JP3200365B2 - Manufacturing method of fluororesin coated aluminum alloy member - Google Patents
Manufacturing method of fluororesin coated aluminum alloy memberInfo
- Publication number
- JP3200365B2 JP3200365B2 JP15749496A JP15749496A JP3200365B2 JP 3200365 B2 JP3200365 B2 JP 3200365B2 JP 15749496 A JP15749496 A JP 15749496A JP 15749496 A JP15749496 A JP 15749496A JP 3200365 B2 JP3200365 B2 JP 3200365B2
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- aluminum alloy
- net
- oxide film
- anodic oxide
- 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 - Fee Related
Links
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 238000011282 treatment Methods 0.000 claims description 85
- 239000010407 anodic oxide Substances 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 30
- 238000007789 sealing Methods 0.000 claims description 30
- 239000011247 coating layer Substances 0.000 claims description 27
- 238000007788 roughening Methods 0.000 claims description 26
- 238000005096 rolling process Methods 0.000 claims description 18
- 238000007743 anodising Methods 0.000 claims description 15
- 238000005422 blasting Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 26
- 239000002585 base Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】この発明は表面フッ素樹脂塗
膜を形成したアルミニウム合金部材の製造方法に関する
ものであり、特にアルミニウム合金基材の表面に陽極酸
化皮膜を形成してからその陽極酸化皮膜上にフッ素樹脂
塗膜を形成したアルミニウム合金部材の製造方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an aluminum alloy member having a surface fluororesin coating film formed thereon, and more particularly to a method for forming an anodic oxide film on a surface of an aluminum alloy substrate and then forming the anodic oxide film on the surface. And a method for manufacturing an aluminum alloy member having a fluororesin coating film formed thereon.
【０００２】[0002]
【従来の技術】フッ素樹脂は、優れた表面潤滑性を有す
るところから、アルミニウム合金からなる基材の表面に
フッ素樹脂塗膜を形成した部材が、例えばフライパンや
炊飯器等の厨房部品、あるいはプリンタやファクシミ
リ、コピー機などの定着用ヒートロール、そのほか“こ
げつき”や汚れの付着の防止、あるいは傷付き防止が望
まれる種々の用途に従来から広く使用されている。2. Description of the Related Art Since fluororesin has excellent surface lubricity, a member formed by coating a fluororesin coating on the surface of a base material made of an aluminum alloy can be used, for example, in kitchen parts such as frying pans and rice cookers, or in printers. It has been widely used for fixing rolls such as facsimile machines, facsimile machines, copiers, etc., and various other applications where prevention of "burning" and adhesion of dirt or prevention of scratching is desired.
【０００３】ところでフッ素樹脂、特に高級用途のＰＴ
ＦＥ、ＰＦＡ、ＦＥＰなどのフッ素樹脂は、アルミニウ
ム合金に対する親和性がほとんどないため、アルミニウ
ム合金基材表面に直接フッ素樹脂を塗装、焼付けした場
合、基材表面に対するフッ素樹脂塗膜の密着性が弱く、
そこでフッ素樹脂塗装アルミニウム合金部材を製造する
にあたっては、一般に予めアルミニウム合金基材表面に
化学的エッチングによる粗面化処理や電気化学的エッチ
ングによる粗面化処理、あるいはブラッシングやブラス
トなどの機械的粗面化処理を施して微細な凹凸を形成し
ておき、その凹凸によるアンカー効果によってフッ素樹
脂塗膜の密着性を確保することが行なわれている。By the way, fluororesins, especially PT for high-grade applications
Fluorine resins such as FE, PFA, and FEP have little affinity for aluminum alloys. Therefore, when the fluororesin is directly applied to the aluminum alloy substrate surface and baked, the adhesion of the fluororesin coating film to the substrate surface is weak. ,
Therefore, when manufacturing a fluororesin-coated aluminum alloy member, in general, a surface roughening treatment by chemical etching or a roughening treatment by electrochemical etching, or a mechanically rough surface such as brushing or blasting is performed on the surface of the aluminum alloy base material. It has been practiced to form fine irregularities by performing a surface treatment, and to secure the adhesion of the fluororesin coating film by an anchor effect due to the irregularities.
【０００４】一方、フッ素樹脂塗膜はピンホールが生じ
やすいため、このピンホールを通じてアルミニウム合金
基材が腐食されやすく、そこでフッ素樹脂の塗装前に予
めアルミニウム合金基材表面に陽極酸化処理を施してお
き、フッ素樹脂塗膜の下地面を陽極酸化皮膜としておく
ことによって、耐食性を向上させることが従来から行な
われている。なおこの陽極酸化処理と前述のような基材
表面の粗面化処理とを併用する場合、陽極酸化処理前に
粗面化処理を行なって基材表面に微細な凹凸を形成し、
その後に陽極酸化処理を施すのが通常である。[0004] On the other hand, since the fluororesin coating film easily forms pinholes, the aluminum alloy substrate is easily corroded through the pinholes. Conventionally, the corrosion resistance has been improved by setting the lower ground of the fluororesin coating film as an anodic oxide film. When using the anodizing treatment and the surface roughening treatment of the base material as described above in combination, forming a rough surface on the base material surface by performing a roughening treatment before the anodizing treatment,
After that, an anodic oxidation treatment is usually performed.
【０００５】[0005]
【発明が解決しようとする課題】上述のようにアルミニ
ウム合金基材表面に粗面化処理を施し、陽極酸化皮膜を
形成してからフッ素樹脂の塗装、焼付けを行なえば、耐
食性が良好でしかもフッ素樹脂塗膜の密着性がある程度
良好なフッ素樹脂塗装アルミニウム合金部材が得られ
る。しかしながら実際にこのようにしてフッ素樹脂塗装
アルミニウム合金部材を製造した場合、必ずしも充分な
フッ素樹脂塗膜の密着性が得られるとは限らないのが実
情であった。As described above, if the surface of the aluminum alloy substrate is roughened to form an anodized film and then coated and baked with a fluororesin, the corrosion resistance is good and the fluorine is good. A fluororesin-coated aluminum alloy member having a certain degree of adhesion of the resin coating film can be obtained. However, when the fluororesin-coated aluminum alloy member was actually manufactured in this way, it was a fact that sufficient adhesion of the fluororesin coating film was not always obtained.
【０００６】すなわち、フッ素樹脂塗膜の密着性をより
高めるべく、陽極酸化処理前の粗面化の程度を大きくす
れば、粗面の凹凸の程度や凹凸の形状によっては陽極酸
化皮膜が著しく脆弱化して剥落しやすくなり、その上に
フッ素樹脂塗膜を形成した場合に逆に素材に対するフッ
素樹脂塗膜の密着性が低下してしまうことがある。一
方、粗面化の程度が不足すれば、アンカー効果が充分に
得られないため、フッ素樹脂塗膜の充分な密着性を確保
することが困難となる。したがって陽極酸化処理前の粗
面化処理によっては、確実かつ安定して優れた密着性を
得ることは困難であった。That is, if the degree of surface roughening before the anodic oxidation treatment is increased in order to further increase the adhesion of the fluororesin coating film, the anodic oxide film is extremely fragile depending on the degree of unevenness of the rough surface and the shape of the unevenness. When a fluororesin coating is formed thereon, the adhesion of the fluororesin coating to the material may be reduced. On the other hand, if the degree of surface roughening is insufficient, the anchor effect cannot be sufficiently obtained, so that it is difficult to ensure sufficient adhesion of the fluororesin coating film. Therefore, it has been difficult to surely and stably obtain excellent adhesion by the surface roughening treatment before the anodizing treatment.
【０００７】この発明は以上の事情を背景としてなされ
たもので、アルミニウム合金基材表面の陽極酸化皮膜上
にフッ素樹脂を塗装、焼付けした部材として、耐食性に
優れるばかりでなく、フッ素樹脂の塗膜の密着性が確実
かつ安定して優れたフッ素樹脂塗装アルミニウム合金部
材を製造する方法を提供することを目的とするものであ
る。The present invention has been made in view of the above circumstances, and as a member obtained by coating and baking a fluororesin on an anodic oxide film on the surface of an aluminum alloy substrate, not only has excellent corrosion resistance, but also a fluororesin coating film. It is an object of the present invention to provide a method for producing a fluororesin-coated aluminum alloy member having excellent and stable adhesion.
