KR20010019026A - An apparatus for forming polymer continuously on the surface of metal by dc plasma polymerization - Google Patents

Abstract

PURPOSE: Continuous plasma polymerization device and method are provide to greatly improve properties of a polymerization film by installing a separate chamber so that each of reactive gas and non reactive gas are effectively acted, thereby increasing reaction efficiency of non reactive gas. CONSTITUTION: A continuous plasma polymerization device comprises an unwinding roll unwinding a substrate (1) of which surface is treated in order to transfer to other chamber, a deposition chamber (20) in which the substrate (1) introduced from an unwinding roll is used as an electrode, and separate electrodes (22) oppositely directed to upper and lower sides of the substrate are installed so that both sides of the substrate are polymerized by DC charging plasma, a post-treating chamber (20a) polymerizing again the substrate (1) of which surface is treated in the deposition chamber (20), a winding roll (12) winding the substrate of which surface is treated in the post-treating chamber (20a), a pumping means for maintaining the deposition chamber (20) and the post-treating chamber in vacuum, and a gas inlet introducing a reactive gas and a non reactive gas. A continuous plasma polymerization method comprises the steps of introducing a substrate (1) of which surface is treated into a deposition chamber (20), treating surface of the substrate, post-treating the surface treated substrate in a separate chamber, and discharging the post-treated substrate.

Description

Plasma polymerization continuous processing apparatus and method {AN APPARATUS FOR FORMING POLYMER CONTINUOUSLY ON THE SURFACE OF METAL BY DC PLASMA POLYMERIZATION}

The present invention relates to a plasma polymerization continuous processing apparatus and method.

When treating the surface of a substrate such as a metal plate using plasma by discharge, a coating layer excellent in hardness, wear resistance, and the like is formed. Products with a coating layer are used for magnetic disks, optical disks, ultra hard tools, and the like. In addition, when the coating film formed on the surface of the steel sheet is subjected to plasma treatment, the coated steel sheet is hardened and excellent in durability, corrosion resistance and the like is obtained. In particular, the surface modification effect to improve the hydrophilicity or hydrophobicity can be obtained by the polymer polymerization treatment on the surface of the substrate, the surface-modified material has been applied to various ranges.

The plasma polymerization process injects mainly hydrocarbon-based reactive gas into the chamber and generates a plasma to modify the surface of the substrate on which the plasma is deposited to a desired state. In addition, polymers such as nitrogen, oxygen, and carbon dioxide cannot be polymerized by themselves, but they can be used together with other monomer gases to improve the surface modification effect by injecting a non-polymerizing gas with reactive gas that can help polymer polymerization. Can be.

The mixing ratio of the non-reactive gas, which is added with the reactive gas for plasma polymerization, has a great influence on the properties of the polymerized film. The non-reactive gas compound plays a role of changing the polymer film to be polymerized from hydrophobic to hydrophilic having excellent affinity with water according to the concentration of the non-reactive gas. In particular, nitrogen and the like directly participate in the reaction to change the properties of the polymer. This increase in nitrogen compound can act as a hydrophilic group, which reduces the contact angle. That is, by increasing the ratio of nitrogen in the mixed gas (reactive gas and non-reactive gas) for forming the plasma, the film formed by the polymerization treatment exhibits improved hydrophilic characteristics.

A representative example of the plasma polymerization apparatus thus far is the apparatus disclosed in WO99 / 28530. The configuration of the apparatus is largely provided in the vacuum chamber 20, the electrode 4 installed in the chamber, the vacuum pumps 5 and 6 for adjusting the pressure of the vacuum chamber, the gauges 7 and 8 for measuring the degree of vacuum, and the electrodes. A power supply device 40 for generating a potential difference, and a reactive gas control device 9, 10 for injecting a reactive gas and a non-reactive gas such as nitrogen around the substrate 4a to be surface treated.

After the substrate 4a was installed in the chamber 20 and the rotary pump 5 was started, the thermocouple gauge 7 confirmed that the pressure inside the chamber was maintained at a vacuum of about 10 ^-3 Torr. The diffusion pump 6 is started to confirm with the ion gauge 8 that the pressure inside the chamber is maintained at about 10 ^-6 Torr. The substrate is positioned biased to the anode (or active electrode) by the power source 40 and the opposite electrode 4 is grounded. When the pressure in the chamber is maintained at a constant vacuum, reactive and non-reactive gases are injected in turn around the desired location. The mixing ratio of the gas is controlled by the pressure of the thermoelectric meter. When the pressure in the vacuum chamber reaches a constant pressure, it is discharged by direct current or high frequency. Then, the molecular bonds of the gases are broken in the plasma generated by direct current or high frequency, and the broken chains and activated cations or anions combine to form a polymer on the surface of the substrate placed between the electrodes.

