JPH06120028A - Cobalt-nickel-phosphorus alloy magnetic film and magnetism recording medium thereof as well as manufacturing method thereof - Google Patents
Cobalt-nickel-phosphorus alloy magnetic film and magnetism recording medium thereof as well as manufacturing method thereofInfo
- Publication number
- JPH06120028A JPH06120028A JP4078491A JP4078491A JPH06120028A JP H06120028 A JPH06120028 A JP H06120028A JP 4078491 A JP4078491 A JP 4078491A JP 4078491 A JP4078491 A JP 4078491A JP H06120028 A JPH06120028 A JP H06120028A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- cobalt
- magnetic
- film
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001096 P alloy Inorganic materials 0.000 title claims abstract description 22
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 230000005389 magnetism Effects 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000007747 plating Methods 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 51
- 239000000203 mixture Substances 0.000 description 22
- 239000010409 thin film Substances 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 229910018104 Ni-P Inorganic materials 0.000 description 3
- 241000080590 Niso Species 0.000 description 3
- 229910018536 Ni—P Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- SIBIBHIFKSKVRR-UHFFFAOYSA-N phosphanylidynecobalt Chemical compound [Co]#P SIBIBHIFKSKVRR-UHFFFAOYSA-N 0.000 description 3
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 101150000971 SUS3 gene Proteins 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Magnetic Record Carriers (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Thin Magnetic Films (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、磁気記録媒体用の磁性
膜に関し、特に、コバルト・ニッケル・燐合金の高保磁
力を有するコバルト・ニッケル・燐合金の磁気記録媒体
用の磁性薄膜に関する。本発明は、金属薄膜型磁気記録
媒体に関し、特に、磁気ディスク、磁気テープ、磁気式
エンコーダなどの用途に好適な磁気記録媒体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic film for a magnetic recording medium, and more particularly to a magnetic thin film of a cobalt-nickel-phosphorus alloy having a high coercive force of a cobalt-nickel-phosphorus alloy. The present invention relates to a metal thin film type magnetic recording medium, and more particularly to a magnetic recording medium suitable for applications such as magnetic disks, magnetic tapes and magnetic encoders.
【０００２】[0002]
【従来の技術】磁気記録媒体としては、金属または金属
酸化物などの磁性材料粉末を有機バインダーで基材上に
塗布したいわゆる塗布型の磁気記録媒体が広く使用され
ていたが、最近記録密度の向上という要請に伴ない、非
磁性の基材上に、真空蒸着、スパッタリング及び無電解
めっきなどの手法によって磁性金属の薄膜を形成させ
た、いわゆる金属薄膜型の磁気記録媒体の使用が増加し
てきている。この金属薄膜型の記録媒体は、現在、主と
して、真空蒸着、スパッタリングにより薄膜が形成され
ているが、いずれの方法も高価な設備を必要とし、さら
に薄膜形成に使用する母材の利用効率が非常に低く問題
とされけている。これらの方法に比して、無電解めっき
は、比較的簡単な設備で製造することができるが、磁気
特性の再現性が難しく、生産性も低く問題がある。2. Description of the Related Art As a magnetic recording medium, a so-called coating type magnetic recording medium in which magnetic material powder such as metal or metal oxide is coated on a substrate with an organic binder has been widely used. Along with the demand for improvement, the use of so-called metal thin film type magnetic recording media in which a thin film of magnetic metal is formed on a non-magnetic substrate by a method such as vacuum deposition, sputtering and electroless plating has been increasing. There is. This metal thin film type recording medium currently has a thin film formed mainly by vacuum deposition or sputtering, but both methods require expensive equipment, and the utilization efficiency of the base material used for thin film formation is extremely high. It is a very low problem. Compared to these methods, electroless plating can be manufactured with relatively simple equipment, but it is difficult to reproduce magnetic properties and productivity is low.
