JPS5928639B2 - Fukugohi Fukukinzokubanno Seizouhouhou - Google Patents
Fukugohi Fukukinzokubanno SeizouhouhouInfo
- Publication number
- JPS5928639B2 JPS5928639B2 JP50131425A JP13142575A JPS5928639B2 JP S5928639 B2 JPS5928639 B2 JP S5928639B2 JP 50131425 A JP50131425 A JP 50131425A JP 13142575 A JP13142575 A JP 13142575A JP S5928639 B2 JPS5928639 B2 JP S5928639B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- coated
- metal plate
- resin
- powder
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Description
【発明の詳細な説明】
本発明は有機高分子の水溶性あるいは水分散性の樹脂の
少なくとも一種以上に、水に不溶な有機高分子樹脂の粉
末を添加し、さらに金属の粉末、前記金属の合金粉末の
一種以上を添加したものを主成分とする懸濁液中に、塗
布しようとする金属板を浸漬し、塗布する金属板を陰極
あるいは陽極として電解処理を行い、さらに加熱処理を
行うことによつて、有機高分子と無機物とから成る複合
材を被覆した被覆金属板を製造する方法にかかり、その
目的とするところは、均一に塗布された、すぐれた耐食
性を有する複合被覆金属板を製造することにある。DETAILED DESCRIPTION OF THE INVENTION The present invention involves adding a water-insoluble organic polymer resin powder to at least one type of water-soluble or water-dispersible organic polymer resin; The metal plate to be coated is immersed in a suspension whose main component is one or more alloy powders added, electrolytic treatment is performed using the metal plate to be coated as a cathode or anode, and further heat treatment is performed. has developed a method for manufacturing a coated metal plate coated with a composite material consisting of an organic polymer and an inorganic substance, and the objective is to produce a composite coated metal plate coated uniformly and with excellent corrosion resistance. It lies in manufacturing.
従来、被覆金属板を製造する方法として、有機高分子を
主成分とする場合について説明すると、（１）有機高分
子樹脂を有機溶剤によつて洛解し、粘度調整を行つたも
のを、ロールコート、ナイフコート、スプレーコート、
あるいは浸漬する方法で塗布し、ついで、加熱処理を行
つて、有機溶剤を飛散せしめて硬化する製造方法、（２
）有機高分子樹脂粉末と粘着性のある溶液とを混練した
ものを、前記（１）と同様な方法で塗布し、ついで加熱
処理を行つて、溶剤を飛散せしめて硬化する製造方法、
（３）粉末を溶射によつて塗装する方法、（４）有機高
分子樹脂の粉末を有機溶媒中に分散させて電気泳動によ
つて塗布し、さらに加熱処理する製造方法、（５）有機
高分子樹脂の水分散性のものを用い電気泳動によつて電
着塗装を施し、加熱処理を行い、乾燥する方法、（６）
有機高分子樹脂の粉末を静電気装置を用いて塗装し、加
熱処理する方法などがある。Conventional methods for manufacturing coated metal plates using organic polymer as the main component are as follows: (1) Organic polymer resin is dissolved with an organic solvent to adjust the viscosity, and then rolled. coat, knife coat, spray coat,
Alternatively, a manufacturing method in which coating is applied by dipping, followed by heat treatment to scatter an organic solvent and harden (2)
) A manufacturing method in which a mixture of an organic polymer resin powder and a sticky solution is applied in the same manner as in (1) above, and then heat treated to scatter the solvent and harden;
(3) A method in which powder is applied by thermal spraying, (4) A manufacturing method in which organic polymer resin powder is dispersed in an organic solvent, applied by electrophoresis, and then heat-treated; A method in which electrodeposition is applied by electrophoresis using a water-dispersible molecular resin, followed by heat treatment and drying, (6)
There is a method in which organic polymer resin powder is coated using an electrostatic device and heat treated.
前記のなかで、（１）、（２）、（３）による方法では
薄くして均一に塗布量をコントロールすることが難しい
のが実情であり、塗膜の均一性が品質管理上、しばしば
トラブルの原因の一つになつている。また、塗布量が薄
くても満足できる用途に対しては、経済的な面から非常
に不利な方法である。さらに有機高分子と無機物の粉末
の複合材を被覆しようとする場合には一層困難となる。
また、前記（１）、（２）（４）による方法では有機溶
剤が使用されており、これらの有機溶剤が公害の対象と
なることはしばしば経１験されることである。前記（５
）による方法では有機高分子樹脂そのものが強いイオン
性を有することが必要であり、使用できる樹脂が限定さ
れる。たとえば、水に不溶なナイロン、ポリエチレンな
どは、通常の手段では電着できない。前記（６）の方法
によると、樹脂粉末と基材との密着性が悪く、加熱処理
時間までの工程で、わずかな衝撃や接触によつて、塗布
された粉末が離脱しやすい欠点がある。金属粉末を含む
場合は、さらに密着性が低下する。これに対して、特開
昭５０−７５６２３では、プラスの電荷を有した粒径１
〜５００ｍμのアルミナゾルと有機高分子樹脂粉末から
なる懸濁液中に、塗布しようとする金属板を浸漬し、塗
布する金属板を陰極として電解処理する方法が述べられ
ている。Among the above methods, the reality is that it is difficult to control the coating amount thinly and uniformly using methods (1), (2), and (3), and the uniformity of the coating is often a problem in terms of quality control. It has become one of the causes. Furthermore, this method is very disadvantageous from an economical point of view for applications where a thin coating amount is sufficient. Furthermore, it becomes even more difficult when attempting to coat a composite material of an organic polymer and an inorganic powder.