【０００８】[0008]
【課題を解決するための手段】前述のような課題を解決
するべく本発明者等が鋭意実験・検討を重ねた結果、ア
ルミニウム合金基材表面の陽極酸化皮膜に、網目の径が
特定の範囲内にあるネット状のクラックを形成し、その
ネット状クラックにフッ素樹脂を侵入含浸させることに
よって、耐食性と密着性とを兼ね備えたフッ素樹脂塗装
アルミニウム合金部材が得られること、さらに上述のよ
うに網目の径が特定の範囲内にあるネット状のクラック
を有する陽極酸化皮膜を形成するために必要なプロセ
ス、条件を見出し、この発明をなすに至ったのである。The inventors of the present invention have conducted intensive experiments and studies in order to solve the above-mentioned problems. As a result, the diameter of the mesh on the anodic oxide film on the surface of the aluminum alloy base material is within a specific range. By forming a net-like crack in the inside and impregnating and impregnating the net-like crack with a fluororesin, a fluororesin-coated aluminum alloy member having both corrosion resistance and adhesion can be obtained. The present inventors have found the processes and conditions necessary for forming an anodic oxide film having a net-like crack having a specific diameter within a specific range, and have accomplished the present invention.
【０００９】[0009]
【００１０】[0010]
【００１１】具体的には、請求項１の発明のフッ素樹脂
塗装アルミニウム合金部材の製造方法は、アルミニウム
合金からなる基材の表面に陽極酸化処理を施して２〜３
０μｍの厚みの陽極酸化皮膜を生成させた後、封孔処理
を行ない、その後１５０℃以上の温度に３℃／ｍｉｎ以
上の加熱速度で昇温させる空焼き処理を行ない、しかる
後、陽極酸化皮膜表面にフッ素樹脂を塗装、焼付けして
１０〜７０μｍの厚みのフッ素樹脂塗膜層を形成し、こ
れによって、陽極酸化皮膜にネット状クラックが形成さ
れていてかつネット状クラックの単位網目部分の最大径
が５〜３００μｍの範囲内にあり、しかもそのネット状
クラック内にフッ素樹脂が前記塗膜層から連続して侵入
含浸されているフッ素樹脂塗装アルミニウム合金部材を
得ることを特徴とするものである。More specifically, the method for producing a fluororesin-coated aluminum alloy member according to the first aspect of the present invention comprises the steps of:
After forming an anodic oxide film having a thickness of 0 μm, a sealing treatment is performed, and then a baking treatment is performed to raise the temperature to 150 ° C. or more at a heating rate of 3 ° C./min or more. The surface is coated with a fluororesin and baked to form a fluororesin coating layer having a thickness of 10 to 70 μm, whereby a net-like crack is formed on the anodic oxide film and a maximum of a unit network portion of the net-like crack is formed. It is characterized in that a fluororesin-coated aluminum alloy member having a diameter in the range of 5 to 300 μm and in which the fluorocarbon resin continuously penetrates and impregnates the net-like cracks from the coating layer is obtained. .
【００１２】一方請求項２の発明のフッ素樹脂塗装アル
ミニウム合金部材の製造方法は、アルミニウム合金から
なる基材の表面に陽極酸化処理を施して２〜３０μｍの
厚みの陽極酸化皮膜を生成させた後、ショットブラスト
もしくは合計圧延率が５％以下の２方向以上のスキンパ
ス圧延を行ない、しかる後、陽極酸化皮膜表面にフッ素
樹脂を塗装、焼付けして１０〜７０μｍの厚みのフッ素
樹脂塗膜層を形成し、これによって、陽極酸化皮膜にネ
ット状クラックが形成されていてかつネット状クラック
の単位網目部分の最大径が５〜３００μｍの範囲内にあ
り、しかもそのネット状クラック内にフッ素樹脂が前記
塗膜層から連続して侵入含浸されているフッ素樹脂塗装
アルミニウム合金部材を得ることを特徴とするものであ
る。According to a second aspect of the present invention, there is provided a method for producing a fluororesin-coated aluminum alloy member, comprising the steps of: subjecting a surface of an aluminum alloy to anodizing treatment to form an anodized film having a thickness of 2 to 30 μm; Then, shot blasting or skin pass rolling in two or more directions with a total rolling ratio of 5% or less is performed, and then a fluororesin is applied to the surface of the anodic oxide film and baked to form a fluororesin coating layer having a thickness of 10 to 70 μm. As a result, a net-like crack is formed on the anodic oxide film, the maximum diameter of the unit mesh portion of the net-like crack is in the range of 5 to 300 μm, and the fluororesin is coated in the net-like crack. The present invention is characterized in that a fluororesin-coated aluminum alloy member continuously infiltrated and impregnated from a film layer is obtained.
【００１３】そしてまた請求項３の発明のフッ素樹脂塗
装アルミニウム合金部材の製造方法は、請求項１もしく
は請求項２に記載のフッ素樹脂塗装アルミニウム合金部
材の製造方法において、アルミニウム合金からなる基材
に対する前記陽極酸化処理の前に、予め基材表面に、粗
度Ｒｚが３〜１５μｍとなるように粗面化処理を施して
おくことを特徴とするものである。According to a third aspect of the present invention, there is provided a method of manufacturing a fluororesin-coated aluminum alloy member according to the first or second aspect, wherein Prior to the anodizing treatment, the surface of the base material is previously subjected to a surface roughening treatment so as to have a roughness Rz of 3 to 15 μm.
【００１４】次にこの発明の方法によって得られるフッ
素樹脂塗装アルミニウム合金部材の構成および作用につ
いて説明する。Next, the structure and operation of the fluororesin-coated aluminum alloy member obtained by the method of the present invention will be described.
【００１５】この発明の方法によるフッ素樹脂塗装アル
ミニウム合金部材の模式的な断面を図１に示し、またフ
ッ素樹脂塗膜層を除去した状態での陽極酸化皮膜の表面
状況（クラック発生状況）を模式的に図２に示す。図１
において、アルミニウム合金基材１の表面部分には陽極
酸化皮膜２が形成され、その陽極酸化皮膜２上にフッ素
樹脂塗膜層３が形成されている。そして前記陽極酸化皮
膜２には、図２に模式的に示すようなネット状のクラッ
ク４が形成されている。ここで、ネット状のクラックと
は、各クラックが陽極酸化皮膜の表面に平行な面内にお
いて連続しており、かつそのクラックが多数の箇所で前
記面内において２方向以上に分岐して、しかもその分岐
した先のクラックもさらに連続しかつ２ケ所以上に分岐
している構造のクラックを意味する。具体的には、亀甲
状、モザイク状、格子状、その他各種不定形状をなす種
々の網目形状が複合したもの、ということができる。FIG. 1 shows a schematic cross section of a fluororesin-coated aluminum alloy member according to the method of the present invention. FIG. 1 schematically shows the surface condition (crack occurrence condition) of the anodic oxide film with the fluororesin coating layer removed. FIG. FIG.
2, an anodic oxide film 2 is formed on the surface of an aluminum alloy substrate 1, and a fluororesin coating layer 3 is formed on the anodic oxide film 2. The anodic oxide film 2 has a net-like crack 4 as schematically shown in FIG. Here, the net-shaped crack means that each crack is continuous in a plane parallel to the surface of the anodic oxide film, and the crack is branched in two or more directions in the plane at many places, and The crack at the branch point also means a crack having a structure that is further continuous and branched to two or more places. Specifically, it can be said to be a composite of various mesh shapes forming a tortoiseshell shape, a mosaic shape, a lattice shape, and other various indefinite shapes.
