WO2024034766A1

WO2024034766A1 - Method for enhancing surface electrical conductivity of polymer material

Info

Publication number: WO2024034766A1
Application number: PCT/KR2023/003698
Authority: WO
Inventors: 김명진; 길재근; 김범석
Original assignee: (주)라드피온
Priority date: 2022-08-11
Filing date: 2023-03-21
Publication date: 2024-02-15
Also published as: KR20240022110A

Abstract

Disclosed is a method for enhancing the surface electrical conductivity of a polymer material. In the disclosed method, a polymer material containing C-O bonds, C=O bonds, or C-H bonds is prepared, and in the surface of the prepared polymer material, the C-O bonds, C=O bonds, or C-H bonds are broken and carbon-carbon bonds are generated and increased, wherein in order to generate and increase carbon-carbon bonds in the surface of the polymer material, at least one of ion injection, structure rearrangement by heating, irradiation, electron beam irradiation, gamma irradiation, and chemical dissolution and recombination is performed on the surface of the polymer material.

Description

Method for improving surface electrical conductivity of polymer materials

The present invention relates to a method of improving the surface electrical conductivity of a polymer material, and more specifically, to a method of improving the surface electrical conductivity of a polymer material by modifying the surface structure of the polymer material by chemical or physical modification of the surface.

Polymer materials are used in various industrial fields because they are easy to mold and process, and their production costs are low. Recently, it has been used in various devices or equipment in various industries such as semiconductors, electric vehicles, electric batteries, aircraft, and mobile devices. However, despite the above advantages, polymer materials are not electrically conductive, so their field of use is limited. As an example, damage to the above-described equipment or devices occurs due to surface capacitance static electricity. In particular, polymer materials such as PP, PET, PC, PFA, PI, LDPE, HDPE, PMA, PEEK, and Teflon are nonconductors, so static electricity easily accumulates on their surfaces, and as static electricity accumulates, an arc is generated, causing serious component damage. is causing.

To solve this problem, a method of temporarily removing static electricity by radiation using isotopes is used, or, as a permanent or semi-permanent method, mixing carbon powder with a polymer material, plasma nitriding surface treatment, or using a conductive metal as a polymer material. A method of depositing on the surface is used.

However, existing methods have limitations such as clean room contamination, inability to treat large areas, and low mass productivity. In particular, the method of mixing carbon powder with polymer materials is less economical in that it uses expensive carbon powder, and has low conductivity. The method of depositing metal can result in dimensional deformation of parts/products made of polymer materials, and the deposited material can be worn or peeled off by external physical and chemical factors. In addition, the deposited metal material is vulnerable to strong acids or alkalis, and there is a risk that metal/carbon separated from the polymer material may be released.

[Prior art literature]

[Patent Document] Republic of Korea Patent Publication No. 10-2018-0031531 (published on March 28, 2018)

The present invention is intended to solve the problems of the prior art, by generating and increasing bond structures between carbons (single bond structure between carbons, double bond structure between carbons, triple bond structure between carbons) on the surface of polymer materials, thereby producing polymer materials. The problem to be solved is to provide a method to improve the surface electrical conductivity of.

Another problem that the present invention aims to solve is to generate and increase the bond structure between carbons (single bond structure between carbons, double bond structure between carbons, triple bond structure between carbons) on the surface of polymer materials by ion implantation method, The aim is to provide a method for improving the surface electrical conductivity of a polymer material, which allows large-area treatment and increases ion implantation uniformity during large-area treatment.

A method of improving the surface electrical conductivity of a polymer material according to one aspect of the present invention prepares a polymer material containing a C-O bond, a C=O bond, or a C-H bond, and, on the surface of the prepared polymer material, C-O bond, C=O Structural rearrangement by ion implantation, heating, on the surface of the polymer material to break bonds or C-H bonds, generate and increase carbon-carbon bonds, and generate and increase carbon-carbon bonds on the surface of the polymer material. , using at least one of radiation irradiation, electron beam irradiation, gamma ray irradiation, and chemical dissolution and recombination.

