JP3661734B2 - Needle-like hematite particle powder for nonmagnetic underlayer of magnetic recording medium using metal magnetic particle powder containing iron as main component, and magnetic recording medium having nonmagnetic underlayer using the acicular hematite particle powder - Google Patents

Description

【０１４８】
得られたヘマタイト粒子を含む塗料を厚さ１２μｍのポリエチレンテレフタレートフィルム上にアプリケーターを用いて５５μｍの厚さに塗布し、次いで、乾燥させることにより非磁性下地層を形成した。非磁性下地層の厚みは３．４μｍであった。
【０１４９】
得られた非磁性下地層は、光沢が１９８％、表面粗度Ｒａが６．８ｎｍであり、基体のヤング率（相対値）は１２６であった。
【０１５０】
＜磁気記録層の製造＞
鉄を主成分とする針状金属磁性粒子粉末（平均長軸径０．１５３μｍ、平均短軸径０．０２１２μｍ、軸比７．２、保磁力１８６６Ｏｅ、飽和磁化値１３０．６ｅｍｕ／ｇ）１２ｇ、研磨剤（商品名：ＡＫＰ−３０、住友化学（株）製）１．２ｇ、カーボンブラック（商品名：＃３２５０Ｂ、三菱化成（株）製）０．１２ｇ、結合剤樹脂溶液（スルホン酸ナトリウム基を有する塩化ビニル−酢酸ビニル共重合樹脂３０重量％とシクロヘキサノン７０重量％）及びシクロヘキサノンとを混合して混合物（固形分率７８％）を得、この混合物を更にプラストミルで３０分間混練して混練物を得た。
【０１５１】
この混練物を１４０ｍｌガラス瓶に１．５ｍｍφガラスビーズ９５ｇ、結合剤樹脂溶液（スルホン酸ナトリウム基を有するポリウレタン樹脂３０重量％、溶剤（メチルエチルケトン：トルエン＝１：１）７０重量％）、シクロヘキサノン、メチルエチルケトン及びトルエンとともに添加し、ペイントシェーカーで６時間混合・分散を行って磁性塗料を得た。その後、潤滑剤及び硬化剤を加え、さらに、ペイントシェーカーで１５分間混合・分散した。
【０１５２】
得られた磁性塗料の組成は下記の通りであった。

【０１５３】
磁性塗料を前記非磁性下地層の上にアプリケーターを用いて１５μｍの厚さに塗布した後、磁場中において配向・乾燥し、次いで、カレンダー処理を行った後、６０℃で２４時間硬化反応を行い０．５インチ幅にスリットして磁気テープを得た。磁気記録層の厚みは１．０μｍであった。
【０１５４】
得られた磁気テープは、Ｈｃが１９５６Ｏｅ、角型比（Ｂｒ／Ｂｍ）が０．８７、光沢度が２２８％、表面粗度Ｒａが６．２ｎｍ、ヤング率（相対値）が１３５、線吸収係数が１．２５、走行耐久性が２６．３分、すり傷特性がＡであった。磁気テープの磁気特性の経時変化は、保磁力については４．４％、飽和磁束密度Ｂｍについては３．６％であった。
【０１５５】
【作用】
本発明において最も重要な点は、粒子内部にＴｉ換算で０．０５〜５０重量％のチタンを含有している針状ヘマタイト粒子からなり、平均長軸径が０．３μｍであって、粉体ｐＨ値が８以上、且つ、可溶性ナトリウムの含有量がＮａ換算で３００ｐｐｍ以下、可溶性硫酸塩の含有量がＳＯ₄ 換算で１５０ｐｐｍ以下である高密度針状ヘマタイト粒子を、非磁性下地層用の非磁性粒子粉末として使用した場合には、該結合剤樹脂中における分散性が優れていることに起因して、非磁性下地層の表面平滑性と基体の強度を向上させることができ、当該非磁性下地層の上に磁気記録層を設けた場合に、磁気記録層の光透過率を小さくし、表面平滑で、強度が大きく、且つ、耐久性に優れている磁気記録媒体を得ることができるとともに、磁気記録層中に分散させている鉄を主成分とする金属磁性粒子粉末の腐蝕に伴う磁気特性の劣化を抑制することができるという事実である。
【０１５６】
非磁性下地層の表面平滑性と基体の強度をより向上させることができた理由について、本発明者は、高密度針状ヘマタイト粒子相互を強固に架橋して凝集させる原因となっている可溶性ナトリウム塩や可溶性硫酸塩を十分水洗除去することができたことに起因して、凝集物が解きほぐされて、実質的に独立している粒子とすることができ、その結果、ビヒクル中における分散性が優れた針状ヘマタイト粒子粉末が得られることによるものと考えている。
【０１５７】
本発明に係る針状ヘマタイト粒子粉末はビヒクル中における分散性が優れているという事実について、以下に説明する。
【０１５８】
前駆体として使用する針状ゲータイト粒子粉末は、前述した通り、各種製造法により製造されるが、いずれの方法においても針状ゲータイト粒子を製造する主な原料が硫酸第一鉄である場合には当然反応母液中に硫酸塩〔ＳＯ₄ ^--〕が多量に存在するのである。
【０１５９】
特に、酸性溶液中からゲータイト粒子を生成する場合には、同時に、Ｎａ₂ ＳＯ₄ 等水可溶性硫酸塩を生じるとともに、反応母液にはＫ⁺ 、ＮＨ₄ ⁺ 、Ｎａ⁺ 等アルカリ金属を含んでいるので、アルカリ金属や硫酸塩を含む沈澱を生じ易く、この沈澱はＲＦｅ₃ （ＳＯ₄ ）（ＯＨ）₆ （Ｒ＝Ｋ⁺ 、ＮＨ₄ ⁺ 、Ｎａ⁺ ）で示される。これら沈澱物は難溶性の含硫鉄塩で常法による水洗によっては除去することができない。この難溶性塩はその後の加熱処理工程において可溶性ナトリウム塩や可溶性硫酸塩になるが、この可溶性ナトリウム塩や可溶性硫酸塩は、高密度化のための高温加熱処理工程において針状ヘマタイト粒子の形状の変形、粒子相互間の焼結を防止するために必須である焼結防止剤によって、針状ヘマタイト粒子相互を架橋しながら粒子内部及び粒子表面に強固に結合されることにより、針状ヘマタイト粒子相互間の凝集が一層強まる。その結果、殊に、粒子内部や凝集物内部に閉じ込められた可溶性硫酸塩や可溶性ナトリウム塩は、常法による水洗によって除去することが極めて困難となる。
【０１６０】
硫酸第一鉄と水酸化ナトリウムとを用いてアルカリ性水溶液中で針状ゲータイト粒子を生成する場合には、同時に生成される硫酸塩はＮａ₂ ＳＯ₄ であり、また、母液中にＮａＯＨが存在し、これらは共に可溶性であるため針状ゲータイト粒子を十分水洗すれば本質的にはＮａ₂ ＳＯ₄ およびＮａＯＨを除去できるはずである。しかし、一般には針状ゲータイト粒子の結晶性が小さい為、水洗効率が悪く、常法により水洗した場合、なお、粒子中に可溶性硫酸塩〔ＳＯ₄ ^--〕、可溶性ナトリウム塩〔Ｎａ⁺ 〕等水可溶性分を含んでいる。そして、この水可溶性分は、前述した通り、焼結防止剤によって針状ヘマタイト粒子相互を架橋しながら粒子内部及び粒子表面に強固に結合されることにより、針状ヘマタイト粒子相互間の凝集が一層強まる。その結果、殊に、粒子内部や凝集物内部に閉じ込められた可溶性硫酸塩や可溶性ナトリウム塩は、常法による水洗によって除去することが極めて困難となる。
【０１６１】
上述した通り、可溶性ナトリウム塩や可溶性硫酸塩が焼結防止剤を介在して粒子内部や粒子表面及び凝集物内部に強く結合されている高密度ヘマタイト粒子は、湿式粉砕して粗粒をほぐした後、スラリーのｐＨ値を１３以上に調整し、８０℃以上の温度で加熱処理すると、アルカリ性水溶液が高密度ヘマタイト粒子の粒子内部まで十分浸透し、その結果、粒子内部や粒子表面及び凝集物内部に強く結合している焼結防止剤の結合力が徐々に弱まり、粒子内部や粒子表面及び凝集物内部から解離され、同時に水可溶性ナトリウム塩や水可溶性硫酸塩も水洗除去しやすくなるものと考えられる。
【０１６２】
磁気記録媒体表面及び磁気記録媒体自体の耐久性が向上した理由については未だ明らかではないが、本発明者は、粒子内部にチタンが均一に含有されているヘマタイト粒子を非磁性粒子として用いたことや、該ヘマタイト粒子の可溶性塩の含有量が少ないこと及びｐＨ値が特定範囲であることなどの相乗効果に起因して、後出実施例に示す通り、ヘマタイト粒子のビヒクル中における結合剤樹脂との樹脂吸着強度が高まり、その結果、非磁性下地層中におけるヘマタイト粒子と結合剤樹脂との密着度や非磁性下地層自体の非磁性支持体への密着度が高まったことによるものと考えている。
【０１６３】
磁気記録層中に分散されている鉄を主成分とする金属磁性粒子粉末の腐蝕に伴う磁気特性の劣化が抑制される理由について、本発明者は、金属の腐蝕を促進する可溶性ナトリウム塩や可溶性硫酸塩等の可溶性分が高密度針状ヘマタイト粒子中に少ないこと及びヘマタイト粒子自体の粉体ｐＨ値が８以上と高いことに起因して鉄を主成分とする金属磁性粒子粉末の腐蝕の進行が抑制できたものと考えている。
【０１６４】
事実、本発明者は、後出の実施例及び比較例に示す通り、湿式粉砕後の高密度ヘマタイト粒子を８０℃以上の温度、ｐＨ値が１３未満のアルカリ水溶液で加熱処理した場合、湿式粉砕後の高密度ヘマタイト粒子を８０℃未満の温度、ｐＨ値が１３以上のアルカリ水溶液で加熱処理した場合、高密度ヘマタイト粒子を湿式粉砕をすることなく粗粒を含んだままで８０℃以上の温度下、ｐＨ値１３以上のアルカリ性水溶液中で加熱処理した場合のいずれの場合にも、鉄を主成分とする金属磁性粒子粉末の腐蝕の進行を十分に抑制できないことから、可溶性分が少ないことと、粉体ｐＨ値が８以上であることの相乗効果により鉄を主成分とする金属磁性粒子粉末の腐蝕の進行が抑制できるという現象を確認している。
【０１６５】
【実施例】
次に、実施例並びに比較例を挙げる。
【０１６６】
＜針状ゲータイト粒子粉末の種類＞
針状ヘマタイト粒子を製造するための前駆体として下記の前駆体１乃至８を準備した。
【０１６７】
【表１】

