JP2012111137A - Resin-coated aluminum plate and method of manufacturing the same - Google Patents
Resin-coated aluminum plate and method of manufacturing the same Download PDFInfo
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本発明は、コンデンサケース、各種センサーキャップ材などの深絞り加工に用いて好適な樹脂被覆アルミニウム板及びその製造方法に関する。 The present invention relates to a resin-coated aluminum plate suitable for use in deep drawing of a capacitor case, various sensor cap materials, and the like, and a method for manufacturing the same.
コンデンサケース、各種センサーキャップ材などの外装材には加工性に優れるアルミニウム板が用いられ、その表面には、絶縁性、耐食性、印字性等の性能確保を目的に、エポキシなどの樹脂被覆が施される。加工後に塗装またはラミネートされる場合もあるが、生産性向上のため、加工前に塗装（プレコート）したものが主流になりつつある。
このような樹脂被覆アルミニウム板として、例えば特許文献１〜特許文献３に記載のものがある。
Aluminum sheets with excellent processability are used for the exterior materials such as capacitor cases and various sensor cap materials, and the surface is coated with a resin coating such as epoxy to ensure performance such as insulation, corrosion resistance, and printability. Is done. In some cases, it may be painted or laminated after processing, but for the purpose of improving productivity, those that have been coated (precoated) before processing are becoming mainstream.
Examples of such resin-coated aluminum plates include those described in Patent Documents 1 to 3.
特許文献１及び特許文献２には、化成皮膜による下地皮膜が形成されたアルミニウム板に樹脂層が形成されたものが記載されている。化成皮膜としては、通常のクロメート処理等が挙げられ、樹脂としては、エポキシ系の樹脂が用いられている。
特許文献１では、樹脂の数平均分子量が５０００〜３００００であり、潤滑剤を樹脂１００重量部に対し０．１〜１０重量部含有し、この樹脂層の引張強度が４０Ｎ／ｍｍ2以上、伸びが２％以上、厚さが３〜３０μｍであり、樹脂被覆アルミニウム板を圧下率４０％まで圧延した場合の碁盤目試験での碁盤目残存率が６０％以上であることが記載されている。
Patent Document 1 and Patent Document 2 describe a resin plate formed on an aluminum plate on which a base film is formed by a chemical conversion film. Examples of the chemical conversion film include a normal chromate treatment, and an epoxy resin is used as the resin.
In Patent Document 1, the number average molecular weight of the resin is 5000 to 30000, the lubricant is contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin, and the tensile strength of the resin layer is 40 N / mm 2 or more. Is 2% or more, the thickness is 3 to 30 μm, and the cross-cut remaining rate in the cross-cut test when the resin-coated aluminum plate is rolled down to 40% is described as being 60% or more.
特許文献２では、樹脂塗膜として、（ａ）数平均分子量３００００〜８００００、塗膜のＦＴ−ＩＲ分析において８３０ｃｍ-1の吸光度ｈ1、７５０ｃｍ-1の吸光度ｈ2の比ｈ2／ｈ1が０．１〜１０のエポキシ樹脂、（ｂ）数平均分子量７０００〜３００００、ガラス転移温度が−２０℃以上のポリエステル樹脂、（ｃ）アミノ樹脂、（ｄ）イソシアネート樹脂を含有する混合物の硬化物であり、（ａ）〜（ｄ）の合計含有量を１００質量部とすると、（ａ）７０〜９８質量部、（ｂ）０〜２０質量部、（ｃ）０〜２０質量部、（ｄ）２〜２０質量部を含有することが記載されている。 In Patent Document 2, (a) a number average molecular weight of 30,000 to 80,000, and a ratio h 2 / h 1 of an absorbance h 1 of 830 cm −1 and an absorbance h 2 of 750 cm −1 in FT-IR analysis of the coating film as a resin coating film. 0.1 to 10 epoxy resin, (b) a number average molecular weight of 7000 to 30000, a glass resin having a glass transition temperature of −20 ° C. or higher, (c) an amino resin, and (d) a cured product of a mixture containing an isocyanate resin When the total content of (a) to (d) is 100 parts by mass, (a) 70 to 98 parts by mass, (b) 0 to 20 parts by mass, (c) 0 to 20 parts by mass, (d ) Containing 2 to 20 parts by mass.