【００１６】上述のような陽極酸化皮膜２のネット状ク
ラック４内には、図１に示すようにその上のフッ素樹脂
皮膜３から連続するフッ素樹脂３Ａが侵入含浸されてい
る。ここで、ネット状クラック内へのフッ素樹脂の侵入
含浸は、フッ素樹脂塗膜層を形成するためのフッ素樹脂
塗装焼付け時になされるが、塗装焼付け処理後の冷却時
に基材、陽極酸化皮膜が収縮してクラックの開口度が縮
小される際にクラック内のフッ素樹脂が締め付けられ、
しかもクラック内のフッ素樹脂はネット状クラックに沿
って面方向に連続、分岐したネット状をなしているた
め、そのクラック内のフッ素樹脂と一体化しているフッ
素樹脂塗膜層が陽極酸化皮膜に対して強力に保持され、
極めて高い密着性を示すことになる。As shown in FIG. 1, the fluororesin 3A continuous from the fluororesin film 3 thereon penetrates and impregnates into the net-like cracks 4 of the anodic oxide film 2 as described above. Here, the penetration and impregnation of the fluororesin into the net-like cracks is performed at the time of baking of the fluororesin paint for forming the fluororesin coating layer, but the base material and the anodic oxide film shrink during cooling after the baking treatment. When the opening degree of the crack is reduced, the fluorine resin in the crack is tightened,
In addition, since the fluororesin in the crack is continuous and branched in the surface direction along the net-like crack, the fluororesin coating layer integrated with the fluororesin in the crack is not anodic oxide film. And strongly held,
It will exhibit extremely high adhesion.
【００１７】ここで、陽極酸化皮膜のネット状クラック
は、各単位網目部分の最大径Ｌ（図２参照）が、５〜３
００μｍの範囲内にあることが必要である。単位網目部
分の最大径Ｌが５μｍ未満ではクラックの分布密度が高
くなり過ぎて陽極酸化皮膜が脆くなり、そのため逆に密
着性が低下してしまう。一方、逆に３００μｍを越える
場合には、陽極酸化皮膜へのフッ素樹脂食い込み部分の
分布密度が少な過ぎて、フッ素樹脂塗膜層の充分な密着
力向上効果が得られない。Here, the maximum diameter L (see FIG. 2) of each unit mesh portion of the net-like crack of the anodic oxide film is 5 to 3 mm.
It must be within the range of 00 μm. If the maximum diameter L of the unit network portion is less than 5 μm, the distribution density of cracks becomes too high, and the anodic oxide film becomes brittle, and consequently, the adhesion decreases. On the other hand, if the thickness exceeds 300 μm, the distribution density of the portion where the fluororesin bites into the anodic oxide film is too low, and a sufficient effect of improving the adhesion of the fluororesin coating layer cannot be obtained.
【００１８】さらに陽極酸化皮膜は、その厚みが２〜３
０μｍの範囲内であることが必要である。陽極酸化皮膜
の膜厚が２μｍ未満ではネット状クラックを形成するこ
とが困難となり、また仮にネット状クラックが形成され
たとしてもその深さが浅く、それに伴なってフッ素樹脂
の侵入深さも小さくなるため、充分な密着力を得ること
ができない。一方陽極酸化皮膜の膜厚を３０μｍを越え
て厚くしても、耐食性は飽和し、コスト上昇を招くだけ
である。なおネット状クラックは陽極酸化皮膜が厚いほ
ど形成させやすいから、陽極酸化皮膜の厚みは２〜３０
μｍの範囲内でも特に１０μｍ以上が好ましい。Further, the anodic oxide film has a thickness of 2-3.
It must be within the range of 0 μm. If the thickness of the anodic oxide film is less than 2 μm, it is difficult to form a net-like crack, and even if a net-like crack is formed, its depth is shallow, and accordingly, the penetration depth of the fluororesin becomes small. Therefore, sufficient adhesion cannot be obtained. On the other hand, even if the thickness of the anodic oxide film exceeds 30 μm, the corrosion resistance is saturated and the cost is merely increased. Note that the thickness of the anodic oxide film is 2 to 30 since the net-like crack is easily formed as the anodic oxide film is thicker.
Even within the range of μm, it is particularly preferably 10 μm or more.
【００１９】一方フッ素樹脂塗膜層の厚さとしては、耐
摩耗性、摺動潤滑性等の点から１０〜７０μｍの範囲内
であることが必要である。１０μｍ未満ではこれらの効
果が充分に得られず、一方７０μｍを越えて厚くするこ
とは、経済的に無駄となるだけである。On the other hand, the thickness of the fluororesin coating layer must be in the range of 10 to 70 μm from the viewpoint of wear resistance, sliding lubrication and the like. If the thickness is less than 10 μm, these effects cannot be sufficiently obtained. On the other hand, increasing the thickness beyond 70 μm is only economically useless.
【００２０】基材のアルミニウム合金の種類、成分組成
は、基本的に特に限定されるものではなく、要は最終的
な用途、要求特性に応じて最適のものを選択すれば良い
が、陽極酸化処理−封孔処理−空焼き処理−フッ素樹脂
塗装焼付け処理のプロセスによって陽極酸化皮膜にネッ
ト状のクラックを生ぜしめやすいアルミニウム合金を用
いることが望ましい。本発明者等の研究によれば、２．
０ｗｔ％以上のＭｇ、３．０ｗｔ％以上のＺｎ、０．７
ｗｔ％以上のＭｎのうちいずれか１種または２種以上を
含有しているアルミニウム合金の場合に、前記プロセス
で陽極酸化皮膜にネット状クラックを生じさせやすいこ
とが判明した。但しＭｇ量が６．０ｗｔ％以上となれば
圧延加工が困難となり、Ｚｎ量が７．０ｗｔ％以上とな
れば陽極酸化皮膜の耐食性が低下し、Ｍｎ量が３．０ｗ
ｔ％以上となれば粗大な金属間化合物が生成されて圧延
性や成形加工性を損ないやすいから、Ｍｇを含有させる
場合のＭｇ量は２．０ｗｔ％以上、６．０ｗｔ％未満、
Ｚｎを含有させる場合のＺｎ量は３．０ｗｔ％以上、
７．０ｗｔ％未満、Ｍｎを含有させる場合のＭｎ量は
０．７ｗｔ％以上、３．０ｗｔ％未満の範囲内とするこ
とが望ましい。なお上記のＭｇ，Ｚｎ，Ｍｎ以外の合金
元素については、陽極酸化皮膜に対するネット状クラッ
クの形成に本質的な影響は与えず、したがってＪＩＳ規
格やＡＡ規格によって規定される各種アルミニウム合金
に含まれる程度は含有されていても良い。The type and composition of the aluminum alloy as the base material are not particularly limited, and the most important thing is to select the most suitable one according to the final use and required characteristics. It is desirable to use an aluminum alloy that easily causes net-like cracks in the anodic oxide film by the processes of treatment, sealing, baking, and baking of fluororesin paint. According to the research of the present inventors, 2.
0 wt% or more Mg, 3.0 wt% or more Zn, 0.7
It has been found that in the case of an aluminum alloy containing one or more of Mn of wt% or more, net cracks are easily generated in the anodized film in the above process. However, when the Mg content is 6.0 wt% or more, rolling becomes difficult, and when the Zn content is 7.0 wt% or more, the corrosion resistance of the anodic oxide film is reduced, and the Mn content is 3.0 w / w.
When the content is more than t%, a coarse intermetallic compound is generated and the rollability and the formability are easily impaired. Therefore, when Mg is contained, the amount of Mg is 2.0 wt% or more and less than 6.0 wt%.
When Zn is contained, the Zn content is 3.0 wt% or more,
It is desirable that the amount of Mn is less than 7.0 wt% and the content of Mn is 0.7 wt% or more and less than 3.0 wt%. Note that alloy elements other than Mg, Zn, and Mn do not have an essential effect on the formation of net-like cracks in the anodic oxide film, and are therefore contained in various aluminum alloys specified by JIS and AA standards. May be contained.
【００２１】次にこの発明のフッ素樹脂塗装アルミニウ
ム合金部材の製造方法のうち、先ず請求項１の発明の方
法について説明する。Next, of the method for manufacturing a fluororesin-coated aluminum alloy member of the present invention, the method of the first aspect of the present invention will be described first.
【００２２】この発明のフッ素樹脂塗装アルミニウム合
金部材の製造にあたっては、常法によって製造されたア
ルミニウム合金基材に対して、基本的には先ず陽極酸化
処理を施せば良いが、フッ素樹脂塗膜層の密着性をより
向上させるため、あるいはフッ素樹脂塗装後の表面をマ
ット状に調整するため、必要に応じて請求項３に規定し
たように、陽極酸化処理前に予め予備処理として基材表
面に粗面化処理を施しても良い。In manufacturing the fluororesin-coated aluminum alloy member of the present invention, the aluminum alloy substrate manufactured by a conventional method may be basically first subjected to anodizing treatment. In order to further improve the adhesion of the base material or to adjust the surface after the fluororesin coating to a mat-like shape, the surface of the base material is preliminarily treated as a preliminary treatment before the anodic oxidation treatment, if necessary, as defined in claim 3. A roughening treatment may be performed.
