JP6535242B2 - Aluminum substrate for magnetic recording medium and method of manufacturing the same - Google Patents
Aluminum substrate for magnetic recording medium and method of manufacturing the same Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims description 76
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 51
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- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、磁気記録媒体用の基板として好適な皮膜が形成されたアルミニウム基板、およびその製造方法に関する。 The present invention relates to an aluminum substrate on which a film suitable as a substrate for a magnetic recording medium is formed, and a method of manufacturing the same.
磁気記録媒体用アルミニウム基板としては、もっぱらＪＩＳ Ｈ４０００−２０１４に規定されたＡ５０８６合金が使われている。この合金単独では、磁気記録媒体に適した表面平滑性や表面無欠陥性、耐疵付性などが不十分であるため、表面処理として無電解ＮｉＰめっきが施されている。 As an aluminum substrate for a magnetic recording medium, an A5086 alloy specified in JIS H4000-2014 is used exclusively. Since this alloy alone is insufficient in surface smoothness, surface nondefectiveness, scratch resistance and the like suitable for a magnetic recording medium, electroless NiP plating is applied as a surface treatment.
無電解ＮｉＰめっきを施すことで、表面に現れる晶出物や介在物を覆い隠し表面無欠陥性を実現することができる。また、結晶粒界を覆うことで研磨により高い平滑性を実現することができる。さらには、表面硬度を高くすることで耐疵付性を改善することができる。 By applying the electroless NiP plating, it is possible to hide the crystallized substances and inclusions appearing on the surface and to realize the surface defect free property. In addition, high smoothness can be realized by polishing by covering grain boundaries. Furthermore, by making the surface hardness high, it is possible to improve the scratch resistance.
しかしながら、従来使われているＮｉＰめっきは、３００℃以上に加熱処理されると結晶化し、表面の平滑性が劣化するだけでなく、強磁性を示すことになり磁気記録媒体用基板として不適切となる。
一方で、磁気記録媒体に求められる性能として、高記録密度があり、そのためには磁性層成膜時の温度条件の緩和が求められている。
However, conventionally used NiP plating crystallizes when it is heat-treated to 300 ° C. or more, and not only the surface smoothness is degraded, but it also exhibits ferromagnetism, which is inappropriate as a substrate for a magnetic recording medium. Become.
On the other hand, there is a high recording density as a performance required for a magnetic recording medium, and for that purpose, relaxation of temperature conditions at the time of forming a magnetic layer is required.
特許文献１では、ＮｉＰめっきのもつ３００℃以上の温度での熱処理による磁性の発現を抑制するために、Ｎｉ−Ｐ−Ｗめっきが提案されている。
ＮｉＰめっき以外の表面処理として、例えば特許文献２では、アルマイト基板の表面処理として、酸化シリコンを塗布し熱処理することでアルマイト基板表面を平滑化する表面処理方法が提案されている。
As surface treatment other than NiP plating, for example, as a surface treatment of an alumite substrate, Patent Document 2 proposes a surface treatment method in which silicon oxide is applied and heat treated to smooth the surface of the alumite substrate.
また、高記録密度に対応するためには、記録ヘッドの基板表面への衝突に伴う疵発生を抑制することも重要である。磁気記録では、記録媒体の表面を高さ数ｎｍで記録再生ヘッドが高速で移動しており、ヘッドと基板との衝突により基板表面の変形を防ぐことが重要である。そのため、厚さ１０μｍ程度のＮｉＰめっきが用いられている。基板表面に要求される硬度は、耐疵付性を実現するために求められる。
特許文献３では、アルミニウム基板上に窒化珪素質連続薄膜が形成された磁気ディスク基板が開示されている。当該基板の製造方法として、アルミニウム基板上に無機ポリシラザンを塗工した後、大気中２００℃で１時間熱処理することで、厚さ約１μｍでニッケルリンめっき基板よりも高い硬度と平滑性を実現できることが開示されている。
Further, in order to cope with high recording density, it is also important to suppress the generation of wrinkles caused by the collision of the recording head with the substrate surface. In magnetic recording, the recording and reproducing head is moving at a high speed of several nm on the surface of the recording medium, and it is important to prevent the deformation of the substrate surface due to the collision between the head and the substrate. Therefore, NiP plating having a thickness of about 10 μm is used. The hardness required for the substrate surface is required to achieve the resistance to brazing.
Patent Document 3 discloses a magnetic disk substrate in which a silicon nitride continuous thin film is formed on an aluminum substrate. As a method of manufacturing the substrate, after applying an inorganic polysilazane on an aluminum substrate, heat treatment at 200 ° C. in the atmosphere for 1 hour can realize higher hardness and smoothness than a nickel phosphorus plated substrate with a thickness of about 1 μm. Is disclosed.
しかしながら、特許文献１に記載のＮｉ−Ｐ−Ｗめっきでも、耐熱温度は３２０℃に留まる。また、特許文献２には、アルマイト処理を行ったアルミニウム基板上にオルガノシロキサン溶液を塗工し、１５０℃から３５０℃で焼付けを行うことで、アルマイト表面を平滑にできることは開示されている。すなわち、陽極酸化処理により生じる表面の凹凸や微細気孔を有機シリコンで塗工、熱処理することにより平滑化できることが開示されている。しかしながら、磁気記録媒体用基板として特に重要な耐熱性や耐疵付性に関しては何ら言及されていない。また、塗工される有機シリコンとして適した組成、物性等にも何ら言及されていない。
However, even with the Ni-P-W plating described in
また、特許文献３に記載の磁気ディスク基板は、アルミニウム基板上に硬度の高い皮膜を形成しても、厚さが１μｍである場合には、現行汎用されているＮｉＰめっき（厚さ〜１０μｍ）基板に比べて耐疵付性は大きく劣る。 In addition, even if the magnetic disk substrate described in Patent Document 3 forms a film with high hardness on an aluminum substrate, when the thickness is 1 μm, the NiP plating currently used widely (thickness 10 μm) The resistance to scratching is significantly inferior to that of the substrate.
本発明は、このような状況を鑑みてなされたものであり、耐疵付性と耐熱性に優れた磁気記録媒体用アルミニウム基板を提供することを目的とする。 The present invention has been made in view of such circumstances, and it is an object of the present invention to provide an aluminum substrate for a magnetic recording medium which is excellent in scratch resistance and heat resistance.