これら特許文献記載のものに対して、本出願人は、純アルミニウム又はアルミニウム合金表面に有孔率５％以下の無孔質陽極酸化皮膜を形成し、その上層に数平均分子量が２，０００〜１００，０００であるエポキシ系樹脂をシランカップリング剤を介して被覆することにより、エポキシ系樹脂の密着力を高めたものを提案した（特許文献３）。この場合、無孔質陽極酸化皮膜の膜厚が３０〜２００ｎｍ、シランカップリング剤の無孔質陽極酸化皮膜上への塗布量が０．５〜１０ｍｇ／ｍ２、エポキシ系樹脂の数平均分子量が５，０００〜８０，０００でその被覆の厚さが２〜２０μｍであるのが好ましい。 For those described in these patent documents, the present applicant forms a nonporous anodic oxide film having a porosity of 5% or less on the surface of pure aluminum or aluminum alloy, and the number average molecular weight is 2,000 to The thing which improved the adhesive force of the epoxy-type resin by coat | covering the epoxy-type resin which is 100,000 through a silane coupling agent was proposed (patent document 3). In this case, the film thickness of the nonporous anodic oxide film is 30 to 200 nm, the coating amount of the silane coupling agent on the nonporous anodic oxide film is 0.5 to 10 mg / m 2 , and the number average molecular weight of the epoxy resin Is preferably 5,000 to 80,000 and the coating thickness is preferably 2 to 20 μm.
特許文献３に記載の樹脂被覆アルミニウム板により、樹脂の密着力が向上したが、本発明は、樹脂の伸びを改善して可塑性を向上させ、さらに高い加工度であっても樹脂膜の剥離、肌荒れの発生を有効に防止することを目的とする。 The resin-coated aluminum plate described in Patent Document 3 has improved the adhesion of the resin, but the present invention improves the plasticity by improving the elongation of the resin, and the resin film can be peeled even at a high degree of processing. The object is to effectively prevent the occurrence of rough skin.
本発明の樹脂被覆アルミニウム板は、純アルミニウム又はアルミニウム合金表面に有孔率５％以下の無孔質陽極酸化皮膜が形成され、この無孔質陽極酸化皮膜の上に変性エポキシ系樹脂からなる樹脂膜が被覆されてなり、前記無孔質陽極酸化皮膜の膜厚は３０〜２００ｎｍであり、前記樹脂膜の膜厚は３〜２０μｍであり、前記変性エポキシ樹脂の変性率が５０％以下であることを特徴とする。 In the resin-coated aluminum plate of the present invention, a nonporous anodic oxide film having a porosity of 5% or less is formed on the surface of pure aluminum or an aluminum alloy, and a resin comprising a modified epoxy resin on the nonporous anodic oxide film A film is coated, the nonporous anodic oxide film has a thickness of 30 to 200 nm, the resin film has a thickness of 3 to 20 μm, and the modified epoxy resin has a modification rate of 50% or less. It is characterized by that.
以下に、その構成及び条件の限定理由について説明する。
［純アルミニウム又はアルミニウム合金］
本発明では、基材として純アルミニウム又はアルミニウム合金が用いられる。純アルミニウム基材としては純度９９．０％以上の純アルミニウムを用いることができる。また、アルミニウム合金基材としては、種々のアルミニウム合金を用いることができ、本発明としては特にその組成が限定されるものではない。好適には、１０００系、３０００系（Ａｌ−Ｍｎ系）合金、５０００系（Ａｌ−Ｍｇ系）合金などを挙げることができる。以下では、純アルミニウム又はアルミニウム合金を単にアルミニウムと表記する。
The reasons for limiting the configuration and conditions will be described below.
[Pure aluminum or aluminum alloy]
In the present invention, pure aluminum or an aluminum alloy is used as the base material. Pure aluminum having a purity of 99.0% or more can be used as the pure aluminum substrate. Moreover, as an aluminum alloy base material, various aluminum alloys can be used, and the composition is not particularly limited in the present invention. Preferable examples include 1000 series, 3000 series (Al-Mn series) alloys, 5000 series (Al-Mg series) alloys, and the like. Hereinafter, pure aluminum or an aluminum alloy is simply referred to as aluminum.