In order to generate and increase bonds between carbons on the surface of the polymer material, ions are implanted into the surface of the polymer material using an ion implantation system, wherein the ion implantation is performed using one or more types of gas ions and one or more types of metal ions. , or one or more gas ions and one or more metal ions are injected into the surface of the polymer material.

The ion implantation system includes a vacuum chamber, an ion generator, an ion accelerator that accelerates ions generated in the ion generator into the vacuum chamber, and a device that supports the polymer material within the vacuum chamber and moves the polymer material. and a supporting unit, wherein for the ion implantation, the polymer material is placed in the vacuum chamber so as to be supported by the supporting unit, and the ions generated in the ion generator are accelerated into the vacuum chamber by the ion accelerator. ions are injected into the surface of the polymer material, and after the ions are injected into one area of the surface of the polymer material, the polymer material is moved to inject the ions into another area of the surface of the polymer material.

The supporting unit includes a first rotary gripper and a second rotary gripper that are located in opposite directions and include grip fingers that grip one edge and an opposite edge of the polymer material and a motor that rotates the figure finger, and the first A first X-axis transfer unit and a second X-axis transfer unit for moving the rotary gripper and the second rotary gripper along the It includes a Y-axis transfer unit and a second Y-axis transfer unit, wherein the grip of the second rotary gripper on the polymer material is released, and the second rotary gripper is positioned at the farthest position from the polymer material by the second Y-axis transfer unit. In a state in which the first rotary gripper grips the polymer material, the first X-axis transfer unit and the first Y-axis transfer unit move the first rotary gripper in the X-axis direction and the Y-axis direction. I order it.

According to the present invention, the surface electrical conductivity of polymer materials can be improved by generating and increasing bond structures between carbons (single bond structure between carbons, double bond structure between carbons, triple bond structure between carbons) on the surface of molecular materials. .

In addition, according to the present invention, the surface electrical conductivity of the polymer material is increased by generating and increasing bond structures between carbons (single bond structure between carbons, double bond structure between carbons, triple bond structure between carbons) on the surface of the polymer material by ion implantation. However, large-area treatment is possible, and when treating large areas, ion implantation uniformity can be improved.

Figure 1 shows a method that can be applied to improve the surface electrical conductivity of polymer materials.

It lists the methods,

Figure 2 shows the method of improving surface electrical conductivity shown in Figure 1 by ion implantation.

This is a flowchart showing an example of a method for improving the surface electrical conductivity of a material,

Figure 3 shows the ion implantation system used in the method shown in Figure 2.

It is a drawing,

Figure 4 illustrates an example of a change in the structure of a polymer material due to ion implantation.

ego,

Figure 5 shows the surface of polycarbonate implanted with N, Ar, Kr, and Xe ions, respectively.

This is an FT-IR analysis graph,

Figure 6 is a graph showing the surface resistance measurement results of polycarbonate implanted with N ions and Xe ions, respectively.

Figure 7 is a diagram for explaining an ion implantation system equipped with a supporting unit;

Figure 8 is a cross-sectional view taken along A-A in Figure 7;

Figure 9 is for explaining an ion implantation method according to another embodiment of the present invention.

It is a drawing,

Figure 10 is a sputtering ion implantation system applicable to the method shown in Figure 9.

This is a drawing to explain the type ion generator,

Figures 11 and 12 show diagrams applicable to the sputtering type ion generator shown in Figure 10.

This is a diagram showing a composite metal sputtering target.

Hereinafter, embodiments of the present invention will be described with reference to the attached drawings.

The invention is explained in detail so that those skilled in the art can easily implement it. The invention may be implemented in many different forms and is not limited to the embodiments described herein.

In explaining the present invention, the size or shape of components shown in the drawings may be exaggerated or simplified for clarity and convenience of explanation.

Additionally, terms specifically defined in consideration of the configuration and operation of the present invention may vary depending on the intention or custom of the user or operator. These terms should be interpreted as meanings and concepts consistent with the technical idea of the present invention based on the content throughout this specification.