本発明者は、鋭意研究を重ねた結果、アルミニウム合金の少なくとも一方の表面に、特定の厚みの陽極酸化皮膜を形成し、その上にさらに特定のシリカ転化させた膜を形成することにより、耐疵付性及び耐熱性に優れた磁気記録媒体用アルミニウム基板が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventor has developed an anodic oxide film having a specific thickness on at least one surface of an aluminum alloy, and further forming a specific silica-converted film thereon. The inventors have found that an aluminum substrate for a magnetic recording medium having excellent adhesion and heat resistance can be obtained, and the present invention has been completed.
すなわち、本発明は、以下の［１］〜［９］に係るものである。
［１］ アルミニウム基板上に、厚さ７μｍ以上２５μｍ以下の陽極酸化皮膜が形成され、前記陽極酸化皮膜上にメチルヒドロポリシラザンを含むポリシラザン溶液をレベリング効果が発現する量塗工し、シリカ転化させた膜が形成されていることを特徴とする磁気記録媒体用アルミニウム基板。
［２］ 前記メチルヒドロポリシラザンを含むポリシラザン溶液が、メチルヒドロポリシラザンと無機ポリシラザンとの混合物であることを特徴とする前記［１］に記載の磁気記録媒体用アルミニウム基板。
［３］ 前記混合物におけるメチルヒドロポリシラザンと無機ポリシラザンとの配合比が１０：０〜２：８（重量比）の範囲であることを特徴とする前記［２］に記載の磁気記録媒体用アルミニウム基板。
［４］ 前記シリカ転化させた膜が膜厚０．２μｍ以上のシリカ層であることを特徴とする前記［１］〜［３］のいずれか１に記載の磁気記録媒体用アルミニウム基板。
［５］ アルミニウム基板上に厚さ７μｍ以上２５μｍ以下の陽極酸化皮膜を形成する工程と、前記陽極酸化皮膜上にメチルヒドロポリシラザンを含むポリシラザン溶液をレベリング効果が発現する量塗工した後、加熱によりシリカ転化させて膜を形成する工程を含むことを特徴とする磁気記録媒体用アルミニウム基板の製造方法。
［６］ 前記陽極酸化皮膜を少なくともシュウ酸を含む陽極酸化処理液により形成することを特徴とする前記［５］に記載の磁気記録媒体用アルミニウム基板の製造方法。
［７］ 前記メチルヒドロポリシラザンを含むポリシラザン溶液が、メチルヒドロポリシラザンと無機ポリシラザンとの混合物であることを特徴とする前記［５］又は［６］に記載の磁気記録媒体用アルミニウム基板の製造方法。
［８］ 前記混合物におけるメチルヒドロポリシラザンと無機ポリシラザンとの配合比が１０：０〜２：８（重量比）の範囲であることを特徴とする前記［７］に記載の磁気記録媒体用アルミニウム基板の製造方法。
［９］ 前記シリカ転化させた膜が膜厚０．２μｍ以上のシリカ層であることを特徴とする前記［５］〜［８］のいずれか１に記載の磁気記録媒体用アルミニウム基板の製造方法。
That is, the present invention relates to the following [1] to [9].
[1] An anodic oxide film having a thickness of 7 μm to 25 μm is formed on an aluminum substrate, and a polysilazane solution containing methylhydropolysilazane is coated on the anodic oxide film in such an amount that the leveling effect is exhibited, An aluminum substrate for a magnetic recording medium, characterized in that a film is formed.
[2] The aluminum substrate for a magnetic recording medium according to [1], wherein the polysilazane solution containing methylhydropolysilazane is a mixture of methylhydropolysilazane and an inorganic polysilazane.
[3] The aluminum substrate for a magnetic recording medium according to the above [2], wherein the compounding ratio of methylhydropolysilazane to inorganic polysilazane in the mixture is in the range of 10: 0 to 2: 8 (weight ratio). .
[4] The aluminum substrate for a magnetic recording medium according to any one of the above [1] to [3], wherein the film converted into silica is a silica layer having a thickness of 0.2 μm or more.
[5] A step of forming an anodic oxide film having a thickness of 7 μm to 25 μm on an aluminum substrate, and a polysilazane solution containing methylhydropolysilazane coated on the anodic oxide film in an amount to develop a leveling effect. A method for producing an aluminum substrate for a magnetic recording medium, comprising the step of converting into silica to form a film.
[6] The method for producing an aluminum substrate for a magnetic recording medium according to [5], wherein the anodized film is formed by an anodizing solution containing at least oxalic acid.
[7] The method for producing an aluminum substrate for a magnetic recording medium according to [5] or [6], wherein the polysilazane solution containing methylhydropolysilazane is a mixture of methylhydropolysilazane and an inorganic polysilazane.
[8] The aluminum substrate for a magnetic recording medium according to the above [7], wherein the compounding ratio of methylhydropolysilazane to inorganic polysilazane in the mixture is in the range of 10: 0 to 2: 8 (weight ratio). Manufacturing method.
[9] The method for producing an aluminum substrate for a magnetic recording medium according to any one of the above [5] to [8], wherein the film converted into silica is a silica layer having a thickness of 0.2 μm or more. .
本発明によれば、耐熱性及び耐疵付性に非常に優れた磁気記録媒体用アルミニウム基板を提供することができる。 According to the present invention, it is possible to provide an aluminum substrate for a magnetic recording medium which is extremely excellent in heat resistance and scratch resistance.
本発明に係る磁気記録媒体用アルミニウム基板は、アルミニウム（以下、単に「アルミ」と称することもある。）基板上に、厚さ７μｍ以上２５μｍ以下の陽極酸化皮膜が形成され、前記陽極酸化皮膜上にメチルヒドロポリシラザンを含むポリシラザン溶液をレベリング効果が発現する量塗工し、シリカ転化させた膜が形成されていることを特徴とする。 In the aluminum substrate for a magnetic recording medium according to the present invention, an anodic oxide film having a thickness of 7 μm to 25 μm is formed on an aluminum (hereinafter sometimes simply referred to as “aluminum”) substrate, and the anodic oxide film is formed It is characterized in that a polysilazane solution containing methylhydropolysilazane is applied to an amount such that a leveling effect is exhibited, and a film converted to silica is formed.