【０１６８】
＜低密度針状ヘマタイト粒子粉末の製造＞
中間粒子１〜１５及び比較中間粒子１〜１５
前駆体である針状ゲータイト粒子粉末の種類、焼結防止剤の種類及び量、加熱脱水温度及び時間を種々変化させた以外は、前記本発明の実施の形態と同様にして低密度針状ヘマタイト粒子を得た。尚、比較中間粒子４で得られた粒子は、ゲータイト粒子である。
【０１６９】
この時の主要製造条件及び諸特性を表２乃至表５に示す。
【０１７０】
【表２】

【０１７１】
【表３】

【０１７２】
【表４】

【０１７３】
【表５】

【０１７４】
＜高密度針状ヘマタイト粒子粉末の製造＞
中間粒子１６〜３０及び比較中間粒子１６〜２９
低密度針状ヘマタイト粒子粉末の種類、高密度化加熱処理の温度及び時間を種々変化させた以外は、前記本発明の実施の形態と同様にして高密度針状ヘマタイト粒子を得た。
【０１７５】
この時の主要製造条件及び諸特性を表６及び表７に示す。
【０１７６】
【表６】

【０１７７】
【表７】

【０１７８】
＜針状ヘマタイト粒子のアルカリ水溶液中における処理＞
実施例１〜１５及び比較例１〜９
高密度針状ヘマタイト粒子粉末の種類、湿式粉砕の有無、アルカリ水溶液中における加熱処理の有無、スラリーのｐＨ値、加熱温度及び加熱時間を種々変化させた以外は、前記本発明の実施の形態と同様にして針状ヘマタイト粒子を得た。
【０１７９】
この時の主要製造条件及び諸特性を表８乃至表１１に示す。
【０１８０】
【表８】

【０１８１】
【表９】

【０１８２】
【表１０】

【０１８３】
【表１１】

【０１８４】
＜針状ヘマタイト粒子の表面被覆処理＞
実施例１６
アルカリ性水溶液中における加熱処理後にデカンテーション法により水洗して得られた実施例３１のｐＨ値が１０．５のスラリーは、スラリー濃度が９８ｇ／ｌであった。このスラリー５ｌを再度加熱して６０℃とし、このスラリー中に１．０ＮのＮａＡｌＯ₂ 溶液５４４ｍｌ（針状ヘマタイト粒子に対しＡｌ換算で３．０ｗｔ％に相当する。）を加え、３０分間保持した後、酢酸を用いてｐＨ値を８．５に調整した。次いで、前記本発明の実施の形態と同様にして濾別、水洗、乾燥、粉砕して粒子表面が被覆物により被覆されている針状ヘマタイト粒子粉末を得た。
【０１８５】
この時の主要製造条件及び諸特性を表１２及び表１３に示す。
【０１８６】
実施例１７〜３０
針状ヘマタイト粒子粉末の種類、表面処理物の種類及び量を種々変化させた以外は、実施例１６と同様にして表面被覆針状ヘマタイト粒子を得た。
【０１８７】
この時の主要製造条件及び諸特性を表１２及び表１３に示す。
【０１８８】
【表１２】

【０１８９】
【表１３】

【０１９０】
＜非磁性下地層の製造＞
下地層１〜３０及び比較下地層１〜１６
実施例１〜３０及び比較中間粒子１、３、１６〜１９、２４、比較例１〜９で得られた針状ヘマタイト粒子を用いて前記本発明の実施の形態と同様にして非磁性下地層を得た。
【０１９１】
この時の主要製造条件及び諸特性を表１４乃至表１６に示す。
【０１９２】
【表１４】

【０１９３】
【表１５】

【０１９４】
【表１６】

【０１９５】
＜鉄を主成分とする金属磁性粒子粉末を使用している磁気記録媒体の製造＞
実施例３１〜６０及び比較例１０〜２５
下地層１〜３０及び比較下地層１〜１６で得られた非磁性下地層の種類、鉄を主成分とする針状金属磁性粒子粉末の種類を種々変化させた以外は、前記本発明の実施の形態と同様にして鉄を主成分とする金属磁性粉末を使用している磁気記録媒体を製造した。
【０１９６】
この時の主要製造条件及び諸特性を表１７乃至表１９に示す。
【０１９７】
【表１７】