【０００３】[0003]
【発明が解決しようとする問題点】めっき法による磁気
記録媒体として、コバルト燐合金（Ｃｏ−Ｐ）及びコバ
ルトニッケル燐合金（Ｃｏ−Ｎｉ−Ｐ）の磁性膜は知ら
れている。しかし、これ等の合金膜を一定範囲の組成に
制御して、電気めっきにより製造することは非常に難し
い。特に、コバルトニッケル燐（Ｃｏ−Ｎｉ−Ｐ）合金
は、コバルト燐合金に比して、高い保磁力等の良好な磁
気特性が得られ易いとされているが、コバルトニッケル
燐合金について、良好な磁気特性が得られる組成範囲は
未だ確定されておらず、また、一定の組成のものが得ら
れるように、その組成を制御する手法も確立されていな
い。したがって、良好な磁気特性を有するＣｏ−Ｎｉ−
Ｐ合金膜は、再現性良く作製されていない。ところで、
コバルト燐合金のめっき膜は、銅（Ｃｕ）又はアルミニ
ウム（Ａｌ）の非磁性金属或は有機フィルム上に形成さ
れて用いられているが、機械的強度或は熱膨張などが要
求される使用目的の場合には、Ｃｕ又はＡｌの非磁性金
属の基材は適していないために、このような場合には、
Ｆｅ−Ｃｒ−Ｎｉ系の非磁性ステンレス鋼が使用される
ことが多い。しかし、このステンレス基材上に一定組成
のコバルトニッケル燐合金膜を電気めっきにより安定し
て形成することは、更に難しく、問題とされている。本
発明は、従来のコバルトニッケル燐合金の磁性薄膜の組
成及びその製法に係る問題点を解決することを目的とし
ている。Magnetic films of cobalt phosphorus alloy (Co-P) and cobalt nickel phosphorus alloy (Co-Ni-P) are known as magnetic recording media by the plating method. However, it is very difficult to control the composition of these alloy films within a certain range and manufacture them by electroplating. In particular, cobalt nickel phosphorus (Co-Ni-P) alloy is said to be more likely to obtain good magnetic characteristics such as higher coercive force than cobalt phosphorus alloy, but cobalt nickel phosphorus alloy is preferable. The composition range in which the magnetic characteristics are obtained has not yet been determined, and a method for controlling the composition so that a certain composition can be obtained has not been established. Therefore, Co-Ni- with good magnetic properties
The P alloy film is not produced with good reproducibility. by the way,
The cobalt-phosphorus alloy plating film is used by being formed on a non-magnetic metal such as copper (Cu) or aluminum (Al) or an organic film, but it is required to have mechanical strength or thermal expansion. In this case, the non-magnetic metal base material of Cu or Al is not suitable, and in such a case,
Fe-Cr-Ni-based non-magnetic stainless steel is often used. However, it is more difficult and problematic to stably form a cobalt-nickel-phosphorus alloy film having a constant composition on this stainless steel substrate by electroplating. An object of the present invention is to solve the problems relating to the composition of a magnetic thin film of a conventional cobalt nickel phosphorus alloy and its manufacturing method.
【０００４】[0004]
【問題点を解決するための手段】本発明は、磁気記録媒
体として、Ｃｏ−Ｎｉ−Ｐ合金膜を電気めっき法で形成
するために、良好な磁気特性が得られるＣｏ−Ｎｉ−Ｐ
合金膜の組成範囲を確立すると共に、その組成範囲内の
Ｃｏ−Ｎｉ−Ｐ合金膜を、非磁性材料、特にＦｅ−Ｃｒ
−Ｎｉ系非磁性ステンレス鋼基材上に形成するめっき条
件を確立して、良好な磁気特性を有するＣｏ−Ｎｉ−Ｐ
合金膜を非磁性ステンレス鋼基材上に形成する方法を提
供することを目的としている。本発明は、電解液の組成
及び電解めっき条件を変えて、Ｃｏ−Ｎｉ−Ｐ合金薄膜
を形成し、形成された薄膜の膜組成と磁気特性を測定す
ることにより、Ｃｏ−Ｎｉ−Ｐ合金について、良好な磁
気特性の得られる組成とそのめっき条件について研究を
行い、またＦｅ−Ｃｒ−Ｎｉ系非磁性ステンレス鋼基材
への好適な組成のＣｏ−Ｎｉ−Ｐ合金薄膜を形成するた
めの下地処理条件について研究を行って、本発明に到達
した。According to the present invention, a Co-Ni-P alloy film as a magnetic recording medium is formed by electroplating, so that good magnetic characteristics can be obtained.
The composition range of the alloy film is established, and the Co-Ni-P alloy film within the composition range is used as a non-magnetic material, especially Fe-Cr
Co-Ni-P having good magnetic properties by establishing plating conditions for forming on a Ni-based non-magnetic stainless steel substrate
It is an object of the present invention to provide a method for forming an alloy film on a non-magnetic stainless steel substrate. The present invention relates to a Co-Ni-P alloy by changing the composition of the electrolytic solution and electrolytic plating conditions to form a Co-Ni-P alloy thin film and measuring the film composition and magnetic properties of the formed thin film. , A base for forming a Co-Ni-P alloy thin film having a suitable composition on a Fe-Cr-Ni-based nonmagnetic stainless steel substrate Research was conducted on processing conditions to arrive at the present invention.