＜アルミニウム基板＞
本発明で基板として用いるアルミニウム合金（単に「アルミニウム」と称することもある。）は、その化学成分組成については、磁気記録媒体用として必要な強度を持ち陽極酸化皮膜の形成に用いられうるものである限り、特に限定されるものではないが、例えば、Ｍｇ：３．５重量％以上６重量％以下、Ｃｕ：０．０２重量％以上０．５重量％以下、Ｓｉ：０．０５重量％以下、Ｆｅ：０．０５重量％以下含有し、かつＣｒ：０．０５重量％以上０．６重量％以下、Ｍｎ：０．０５重量％以上１．５重量％以下、およびＺｒ：０．０５重量％以上０．６重量％以下よりなる群から選ばれる少なくとも一つを含有し、残部がＡｌおよび不可避的不純物からなるアルミニウム合金であり、かつ、表面における金属間化合物の最大長さが１０μｍ以下であり、基板表面１ｍｍ２当たりの、最大長さが５μｍ以上である金属間化合物の個数が１個以下のアルミニウム合金などを例示することができる。
<Aluminum substrate>
The aluminum alloy (sometimes simply referred to as "aluminum") used as a substrate in the present invention has a necessary chemical composition for the magnetic recording medium and can be used to form an anodic oxide film having a necessary strength. As long as it is not particularly limited, for example, Mg: 3.5 wt% or more and 6 wt% or less, Cu: 0.02 wt% or more and 0.5 wt% or less, Si: 0.05 wt% or less , Fe: 0.05 wt% or less, Cr: 0.05 wt% or more and 0.6 wt% or less, Mn: 0.05 wt% or more and 1.5 wt% or less, and Zr: 0.05 wt% Aluminum alloy containing at least one selected from the group consisting of at least 0.5% by weight and the balance being Al and unavoidable impurities, and the maximum length of the intermetallic compound on the surface being 10 μm A lower, per
＜陽極酸化皮膜＞
本発明における陽極酸化皮膜は、アルミニウム基板上に形成された膜厚７μｍ以上２５μｍ以下の陽極酸化皮膜であり、アルミニウム合金基材の全面がこの陽極酸化皮膜で覆われている。
<Anode oxide film>
The anodized film in the present invention is an anodized film having a thickness of 7 μm to 25 μm formed on an aluminum substrate, and the entire surface of the aluminum alloy substrate is covered with the anodized film.
陽極酸化皮膜を形成する時の陽極酸化処理液としては、少なくともシュウ酸を含む陽極酸化処理液を用いることが好ましい。これは陽極酸化皮膜がアルミニウム合金基材にシュウ酸系皮膜を形成することで、硬度が高く高温耐クラック性を向上させることができるからである。
即ち、一般的な陽極酸化処理液として、シュウ酸、ギ酸等の有機酸、リン酸、クロム酸、硫酸などの無機酸が挙げられるが、硬度が高く高温でのクラックの発生を著しく低減させるという観点から、少なくともシュウ酸を含む陽極酸化処理液を用いることが好ましい。陽極酸化処理液中のシュウ酸濃度は、所望とする作用効果を有効に発揮することができるように適宜適切に制御すれば良い。陽極酸化処理液中のシュウ酸濃度の下限は、好ましくは１０ｇ／Ｌであり、より好ましくは１５ｇ／Ｌである。また、当該シュウ酸濃度の上限は、好ましくは５０ｇ／Ｌであり、より好ましくは４０ｇ／Ｌである。
It is preferable to use an anodizing solution containing at least oxalic acid as an anodizing solution when forming an anodized film. This is because the anodic oxide film forms an oxalic acid-based film on the aluminum alloy substrate, whereby the hardness is high and the high temperature crack resistance can be improved.
That is, as a general anodizing treatment solution, organic acids such as oxalic acid and formic acid, and inorganic acids such as phosphoric acid, chromic acid and sulfuric acid can be mentioned, but the hardness is high and the occurrence of cracks at high temperatures is significantly reduced. From the viewpoint, it is preferable to use an anodizing solution containing at least oxalic acid. The concentration of oxalic acid in the anodizing treatment solution may be appropriately controlled appropriately so that the desired effect can be exhibited effectively. The lower limit of the oxalic acid concentration in the anodizing solution is preferably 10 g / L, more preferably 15 g / L. The upper limit of the oxalic acid concentration is preferably 50 g / L, more preferably 40 g / L.
陽極酸化皮膜の厚膜化や皮膜形成の高速化の方法として、少なくともシュウ酸を含む混酸溶液（陽極酸化処理液）による陽極酸化処理を行うことが好ましい。このときの、シュウ酸と混ぜる他の酸溶液は、特に限定されない。例えば、蟻酸等の有機酸、クロム酸、硫酸、リン酸などの無機酸等が挙げられ、これらの中から一つ以上の酸溶液を選んで用いることができる。このように、少なくともシュウ酸を含む溶液（陽極酸化処理液）を用いることによって、形成される多孔質の陽極酸化皮膜は処理溶液による溶解が少なく、陽極酸化皮膜の厚膜化が可能になると共に、耐クラック性（クラックが生じない特性）に優れる皮膜となる。 As a method of increasing the thickness of the anodized film and speeding up the film formation, it is preferable to perform anodizing treatment with a mixed acid solution (anodic oxidation treatment solution) containing at least oxalic acid. The other acid solution to be mixed with oxalic acid at this time is not particularly limited. Examples thereof include organic acids such as formic acid, and inorganic acids such as chromic acid, sulfuric acid, and phosphoric acid, and one or more acid solutions can be selected and used from these. As described above, by using a solution containing at least oxalic acid (anodic oxidation treatment solution), the porous anodic oxide film formed is less dissolved by the treatment solution, and it becomes possible to thicken the anodic oxide film. And a film excellent in crack resistance (characteristics that cause no cracks).
上述した混酸溶液（シュウ酸を含む溶液）による陽極酸化処理では、各種酸濃度、処理温度、電解電圧、電流密度は特に定めるものではなく、適宜処理条件を選択すればよい。 In the anodizing treatment with the mixed acid solution (a solution containing oxalic acid) described above, the concentration of various acids, the treatment temperature, the electrolytic voltage, and the current density are not particularly limited, and treatment conditions may be appropriately selected.
その他の陽極酸化処理条件についても、特に定めるものではないが、例えば陽極酸化処理を行う際の温度は、生産性を損なうことなく、また陽極酸化皮膜の溶解が顕著に起こらない範囲で設定すればよく、おおむね、０〜５０℃とすることが好ましい。また、陽極酸化処理を行う際の処理時間も、同様に適宜設定することができ、特に限定されないが、たとえば１０〜３００分行うことができる。 Other anodic oxidation treatment conditions are not particularly limited, but for example, the temperature at the time of anodizing treatment should be set within a range where the dissolution of the anodic oxide film does not significantly occur without impairing the productivity. It is preferable that the temperature be approximately 0 to 50 ° C. Moreover, the processing time at the time of performing anodizing processing can also be suitably set similarly, Although it does not specifically limit, For example, it can carry out for 10 to 300 minutes.