Furthermore, organic solvents are used in the methods (1), (2), and (4) above, and it is often experienced that these organic solvents become objects of pollution. Said (5
) requires that the organic polymer resin itself has strong ionicity, which limits the types of resins that can be used. For example, nylon, polyethylene, etc., which are insoluble in water, cannot be electrodeposited by normal means. According to the method (6) above, the adhesion between the resin powder and the base material is poor, and the applied powder tends to separate due to slight impact or contact during the process up to the heat treatment time. When metal powder is included, the adhesion is further reduced. On the other hand, in JP-A-50-75623, positively charged particles with a diameter of 1
A method is described in which a metal plate to be coated is immersed in a suspension consisting of an alumina sol of ~500 mμ and an organic polymer resin powder, and electrolytically treated using the metal plate to be coated as a cathode.
この方法によると、処理時の電気量によつて容易に被覆
厚みをコントロールすることができ、しかも有害な有機
溶剤を使用する必要がない。また、前述したナイロン、
ポリエチレンなど水に不溶な樹脂粉末と無機物とから成
るものでも容易に電着塗装することができ、しかも有害
な有機溶剤を使用しないので、公害が生じる恐れがない
。本発明は、前記の特開昭５０−７５６２３の発明をさ
らに発展させ、複合電着分の密着性の向土を図つたもの
である。According to this method, the coating thickness can be easily controlled by adjusting the amount of electricity during treatment, and there is no need to use harmful organic solvents. In addition, the nylon mentioned above,
Even materials made of water-insoluble resin powder such as polyethylene and inorganic substances can be easily electrodeposited, and since no harmful organic solvents are used, there is no risk of pollution. The present invention further develops the invention of JP-A-50-75623 and aims to improve the adhesion of composite electrodeposition.
すなわち水溶性あるいは水分散性の有機高分子樹脂に水
に不溶な有機高分子樹脂粉末と、金属の粉末、あるいは
前記金属の合金粉末を添加したものを主成分とする懸濁
液中に、塗布しようとする金属板を陰極あるいは陽極と
して処理する方法である。本発明と、前記の特開昭５０
−７５６２３についてその著しい差異を説明すると、特
開昭５０−７５６２３は、粒径１〜５００ｍμのアルミ
ナゾルに、粒径２００μ以下のナイロン、ポリエチレン
などの水に不溶の有機高分子の一種以上を添加した懸濁
液、あるいはこれに、さらにシリケートゾル、チタンゾ
ル、ニツケルゾルの一種以上を、前記アルミナゾルと同
量か、それ以下の範囲で添加した懸濁液に、塗布される
べき金属板を浸漬して陰極とし、電解処理後さらに加熱
乾燥するものである。That is, it is applied into a suspension whose main components are a water-soluble or water-dispersible organic polymer resin, a water-insoluble organic polymer resin powder, and a metal powder or an alloy powder of the metals. This method treats the metal plate to be used as a cathode or an anode. The present invention and the above-mentioned Japanese Patent Application Laid-Open No.
To explain the remarkable difference in JP-A No. 50-75623, JP-A-50-75623 uses alumina sol with a particle size of 1 to 500 μm to which one or more types of water-insoluble organic polymers such as nylon and polyethylene with a particle size of 200 μm or less are added. The metal plate to be coated is immersed in a suspension, or a suspension in which at least one of silicate sol, titanium sol, and nickel sol is added in an amount equal to or less than the alumina sol, and the metal plate to be coated is immersed in the cathode. After the electrolytic treatment, it is further heated and dried.
これに対して本発明は、エポキシ系、フエノール系など
の水溶性または水分散性の樹脂に、前記の特開昭５０−
７５６２３の組成物を添加して、陽極または陰極処理を
可能にしたものである。つぎに、本発明の方法について
詳細に説明する。主成分である水溶性あるいは水分散性
の有機高分子樹脂は電着物の密着性に対して効果があり
、これらの樹脂には、エポキシ系、フエノール系、アル
キツド系、アクリル系、ブタジエン系などが含まれる。
その粒径は１μ以下である。１μ以上になると電着の外
観を悪くするので適当でない。In contrast, the present invention uses water-soluble or water-dispersible resins such as epoxy and phenol resins to
75623 was added to enable anodic or cathodic treatment. Next, the method of the present invention will be explained in detail. Water-soluble or water-dispersible organic polymer resins, which are the main components, have an effect on the adhesion of electrodeposit, and these resins include epoxy, phenol, alkyd, acrylic, and butadiene resins. included.
Its particle size is less than 1 micron. If it exceeds 1 μm, the appearance of the electrodeposition will deteriorate, so it is not suitable.
その濃度は固形分として２〜５０９／ｌが適当である。
２９／ｌ以下の場合は添加の効果がみられず、５０９／
ｌ以上の場合は電着のつきまわり性が悪くなる。The appropriate concentration is 2 to 509/l in terms of solid content.
If it is less than 29/l, no effect of addition is seen, and 509/l or less.
If it is more than l, the throwing power of electrodeposition becomes poor.
つぎに、水分散性のゾルである金属の化合物のゾルは、
粒径１〜５００ｍμで、亜鉛、スズ、クロム、ニツケル
、チタン、ジルコニウム、アルミニウムなどが含まれる
。Next, the sol of a metal compound, which is a water-dispersible sol, is
It has a particle size of 1 to 500 mμ and contains zinc, tin, chromium, nickel, titanium, zirconium, aluminum, etc.