［無孔質陽極酸化皮膜（有孔率５％以下）］
樹脂を被覆する下地として無孔質陽極酸化皮膜がアルミニウム表面に設けられている。
ここで、無孔質陽極酸化皮膜とは、皮膜が均一に形成された部位の断面観察において、皮膜表面からアルミニウム素地に向けて、規則的に形成される孔（通常開口部は１〜１０ｎｍで皮膜厚さに対して６０％以上の深さを有する）が５％（表面から見た孔の総面積の比率）以下（孔が存在しないものも含まれる）の無孔質な皮膜である。有孔率がゼロ％の無孔質な皮膜は、有孔率が数％の皮膜に対して、格段に耐食性に優れるのでより好ましい。
なお、無孔質陽極酸化皮膜が薄いと、均一な皮膜形成が難しく、樹脂との密着性が低下する。そのため、膜厚は３０ｎｍ以上が好ましく、５０ｎｍ以上がより好ましい。一方、膜厚が厚いと、深絞り加工時に陽極酸化皮膜のクラックが発生し、樹脂との密着性が低下する。そのため、膜厚は２００ｎｍ以下が好ましく、１５０ｎｍ以下がより好ましい。
[Nonporous anodic oxide film (porosity 5% or less)]
A nonporous anodic oxide film is provided on the aluminum surface as a base for coating the resin.
Here, the non-porous anodic oxide film refers to pores that are regularly formed from the surface of the film toward the aluminum substrate (normally the opening is 1 to 10 nm) in cross-sectional observation of the site where the film is uniformly formed. It is a non-porous film having a depth of 60% or more with respect to the film thickness) and 5% (the ratio of the total area of the holes viewed from the surface) or less (including those having no holes). A non-porous film having a porosity of zero% is more preferable because it has much better corrosion resistance than a film having a porosity of several%.
If the nonporous anodic oxide film is thin, it is difficult to form a uniform film and the adhesion to the resin is lowered. Therefore, the film thickness is preferably 30 nm or more, and more preferably 50 nm or more. On the other hand, if the film thickness is large, cracks in the anodized film occur during deep drawing, and the adhesion to the resin is reduced. Therefore, the film thickness is preferably 200 nm or less, and more preferably 150 nm or less.
［樹脂膜］
樹脂膜は、高温高湿下での耐久性・耐熱性向上、電子部品表面の絶縁性確保等のために設けられ、この樹脂膜自体の伸びを改善し、可塑性をさらに向上させて、密着性、耐肌荒れ性を良くするために、変性エポキシ樹脂が用いられる。変性の内容としては、例えば、脂肪族変性（ジカルボン酸、モノカルボン酸、アルキルフェノールなどによる）、ウレタン変性などが挙げられる。変性率が高くなり過ぎると、耐熱性や耐溶剤性が劣化するおそれがあるので、５０％以下とするのが好ましい。２０〜４０％の変性率とするのがより好ましい。
形成する変性エポキシ樹脂の厚さは、性能を確保するため適切な厚さが望ましい。厚さが薄いと、ケース加工時に樹脂に割れが生じやすく、性能が劣る。このため３μｍ以上が好ましく、５μｍ以上がより好ましい。一方、変性エポキシ樹脂が厚過ぎると経済的に不合理である。このため２０μｍ以下が好ましく、８μｍ以下がより好ましい。
[Resin film]
The resin film is provided to improve durability and heat resistance under high temperature and high humidity, to ensure the insulation of the surface of electronic parts, etc., improving the elongation of the resin film itself, further improving the plasticity, and improving adhesion In order to improve the rough skin resistance, a modified epoxy resin is used. Examples of the contents of modification include aliphatic modification (with dicarboxylic acid, monocarboxylic acid, alkylphenol, etc.), urethane modification, and the like. If the modification rate becomes too high, the heat resistance and solvent resistance may be deteriorated. More preferably, the modification rate is 20 to 40%.
The thickness of the modified epoxy resin to be formed is preferably an appropriate thickness to ensure performance. If the thickness is thin, the resin is liable to crack during case processing, and the performance is poor. For this reason, 3 micrometers or more are preferable and 5 micrometers or more are more preferable. On the other hand, if the modified epoxy resin is too thick, it is economically unreasonable. For this reason, 20 micrometers or less are preferable and 8 micrometers or less are more preferable.