【０１９８】
【表１８】

【０１９９】
【表１９】

【０２００】
【発明の効果】
本発明に係る針状ヘマタイト粒子粉末は、前出実施例に示した通り、非磁性下地層用非磁性粉末として用いた場合、粉体ｐＨ値が８以上であって可溶性塩の含有量が少ないことに起因してビヒクル中での分散性が優れているので基体としての強度と表面性に優れている非磁性下地層を得ることができ、該非磁性下地層を用いて磁気記録媒体とした場合において光透過率が小さく、表面平滑で、強度が大きい磁気記録媒体を得ることができ、しかも、該磁気記録媒体は、非磁性下地層用非磁性粉末である針状ヘマタイト粒子が粒子内部にチタンを均一に含有していることに起因して耐久性に優れたものであるので、高密度磁気記録媒体の非磁性下地層用として好ましいものである。
【０２０１】
そして、本発明に係る磁気記録媒体は、上述した通り、光透過率が小さく、表面平滑で、強度が大きく、且つ、耐久性に優れているとともに、磁気記録層中の鉄を主成分とする針状金属磁性粒子粉末の腐蝕に伴う磁気特性の劣化を抑制することができるので、高密度磁気記録媒体として好ましいものである。[0001]
[Industrial application fields]
The present invention has a low light transmittance, a smooth surface, high strength, excellent durability, and corrosion of metal magnetic particle powder mainly composed of iron dispersed in a magnetic recording layer. Provided is a needle-like hematite particle powder suitable as a nonmagnetic particle powder for a nonmagnetic underlayer in order to obtain a magnetic recording medium having a nonmagnetic underlayer in which the accompanying deterioration of magnetic properties is suppressed.
[0002]
[Prior art]
In recent years, as video recording and audio magnetic recording / reproducing devices have been recorded for a long time and reduced in size and weight, the performance of magnetic recording media such as magnetic tapes and magnetic disks has been improved, that is, higher recording density and higher output characteristics. In particular, there is an increasing demand for improvement of frequency characteristics and low noise.
[0003]
In order to improve these various characteristics of the magnetic recording medium, various attempts have been made in terms of both high performance of the magnetic particle powder and thinning of the magnetic layer.
[0004]
First, the performance enhancement of the magnetic particle powder will be described.
[0005]
A characteristic of the magnetic particle powder suitable for satisfying the above requirements for the magnetic recording medium is that it has a high coercive force and a large saturation magnetization.
[0006]
In recent years, acicular metal magnetic particle powders mainly composed of iron obtained by heating and reducing acicular goethite particles or acicular hematite particles in a reducing gas as magnetic powders suitable for high output and high density recording have been widely used. in use.
[0007]
The acicular metal magnetic particle powder mainly composed of iron has high coercive force and large saturation magnetization, but the acicular metal magnetic particle powder mainly composed of iron used for magnetic recording media is 1 μm or less, especially about 0.01 to 0.3 μm, so that it is easy to be corroded, magnetic characteristics are deteriorated, and particularly, the saturation magnetization and the coercive force are reduced. is there.
[0008]
Therefore, in order to maintain the characteristics of magnetic recording media that use metal magnetic particle powder containing iron as a main component as a magnetic particle powder over a long period of time, corrosion of acicular metal magnetic particles containing iron as a main component is required. It is strongly required to suppress as much as possible.
[0009]
Next, the thinning of the magnetic recording layer will be described.
[0010]
Recently, the demand for higher image quality of video tapes is increasing, and the frequency of the carrier signal to be recorded is higher than that of conventional video tapes. That is, it has shifted to the short wavelength region, and as a result, the magnetization depth from the surface of the magnetic tape is remarkably shallow.
[0011]
In order to improve the high output characteristics of a magnetic recording medium, particularly the S / N ratio, with respect to a short wavelength signal, it is strongly required to make the magnetic recording layer thinner. This is the case, for example, “Development of Magnetic Materials and Highly Dispersed Magnetic Powder Technology” (1982), page 312 published by the General Technology Center Co., Ltd. The high output characteristics can be maintained with low noise with respect to the wavelength signal. For this purpose, both the coercive force Hc and the residual magnetization Br are required to be large and the coating film must be thinner. "..." as described.
[0012]
As the magnetic recording layer becomes thinner, several problems have arisen. First, it is a problem of smoothing and uneven thickness of the magnetic recording layer. As is well known, in order to make the magnetic recording layer smooth and free of uneven thickness, the surface of the base film must also be smooth. . This is the case, for example, published by the Engineering Information Center Publishing Department, "Magnetic Tape-Friction and Wear Occurrence Factors and Trouble Countermeasures for the Head Running System-Comprehensive Technical Documents" “The surface roughness of the magnetic layer after curing is strongly dependent on the surface roughness of the base (back surface roughness), and the two are almost proportional to each other. As the surface of the base is smoothened, the uniform and large head output is obtained and the S / N is improved.
[0013]
Secondly, the base film is also made thinner like the magnetic layer, and as a result, the strength of the base film has become a problem. This fact is, for example, the above-mentioned “Development of magnetic materials and high dispersion technology of magnetic powder” on page 77 “… ...... High density recording is a major theme imposed on the current magnetic tape. In order to shorten the length of the tape and miniaturize the cassette, it is important for long-time recording, which requires reducing the thickness of the film base. As the tape becomes thinner, the tape stiffness decreases sharply, making it difficult to run smoothly on the recorder. The improvement is greatly desired.
[0014]
By the way, determination of the end of the magnetic tape of a magnetic recording medium such as a video tape is currently performed by detecting a portion of the magnetic recording medium having a high light transmittance with a video deck. Magnetic recording media become difficult to detect if the light transmittance of the entire magnetic recording layer increases as the magnetic recording medium becomes thinner or the magnetic particle powder dispersed in the magnetic recording layer becomes ultrafine. The light transmittance is reduced by adding carbon black or the like to the layer. Therefore, the addition of carbon black or the like to the magnetic recording layer is essential in the current video tape.
[0015]
However, the addition of a large amount of nonmagnetic carbon black or the like not only inhibits high density recording, but also inhibits thinning. In order to further reduce the thickness of the magnetic tape by reducing the magnetization depth from the surface of the magnetic tape, it is strongly required to reduce the nonmagnetic particle powder such as carbon black added to the magnetic recording layer as much as possible. Yes.
[0016]
Therefore, there is a strong demand for a magnetic recording medium having a low light transmittance even if the amount of carbon black added to the magnetic recording layer is reduced. From this point, improvement of the substrate is also strongly demanded.
[0017]
Furthermore, the demand for higher performance of magnetic recording media has not been limited recently, and the surface of the magnetic recording layer and the magnetic recording medium itself have been reduced along with the thinning of the magnetic recording layer and the thinning of the nonmagnetic support described above. Therefore, it is strongly required to improve the durability of the magnetic recording layer surface and the magnetic recording medium itself.
[0018]
This fact is disclosed in Japanese Patent Application Laid-Open No. 5-298679, “......... in recent years, with the development of magnetic recording, the demand for high image quality and high sound quality is increasing. There is a demand for higher density, lower noise by smoothing the surface of the magnetic tape, and higher C / N .... However, while the magnetic tape is running, As a result of the increase in the friction coefficient of contact, the magnetic layer of the magnetic recording medium tends to be damaged or the magnetic layer tends to peel off after a short period of use. However, since the ferromagnetic powder tends to fall off from the magnetic layer and cause clogging of the magnetic head, it is desired to improve the running durability of the magnetic layer of the magnetic recording medium. It is clear from the description made.
[0019]
Various attempts have been made to improve the substrate for forming the magnetic recording layer as the magnetic recording layer is thinned or the nonmagnetic support is thinned. At least one underlayer (hereinafter referred to as a nonmagnetic underlayer) in which nonmagnetic particle powder such as hematite particles is dispersed in a binder has been provided and has already been put into practical use. (Japanese Patent Publication Nos. 6-93297, 62-159338, 63-187418, 4-167225, 4-325915, 5-73882, JP-A-5-182177, JP-A-5-347017, JP-A-6-60362, etc.)
[0020]
Further, as a nonmagnetic particle powder for a nonmagnetic underlayer, there is known a nonmagnetic particle whose surface is treated with a titanium compound or the like for the purpose of improving dispersibility in a vehicle (Japanese Patent No. 2571350). ,Japanese Patent No. 2582051, Japanese Patent Laid-Open No. 6-60362, Japanese Patent Laid-Open No. 9-22524, Japanese Patent Laid-Open No. 9-27117).
[0021]
[Problems to be solved by the invention]
In addition to thinning of the magnetic recording layer, as the nonmagnetic support is thinned, the light transmittance is small, the surface is smooth, the strength is high, and the durability is excellent. A magnetic recording medium in which the corrosion of the metal magnetic particle powder containing iron as a main component dispersed therein is suppressed is currently most demanded, but such a magnetic recording medium has not yet been obtained.
[0022]
That is, a magnetic recording medium manufactured using a substrate having a nonmagnetic underlayer formed by dispersing nonmagnetic powder in a binder resin on a nonmagnetic support has a low light transmittance, a smooth surface, and strength. However, there was a problem that the durability was poor.
[0023]
This fact is disclosed in Japanese Patent Application Laid-Open No. 5-182177, "If the magnetic layer is provided as an upper layer after providing a non-magnetic thick undercoat layer on the support surface, the effect of the surface roughness of the support is described. However, there is a problem that the head wear and durability are not improved because the thermosetting resin is used as a binder as a non-magnetic lower layer, and the lower layer is hardened and magnetic. It is considered that the friction between the layer and the head and the contact with other members are performed in an unbuffered state, and the magnetic recording medium having such a lower layer is slightly inflexible. ... ”As described.
[0024]
Further, it has been pointed out that the metal magnetic particle powder containing iron as a main component dispersed in the magnetic recording layer is corroded after the production, resulting in a significant decrease in magnetic properties.
[0025]
Therefore, the present invention can improve the surface smoothness and strength of the nonmagnetic underlayer, and when the magnetic recording layer is provided on the nonmagnetic underlayer, the light transmittance is small, the surface is smooth, The magnetic recording medium has high strength and excellent durability, and deterioration of magnetic properties due to corrosion of iron-based metal magnetic particle powder dispersed in the magnetic recording layer is suppressed. Obtaining a magnetic recording medium is a technical problem.
[0026]
[Means for solving the problems]
The technical problem can be achieved by the present invention as follows.
[0027]
That is, the present invention consists of acicular hematite particles containing 0.05 to 50% by weight of titanium in terms of Ti inside the particles, the average major axis diameter is 0.3 μm or less, and the powder pH value Is 8 or more, the content of soluble sodium salt is 300 ppm or less in terms of Na, and the content of soluble sulfate is SO_FourIt is acicular hematite particle powder for a nonmagnetic underlayer of a magnetic recording medium using a metal magnetic particle powder containing iron as a main component, wherein the acicular hematite particle powder is 150 ppm or less in terms of conversion.
[0028]
Further, the present invention is characterized in that the particle surface is composed of the acicular hematite particle powder coated with at least one of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. The needle-shaped hematite particle powder for a nonmagnetic underlayer of a magnetic recording medium using a metal magnetic particle powder containing iron as a main component.
[0029]
The present invention also comprises a nonmagnetic underlayer comprising a nonmagnetic support, a nonmagnetic particle powder and a binder resin formed on the nonmagnetic support, and iron formed on the nonmagnetic underlayer as a main component. A magnetic recording medium comprising a metal magnetic particle powder and a magnetic recording layer comprising a binder resin, wherein the non-magnetic particle powder is any one of the acicular hematite particle powders as a main component A magnetic recording medium using the metal magnetic particle powder.
[0030]
The configuration of the present invention will be described in more detail as follows.
[0031]
First, the acicular hematite particle powder for a nonmagnetic underlayer of a magnetic recording medium using the metal magnetic particle powder containing iron as a main component according to the present invention will be described.
[0032]
The acicular hematite particle powder according to the present invention contains 0.05 to 50% by weight of titanium in terms of Ti inside the particle.
[0033]
When the amount of titanium is less than 0.05% by weight in terms of Ti with respect to hematite particles containing titanium, the obtained magnetic recording medium does not have sufficient durability. If it exceeds 50% by weight, the obtained magnetic recording medium has sufficient durability, but the effect is saturated, so there is no point in containing it more than necessary. Preferably it is 0.1-45 weight%, More preferably, it is 0.5-35 weight%, More preferably, it is 1.0-20 weight%.
[0034]
The acicular hematite particle powder according to the present invention has an axial ratio (average major axis diameter: average minor axis diameter, hereinafter simply referred to as “axial ratio”) of 2: 1 or more, preferably 3: 1 or more. . In consideration of the dispersibility in the vehicle, the upper limit is preferably 20: 1 or less, preferably 10: 1 or less. Here, the acicular particles mean not only acicular shapes but also spindle shapes, rice grains, and the like.
[0035]
When the axial ratio is less than 2, it is difficult to obtain a desired coating film strength.
[0036]
The average major axis diameter of the acicular hematite particle powder according to the present invention is 0.3 μm or less. When the average major axis diameter exceeds 0.3 μm, the particle size is too large, which is not preferable because the surface smoothness of the coating film is impaired. When the average major axis diameter of the hematite particles is less than 0.005 μm, dispersion in the vehicle becomes difficult. Considering the dispersibility in the vehicle and the surface smoothness of the coating film, 0.02 to 0.28 μm is preferable.
[0037]
The acicular hematite particles according to the present invention preferably have an average minor axis diameter of 0.0025 to 0.15 μm. When it is less than 0.0025 μm, it is not preferable because dispersion in the vehicle becomes difficult. When the average minor axis diameter exceeds 0.15 μm, the particle size is too large, which is not preferable because the surface smoothness of the coating film is impaired. In consideration of the dispersibility in the vehicle and the surface smoothness of the coating film, 0.01 to 0.10 μm is preferable.
[0038]
The powder pH value of hematite particles is 8 or more. When the pH value of the powder is less than 8, the metal magnetic particle powder mainly composed of iron contained in the magnetic recording layer formed on the nonmagnetic underlayer is gradually corroded to deteriorate the magnetic characteristics. cause. In consideration of the corrosion prevention effect of the metal magnetic particle powder containing iron as a main component, the powder pH value is preferably 8.5 or more, more preferably 9.0 or more. The upper limit is a powder pH value of 12, preferably a powder pH value of 11, more preferably a powder pH value of 10.5.
[0039]
The content of the soluble sodium salt of the acicular hematite particles is 300 ppm or less in terms of Na. When it exceeds 300 ppm, the metal magnetic particle powder mainly composed of iron contained in the magnetic recording layer formed on the nonmagnetic underlayer is gradually corroded to cause deterioration of magnetic properties. In addition, the dispersion characteristics of the hematite particles in the vehicle are liable to be impaired, and the white flower phenomenon may occur in the storage state of the magnetic recording medium, particularly in a high humidity environment. Considering the corrosion prevention effect of the metal magnetic particle powder containing iron as a main component, it is preferably 250 ppm or less, more preferably 200 ppm or less, and still more preferably 150 ppm or less. Considering industrial properties such as productivity, the lower limit is about 0.01 ppm.
[0040]
The content of soluble sulfate in acicular hematite particles is SO_FourIt is 150 ppm or less in terms of conversion. When it exceeds 150 ppm, the metal magnetic particle powder mainly composed of iron contained in the magnetic recording layer formed on the nonmagnetic underlayer is gradually corroded to cause deterioration of magnetic properties. In addition, the dispersion characteristics of the hematite particles in the vehicle are liable to be impaired, and the white flower phenomenon may occur in the storage state of the magnetic recording medium, particularly in a high humidity environment. Considering the corrosion prevention effect of the metal magnetic particle powder containing iron as a main component, it is preferably 70 ppm or less, more preferably 50 ppm or less. Considering industrial properties such as productivity, the lower limit is about 0.01 ppm.
[0041]
The acicular hematite particles according to the present invention have a BET specific surface area value of 35 m.²/ G or more is preferable. 35m²If it is less than / g, the hematite particles are coarse or particles are sintered between the particles, which adversely affects the surface smoothness of the coating film. Preferably 37m²/ G or more, more preferably 40 m²/ G and the upper limit is 150 m²/ G. Considering dispersibility in the vehicle, preferably 100 m²/ G or less, more preferably 80 m²/ G or less.
[0042]
The acicular hematite particles according to the present invention preferably have a major axis diameter particle size distribution of 1.50 or less in terms of geometric standard deviation. When the ratio exceeds 1.5, the existing coarse particles adversely affect the surface smoothness of the coating film, which is not preferable. Considering the surface smoothness of the coating film, it is preferably 1.48 or less, more preferably 1.45 or less. Considering industrial productivity, the lower limit of the particle size distribution of the major axis diameter of the hematite particles obtained is 1.01 in terms of geometric standard deviation.
[0043]
The acicular hematite particles according to the present invention are highly densified. Specific surface area S measured by BET method_BETSurface area S calculated from the major axis and minor axis diameters measured from the values and particles shown in the electron micrograph_TEMWhen expressed as a ratio to the value, it has 0.5 to 2.5.
[0044]
S_BET/ S_TEMWhen the value of is less than 0.5, the densification of the hematite particles has been achieved, but the particles are bonded together by sintering between the particles, the particle diameter is increased, the surface of the coating film Smoothness is not enough. S_BET/ S_TEMWhen the value exceeds 2.5, densification is not sufficient, and there are a large number of pores on the particle surface, resulting in insufficient dispersibility in the vehicle. Considering the surface smoothness of the coating and the dispersibility in the vehicle, S_BET/ S_TEMIs preferably 0.7 to 2.0, more preferably 0.8 to 1.6.
[0045]
S_BET/ S_TEMThe smaller the value, the higher the density of acicular non-magnetic particles containing iron as a main component is achieved, but the particles are bonded together by sintering between the particles, and the particle diameter is increased. The surface smoothness of the film tends to be insufficient. S_BET/ S_TEMWhen the value of is large, it is difficult to say that the densification is sufficient, and there are many pores on the particle surface, and the dispersibility in the vehicle tends to be insufficient.
[0046]
The acicular hematite particles according to the present invention have a resin adsorption strength of 65% or more, preferably 68% or more, and more preferably 70% or more. The upper limit is preferably about 95%.
