WO2022254923A1

WO2022254923A1 - Nickel-phosphorus alloy coated substrate, solution for electroless plating of nickel-phosphorus alloy film, and method for producing nickel-phosphorus alloy coated substrate

Info

Publication number: WO2022254923A1
Application number: PCT/JP2022/015275
Authority: WO
Inventors: 真利江佐々木; 彩香瀧本; 和正嶋田; 隆広吉田
Original assignee: 東洋鋼鈑株式会社
Priority date: 2021-06-03
Filing date: 2022-03-29
Publication date: 2022-12-08
Also published as: JP2022185929A; TW202307265A

Abstract

The present invention provides: a solution for electroless plating, the solution being capable of reducing the film thickness distribution of an NiP film on the outer peripheral edge of a substrate without deteriorating the corrosion resistance of the NiP film; a method for producing an NiP coated substrate, the method using this solution for electroless plating; and an NiP coated substrate which is able to be produced by this method for producing an NiP coated substrate.　This solution for electroless plating of an NiP film contains nickel ions, hypophosphite ions, a complexing agent and indium ions; and the concentration of the indium ions is from 0.18 ppm to 1.8 ppm. This method for producing an NiP coated substrate comprises a process for forming an NiP film by means of the above-described solution. This NiP coated substrate comprises a substrate and an NiP film that is formed on the substrate; and the NiP film contains indium at a concentration of 70 ppm to 620 ppm.

Description

Nickel-Phosphorus Alloy Coated Substrate, Solution for Electroless Plating of Nickel-Phosphorus Alloy Film, and Method for Producing Nickel-Phosphorus Alloy Coated Substrate

The present invention relates to a nickel-phosphorus alloy coated substrate, a solution for electroless plating of a nickel-phosphorus alloy film, and a method for manufacturing a nickel-phosphorus alloy coated substrate.

Magnetic recording media used in hard disk drives are generally manufactured by forming a nickel-phosphorus alloy (NiP) film on a substrate by electroless plating, polishing the NiP film, and forming a magnetic layer on the NiP film. be done.

Patent Document 1 describes a magnetic recording medium having a nonmagnetic substrate, a nickel-phosphorus plating film, and a magnetic layer. This NiP plating film contains 0.05 to 1% by weight of at least one selected from the group consisting of tin, manganese, indium and antimony.

Patent Document 2 describes an aqueous plating bath composition for the electroless deposition of nickel and nickel alloys. This composition contains a nickel ion source and a stabilizer, and the stabilizer comprises at least one metal ion selected from indium ions and gallium ions, elemental iodine, an iodide ion-containing compound, and iodic acid. It contains at least one selected from ion-containing compounds and periodate ion-containing compounds. The concentration of at least one metal ion selected from indium ions and gallium ions is within the range of 0.01 to 0.5 mmol/L.

JP-A-01-269224 Japanese Patent No. 6667525

When a NiP film is formed on a substrate by electroless plating, a relatively thick NiP film may be formed in the vicinity of the outer peripheral edge of the substrate. Polishing of the NiP film is performed in order to uniformize such a film thickness distribution. However, longer polishing times can lead to poor quality (eg, increased defects) of the NiP film. Therefore, it is desired to reduce the film thickness distribution of the NiP film formed by electroless plating to shorten the polishing time. Also, the NiP film is required to have high corrosion resistance.

Therefore, a solution for electroless plating capable of reducing the thickness distribution of the NiP film at the outer peripheral edge of the substrate without impairing the corrosion resistance of the NiP film, a method for manufacturing a NiP-coated substrate using the solution, and the A manufacturable NiP coated substrate is provided.

According to one aspect of the present invention, the nickel- A phosphorous alloy coated substrate is provided.

According to one aspect of the present invention, a nickel-phosphorus alloy film containing nickel ions, hypophosphite ions, a complexing agent, and indium ions, wherein the concentration of the indium ions is 0.18 to 1.8 ppm. A solution for electroless plating of is provided.