これらの金属化合物のゾルの濃度は１〜１００９／ｌが
適当であり、各種の金属化合物のゾルを混合して使用す
ることはさしつかえない。金属化合物のゾルの濃度が１
９／ｌ以下になると添加の効果がみられず、粉末と金属
板との密着性が悪い。また、１００９／ｌ以上になつて
も塗膜形成におよぼす効果は同じであ゛り、逆に懸濁液
の粘度を増し、作業性を悪くするので適当でない。適用
できる有機高分子樹脂の粉末は、金属化合物のゾルや、
水と著しく反応しないものがあれば、ほとんどすべての
粉末が利用できる。The concentration of sols of these metal compounds is suitably 1 to 1009/l, and sols of various metal compounds may be mixed and used. The concentration of the metal compound sol is 1
If it is less than 9/l, the effect of addition is not seen and the adhesion between the powder and the metal plate is poor. Moreover, even if it exceeds 1009/l, the effect on coating film formation is the same, but on the contrary, it increases the viscosity of the suspension and impairs workability, so it is not suitable. Applicable organic polymer resin powders include metal compound sols,
Almost any powder can be used as long as it does not react significantly with water.
たとえば、ナイロン、ポリエチレン、ポリプロピレン、
ポリアミド、ジアクリルフタレート、エチレン酢酸ビニ
ル共重合樹脂、セルローズアセテートブチレート、ポリ
ウレタン、ポリスチロール、ポリカーボネート、塩化ビ
ニル樹脂、ポリフツ化ビニル樹脂、エポキシ樹脂、アク
リル樹脂などの有機高分子が含まれる。これらの粉末は
混合して使用することができる。粉末の大きさは、一般
的には、小さいもの程緻密な被覆層が得られ、大きくな
ると仕上りがポーラスとなり、被覆層の密着性が悪くな
る傾向がある。しかし、本発明の処理のあと、口ール圧
着、あるいは、さらに熱処理をすると被覆層の密着性が
改善されるので、粉末の大きさは、粒径２００μ以下で
あれば、特に制限されない。樹脂粉末の添加量は、粉末
の大きさ、種類、組み合わせによつて異なるが、１００
９／ｌまでは作業性に何ら影響をおよぼさないものもあ
る。２〜３ｇ／！のように、添加量が少ないときには、
電着効率が悪くなる傾向がある。For example, nylon, polyethylene, polypropylene,
Organic polymers include polyamide, diacrylphthalate, ethylene vinyl acetate copolymer resin, cellulose acetate butyrate, polyurethane, polystyrene, polycarbonate, vinyl chloride resin, polyvinyl fluoride resin, epoxy resin, and acrylic resin. These powders can be used in combination. In general, the smaller the powder size, the denser the coating layer can be obtained, and the larger the powder size, the more porous the finish and the poorer adhesion of the coating layer. However, since the adhesion of the coating layer is improved if the treatment of the present invention is followed by mouth compression bonding or further heat treatment, the size of the powder is not particularly limited as long as the particle size is 200 μm or less. The amount of resin powder added varies depending on the size, type, and combination of powders, but
Some materials have no effect on workability up to 9/l. 2~3g/! When the amount added is small, as in
Electrodeposition efficiency tends to deteriorate.
つぎに、耐食性をさらに改善するためには、金属粉末、
合金粉末を添加することが好ましい。Next, in order to further improve corrosion resistance, metal powder,
Preferably, alloy powder is added.
これらの粉末に、アルミニウム、亜鉛、クロム、コバル
ト、ニツケル、鉄、スズ、鉛、銅、マンガン、チタン、
モリブデン、ジルコニウム、ビスマス、アンチモン、タ
ングステンなどの粉末、あるいはこれらの合金粉末が含
まれる。また、混合して使用してもさしつかえない。粉
末の大きさは粒径２００μ以下が適当である。粒径２０
０μ以上になると、添加の効果が半減し、逆に電着被覆
層はポーラスとなり、耐食性を低下させるなどの悪影響
がみられる。添加量は樹脂粉末の場合と同様に、粉末の
種類、大きさ、組み合わせによつて異なるが、７００９
／ｌまでは、作業性に何ら悪影響を及ぼさないものもあ
る。２〜３９／ｌ以下の場合、添加による耐食性への効
果はみられない。These powders include aluminum, zinc, chromium, cobalt, nickel, iron, tin, lead, copper, manganese, titanium,
It includes powders of molybdenum, zirconium, bismuth, antimony, tungsten, etc., or powders of alloys thereof. It is also possible to use them in combination. The appropriate size of the powder is a particle size of 200 μm or less. Particle size 20
When the amount exceeds 0μ, the effect of addition is reduced by half, and on the contrary, the electrodeposited coating layer becomes porous, resulting in adverse effects such as a decrease in corrosion resistance. As with resin powder, the amount added varies depending on the type, size, and combination of powder, but 7009
There are some materials that do not have any adverse effect on workability up to /l. In the case of 2 to 39/l or less, no effect on corrosion resistance is observed by addition.
懸濁液の温度は１０〜７『Ｃが適当である。The temperature of the suspension is suitably 10 to 7 degrees Celsius.
７０℃以上になると、液の蒸発などによつて安定性が悪
くなる。When the temperature exceeds 70°C, stability deteriorates due to evaporation of the liquid.
