containing a zirconium compound in an amount of 0.01 to 1 in a weight ratio of zinc / zirconium is extremely improved.
The rust preventive for aluminum used in the present invention contains a zirconium compound selected from the group consisting of zirconium oxides, oxyacid salts, organic acid salts, fluoro complex salts, and mixtures thereof. Examples of zirconium oxide include ZrO 2 , ZrO 3 2H 2 O or K 4 ZrO 4 .4H 2 O 2 .2H 2 O. Examples of zirconium oxyacid salts include Zr (NO 3 ) 4 , Zr (NO 3 ) 2 , Zr (SO 4 ) 2 , Zr (H 2 PO 4 ) 2 , ZrP 2 O 7, or ZrSiO 4 . Examples of the organic acid salt of zirconium include Zr (CH 3 CO 2 ) 4 or ZrO (CH 3 CO 2 ) 2 . Examples of the fluoro complex salt of zirconium include hexafluoro zirconate or octafluoro zirconate. The zirconium compound is present in the treating agent in an amount of 0.01 to 5% by weight, preferably 0.1 to 2% by weight as the amount of zirconium.
[0007]
In the present invention, a rust preventive agent for aluminum containing a zirconium compound is characterized by containing a zinc compound in an amount of 0.01 to 1, preferably 0.1 to 0.7 in terms of a weight ratio of zinc / zirconium. . Zinc compounds that can be used include zinc compounds such as zinc nitrate, zinc sulfate, zinc carbonate, and zinc oxide. A zinc compound can be mix | blended in the quantity of 10-10,000 ppm in a processing agent with the quantity of zinc, Preferably it is the quantity of 100-5,000 ppm. If the added amount of zinc is small, the above-mentioned corrosion resistance is not exhibited, and if the added amount of zinc is too large, improvement in corrosion resistance is not seen for the added amount of blending, and on the contrary, physical properties of the film are deteriorated.
[0008]
The antirust treatment agent may contain a water-soluble resin, acid, base, surfactant, antibacterial agent and the like in addition to the above components.
[0009]
The water-soluble resin has a hydroxyl group, a carboxyl group or an amide group as a hydrophilic group. The water-soluble resin has an effect of improving corrosion resistance by crosslinking the coating of zirconium and zinc and imparting hydrophilicity to the coating surface. More specifically, examples of the water-soluble resin include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyamide, and cellulose.
[0010]
The treatment bath is adjusted to a pH of 1-5, preferably 2-4. The pH is adjusted using an acid such as nitric acid, hydrofluoric acid, sulfuric acid or the like, or a base such as ammonia, triethanolamine or guanidine. If the pH is higher than 5, the stability of the bath is deteriorated. On the other hand, if the pH is lower than 1, bath aging is premature and the practicality is poor.
[0011]
As the surfactant, a general surfactant or a surfactant having a defoaming action is preferably used. In general, nonionic surfactants such as propylene glycol-ethylene oxide addition reaction products, polyalkylene alcohol ethers and polyalkylene alkylphenyl ethers are considered.
[0012]
The antibacterial agent used in the present invention is generally a compound having an antibacterial action, such as 2,2′-dithio-bis (pyridine-1-oxide), zinc pyrithione, 1,2-dibromo-2,4-dicyanobutane, -Methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-thiocyanomethyl-benzothiazole, and 2- Examples include pyridine-thiol-1-oxide sodium. The antibacterial agent is preferably used in an amount of 0.5 to 30% by weight based on the solid content of the treatment agent. The antibacterial agent is retained in the film of the treatment agent, and can effectively prevent the growth of bacteria, mold and yeast over a long period of time.
[0013]
The aluminum base material may be attached to the treatment agent by dipping or coating, but the specific procedure is as follows: aluminum alloy degreasing → water washing → rust prevention / hydrophilization treatment → baking .
[0014]
Degreasing may be basically performed by any method as long as the oil and dirt on the surface of the aluminum alloy are removed. Basically, degreasing is not necessary when there is no oil or dirt on the aluminum surface. Surface adjustment may be performed between the degreasing and the next rust prevention / hydrophilization treatment. For surface adjustment, general materials are used, but examples include chromate treatment, cleaning with acid, boehmite treatment, and alumite treatment. In short, anything that does not completely cover the aluminum substrate like paint is required. Good. These degreasing or surface adjustments vary depending on the type of aluminum alloy. For example, in the case of pure aluminum plate 1100 or aluminum alloy 3003, Surf Cleaner 322N-8 (mainly sodium phosphate is used) and mixed acid (nitric acid + sulfuric acid) ) Has the best corrosion resistance.
