KR101798786B1 - ELECTROLYTES FOR Fe-Ni ALLOY FOIL, METHOD FOR MANUFACTURING Fe-Ni ALLOY FOIL USING THE SAME, AND Fe-Ni ALLOY FOIL - Google Patents

Abstract

The present invention relates to an electrolyte for an iron-nickel alloy foil and, specifically, to an electrolyte for an iron-nickel alloy foil, which is suitable for an OLED, a manufacturing method for an iron-nickel alloy foil using the same, and an iron-nickel alloy foil manufactured by the same. According to an aspect of the present invention, the electrolyte includes: 5-20 g/L of iron ions; 20-50 g/L of nickel ions; 30 g/L or less of sodium; 5 g/L or less of boron; 1-100 ppm of saccharine; and 5-25 ppm (not including 5 and 25) of poly phenylene sulfide (PPS).

Description

METHOD FOR MANUFACTURING Fe-Ni ALLOY FOIL USING THE SAME, AND Fe-Ni ALLOY FOIL <br> <br> <br> Patents - stay tuned to the technology METHOD FOR MANUFACTURING Fe-Ni ALLOY FOIL USING THE SAME AND Fe-Ni ALLOY FOIL }

The present invention relates to an iron-nickel alloy foil, and more particularly, to an electrolyte for an iron-nickel alloy foil suitable for an organic light emitting diode (OLED) material, a method for producing an iron- Nickel alloy foil.

Organic light emitting diodes (OLEDs) are emerging as next-generation displays that can replace LCDs (liquid crystal displays) in the display market.

OLEDs have the advantage that they emit light and colors themselves, can control the amount of light, consume less power, respond quickly, and have few afterimages. Also, the color is rich and bright, and the viewing angle is wide.

With these advantages, OLED display industry is focusing on automobile, mobile and TV market recently.

The fabrication of full color devices consisting of RGB sub-pixels used in the manufacture of OLED displays takes place in high temperature deposition equipment. The deposition apparatus is composed of a substrate, a deposition mask, a frame, and the like. As the deposition process is performed at a high temperature, the deposition apparatus is affected by temperature, and a positional difference occurs due to a dimensional change due to a thermal expansion coefficient. Therefore, there is a problem that the position and dimensional accuracy of the evaporation material adhered on the substrate is lowered. Therefore, in order to precisely control the position of the mask, prevent thermal expansion, and satisfy the accuracy of the mask and the substrate, it is essential to select the mask and the frame material at the same level as the coefficient of thermal expansion of the substrate.

On the other hand, as the material of the deposition mask, iron-nickel (Fe-Ni) alloy-based invar alloy (Fe-36% Ni) is mainly used. The invar alloy produced by the conventional rolling process has difficulty in controlling the surface roughness (protrusion, pupil) and the thickness, and thus the characteristics of the device are deteriorated and the manufacturing yield is remarkably lowered. In addition, when a very thin product (18 μm or less) is produced, surface defects due to impurities and manufacturing cost increase.

However, since high-quality displays such as mobile phones, notebooks, and TVs are continuously required, it is important to control surface roughness of metal foil, which is a raw material of OLED metal masks. That is, if a pattern is formed on a metal foil having a high surface roughness, the shape of the pattern becomes inaccurate and the uniformity becomes low, which is unsuitable as a high-quality vapor deposition mask.

Further, as miniaturization of pixels of a display device is required, it is technically difficult to form a high-resolution pattern using a thick metal foil (having a thickness of more than 18 mu m). For example, when a through-pattern is to be formed on a thick metal foil, there is a problem that an exact pattern can not be realized due to interference between adjacent patterns in the etching process because the thickness is thick.

As an alternative to this, an iron-nickel alloy foil having a thickness of 18 μm or less can be produced through electroforming instead of the conventional rolling method.

However, when the thickness is reduced, the strength is lowered, and various problems are caused in the process due to not only the deformation of the substrate but also the tearing of the metal foil during the manufacturing of the vapor deposition mask.