[0047]
The needle-like hematite particles according to the present invention may be coated on the particle surface with at least one of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide, if necessary. The needle-like hematite particles whose particle surfaces are coated with a coating have a good affinity with the binder resin when dispersed in a vehicle, and a desired degree of dispersion is easily obtained.
[0048]
In the case of aluminum hydroxide or aluminum oxide, the amount of the above coating is calculated in terms of Al, and in the case of silicon hydroxide or silicon oxide, SiO.₂It is preferably 0.01 to 50% by weight based on the total weight of the particles. If it is less than 0.01% by weight, there is almost no effect of improving dispersibility by coating, and if it exceeds 50.00% by weight, the coating effect is saturated, so there is no meaning to add more than necessary. Considering the dispersibility and productivity in the vehicle, 0.05 to 20% by weight is more preferable.
[0049]
Average major axis diameter, powder pH value, soluble sodium salt content, soluble sulfate content, axial ratio (major axis), which are various characteristics of acicular hematite particle powder coated with a surface coating on the particle surface Diameter / minor axis diameter), average minor axis diameter, BET specific surface area, particle size distribution of major axis diameter, resin adsorption strength, degree of densification, etc. are almost the same as acicular hematite particle powder not coated with surface coating It is.
[0050]
Next, the magnetic recording medium according to the present invention will be described.
The nonmagnetic underlayer in the present invention is formed on a nonmagnetic support and is composed of acicular hematite particle powder and a binder resin.
[0051]
Nonmagnetic supports include polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, synthetic resin films such as polyamide, polyamideimide, and polyimide, which are currently widely used for magnetic recording media, metal foils such as aluminum and stainless steel, A board and various types of paper can be used, and the thickness varies depending on the material, but is usually preferably 1.0 to 300 μm, more preferably 2.0 to 200 μm. In the case of a magnetic disk, polyethylene terephthalate is usually used as the nonmagnetic support, and the thickness is usually 50 to 300 μm, preferably 60 to 200 μm. In the case of magnetic tape, in the case of polyethylene terephthalate, the thickness is usually 3 to 100 μm, preferably 4 to 20 μm. In the case of polyethylene naphthalate, the thickness is usually 3 to 50 μm, preferably 4 to 20 μm. The thickness is usually 2 to 10 μm, preferably 3 to 7 μm.
[0052]
The coating thickness of the nonmagnetic underlayer formed on the nonmagnetic support in the present invention is in the range of 0.2 to 10.0 μm. When the thickness is less than 0.2 μm, it is difficult to improve the surface roughness of the nonmagnetic support, and the strength tends to be insufficient. In order to obtain a thin magnetic recording medium, the upper limit is preferably about 10.0 μm, more preferably in the range of 0.5 to 5.0 μm.
[0053]
As binder resins, vinyl chloride vinyl acetate copolymer, urethane resin, vinyl chloride vinyl acetate maleate urethane elastomer, butadiene acrylonitrile copolymer, polyvinyl butyral, nitrocellulose, etc. that are currently widely used in the production of magnetic recording media Cellulose derivatives, polyester resins, synthetic rubber resins such as polybutadiene, epoxy resins, polyamide resins, polyisocyanate polymers, electron beam curable acrylic urethane resins, and mixtures thereof can be used. In addition, each binder resin has —OH, —COOH, —SO._ThreeM, -OPO₂M₂, -NH₂And the like (where M is H, Na, K). Considering the dispersibility of the particles, polar groups —COOH, —SO_ThreeBinder resins containing Na are preferred.
[0054]
The blending ratio of the acicular hematite particle powder and the binder resin in the nonmagnetic underlayer is 5 to 2000 parts by weight, preferably 100 to 1000 parts by weight of the acicular hematite particles with respect to 100 parts by weight of the binder resin.
[0055]
Note that a lubricant, an abrasive, an antistatic agent, and the like used in the production of a normal magnetic recording medium may be added to the nonmagnetic underlayer as necessary.
[0056]
The nonmagnetic underlayer containing acicular hematite particles that are not coated with the surface coating according to the present invention has a coating film glossiness of 185 to 280%, preferably 190 to 280%, more preferably 195 to 280%. The coating film surface roughness Ra is 2.0 to 10.0 nm, preferably 2.0 to 9.0 nm, and more preferably 2.0 to 8.0 nm.
The nonmagnetic underlayer containing acicular hematite particles coated with the surface coating according to the present invention has a coating film glossiness of 190 to 280%, preferably 193 to 280%, more preferably 196 to 280%. The coating film surface roughness Ra is 2.0 to 9.0 nm, preferably 2.0 to 8.0 nm, and more preferably 2.0 to 7.4 nm.
[0057]
In a magnetic recording medium, a magnetic recording layer made of a metal magnetic particle powder mainly composed of iron and a binder resin is provided on a nonmagnetic underlayer formed on a nonmagnetic support.
[0058]
The acicular metal magnetic particles mainly composed of iron have an average major axis diameter of 0.01 to 0.50 μm, preferably 0.03 to 0.30 μm, and an axial ratio of 3: 1 or more, preferably 5 In consideration of the dispersibility in the vehicle, the upper limit is 15: 1 or less, preferably 10: 1 or less. A spindle shape, a rice grain shape, etc. may be sufficient.
[0059]
The composition is particles containing 50 to 99% by weight of iron, preferably 60 to 95% by weight, and Co, Al, Ni, P, Si, B, Nd, La, Y other than iron if necessary. Etc. may be contained.
[0060]
In consideration of characteristics such as high density recording, the coercive force is preferably 1200 to 3200 Oe, more preferably 1500 to 2500 Oe, and saturation magnetization 100-170 emu / g is preferable, More preferably, it is 130-150 emu / g.
[0061]
As the binder resin in the magnetic recording layer, the binder resin used to form the nonmagnetic underlayer can be used.
[0062]
The coating thickness of the magnetic recording layer provided on the nonmagnetic underlayer is in the range of 0.01 to 5.0 μm. If the thickness is less than 0.01 μm, uniform coating is difficult and phenomena such as uneven coating tend to occur, which is not preferable. If it exceeds 5.0 μm, it is difficult to obtain desired electromagnetic conversion characteristics due to the influence of the demagnetizing field. Preferably it is the range of 0.05-1.0 micrometer.
[0063]
The blending ratio of the acicular metal magnetic particle powder containing iron as a main component and the binder resin in the magnetic recording layer is 200 to 200 wt. The amount is 2000 parts by weight, preferably 300-1500 parts by weight.
[0064]
In the magnetic recording layer, commonly used lubricants, abrasives, antistatic agents and the like may be added.
[0065]
The magnetic recording medium having a nonmagnetic underlayer containing acicular hematite particles according to the present invention has a coercive force of 900 to 3500 Oe, preferably 1000 to 3500 Oe, more preferably 1500 to 3500 Oe, and a square ratio (residual magnetic flux density Br / The saturation magnetic flux density Bm) is 0.85 to 0.95, preferably 0.86 to 0.95, the glossiness of the coating film is 200 to 300%, preferably 210 to 300%, and the coating film surface roughness Ra is 10. 0.0 nm or less, preferably 2.0 to 9.0 nm, more preferably 2.0 to 8.0 nm, and the linear absorption coefficient of the coating film is 1.10 to 2.00 μm.^-1Preferably 1.20 to 2.00 μm^-1Of the durability, the running durability is 15 minutes or more, preferably 17 minutes or more, more preferably 22 minutes or more, and the scratch resistance is B or more, preferably A. Further, the corrosivity shown by the change rate (%) of the coercive force is 10.0% or less, preferably 9.5% or less, and the corrosivity shown by the change rate (%) of Bm is 10.0% or less, preferably 9 .5% or less.
[0066]
Next, a method for producing acicular hematite particle powder according to the present invention will be described.
[0067]
First, a method for producing acicular goethite particle powder containing titanium substantially uniformly inside the particles, which is a starting material of acicular hematite particles containing titanium uniformly inside the particles according to the present invention, will be described.
[0068]
Needle-like goethite particles containing titanium almost uniformly inside the particles react with ferrous salt and either alkali hydroxide, alkali carbonate or alkali hydroxide / alkali carbonate, as will be described in detail later. In order to produce acicular goethite particles by aeration of oxygen-containing gas such as air into a suspension containing iron-containing precipitates such as iron hydroxide and iron carbonate obtained as above, oxygen-containing gas such as air is used. It can be obtained by the presence of a titanium compound before aeration. Specifically, it may be added to any one of a ferrous salt aqueous solution, an alkali hydroxide or alkali carbonate aqueous solution, and an iron-containing precipitate, and most preferably a ferrous salt aqueous solution.
[0069]
As the titanium compound, titanium sulfate, titanium oxysulfate, titanium chloride, titanium nitrate, or the like can be used.
[0070]
The needle-like goethite particles obtained in this way are particles containing titanium substantially uniformly from the center of the particle to the particle surface.
[0071]
The typical basic reaction of needle-like goethite particles is as follows: (1) A suspension containing ferrous hydroxide colloid obtained by adding an equivalent amount or more of an aqueous alkali hydroxide solution to an aqueous ferrous salt solution is adjusted to pH 11 or more. A method of generating needle-like goethite particles by performing an oxidation reaction by bubbling an oxygen-containing gas at a temperature of 80 ° C. or lower, and (2) FeCO obtained by reacting a ferrous salt aqueous solution and an alkali carbonate aqueous solution._ThreeA method for producing goethite particles having a spindle shape by aeration of a suspension containing nitrobenzene, if necessary, followed by an oxygen-containing gas and an oxidation reaction; (3) ferrous salt aqueous solution and alkaline carbonate aqueous solution Aged suspension containing iron-containing precipitate obtained by reacting with alkali hydroxide is aged if necessary, and then oxygenated gas is passed through to conduct oxidation reaction to produce spindle-shaped goethite particles (4) An oxygen-containing gas is bubbled through a ferrous salt aqueous solution containing a ferrous hydroxide colloid obtained by adding less than an equivalent amount of an alkali hydroxide aqueous solution or an alkali carbonate aqueous solution to a ferrous salt aqueous solution. By performing an oxidation reaction, acicular goethite core particles are generated, and then the ferrous salt aqueous solution containing the acicular goethite core particles is added to the Fe ferrous salt aqueous solution.²⁺A method of growing an acicular goethite core particle by aeration of an oxygen-containing gas after adding an alkali hydroxide aqueous solution of an equivalent amount or more to the above, (5) an aqueous alkali hydroxide solution or carbonic acid of less than an equivalent amount in the ferrous salt aqueous solution Acicular goethite core particles are produced by performing an oxidation reaction by bubbling an oxygen-containing gas into a ferrous salt aqueous solution containing ferrous hydroxide colloid obtained by adding an alkaline aqueous solution, and then generating the acicular goethite In the ferrous salt aqueous solution containing the core particles, Fe in the ferrous salt aqueous solution is added.²⁺A method of growing an acicular goethite core particle by aeration of an oxygen-containing gas after adding an alkali carbonate aqueous solution of an equivalent amount or more with respect to (6) an alkali hydroxide or alkali carbonate aqueous solution less than the equivalent of ferrous salt aqueous solution The needle-like goethite core particles are generated by conducting an oxidation reaction by aerating an oxygen-containing gas to an aqueous ferrous salt solution containing ferrous hydroxide colloid obtained by adding, and then in the acidic to neutral region There is a method of growing the acicular goethite core particles.
[0072]
In addition, during the formation reaction of goethite particles, foreign elements such as Ni, Zn, P, and Si that are usually added to improve various characteristics such as the major axis diameter, minor axis diameter, and axial ratio of the particles are added. There is no problem. The obtained acicular goethite particle powder usually has an average major axis diameter of 0.005 to 0.4 μm, an average minor axis diameter of 0.0025 to 0.20 μm, and a BET specific surface area value of 50 to 250 m.²/ G, soluble sodium salt is 300 to 1500 ppm in terms of Na, soluble sulfate is SO_FourContaining 100 to 3000 ppm in terms of conversion.
[0073]
Next, a method for producing acicular hematite particle powder containing titanium almost uniformly inside the particles will be described.
[0074]
The hematite particles containing titanium almost uniformly inside the particles can be obtained by heating and dehydrating the goethite particles containing titanium almost uniformly inside the particles.
[0075]
The heat dehydration temperature is preferably 550 to 850 ° C. in consideration of the degree of densification of acicular hematite particles containing titanium uniformly in the obtained particles.
[0076]
In particular, when heat-dehydrating at a high temperature of 550 ° C. or higher, as is well known, the surface of the needle-like goethite particles may be coated with a sintering inhibitor prior to the heat-dehydration of the needle-like goethite particles. preferable.
[0077]
As sintering inhibitors, commonly used phosphorus compounds such as sodium hexametaphosphate, polyphosphoric acid, orthophosphoric acid, No. 3 water glass, silicon compounds such as sodium orthosilicate, sodium metasilicate, colloidal silica, boron such as boric acid Use aluminum salts such as compounds, aluminum acetate, aluminum sulfate, aluminum chloride, and aluminum nitrate, alkali aluminates such as sodium aluminate, aluminum compounds such as alumina sol and aluminum hydroxide, and titanium compounds such as titanium oxysulfate. Can do.
[0078]
The amount of the sintering inhibitor present on the surface of the acicular goethite particles varies depending on the type and amount of the sintering inhibitor, the pH value in the alkaline aqueous solution, the heat treatment temperature, etc. It is about 0.05 to 10% by weight.
[0079]
Needle-like goethite particle powder whose particle surface is coated with a sintering inhibitor is usually 500 to 2000 ppm of soluble sodium salt in terms of Na and SO in soluble sulfate._FourIt contains 300 to 3000 ppm in terms of conversion, and the BET specific surface area value is 50 to 250 m.²/ G or so. The coating treatment with the sintering inhibitor may be performed by adding the sintering inhibitor to an aqueous suspension containing acicular goethite particles, mixing and stirring, and then filtering, washing, and drying.
[0080]
In order to obtain high-density needle-like hematite particles that retain the particle shape of the needle-like goethite particles, the needle-like goethite particles are preliminarily heated at a low temperature of 250 to 550 ° C. and contain titanium in the particles. It is preferable to obtain density acicular hematite particles, and then heat-treat the low density acicular hematite particles at a temperature of 550 to 850 ° C.
[0081]
When the heating temperature is less than 250 ° C., the dehydration reaction takes a long time. When the heating temperature exceeds 550 ° C., a dehydration reaction occurs abruptly, and the shape of the particles tends to collapse, or sintering between the particles tends to occur. Low density acicular hematite particles obtained by low-temperature heat treatment are obtained from goethite particles to H₂O is dehydrated and is a low-density particle having many dewatering holes, and the BET specific surface area value is about 1.2 to 2 times that of acicular goethite particles as a starting material. The low density hematite particle powder usually has an average major axis diameter of 0.005 to 0.30 μm, an average minor axis diameter of 0.0025 to 0.15 μm, and a BET specific surface area value of 70 to 350 m.²/ G, soluble sodium salt is 500 to 2000 ppm in terms of Na, soluble sulfate is SO_FourContaining 300 to 4000 ppm in terms of conversion.
[0082]
Next, the low density hematite particle powder is heated to a high temperature at 550 ° C. or higher to obtain acicular hematite particles that have been densified. The upper limit of the heating temperature is preferably 850 ° C. When the heating temperature is less than 550 ° C., the densification is insufficient, and thus there are many dehydration holes in the particle surface and the particle surface of the hematite particles. Yes, when a nonmagnetic underlayer is formed, it is difficult to obtain a coating film having a smooth surface. When the heating temperature exceeds 850 ° C., the density of the hematite particles is sufficiently increased. However, since the particles and each other are sintered, the particle diameter is increased, and the coating film having a smooth surface is similarly formed. It is difficult to obtain. High-density hematite particle powder usually has a soluble sodium salt of 500 to 4000 ppm in terms of Na and a soluble sulfate salt of SO._FourIt contains 300 to 5000 ppm in terms of conversion, and the BET specific surface area value is 35 to 150 m.²/ G or so.
[0083]
The high-density needle-shaped hematite particles are coarsely pulverized by a dry process to loosen the coarse particles, and then slurried, followed by wet pulverization to further loosen the coarse particles. The wet pulverization may be performed using a ball mill, a sand grinder, a dyno mill, a colloid mill, or the like so that coarse grains of at least 44 μm or more are eliminated. The degree of wet pulverization is 10% or less, preferably 5% or less, and more preferably 0% for coarse particles of 44 μm or more. When coarse particles of 44 μm or more remain exceeding 10%, it is difficult to obtain a treatment effect in an aqueous alkaline solution in the next step.
[0084]
The slurry containing the high-density needle-like hematite particles from which coarse particles have been removed is heated at a temperature of 80 ° C. or higher after adding an alkaline aqueous solution such as sodium hydroxide to the slurry to adjust the pH value to 13 or higher.
[0085]
The concentration of the alkaline suspension having a pH value of 13 or more containing the high-density needle-like hematite particle powder is preferably 50 to 250 g / l.
[0086]
When the pH value in an alkaline suspension containing high-density needle-like hematite particle powder is less than 13, solid cross-linking caused by the sintering inhibitor present on the particle surface of the hematite particles can be effectively removed. Therefore, it is impossible to wash out soluble sodium salts, soluble sulfates, etc. present in the particle interior and on the particle surface. The upper limit of the pH value is about 14. Removal of solid cross-linking caused by the sintering inhibitor present on the surface of the hematite particles, the effect of washing out soluble sodium salts, soluble sulfates, etc., as well as alkali such as sodium adhering to the surface of the hematite particles during alkaline aqueous solution treatment Considering the cleaning effect for removal, the pH value is preferably in the range of 13.1 to 13.8.
[0087]
The heating temperature of the alkaline aqueous solution having a pH value of 13 or more containing the high-density needle-like hematite particle powder is preferably 80 ° C. or more, more preferably 90 ° C. or more. When the temperature is lower than 80 ° C., it is difficult to effectively remove the solid crosslinking caused by the sintering inhibitor existing on the surface of the hematite particles. The upper limit of the heating temperature is preferably 103 ° C, more preferably 100 ° C. When the temperature exceeds 103 ° C., the solid cross-linking can be effectively removed, but an autoclave or the like is required, and under normal pressure, the liquid to be treated boils and is not industrially advantageous.
[0088]
High-density needle-shaped hematite particles heat-treated in an aqueous alkaline solution are separated by filtration and washed with water in the usual manner, so that the soluble sodium salt or soluble sulfate salt washed out from the inside of the particle or the surface of the particle, or the hematite particles during the aqueous alkaline treatment The alkali such as sodium attached to the surface is removed and then dried.
[0089]
By the method described above, acicular hematite particles containing titanium inside the particles according to the present invention can be obtained.
[0090]