【００２３】この粗面化処理としては、酸性エッチング
液あるいはアルカリエッチング液を用いた化学的粗面化
処理、あるいは電解エッチングを利用した電気化学的粗
面化処理、さらにはブラッシングやブラスト等の機械的
エッチングのいずれを用いても、あるいはこれらのいく
つかを組合せても良い。但し、粗面化処理による凹凸が
大き過ぎたり、凸部の幅が狭かったりした場合には、陽
極酸化皮膜が脆弱となってかえって密着性が低下するお
それがある。具体的には、表面粗さがＲｚ値で１５μｍ
を越えればかえって密着性が劣るようになり、Ｒｚが３
μｍ未満では粗面化による密着性向上の効果が得られな
いから、予め粗面化処理を施す場合には、表面粗さがＲ
ｚ値で３〜１５μｍの範囲内となるように調整する必要
がある。As the surface roughening treatment, a chemical surface roughening treatment using an acidic etching solution or an alkali etching solution, an electrochemical surface roughening treatment using electrolytic etching, and a machine such as brushing or blasting are used. Any of the typical etchings may be used, or some of them may be combined. However, if the roughness due to the surface roughening treatment is too large or the width of the protrusion is narrow, the anodic oxide film may become brittle and the adhesion may be reduced. Specifically, the surface roughness is 15 μm in Rz value.
If R exceeds 3, the adhesiveness becomes worse, and Rz is 3
If the surface roughness is less than μm, the effect of improving the adhesion due to the surface roughening cannot be obtained.
It is necessary to adjust the z value so that it is in the range of 3 to 15 μm.
【００２４】陽極酸化処理については、形成される陽極
酸化皮膜が厚く、また硬質である方がネット状クラック
を導入しやすくなる。そこで陽極酸化処理としては硫酸
浴電解を適用することが望ましく、またその場合の条件
としては、硫酸濃度２００ｇ／ｌ未満、電流密度１Ａ／
ｄｍ2 以上、浴温２０℃以下、溶存Ａｌ濃度２０ｇ／ｌ
未満とすることが望ましい。これらの条件範囲内の硫酸
浴陽極酸化処理を施せば、単位網目部分の最大径５〜３
００μｍのネット状クラックを導入しやすくなる。なお
これらの条件を外れてもネット状クラックを形成し得る
こともあるが、単位網目部分の最大径を３００μｍ以下
に調整することが困難となることが多い。Regarding the anodic oxidation treatment, the thicker and harder the anodic oxide film formed, the easier it is to introduce net-like cracks. Therefore, it is desirable to apply sulfuric acid bath electrolysis as the anodic oxidation treatment. In this case, the conditions are that the sulfuric acid concentration is less than 200 g / l and the current density is 1 A /
dm 2 or more, bath temperature 20 ° C. or less, dissolved Al concentration 20 g / l
It is desirable to be less than. By performing the sulfuric acid bath anodic oxidation treatment within these condition ranges, the maximum diameter of the unit mesh portion is 5 to 3 mm.
It becomes easy to introduce a net-shaped crack of 00 μm. It should be noted that a net-like crack may be formed even if these conditions are not satisfied, but it is often difficult to adjust the maximum diameter of the unit mesh portion to 300 μm or less.
【００２５】さらに陽極酸化処理後には、封孔処理を行
なう必要がある。すなわち、封孔処理を行なっておくこ
とによってネット状クラックの芽（起点）を形成させ、
その後の空焼き処理で陽極酸化皮膜にネット状クラック
の芽を成長させ、さらにその後のフッ素樹脂の塗装焼付
けにおいてネット状クラックを完成させることが可能と
なるのである。After the anodizing treatment, it is necessary to perform a sealing treatment. That is, the buds (starting points) of net-like cracks are formed by performing the sealing treatment,
Subsequent baking treatment allows the growth of net-like cracks to grow on the anodic oxide film, and it is possible to complete the net-like cracks in the subsequent baking of a fluororesin.
【００２６】この封孔処理としては、ネット状クラック
の芽を充分に生成させるためには、８０℃以上で１０分
上の浸漬処理、あるいは常圧下または加圧下での５分以
上の蒸気封孔処理を適用することが望ましい。浸漬封孔
の場合、蒸留水を用いるか、あるいは酢酸Ｎｉ、硫酸Ｃ
ｏ等の封孔助剤を添加した封孔液を用いれば良い。この
浸漬処理の場合、封孔液の温度が８０℃以下では、最終
的に単位網目部分の最大径が５〜３００μｍの範囲内の
ネット状クラックを形成するための芽を生成させること
が困難となり、また封孔処理の時間が１０分未満でも同
様である。一方蒸気封孔の場合、処理時間が５分未満で
も同様に単位網目部分の最大径が５〜３００μｍの範囲
内のネット状クラックの芽を形成することが困難とな
る。In order to sufficiently generate buds of net-like cracks, the sealing treatment may be immersion treatment at 80 ° C. or more for 10 minutes, or steam sealing at normal pressure or under pressure for 5 minutes or more. It is desirable to apply processing. In the case of immersion sealing, use distilled water, Ni acetate acetate, sulfuric acid C
A sealing liquid containing a sealing aid such as o may be used. In the case of this immersion treatment, when the temperature of the sealing liquid is 80 ° C. or lower, it is difficult to generate buds for forming net-like cracks in the range where the maximum diameter of the unit network portion is finally in the range of 5 to 300 μm. The same applies when the time for the sealing treatment is less than 10 minutes. On the other hand, in the case of steam sealing, even if the treatment time is less than 5 minutes, similarly, it is difficult to form a bud of a net-like crack in which the maximum diameter of the unit mesh portion is in the range of 5 to 300 μm.
【００２７】上述のように封孔処理を行なった後には、
３℃／ｍｉｎ以上の加熱速度で１５０℃以上の温度に昇
温する空焼き処理を行なう。この空焼き処理は、封孔処
理と同様に、最終的に単位網目部分の最大径が５〜３０
０μｍの範囲内のネット状クラックを形成するために必
要な工程であり、この空焼き処理を施すことによって、
封孔処理が導入されたネット状クラックの芽が成長し、
一部ではネット状クラックの形成が開始される。すなわ
ち、陽極酸化皮膜の熱膨張率はアルミニウム合金基材の
母材合金部分の熱膨張率よりも格段に小さいため、空焼
き処理の昇温過程での母材合金部分の熱膨張によってク
ラックの芽が成長し、一部ではクラックが連続するよう
になる。この空焼き処理の加熱昇温速度が３℃／ｍｉｎ
未満、昇温到達温度が１５０℃未満では、最終的に前記
サイズのネット状クラックを形成することが困難とな
る。なおこの空焼き処理において１５０℃以上の温度に
到達した後には、基本的にはその到達温度で保持する必
要はないが、保持する場合は経済性の点から３０分以下
が望ましい。但し、その後に塗布されるフッ素樹脂塗膜
層の均一性を確保しまたブリスターの発生を防止するた
めに陽極酸化皮膜の表面の汚れを焼き飛ばす必要がある
場合には、３〜４時間程度保持しても良い。一方空焼き
処理における昇温到達温度の上限は特に限定しないが、
基材の溶解を防止しまた陽極酸化皮膜の剥離を防止する
ためには、６００℃以下とすることが望ましい。さら
に、空焼き処理の昇温速度の上限も特に限定しないが、
通常の加熱設備では３００℃／ｍｉｎ程度以下が限界と
なる。After performing the sealing treatment as described above,
An empty baking process is performed in which the temperature is increased to 150 ° C. or more at a heating rate of 3 ° C./min or more. In this empty baking process, similarly to the sealing process, the maximum diameter of the unit mesh portion finally becomes 5 to 30.
This is a step necessary for forming a net-like crack in a range of 0 μm.
Growing buds of net-like cracks introduced with sealing treatment,
In some cases, the formation of net-like cracks is started. That is, since the coefficient of thermal expansion of the anodic oxide film is much smaller than the coefficient of thermal expansion of the base metal alloy portion of the aluminum alloy base material, crack sprouts due to the thermal expansion of the base metal alloy portion during the temperature rise process of the baking treatment. Grow, and cracks become continuous in part. The heating rate of this empty baking process is 3 ° C./min.