［シランカップリング剤］
本発明の樹脂被覆アルミニウム板において、前記樹脂膜は前記無孔質陽極酸化皮膜の上に０．５〜１０ｍｇ／ｍ２の塗布量のシランカップリング剤を介して設けられているとよい。
無孔質陽極酸化皮膜にシランカップリング剤を塗布してエポキシ樹脂を被覆することでエポキシ樹脂でも無孔質陽極酸化皮膜に対して高い密着性が得られ、絞り比の高いケース成形が可能となる。
シランカップリング剤にはアミノ系、エポキシ系、アクリル系等を用いることができ、本発明としては特定のものに限定されるものではない。
シランカップリング剤の塗布量は、その機能を良好にするため適量が望ましい。少ないと密着性向上の効果は認められない。０．５ｍｇ／ｍ２以上が好ましく、１ｍｇ／ｍ２がより好ましい。一方、シランカップリング剤をあまりに多く塗布すると、シランカップリング剤自体の凝集力が低下する場合があり、塗膜が剥離しやすくなる。このため、１０ｍｇ／ｍ２以下が好ましく、５ｍｇ／ｍ２以下がより好ましい。
[Silane coupling agent]
In the resin-coated aluminum plate of the present invention, the resin film may be provided on the nonporous anodic oxide film via a silane coupling agent having a coating amount of 0.5 to 10 mg / m 2 .
By applying a silane coupling agent to the nonporous anodic oxide film and coating the epoxy resin, high adhesion to the nonporous anodic oxide film can be obtained even with an epoxy resin, enabling case molding with a high drawing ratio. Become.
As the silane coupling agent, amino-based, epoxy-based, acrylic-based and the like can be used, and the present invention is not limited to a specific one.
The application amount of the silane coupling agent is preferably an appropriate amount in order to improve its function. If it is less, the effect of improving the adhesion is not recognized. 0.5 mg / m 2 or more is preferable, and 1 mg / m 2 is more preferable. On the other hand, if too much silane coupling agent is applied, the cohesive strength of the silane coupling agent itself may be reduced, and the coating film is easily peeled off. For this reason, 10 mg / m 2 or less is preferable, and 5 mg / m 2 or less is more preferable.
本発明の製造方法は、前記樹脂被覆アルミニウム板の製造方法であって、前記変性エポキシ樹脂の焼き付け材料温度を２００〜２８０℃とすることを特徴とする。
もう少し詳しく述べると、アルミニウム基板上に液体樹脂塗料を塗布、又はフィルムを貼付した後に、高温短時間の加熱、いわゆる焼き付け処理を行うことにより、基板表面を被覆するものである。
変性エポキシ樹脂は、焼き付け時に脱水反応により硬化して密着する。焼き付け材料温度が２００℃未満では耐水性が十分でなく、加水分解により密着性が低下するおそれがあり、２８０℃を超えると、塗膜の変色、劣化が生じるおそれがあるので好ましくない。脱水反応を促進させるために通常よりも高温とするとよく、２４０〜２６０℃の焼き付け温度とするのがより好ましい。
The production method of the present invention is a method for producing the resin-coated aluminum plate, wherein the baking temperature of the modified epoxy resin is 200 to 280 ° C.
More specifically, the surface of the substrate is coated by applying a liquid resin paint or applying a film on the aluminum substrate, followed by high-temperature and short-time heating, so-called baking treatment.
The modified epoxy resin is cured and adhered by a dehydration reaction during baking. If the baking material temperature is less than 200 ° C., the water resistance is not sufficient, and the adhesion may be lowered by hydrolysis. If it exceeds 280 ° C., the coating film may be discolored or deteriorated, which is not preferable. In order to promote the dehydration reaction, the temperature may be higher than usual, and a baking temperature of 240 to 260 ° C. is more preferable.
また、本発明の製造方法は、前記樹脂被覆アルミニウム板の製造方法であって、前記変性エポキシ樹脂を焼き付け冷却した後、１８０〜２４０℃の温度に０．５時間以上再加熱することを特徴とする。
変性エポキシ樹脂の焼き付け材料温度を高くする代わりに、再加熱して脱水反応を促進させるのである。焼き付け材料温度を高くできない変性種の場合等に特に効果的である。再加熱温度が１８０℃未満、あるいは時間が０．５時間未満では脱水が十分でなく、密着性が低下するおそれがあり、２４０℃を超えると、塗膜の変色、劣化が生じるおそれがあるので好ましくない。再加熱条件としては、２００〜２２０℃で１時間以上がより好ましい。この再加熱する場合は、樹脂の焼き付け材料温度は例えば２３０℃未満であってもよい。なお、加熱時間の上限としては２時間も行えば十分である。
The production method of the present invention is a production method of the resin-coated aluminum plate, wherein the modified epoxy resin is baked and cooled, and then reheated to a temperature of 180 to 240 ° C. for 0.5 hours or more. To do.