【０００５】すなわち、本発明は、コバルトが７５乃至
８７重量％、ニッケルが８．５乃至２２重量％、燐が
２．５乃至４．５重量％よりなり、厚さが０．０５μｍ
乃至５０μｍであることを特徴とする磁気記録媒体用コ
バルトニッケル燐合金磁性膜にあり、また、本発明は、
非磁性の鉄・クロム・ニッケル系合金の基材上に下地層
が形成されており、該下地層の上に、コバルトが７５乃
至８７重量％，ニッケルが８．５乃至２２重量％，Ｐが
２．５乃至４．５重量％よりなり、厚さが０．０５乃至
５０μｍであるコバルト・ニッケル・燐合金製磁性膜が
形成されていることを特徴とする磁気記録媒体にあり、
さらに、本発明は、液のｐＨが２．０乃至４．５であっ
て、コバルト塩濃度が０．１乃至０．７２モル／リット
ル、ニッケル塩濃度が０．０４乃至０．３１モル／リッ
トル及び燐酸塩の濃度が０．０９乃至０．５モル／リッ
トルを含むメッキ用電解液に、温度４０乃至６０℃で、
電流密度３０乃至１５０Ａ／ｄｍ2の電解電流及び通電
時間が０．５ミリ秒乃至１０ミリ秒の通電を、パルス的
に繰り返すことにより、非磁性基材上に、コバルトが７
５乃至８７重量％、ニッケルが８．５乃至２２重量％及
び燐が２．５乃至４．５重量％よりなり、厚さが０．０
５乃至５０μｍであるコバルト・ニッケル・燐合金膜を
形成することを特徴とする磁気記録媒体の製造方法にあ
る。That is, the present invention comprises 75 to 87% by weight of cobalt, 8.5 to 22% by weight of nickel, 2.5 to 4.5% by weight of phosphorus, and has a thickness of 0.05 μm.
To 50 μm, the present invention provides a cobalt-nickel-phosphorus alloy magnetic film for a magnetic recording medium.
An underlayer is formed on a base material of a non-magnetic iron-chromium-nickel-based alloy, and cobalt is 75 to 87% by weight, nickel is 8.5 to 22% by weight, and P is P on the underlayer. A magnetic recording medium is characterized in that a magnetic film made of a cobalt-nickel-phosphorus alloy having a thickness of 0.05 to 50 μm and having a thickness of 2.5 to 4.5% by weight is formed.
Furthermore, in the present invention, the pH of the liquid is 2.0 to 4.5, the cobalt salt concentration is 0.1 to 0.72 mol / liter, and the nickel salt concentration is 0.04 to 0.31 mol / liter. And a plating electrolyte containing a phosphate concentration of 0.09 to 0.5 mol / liter at a temperature of 40 to 60 ° C.
By repeating the electrolysis current with a current density of 30 to 150 A / dm 2 and the energization time of 0.5 ms to 10 ms in a pulsed manner, 7
5 to 87% by weight, 8.5 to 22% by weight of nickel and 2.5 to 4.5% by weight of phosphorus, and a thickness of 0.0
A method of manufacturing a magnetic recording medium is characterized in that a cobalt-nickel-phosphorus alloy film having a thickness of 5 to 50 μm is formed.
【０００６】磁気記録媒体は、４００ （Ｏｅ：エール
ステッド） 以上の保磁力が必要とされているが、本発
明の磁性膜は、６００ Ｏｅ以上の保磁力を有し、高密
度記録或は外部磁界等による減磁を少なくすることがで
きる。この高い保磁力を得るためには、コバルトは、７
５〜８７重量％含有される。コバルトの含有量が７５％
以下では保磁力は急激に低下し、また８６％を越すと６
００ｏｅ以上の保磁力は得られなくなる。またニッケル
は８〜２２重量％含有される。ニッケルの含有量が８．
５〜２２重量％の範囲外では保磁力は６００Ｏｅの高い
保磁力を得ることができない。Ｐは２．５〜４．５重量
％の範囲で含有される。この範囲外では保磁力は６００
Ｏｅ以下となるので、この狭い範囲に制御する必要が
ある。また、コバルト含有量を８４乃至８７重量％、ニ
ッケル含有量を９乃至１２重量％及び燐含有量を３乃至
４．５重量％とすると、８００乃至９００ Ｏｅ以上の
更に高い保磁力を有するＣｏ−Ｎｉ−Ｐ合金磁性膜を得
ることができるので好ましい。The magnetic recording medium is required to have a coercive force of 400 (Oe: Oersted) or more, but the magnetic film of the present invention has a coercive force of 600 Oe or more, and can be used for high density recording or external recording. Demagnetization due to a magnetic field or the like can be reduced. To obtain this high coercive force, cobalt is 7
It is contained in an amount of 5 to 87% by weight. 75% cobalt content
Below, the coercive force drops sharply, and when it exceeds 86%, it becomes 6
A coercive force of 00 oe or more cannot be obtained. Further, nickel is contained in an amount of 8 to 22% by weight. Nickel content is 8.