In order to clearly explain the present invention, descriptions of parts unrelated to the technical idea of the present invention have been omitted, and identical or similar components are assigned the same reference numerals throughout the specification.

The present invention is a method for improving surface electrical conductivity by changing the surface properties of various polymer materials such as polycarbonate or polyimide containing C-O bonds, C=O bonds, or C-H bonds, for example, as shown in Formula 1 and Formula 2. , in order to change the surface properties of the polymer material, at least one of ion implantation, structural rearrangement by heating, radiation irradiation, electron beam irradiation, gamma ray irradiation, and chemical dissolution and recombination is performed on the surface of the polymer material listed in Figure 1. Use it.

By the treatment listed above, the C-O bond, C=O bond or C-H bond in the chemical bond structure on the surface of the polymer material is destroyed, and inter-carbon bonds such as C-C, C=C, and C≡C are generated and increased.

Figure 2 is a flowchart schematically showing a method through ion implantation among the methods of increasing bonds between carbons to increase the surface electrical conductivity of polymer materials, and Figure 3 is a conceptual diagram of the ion implantation system applied to the method shown in Figure 2. This is a drawing shown as .

Referring to Figures 2 and 3, the method of improving the surface electrical conductivity of a polymer material through ion implantation includes preparing a polymer material (2) as an object (S1), and placing the prepared polymer material (2) in a vacuum chamber (40). ), a step (S2) of positioning the ion within the ion generator, a step (S3) of the ion generator 10 generating ions according to the power supply from the power supply unit, and accelerating the generated ions using the ion accelerator 20. , including the step (S4) of injecting onto the surface of the polymer material 2 prepared in the vacuum chamber 40. At this time, for accurate ion injection, the ion injection direction can be controlled with a magnet. In addition, a step of cleaning the surface of the polymer material 2 in the ion chamber 40 with plasma may be additionally provided before ion implantation.

The ion generator 10 generates ions by removing one or more electrons from atoms or molecules using a microwave, laser, or hot electron, and the ion accelerator 20 accelerates the ions by applying an electric field to them. It plays a role in injecting the polymer into the surface. A cooling means may be installed in the vacuum chamber 40 to prevent excessive temperature rise due to heat generated during the process. In addition, the ion implantation system includes an ion beam profile monitor 50 for monitoring the profile of the ion beam, an ion beam position monitor 60 for monitoring the position of the ion beam within the vacuum chamber 40, and a heat content within the vacuum chamber 40. It may include information providing units including a calorimeter 70 that measures , and a control unit 80 controlling the overall ion implantation operation of the system using information received from the information providing units.

By ion injection into the surface of a polymer material, ions are incident on the surface of the polymer material, collide with atomic nuclei and excite electrons, causing energy transfer.

At this time, as shown in Figure 4, the linear molecular chain of the polymer material transfers energy through collision with ions injected with high energy, resulting in chain scission and the molecular chain of the network through the bonding of the severed chains. A structure is formed or an unsaturated bond is formed.

According to one example, plate-shaped polycarbonate (PC) was prepared as a polymer material, placed in a vacuum chamber, and ion implantation was performed on the surface of the polycarbonate. When N, Ar, Kr, and saw. The experimental conditions were 50 keV energy for N, Ar, Kr, and

As can be seen from the FT-IR analysis graph in Figure 5, when comparing before and after ion injection, it was confirmed that C=O, C-O, and C-H bonds were significantly reduced, and the occurrence and increase of C-C bonds could be confirmed. This is because ion implantation destroys C-O, C=O, and C-H bonds from the surface of polycarbonate, resulting in the release of hydrogen and oxygen and generating C-C bonds.

In addition, N ions and Xe ions were each injected into the surface of polycarbonate at a dosage of 1 It was confirmed that this increased to 91.3%, and in the case of Xe ion implantation, the amount of carbon (C), which was 88% before implantation, increased to 92.3%.