Instead of increasing the temperature of the baking material for the modified epoxy resin, it is reheated to accelerate the dehydration reaction. This is particularly effective in the case of a modified species that cannot raise the baking material temperature. If the reheating temperature is less than 180 ° C. or less than 0.5 hour, dehydration is not sufficient and the adhesion may be lowered, and if it exceeds 240 ° C., discoloration and deterioration of the coating film may occur. It is not preferable. The reheating condition is more preferably 200 to 220 ° C. for 1 hour or longer. In the case of reheating, the temperature of the resin baking material may be, for example, less than 230 ° C. It should be noted that the upper limit of the heating time is sufficient for 2 hours.
本発明によれば、無孔質陽極酸化皮膜に変性エポキシ樹脂を被覆したので、変色や白濁等に対する優れた耐食性を有するとともに、樹脂の伸びが改善されて加工性がさらに向上し、加工度が高くても剥離の発生が防止される。 According to the present invention, since the non-porous anodic oxide film is coated with the modified epoxy resin, it has excellent corrosion resistance against discoloration, white turbidity, etc., and the elongation of the resin is improved to further improve the workability and the workability. Even if it is high, the occurrence of peeling is prevented.
以下、本発明に係る樹脂被覆アルミニウム板の一実施形態を説明する。
この樹脂被覆アルミニウム板は、純アルミニウム又はアルミニウム合金表面に有孔率５％以下の無孔質陽極酸化皮膜が形成され、この無孔質陽極酸化皮膜の上に変性エポキシ系樹脂からなる樹脂膜がシランカップリング剤を介して被覆されてなり、前記無孔質陽極酸化皮膜の膜厚は３０〜２００ｎｍであり、前記樹脂膜の膜厚は３〜２０μｍであり、前記変性エポキシ樹脂の変性率が５０％以下である。
Hereinafter, an embodiment of a resin-coated aluminum plate according to the present invention will be described.
In this resin-coated aluminum plate, a nonporous anodic oxide film having a porosity of 5% or less is formed on the surface of pure aluminum or an aluminum alloy, and a resin film made of a modified epoxy resin is formed on the nonporous anodic oxide film. It is coated via a silane coupling agent, the nonporous anodic oxide film has a thickness of 30 to 200 nm, the resin film has a thickness of 3 to 20 μm, and the modification rate of the modified epoxy resin is 50% or less.
アルミニウムとして、１０００系、３０００系（Ａｌ−Ｍｎ系）合金、５０００系（Ａｌ−Ｍｇ系）合金などを用いる。このアルミニウムに対し、陽極酸化処理を行う。 As the aluminum, 1000 series, 3000 series (Al-Mn series) alloy, 5000 series (Al-Mg series) alloy, or the like is used. Anodization treatment is performed on this aluminum.
［陽極酸化］
陽極酸化処理に先立って前処理を行う。前処理は特に限定されるものではない。例えば、アルカリ性の脱脂液で洗浄し、水酸化ナトリウム水溶液でアルカリエッチング、硝酸水溶液でデスマット処理を行う。
陽極酸化処理は、酸化皮膜の溶解力が低い電解液を用いて行い、電圧を調整して好適には厚さ３０〜２００ｎｍの無孔質陽極酸化皮膜を形成させる。
陽極酸化の電解液は、リン酸アンモニウム、リン酸水素アンモニウム、リン酸二水素アンモニウム、リン酸アンモニウムといったリン酸塩、もしくは珪酸ナトリウム、珪酸カリウム、珪酸リチウムといった珪酸塩の水溶液であれば、酸化被膜の溶解力が低く、有孔率５％以下の無孔質陽極酸化皮膜が形成される。
陽極酸化皮膜の膜厚は、好ましくは、３０ｎｍ以上、より好ましくは５０ｎｍ以上で、好ましくは２００ｎｍ以下、より好ましくは１５０ｎｍ以下とする。
[anodization]
A pretreatment is performed prior to the anodizing treatment. The pretreatment is not particularly limited. For example, it is washed with an alkaline degreasing solution, alkali etched with an aqueous sodium hydroxide solution, and desmutted with an aqueous nitric acid solution.