[0015]
As described above, the rust prevention / hydrophilic treatment may be performed by any method such as dipping, coating, spraying, etc., as long as it is adhered to the surface of the aluminum alloy substrate. A desirable method is immersion, and the treatment temperature is 20 to 70 ° C, preferably 40 to 60 ° C, more specifically about 50 ° C. When the treatment temperature is too high, the reactivity becomes high, the bath aging is fast and the practicality becomes poor. On the other hand, if the processing temperature is lower than 20 ° C., the processing time will be long, and there is no need to make it lower. The treatment time is 5 to 90 seconds, desirably 10 to 90 seconds, more preferably 10 to 60 seconds, and most preferably about 30 seconds. If the treatment time is very long, the bath aging becomes faster and the practicality is lost. The treatment time may be short as long as the treatment agent adheres to the substrate.
[0016]
After the rust prevention and hydrophilic treatment, baking is performed to complete the cross-linking. Baking is performed at a temperature of 100 to 200 ° C. for 3 to 60 minutes. Preferably, baking is performed at 130 to 180 ° C. for 10 to 40 minutes, more preferably at 150 to 170 ° C. for 10 to 30 minutes. Here, the baking temperature means the arrival temperature of the object to be coated. When the baking temperature is higher than 200 ° C, it becomes burnt odor, and when it is lower than 100 ° C, sufficient corrosion resistance is not obtained. If the baking time is long, the hydrophilicity of the surface is lowered. Conversely, if the baking time is short, sufficient corrosion resistance cannot be obtained.
[0017]
【The invention's effect】
In the present invention, in a non-chromium type rust preventive agent for aluminum using a specific zirconium compound, the corrosion resistance becomes extremely high by adding a predetermined amount of zinc compound, and the effectiveness of aluminum as a rust preventive agent is remarkably increased. To do.
[0018]
【Example】
The invention is explained in more detail by means of examples. The present invention should not be construed as limited to these examples.
[0019]
Example 1
Preparation of surface treatment agent for coil 0.19 g of zinc carbonate was added little by little to 56.75 g of a 40% aqueous solution of zircon hydrofluoric acid (22.7 g of zircon hydrofluoric acid). When all are dissolved, 500 g of pure water is added, and 0.24 g of polyacrylic acid copolymer resin is added. Subsequently, 200 g of a 10% aqueous solution of polyvinyl alcohol (20 g of polyvinyl alcohol) was added, and the remaining water was added to adjust the total amount to 1000 g.
[0020]
Coil surface treatment A coil material for a heat exchanger was immersed in a 3% solution of Surf Cleaner 322N-8 (manufactured by Nippon Paint Co., Ltd.) and then held at 70C for 30 seconds. The obtained coil was immersed in the treatment bath. The bath temperature of the treatment agent was 50 ° C., and the treatment time was 30 seconds. After the treatment, the panel was taken out and baked at 160 ° C. The obtained treated panel was subjected to a salt spray test and a wet test, and the results are shown in Table 2.
[0021]
Test method and evaluation standard of salt spray test Test method: JIS standard JIS Z 2371
Evaluation criteria: Evaluation is based on 10 points and evaluated according to Table 1 below. 10 indicates a state where there is no rust, and 0 indicates a state where rust is generated on the entire surface.
[0022]
Test method of wet test and evaluation criteria Test method: After leaving the coil in a wet tester (50C, humidity 99%), observe the rust generation after 240 hours.
Evaluation criteria: The same evaluation criteria in Table 1 as in the salt spray test were followed.
[0023]
[Table 1]
Example 2
The same treatment as in Example 1 was conducted except that zinc carbonate added to the antirust treatment agent was changed to 1.9 g. The results of the salt spray test and the wet test are shown in Table 2.
[0025]
Example 3
The same treatment as in Example 1 was conducted except that the carbonization amount of zinc carbonate was changed to 19.2 g. The results of the salt spray test and the wet test are shown in Table 2.
[0026]
Example 4
The same treatment as in Example 1 was conducted except that the amount of zinc carbonate added was 39.2 g. The results of the salt spray test and the wet test are shown in Table 2.