If the temperature is less than 150 ° C., it is difficult to finally form a net crack having the above-mentioned size. After reaching a temperature of 150 ° C. or more in this baking process, it is basically not necessary to hold the temperature at that temperature, but if it is held, it is preferably 30 minutes or less from the viewpoint of economy. However, if it is necessary to burn off the dirt on the surface of the anodic oxide film in order to ensure the uniformity of the fluororesin coating layer applied thereafter and to prevent blistering, hold for about 3 to 4 hours. You may. On the other hand, the upper limit of the temperature attained in the baking process is not particularly limited,
In order to prevent the dissolution of the base material and the peeling of the anodic oxide film, the temperature is desirably 600 ° C. or lower. Further, the upper limit of the heating rate of the baking process is not particularly limited,
In ordinary heating equipment, the limit is about 300 ° C./min or less.
【００２８】上述のように空焼き処理を施した後には、
フッ素樹脂の塗装、焼付けを行なって、フッ素樹脂塗膜
層を形成する。フッ素樹脂の塗装、焼付けは常法に従っ
て行なえば良いが、塗装は、フッ素樹脂微粒子の懸濁液
を塗布もしくは吹付けたりすれば良い。また塗装後の焼
付けは一般には３００〜４００℃の高温で１０〜６０分
程度行なうのが通常である。このように焼付け時におい
ては、３００〜４００℃程度の高温で基材のアルミニウ
ム合金が熱膨張して、陽極酸化皮膜との熱膨張差によ
り、その前の封孔処理で成長したクラックがさらに成長
して相互に連続し、単位網目部分の最大径が５〜３００
μｍの範囲内の微細なネット状クラックの完成に至る。
ここで、上述のような基材のアルミニウム合金の熱膨張
によって、焼付け時における陽極酸化皮膜の表面におけ
るクラックの開口幅は平均１μｍ以上となり、溶融した
フッ素樹脂がクラック内に容易に侵入し、クラック内に
フッ素樹脂が充填されることになる。そして焼付け終了
後の冷却過程でアルミニウム合金基材が収縮するに伴な
って陽極酸化皮膜の開口幅が狭くなり、クラック内のフ
ッ素樹脂が強固に喰え込まれた状態となり、そのクラッ
ク内のフッ素樹脂に一体的に連続する塗膜層が高い密着
力で保持されることになる。After performing the baking process as described above,
The fluororesin is coated and baked to form a fluororesin coating layer. The coating and baking of the fluororesin may be performed according to a conventional method, but the coating may be performed by applying or spraying a suspension of fluororesin fine particles. Further, baking after coating is generally performed at a high temperature of 300 to 400 ° C. for about 10 to 60 minutes. As described above, at the time of baking, the aluminum alloy of the base material thermally expands at a high temperature of about 300 to 400 ° C., and due to a difference in thermal expansion between the aluminum alloy and the anodic oxide film, cracks grown in the previous sealing process further grow. And the maximum diameter of the unit mesh portion is 5 to 300
A fine net-like crack in the range of μm is completed.
Here, due to the thermal expansion of the aluminum alloy of the base material as described above, the opening width of cracks on the surface of the anodic oxide film at the time of baking becomes 1 μm or more on average, and the molten fluororesin easily penetrates into the cracks. Is filled with the fluororesin. Then, in the cooling process after the baking, the opening width of the anodic oxide film becomes narrower as the aluminum alloy base material shrinks, and the fluororesin in the crack becomes firmly engulfed. Thus, a coating layer that is continuously integrated with the substrate is held with high adhesion.
【００２９】ここで、請求項１の発明の方法により陽極
酸化皮膜のクラックがネット状に形成される理由につい
ては、次のように考えられる。Here, the reason why the cracks of the anodic oxide film are formed in a net shape by the method of the present invention is considered as follows.
【００３０】陽極酸化処理時に陽極酸化皮膜が生成され
るにあたっては皮膜が体積膨張し、その後に封孔処理を
行なうことによって陽極酸化皮膜がさらに体積膨張す
る。しかしながら、陽極酸化皮膜と基材のアルミニウム
合金との界面は強固に密着しているため、陽極酸化皮膜
が平面方向に膨張することはできない。そのため封孔処
理を行なった後の陽極酸化皮膜は、平面方向に全方位か
ら均等に圧縮力を受けている。そしてこの圧縮力によっ
てクラックの芽（起点）が形成され、ネット状に割れる
ようなクラックの芽となる。その後、空焼き処理を行な
うことによって前述の熱膨張差によりネット状クラック
の芽が確立するとともに一部のクラックは成長し、さら
にフッ素樹脂の塗装焼付けによってクラックがさらに成
長して連続的なネット状クラックとなるのである。When the anodic oxide film is formed during the anodizing treatment, the film expands in volume, and then the sealing treatment is performed to further expand the anodic oxide film. However, since the interface between the anodic oxide film and the aluminum alloy as the substrate is firmly adhered, the anodic oxide film cannot expand in the plane direction. Therefore, the anodic oxide film after the sealing treatment is evenly subjected to a compressive force from all directions in the plane direction. The compressive force forms crack buds (starting points), which become crack buds that break into nets. Thereafter, the baking of the net-like cracks is established by the above-mentioned thermal expansion difference by performing the baking process, and some of the cracks grow, and the cracks further grow by the baking of the fluororesin, and the continuous net-like cracks are formed. It becomes a crack.
【００３１】ここで、封孔処理を行なわない場合には、
面内全方位の圧縮力が充分に与えられないため、その後
の空焼き−フッ素樹脂塗装焼付けを通じて仮にクラック
が生じたとしても、全方向に連続するネット状クラック
とはならない。また封孔処理後、空焼きを行なわずにフ
ッ素樹脂の塗装焼付けを行なった場合も、ネット状のク
ラックは形成され難く、また仮にネット状クラックが生
じたとしても、その分布が粗く、単位網目部分の最大径
が３００μｍ以下の微細なネット状とはならない。した
がって陽極酸化処理後の封孔処理と空焼き処理のいずれ
が欠けても、この発明で目的とする単位網目部分の最大
径が３００μｍ以下のネット状クラックを形成すること
は困難となるのである。Here, when the sealing process is not performed,
Since the in-plane omnidirectional compressive force is not sufficiently applied, even if cracks are formed during subsequent baking and baking with a fluororesin, the net-shaped cracks are not continuous in all directions. Also, in the case where the fluororesin is baked after the sealing treatment without baking, the net-like cracks are hardly formed, and even if the net-like cracks are formed, the distribution is coarse, and the unit network is hardly formed. It does not form a fine net shape having a maximum diameter of 300 μm or less. Therefore, irrespective of either the sealing treatment or the baking treatment after the anodic oxidation treatment, it is difficult to form a net-like crack having a maximum diameter of 300 μm or less in the unit network portion intended in the present invention.
【００３２】次に請求項２の製造方法について説明す
る。Next, the manufacturing method of claim 2 will be described.
【００３３】請求項２の発明の方法は、基本的には機械
的外力によって陽極酸化皮膜にネット状のクラックを形
成させるものであり、前記同様に陽極酸化処理前に予め
必要に応じてアルミニウム合金基材表面に粗面化処理を
施しても良い。粗面化処理の望ましい条件は既に述べた
場合と同様である。さらに、必要に応じて粗面化処理を
行なった後の陽極酸化処理も、前記同様に行なえば良
い。The method according to the second aspect of the present invention basically forms a net-like crack in the anodized film by mechanical external force. The surface of the base material may be subjected to a roughening treatment. Desirable conditions for the surface roughening treatment are the same as those described above. Further, if necessary, the anodic oxidation treatment after the surface roughening treatment may be performed in the same manner as described above.
【００３４】陽極酸化処理後の封孔処理は、請求項２の
発明の方法の場合は必須ではないが、必要に応じて前記
同様の条件で行なっても良い。The sealing treatment after the anodizing treatment is not essential in the case of the method according to the second aspect of the present invention, but may be performed under the same conditions as described above, if necessary.