液温の低い方については、作業性のよいところを選べば
よく、特に制限されない。電流密度は特に制限されない
が、短時間に厚く被覆させようとすれば電流密度をあげ
なければならない。電解時の被覆しようとする金属板の
極性は、懸濁液の組成によつて異なり、ＰＨが酸性側の
ときは陰極に、アルカリ性のときは陽極にする方がよい
。As for the lower liquid temperature, it is only necessary to choose a place with good workability, and there is no particular restriction. The current density is not particularly limited, but if a thick coating is to be achieved in a short period of time, the current density must be increased. The polarity of the metal plate to be coated during electrolysis differs depending on the composition of the suspension; it is better to use the cathode when the pH is acidic, and the anode when the pH is alkaline.
また、電解時における攪拌効果については、攪拌しない
方が電着効率はすぐれる傾向があるが、粉末を含む懸濁
液を均一に維持するためには、ある程度の攪拌が必要で
ある。本発明の方法において、粉末を容易に懸濁させる
ためには、界面活性剤、あるいは、アルコールなどを添
加することができる。Regarding the stirring effect during electrolysis, electrodeposition efficiency tends to be better when no stirring is performed, but a certain degree of stirring is necessary to maintain a uniform suspension containing powder. In the method of the present invention, a surfactant, alcohol, or the like may be added to easily suspend the powder.
たとえば、粒径５０μのナイロン粉末を懸濁させるため
には、アルキルベタイン型の界面活性剤を０．１９／ｌ
添加すると、速やかに均一に混合させることができる。
前述のような方法で、懸濁液を調整したのち、塗布され
る金属板を陰極あるいは陽極として電解処理する。この
ようにして金属板土に形成された電着層は、水洗後、あ
るいは水洗を行わずに乾燥される。For example, in order to suspend nylon powder with a particle size of 50μ, 0.19/l of alkyl betaine type surfactant is added.
When added, the mixture can be quickly and uniformly mixed.
After preparing the suspension in the manner described above, the metal plate to be coated is electrolytically treated as a cathode or an anode. The electrodeposited layer thus formed on the metal plate is dried after washing with water or without washing with water.
上記の方法によつて得られた有機高分子樹脂と無機物の
複合材から成る被覆金属板は、熱処理される。熱処理条
件は粉末の種類、塗布量によつて異なるので、単純に決
めることはできないが、目的に応じて決める必要がある
。目安として、樹脂粉末が溶融状態になることが必要で
ある。なお、熱処理の前後に圧着ロールを通すと表面の
仕上がりが著しく改善される。本発明は、種々の金属板
や金属の成形加工部品の表面処理に利用することができ
る。The coated metal plate made of a composite material of organic polymer resin and inorganic material obtained by the above method is heat treated. Heat treatment conditions cannot be determined simply because they vary depending on the type of powder and the amount of application, but must be determined depending on the purpose. As a guideline, it is necessary for the resin powder to be in a molten state. Note that passing the film through a pressure roll before and after heat treatment significantly improves the surface finish. The present invention can be used for surface treatment of various metal plates and molded metal parts.
たとえば、鋼板や、電解クロム酸処理板、クロム、スズ
、亜鉛、ニツケル、アルミニウムなどのめつき板、ある
いは、これらの合金めつき板が含まれる。勿論これらの
めつき板の表面にクロメート処理、あるいは、リン酸塩
処理などの化成処理が施されていてもさしつかえない。
つぎに本発明の方法について実施例で詳細に説明する。Examples include steel plates, electrolytic chromic acid treated plates, plates plated with chromium, tin, zinc, nickel, aluminum, etc., and plates plated with alloys thereof. Of course, the surface of these plated plates may be subjected to chemical conversion treatment such as chromate treatment or phosphate treatment.
Next, the method of the present invention will be explained in detail using Examples.
実施例 １
板厚０．５詣の軟鋼板を７０ｙ／ｌの水酸化ナトリウム
溶液、浴温７０℃に１０秒間浸漬して、脱脂処理を行い
、水洗したのち、７０９／ｌの硫酸液、浴温２０℃に５
秒問浸漬による酸洗処理を行い、水洗したのち、直ちに
本発明の処理を行つた。Example 1 A mild steel plate with a thickness of 0.5 mm was immersed in a 70 y/l sodium hydroxide solution for 10 seconds at a bath temperature of 70°C to perform degreasing treatment, rinsed with water, and then soaked in a 709 y/l sulfuric acid solution and bath. 5 to 20℃
After performing pickling treatment by dipping for a few seconds and washing with water, the treatment of the present invention was immediately performed.
本発明の処理浴組成
得られた被覆金属板は緑色を呈し、２５０℃で２分間加
熱処理したところ、膜厚１４μの薄い緑色の被覆板が得
られた。The coated metal plate obtained from the treatment bath composition of the present invention exhibited a green color, and when heat treated at 250° C. for 2 minutes, a thin green coated plate with a film thickness of 14 μm was obtained.