Accordingly, there is a demand for a method for producing an iron-nickel alloy foil having a low thickness and a low lightness in the production of an iron-nickel alloy foil by the electrolytic process.

Korean Patent Publication No. 2016-0077466

An aspect of the present invention is to provide an iron-nickel alloy foil electrolyte capable of producing an iron-nickel alloy foil having high strength and low lightness in providing an iron-nickel alloy foil for an OLED, an iron-nickel alloy foil using the electrolyte, And an iron-nickel alloy foil produced therefrom.

An aspect of the present invention is an electrolyte solution containing an iron compound and a nickel compound for producing an iron-nickel alloy foil by electroforming,

Wherein the electrolytic solution contains 5 to 20 g / L of iron ions, 20 to 50 g / L of nickel ion, 30 g / L of sodium, 5 g / L of boron, 1 to 100 ppm of saccharin, 5 to less than 25 ppm of PPS phenylene sulfide). The present invention also provides an electrolyte for an iron-nickel alloy foil.

According to another aspect of the present invention, there is provided a method of manufacturing an iron-nickel alloy foil by electrolytic solution using the electrolytic solution,

Supplying an electrolytic solution into a gap surrounded by a rotating cylindrical negative electrode drum and a pair of arc-shaped insoluble positive electrodes opposed to the rotating negative-electrode drum, and supplying an electrolytic solution to the electrolytic bath to form an iron-nickel alloy on the surface of the negative electrode drum Nickel alloy alloy foil, wherein the electrolytic solution is supplied from a liquid-supply portion provided in the electrolytic bath.

According to still another aspect of the present invention, there is provided an iron-nickel alloy foil produced by the above-

The iron-nickel alloy foil has an iron-nickel alloy foil having a nickel content of 36 to 42 wt% and the balance of iron (Fe) and unavoidable impurities, and having a surface roughness (Rz) of 2 μm or less.

According to the present invention, in the iron-nickel alloy foil produced by the electroforming method, the iron-nickel alloy foil which has excellent physical properties such as high strength and low lightness and has a thin thickness is provided by optimizing the components of the electrolytic solution used in the electroforming process can do. This can be suitably applied as a material for an OLED.

FIG. 1 is a schematic drawing of an apparatus for manufacturing an iron-nickel alloy foil according to the electroforming method.
2 is a plan view image of a surface of an iron-nickel alloy foil (Inventive Example 3) observed with a 3-D profile according to an embodiment of the present invention.
3 is an image of a top view of a surface of an iron-nickel alloy foil (Comparative Example 4) according to an embodiment of the present invention observed with a 3-D profile.

The present inventors have intensively studied ways to lower the surface roughness and increase the tensile strength of iron-nickel alloy foils in providing iron-nickel (Fe-Ni) alloy foils manufactured by electroforming . As a result, it has been confirmed that an intended iron-nickel alloy foil can be provided in the case of optimizing the components of the electrolytic solution used in the electrolytic process for producing the iron-nickel alloy foil, and the present invention has been accomplished.

An iron-nickel alloy foil through electroforming can be prepared as follows.

1, the electrophotographic method is a method in which a liquid-receiving portion 14 is formed in a gap surrounded by a rotating cylindrical negative-electrode drum 12 provided in an electrolytic bath 11 and a pair of circular insoluble anodes 13 opposed thereto, To deposit a Fe-Ni alloy on the surface of the negative electrode drum, and winding the same to form a metal foil. The Fe-Ni-based alloy metal foil 1 produced by this electrolytic process has an advantage that the average grain size is small and the mechanical properties are excellent, and further, the manufacturing cost is low and the manufacturing cost is low .

Hereinafter, the present invention will be described in detail.

An electrolyte solution for an iron-nickel alloy foil according to one aspect of the present invention is an electrolyte solution containing an iron compound and a nickel compound for producing an iron-nickel alloy foil by electroforming, wherein the electrolyte solution contains 5 to 20 g / Sodium borate of 30 g / L or less (excluding 0), boron of 5 g / L or less (excluding 0), saccharin of 1 to 100 ppm, PPS (polyphenylene sulfide) of more than 5 ppm to less than 25 ppm .