Outside the range of 5 to 22% by weight, a high coercive force of 600 Oe cannot be obtained. P is contained in the range of 2.5 to 4.5% by weight. Outside this range, the coercive force is 600
Since it is less than Oe, it is necessary to control within this narrow range. Further, when the cobalt content is 84 to 87% by weight, the nickel content is 9 to 12% by weight, and the phosphorus content is 3 to 4.5% by weight, Co- having a higher coercive force of 800 to 900 Oe or more is obtained. It is preferable because a Ni-P alloy magnetic film can be obtained.
【０００７】また、本発明において、Ｃｏ−Ｎｉ−Ｐ合
金磁性膜は、電解めっきによって得られる。この電解液
としては、液のｐＨが２．０乃至４．５であって、コバ
ルト塩濃度が０．１乃至０．７２モル／リットル、ニッ
ケル塩濃度が０．０４乃至０．３１モル／リットル及び
燐酸塩の濃度が０．０９乃至０．５モル／リットルを含
むメッキ用電解液が使用される。このような電解液は、
例えば次の組成に調製することによって得られる。すな
わち、 ＣｏＳＯ4・７Ｈ2Ｏ ３０〜２００ｇ／ｌ ＮｉＳＯ4・６Ｈ2Ｏ １２〜８０ｇ／ｌ ＮＨ4Ｃｌ ４０〜１００ｇ／ｌ ＮａＨ2ＰＯ2・Ｈ2Ｏ １０〜５０ｇ／ｌ 湿潤材 ４ｇ／ｌ以下 光沢剤 １ｇ／ｌ以下 この電解液のｐＨは、２．０〜４．５であり、４０〜６
０℃の温度で電解めっきを行うことにより良好な磁気特
性を得ることができる。In the present invention, the Co-Ni-P alloy magnetic film is obtained by electrolytic plating. The electrolytic solution has a pH of 2.0 to 4.5, a cobalt salt concentration of 0.1 to 0.72 mol / liter, and a nickel salt concentration of 0.04 to 0.31 mol / liter. And a plating electrolyte containing a phosphate concentration of 0.09 to 0.5 mol / liter. Such an electrolyte is
For example, it can be obtained by preparing the following composition. That is, CoSO 4 .7H 2 O 30 to 200 g / l NiSO 4 .6H 2 O 12 to 80 g / l NH 4 Cl 40 to 100 g / l NaH 2 PO 2 .H 2 O 10 to 50 g / l Wetting agent 4 g / l Brightener 1 g / l or less The pH of this electrolytic solution is 2.0 to 4.5 and 40 to 6
Good magnetic characteristics can be obtained by performing electrolytic plating at a temperature of 0 ° C.
【０００８】しかし、本発明において、膜組成は、電流
密度や通電時間によって影響されて、大きく変動するこ
とが解った。即ち、電流密度が低い場合には、めっき時
間が長くなると共に、めっき膜のＣｏ量は減少するが、
逆にＮｉ，Ｐ量は増加するので、Ｃｏ，Ｎｉ及びＰを同
時に好適な組成範囲に制御することはできない。一方電
流密度を高くすると、めっき膜のＣｏ，Ｎｉ量は非常に
短時間内に目標組成に近づきほぼ一定値で安定するが、
Ｐ成分は短時間に高濃度のところで安定する。したがっ
て、長時間めっきを続ける場合には、膜組成の制御は不
可能である。However, in the present invention, it has been found that the film composition is greatly affected by the current density and the energization time. That is, when the current density is low, the plating time becomes longer and the amount of Co in the plated film decreases,
On the contrary, since the amounts of Ni and P increase, it is impossible to simultaneously control Co, Ni and P in a suitable composition range. On the other hand, when the current density is increased, the Co and Ni contents of the plated film approach the target composition within a very short time and stabilize at a substantially constant value.
The P component stabilizes at high concentration in a short time. Therefore, when plating is continued for a long time, it is impossible to control the film composition.
【０００９】しかしながら、上記の電解液を用い、電流
密度を３０〜１５０Ａ／ｄｍ2の範囲とし、通電時間を
０．５〜１０ｍｓｅｃの範囲の短時間めっきを繰り返す
ことによりＣｏ，Ｎｉ，Ｐを同時に制御することができ
る。電流密度は、３０〜１５０Ａ／ｄｍ2の範囲とされ
る。電流密度が３０Ａ／ｄｍ2より低い場合には、最適
値のＣｏ量よりも高くなり、またＮｉ量は最適値より低
くなり、また結晶粒が大きくなり高い保磁力は得られな
い。電流密度が１５０Ａ／ｄｍ2以上になるとＣｏ量は
大幅に低くなりＮｉ量は逆に増加して保磁力は著しく低
くなる。However, Co, Ni, and P are simultaneously prepared by repeating the short-time plating in which the current density is in the range of 30 to 150 A / dm 2 and the energization time is in the range of 0.5 to 10 msec using the above electrolytic solution. Can be controlled. The current density is in the range of 30 to 150 A / dm 2 . When the current density is lower than 30 A / dm 2 , the Co content is higher than the optimum value, the Ni content is lower than the optimum value, and the crystal grains are large, so that a high coercive force cannot be obtained. When the current density is 150 A / dm 2 or more, the Co amount is significantly reduced, the Ni amount is increased, and the coercive force is significantly reduced.