被覆金属板の素地金属との密着性は、８ｍｎのエリクセ
ン張り出しにおいても被覆層の剥離は認められなかつた
。また、ＪＩＳＺ２３７ｌに規定された塩水噴霧におけ
る耐食性試験では、２００時間経過しても赤錆の発生は
認められなかつた。これに対してポリアクリルアミドを
含まないものは、２００時間を経過すると赤錆の発生が
みられた。クロムのゾルやポリアクリルアミドを除いた
ものをスプレーで被覆したものは、粉末と原板との密着
性が悪く、わずかな衝撃に対しても粉末が原板より離脱
した。また、粉末が原板より離脱しないように注意して
加熱処理したものは、１０時間で赤錆の発生がみられた
。実施例 ２
実施例１と同様な脱脂、酸洗の前処理を行つた軟鋼板に
、本発明の処理を行つた。As for the adhesion of the coated metal plate to the base metal, no peeling of the coating layer was observed even with an Erichsen overhang of 8 mm. Furthermore, in a salt spray corrosion resistance test specified in JIS Z237l, no red rust was observed even after 200 hours. On the other hand, for those containing no polyacrylamide, red rust appeared after 200 hours. When spray-coated with a material other than chromium sol or polyacrylamide, the adhesion between the powder and the original plate was poor, and the powder separated from the original plate even with the slightest impact. In addition, when heat treatment was performed to prevent the powder from separating from the original plate, red rust appeared after 10 hours. Example 2 A mild steel plate that had undergone the same pretreatment of degreasing and pickling as in Example 1 was subjected to the treatment of the present invention.
本発明の処理
浴組成
得られた被覆金属板は灰色を呈し、２５０℃で２分間加
熱処理したところ、膜厚１４μの灰色の被覆板が得られ
た。The coated metal plate obtained from the treatment bath composition of the present invention had a gray color, and when heat treated at 250° C. for 2 minutes, a gray coated plate with a film thickness of 14 μm was obtained.
被覆金属板の素地金属との密着性は８ｍｍのエリクセン
張り出しにおいても被覆層の剥離は認められなかつた。
また、ＪＩＳＺ２３７ｌに規定された塩水噴霧における
耐食性試験では、５００時間を経過しても赤錆の発生は
認められず、亜鉛粉末添加の効果がみられた。これに対
して、クロムのゾルやポリアクリルアミドを除いたもの
をスプレーで被覆したものは、粉末と原板との密着性が
悪く、わずかな衝撃に対しても粉末が原板より離脱した
。また、粉末が原板より離脱しないように注意して加熱
処理したものは、２４時間で赤錆の発生がみられた。実
施例 ３
実施例１と同様な軟鋼板に１０ｆ１／ゴ（片面）の電気
亜鉛めつきを施したのち、クロメート処理してから、本
発明の処理を行つた。Regarding the adhesion of the coated metal plate to the base metal, no peeling of the coating layer was observed even when the Erichsen overhang was 8 mm.
In addition, in a corrosion resistance test using salt spray as specified in JIS Z237l, no red rust was observed even after 500 hours, indicating the effectiveness of the addition of zinc powder. On the other hand, when spray-coated with a material excluding chromium sol or polyacrylamide, the adhesion between the powder and the original plate was poor, and the powder separated from the original plate even with the slightest impact. In addition, when heat treatment was performed to prevent the powder from separating from the original plate, red rust appeared within 24 hours. Example 3 A mild steel plate similar to that in Example 1 was electrogalvanized to 10 f1/g (one side), then chromate treated, and then subjected to the treatment of the present invention.
本発明の処理
得られた被覆金属板は灰色を呈し、４００℃で３０秒間
加熱処理したところ、膜厚２０μの灰色の被覆板が得ら
れた。The coated metal plate obtained by the treatment of the present invention had a gray color, and when it was heat-treated at 400° C. for 30 seconds, a gray coated plate with a film thickness of 20 μm was obtained.
被覆金属板の素地金属との密着性や耐食性は、実施例２
と同様にすぐれていた。実施例 ４
板厚０．５ｍｍの軟鋼板を７０９／ｌの水酸化ナトリウ
ム溶液、浴温７０℃に１０秒の浸漬処理による脱脂処理
を行い、水洗したのち、７０９／ｆ硫酸、浴温２０℃に
５秒の浸漬による酸洗処理を行い、水洗したのち直ちに
本発明の処理を行つた。The adhesion and corrosion resistance of the coated metal plate to the base metal were determined in Example 2.
It was equally excellent. Example 4 A mild steel plate with a thickness of 0.5 mm was degreased by immersion in a 709/l sodium hydroxide solution at a bath temperature of 70°C for 10 seconds, washed with water, and then soaked in 709/f sulfuric acid at a bath temperature of 20°C. A pickling treatment was performed by dipping for 5 seconds, and after washing with water, the treatment of the present invention was immediately performed.
本発明の処理浴組成
得られた塗膜は白色を示し、１７０℃で１５秒間加熱処
理を行つたところ１００μの半透明の塗膜が得られた。The coating film obtained from the treatment bath composition of the present invention was white, and when heat treated at 170° C. for 15 seconds, a translucent coating film of 100 μm was obtained.