In the case of the device, a reactive gas and a non-reactive gas are injected together at different mixing ratios in one chamber. Unlike the above apparatus, in the apparatus for continuously performing plasma polymerization treatment (see FIG. 2), the hydrophilic property of the substrate is improved by injecting a reactive gas and a non-reactive gas together. In the continuous apparatus, mixed gas is continuously injected and vacuum is exhausted. As a result, polymerization of reactive gas occurs from the beginning to the end of the deposition chamber to be polymerized, and powder by the reactive gas is formed during the polymerization process. This is because the reaction efficiency of the reactive gas is lowered. In this case, the hydrophilic property of the surface of the substrate to be polymerized is poor, and the adhesion of the polymerized film is also inferior.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and provides an apparatus and method for plasma polymerizing continuous processing that improves the apparatus to effectively operate the reactive gas and the non-reactive gas, and enhances the reaction efficiency of the non-reactive gas. There is a purpose.

1 is a schematic diagram showing a plasma polymerization apparatus according to the prior art.

2 is a schematic cross-sectional view of a plasma polymerization continuous processing apparatus in which an unwinding chamber and a winding chamber are separated.

Figure 3 is a schematic cross-sectional view showing a plasma polymerization continuous processing apparatus further provided with a post-treatment chamber according to the present invention.

*** Explanation of symbols for main parts of drawing ***

1: substrate (sample electrode) 4: counter electrode (cathode electrode)

4a: Base 5: Rotary Pump

6: Diffusion pump 7: Thermocouple gauge

8: Ion gauge 9: Gas inlet

10: gas inlet 11: unwinding roll

12: winding roll 20: deposition chamber

20a: after-treatment chamber 21: differential pressure roll

22: counter electrode 23: gas inlet

24: exhaust port 25: gas inlet

26: exhaust vent 36: loosening chamber

38: winding chamber 40: power supply

42: tension roll

The present invention relates to a plasma polymerization continuous processing apparatus and method, to provide a plasma polymerization continuous processing apparatus and method for post-treatment with an unreacted gas in order to solve the above problems.

In detail, an unwinding roll for releasing the substrate to be surface treated and transported to another chamber, and a substrate introduced from the unrolling roll as an electrode, and a separate counter electrode facing the upper and lower sides of the substrate are installed. A deposition chamber for performing plasma polymerization on both surfaces of the substrate by the discharge plasma, a post-treatment chamber for plasma-polymerizing the substrate surface-treated in the deposition chamber, and a winding for winding the substrate surface-treated in the post-treatment chamber. Provided is a DC power plasma polymerization continuous processing apparatus including a winding roll, a pumping means for maintaining the deposition chamber and the after-treatment chamber in a vacuum, and a gas inlet for introducing a reactive gas and a non-reactive gas.

In addition, the present invention is a step of introducing a substrate to be surface-treated into the deposition chamber, and using the substrate as an electrode and injecting a reactive gas and a non-reactive gas into the deposition chamber while the opposite electrode is installed on the upper, lower, left and right sides of the substrate and It provides a plasma polymerization continuous processing method comprising the step of generating a DC power plasma surface treatment, the post-treatment of the surface-treated substrate in a separate chamber and the step of discharging the post-treated substrate.

The non-reactive gas is composed of oxygen, nitrogen, argon or a mixture of these gases, the amount of 10 to 100% of the reactive gas is injected into the deposition chamber, and the amount of 10 to 500% of the reactive gas to the post-treatment chamber. Inject.

Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings.

Plasma polymerization continuous processing apparatus according to an embodiment of the present invention shown in Figure 3, an unwinding chamber 36 including a unwinding roll 11 for releasing the substrate to be surface-treated and transferred to another chamber, and unwinding of the unwinding chamber A deposition chamber 20 in which a substrate 1 introduced from a roll is used as an anode, and a separate cathode 22 facing each other above and below the anode, the substrate, is plasma-polymerized on both surfaces of the substrate by a direct-current discharge plasma. And a winding chamber 38 including a post-treatment chamber 20a for performing plasma polymerization on the substrate treated in the deposition chamber and a winding roll 12 for winding the substrate treated in the post-treatment chamber. And pumping means (not shown) for maintaining the deposition chamber and the aftertreatment chamber under vacuum, and gas inlets 23 and 25 for introducing a reactive gas and a non-reactive gas.

The apparatus according to the present invention can further improve the properties of the polymerized film by performing another process on the deposited substrate by separately providing a post-treatment chamber 20a in addition to the deposition chamber. Unlike the case shown in FIG. 3, in the apparatus in which the unwinding roll and the winding roll are included in one transfer chamber, it may be preferable to provide a post-treatment chamber between the deposition chamber and the winding roll of the transfer chamber.

In addition, a differential pressure roll 21 is provided between the deposition chamber 20 and the post-treatment chamber 20a as a differential pressure means. The differential pressure means serves to maintain a different gas atmosphere between the deposition chamber and the aftertreatment chamber.

The apparatus shown in Fig. 3 performs a plasma polymerization continuous process by the following method.

Introducing a substrate to be surface-treated into the deposition chamber, injecting a reactive gas and a non-reactive gas into the deposition chamber while using the substrate as an anode and having opposing electrodes (cathode electrodes) disposed above, below, left, and right of the substrate; Surface treatment by generating a DC power plasma, post-processing the surface-treated substrate in a separate chamber and discharging the post-treated substrate.