According to one aspect of the present invention, there is provided a method for manufacturing a nickel-phosphorus alloy coated substrate, which includes forming a nickel-phosphorus alloy film by electroless plating using the solution of the above aspects.

According to one aspect of the present invention, there is provided a magnetic recording medium having the nickel-phosphorus alloy-coated substrate of the aspect described above.

According to the present invention, the thickness distribution of the NiP film at the outer peripheral edge of the substrate can be reduced without impairing the corrosion resistance of the NiP film.
This specification includes the disclosure content of Japanese Patent Application No. 2021-093867, which is the basis of priority of this application.

The embodiment will be described below. The present invention is not limited to the following embodiments, and various design changes can be made without departing from the spirit of the invention described in the claims. In the present application, a numerical range represented using the symbol "~" includes the numerical values described before and after the symbol "~" as the lower and upper limits, respectively.

(1) Solution for Electroless Plating of NiP Film A solution for electroless plating according to an embodiment contains nickel ions, hypophosphite ions, a complexing agent, and indium ions.

The concentration of indium ions in the solution is 0.18-1.8 ppm, 0.3-1.5 ppm, or 0.3-0.8 ppm. This makes it possible to form a NiP film having high corrosion resistance and a narrow film thickness distribution at the outer peripheral edge of the substrate, as will be shown in Examples to be described later. Water-soluble indium salts such as indium nitrate, indium sulfate, and indium chloride can be used as a source of indium ions. These indium salts may be used alone or in combination of two or more.

Other components contained in the solution according to the embodiment and their concentrations may be similar to solutions generally used for electroless plating of NiP films.

　Water-soluble nickel salts such as nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, and nickel sulfamate are used as nickel ion sources. These nickel salts may be used alone or in combination of two or more. The concentration of nickel ions in the solution may be, for example, 1-30 g/L.

As a source of hypophosphite ions, for example, hypophosphorous acid or a salt thereof such as sodium hypophosphite or potassium hypophosphite can be used. The concentration of hypophosphite ions in solution may be from 5 to 80 g/L. Hypophosphite ion acts as a reducing agent.

Complexing agents include dicarboxylic acids or alkali salts thereof such as tartaric acid, malic acid, citric acid, succinic acid, malonic acid, glycolic acid, gluconic acid, oxalic acid, phthalic acid, fumaric acid, maleic acid, lactic acid, or These sodium salts, potassium salts, or ammonium salts can be used. Two or more of these may be used in combination, and at least one of them may be an oxydicarboxylic acid. The concentration of the complexing agent in the solution may be 0.01-2.0 mol/L.

A stabilizer, pH adjuster, brightener, anti-mold agent, or surfactant may be added to the solution according to the embodiment. As a stabilizer, a lead compound, such as lead(II) acetate, can be used, in which case the solution according to embodiments contains lead ions. Acids, alkalis, or salts can be used as pH adjusters. A solution according to embodiments may include water as a solvent.

The solution according to the embodiment does not have to contain iodine. Here, "not containing" means substantially not containing, and specifically means not detected by inductively coupled plasma atomic emission spectrometry (ICP-AES). Also, the chemical species of iodine is not limited, and includes, for example, simple iodine, iodide ion, iodate ion, and periodate ion. Accordingly, solutions according to embodiments may not contain elemental iodine, iodide ions, iodate ions, or periodate ions.

(2) NiP-coated substrate A NiP-coated substrate is obtained by immersing the substrate in the above solution and performing electroless plating. A NiP-coated substrate has a substrate and a NiP film formed thereon.

The substrate may have an annular shape. Also, the substrate may be non-conductive (insulating), conductive, or semi-conductive. Non-conductive substrates include substrates made of glass, ceramics, or plastics. Conductive substrates include substrates made of metals or conductive metal oxides. Semiconductive substrates include substrates made of semimetals or compound semiconductors. In particular, the substrate may be made of aluminum, an aluminum alloy or glass.