As a water washing method, if a method commonly used in industry such as a method of washing by decantation, a method of washing by a dilution method using a filter thickener, a method of washing by passing water through a filter press, etc. is used. Good.
[0091]
If the soluble sodium salt or soluble sulfate contained in the high-density hematite particles is washed out with water, the subsequent steps, for example, in the coating treatment step to be described later, on the particle surface of the hematite particles. Even if soluble sodium salt or soluble sulfate is adhered, it can be easily removed by washing with water.
[0092]
The needle-like hematite particles according to the present invention are heat-treated in an alkaline aqueous solution, if necessary, and then filtered and washed by a conventional method, then aluminum hydroxide, aluminum oxide, silicon hydroxide and It can be coated with at least one oxide of silicon.
[0093]
The coating treatment is performed by adding an aluminum compound, a silicon compound or both of the compounds to an aqueous suspension obtained by dispersing a cake, slurry, or dry powder of acicular hematite particles in an aqueous solution, and mixing and stirring, or If necessary, by adjusting the pH value, the surface of the acicular hematite particles may be coated with aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide, Then, it is filtered, washed with water, dried and pulverized. If necessary, a deaeration / consolidation process may be further performed.
[0094]
As the aluminum compound in the present invention, the same as the above-mentioned sintering inhibitor can be used.
[0095]
The addition amount of the aluminum compound is 0.01 to 50.00% by weight in terms of Al with respect to the acicular hematite particle powder. If it is less than 0.01% by weight, the dispersion in the vehicle is insufficient, and if it exceeds 50.00% by weight, the coating effect is saturated, so there is no point in adding more than necessary.
[0096]
As the silicon compound in the present invention, the same compounds as the above-mentioned sintering inhibitor can be used.
[0097]
The amount of silicon compound added is SiO to acicular hematite particle powder.₂It is 0.01 to 50.00% by weight in terms of conversion. If it is less than 0.01% by weight, the dispersion in the vehicle is insufficient, and if it exceeds 50.00% by weight, the coating effect is saturated, so there is no point in adding more than necessary.
[0098]
When an aluminum compound and a silicon compound are used in combination, the equivalent amount of Al and SiO₂0.01 to 50.00% by weight in total with the converted amount is preferable.
[0099]
Next, a method for producing a magnetic recording medium substrate having a nonmagnetic underlayer in the present invention will be described.
[0100]
The substrate for a magnetic recording medium in the present invention is formed by applying a nonmagnetic coating material containing needle-like nonmagnetic particle powder containing iron as a main component, a binder resin, and a solvent on a nonmagnetic support to form a coating film. Obtained by drying.
[0101]
As the solvent, methyl ethyl ketone, toluene, cyclohexanone, methyl isobutyl ketone, tetrahydrofuran and a mixture thereof can be used.
[0102]
The amount of the solvent used is 50 to 1000 parts by weight in total with respect to 100 parts by weight of the nonmagnetic particle powder. If it is less than 50 parts by weight, the viscosity becomes too high when it is used as a non-magnetic paint, making application difficult. When it exceeds 1000 parts by weight, the volatilization amount of the solvent at the time of forming the coating film becomes too large, which is industrially disadvantageous.
[0103]
Next, a method for manufacturing a magnetic recording medium according to the present invention will be described.
[0104]
The magnetic recording medium according to the present invention is formed by applying a nonmagnetic paint containing needle-like metal magnetic particle powder containing iron as a main component, a binder resin, and a solvent on a nonmagnetic underlayer to form a coating film. It is obtained by drying to form a magnetic recording layer.
[0105]
As the solvent, methyl ethyl ketone, toluene, cyclohexanone, methyl isobutyl ketone, tetrahydrofuran and a mixture thereof can be used.
[0106]
The total amount of the solvent used is 65 to 1000 parts by weight with respect to 100 parts by weight of the nonmagnetic particle powder. If it is less than 65 parts by weight, the viscosity becomes too high when it is used as a non-magnetic paint, making application difficult. When it exceeds 1000 parts by weight, the volatilization amount of the solvent at the time of forming the coating film becomes too large, which is industrially disadvantageous.
[0107]
DETAILED DESCRIPTION OF THE INVENTION
A typical embodiment of the present invention is as follows.
[0108]
The remaining amount of the sieve is obtained by separately obtaining the slurry concentration after the wet pulverization, and passing the slurry corresponding to the solid content of 100 g through the sieve of 325 mesh (opening 44 μm), the amount of the solid content remaining in the sieve Was determined by quantitative determination.
[0109]
The average major axis diameter and average minor axis diameter of the particles are the major axis diameter and minor axis diameter of about 350 particles shown in the photograph obtained by enlarging the electron micrograph (× 30000) four times in the vertical and horizontal directions, respectively. Each was measured and indicated by its average value. The axial ratio is the ratio of the average major axis diameter to the average minor axis diameter.
[0110]
The geometric standard deviation value (σg) of the major axis diameter of the particle was indicated by a value obtained by the following method. That is, the value obtained by measuring the major axis diameter of the particles shown in the above enlarged photograph is calculated on the basis of the actual major axis diameter and the number of particles calculated from the measured values, and the horizontal axis on the log normal probability paper according to a statistical method. The major axis diameter of the particles is plotted on the vertical axis, and the cumulative number of particles belonging to each of the predetermined major axis diameter sections (under the integrated sieve) is plotted in percentage on the vertical axis. Then, the value of the major axis diameter corresponding to the number of particles of 50% and 84.13% is read from this graph, and the geometrical standard deviation value (σg) = major axis diameter / integrated at 84.13% under the cumulative sieve. The value was calculated according to the major axis diameter (geometric mean diameter) at 50% under the sieve. The smaller the geometric standard deviation value, the better the particle size distribution of the major axis diameter of the particles.
[0111]
The specific surface area was shown by the value measured by BET method.
[0112]
As described above, the degree of densification of the hematite particles is S_BET/ S_TEMIt showed in. Where S_BETIs the value of the specific surface area measured by the BET method. S_TEMIs a value calculated according to the following formula, assuming that the particles are rectangular parallelepiped using the average major axis diameter lcm and the average minor axis diameter wcm of the particles measured from the electron micrograph.
[0113]
S_TEM(M²/ G) = [(4lw + 2w²) / (Lw²・ Ρ_p)] × 10^-Four
(However, ρ_pIs the true specific gravity of hematite, 5.2 g / cm^ThreeWas used. )
S_TEMIs the specific surface area of the particles with no dehydration pores inside and on the particle surface and a smooth surface._BET/ S_TEMWhen the value of is close to 1, it means that the surface of the hematite particle has few dehydration holes and has a smooth surface, in other words, a high-density particle.
[0114]
The amount of each of Ti, Al, Si, P, and B present inside or on the surface of acicular hematite particles was measured by fluorescent X-ray analysis.
[0115]
The pH value of the powder was measured by weighing 5 g of a sample into a 300 ml Erlenmeyer flask, adding 100 ml of boiled pure water, heating and holding the boiled state for about 5 minutes, then plugging it and letting it cool to room temperature. After adding water corresponding to the above, stoppered again, shaken for 1 minute, allowed to stand for 5 minutes, and then measured the pH of the obtained supernatant according to JIS Z 8802-7. It was.
[0116]
The content of the soluble sodium salt and the content of the soluble sulfate were determined by changing the supernatant prepared for measurement of the powder pH value as No. Filter using 5C filter paper and add Na in the filtrate.⁺And SO_Four ^2-Was measured using an inductively coupled plasma optical emission spectrometer (manufactured by Seiko Instruments Inc.).
[0117]
The coating viscosity at 25 ° C. of the obtained coating was measured using an E-type viscometer EMD-R (manufactured by Tokyo Keiki Co., Ltd.) and indicated by a value at a shear rate D = 1.92 l / sec. .
[0118]
The resin adsorption strength indicates the degree to which the resin is adsorbed on the hematite particles, and the closer the value obtained by the following method is to 100, the stronger the resin is adsorbed on the hematite particles and the better. First, the resin adsorption amount Wa is obtained.
[0119]
20 g of hematite particles and 56 g of a mixed solvent (methyl ethyl ketone 27.0 g, toluene 16.2 g, cyclohexanone 10.8 g) in which 2 g of a vinyl chloride resin having a sodium sulfonate group are dissolved are placed in a 100 ml plastic bottle together with 120 g of 3 mmφ steel beads. Mix and disperse with a paint shaker for minutes.
[0120]
Next, 50 g of this coating composition is taken out, put into a 50 ml settling tube, and centrifuged at 10000 rpm for 15 minutes to separate the solid portion and the solvent portion. Then, the resin solid content concentration contained in the solvent portion is quantified by a gravimetric method, and the amount of resin present in the solid portion is obtained by subtracting from the charged resin amount, and this is obtained as the resin adsorption amount Wa (mg / g to hematite particles). ).
[0121]
Next, only the solid part separated previously was taken out into a 100 ml tall beaker, and 50 g of a mixed solvent (methyl ethyl ketone 25.0 g, toluene 15.0 g, cyclohexanone 10.0 g) was added thereto, and ultrasonic dispersion was performed for 15 minutes. After making it into a suspended state, it is placed in a 50 ml settling tube and centrifuged at 10,000 rpm for 15 minutes to separate the solid portion and the solvent portion. Then, by measuring the resin solid content concentration in the solvent portion, the amount of resin extracted into the solvent phase out of the resin adsorbed on the surface of the hematite particles is quantified.
[0122]
Further, the operation from taking out the total amount of only the solid portion into a 100 ml tall beaker to determining the amount of the resin dissolved in the solvent phase was repeated twice, and the total amount We (mg of resin extracted in the solvent phase was totaled 3 times. / G), and the value obtained according to the following formula was defined as the resin adsorption strength T (%).
[0123]
T (%) = [(Wa-We) / Wa] × 100
[0124]
The glossiness of the coating surface of the nonmagnetic underlayer and magnetic recording layer was determined by measuring the 45 ° glossiness of the coating using “Gloss Meter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.).
[0125]
Surface roughness Ra measured the centerline average roughness of the coating film using "Surfcom-575A" (made by Tokyo Seimitsu Co., Ltd.).
[0126]
Regarding the durability of the magnetic recording medium, the following running durability and scratch characteristics were evaluated.
[0127]
The running durability was evaluated based on the actual operating time at a load of 200 gw and a relative speed of the head and the tape of 16 m / s using “Media Duability Tester MDT-3000” (manufactured by Steinberg Associates). Indicates that the running durability is good.
[0128]
For the scratch characteristics, the surface of the tape after running was observed with a microscope, the presence or absence of the scratch was visually evaluated, and the following four grades were evaluated.
A: No scratch
B: Some scratches
C: Scratch
D: Severe scratches
[0129]
The coating film strength was obtained by measuring the Young's modulus of the coating film using “Autograph” (manufactured by Shimadzu Corporation). The Young's modulus was expressed as a relative value with a commercially available video tape “AV T-120 (manufactured by Victor Company of Japan)”. It shows that it is so favorable that a relative value is high.
[0130]
The magnetic characteristics were measured using a “vibrating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.) up to an external magnetic field of 10 KOe.
[0131]
The change over time in the magnetic properties of the magnetic recording medium accompanying the corrosion of the metal magnetic particle powder containing iron as a main component in the magnetic recording layer is that the magnetic recording medium is left for 14 days in an environment of a temperature of 60 ° C. and a relative humidity of 90%. The coercive force value and saturation magnetic flux density value before and after standing were measured, and the value obtained by dividing the amount of change by the value before standing was expressed as a percentage.
[0132]
The degree of light transmission is indicated by a linear absorption coefficient calculated by inserting the value of light transmittance measured for a magnetic recording medium using a “photoelectric spectrophotometer UV-2100” (manufactured by Shimadzu Corporation) into the following equation. It was. The larger the value of the linear absorption coefficient, the more difficult it is to transmit light.
[0133]
In measuring the value of light transmittance, the same nonmagnetic support as the nonmagnetic support used in the magnetic recording medium was used as a blank.
[0134]
Linear absorption coefficient (μm^-1) = Ln (1 / t) / FT
t: Light transmittance at λ = 900 nm (−)
FT: Thickness (μm) of coating layer of film used for measurement (total thickness of nonmagnetic underlayer and magnetic recording layer)
[0135]
The thicknesses of the nonmagnetic support, the nonmagnetic underlayer and the magnetic recording layer constituting the magnetic recording medium were measured as follows.
First, the film thickness (A) of the nonmagnetic support is measured using a digital electronic micrometer K351C (manufactured by Anritsu Electric Co., Ltd.). Next, the thickness (B) of the nonmagnetic support and the nonmagnetic underlayer formed on the nonmagnetic support (the sum of the thickness of the nonmagnetic support and the nonmagnetic underlayer) was measured in the same manner. To do. Further, the thickness (C) of the magnetic recording medium obtained by forming the magnetic recording layer on the nonmagnetic underlayer (the sum of the thickness of the nonmagnetic support, the thickness of the nonmagnetic underlayer, and the thickness of the magnetic recording layer). ) Is measured in the same manner. The thickness of the nonmagnetic underlayer is indicated by B-A, and the thickness of the magnetic recording layer is indicated by CB.
[0136]
<Manufacture of acicular hematite particles>
Using a ferrous sulfate aqueous solution, a titanium oxysulfate aqueous solution, and a sodium carbonate aqueous solution, 3.18 wt% titanium in terms of Ti obtained by the above-described goethite particle production method (2) is uniformly contained inside the particles. Needle-like goethite particles (average major axis diameter 0.176 μm, average minor axis diameter 0.0215 μm, axial ratio 8.2, BET specific surface area 112.6 m²/ G, soluble sodium salt content is 1260 ppm in terms of Na, soluble sulfate content is SO_FourIn conversion, 631 ppm, powder pH value 6.5 and geometric standard deviation value 1.32) 1200 g were suspended in water to form a slurry, and the solid content concentration was adjusted to 8 g / l. 150 l of this slurry was heated to a temperature of 60 ° C., and 0.1N NaOH aqueous solution was added to adjust the pH value of the slurry to 10.3.
[0137]
Next, 24.0 g of No. 3 water glass was gradually added to the alkaline slurry as a sintering inhibitor. After the addition was completed, aging was performed for 60 minutes. Next, a 0.1N acetic acid solution was added to the slurry to adjust the pH value of the slurry to 5.8. Thereafter, filtration, washing with water, drying and pulverization were performed by a conventional method to obtain acicular goethite particle powder in which a silicon oxide was coated on the particle surface. SiO₂The amount was 0.56 wt%.
[0138]
1000 g of the obtained acicular goethite particle powder was put into a stainless steel rotary furnace and dehydrated by heat treatment at 300 ° C. for 30 minutes in the air while being rotated to obtain low density acicular hematite particles. The obtained low density acicular hematite particles containing titanium have an average major axis diameter of 0.143 μm, an average minor axis diameter of 0.0194 μm, an axial ratio of 7.4, and a BET specific surface area value (S_BET) 146.5m²/ G, density degree S_BET/ S_TEMIs 3.46, the content of soluble sodium salt is 1663 ppm in terms of Na, and the content of soluble sulfate is SO_FourIn terms of conversion, it was 885 ppm, the Ti content was 3.50 wt%, the powder pH value was 6.1, and the geometric standard deviation value was 1.35.
[0139]
Next, 850 g of the low-density needle-like hematite particle powder was put into a ceramic rotary furnace and heat-treated at 630 ° C. for 15 minutes in the air while being driven to rotate, thereby sealing the dehydration holes. The densified acicular hematite particles have an average major axis diameter of 0.141 μm, an average minor axis diameter of 0.0198 μm, an axial ratio of 7.1, and a BET specific surface area value (S_BET) Is 50.3m²/ G, degree of densification S_BET/ S_TEMIs 1.21, the content of soluble sodium salt is 2744 ppm in terms of Na, and the content of soluble sulfate is SO_FourIn conversion, it was 2832 ppm, the powder pH value was 5.4, and the geometric standard deviation value was 1.35. SiO₂The amount was 0.61 wt%. The resin adsorption strength was 53.5%.
[0140]
After 800 g of the obtained high-density needle-like hematite particle powder was coarsely pulverized in advance with a Nara type pulverizer, it was put into 4.7 l of pure water and peptized for 60 minutes using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). did.
[0141]
Next, the obtained slurry of high-density needle-like hematite particles was mixed and dispersed for 3 hours at a shaft rotational speed of 2000 rpm while circulating through a horizontal SGM (Dispamat SL: manufactured by ESC Adchem). The sieve residue of needle-like hematite particles in the obtained slurry at 325 mesh (aperture 44 μm) was 0%.
[0142]
The concentration of the resulting high-density needle-like hematite particle slurry was 100 g / l, and 7 l of the slurry was collected. While stirring the slurry, 6N NaOH aqueous solution was added to adjust the pH value of the slurry to 13.3. Next, this slurry was heated with stirring to a temperature of 95 ° C. and held at that temperature for 3 hours.
[0143]
Next, this slurry was washed with water by a decantation method to obtain a slurry having a pH value of 10.5. To ensure accuracy, the slurry concentration at this point was confirmed to be 98 g / l.
[0144]
Next, 2 l of the obtained water washing slurry was filtered using a Buchner funnel, pure water was passed through, and the filtrate was washed with water until the electric conductivity of the filtrate became 30 μs or less. Thus, acicular hematite particle powder was obtained. The obtained acicular hematite particle powder containing 3.50% by weight of titanium in terms of Ti uniformly in the inside of the particle has a major axis diameter of 0.143 μm, a minor axis diameter of 0.0195 μm, and an axial ratio of 7 .3, geometric standard deviation value σg of particle size (major axis diameter) is 1.35, BET specific surface area value (S_BET) Is 49.9m²/ G, degree of densification (S_BET/ S_TEM) Is 1.18, the powder pH value is 9.1, the content of soluble sodium salt is 118 ppm in terms of Na, and the content of soluble sulfate is SO_FourIt was 26 ppm in terms of conversion. The resin adsorption strength was 77.6%.
[0145]
<Manufacture of nonmagnetic underlayer>
12 g of acicular hematite particle powder uniformly containing 3.50% by weight of titanium in terms of Ti obtained above and binder resin solution (vinyl chloride-vinyl acetate copolymer having sodium sulfonate group) 30% by weight of resin, 70% by weight of cyclohexanone) and cyclohexanone were mixed to obtain a mixture (solid content rate 72%), and this mixture was further kneaded with a plastmill for 30 minutes to obtain a kneaded product.
[0146]
This kneaded product is placed in a 140 ml glass bottle with 95 g of 1.5 mmφ glass beads, a binder resin solution (30% by weight of a polyurethane resin having a sodium sulfonate group, 70% by weight of a solvent (methyl ethyl ketone: toluene = 1: 1)), cyclohexanone, methyl ethyl ketone and It was added together with toluene and mixed and dispersed for 6 hours with a paint shaker to obtain a coating composition.
[0147]
The composition of the paint containing the obtained hematite particles was as follows.