The remaining solvent of the electrolytic solution is preferably pure water, more preferably ultra pure water.

The concentration of iron ions and the concentration of nickel ions in the electrolyte are determined by the composition of the iron-nickel alloy foil to be produced. When the concentration of iron ions and the concentration of nickel ions are lower than the above-mentioned range, the iron- Nickel content is low. On the other hand, if it is higher than the above range, the metal ion in the electrolyte becomes excessively high and it becomes impossible to provide an iron-nickel alloy foil containing nickel in an intended amount.

The above-mentioned concentrations of iron ions may be dissolved in the form of a salt such as iron sulfate, ferric chloride, or ferrous sulfate, or the electrolytic iron or iron powder may be dissolved in hydrochloric acid or sulfuric acid. The nickel ion may be used in the form of a salt such as nickel chloride, nickel sulfate, and nickel sulfamate, or may be prepared by dissolving ferronickel or the like in an acid.

Sodium in the electrolyte solution component is added to lower the cell voltage composed of the cathode, anode, and electrolyte by reducing the resistance of the electrolyte solution, and is preferably 30 g / L or less An intended effect can be obtained. If the concentration of the above-mentioned sodium exceeds 30 g / L, the cell voltage is further lowered, but the red powder phenomenon occurs and the target product can not be manufactured There is a problem.

The boron is added to maintain the pH of the electrolytic solution at a constant level. When the amount of boron is preferably 5 g / L or less in the electrolytic solution, an intended effect can be obtained. The pH of the electrolyte is an important factor affecting not only the electrolyte itself, but also the overall properties of the product. In particular, it is very important to maintain the pH at a constant value because the vicinity of the cathode is a region where the local pH easily changes.

Particularly, the present invention is characterized by including PPS in addition to saccharin in the electrolytic solution containing the above-mentioned components in order to lower the surface roughness of the iron-nickel alloy foil and to increase the tensile strength.

When stress is concentrated on the plated surface of the iron-nickel alloy foil through the electroplating process, the powder is discharged as a result of being obstructed by crystallization of the adsorbed element. As a result, .

In order to prevent this, it is preferable to add saccharin as an additive for relieving stress in the present invention. When the saccharin is added at 1 to 100 ppm, the desired effect can be obtained. If the content of saccharin is less than 1 ppm, the effect of stress relaxation is very small, whereas if it exceeds 100 ppm, the effect is saturated.

More preferably from 10 to 60 ppm, and even more preferably from 45 to 55 ppm.

The PPS to be added together with the saccharin is added in order to impart a leveling effect in addition to the luster effect in electrolytic plating, and further functions to lower the roughness of the plated tissue through interactions with the saccharin.

When the PPS is added in an amount of more than 5 ppm and less than 25 ppm, the desired effect can be obtained. If the content of the PPS is less than 5 ppm, the alternating action capability is lowered and alloy foil having unevenness in roughness may be produced. On the other hand, if it is added in an amount of 25 ppm or more, the function of the characteristic expression can not be performed, and there is a problem that large protrusions appear on the surface.

It is more advantageous to add the PPS at 10 to 20 ppm.

It is preferable that the pH of the electrolytic solution for iron-nickel alloy foil of the present invention having the above-mentioned composition is 1.0 to 3.0. When the pH of the electrolytic solution is too low to be less than 1.0 or exceeds 3.0, it is not easy to prepare an iron-nickel alloy foil using the electrolytic process.

Therefore, it is preferable to control the pH of the electrolytic solution to 1.0 to 3.0.

Hereinafter, a method for manufacturing an iron-nickel alloy foil, which is another aspect of the present invention, will be described in detail.

The iron-nickel alloy foil of the present invention can be produced by the electrolytic process, preferably using the electrolytic solution of the present invention described above.

Preferably, the step of supplying the electrolytic solution of the present invention to the gap surrounded by the rotating cylindrical negative-electrode drum and the pair of arc-shaped insoluble anodes opposing to each other, and supplying electric current to the electrolytic bath, And electrodepositing an iron-nickel alloy on the surface to produce an iron-nickel alloy foil.