The post-treatment may inject only a non-reactive gas, or may be polymerized by injecting a reactive gas and a non-reactive gas together at a predetermined ratio.

When the polymerization process is performed in a different gas atmosphere between the deposition chamber and the aftertreatment chamber as described above, the polymerization chamber by the reactive gas is dominant in the deposition chamber to deposit a film on the surface of the substrate. This increases the hydrophilicity of the polymer film.

The non-reactive gas consists of oxygen, nitrogen, argon or a mixture of these gases.

In addition, the mixing ratio of the non-reactive gas added with the reactive gas for plasma polymerization has a great influence on the properties of the polymerized film, and the non-reactive gas compound has a high affinity with water in hydrophobicity depending on the concentration of the non-reactive gas. The non-reactive gas is suitable to inject 10 to 100% of the reactive gas into the deposition chamber and 10 to 500% of the reactive gas into the aftertreatment chamber. Do.

Example 1

In order to find out the effect of polymerization according to the present invention, the following experiment was carried out. First, C ₂ H ₂ was injected into the deposition chamber and N ₂ was injected into the non-reactive gas at a ratio of 1: 1, and only N ₂ , the non-reactive gas, was injected into the aftertreatment chamber. The discharge current was 2A, the internal vacuum degree of the chamber was 0.3 Torr, the gas flow rate was 250 SCCM, and the processing time was 30 seconds. After the plasma polymerization treatment, the treatment effect was examined by measuring the contact angle. In addition, the result of comparing the case of surface treatment without post-treatment after measuring water for 1 hour and drying it for 1 hour as a cycle was measured for the duration of hydrophilicity for several decades. .

Table 1. Comparison of properties with and without post-treatment

division If no post-processing Post-processing Contact angle measurement (degrees) 84 40 Aging Test Poor hydrophilicity after 20 cycles Good hydrophilicity after 100 cycles

As can be seen from the above table, the post-treatment reduces the contact angle, that is, the hydrophilic property is improved and the hydrophilicity due to surface modification lasts longer.

Example 2

The experiment was conducted similarly to Example 1. Deposition chamber has an N ₂ to C ₂ H ₂ as a reactive gas to the reactive gas 1: injection at a ratio of 1: 1, and the post-processing chamber, the C ₂ H ₂ and N ₂ 1: was injected at a rate of 9. The discharge current was 1A, the internal vacuum degree of the chamber was 0.3 Torr, the gas flow rate was 250 SCCM, and the treatment time was 30 seconds. After the plasma polymerization treatment, the treatment effect was examined by measuring the contact angle. In addition, the sustainability of the hydrophilicity was measured together (Aging Test) and the results compared with the surface treatment without post-treatment are shown in Table 2.

Table 1. Comparison of properties with and without post-treatment

division If no post-processing Post-processing Contact angle measurement (degrees) 105 50 Aging Test Poor hydrophilicity after 30 cycles Good hydrophilicity after 100 cycles

As can be seen in Table 2 above, by adding a small amount of reactive gas to the aftertreatment chamber together with the non-reactive gas, the hydrophilic property was improved and the sustainability was good.

This result is judged to be because the polymer film formed in the deposition chamber was polymerized with the non-reactive gas again in the post-treatment chamber to form a morphology having excellent hydrophilicity and improved adhesion of the polymer film.

According to the present invention, by installing a separate chamber so that the reactive gas and the non-reactive gas can work effectively, the reaction efficiency of the non-reactive gas is improved, thereby greatly improving the properties of the polymerized membrane, and in particular, the hydrophilic characteristics are increased depending on the concentration of the non-reactive gas. Provided is a plasma polymerization continuous processing apparatus for forming an excellent quality polymer film.

Claims (4)

An unwinding roll for releasing the surface-treated substrate and transferring it to another chamber; A deposition chamber which uses a substrate introduced from the unwinding roll as an electrode and installs a separate counter electrode facing each other above and below the substrate to perform plasma polymerization on both surfaces of the substrate by direct-current discharge plasma; A post-treatment chamber for performing plasma-polymerization treatment again on the surface-treated substrate in the deposition chamber; Winding rolls for winding the substrate treated in the post-treatment chamber, Pumping means for maintaining the deposition chamber and the aftertreatment chamber in vacuum; DC power plasma polymerization continuous processing apparatus comprising a gas inlet for introducing a reactive gas and non-reactive gas. Introducing a substrate to be surface treated into the deposition chamber; Injecting a reactive gas and a non-reactive gas into the deposition chamber using the substrate as an electrode and opposing electrodes on the top, bottom, left and right sides of the substrate, generating a DC power plasma, and performing surface treatment; Post-treating the surface treated substrate in a separate chamber; and Plasma polymerization continuous processing method comprising the step of discharging the post-treated substrate. The plasma polymerization continuous processing method according to claim 2, wherein the post-treatment is polymerized by injecting only a non-reactive gas. The method of claim 2, wherein the post-treatment is performed by injecting a reactive gas and a non-reactive gas to polymerize.