[0148]
The obtained paint containing hematite particles was applied on a polyethylene terephthalate film having a thickness of 12 μm to a thickness of 55 μm using an applicator, and then dried to form a nonmagnetic underlayer. The thickness of the nonmagnetic underlayer was 3.4 μm.
[0149]
The obtained nonmagnetic underlayer had a gloss of 198%, a surface roughness Ra of 6.8 nm, and a Young's modulus (relative value) of the substrate of 126.
[0150]
<Manufacture of magnetic recording layer>
12 g of acicular metal magnetic particle powder containing iron as a main component (average major axis diameter 0.153 μm, average minor axis diameter 0.0212 μm, axial ratio 7.2, coercive force 1866 Oe, saturation magnetization 130.6 emu / g), Abrasive (trade name: AKP-30, manufactured by Sumitomo Chemical Co., Ltd.) 1.2 g, carbon black (trade name: # 3250B, manufactured by Mitsubishi Kasei Co., Ltd.) 0.12 g, binder resin solution (sodium sulfonate group) 30% by weight of a vinyl chloride-vinyl acetate copolymer resin and 70% by weight of cyclohexanone) and cyclohexanone are mixed to obtain a mixture (solid content ratio 78%), and this mixture is further kneaded with a plast mill for 30 minutes. Got.
[0151]
This kneaded product is placed in a 140 ml glass bottle with 95 g of 1.5 mmφ glass beads, a binder resin solution (30% by weight of a polyurethane resin having a sodium sulfonate group, 70% by weight of a solvent (methyl ethyl ketone: toluene = 1: 1)), cyclohexanone, methyl ethyl ketone and It was added together with toluene, and mixed and dispersed for 6 hours with a paint shaker to obtain a magnetic paint. Then, a lubricant and a curing agent were added, and further mixed and dispersed for 15 minutes with a paint shaker.
[0152]
The composition of the obtained magnetic paint was as follows.