【００３５】陽極酸化処理に引続いて、あるいは陽極酸
化処理後に封孔処理を行なってから、機械的にネット状
クラックを導入するための処理を行なう。この処理とし
ては、ショットブラストもしくは合計圧延率５％以下の
２方向以上のスキンパス圧延を適用する。Subsequent to the anodizing treatment or after the anodizing treatment, a sealing treatment is performed, and then a treatment for mechanically introducing a net crack is performed. As this processing, shot blasting or skin pass rolling in two or more directions with a total rolling reduction of 5% or less is applied.
【００３６】ショットブラストを適用した場合、陽極酸
化皮膜におけるボールの衝突した箇所を起点にして放射
状のクラックの芽が形成され、かつ複数のボールが陽極
酸化皮膜の異なる箇所に衝突することによって、多数の
放射状のクラックの芽が分散して形成されることにな
る。そしてその後の塗装焼付け処理において、前記同様
にクラックの芽が成長し、連続したネット状のクラック
が形成される。また場合によっては、ショットブラスト
の段階でネット状クラックの完成に至る。但し、ショッ
トブラストが強過ぎる場合には、陽極酸化皮膜が基材の
アルミニウム合金から剥離して、密着性、耐久性が低下
してしまうおそれがある。本発明者等の実験によれば、
ネット状クラックが形成された状態においてネット状ク
ラックの単位網目部分の最大径の平均が２０μｍ以下で
剥離が生じやすくなることが判明している。そこでショ
ットブラストを適用する場合には、ネット状クラックの
単位網目部分の最大径の平均が２０μｍ以下とならない
ようにショットブラストのボール径、材質、圧力等を調
整することが望ましい。When shot blasting is applied, radial crack buds are formed starting from the location where the ball collides with the anodic oxide coating, and a plurality of balls collide with different locations of the anodic oxide coating. Radial crack buds are dispersed and formed. Then, in the subsequent paint baking treatment, crack buds grow in the same manner as described above, and continuous net-like cracks are formed. In some cases, a net-like crack is completed at the stage of shot blasting. However, if the shot blast is too strong, the anodic oxide film may peel off from the aluminum alloy of the base material, and the adhesion and durability may be reduced. According to our experiments,
It has been found that in the state where the net-like cracks are formed, the average of the maximum diameters of the unit mesh portions of the net-like cracks is not more than 20 μm, so that the peeling easily occurs. Therefore, when applying shot blast, it is desirable to adjust the ball diameter, material, pressure, etc. of the shot blast so that the average of the maximum diameter of the unit mesh portion of the net-like crack does not become 20 μm or less.
【００３７】一方スキンパス圧延を行なった場合は、陽
極酸化皮膜は展延性に劣るためほとんど圧延方向に伸び
ないのに対し、基材のアルミニウム合金は圧延方向に伸
び、両者間の伸びの差によって陽極酸化皮膜にクラック
が発生する。そして２方向以上にスキンパス圧延するこ
とによって、面内２方向以上のクラックが形成される結
果、ネット状のクラックが形成されることになる。もち
ろん場合によっては２方向以上のスキンパス圧延時には
２方向以上のクラックの芽のみが導入され、その後のフ
ッ素樹脂塗装焼付け処理時にクラックが成長して連続
し、ネット状のクラックとなる場合もある。このように
２方向以上のスキンパス圧延によってネットク状クラッ
クを導入する場合、圧延率が２方向以上の合計で５％を
越えれば皮膜が剥離して、密着性と耐久性が低下するか
ら、合計圧延率は５％以下とする必要がある。On the other hand, when skin pass rolling is performed, the anodic oxide film hardly expands in the rolling direction due to poor ductility, whereas the aluminum alloy as the base material expands in the rolling direction, and the difference in elongation between the two increases the anodic oxide film. Cracks occur in the oxide film. Then, by performing skin pass rolling in two or more directions, cracks in two or more in-plane directions are formed. As a result, net-like cracks are formed. Of course, in some cases, only crack buds in two or more directions are introduced during skin pass rolling in two or more directions, and the cracks grow and continue to form net-like cracks during the subsequent baking treatment of fluororesin paint. When a net crack is introduced by skin pass rolling in two or more directions as described above, if the rolling ratio exceeds 5% in total in two or more directions, the coating peels off, and the adhesion and durability are reduced. The rate must be 5% or less.
【００３８】以上のようにして陽極酸化皮膜に機械的に
ネット状クラックもしくはその芽を導入した後には、前
記同様にフッ素樹脂の塗装焼付けを行なう。この塗装焼
付け時には、ネット状クラックの芽が成長し、連続した
ネット状クラックが完成されるとともに、塗装したフッ
素樹脂がネット状クラック内に侵入し、既に述べたと同
様に表面のフッ素樹脂塗膜層から連続一体に陽極酸化皮
膜中のネット状クラックにフッ素樹脂が侵入含浸された
部材が得られる。After mechanically introducing net-like cracks or their buds into the anodic oxide film as described above, baking of a fluororesin is performed in the same manner as described above. At the time of this paint baking, the buds of the net-like cracks grow and the continuous net-like cracks are completed, and the coated fluororesin penetrates into the net-like cracks, and the fluororesin coating layer on the surface as described above. Thus, a member in which the net-like cracks in the anodic oxide film are infiltrated and impregnated with the fluororesin continuously and integrally is obtained.
【００３９】なお上述のように機械的外力によってネッ
ト状クラックを導入する場合には、フッ素樹脂の塗装焼
付け前に空焼き処理を行なう必要はないが、表面の清浄
化のため、すなわち表面に付着している汚れを焼き飛ば
すために空焼きを行なっても良い。When the net-like cracks are introduced by a mechanical external force as described above, it is not necessary to perform the baking treatment before the baking of the fluororesin, but it is necessary to clean the surface, that is, to adhere to the surface. Empty baking may be performed in order to burn off the dirt that has been made.
【００４０】[0040]
［実施例１］表１、表２の条件符号Ａ〜Ｆに示す各合金
からなる圧延板を基材として用い、その表面に表１、表
２中に示す各条件で粗面化処理、陽極酸化処理、封孔処
理をその順に施した。但し一部のサンプルについては、
比較のため粗面化処理もしくは封孔処理を行なわなかっ
た。また封孔処理は、いずれも浸漬処理を適用した。[Example 1] Rolled plates made of alloys indicated by condition codes A to F in Tables 1 and 2 were used as a base material, and the surface thereof was subjected to a surface roughening treatment under the conditions shown in Tables 1 and 2 and an anode. An oxidation treatment and a sealing treatment were performed in that order. However, for some samples,
For comparison, no roughening treatment or sealing treatment was performed. In addition, immersion treatment was applied for all the sealing treatments.
【００４１】封孔処理後の各サンプルに対し、５℃／ｍ
ｉｎの加熱速度で昇温して２５０℃で３０分保持する空
焼き処理を行ない、さらにフッ素樹脂としてＰＦＡを用
いて膜厚２０μｍに塗布後、３８０℃×３０分の焼付け
を行なった。For each sample after the sealing treatment, 5 ° C./m
An air baking treatment was performed in which the temperature was raised at a heating rate of in and held at 250 ° C. for 30 minutes. Further, PFA was applied as a fluororesin to a thickness of 20 μm, followed by baking at 380 ° C. for 30 minutes.
【００４２】上記のプロセス中において、粗面化処理直
後の基材表面の粗度（Ｒｚ）を測定し、また最終的にフ
ッ素樹脂の塗装、焼付けを行なった後に表面の塗膜層を
除去して陽極酸化皮膜表面のクラック発生状況を調べ、
さらに密着性（耐剥離性）評価として、ＪＩＳ Ｋ５４
００に従い、碁盤目テープ法試験をフッ素樹脂塗装焼付
のままの状態、および水道水による２時間の煮沸後の状
態でそれぞれ２０回行なったので、これらの結果を表
３、表４に示す。During the above-mentioned process, the roughness (Rz) of the substrate surface immediately after the surface roughening treatment was measured, and finally, after coating and baking with a fluororesin, the coating film layer on the surface was removed. To check the state of cracks on the anodic oxide film surface,
Further, as evaluation of adhesion (peeling resistance), JIS K54
According to No. 00, the crosscut tape test was carried out 20 times in each of the state in which the fluororesin paint was baked and the state after boiling for 2 hours in tap water, and the results are shown in Tables 3 and 4.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【表２】 [Table 2]
【００４５】[0045]
【表３】 [Table 3]
【００４６】[0046]
【表４】 [Table 4]
【００４７】表１〜表４において、製造符号Ａ，Ｂ，Ｅ
はいずれもこの発明の製造プロセス条件に従って製造し
て、陽極酸化皮膜に単位網目部分の最大径が５〜３００
μｍの範囲内のネット状クラックが形成された例であ
り、そのうちＡ，Ｂは陽極酸化処理前に予めアルカリエ
ッチングによる粗面化処理を行なった例、Ｅは粗面化処
理を行なわなかった例である。そして本発明例Ａ，Ｂで
は碁盤目テープ法試験でも充分な耐剥離性を示し、フッ
素樹脂塗膜層の密着性が著しく優れていることが判明し
た。また本発明例Ｅでは粗面化処理を行なわなかったた
め、Ａ，Ｂよりも若干密着性は劣るが、他の比較例と比
べれば格段に優れた密着性を示すことが判明した。In Tables 1 to 4, production codes A, B, E
Are manufactured according to the manufacturing process conditions of the present invention, and the maximum diameter of the unit network portion is 5 to 300 in the anodic oxide film.