陽極酸化処理を行うときの電解電圧（陽極酸化皮膜形成電圧）や電流密度は、所望の陽極酸化皮膜が得られるように、適宜適切に調節すればよい。このうち電解電圧については、電解電圧が低いと電流密度が小さくなって成膜速度が遅くなり、一方、電解電圧が高すぎると大電流により皮膜の溶解によって陽極酸化皮膜が形成されなくなる傾向がある。電解電圧による影響は、使用する電解処理液（陽極酸化処理溶液）の組成や、陽極酸化皮膜を行う温度などにも関係するため、適宜設定すればよい。陽極酸化処理時の電解電圧は、具体的には５〜１５０Ｖ程度が好ましく、より好ましくは２０〜１２０Ｖ程度である。また、陽極酸化処理時に流す電流密度は、１００Ａ／ｄｍ２以下であることが好ましく、５０Ａ／ｄｍ２以下であることがより好ましく、３０Ａ／ｄｍ２以下であることが更に好ましい。 The electrolytic voltage (anodized film formation voltage) and the current density when anodizing treatment is performed may be appropriately adjusted appropriately so as to obtain a desired anodized film. Among these, when the electrolytic voltage is low, the current density decreases and the film forming speed becomes slow when the electrolytic voltage is low. On the other hand, when the electrolytic voltage is too high, the anodic oxide film tends not to be formed due to dissolution of the film due to a large current. . The influence of the electrolytic voltage is related to the composition of the electrolytic treatment solution (anodic oxidation treatment solution) to be used, the temperature at which the anodic oxide film is formed, and the like, and therefore, may be set appropriately. Specifically, the electrolytic voltage at the time of anodizing treatment is preferably about 5 to 150 V, and more preferably about 20 to 120 V. Further, the current density to be applied at the time of anodizing treatment is preferably 100 A / dm 2 or less, more preferably 50 A / dm 2 or less, and still more preferably 30 A / dm 2 or less.
上記のようにして形成される陽極酸化皮膜の厚みは、耐疵付性を担う重要な因子であり、良好な耐疵付性を得る観点から、７μｍ以上とすることが好ましく、より好ましくは９μｍ以上であり、さらに好ましくは１２μｍ以上である。なお、陽極酸化皮膜単独の場合には陽極酸化皮膜の厚さが１５μｍ以上でＮｉ−Ｐめっきと同等の耐疵付性が得られるが、本発明においてはシリカ転化した膜（シリカ膜）と組み合わせることから、７μｍ以上であれば上記効果を得ることができる。 The thickness of the anodized film formed as described above is an important factor responsible for the resistance to brazing, and from the viewpoint of obtaining good resistance to brazing, the thickness is preferably 7 μm or more, more preferably 9 μm. Or more, and more preferably 12 μm or more. In addition, in the case of anodized film alone, when the thickness of the anodized film is 15 μm or more, the same brazing resistance as Ni-P plating is obtained, but in the present invention, it is combined with a film converted to silica (silica film) Therefore, if it is 7 micrometers or more, the above-mentioned effect can be acquired.
一方、陽極酸化皮膜の厚みがあまり厚くなると、コストが増大し、かえって耐疵付性が低下することから、２５μｍ以下とすることが好ましく、より好ましくは２０μｍ以下である。 On the other hand, if the thickness of the anodized film is too large, the cost increases and the resistance to scratching decreases, so the thickness is preferably 25 μm or less, more preferably 20 μm or less.
＜シリカ転化させた膜＞
前記陽極酸化皮膜上にメチルヒドロポリシラザンを含むポリシラザン溶液をレベリング効果が発現する量塗工し、シリカ転化させた膜（シリカ膜）を形成する。
ポリシラザン溶液を塗工後、水蒸気を含む雰囲気にて熱処理をすることにより、シリカ転化する。
シリカ膜により、陽極酸化皮膜の細孔や合金中の介在物、晶出物由来のピットを目詰めすることができることから、欠陥の無い平滑な面を実現でき、また耐疵付性を改善することができる。
<Silica converted membrane>
A polysilazane solution containing methylhydropolysilazane is coated on the anodized film in such an amount that the leveling effect is exhibited, thereby forming a film converted to silica (silica film).
After the polysilazane solution is applied, it is converted into silica by heat treatment in an atmosphere containing water vapor.
Since the silica film can close the pores of the anodic oxide film, inclusions in the alloy, and pits derived from the crystallized matter, it is possible to realize a smooth surface free from defects and to improve the scratch resistance. be able to.
ポリシラザン溶液はメチルヒドロポリシラザンを含むことにより陽極酸化単体に比べて耐疵付性が改善される。また、さらに膜硬度を向上できる点からメチルヒドロポリシラザンと無機ポリシラザンとの混合物であることが好ましい。無機ポリシラザンとメチルヒドロポリシラザンとの配合比は０：１０〜８：２（重量比）の範囲であることが好ましく、２：８〜５：５（重量比）がより好ましい。 By containing methylhydropolysilazane, the polysilazane solution has improved resistance to scratching as compared to anodized single substance. In addition, a mixture of methylhydropolysilazane and inorganic polysilazane is preferable from the viewpoint that the film hardness can be further improved. The compounding ratio of the inorganic polysilazane to the methylhydropolysilazane is preferably in the range of 0:10 to 8: 2 (weight ratio), and more preferably 2: 8 to 5: 5 (weight ratio).
無機ポリシラザンの好ましい例としてパーヒドロポリシラザンが挙げられるが、パーヒドロポリシラザンは水蒸気と反応し、ＳｉＯ２に転化することは良く知られている。この場合、Ｓｉ−Ｏ−Ｓｉが３次元のネットワークでつながり、溶融石英類似の構造となるため、硬いく柔軟性に欠ける皮膜となる。
これに対して、シリコン原子にメチル基が結合したメチルヒドロポリシラザンを水蒸気と反応させると、Ｓｉ−Ｏ−Ｓｉの骨格がメチル基のために硬い構造を作ることができず、柔軟性を有する膜となる。両者を適当な割合で混合し、水蒸気と反応させることにより、Ｓｉ−Ｏ−Ｓｉの３次元ネットワークの一部をメチル基で終端させた柔軟性を有するシリカ骨格を形成させることができる。
適度に柔軟性を持つ膜は、アルミニウム基板との熱膨張差に起因する応力を緩和するので、耐熱性の改善が期待される。
Perhydropolysilazane is mentioned as a preferred example of the inorganic polysilazane, but it is well known that perhydropolysilazane reacts with water vapor to convert to SiO 2 . In this case, Si—O—Si is connected by a three-dimensional network to form a structure similar to fused quartz, resulting in a hard and non-flexible film.