[0153]
After applying a magnetic coating on the nonmagnetic underlayer to a thickness of 15 μm using an applicator, orientation and drying in a magnetic field, followed by calendering, a curing reaction is performed at 60 ° C. for 24 hours. A magnetic tape was obtained by slitting to a width of 0.5 inch. The thickness of the magnetic recording layer was 1.0 μm.
[0154]
The obtained magnetic tape had Hc of 1956 Oe, squareness ratio (Br / Bm) of 0.87, glossiness of 228%, surface roughness Ra of 6.2 nm, Young's modulus (relative value) of 135, linear absorption The coefficient was 1.25, the running durability was 26.3 minutes, and the scratch characteristics were A. The changes over time in the magnetic properties of the magnetic tape were 4.4% for the coercive force and 3.6% for the saturation magnetic flux density Bm.
[0155]
[Action]
The most important point in the present invention consists of acicular hematite particles containing 0.05 to 50% by weight of titanium in terms of Ti inside the particles, the average major axis diameter is 0.3 μm, and the powder The pH value is 8 or more, the content of soluble sodium is 300 ppm or less in terms of Na, and the content of soluble sulfate is SO_FourWhen high-density acicular hematite particles having a conversion of 150 ppm or less are used as the non-magnetic particle powder for the non-magnetic underlayer, the non-dispersibility in the binder resin is excellent. The surface smoothness of the magnetic underlayer and the strength of the substrate can be improved. When a magnetic recording layer is provided on the nonmagnetic underlayer, the light transmittance of the magnetic recording layer is reduced, the surface is smooth, A magnetic recording medium having high strength and excellent durability can be obtained, and the magnetic properties of the metal magnetic particle powder mainly composed of iron dispersed in the magnetic recording layer are deteriorated due to corrosion. The fact that it can be suppressed.
[0156]
Regarding the reason why the surface smoothness of the non-magnetic underlayer and the strength of the substrate could be further improved, the present inventor found that soluble sodium causing high-density acicular hematite particles to be firmly crosslinked and aggregated Due to the fact that the salt and soluble sulfate can be sufficiently washed away, the agglomerates can be unraveled into substantially independent particles, resulting in dispersibility in the vehicle. Is considered to be due to obtaining excellent needle-like hematite particle powder.
[0157]
The fact that the acicular hematite particle powder according to the present invention has excellent dispersibility in the vehicle will be described below.
[0158]
As described above, the acicular goethite particles used as a precursor are produced by various production methods. In any method, when the main raw material for producing acicular goethite particles is ferrous sulfate. Of course, sulfate [SO_Four ^-] Are present in large quantities.
[0159]
In particular, when producing goethite particles from an acidic solution, Na₂SO_FourThis produces iso-water soluble sulfate and the reaction mother liquor has K⁺, NH_Four ⁺, Na⁺Since it contains an alkali metal such as an alkali metal, a precipitate containing an alkali metal or sulfate is likely to be formed._Three(SO_Four) (OH)₆(R = K⁺, NH_Four ⁺, Na⁺). These precipitates are sparingly soluble sulfur-containing iron salts and cannot be removed by conventional water washing. This hardly soluble salt becomes a soluble sodium salt or soluble sulfate in the subsequent heat treatment step, but this soluble sodium salt or soluble sulfate is in the form of needle-shaped hematite particles in the high temperature heat treatment step for densification. The anti-sintering agent, which is essential to prevent deformation and sintering between particles, is firmly bonded to the inside and the surface of the particles while cross-linking the needle-like hematite particles. Aggregation between them is further strengthened. As a result, in particular, soluble sulfates and soluble sodium salts trapped inside the particles and aggregates are extremely difficult to remove by washing with water by a conventional method.
[0160]
When producing acicular goethite particles in an alkaline aqueous solution using ferrous sulfate and sodium hydroxide, the sulfate produced simultaneously is Na₂SO_FourIn addition, NaOH exists in the mother liquor, and both of them are soluble, so if the needle-like goethite particles are sufficiently washed with water, essentially Na₂SO_FourAnd should be able to remove NaOH. However, since the crystallinity of needle-like goethite particles is generally low, the washing efficiency is poor. When washing with water by a conventional method, soluble sulfate [SO_Four ^-], Soluble sodium salt [Na⁺] Contains water soluble content. As described above, this water-soluble component is firmly bonded to the inside and the surface of the particles while cross-linking the acicular hematite particles with the sintering inhibitor, thereby further aggregating the acicular hematite particles. Strengthen. As a result, in particular, soluble sulfates and soluble sodium salts trapped inside the particles and aggregates are extremely difficult to remove by washing with water by a conventional method.
[0161]
As described above, high-density hematite particles in which soluble sodium salt and soluble sulfate are strongly bonded to the inside of the particle, the surface of the particle, and the inside of the aggregate via an anti-sintering agent are wet-ground to loosen the coarse particles. After that, when the pH value of the slurry is adjusted to 13 or more and heat treatment is performed at a temperature of 80 ° C. or more, the alkaline aqueous solution sufficiently penetrates into the particles of the high-density hematite particles. It is thought that the binding force of the sintering inhibitor that is strongly bonded to the surface gradually weakens and dissociates from the inside of the particles, the surface of the particles, and the inside of the aggregates, and at the same time, water-soluble sodium salts and water-soluble sulfates can be easily washed away with water. It is done.
[0162]
Although the reason why the durability of the magnetic recording medium surface and the magnetic recording medium itself has improved is not yet clear, the present inventor used hematite particles containing titanium uniformly in the particles as nonmagnetic particles. Further, due to synergistic effects such as a low content of soluble salt of the hematite particles and a pH value in a specific range, the binder resin in the vehicle of hematite particles and As a result, the adhesion strength between the hematite particles and the binder resin in the nonmagnetic underlayer and the adhesion of the nonmagnetic underlayer itself to the nonmagnetic support increased. Yes.
[0163]
Regarding the reason why the deterioration of the magnetic properties accompanying the corrosion of the metal magnetic particle powder containing iron as a main component dispersed in the magnetic recording layer is suppressed, the present inventor Progression of corrosion of metal magnetic particle powder containing iron as a main component due to low soluble matter such as sulfate in high density acicular hematite particles and high powder pH value of 8 or more. Is considered to have been suppressed.
[0164]
In fact, the present inventor, as shown in the examples and comparative examples described later, wet-pulverized when high-density hematite particles after wet pulverization are heat-treated with an alkaline aqueous solution having a temperature of 80 ° C. or higher and a pH value of less than 13. When the subsequent high-density hematite particles are heat-treated with an alkaline aqueous solution having a temperature of less than 80 ° C. and a pH value of 13 or more, the high-density hematite particles are kept at a temperature of 80 ° C. or more while containing coarse particles without wet grinding. In any case where the heat treatment is performed in an alkaline aqueous solution having a pH value of 13 or more, the progress of the corrosion of the metal magnetic particle powder containing iron as a main component cannot be sufficiently suppressed. It has been confirmed that the progress of corrosion of the metal magnetic particle powder containing iron as a main component can be suppressed by the synergistic effect that the powder pH value is 8 or more.
[0165]
【Example】
Next, examples and comparative examples are given.
[0166]
<Types of acicular goethite particle powder>
The following precursors 1 to 8 were prepared as precursors for producing acicular hematite particles.
[0167]
[Table 1]