A case where net-like cracks in the range of μm were formed, wherein A and B were cases where surface roughening treatment was performed in advance by alkali etching before anodizing treatment, and E was cases where surface roughening treatment was not performed. It is. In Examples A and B of the present invention, it was found that even in the cross-cut tape test, sufficient peeling resistance was exhibited, and the adhesion of the fluororesin coating layer was remarkably excellent. Further, in Example E of the present invention, since the surface roughening treatment was not performed, the adhesiveness was slightly inferior to A and B, but it was found that the adhesiveness was remarkably excellent as compared with other comparative examples.
【００４８】一方製造符号Ｃは陽極酸化皮膜の膜厚が１
μｍとこの発明で規定する厚さ範囲に満たなかった比較
例であるが、この場合には陽極酸化皮膜にクラックが生
成されず、その結果フッ素樹脂塗膜層の密着性が劣って
いた。さらに製造符号Ｄは、ネット状クラックの形成に
有利なＭｇ，Ｚｎ，Ｍｎのいずれをも実質的に含有しな
いアルミニウム合金を基材として用いた比較例であっ
て、この場合は陽極酸化皮膜のクラックは粗大な縦長ブ
ロック状となり、この発明で規定する単位網目部分最大
径５〜３００μｍの範囲内のネット状クラックが得られ
ず、そのためフッ素樹脂塗膜層の密着性も劣っていた。
また製造符号Ｆは封孔処理を行なわなかった比較例であ
って、この場合は陽極酸化皮膜のクラックは一方向クラ
ックとなってしまい、フッ素樹脂塗膜層の密着性も劣っ
ていた。On the other hand, the production code C indicates that the thickness of the anodic oxide film is 1
In this case, no crack was formed in the anodized film, and as a result, the adhesion of the fluororesin coating layer was poor. Production code D is a comparative example using an aluminum alloy substantially free of any of Mg, Zn, and Mn, which is advantageous for forming a net-like crack, as a base material. Was in the form of a coarse vertical block, and a net-like crack having a unit network portion maximum diameter of 5 to 300 μm as defined in the present invention was not obtained, and thus the adhesion of the fluororesin coating layer was poor.
Production code F is a comparative example in which no sealing treatment was performed. In this case, the cracks in the anodic oxide film were one-way cracks, and the adhesion of the fluororesin coating layer was poor.
【００４９】ここで、本発明例Ａによって得られたフッ
素樹脂塗装アルミニウム合金部材について、アルミニウ
ム合金基材および陽極酸化皮膜をエッチングによって除
去した後のフッ素樹脂の状況を裏面側（アルミニウム合
金基材が位置していた側）からの状況を、図３、図４に
示す。図３は垂直方向に見た状況、図４は垂直方向に対
し傾斜した方向から見た状況であり、これらの図から、
陽極酸化皮膜のネット状クラックに沿ってフッ素樹脂が
ネット状に侵入していることが観察される。Here, regarding the fluororesin-coated aluminum alloy member obtained in Example A of the present invention, the condition of the fluororesin after the aluminum alloy substrate and the anodic oxide film were removed by etching was changed to the back side (the aluminum alloy substrate was FIG. 3 and FIG. 4 show the situation from the side where it was located). FIG. 3 shows a situation when viewed in the vertical direction, and FIG. 4 shows a situation when viewed from a direction inclined with respect to the vertical direction.
It is observed that the fluororesin penetrates the net along the net cracks of the anodized film.
【００５０】［実施例２］表５に示すような条件でアル
ミニウム合金基材表面に粗面化処理、陽極酸化処理、封
孔処理を行なった後、機械的クラック導入手段として、
圧延率２％のスキンパス圧延を、各圧延方向が直交する
ように２方向に行ない、その後洗浄してからフッ素樹脂
としてＰＦＡを膜厚２０μｍで塗布して焼付けた。焼付
け条件は３８０℃×３０分とした。Example 2 After subjecting the surface of the aluminum alloy substrate to a roughening treatment, an anodic oxidation treatment and a sealing treatment under the conditions shown in Table 5, a mechanical crack introducing means was used.
Skin pass rolling at a rolling rate of 2% was performed in two directions so that the rolling directions were orthogonal to each other, and after washing, PFA was applied as a fluororesin in a film thickness of 20 μm and baked. The baking condition was 380 ° C. × 30 minutes.
【００５１】上記プロセス中において、粗面化処理直後
の基材表面の粗度（Ｒｚ）を測定し、また最終的にフッ
素樹脂の塗装、焼付けを行なった後に陽極酸化皮膜表面
のクラック発生状況を調べた。さらにフッ素樹脂塗膜層
の密着性（耐剥離性）評価として実施例１と同様な碁盤
目テープ法試験を行なった。これらの結果を表６に示
す。During the above process, the roughness (Rz) of the surface of the substrate immediately after the surface roughening treatment was measured, and finally, after the coating and baking of a fluororesin, the state of occurrence of cracks on the surface of the anodic oxide film was measured. Examined. Further, a cross-cut tape test similar to that in Example 1 was performed to evaluate the adhesion (peeling resistance) of the fluororesin coating layer. Table 6 shows the results.
【００５２】[0052]
【表５】 [Table 5]
【００５３】[0053]
【表６】 [Table 6]
【００５４】表６から明らかなように、２方向のスキン
パス圧延によって陽極酸化皮膜にネット状クラックを導
入した実施例２の場合も、フッ素樹脂塗膜層の密着性が
実施例１の場合と同様に優れていることが判明した。As is apparent from Table 6, in the case of Example 2 in which net cracks were introduced into the anodized film by skin pass rolling in two directions, the adhesion of the fluororesin coating layer was the same as in Example 1. Turned out to be excellent.
【００５５】[0055]
【発明の効果】請求項１〜請求項３の発明の製造方法に
よって得られたフッ素樹脂塗装アルミニウム合金部材に
おいては、表面のフッ素樹脂塗膜層から一体に連続する
フッ素樹脂が、その下側の陽極酸化皮膜に形成された単
位網目部分最大径５〜３００μｍのネット状クラック内
に侵入含浸されて、フッ素樹脂塗膜層が強固に固定され
ているため、フッ素樹脂塗膜層の密着性が確実かつ安定
して優れており、また陽極酸化皮膜の存在により耐食性
も優れている。したがって請求項１〜請求項３の発明の
製造方法によれば、フッ素樹脂塗膜層の密着性が優れる
と同時に耐食性も優れるフッ素樹脂塗装アルミニウム合
金部材を、実際の量産的規模の製造において確実かつ安
定して容易に製造することができる。In the fluororesin-coated aluminum alloy member obtained by the production method according to the first to third aspects of the present invention, the fluororesin integrally continuous from the fluororesin coating layer on the surface is formed on the lower side. The unit network formed on the anodic oxide film is penetrated and impregnated into net-like cracks with a maximum diameter of 5 to 300 μm, and the fluororesin coating layer is firmly fixed. It is stable and excellent, and has excellent corrosion resistance due to the presence of the anodic oxide film. Therefore, according to the manufacturing method of the invention of claims 1 to 3, a fluororesin-coated aluminum alloy member having excellent corrosion resistance as well as excellent adhesion of the fluororesin coating layer can be reliably and practically manufactured on a mass production scale. It can be manufactured stably and easily.