On the other hand, when methylhydropolysilazane in which a methyl group is bonded to a silicon atom is reacted with water vapor, the Si-O-Si skeleton can not form a hard structure due to the methyl group, and the film has flexibility. It becomes. By mixing the two in appropriate proportions and reacting with water vapor, it is possible to form a flexible silica skeleton in which a part of a three-dimensional network of Si-O-Si is terminated with a methyl group.
Since the film having a suitable degree of flexibility relieves the stress caused by the thermal expansion difference with the aluminum substrate, the improvement of the heat resistance is expected.
レベリング効果が発現する量とは、ある程度平滑性が担保できる量であり、その量は陽極酸化皮膜の厚さやポリシラザン溶液の濃度、有機：無機の混合比率、塗工方法等によって変化するが、一般的には基板単位面積当たりに塗工されるポリシラザン量として０．１５ｍｇ／ｃｍ２以上が好ましく、０．２ｍｇ／ｃｍ２以上がより好ましく、０．４ｍｇ／ｃｍ２以上がさらに好ましい。塗工されるポリシラザン量の上限はレベリング効果の発現ではなく、シリカ転化された状態での膜厚さが３μｍ以内という制約で決まる。
ポリシラザンの塗工量は、塗工前の基板重量と塗工後の基板重量の差および基板内外径から計算される面積から求めることができる。
The amount at which the leveling effect appears is an amount that can ensure smoothness to some extent, and the amount varies depending on the thickness of the anodized film, the concentration of the polysilazane solution, the mixing ratio of organic: inorganic, the coating method, etc. Specifically, the amount of polysilazane coated per substrate area is preferably 0.15 mg / cm 2 or more, more preferably 0.2 mg / cm 2 or more, and still more preferably 0.4 mg / cm 2 or more. The upper limit of the amount of polysilazane to be coated is determined not by the expression of the leveling effect, but by the restriction that the film thickness in the silica-converted state is within 3 μm.
The coating amount of polysilazane can be determined from the difference between the substrate weight before coating and the substrate weight after coating, and the area calculated from the substrate inner and outer diameters.
また、シリカ膜は膜厚０．２μｍ以上のシリカ層であることが好ましく、０．３μｍ以上がより好ましい。また、３μｍ以下が好ましく、２μｍ以下がより好ましい。
シリカ転化させた膜の膜厚は、皮膜の断面を走査型顕微鏡（ＳＥＭ）観察及び元素マッピングを行うことによって測定することができる。また、陽極酸化皮膜が多孔質である場合には、孔の中にポリシラザン溶液が含浸され、シリカ転化していてもよい。
The silica film is preferably a silica layer having a thickness of 0.2 μm or more, more preferably 0.3 μm or more. Moreover, 3 micrometers or less are preferable and 2 micrometers or less are more preferable.
The film thickness of the silica-converted film can be measured by scanning microscope (SEM) observation and element mapping of the cross section of the film. When the anodized film is porous, the pores may be impregnated with a polysilazane solution and converted to silica.
＜磁気記録媒体用アルミニウム基板の製造方法＞
本発明に係る磁気記録媒体用アルミニウム基板の製造方法は、アルミニウム基板上に厚さ７μｍ以上２５μｍ以下の陽極酸化皮膜を形成する工程と、前記陽極酸化皮膜上にメチルヒドロポリシラザンを含むポリシラザン溶液をレベリング効果が発現する量塗工した後、加熱によりシリカ転化させて膜を形成する工程を含むことを特徴とする。陽極酸化皮膜及びシリカ膜はアルミニウム基板の少なくとも一方の表面に形成されていればよいが、基板表面の効率的利用の点から、両方の表面に形成されていることが好ましい。
<Method of manufacturing aluminum substrate for magnetic recording medium>
The method for producing an aluminum substrate for a magnetic recording medium according to the present invention comprises the steps of: forming an anodic oxide film having a thickness of 7 μm to 25 μm on an aluminum substrate; and leveling a polysilazane solution containing methylhydropolysilazane on the anodic oxide film. The method is characterized in that it comprises a step of converting to silica by heating to form a film after the coating is applied in such an amount that the effect appears. The anodized film and the silica film may be formed on at least one surface of the aluminum substrate, but are preferably formed on both surfaces in terms of efficient use of the substrate surface.
好ましいアルミニウム基板、陽極酸化皮膜、シリカ膜は先述したとおりである。
アルミニウム基板に陽極酸化皮膜を形成する工程は、公知の方法により行うことができるが、例えば基板となるアルミニウム合金を、シュウ酸、ギ酸等の有機酸、リン酸、クロム酸、硫酸などの無機酸等を含む溶液中で通電することにより形成することができる。この場合、陽極酸化皮膜厚さは、通電時間により調整することが可能である。
ここで、前述したように、高温でのクラックの発生を著しく低減させつつ耐電圧性を向上させるという観点からは、少なくともシュウ酸を含む陽極酸化処理液を用いることが好ましい。
Preferred aluminum substrates, anodized films and silica films are as described above.
The step of forming the anodized film on the aluminum substrate can be carried out by a known method. For example, the aluminum alloy to be the substrate is an organic acid such as oxalic acid or formic acid, or an inorganic acid such as phosphoric acid, chromic acid or sulfuric acid It can form by supplying with electricity in the solution containing the above. In this case, the anodized film thickness can be adjusted by the current application time.
Here, as described above, it is preferable to use an anodizing solution containing at least oxalic acid from the viewpoint of improving the voltage resistance while significantly reducing the occurrence of cracks at high temperatures.