The NiP film contains In at a concentration of 70-620 ppm, preferably 170-410 ppm, more preferably 170-200 ppm. Such a NiP film has a high corrosion resistance and a small film thickness distribution at the outer peripheral edge of the substrate, as will be shown in Examples described later. Also, the NiP film may contain phosphorus (P) at a concentration of 10 to 13% by weight. The composition of the NiP film can be obtained by dissolving the NiP film in nitric acid and quantifying the elements in the resulting solution by ICP-AES. The NiP film may not contain iodine. Here, "does not contain" means that it does not substantially contain, and specifically means that it is not detected by ICP-AES. Also, the chemical species of iodine is not limited, and includes, for example, simple iodine, iodide ion, iodate ion, and periodate ion. Therefore, the NiP film need not contain elemental iodine, iodide ions, iodate ions, or periodate ions.

The NiP film has a sufficiently small film thickness distribution at the outer edge of the NiP-coated substrate. Specifically, the maximum value of the height of the surface of the NiP film from the reference plane in the region where the distance from the outer peripheral edge of the NiP-coated substrate is 0 to 2 mm is 3% or less, 2% or less with respect to the thickness of the NiP film. .9% or less, 2.8% or less, 2.5% or less, or 2.4% or less, and 0% or more, 0% or more, or 1.6% or more with respect to the thickness of the NiP film. obtain. The maximum height of the surface of the NiP film from the reference plane in the area where the distance from the outer peripheral edge of the NiP-coated substrate is 0 to 2 mm was measured using a stylus surface profilometer (for example, "Dektak 150" manufactured by Bruker). ) is obtained based on the surface profile of the NiP film measured by ). The reference planes are a first point on the surface of the NiP film that is 2 to 5 mm away from the outer edge of the NiP-coated substrate toward the center of the NiP-coated substrate, and a point that is 1 to 5 mm from the first point toward the center of the NiP-coated substrate. A second point on the surface of the distant NiP film is defined as a plane containing a straight line.

Furthermore, the NiP film has good corrosion resistance. Specifically, when the NiP-coated substrate is immersed in 30% nitric acid heated to 45° C. for 150 seconds, the area ratio of holes formed on the surface of the NiP film can be 0.75% or less. The area ratio of the holes is determined from an image of the surface of the NiP film observed with an optical microscope after the NiP-coated substrate was immersed in nitric acid.

A NiP-coated substrate can be used for any purpose. For example, a magnetic recording medium can be manufactured by forming a magnetic layer on a NiP-coated substrate.

Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the invention described in the scope of claims. It can be carried out. The above embodiments may also be combined to provide further embodiments.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

27 g/L nickel sulfate, 30 g/L sodium hypophosphite, 30 g/L lactic acid, 30 g/L malic acid, 6 g/L succinic acid, 20.5 g/L sodium hydroxide, and lead acetate An aqueous solution containing (II) was prepared. Additionally, in Examples 1-8 and Comparative Examples 2-4, indium nitrate was added to the solution. In Comparative Example 5, bismuth(III) sulfate was added to the solution. In Comparative Example 6, antimony(III) acetate was added to the solution. In Comparative Example 7, ammonium molybdate tetrahydrate was added to the solution. The amount of each addition was set so that the solution after addition contained In, Bi, Sb, or Mo ions at the concentrations shown in Table 1. In this way, the plating solution of each example and comparative example was obtained.

An annular aluminum alloy plate (JIS A-5052, inner diameter 25 mm, outer diameter 95 mm) was subjected to alkali etching treatment and zinc replacement treatment. An aluminum alloy plate was immersed in a plating solution heated to 85°C. As a result, a NiP film having a thickness shown in Table 1 was formed on the aluminum alloy plate. In this way, specimens of each example and comparative example were obtained.

(1) Elemental Analysis The NiP film of each specimen was dissolved in nitric acid, and the elements in the resulting solution were quantified by ICP-AES. The In concentration (that is, the In concentration in the NiP film) and the P concentration (that is, the P concentration in the NiP film) were determined based on the total amount of Ni, P, Pb, and In. The results are shown in Table 1.