The anodizing treatment is performed using an electrolytic solution having a low dissolving power of the oxide film, and the voltage is adjusted to form a nonporous anodized film having a thickness of preferably 30 to 200 nm.
If the anodizing electrolyte is an aqueous solution of a phosphate such as ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, or ammonium phosphate, or an aqueous solution of silicate such as sodium silicate, potassium silicate, or lithium silicate, an oxide film Thus, a nonporous anodic oxide film having a porosity of 5% or less is formed.
The film thickness of the anodized film is preferably 30 nm or more, more preferably 50 nm or more, preferably 200 nm or less, more preferably 150 nm or less.
［シランカップリング剤］
陽極酸化皮膜表面に、アミノ系、エポキシ系、アクリル系等のシランカップリング剤を塗布することで、樹脂との密着性を向上させる。シランカップリング剤の塗布量は、好ましくは０．５ｍｇ／ｍ２以上、より好ましくは１ｍｇ／ｍ２以上とし、好ましくは１０ｍｇ／ｍ２以下、より好ましくは５ｍｇ／ｍ２以下、とする。
[Silane coupling agent]
Adhesion with the resin is improved by applying an amino-based, epoxy-based or acrylic-based silane coupling agent to the surface of the anodized film. The coating amount of the silane coupling agent is preferably 0.5 mg / m 2 or more, more preferably 1 mg / m 2 or more, preferably 10 mg / m 2 or less, more preferably 5 mg / m 2 or less.
［樹脂膜］
シランカップリング剤を塗布したアルミニウム陽極酸化板の表面に、変性エポキシ系樹脂からなる樹脂膜を被覆する。この樹脂膜は、塗料を塗布して加熱乾燥により焼き付けるか、フィルムを加熱溶解して貼り合わせてもよい。塗布方法は、ロールコート法、スプレーコート法、バーコート法、ディップ法、などを用いることができる。
変性エポキシ系樹脂は、ビスフェノールＡ型、ビスフェノールＦ型、ノボラック型などをベースに、例えば、脂肪族変性（ジカルボン酸、モノカルボン酸、アルキルフェノールなどによる）、ウレタン変性などの変性処理がなされたものを用いることができる。
この変性エポキシ樹脂を用いることにより、樹脂膜自体の伸びを改善し、可塑性をさらに向上させて、密着性、耐肌荒れ性を良くする。変性率が高くなり過ぎると、耐熱性や耐溶剤性が劣化するおそれがあるので、５０％以下とするのが好ましい。２０〜４０％の変性率とするのがより好ましい。
この樹脂膜の厚さは、好ましくは３μｍ以上、より好ましくは５μｍ以上で、好ましくは２０μｍ以下、より好ましくは８μｍ以下とする。
[Resin film]
A resin film made of a modified epoxy resin is coated on the surface of an aluminum anodized plate coated with a silane coupling agent. The resin film may be bonded by applying a paint and baking it by heat drying, or by heating and dissolving the film. As a coating method, a roll coating method, a spray coating method, a bar coating method, a dip method, or the like can be used.
The modified epoxy resin is based on bisphenol A type, bisphenol F type, novolak type, etc., for example, modified with aliphatic modification (by dicarboxylic acid, monocarboxylic acid, alkylphenol, etc.), urethane modification, etc. Can be used.
By using this modified epoxy resin, the elongation of the resin film itself is improved, the plasticity is further improved, and the adhesion and rough skin resistance are improved. If the modification rate becomes too high, the heat resistance and solvent resistance may be deteriorated. More preferably, the modification rate is 20 to 40%.
The thickness of the resin film is preferably 3 μm or more, more preferably 5 μm or more, preferably 20 μm or less, more preferably 8 μm or less.