陽極酸化皮膜上にポリシラザン溶液を塗工する際には、ディップコート、スプレーコート、スピンコート等によって塗工することができる。中でもスピンコートが均一な膜厚さを実現できる点から好ましい。
なお、ポリシラザン溶液の濃度を調整する場合に用いる溶剤としては、分子構造中に水酸基（−ＯＨ）を含むアルコール類はポリシラザンと反応するために使用できない。石油系有機溶剤、キシレン等の芳香族溶剤、ジブチルエーテル等のアルキルエーテルが好ましい。濃度は、塗工方法や条件によって適切な範囲に設定すれば良いが、ポリシラザン濃度として２０重量％から６０重量％が一般的である。濃度が濃いと粘度が高くなり塗工しにくくなる。一方、濃度が低くなり過ぎると溶剤乾燥後に十分な膜厚さを得ることができない。
When applying the polysilazane solution on the anodized film, it can be applied by dip coating, spray coating, spin coating or the like. Above all, spin coating is preferable from the point that a uniform film thickness can be realized.
In addition, as a solvent used when adjusting the density | concentration of polysilazane solution, in order to react with polysilazane, alcohol containing a hydroxyl group (-OH) in molecular structure can not be used. Preferred are petroleum-based organic solvents, aromatic solvents such as xylene, and alkyl ethers such as dibutyl ether. The concentration may be set in an appropriate range depending on the coating method and conditions, but it is generally 20% by weight to 60% by weight as the polysilazane concentration. When the concentration is high, the viscosity is high and coating becomes difficult. On the other hand, if the concentration is too low, a sufficient film thickness can not be obtained after solvent drying.
ポリシラザン溶液を塗工後、加熱によりシリカ（ＳｉＯ２）に転化し、シリカ膜とすることができる。
ポリシラザンのシリカ転化には水との反応が必要であり、加熱雰囲気に水蒸気を導入すれば良い。加熱温度は２００〜３７０℃がシリカ転化を効率的に進める点から好ましい。また、加熱時間は２０分〜２時間が十分なシリカ転化と生産性の点から好ましい。
After the polysilazane solution is applied, it can be converted to silica (SiO 2 ) by heating to form a silica film.
The conversion of polysilazane into silica requires a reaction with water, and water vapor may be introduced into the heating atmosphere. The heating temperature is preferably 200 to 370 ° C. in terms of efficiently advancing the silica conversion. The heating time is preferably 20 minutes to 2 hours from the viewpoint of sufficient silica conversion and productivity.
陽極酸化皮膜及びシリカ転化させた膜をアルミニウム基板の両方の面に形成させる場合、例えばアルミニウム合金を陽極酸化処理液に浸漬、通電を行うことでアルミニウム合金の両面に陽極酸化皮膜を形成し、その後、一方の表面にメチルヒドロポリシラザンを含むポリシラザン溶液に塗工、熱処理によるシリカ転化を行い、次いで他方の表面についても同様に塗工、熱処理によるシリカ転化を行うことにより得ることができる。
また、一方の表面に該ポリシラザン溶液を塗工して乾燥させ、他方の表面にも該ポリシラザン溶液を塗工した後に熱処理をすることにより、両面を一度にシリカ転化させることもできる。さらには、両方の表面に一度に該ポリシラザン溶液を塗工し、熱処理によるシリカ転化を行ってもよい。
When forming an anodized film and a film converted into silica on both sides of an aluminum substrate, for example, an aluminum alloy is immersed in an anodizing treatment solution and electricity is applied to form anodized films on both sides of the aluminum alloy, and then The composition can be obtained by coating on one surface a polysilazane solution containing methylhydropolysilazane, performing silica conversion by heat treatment, and then coating the other surface in the same manner and converting silica by heat treatment.
Alternatively, the polysilazane solution may be coated on one surface and dried, and the other surface may be coated with the polysilazane solution followed by heat treatment to convert both sides into silica at one time. Furthermore, the polysilazane solution may be applied to both surfaces at one time, and silica conversion by heat treatment may be performed.
以下に、実施例及び比較例を挙げて本発明をさらに具体的に説明するが、本発明は、これらの実施例に限定されるものではなく、その趣旨に適合し得る範囲で変更を加えて実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to these examples, and various modifications may be made as long as they are compatible with the gist of the present invention. It is also possible to implement, and all are included in the technical scope of the present invention.
＜シリカ膜＞
下記表１に示す組成比でメチルヒドロポリシラザンとパーヒドロポリシラザン（Ｍｅｒｃｋ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ（旧ＡＺ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ社製、ＮＬ１２０Ａ−２０およびＨＴＡ１５００）の混合物を調製し、厚さ１０μｍの陽極酸化皮膜上に上記混合物を塗工、水蒸気を含む雰囲気中３００℃で１時間熱処理してシリカ転化させた後、各温度で１５分の熱履歴を加えた。なお、厚さ１０μｍの陽極酸化皮膜は、アルミニウム合金をシュウ酸を３０ｇ／Ｌ含む３０℃の溶液中で通電することにより形成させた。陽極酸化皮膜厚さは、通電時間により調整できる。
目視および光学顕微鏡観察で膜の亀裂やはく離が認められない温度を耐熱温度とした。結果を表１に示す。なお、表１の結果は、シリカ膜厚さ０．３μｍと２μｍで差は認められなかった。また、表中「ＰＨＰＳ」とはパーヒドロポリシラザンを意味し、「ＭＨＰＳ」とはメチルヒドロポリシラザンを意味する。
<Silica membrane>
A mixture of methylhydropolysilazane and perhydropolysilazane (Merck Performance Materials (formerly AZ Electronic Materials, NL120A-20 and HTA1500) is prepared at the composition ratio shown in Table 1 below, and the above mixture is formed on an anodized film with a thickness of 10 μm. And heat-treated in a steam-containing atmosphere for 1 hour at 300 ° C. to convert to silica, and then a thermal history of 15 minutes was added at each temperature. It was formed by applying a current of 30 g / L of acid in a solution at 30 ° C. The thickness of the anodized film can be adjusted by the current application time.
The temperature at which no cracking or peeling of the film was observed by visual observation and optical microscope observation was taken as the heat resistant temperature. The results are shown in Table 1. In the results shown in Table 1, no difference was observed between the silica film thickness of 0.3 μm and 2 μm. Further, in the table, "PHPS" means perhydropolysilazane, and "MHPS" means methylhydropolysilazane.