【００１０】一方、Ｐ組成を制御するためには電流密度
の制御に加えて通電時間による制御が行われる。Ｐ量を
制御するための好適な通電時間は電流密度によって異な
るが、電流密度が３０〜１５０Ａ／ｄｍ2の範囲内であ
れば、通電時間が０．５〜１０ｍｓｅｃの範囲でＰ量を
制御可能で６００ Ｏｅ以上の保磁力が得られる。しか
し、通電時間が非常に短時間の場合には、必要な膜厚を
得るための全めっき時間は長くなり生産性が低下するの
で、０．５ｍｓｅｃ以上とすることが望ましい。On the other hand, in order to control the P composition, in addition to control of the current density, control by the energization time is performed. The suitable energization time for controlling the amount of P depends on the current density, but if the current density is within the range of 30 to 150 A / dm 2 , the amount of P can be controlled within the range of 0.5 to 10 msec. Gives a coercive force of 600 Oe or more. However, when the energization time is extremely short, the total plating time for obtaining the required film thickness becomes long and the productivity is lowered, so 0.5 msec or more is desirable.
【００１１】本発明においては、電解めっき時の通電は
パルス状に繰り返されるので、ステンレス鋼等の非磁性
基材上に形成されるＣｏ−Ｎｉ−Ｐ合金磁性膜は、極め
て薄いＣｏ−Ｎｉ−Ｐ合金膜の積み重ねられた複数層か
ら形成されることとなり、膜組成の調整が容易となる。In the present invention, since the electric current during the electrolytic plating is repeated in a pulsed manner, the Co-Ni-P alloy magnetic film formed on the non-magnetic base material such as stainless steel is extremely thin Co-Ni-. Since the P alloy film is formed of a plurality of stacked layers, the film composition can be easily adjusted.
【００１２】ＳＵＳ３０４に代表されるステンレス基材
上にめっきを施す場合、その表面に形成される不動態被
膜はめっき性を損なうため、ステンレス基材上に直接Ｃ
ｏ−Ｎｉ−Ｐめっき被膜を施すには、まずステンレス基
材上に、Ｎｉ被膜を施して不動態被膜の影響を除去する
と共にめっき膜の密着性を向上させ、さらに、ＮｉＰ被
膜を施してその上に形成されるＣｏ−Ｎｉ−Ｐ被膜の結
晶粒を一定とし、安定析出させる。その結果、良好な磁
気特性を有するＣｏ−Ｎｉ−Ｐ合金被膜を安定して得る
ことができる。When a stainless steel substrate represented by SUS304 is plated, the passivation film formed on the surface impairs the plating property.
In order to apply the o-Ni-P plating film, first, the Ni film is applied on the stainless steel base material to remove the influence of the passivation film and improve the adhesion of the plating film, and then the NiP film is applied to form the Ni-P plating film. The crystal grains of the Co-Ni-P coating formed on the top surface are kept constant and are stably deposited. As a result, a Co-Ni-P alloy coating film having good magnetic properties can be stably obtained.
【００１３】[0013]
【作用】本発明は、非磁性の鉄・クロム・ニッケル系合
金の基材上に下地層を形成させ、該下地層の上に、コバ
ルトが７５乃至８７重量％，ニッケルが８．５乃至２２
重量％，Ｐが２．５乃至４．５重量％よりなり、厚さが
０．０５乃至５０μｍであるコバルト・ニッケル・燐合
金製磁性膜が形成させるので、６００ Ｏｅ以上の高い
保磁力を有する磁性膜が安定してかつ容易に製造するこ
とができる。According to the present invention, an underlayer is formed on a base material of a non-magnetic iron / chromium / nickel alloy, and cobalt is 75 to 87% by weight and nickel is 8.5 to 22% on the underlayer.
%, P is 2.5 to 4.5% by weight, and a cobalt-nickel-phosphorus alloy magnetic film having a thickness of 0.05 to 50 μm is formed, so that it has a high coercive force of 600 Oe or more. The magnetic film can be stably and easily manufactured.