この変性エポキシ樹脂は、焼き付け時に脱水反応により硬化して密着する。焼き付け材料温度は２００〜２８０℃とするのが好ましく、２００℃未満では耐水性が十分でなく、加水分解により密着性が低下するおそれがあり、２８０℃を超えると、塗膜の変色、劣化が生じるおそれがあるので好ましくない。脱水反応を促進させるために通常よりも高温とするとよく、２４０〜２６０℃の焼き付け温度とするのがより好ましい。 This modified epoxy resin is cured and adhered by a dehydration reaction during baking. The baking material temperature is preferably 200 to 280 ° C. If it is less than 200 ° C, the water resistance is not sufficient, and the adhesion may be lowered by hydrolysis. If it exceeds 280 ° C, discoloration and deterioration of the coating film may occur. Since it may occur, it is not preferable. In order to promote the dehydration reaction, the temperature may be higher than usual, and a baking temperature of 240 to 260 ° C. is more preferable.
以上により得られる樹脂被覆アルミニウム板は、絞り加工などの成形加工を経て電解コンデンサケースなどに好適に利用される。但し、本発明の樹脂被覆アルミニウム板としては、利用分野がこれに限定されるものではなく、電化製品、容器、機械部品などの用途にも利用することができる。 The resin-coated aluminum plate obtained as described above is suitably used for an electrolytic capacitor case or the like after forming such as drawing. However, the application field of the resin-coated aluminum plate of the present invention is not limited to this, and it can also be used for applications such as electrical appliances, containers, and machine parts.
なお、変性エポキシ樹脂の変性種によっては、焼き付け温度を前述の高温にまで高めることができない場合があるので、その場合は、焼き付け後に再加熱するとよい。再加熱条件としては、１８０〜２４０℃の温度で０．５時間以上とされる。温度が１８０℃未満、あるいは時間が０．５時間未満では脱水が十分でなく、密着性が低下するおそれがあり、２４０℃を超えると、塗膜の変色、劣化が生じるおそれがあるので好ましくない。２００〜２２０℃で１時間以上がより好ましい。 Note that, depending on the modified species of the modified epoxy resin, the baking temperature may not be increased to the above-described high temperature. In that case, it is preferable to reheat after baking. As reheating conditions, a temperature of 180 to 240 ° C. is set to 0.5 hours or longer. If the temperature is less than 180 ° C, or if the time is less than 0.5 hours, dehydration is not sufficient and the adhesion may be lowered. If it exceeds 240 ° C, discoloration and deterioration of the coating film may occur, which is not preferable. . One hour or more is more preferable at 200 to 220 ° C.
以下に、本発明の実施例を説明する。
厚さ０．３ｍｍのＪＩＳ１１００アルミニウム板を、５％水酸化ナトリウム水溶液で５０℃で１０秒間エッチングして脱脂処理した後、１０秒間水洗した。さらに、１０％硝酸溶液に室温で１０秒間浸漬して中和した後、１０秒間水洗して乾燥した。
次いで、ケイ酸塩水溶液を電解液として、所定の電解電圧で陽極酸化処理を行った。電解時間は、無孔質陽極酸化皮膜が十分形成される時間とした。
陽極酸化処理後、１０秒間水洗して乾燥し、さらにシランカップリング剤を表１に示す量で塗布した。比較例として、下地処理をリン酸クロメート処理としたもの、シランカップリング剤を塗布しなかったものも作製した。
Examples of the present invention will be described below.
A 0.3 mm thick JIS1100 aluminum plate was degreased by etching with a 5% aqueous sodium hydroxide solution at 50 ° C. for 10 seconds, and then washed with water for 10 seconds. Furthermore, it was neutralized by being immersed in a 10% nitric acid solution at room temperature for 10 seconds, washed with water for 10 seconds and dried.
Next, an anodic oxidation treatment was performed at a predetermined electrolytic voltage using an aqueous silicate solution as an electrolytic solution. The electrolysis time was set to a time for sufficiently forming the nonporous anodic oxide film.
After the anodizing treatment, it was washed with water for 10 seconds and dried, and a silane coupling agent was applied in an amount shown in Table 1. As a comparative example, a base treatment with a phosphate chromate treatment and a silane coupling agent not applied were prepared.