[0168]
<Production of low density acicular hematite particle powder>
Intermediate particles 1-15as well asComparative intermediate particles 1-15
The low density acicular hematite is the same as the embodiment of the present invention except that the precursor acicular goethite particle powder, the kind and amount of the sintering inhibitor, the heat dehydration temperature and the time are variously changed. Particles were obtained. still,Comparative intermediate particle 4The particles obtained in (1) are goethite particles.
[0169]
Tables 2 to 5 show main manufacturing conditions and various characteristics at this time.
[0170]
[Table 2]

[0171]
[Table 3]

[0172]
[Table 4]

[0173]
[Table 5]

[0174]
<Production of high density acicular hematite particle powder>
Intermediate particles 16-30as well asComparative intermediate particles 16-29
High-density needle-like hematite particles were obtained in the same manner as in the embodiment of the present invention, except that the kind of low-density needle-like hematite particles, the temperature and time of the densification heat treatment were variously changed.
[0175]
Tables 6 and 7 show the main production conditions and various characteristics at this time.
[0176]
[Table 6]

[0177]
[Table 7]

[0178]
<Treatment of acicular hematite particles in aqueous alkali solution>
Examples 1-15as well asComparative Examples 1-9
Except for various changes in the type of high-density acicular hematite particle powder, presence or absence of wet pulverization, presence or absence of heat treatment in an alkaline aqueous solution, slurry pH value, heating temperature and heating time, Similarly, acicular hematite particles were obtained.
[0179]
Tables 8 to 11 show main manufacturing conditions and various characteristics at this time.
[0180]
[Table 8]

[0181]
[Table 9]

[0182]
[Table 10]

[0183]
[Table 11]

[0184]
<Surface coating treatment of acicular hematite particles>
Example 16
The slurry having a pH value of 10.5 in Example 31 obtained by washing with water by decantation after the heat treatment in the alkaline aqueous solution had a slurry concentration of 98 g / l. 5 l of this slurry was heated again to 60 ° C., and 1.0 N NaAlO was added to the slurry.₂ 544 ml of a solution (corresponding to 3.0 wt% in terms of Al with respect to needle-like hematite particles) was added and maintained for 30 minutes, and then the pH value was adjusted to 8.5 using acetic acid. Next, in the same manner as in the embodiment of the present invention, filtration, washing, drying, and pulverization were performed to obtain acicular hematite particle powder whose particle surface was covered with a coating.
[0185]
Tables 12 and 13 show the main production conditions and various characteristics at this time.
[0186]
Examples 17-30
Except for various changes in the type of acicular hematite particle powder and the type and amount of the surface treatment product,Example 16In the same manner, surface-coated needle-like hematite particles were obtained.
[0187]
Tables 12 and 13 show the main production conditions and various characteristics at this time.
[0188]
[Table 12]

[0189]
[Table 13]

[0190]
<Manufacture of nonmagnetic underlayer>
Underlayer 1-30as well asComparative underlayers 1-16
Examples 1-30as well asComparative intermediate particles 1, 3, 16-19, 24, Comparative Examples 1-9Using the acicular hematite particles obtained in the above, a nonmagnetic underlayer was obtained in the same manner as in the embodiment of the present invention.
[0191]
Tables 14 to 16 show the main manufacturing conditions and various characteristics at this time.
[0192]
[Table 14]

[0193]
[Table 15]

[0194]
[Table 16]

[0195]
<Manufacture of magnetic recording medium using metal magnetic particle powder containing iron as main component>
Examples 31-60as well asComparative Examples 10-25
Underlayer 1-30as well asComparative underlayers 1-16The main component of iron is the same as that of the embodiment of the present invention, except that the type of nonmagnetic underlayer obtained in the above and the type of acicular metal magnetic particle powder containing iron as a main component are variously changed. A magnetic recording medium using metal magnetic powder was produced.
[0196]
Tables 17 to 19 show the main manufacturing conditions and various characteristics at this time.
[0197]
[Table 17]

[0198]
[Table 18]

[0199]
[Table 19]

[0200]
【The invention's effect】
The acicular hematite particle powder according to the present invention has a powder pH value of 8 or more and a low content of soluble salt when used as a nonmagnetic powder for a nonmagnetic underlayer, as shown in the previous examples. As a result, the dispersibility in the vehicle is excellent, so that a nonmagnetic underlayer excellent in strength and surface properties as a substrate can be obtained, and when the nonmagnetic underlayer is used as a magnetic recording medium In addition, it is possible to obtain a magnetic recording medium having a low light transmittance, a smooth surface, and a high strength. Since it is excellent in durability due to its uniform content, it is preferable for a non-magnetic underlayer of a high-density magnetic recording medium.
[0201]
The magnetic recording medium according to the present invention, as described above, has a low light transmittance, a smooth surface, a high strength, excellent durability, and iron in the magnetic recording layer as a main component. Since it is possible to suppress the deterioration of the magnetic properties accompanying the corrosion of the acicular metal magnetic particle powder, it is preferable as a high-density magnetic recording medium.

Claims (3)

It consists of acicular hematite particles containing 0.05 to 50 wt% titanium in terms of Ti inside the particles, the average major axis diameter is 0.3 μm or less, the powder pH value is 8 or more, and Metallic magnetic particle powder based on iron, characterized in that it is acicular hematite particle powder having a soluble sodium salt content of 300 ppm or less in terms of Na and a soluble sulfate content of 150 ppm or less in terms of SO ₄ Needle-like hematite particle powder for non-magnetic underlayer of magnetic recording medium using 2. The acicular hematite particle powder according to claim 1, wherein the particle surface is coated with at least one of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. Needle-like hematite particle powder for non-magnetic underlayer of magnetic recording medium using metal magnetic particle powder mainly composed of iron. A nonmagnetic underlayer comprising a nonmagnetic support, a nonmagnetic particle powder formed on the nonmagnetic support and a binder resin, and a metal magnetic particle powder mainly composed of iron formed on the nonmagnetic underlayer And a magnetic recording layer comprising a binder resin, wherein the non-magnetic particle powder is the acicular hematite particle powder according to claim 1 or 2, wherein iron is a main component. Magnetic recording medium using metallic magnetic particle powder.