【００１４】[0014]
【実施例】本発明の実施の態様について、以下に本発明
を具体化した例を挙げて説明するが、本発明は、以下の
説明により何等制限を受けるものではない。 例１． ＣｏＳＯ4・７Ｈ2Ｏ １２０ｇ／ｌ ＮｉＳＯ4・６Ｈ2Ｏ ８０ｇ／ｌ ＮＨ4Ｃｌ ６０ｇ／ｌ ＮａＨ2ＰＯ2 ３０ｇ／ｌ を配合した水溶液５ｌをめっき液とし、ＰＨ３．０，液
温５３℃で直径６ｍｍの非磁性ステンレス鋼（ＳＵＳ３
０４）に電解めっきによりＣｏ−Ｎｉ−Ｐ合金被膜を形
成した。ＳＵＳ３０４には下地処理としてまずＮｉＣｌ
2・６Ｈ2Ｏ２５０ｇ／ｌ，ＨＣｌ１００ｇ／ｌを含む電
解液中で３Ａ／ｄｍ2の電解電流を２分間通電してＮｉ
被膜を施した後、無電解めっきによりＮｉＰ被膜を形成
した。EXAMPLES The embodiments of the present invention will be described below with reference to specific examples of the present invention, but the present invention is not limited by the following description. Example 1. CoSO 4 · 7H 2 O 120 g / l NiSO 4 · 6H 2 O 80 g / l NH 4 Cl 60 g / l NaH 2 PO 2 30 g / l as an aqueous solution was added as a plating solution, pH 3.0, at a liquid temperature of 53 ° C. Non-magnetic stainless steel with a diameter of 6 mm (SUS3
A Co-Ni-P alloy coating film was formed on the surface 04) by electrolytic plating. For SUS304, first NiCl is used as a base treatment.
2 · 6H 2 O250g / l, Ni energized electrolytic current of 3A / dm 2 in an electrolyte containing HCl100g / l 2 minutes
After applying the coating, a NiP coating was formed by electroless plating.
【００１５】第一表にめっき条件とめっき膜の組成およ
び保磁力を示したが、本例による試料（試料番号１乃至
６）の場合は、良好な磁気特性が得られており、また、
比較例（試料番号７乃至９）に比して、優れた磁気特性
が得られている。 第一表 試料 電流密度 通電方式 膜厚 めっき膜組成（ｗｔ％） 保磁力Ｎｏ （A/dm） 通電時間 (μm） Ｃｏ Ｎｉ Ｐ （Oe） １ ４０ 断続 １０ ８４．０ １１．５ ４．３ ７７０ １ミリ秒 ２ ６０ 断続 １０ ８５．２ １０．４ ３．７ ８６０ １ミリ秒 ３ ８０ 断続 １０ ８４．４ １１．９ ３．３ ８５０ ５ミリ秒 ４ １００ 断続 １０ ８４．６ １１．５ ２．８ ７８０ ５ミリ秒 ５ １４０ 断続 １０ ８２．６ １２ ２．８ ６８０ ２ミリ秒 ６ １５０ 断続 １０ ７５．７ ２０．４ ３．５ ６６０ ２ミリ秒 ７ ２００ 断続 １０ ２２．９ ７３．２ ３．６ ２９０ ２ミリ秒 ８ ２０ 断続 １０ ８７．０ ８．３ ４．３ ４００ １ミリ秒 ９ ４ 連続 １５ ７９．９ １２．８ ７．１ ４０ Table 1 shows the plating conditions, the composition of the plated film and
And the coercive force are shown.
In the case of 6), good magnetic properties are obtained, and
Excellent magnetic properties compared to Comparative Examples (Sample Nos. 7 to 9)
Has been obtained.Table 1 Sample Current density Conduction method Film thicknessPlating film composition (wt%) Coercive forceNo (A / dm) Energization time (μm) Co Ni P (Oe) 1 40 intermittent 10 84.0 11.5 4.3 770 1 millisecond 2 60 Intermittent 10 85.2 10.4 3.7 860 1 millisecond 3 80 Intermittent 10 84.4 11.9 3.3 8505 ms 4 100 Intermittent 10 84.6 11.5 2.8 7805 ms 5 140 Intermittent 10 82.6 12 2.8 6802 ms 6 150 Intermittent 10 75.7 20.4 3.5 6602 ms 7 200 Intermittent 10 22.9 73.2 3.6 2902 ms 8 20 Intermittent 10 87.0 8.3 4.3 4001 millisecond 9 4 continuous 15 79.9 12.8 7.1 40
【００１６】例２． ＣｏＳＯ4・７Ｈ2Ｏ １２０ｇ／ｌ ＮｉＳＯ4・６Ｈ2Ｏ ８０ｇ／ｌ ＮＨ4Ｃｌ ６０ｇ／ｌ ＮａＨ2ＰＯ2 ３０ｇ／ｌ 湿潤剤 ２ｇ／ｌ 光沢剤 １ｇ／ｌ を配合した水溶液５ｌをめっき液としＰＨ３．０，液温
５０℃，で直径６ｍｍのＳＵＳ３０４に電解めっきによ
りＣｏ−Ｎｉ−Ｐ合金被膜を形成した。下地処理は実施
例１の場合と同様に行った。第二表にめっき条件とめっ
き被膜の組成および保磁力を示す。Example 2. CoSO 4 · 7H 2 O 120 g / l NiSO 4 · 6H 2 O 80 g / l NH 4 Cl 60 g / l NaH 2 PO 2 30 g / l Wetting agent 2 g / l Brightening agent 1 g / l Aqueous solution 5 l was used as a plating solution A Co-Ni-P alloy coating was formed on SUS304 having a diameter of 6 mm at pH 3.0 and a liquid temperature of 50 ° C by electrolytic plating. The base treatment was performed in the same manner as in Example 1. Table 2 shows the plating conditions, the composition of the plating film and the coercive force.