上記で形成された無孔質陽極酸化皮膜の膜厚を以下の方法で測定した。
すなわち、陽極酸化後の皮膜表面について、任意の２０箇所を５万倍の電子顕微鏡で観察し、全面積に対する孔の面積の割合を求めた。膜厚は、皮膜をダイヤモンド刃を備えたスーパーミクロトームで切断し、切断した断面を透過顕微鏡観察して測定した。
得られた陽極酸化皮膜の表面に、表１に示す変性率による変性エポキシ系樹脂塗料を、表１の膜厚になるようにバーコーターで塗布し、焼付けした。変性種はウレタンとした。焼き付け時間は４０秒とし、焼き付け温度を表１に示すように変えて焼き付けた。焼き付け後に再加熱（２００℃×１時間）を加えたものは再加熱「有」とし、焼き付けた後に再加熱することなく供試材としたものを再加熱「無」とした。
The film thickness of the nonporous anodic oxide film formed above was measured by the following method.
That is, about 20 points | pieces with the 50,000 times electron microscope about the film | membrane surface after anodization, the ratio of the area of the hole with respect to the whole area was calculated | required. The film thickness was measured by cutting the film with a supermicrotome equipped with a diamond blade and observing the cut section with a transmission microscope.
A modified epoxy resin coating having a modification rate shown in Table 1 was applied to the surface of the obtained anodized film with a bar coater so as to have a film thickness shown in Table 1, and baked. The modified species was urethane. The baking time was 40 seconds, and the baking temperature was changed as shown in Table 1 for baking. The sample that was reheated after baking (200 ° C. × 1 hour) was reheated “Yes”, and the sample material that was baked and not reheated was reheated “No”.
得られた供試材について、以下の項目について評価し、その結果を表１に示した。
密着性評価：圧延率６０％で冷間圧延した後、碁盤目試験を行ない、残マス数を百分率で表した。残マス数６０％以上を合格とした。
耐肌荒れ性：圧延率６０％で冷間圧延した後、樹脂膜の表面状態を顕微鏡で観察することにより、３段階評価し、肌荒れが認められなかったものを◎、若干の肌荒れが認められたものの実用上問題ないとされるものを○、微小クラック等による肌荒れが認められたものを×とした。
熱着色性：２６０℃×１０分間で加熱し、加熱後の着色度合いを目視で評価した。着色が全く認められなかったものを◎、若干の着色が認められたが実用上問題ないとされるものを○、着色が認められたものを×とした。
高温高湿耐久性（耐加水分解性の指標となる）：オートクレーブにて１２１℃×２４時間後の樹脂の状態を目視で評価した。変化なしが◎、わずかな変化が認められるものの実用上問題なしとされるものを○、劣化したものを×とした。
The obtained test materials were evaluated for the following items, and the results are shown in Table 1.
Adhesion evaluation: After cold rolling at a rolling rate of 60%, a cross cut test was conducted, and the number of remaining masses was expressed as a percentage. The remaining mass number of 60% or more was regarded as acceptable.
Surface roughness resistance: After cold rolling at a rolling rate of 60%, the surface state of the resin film was observed with a microscope, and was evaluated in three stages. A case where no surface roughness was observed was ◎, and some surface roughness was observed. The case where there was no problem in practical use was rated as o, and the case where rough skin due to microcracks was recognized as x.
Thermal coloring property: Heated at 260 ° C. for 10 minutes, and the degree of coloring after heating was visually evaluated. The case where coloring was not recognized at all was marked as ◎, the case where some coloring was recognized but practically no problem was marked as ◯, and the case where coloring was recognized as x.
High-temperature and high-humidity durability (becomes an index for hydrolysis resistance): The state of the resin after 121 hours × 24 hours in an autoclave was visually evaluated. No change was indicated as ◎, a slight change was recognized, but no problem was found in practical use, and 劣化 was indicated as deteriorated.
表１から明らかなように、本発明の樹脂被覆アルミニウム板では、優れた密着性、耐肌荒れ性、耐熱着色性、高温高湿耐久性を有している。
なお、本発明は上記実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。
As is apparent from Table 1, the resin-coated aluminum plate of the present invention has excellent adhesion, rough skin resistance, heat-resistant coloring, and high-temperature and high-humidity durability.
In addition, this invention is not limited to the said embodiment, A various change can be added in the range which does not deviate from the meaning of this invention.
Claims (4)
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| JP2015136890A (en) * | 2014-01-23 | 2015-07-30 | 三菱アルミニウム株式会社 | Resin-coated aluminum sheet and method for producing the same |
| JP2016083794A (en) * | 2014-10-23 | 2016-05-19 | 三菱アルミニウム株式会社 | Resin-coated aluminum sheet and method for producing the same |
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