(2) Surface profile measurement The surface profile of the NiP film of each specimen was measured with a stylus surface profiler (“Dektak 150” manufactured by Bruker). Based on the obtained surface profile, the maximum height (maximum height) of the surface of the NiP film from the reference plane was determined in a region with a distance of 0 to 2 mm from the outer peripheral edge of the specimen. The same measurement was performed 7 times, and the average of the maximum height values was obtained. The results are shown in Table 1. A first point on the surface of the NiP film 2 to 5 mm away from the outer peripheral edge of the test piece toward the center of the test piece and a NiP film 1 to 5 mm away from the first point toward the center of the test piece. A plane including a straight line passing through the second point on the surface was used as a reference plane.

(3) Corrosion resistance evaluation Each specimen was immersed in 30% nitric acid heated to 45°C for 150 seconds. An optical microscope image of the surface of the NiP film was image-processed to determine the area ratio of holes formed on the surface. The results are shown in Table 1.

(4) Polishing The specimens of Examples 1 to 8 were polished. The surface profile of the polished specimen was measured, and the maximum height (maximum height) of the surface of the NiP film from the reference plane was obtained in the region where the distance from the outer peripheral edge of the specimen was 0 to 2 mm. . All specimens had a sufficiently small maximum height suitable for use in manufacturing magnetic recording media for hard disk drives.

As shown in Table 1, the NiP films of Examples 1 to 8 containing indium at a concentration of 79 to 620 ppm, formed using a plating solution containing indium at a concentration of 0.18 to 1.8 ppm, The maximum height was too small. In addition, the NiP films of Examples 1 to 8 had small area ratios of corrosion holes. Furthermore, the NiP films of Examples 2 to 7 containing indium at a concentration of 176 to 410 ppm, which were formed using plating solutions containing indium at a concentration of 0.36 to 1.44 ppm, had even smaller maximum heights. rice field. The NiP films of Examples 2 to 4 containing indium at a concentration of 176 to 194 ppm formed using a plating solution containing indium at a concentration of 0.36 to 0.72 ppm had particularly small maximum heights.

The NiP films of Comparative Examples 1 to 4 with an indium concentration of less than 70 ppm or more than 620 ppm, formed using a plating solution having an indium concentration of less than 0.18 ppm or more than 1.8 ppm, have a maximum height of It was big. The NiP films of Comparative Examples 3 and 4 also had a large area ratio of corrosion holes. The NiP films of Comparative Example 5 using the plating solution containing bismuth and Comparative Example 6 using the plating solution containing antimony had a large maximum height and a large area ratio of corrosion holes. The NiP film of Comparative Example 7, which used the plating solution containing molybdenum, had a small maximum height, but a large area ratio of corrosion holes.
All publications, patents and patent applications cited herein are hereby incorporated by reference in their entirety.

Claims

a substrate;
a nickel-phosphorus alloy film formed on the substrate;
has
A nickel-phosphorus alloy coated substrate, wherein the nickel-phosphorus alloy film contains indium at a concentration of 70 to 620 ppm.
The nickel-phosphorus alloy coated substrate according to claim 1, wherein the nickel-phosphorus alloy film contains phosphorus at a concentration of 10 to 13% by weight.
The nickel-phosphorus alloy coated substrate according to claim 1 or 2, wherein said nickel-phosphorus alloy film contains said indium at a concentration of 170 to 410 ppm.
The nickel-phosphorus alloy coated substrate according to any one of claims 1 to 3, wherein the nickel-phosphorus alloy film does not contain iodine.
containing nickel ions, hypophosphite ions, a complexing agent, and indium ions;
A solution for electroless plating of a nickel-phosphorus alloy film, wherein the indium ion concentration is 0.18-1.8 ppm.
The solution according to claim 5, containing the indium ions at a concentration of 0.3 to 1.5 ppm.
The solution according to claim 5 or 6, which does not contain iodine.
The solution according to any one of claims 5 to 7, further comprising lead ions.
A method for producing a nickel-phosphorus alloy coated substrate, comprising forming a nickel-phosphorus alloy film by electroless plating using the solution according to any one of claims 5 to 8.
A magnetic recording medium having the nickel-phosphorus alloy-coated substrate according to any one of claims 1 to 4.