【００１７】例１の場合と同様良好な磁気特性が得られ
ている。 第二表 試料 電流密度 通電方式 膜厚 めっき膜組成（ｗｔ％） 保磁力Ｎｏ （A/dm2） 通電時間 (μm） Ｃｏ Ｎｉ Ｐ （Ｏｅ） １０ ５０ 断続 １０ ８６．３ ９．６ ３．８ ８６０ １ミリ秒 １１ ５０ 断続 ２０ ８６．４ ９．１ ４．４ ９１０ １ミリ秒 １２ ５０ 断続 ３０ ８６．６ ９．２ ４．１ ８５０ １ミリ秒 以上の実施例は非磁性のＦｅ−Ｃｒ−Ｎｉ系合金基材上
にめっき膜を形成した場合であるが、Ｃｕ，Ａｌ等の基
材についても同様の結果が得られている。また、本例を
実施する場合には、Ｃｏ−Ｎｉ−Ｐ合金めっき膜を保護
する保護膜を必要とする場合が多いが、この場合Ｃｒめ
っき、ＮｉＰめっき等の保護膜を用途に応じて形成する
ことが可能であることが確認済みである。Good magnetic properties were obtained as in the case of Example 1.
ing.Table 2 Sample Current density Conduction method Film thicknessPlating film composition (wt%) Coercive forceNo (A / dm 2 ) Energization time (μm) Co Ni P (Oe) 10 50 Intermittent 10 86.3 9.6 3.8 860 1 millisecond 11 50 intermittent 20 86.4 9.1 4.4 910 1 millisecond 12 50 Intermittent 30 86.6 9.2 4.1 850 1 millisecond The above examples are on a non-magnetic Fe-Cr-Ni alloy base material.
When a plating film is formed on the
Similar results were obtained for wood. Also, this example
Protect the Co-Ni-P alloy plating film when performing
In many cases, a protective film that protects
A protective film such as NiP plating is formed according to the application.
It has been confirmed that it is possible.
【００１８】[0018]
【発明の効果】本発明は、非磁性の鉄・クロム・ニッケ
ル系合金の基材上に下地層を形成させ、該下地層の上
に、コバルトが７５乃至８７重量％，ニッケルが８．５
乃至２２重量％，Ｐが２．５乃至４．５重量％よりな
り、厚さが０．０５乃至５０μｍであるコバルト・ニッ
ケル・燐合金製磁性膜が形成させるので、従来のコバル
ト・ニッケル・燐合金磁性膜に比して、高保磁力のめっ
き膜を再現性良く得ることができるので、磁性膜の歩留
まりを向上することができる。したがって、本発明は、
磁気ディスク、磁気テープ、磁気式エンコーダ等の磁気
記録媒体に利用して大きな効果が期待できる。According to the present invention, an underlayer is formed on a base material of a non-magnetic iron / chromium / nickel alloy, and 75 to 87 wt% of cobalt and 8.5 of nickel are deposited on the underlayer.