得られた塗膜は８ｍ７７！のエリクセン張出しにおいて
も塗膜の剥離は認められなかつた。また、ＪＩＳＺ２３
７ｌに規定された塩水噴霧による耐食性試験では４０時
間経過しても錆の発生は認められなかつた。しかし、本
発明の浴組成からアクリル系の水溶性樹脂を除いたもの
は、加熱処理する前にロールに接触した場合処理皮膜の
一部がロールに付着し処理皮膜の均一性が不十分であつ
た。実施例 ５
板厚０．５′７７！７７！の軟鋼板に電解クロム酸処理
（処理皮膜量、Ｃｒとして１．０７１ｇ／Ｄｒｌ？）を
施したのち本発明の処理を行つた。The resulting coating film was 8m77! No peeling of the paint film was observed even during Erichsen overhang. Also, JISZ23
In a corrosion resistance test using salt water spray specified in 7L, no rust was observed even after 40 hours. However, when the bath composition of the present invention excluding the acrylic water-soluble resin comes into contact with the roll before heat treatment, a part of the treated film adheres to the roll, resulting in insufficient uniformity of the treated film. Ta. Example 5 Plate thickness 0.5'77!77! A mild steel plate was subjected to electrolytic chromic acid treatment (treatment film amount: 1.071 g/Drl as Cr) and then subjected to the treatment of the present invention.
本発明の処理
浴組成
得られた塗膜は白色を示し、２０『Ｃで３０秒間加熱処
理を行つたところ、１２μのやや黄色を帯びた半透明の
塗膜が得られた。The coating film obtained from the treatment bath composition of the present invention was white, and when heat treated at 20°C for 30 seconds, a slightly yellowish, translucent coating film of 12μ was obtained.
また、絞り比２．０の深絞り加工を施しても塗膜の剥離
は認められなかつた。塗膜にカミソリで原板に達するま
での深さで、クロスカツトを施したのち塩水噴霧試験に
よる耐食性試験を行つたところ、３００時間経過しても
ブリスタ一の発生はみられず、切り口以外には赤錆の発
生は認められなかつた。一方、本発明の浴組成からブタ
ジエン系水溶性樹脂を除いたものは加熱処理する前にロ
ールに接触した場合処理皮膜の一部がロールに付着し、
処理皮膜の均一性が不十分であつた。実施例 ６
実施例１と同様な軟鋼板を実施例１と同様な前処理を行
つたのち、本願の発明の処理を行つた。Furthermore, no peeling of the coating film was observed even when deep drawing was performed at a drawing ratio of 2.0. After cross-cutting the paint film to a depth that reached the original plate with a razor, a corrosion resistance test using a salt spray test was conducted. No blisters were observed even after 300 hours, and there was no red rust anywhere other than the cut edges. No occurrence of this was observed. On the other hand, if the bath composition of the present invention excluding the butadiene-based water-soluble resin comes into contact with the roll before heat treatment, a part of the treated film will adhere to the roll.
The uniformity of the treated film was insufficient. Example 6 A mild steel plate similar to that in Example 1 was pretreated in the same manner as in Example 1, and then subjected to the treatment of the invention of the present application.
本発明の処理浴組成
得られた塗膜は白色を帯び、２００℃で３０秒間の加熱
処理を行つたところ、やや黄色を帯びた厚み１２μの半
透明の塗膜が得られた。The coating film obtained from the treatment bath composition of the present invention was white in color, and when heat treated at 200° C. for 30 seconds, a slightly yellowish semitransparent coating film with a thickness of 12 μm was obtained.
この塗膜を８ｍ７ｎのエリクセン張出しを行つても塗膜
の剥離は認められなかつた。一方、本発明の浴組成から
フエノール系水溶性樹脂を除いたものは加熱処理する前
にロールに接触した場合処理皮膜の一部がロールに付着
し、処理皮膜の均一性が不十分であつた。実施例 ７
実施例１と同様な軟鋼板に１０９／ゴ（片面）の電気亜
鉛めつきを施したのちクロメート処理を施してから本願
の発明の処理を行つた。Even when this coating film was subjected to an Erichsen overhang of 8 m7n, no peeling of the coating film was observed. On the other hand, when the bath composition of the present invention excluding the phenolic water-soluble resin came into contact with the roll before heat treatment, part of the treated film adhered to the roll, resulting in insufficient uniformity of the treated film. . Example 7 A mild steel plate similar to Example 1 was electrolytically galvanized to 109/G (one side), then chromate treated, and then subjected to the treatment of the present invention.
本発明の処理
浴組成
得られた塗膜は白色を帯び、１７０℃で１５秒間の加熱
処理を行つたところ半透明の塗膜が得られた。The coating film obtained from the treatment bath composition of the present invention was white in color, and a translucent coating film was obtained when heat treated at 170° C. for 15 seconds.
塗膜の密着性は実施例１と同様にすぐれており、塩水噴
霧試験による耐食性は、４０時間経過しても白錆の発生
は認められなかつた。一方、本発明の浴組成からエポキ
シ系水溶性樹脂を除いたものは電解処理後の水洗時にお
いて、処理皮膜が剥離する傾向があり、加熱処理する前
にロールに接触した場合処理皮膜の一部がロールに付着
し、処理皮膜の均一性が不十分であつた。前述のように
本願の発明の浴組成中の水溶性樹脂は処理皮膜の加熱処
理前の密着性に対して著しい効果が認められた。The adhesion of the coating film was excellent as in Example 1, and the corrosion resistance in the salt spray test showed that no white rust was observed even after 40 hours. On the other hand, when the bath composition of the present invention excludes the epoxy-based water-soluble resin, the treated film tends to peel off when washed with water after electrolytic treatment, and if it comes into contact with the roll before heat treatment, part of the treated film will peel off. was attached to the roll, and the uniformity of the treated film was insufficient. As mentioned above, the water-soluble resin in the bath composition of the present invention was found to have a significant effect on the adhesion of the treated film before heat treatment.