The electrolytic solution is supplied from the liquid-supply portion provided in the electrolytic bath.

According to the above, the iron-nickel alloy foil of the present invention is produced under the conditions of a pH of 1.0 to 3.0, a temperature of 45 to 70 ° C., a current density of 10 to 100 A / dm ² and a flow rate of 10 to 100 m ³ / hr .

At this time, if the current density is too low, the working speed is slow and the productivity is deteriorated accordingly. On the other hand, if the current density is too high, the stress increases, and the overvoltage necessary for high current density becomes large, and the side reaction relatively increases on the surface of the anode and the cathode other than the main reaction. As a result, the current efficiency is lowered and deterioration of the electrodeposit such as burning and hydrogen embrittlement occurs.

Also, if the temperature is too high or the flow rate is too low, the nickel composition will be low, while if the temperature is too low or if the flow rate is too high, the nickel composition will increase.

The iron-nickel alloy foil of the present invention produced by the above-described method preferably has a nickel content of 36 to 42 wt%.

When the nickel content is low, there is a problem that the thermal expansion coefficient sharply increases. Therefore, it is preferable that the nickel content is 36 wt% or more. However, when the content is excessively high and exceeds 42% by weight, the thermal expansion coefficient of the alloy foil becomes excessively large as compared with glass or the like, and the material can not be suitably used as a material for OLED.

Therefore, in the present invention, it is preferable to limit the nickel content of the iron-nickel alloy foil to 36 to 42 wt%.

Except for the above-mentioned nickel content, the other component is Fe. However, in the ordinary manufacturing process, impurities which are not intended from the raw material or the surrounding environment may be inevitably incorporated, so that it can not be excluded. These impurities are not specifically mentioned in this specification, as they are known to any person skilled in the art of manufacturing.

Further, the iron-nickel alloy foil of the present invention satisfies the conditions (JIS standard) required for a material for an OLED with a surface roughness (Rz) of 2 탆 or less.

If the surface roughness Rz exceeds 2 탆, the surface is uneven and there is a possibility that a difference in etching depth occurs during the etching process.

The iron-nickel alloy foil of the present invention has a low coefficient of thermal expansion (CTE) of 5.0 ppm / K or less, a tensile strength of 1.0 to 1.5 GPa and an elongation of 1 to 5% Nickel-iron alloy foil having an iron-nickel alloy foil.

The iron-nickel alloy foil of the present invention having the above-described physical properties preferably has a thickness of 4 to 18 탆.

As described above, the present invention can provide an iron-nickel alloy foil having a low thermal expansion coefficient and high strength and low lightness, even though it is a thin film.

The iron-nickel alloy foil of the present invention can be used not only as a material for OLED (for example, encapsulant, FMM, etc.) but also as a current collector for a lithium secondary battery or a substrate material for an electronic device.

Hereinafter, the present invention will be described more specifically by way of examples. It should be noted, however, that the following examples are intended to illustrate and specify the present invention, but not to limit the scope of the present invention. And the scope of the present invention is determined by the matters described in the claims and the matters reasonably deduced therefrom.

( Example )

The electrolytic solution containing 12 g / L of iron ion, 40 g / L of nickel ion, 20 g / L of sodium and 3 g / L of boron was added to the electrolytic solution containing saccharin and PPS at the concentrations shown in the following Table 1, To prepare an iron-nickel alloy foil. At this time, the electrolytic solution was supplied at a flow rate of 35 m ³ / hr under the condition that the pH of the electrolytic solution was 2.0, the temperature was 57 ° C, and the current density was 30 A / dm ² .

The nickel content of the prepared iron-nickel alloy foil was 42%, and the thickness was 13 탆.

The surface roughness (Rz), tensile strength and elongation of each prepared iron-nickel alloy foil were measured and are shown in Table 1 below.

The surface roughness Rz was measured with a 3D profiler as an optical non-contact surface roughness meter. At this time, the magnification was 50 times by combining the viewing angle lens and objective lens magnification, and the measurement area was measured for the total area of 97 mu m x 72 mu m.