To 22 wt%, P is 2.5 to 4.5 wt%, and a cobalt-nickel-phosphorus alloy magnetic film having a thickness of 0.05 to 50 μm is formed. Since a plated film having a high coercive force can be obtained with high reproducibility as compared with the alloy magnetic film, the yield of the magnetic film can be improved. Therefore, the present invention
A large effect can be expected when it is used for magnetic recording media such as magnetic disks, magnetic tapes, and magnetic encoders.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 赤松 吉広 宮城県仙台市太白区太白二丁目10−９ 302号 (72)発明者 深谷 玲子 宮城県仙台市宮城野区東十番丁六十五番地 チサンマンション榴ケ岡1002号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Akamatsu 2-10-9, Taichiro, Taichiro-ku, Sendai-shi, Miyagi Prefecture (72) Inventor Reiko Fukaya, 65, Higashi-jubancho, Miyagino-ku, Sendai-shi, Miyagi 1002 Chisun Mansion Hikeroka issue
Claims (3)
ルが８．５乃至２２重量％、燐が２．５乃至４．５重量
％よりなり、厚さが０．０５μｍ乃至５０μｍであるこ
とを特徴とする磁気記録媒体用コバルトニッケル燐合金
磁性膜。1. Cobalt is 75 to 87% by weight, nickel is 8.5 to 22% by weight, phosphorus is 2.5 to 4.5% by weight, and the thickness is 0.05 μm to 50 μm. A cobalt-nickel-phosphorus alloy magnetic film for a magnetic recording medium.
基材上に下地層が形成されており、該下地層の上に、コ
バルトが７５乃至８７重量％，ニッケルが８．５乃至２
２重量％，Ｐが２．５乃至４．５重量％よりなり、厚さ
が０．０５乃至５０μｍであるコバルト・ニッケル・燐
合金製磁性膜が形成されていることを特徴とする磁気記
録媒体。2. An underlayer is formed on a base material of a non-magnetic iron-chromium-nickel-based alloy, and cobalt is 75 to 87% by weight and nickel is 8.5 to 2 on the underlayer.
2% by weight, P is 2.5 to 4.5% by weight, and a magnetic film made of a cobalt-nickel-phosphorus alloy having a thickness of 0.05 to 50 μm is formed. .
コバルト塩濃度が０．１乃至０．７２モル／リットル、
ニッケル塩濃度が０．０４乃至０．３１モル／リットル
及び燐酸塩の濃度が０．０９乃至０．５モル／リットル
を含むメッキ用電解液に、温度４０乃至６０℃で、電流
密度３０乃至１５０Ａ／ｄｍ2の電解電流及び通電時間
が０．５ミリ秒乃至１０ミリ秒の通電を、パルス的に繰
り返すことにより、非磁性基材上に、コバルトが７５乃
至８７重量％、ニッケルが８．５乃至２２重量％及び燐
が２．５乃至４．５重量％よりなり、厚さが０．０５乃
至５０μｍであるコバルト・ニッケル・燐合金膜を形成
することを特徴とする磁気記録媒体の製造方法。3. The pH of the liquid is 2.0 to 4.5,
Cobalt salt concentration is 0.1 to 0.72 mol / liter,
A plating electrolyte containing a nickel salt concentration of 0.04 to 0.31 mol / liter and a phosphate concentration of 0.09 to 0.5 mol / liter at a temperature of 40 to 60 ° C. and a current density of 30 to 150 A. The electrolysis current of / dm 2 and the energization time of 0.5 ms to 10 ms are repeated in a pulsed manner, whereby 75 to 87 wt% of cobalt and 8.5 of nickel are deposited on the non-magnetic substrate. To 22% by weight and 2.5 to 4.5% by weight of phosphorus, and a cobalt-nickel-phosphorus alloy film having a thickness of 0.05 to 50 μm is formed. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4078491A JP2662904B2 (en) | 1991-02-14 | 1991-02-14 | Cobalt-nickel-phosphorus alloy magnetic film, magnetic recording medium therefor, and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4078491A JP2662904B2 (en) | 1991-02-14 | 1991-02-14 | Cobalt-nickel-phosphorus alloy magnetic film, magnetic recording medium therefor, and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06120028A true JPH06120028A (en) | 1994-04-28 |
| JP2662904B2 JP2662904B2 (en) | 1997-10-15 |
Family
ID=12590252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4078491A Expired - Lifetime JP2662904B2 (en) | 1991-02-14 | 1991-02-14 | Cobalt-nickel-phosphorus alloy magnetic film, magnetic recording medium therefor, and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2662904B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383288C (en) * | 2004-01-15 | 2008-04-23 | 中南大学 | Preparation method of iron-nickel and iron-nickel-chromium alloy foil |
| JP2012077379A (en) * | 2010-09-30 | 2012-04-19 | Seagate Technology Llc | METHOD OF FORMING CoNiP ON SUBSTRATE, AND ARTICLE |
-
1991
- 1991-02-14 JP JP4078491A patent/JP2662904B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383288C (en) * | 2004-01-15 | 2008-04-23 | 中南大学 | Preparation method of iron-nickel and iron-nickel-chromium alloy foil |
| JP2012077379A (en) * | 2010-09-30 | 2012-04-19 | Seagate Technology Llc | METHOD OF FORMING CoNiP ON SUBSTRATE, AND ARTICLE |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2662904B2 (en) | 1997-10-15 |
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