【００５６】[0056]
【００５７】[0057]
【図１】この発明のフッ素樹脂塗装アルミニウム合金部
材の一例を示す模式的な縦断面図である。FIG. 1 is a schematic longitudinal sectional view showing an example of a fluororesin-coated aluminum alloy member of the present invention.
【図２】この発明のフッ素樹脂塗装アルミニウム合金部
材におけるフッ素樹脂を除去した状態での陽極酸化皮膜
の表面のクラック発生状況の一例を模式的に示す平面図
である。FIG. 2 is a plan view schematically showing an example of a state of occurrence of cracks on the surface of the anodic oxide film in a state where the fluororesin is removed from the fluororesin-coated aluminum alloy member of the present invention.
【図３】この発明の実施例１における製造符号Ａによる
フッ素樹脂塗装アルミニウム合金部材において、アルミ
ニウム合金基材および陽極酸化皮膜を溶解除去した状態
のフッ素樹脂の状況を裏面側（基材が位置していた側）
から示す拡大顕微鏡組織写真で、垂直方向から見た組織
写真である。FIG. 3 shows the condition of the fluororesin in a state where the aluminum alloy base material and the anodic oxide film are dissolved and removed in the fluororesin-coated aluminum alloy member with production code A in Example 1 of the present invention on the back side (where the base material is located). Side)
1 is an enlarged microscopic structure photograph shown in FIG.
【図４】この発明の実施例１における製造符号Ａによる
フッ素樹脂塗装アルミニウム合金部材において、アルミ
ニウム合金基材および陽極酸化皮膜を溶解除去した状態
のフッ素樹脂の状況を表面側（基材が位置していた側）
から示す拡大顕微鏡組織写真で、垂直方向に対し傾斜し
た方向から見た組織写真である。FIG. 4 shows the condition of the fluororesin in a state where the aluminum alloy base material and the anodic oxide film are dissolved and removed on the front side (the base material is located) in the fluororesin-coated aluminum alloy member according to the production code A in Example 1 of the present invention. Side)
3 is a magnified microstructure photograph taken from the direction shown in FIG.
１ 基材 ２ 陽極酸化皮膜 ３ フッ素樹脂塗膜層 ４ クラック DESCRIPTION OF SYMBOLS 1 Substrate 2 Anodized film 3 Fluorine resin coating layer 4 Crack
───────────────────────────────────────────────────── フロントページの続き (72)発明者 野本 賢二 東京都中央区日本橋室町４丁目３番18号 スカイアルミニウム株式会社内 (56)参考文献 特開 昭50−12128（ＪＰ，Ａ) 特開 昭60−255996（ＪＰ，Ａ) 特開 昭54−45641（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 11/00- 11/24 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Kenji Nomoto 4-3-1-8 Nihonbashi Muromachi, Chuo-ku, Tokyo Inside Sky Aluminum Co., Ltd. (56) References JP-A-50-12128 (JP, A) JP-A Sho 60-255996 (JP, A) JP-A-54-45641 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C25D 11 / 00-11 / 24
Claims (3)
陽極酸化処理を施して２〜３０μｍの厚みの陽極酸化皮
膜を生成させた後、封孔処理を行ない、その後１５０℃
以上の温度に３℃／ｍｉｎ以上の加熱速度で昇温させる
空焼き処理を行ない、しかる後、陽極酸化皮膜表面にフ
ッ素樹脂を塗装、焼付けして１０〜７０μｍの厚みのフ
ッ素樹脂塗膜層を形成し、これによって、陽極酸化皮膜
にネット状クラックが形成されていてかつネット状クラ
ックの単位網目部分の最大径が５〜３００μｍの範囲内
にあり、しかもそのネット状クラック内にフッ素樹脂が
前記塗膜層から連続して侵入含浸されているフッ素樹脂
塗装アルミニウム合金部材を得ることを特徴とする、フ
ッ素樹脂塗装アルミニウム合金部材の製造方法。1. An anodizing treatment is performed on the surface of a base material made of an aluminum alloy to form an anodic oxide film having a thickness of 2 to 30 μm, and then a sealing treatment is performed.
An air baking treatment is performed to raise the temperature to the above temperature at a heating rate of 3 ° C./min or more. Thereafter, a fluororesin is applied to the surface of the anodic oxide film and baked to form a fluororesin coating layer having a thickness of 10 to 70 μm. Thus, a net-like crack is formed on the anodic oxide film, and the maximum diameter of the unit network portion of the net-like crack is in the range of 5 to 300 μm, and the fluororesin is contained in the net-like crack. A method for producing a fluororesin-coated aluminum alloy member, characterized by obtaining a fluororesin-coated aluminum alloy member continuously infiltrated and impregnated from a coating layer.
陽極酸化処理を施して２〜３０μｍの厚みの陽極酸化皮
膜を生成させた後、ショットブラストもしくは合計圧延
率が５％以下の２方向以上のスキンパス圧延を行ない、
しかる後、陽極酸化皮膜表面にフッ素樹脂を塗装、焼付
けして１０〜７０μｍの厚みのフッ素樹脂塗膜層を形成
し、これによって、陽極酸化皮膜にネット状クラックが
形成されていてかつネット状クラックの単位網目部分の
最大径が５〜３００μｍの範囲内にあり、しかもそのネ
ット状クラック内にフッ素樹脂が前記塗膜層から連続し
て侵入含浸されているフッ素樹脂塗装アルミニウム合金
部材を得ることを特徴とする、フッ素樹脂塗装アルミニ
ウム合金部材の製造方法。2. Anodizing treatment is performed on the surface of a base material made of an aluminum alloy to form an anodic oxide film having a thickness of 2 to 30 μm, and then shot blasting or a total rolling reduction of not less than 5% in two or more directions. Perform skin pass rolling,
Thereafter, a fluororesin is applied to the surface of the anodic oxide film and baked to form a fluororesin coating layer having a thickness of 10 to 70 μm, whereby a net-like crack is formed on the anodic oxide film and the net-like crack is formed. To obtain a fluororesin-coated aluminum alloy member in which the maximum diameter of the unit mesh portion is in the range of 5 to 300 μm, and in which the fluororesin is continuously infiltrated and impregnated from the coating layer into the net-like cracks. A method for producing a fluororesin-coated aluminum alloy member.
素樹脂塗装アルミニウム合金部材の製造方法において、 アルミニウム合金からなる基材に対する前記陽極酸化処
理の前に、予め基材表面に、粗度Ｒｚが３〜１５μｍと
なるように粗面化処理を施しておくことを特徴とする、
フッ素樹脂塗装アルミニウム合金部材の製造方法。3. The method for producing a fluororesin-coated aluminum alloy member according to claim 1 or 2, wherein the surface of the base material made of an aluminum alloy has a roughness Rz before the anodizing treatment on the base material. Is subjected to a surface roughening treatment so as to be 3 to 15 μm,
A method for producing a fluororesin-coated aluminum alloy member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15749496A JP3200365B2 (en) | 1996-05-29 | 1996-05-29 | Manufacturing method of fluororesin coated aluminum alloy member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15749496A JP3200365B2 (en) | 1996-05-29 | 1996-05-29 | Manufacturing method of fluororesin coated aluminum alloy member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09316693A JPH09316693A (en) | 1997-12-09 |
| JP3200365B2 true JP3200365B2 (en) | 2001-08-20 |
Family
ID=15650917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15749496A Expired - Fee Related JP3200365B2 (en) | 1996-05-29 | 1996-05-29 | Manufacturing method of fluororesin coated aluminum alloy member |
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| Country | Link |
|---|---|
| JP (1) | JP3200365B2 (en) |
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| DE102013109394B4 (en) * | 2013-01-18 | 2021-04-01 | Suzuki Motor Corp. | Anodic oxide layer and method of making the same |
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| WO2001049904A1 (en) * | 2000-01-07 | 2001-07-12 | Yamaha Hatsudoki Kabushiki Kaisha | Aluminum parts and production method therefor |
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-
1996
- 1996-05-29 JP JP15749496A patent/JP3200365B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| DE102013109394B4 (en) * | 2013-01-18 | 2021-04-01 | Suzuki Motor Corp. | Anodic oxide layer and method of making the same |
| US10380383B2 (en) | 2016-12-09 | 2019-08-13 | Right Group Central Co., Ltd. | Screen protection filter |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09316693A (en) | 1997-12-09 |
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