Claims (1)
ル系、ブタジエン系などの水容性あるいは水分散性の樹
脂の少なくとも１種以上を固形分として２〜５０ｇ／ｌ
と、粒径１〜５００ｍμのニッケル、チタン、クロム、
亜鉛、アルミニウム、スズなどの酸化物あるいは水酸化
物から成る金属の化合物の少なくとも一種以上を１〜１
００ｇ／ｌ含む溶液に、粒径２００μ以下のナイロン、
ポリエチレン、ポリプロピレン、ポリアミド、ジアクリ
ルフタレート、エチレン酢酸ビニル共重合樹脂、セルロ
ーズアセテートプチレート、ポリウレタン、ポリスチロ
ール、ポリカーボネート、塩化ビニル、エポキシ樹脂、
アクリル樹脂、ポリフッ化ビニル樹脂など水に不溶な有
機高分子粉末の１種以上を添加したものを主成分とする
懸濁液に、金属板を浸漬し、塗布される金属板を陰極、
あるいは陽極として電解処理することによつて粉末を被
覆し、さらに加熱処理を行うことを特徴とする有機高分
子と無機物とから成る複合材を被覆した複合覆金属板の
製造方法。 ２ エポキシ系、フェノール系、アルキッド系、アクリ
ル系、ブタジエン系などの水溶性あるいは水分散性の樹
脂の少なくとも１種以上を固形分として２〜５０ｇ／ｌ
と、粒径１〜５００ｍμのニッケル、チタン、クロム、
亜鉛、アルミニウム、スズなどの酸化物あるいは水酸化
物から成る金属の化合物の少なくとも一種以上を１〜１
００ｇ／ｌ含む溶液に、粒径２００μ以下のナイロン、
ポリエチレン、ポリプロピレン、ポリアミド、ジアクリ
ルフタレート、エチレン酢酸ビニル共重合樹脂、セルロ
ーズアセテートブチレート、ポリウレタン、ポリスチロ
ール、ポリカーボネート、塩化ビニル、エポキシ樹脂、
アクリル樹脂、ポリフッ化ビニル樹脂など水に不溶な有
機高分子粉末の一種以上を添加し、さらに粒径２００μ
以下のアルミニウム、亜鉛、クロム、コバルト、ニッケ
ル、鉄、スズ、鉛、銅、マンガン、チタン、モリブデン
、ジルコニウム、ビスマス、アンチモン、タングステン
などの金属粉末、あるいは前記金属の合金粉末の一種以
上を添加したものを主成分とする懸濁液に、金属板を浸
漬し、塗布される金属板を陰極あるいは陽極として電解
処理することによつて粉末を被覆し、さらに加熱処理を
行うことを特徴とする有機高分子と無機物とから成る複
合材料を被覆した複合被覆金属板の製造方法。[Claims] 1. 2 to 50 g/l of at least one water-soluble or water-dispersible resin such as epoxy, phenol, alkyd, acrylic, butadiene, etc. as a solid content.
and nickel, titanium, chromium, with a particle size of 1 to 500 mμ,
At least one or more metal compounds consisting of oxides or hydroxides such as zinc, aluminum, tin, etc.
Nylon with a particle size of 200μ or less in a solution containing 00g/l,
Polyethylene, polypropylene, polyamide, diacrylphthalate, ethylene vinyl acetate copolymer resin, cellulose acetate butylate, polyurethane, polystyrene, polycarbonate, vinyl chloride, epoxy resin,
A metal plate is immersed in a suspension mainly containing one or more water-insoluble organic polymer powders such as acrylic resin and polyvinyl fluoride resin, and the coated metal plate is used as a cathode,
Alternatively, a method for manufacturing a composite coated metal plate coated with a composite material consisting of an organic polymer and an inorganic substance, characterized in that the powder is coated by electrolytic treatment as an anode, and further heat treatment is performed. 2. At least one type of water-soluble or water-dispersible resin such as epoxy, phenol, alkyd, acrylic, butadiene, etc., as a solid content of 2 to 50 g/l
and nickel, titanium, chromium, with a particle size of 1 to 500 mμ,
At least one or more metal compounds consisting of oxides or hydroxides such as zinc, aluminum, tin, etc.
Nylon with a particle size of 200μ or less in a solution containing 00g/l,
Polyethylene, polypropylene, polyamide, diacrylphthalate, ethylene vinyl acetate copolymer resin, cellulose acetate butyrate, polyurethane, polystyrene, polycarbonate, vinyl chloride, epoxy resin,
At least one type of water-insoluble organic polymer powder such as acrylic resin or polyvinyl fluoride resin is added, and the particle size is 200 μm.