なお、シリカ膜中のメチルヒドロポリシラザンとパーヒドロポリシラザンの比はＡＴＲ法（Ａｔｔｅｎｕａｔｅｄ Ｔｏｔａｌ Ｒｅｆｌｅｃｔｉｏｎ；全反射測定法）により求めることができる。
すなわち、ＡＴＲ法において、Ｓｉ原子に結合したメチル基は１，２７０〜１，２８０ｃｍ−１付近に鋭い特性吸収を示す。また、Ｓｉ−Ｏ−Ｓｉの骨格振動に起因する強い特性吸収が、１，０３０〜１，０５０ｃｍ−１付近に観測される。この両者のピーク高さの比から、シリカ骨格中のメチル基の量を評価できるため、メチルヒドロポリシラザンとパーヒドロポリシラザンの比を求めることができる。
The ratio of methylhydropolysilazane to perhydropolysilazane in the silica film can be determined by the ATR method (Attenuated Total Reflection).
That is, in the ATR method, a methyl group bonded to a Si atom exhibits sharp characteristic absorption in the vicinity of 1,270 to 1,280 cm −1 . Also, strong characteristic absorption due to skeletal vibration of Si-O-Si is observed in the vicinity of 1,030 to 1,050 cm −1 . Since the amount of methyl groups in the silica skeleton can be evaluated from the ratio of the two peak heights, the ratio of methylhydropolysilazane to perhydropolysilazane can be determined.
（ＡＴＲスペクトル測定条件）
装置：パーキンエルマー社製 Ｓｐｅｃｔｒｕｍ Ｓｐｏｔｌｉｇｈｔ ４００
測定方法：１回反射ＡＴＲ Ｇｅ結晶 入射角４８°
分解能：４ｃｍ−１
吸収量：Ａｂｓｏｒｂａｎｃｅ表示
(ATR spectrum measurement conditions)
Device: Perkin
Measurement method: One-time reflection ATR Ge crystal Incident angle 48 °
Resolution: 4 cm -1
Absorption amount: Absorbance display
（ＡＴＲスペクトル測定条件及び解析方法）
測定されたスペクトルについて８７０ｃｍ−１と１，３００ｃｍ−１の両点を直線で結び、１，０３０〜１，０５０ｃｍ−１付近に現れるＳｉ−Ｏ−Ｓｉの骨格振動に由来する特性吸収ピークの当該直線からの値「Ｉ（Ｓｉ−Ｏ−Ｓｉ）」と、１，２６５〜１，２８０ｃｍ−１に現れるＳｉ−ＣＨ３の特性吸収のピークの当該直線からの値「Ｉ（Ｓｉ−ＣＨ３）」との比を求める。得られたＡＴＲスペクトルを図１に示す。この値が、０．０２である場合が無機ポリシラザン（ＰＨＰＳ）とメチルヒドロポリシラザン（ＭＨＰＳ）との配合比は０：１０（重量比）である場合に相当し、０．２５である場合が、ＰＨＰＳとＭＨＰＳとの配合比は８：２（重量比）である場合に相当することから、０．０２以上０．２５以内が好ましいと言える。
なお、図１中、ＰＨＰＳとＭＨＰＳとの比率（重量比）はＨＤ−２０８が８：２、ＨＤ−２１０が６：４、ＨＤ−２１２が４：６、ＨＤ−２１４が２：８のものである。
(ATR spectrum measurement conditions and analysis method)
In the measured spectrum, both points at 870 cm -1 and 1,300 cm -1 are connected by a straight line, and the characteristic absorption peaks derived from the skeletal vibration of Si-O-Si appearing around 1,030-1,050 cm -1 Values from the straight line "I (Si-O-Si) " and values from the straight line of the peak of characteristic absorption of Si-CH 3 appearing at 1,265 to 1,280 cm -1 "I (Si-CH3 )" Find the ratio of The obtained ATR spectrum is shown in FIG. The case where this value is 0.02 corresponds to the case where the blending ratio of inorganic polysilazane (PHPS) and methyl hydropolysilazane (MHPS) is 0:10 (weight ratio), and the case where it is 0.25, Since the mixing ratio of PHPS to MHPS is 8: 2 (weight ratio), it can be said that 0.02 or more and 0.25 or less is preferable.
In FIG. 1, the ratio (weight ratio) of PHPS to MHPS is 8: 2 for HD-208, 6: 4 for HD-210, 4: 6 for HD-212, 2: 8 for HD-214. It is.
＜陽極酸化皮膜＞
アルミニウム基板に厚さ５、１０、１５、２０、３０μｍの陽極酸化皮膜をそれぞれ形成し、耐疵付性を評価した。
結果を図２に示す。陽極酸化皮膜単独でも、厚さ１５μｍ以上であれば、従来のＮｉ−Ｐめっき処理（厚さ１０μｍ）よりも耐疵付性は改善される。すなわち、陽極酸化処理がアルミニウム基板の耐疵付性改善に効果的であることを意味する。陽極酸化皮膜単独の場合、厚さが３０μｍとなると、２０μｍに比べて耐疵付性はわずかではあるが、劣化傾向を示す。これは、陽極酸化処理時間が長くなり、初期に形成された膜の表面近傍が電解液により侵食されたためと推察される。
なお、アルミニウム基板としてはＭｇ：５．５重量％、Ｃｕ：０．０４重量％、Ｓｉ：０．０１重量％、Ｆｅ：０．０１５重量％、Ｍｎ：０．３重量％及びＣｒ：０．５重量％含み、残部がＡｌおよび不可避的不純物からなるアルミニウム合金を用い、シュウ酸を３０ｇ／Ｌ含む３０℃の溶液中で通電することにより陽極酸化皮膜を形成させた。陽極酸化皮膜厚さは、通電時間により調整した。
陽極酸化皮膜の厚さは、渦電流式膜厚計を用いて測定した。測定は、同一の箇所を５回測定し、その平均値を当該箇所の膜厚とした。
<Anode oxide film>
Anodic oxide films with thicknesses of 5, 10, 15, 20 and 30 μm were formed on the aluminum substrate, respectively, and the scratch resistance was evaluated.
The results are shown in FIG. Even with the anodized film alone, if the thickness is 15 μm or more, the scratch resistance is improved as compared to the conventional Ni—P plating treatment (10 μm thickness). That is, it means that anodizing treatment is effective for improving the brazing resistance of the aluminum substrate. In the case of the anodized film alone, when the thickness is 30 μm, although the resistance to scratching is slight compared with 20 μm, it shows a deterioration tendency. This is presumed to be because the anodizing treatment time became long and the vicinity of the surface of the film formed in the early stage was corroded by the electrolytic solution.