The tensile strength and elongation were measured using a microtensile tester at a strain rate of 1 탆 / sec. The specimens were measured for tensile strength by ASTM-SUB.

division Electrolyte composition (ppm) Fe-Ni alloy foil properties Remarks saccharin PPS Surface roughness (탆) Tensile Strength (GPa) Elongation (%) Comparative Example 1 - 20 - - - No product Inventory 1 55 15 1.25 1.34 2.1 - Inventory 2 45 20 1.48 1.17 2.8 - Inventory 3 50 10 1.84 1.21 2.5 - Honorable 4 50 15 1.14 1.23 2.3 - Inventory 5 50 20 0.99 1.25 2.4 - Comparative Example 2 50 5 2.54 1.23 2.2 Excess illumination Comparative Example 3 50 25 0.95 1.22 2.6 Surface projection Comparative Example 4 50 - 3.39 1.23 2.2 Excess illumination

As shown in Table 1, Examples 1 to 5 using an electrolyte containing both saccharine and PPS in an appropriate amount had a low surface roughness (Rz) of 2.0 탆 or less and a high strength of 1.1 GPa or more can confirm.

On the other hand, in Comparative Example 1, as saccharin was not added as an electrolytic solution component, the stress during plating was excessively increased, and plating itself was impossible. Thus, it was impossible to produce an iron-nickel alloy foil.

Also, in Comparative Example 2, in which the PPS content in the electrolyte solution was insufficient, the surface roughness was as high as 2.54 占 퐉, and in Comparative Example 3 in which the PPS content was excessive, surface protrusions occurred and commercialization was impossible.

Also, in Comparative Example 4 in which PPS was not contained in the electrolytic solution at all, the surface roughness was as high as 3.39 占 퐉.

FIGS. 2 and 3 are plan views of the surface of Inventive Example 3 and Comparative Example 4 observed with a 3-D profile, and the surface of Comparative Example 4 compared to Inventive Example 3 can be visually confirmed .

Claims (7)

An electrolytic solution containing an iron compound and a nickel compound for producing an iron-nickel alloy foil by electroforming,
Wherein the electrolytic solution contains 5 to 20 g / L of iron ions, 20 to 50 g / L of nickel ion, 30 g / L of sodium, 5 g / L of boron, 1 to 100 ppm of saccharin, 5 to less than 25 ppm of PPS phenylene sulfide) having a CTE of 5.0 ppm / K or less, a tensile strength of 1.0 to 1.5 GPa, and an elongation of 1 to 5%.
The method according to claim 1,
Wherein the saccharin is contained at 10 to 60 ppm and the PPS is contained at 10 to 20 ppm.
The method according to claim 1,
Wherein the electrolytic solution has a pH of 1.0 to 3.0.
A method for producing an iron-nickel alloy foil by electrolytic solution according to claim 1,
Supplying an electrolytic solution into a gap surrounded by a rotating cylindrical negative electrode drum and a pair of arc-shaped insoluble positive electrodes opposed to the rotating negative-electrode drum, and supplying an electrolytic solution to the electrolytic bath to form an iron-nickel alloy on the surface of the negative electrode drum Electrodeposited to produce an iron-nickel alloy foil,
Wherein the electrolytic solution is supplied from a liquid-supply portion provided in the electrolytic bath.
5. The method of claim 4,
Wherein the iron-nickel alloy foil is produced by the above electrolytic process at a pH of 1.0 to 3.0, a temperature of 45 to 70 ° C, a current density of 10 to 100 A / dm ² and a flow rate of 10 to 100 m ³ / A method for producing an alloy foil.
An iron-nickel alloy foil produced by the manufacturing method of claim 4 or 5,
Wherein the iron-nickel alloy foil has a nickel content of 36 to 42% by weight and the balance of Fe and inevitable impurities and having a surface roughness (Rz) of 2 탆 or less,
An iron-nickel alloy foil having a coefficient of thermal expansion (CTE) of 5.0 ppm / K or less, a tensile strength of 1.0 to 1.5 GPa, and an elongation of 1 to 5%. delete

Images