[0027]
Comparative Example 1
The treatment was exactly the same as in Example 1 except that zinc carbonate was not added. The results of the salt spray test and the wet test are shown in Table 2.
[0028]
Comparative Example 2
The same treatment as in Example 1 was conducted except that the amount of zinc carbonate added was changed to 192 g. The results of the salt spray test and the wet test are shown in Table 2.
[0029]
[Table 2]
Example 5
Preparation of Car Evaporator Treatment Agent 26.26 g of zirconium zirconium fluoride was dissolved in 300 g of water, and 0.24 g of polyacrylic acid copolymer was added thereto as a bath stability. Separately, 20 g of polyvinyl alcohol dissolved in 400 g of water as a crosslinkable resin was added therein, and further, 10 g of polyvinylpyrrolidone dissolved in 10 g of water and 2 g of polyethylene oxide dissolved in 8 g of water were added. Both polyvinylpyrrolidone and polyethylene oxide acted as hydrophilic resins. 0.25 g of nonionic surfactant (Adecanol SO-145 commercially available from Asahi Denka Kogyo Co., Ltd.) and 0.25 g of antifoaming agent (Adecanate B-940 obtained from Asahi Denka Kogyo Co., Ltd.) were added. Then, in consideration of the amount of aluminum ions during operation, an appropriate amount of aluminum nitrate dissolved in 100 g of water was added. After dissolving 2.90 g of zinc nitrate in 100 g of pure water, it was added to the solution, and 3 g of an antibacterial agent (Sulaoff 95 obtained from Takeda Pharmaceutical Co., Ltd.) was also added. The total amount was adjusted to 950 g with water, and the pH was adjusted to 3 with 10% nitric acid and 10% aqueous ammonia. Finally, water was added to bring the total amount to 1000 g.
[0031]
The panel was immersed in a 3% solution of Surf Cleaner 322N-8 (Nihon Paint Co., Ltd.) in an aluminum material, A3003P aluminum alloy panel (Nihon Test Panel Co., Ltd.), and held at 70 ° C. for 30 seconds.
[0032]
It was immersed in the said processing agent using the obtained panel. The bath temperature of the treatment agent was 50 ° C., and the treatment time was 30 seconds. After the treatment, the panel was taken out and baked at 160 ° C. The obtained treatment panel was subjected to the same salt spray test. The results are shown in Table 3.
[0033]
Comparative Example 3
The treatment was performed in the same manner as in Example 5 except that the amount of zinc nitrate was 0. The results of the salt spray test are shown in Table 3.
[0034]
Comparative Example 4
The same treatment as in Example 5 was conducted except that the amount of zinc nitrate was changed to 290 g. The results for the salt spray test are shown in Table 3.
[0035]
[Table 3]
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP08599699A JP4053683B2 (en) | 1999-03-29 | 1999-03-29 | Anti-corrosion treatment agent for aluminum with high corrosion resistance |
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| JP08599699A JP4053683B2 (en) | 1999-03-29 | 1999-03-29 | Anti-corrosion treatment agent for aluminum with high corrosion resistance |
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| JP4812955B2 (en) * | 2001-03-26 | 2011-11-09 | 株式会社クラレ | anti-rust |
| EP1455001B1 (en) | 2001-12-04 | 2013-09-25 | Nippon Steel & Sumitomo Metal Corporation | Metal material coated with metal oxide and/or metal hydroxide and method for production thereof |
| TWI340770B (en) | 2005-12-06 | 2011-04-21 | Nippon Steel Corp | Composite coated metal sheet, treatment agent and method of manufacturing composite coated metal sheet |
| JP4521010B2 (en) * | 2007-04-09 | 2010-08-11 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
| JP5215043B2 (en) * | 2008-06-02 | 2013-06-19 | 日本パーカライジング株式会社 | Metal surface treatment liquid and surface treatment method |
| RU2673849C2 (en) * | 2013-07-10 | 2018-11-30 | Шеметалл Гмбх | Method of coating metal surfaces of substrates and objects coated in accordance with said method |
| JP6461136B2 (en) * | 2013-07-18 | 2019-01-30 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツングＣｈｅｍｅｔａｌｌ ＧｍｂＨ | Method for coating a metal surface of a substrate and articles coated by this method |
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