Added one or more of the following metal powders such as aluminum, zinc, chromium, cobalt, nickel, iron, tin, lead, copper, manganese, titanium, molybdenum, zirconium, bismuth, antimony, and tungsten, or alloy powders of the above metals. A metal plate is coated with powder by dipping a metal plate in a suspension mainly composed of a powder, using the coated metal plate as a cathode or an anode, and then heat-treated. A method for producing a composite coated metal plate coated with a composite material consisting of a polymer and an inorganic substance.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU19136/76A AU509166B2 (en) | 1975-11-04 | 1975-10-29 | Composite coated steel sheet |
| JP50131425A JPS5928639B2 (en) | 1975-11-04 | 1975-11-04 | Fukugohi Fukukinzokubanno Seizouhouhou |
| IT6962176A IT1070067B (en) | 1975-11-04 | 1976-11-02 | PROCEDURE FOR THE PRODUCTION OF STEEL SHEET WITH COMPOSITE COATING |
| FR7633182A FR2330780A1 (en) | 1975-11-04 | 1976-11-03 | PROCESS FOR PREPARING STEEL SHEETS COATED WITH A PLASTIC MATERIAL |
| CA000264946A CA1116548A (en) | 1975-11-04 | 1976-11-03 | Method of producing a composite coated steel sheet |
| DE19762650611 DE2650611B2 (en) | 1975-11-04 | 1976-11-04 | Process for the production of coated steel composite sheets |
| GB4600376A GB1569287A (en) | 1975-11-04 | 1976-11-04 | Method of coating steel sheet by electrodeposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50131425A JPS5928639B2 (en) | 1975-11-04 | 1975-11-04 | Fukugohi Fukukinzokubanno Seizouhouhou |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5256022A JPS5256022A (en) | 1977-05-09 |
| JPS5928639B2 true JPS5928639B2 (en) | 1984-07-14 |
Family
ID=15057651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50131425A Expired JPS5928639B2 (en) | 1975-11-04 | 1975-11-04 | Fukugohi Fukukinzokubanno Seizouhouhou |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5928639B2 (en) |
| AU (1) | AU509166B2 (en) |
| CA (1) | CA1116548A (en) |
| DE (1) | DE2650611B2 (en) |
| FR (1) | FR2330780A1 (en) |
| GB (1) | GB1569287A (en) |
| IT (1) | IT1070067B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4117417A1 (en) * | 1991-05-28 | 1992-12-03 | Herberts Gmbh | AQUEOUS DISPERSION OF A CATHODICALLY DEPOSITABLE BINDING AGENT, METHOD FOR THE PRODUCTION AND THE USE THEREOF |
| DE19618379A1 (en) | 1996-05-08 | 1997-11-13 | Basf Lacke & Farben | Water-dispersible epoxy resins modified with copolymers of vinyl acetate |
| DE19930060A1 (en) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Electrocoating bath with water-soluble polyvinyl alcohol (co) polymers |
| FR2847275B1 (en) * | 2002-11-19 | 2006-03-31 | Usinor | ZINC-BULK STEEL OR ZINC-LINED STEEL COATED WITH A ZINC OR ZINC ALLOY LAYER COMPRISING A POLYMER, AND METHOD OF MANUFACTURING BY ELECTRODEPOSITION |
| JP7064291B2 (en) * | 2016-05-31 | 2022-05-10 | 日本ペイント・オートモーティブコーティングス株式会社 | Cationic electrodeposition coating composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3496668A (en) * | 1968-04-04 | 1970-02-24 | Dittmore Freimuth Corp | Insecticide fogger apparatus |
| JPS4840808A (en) * | 1971-09-23 | 1973-06-15 | ||
| JPS4843731A (en) * | 1971-10-06 | 1973-06-23 | ||
| JPS49101444A (en) * | 1972-12-27 | 1974-09-25 | ||
| JPS501128A (en) * | 1973-05-07 | 1975-01-08 | ||
| JPS5075623A (en) * | 1973-11-08 | 1975-06-20 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1571083A1 (en) * | 1965-10-08 | 1970-12-17 | Metallgesellschaft Ag | Process for the electrophoretic coating of objects |
| FR1494539A (en) * | 1965-10-08 | 1967-09-08 | Metallgesellschaft Ag | Process of coating various objects by electrophoresis |
| GB1164154A (en) * | 1966-08-18 | 1969-09-17 | Ford Motor Co | Painting Compositions |
| FR2235974A1 (en) * | 1973-06-14 | 1975-01-31 | Schein Charles | Polymer powder dispersion in liquid carboxylic polymer - made water soluble by neutralisation, useful for (electro deposition) coating |
-
1975
- 1975-10-29 AU AU19136/76A patent/AU509166B2/en not_active Expired
- 1975-11-04 JP JP50131425A patent/JPS5928639B2/en not_active Expired
-
1976
- 1976-11-02 IT IT6962176A patent/IT1070067B/en active
- 1976-11-03 CA CA000264946A patent/CA1116548A/en not_active Expired
- 1976-11-03 FR FR7633182A patent/FR2330780A1/en active Granted
- 1976-11-04 DE DE19762650611 patent/DE2650611B2/en not_active Ceased
- 1976-11-04 GB GB4600376A patent/GB1569287A/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3496668A (en) * | 1968-04-04 | 1970-02-24 | Dittmore Freimuth Corp | Insecticide fogger apparatus |
| JPS4840808A (en) * | 1971-09-23 | 1973-06-15 | ||
| JPS4843731A (en) * | 1971-10-06 | 1973-06-23 | ||
| JPS49101444A (en) * | 1972-12-27 | 1974-09-25 | ||
| JPS501128A (en) * | 1973-05-07 | 1975-01-08 | ||
| JPS5075623A (en) * | 1973-11-08 | 1975-06-20 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2650611A1 (en) | 1977-05-12 |
| GB1569287A (en) | 1980-06-11 |
| FR2330780A1 (en) | 1977-06-03 |
| IT1070067B (en) | 1985-03-25 |
| DE2650611B2 (en) | 1980-10-30 |
| AU509166B2 (en) | 1980-04-24 |
| FR2330780B1 (en) | 1982-12-03 |
| CA1116548A (en) | 1982-01-19 |
| JPS5256022A (en) | 1977-05-09 |
| AU1913676A (en) | 1978-05-04 |
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