As an aluminum substrate, Mg: 5.5 wt%, Cu: 0.04 wt%, Si: 0.01 wt%, Fe: 0.015 wt%, Mn: 0.3 wt% and Cr: 0.. An anodized film was formed by applying current in a 30 ° C. solution containing 30 g / L of oxalic acid using an aluminum alloy containing 5 wt% and the balance Al and incidental impurities. The anodized film thickness was adjusted by the current application time.
The thickness of the anodized film was measured using an eddy current film thickness meter. In the measurement, the same portion was measured 5 times, and the average value was taken as the film thickness of the portion.
耐疵付き性の評価は、新東科学社製Ｔｙｐｅ１８の連続荷重式引掻強度試験機を用いて測定した。測定は、先端にＲ加工を施し、圧子に半径０．１ｍｍのダイヤモンド球を用いた円錐型引掻針に、１０、２０（あるいは２５）、５０、７０、１００ｇの荷重を負荷して、試験片表面を１０ｍｍ走引した。走引後、試験片表面に形成される疵の深さを測定した。
疵深さは、ＫＬＡ−Ｔｅｎｃｏｒ社アルファステップ段差計を用いて測定した。
図２中、「５μｍ」、「１０μｍ」、「１５μｍ」、「２０μｍ」、「３０μｍ」とはそれぞれ陽極酸化皮膜の膜厚を表し、「Ｇサブ」とは表面を研削し表面処理を行っていないアルミニウム基板を表し、「ＮＰＰ」とは研削後にＮｉＰめっきを施した後表面研磨したアルミニウム基板を表す。
The evaluation of the scratch resistance was measured using a Shinto Scientific Co., Ltd. Type 18 continuous load type scratch strength tester. The measurement is conducted by applying a load of 10, 20 (or 25), 50, 70, 100g to a conical scratching needle which is subjected to rounding at the tip and a diamond ball with a radius of 0.1 mm for the indenter. One surface was pulled 10 mm. After running, the depth of the wrinkles formed on the surface of the test piece was measured.
The weir depth was measured using a KLA-Tencor alpha step profilometer.
In FIG. 2, “5 μm”, “10 μm”, “15 μm”, “20 μm” and “30 μm” respectively indicate the film thickness of the anodized film, and “G sub” is performing surface treatment by grinding the surface "NPP" represents an aluminum substrate that has been subjected to NiP plating after grinding and then surface-polished.
＜陽極酸化皮膜とシリカ膜の組み合わせ＞
陽極酸化皮膜厚さを１０μｍと１５μｍとし、表１に示したＰＨＰＳとＭＨＰＳのブレンド品のうち、ＰＨＰＳ：ＭＨＰＳ（重量比）が８：２、６：４、４：６、２：８及び０：１０の溶液をそれぞれ陽極酸化皮膜に塗工し、水蒸気を含む雰囲気中で３００℃、１時間の熱処理を行うことでシリカ転化し、厚さ０．６μｍおよび１．２μｍのシリカ膜をそれぞれ得た。膜厚は、同一条件で調製した試験片の断面ＳＥＭ観察から求めた。作製した試料について表２にまとめた。
<Combination of anodic oxide film and silica film>
Among the blends of PHPS and MHPS shown in Table 1 with anodized film thicknesses of 10 μm and 15 μm, PHPS: MHPS (weight ratio) 8: 2, 6: 4, 4: 6, 2: 8 and 0 Each of the following solutions is applied to the anodic oxide film, and heat treatment is performed in an atmosphere containing water vapor at 300 ° C. for 1 hour to convert the silica to obtain silica films having a thickness of 0.6 μm and 1.2 μm. The The film thickness was determined from cross-sectional SEM observation of a test piece prepared under the same conditions. The prepared samples are summarized in Table 2.
各試料の耐疵付性を評価は、先の陽極酸化皮膜の耐疵付性の評価と同様の方法により行った。それらの結果を図３〜５に示す。図３は表２におけるＮｏ．７〜１０（記号 ８：２−２、６：４−２、４：６−２、２：８−２）の結果、図４は表２におけるＮｏ．１１〜１３（記号 ６：４−１、４：６−１、０：１０−１）の結果、図５は表２におけるＮｏ．１４〜１７（記号 ６：４−１、６：４−２、４：６−１、４：６−２）の結果である。図３〜５における「ＮＰＰ」とは参照のニッケルリンめっき基板の結果であり、「陽極酸化１０μｍ」とは膜厚１０μｍの陽極酸化皮膜単独での耐疵付性の結果であり、「陽極酸化１５μｍ」とは膜厚１５μｍの陽極酸化皮膜単独での耐疵付性の結果である。
なお、シリカコートの厚さが０．１μｍ以下の場合、ＰＨＰＳとＭＨＰＳのブレンド比によらず押込み荷重が２５ｇｆを超えると、陽極酸化皮膜単独の場合と、耐疵付性に優位な差は認められなかった。
The evaluation of the rust resistance of each sample was performed by the same method as the evaluation of the rust resistance of the anodized film described above. The results are shown in FIGS. FIG. 3 shows No. 1 in Table 2. 7 to 10 (symbols 8: 2-2, 6: 4-2, 4: 6-2, 2: 8-2), FIG. As a result of FIG. 5, the results of Nos. 11 to 13 in Table 2 are shown. It is a result of 14-17 (symbols 6: 4-1, 6: 4-2, 4: 6-1, 4: 6-2). The “NPP” in FIGS. 3 to 5 is the result of the reference nickel phosphorus plating substrate, and the “anodized 10 μm” is the result of the resistance to scratching with an anodic oxide film alone having a thickness of 10 μm. “15 μm” is the result of the scratch resistance of an anodic oxide film alone with a film thickness of 15 μm.
In addition, when the thickness of the silica coat is 0.1 μm or less, when the indentation load exceeds 25 gf regardless of the blend ratio of PHPS and MHPS, the superior difference in the abrasion resistance is recognized from the case of the anodic oxide film alone. It was not done.
以上の結果より、ＭＨＰＳ単体のシリカ前駆体又はＰＨＰＳにＭＨＰＳを混合したシリカ前駆体を、陽極酸化皮膜上に塗工した後にシリカ転化することで、耐熱性、耐疵付性に優れたアルミニウム基板を得ることができる。 From the above results, an aluminum substrate excellent in heat resistance and scratch resistance by applying silica precursor of MHPS alone or silica precursor obtained by mixing MHPS with PHPS on an anodic oxide film and converting to silica You can get
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