In order to determine whether surface electrical conductivity was improved by ion implantation, N ions and As shown in FIG. 6, it was confirmed that when N ions and However, as the ion irradiation amount exceeded 1×1017 ions/cm2, it was confirmed that the slope of the decrease in surface resistance value became gradual. This is a significant change in the chemical bond structure of the polymer surface when a certain amount of ion injection is exceeded. In other words, this is due to the fact that the bond destruction of C=O, C-O, and C-H or the generation and increase of bonds between carbons no longer occur.

In UV-Vis spectroscopic analysis, light transmittance shows clear changes depending on the injection energy, implanted ions, and injection amount. This is because, in relation to the penetration depth and transfer amount of ions, the degree of bonding between carbons, especially C=C bonding, determines the optical properties. affects. Ultimately, ion irradiation causes destruction of bonds such as C-H, C-O, and C=O, and an increase in bonds between carbons such as C-C and C=C occurs due to the cross linking phenomenon, forming a carbon structure on the surface of the polymer material. A net (carbon structural network) is formed.

Figures 7 and 8 are diagrams for explaining an ion implantation system according to another embodiment of the present invention and a method of improving the surface electrical conductivity of a polymer material by implanting ions into the surface of the polymer material using the ion implantation system.

Like the previous embodiment, the ion implantation system of this embodiment includes a vacuum chamber 40, an ion generator 10, and ions that accelerate the ions generated in the ion generator 10 into the vacuum chamber 40. An accelerator 20, an ion beam profile monitor 50 for monitoring the profile of the ion beam, an ion beam position monitor 60 for monitoring the position of the ion beam in the vacuum chamber 40, and the vacuum chamber 40 information providing units including a calorimeter 70 that measures heat resistance, and a device that supports the polymer material 2 within the vacuum chamber 40 and moves the polymer material 2 with respect to accelerated ions. It includes a supporting unit 100 and a control unit 80 that controls the overall ion implantation operation of the system and the supporting unit 100 using information received from the information providing units.

Under the control of the controller 80, the supporting unit 90 moves the polymer material 2 supported by itself precisely and quickly in the X-axis and Y-axis directions within the vacuum chamber 40. Even when the surface of a polymer material is large, ions can be implanted almost uniformly. In addition, the supporting unit 90 holds the polymer material 2 with one of the two grip fingers (a first grip finger and a second grip finger), as will be described below. On the other hand, since it is difficult to implant ions into the area gripped by one grip finger, after gripping the polymer material with the other grip finger, the grip of the grip finger used first is released and then retracted, Ion implantation can be performed in other areas where ion implantation has not been performed. In addition, the supporting unit 90 is configured to rotate the polymer material 2 within the vacuum chamber 40, so it helps to inject the polymer material from the upper and lower surfaces and even to the side.

When using the supporting unit 90 as above, for the ion implantation, the polymer material 2 is placed in the vacuum chamber 40 so as to be supported by the supporting unit 90, and the ion generator 10 ) are accelerated into the vacuum chamber 40 by the ion accelerator 20 to inject ions into the surface of the polymer material 2, and the ions are injected into one area of the surface of the polymer material 2. After injection, the polymer material can be moved to inject ions into other areas of the surface of the polymer material.

According to this embodiment, the supporting unit 90 rotates the

grip fingers

912a, 912b and the

figure fingers

912a, 912b, which are located in opposite directions and grip one edge and the opposite edge of the polymer material. A first rotary gripper (910a) and a second rotary gripper (910b) including motors (914a, 914b), and the first rotary gripper (910a) and the second rotary gripper (910b) along the X-axis direction. A first X-axis transfer unit (920a) and a second X-axis transfer unit (920b) that move the first It includes a transfer unit 940a and a second Y-axis transfer unit 940b.

The grip of the second rotary gripper 910b on the polymer material 2 is released, and the second rotary gripper 910b is moved from the polymer material 2 by the second Y-axis transfer unit 940b. In a state in which the first rotary gripper 910a grips the polymer material 2 in a state in which it is transported backward to a distant position, the first The first rotary gripper 910a can be moved in the X-axis direction and the Y-axis direction.

Conversely, the grip of the first rotary gripper 910a on the polymer material 2 is released, and the first rotary gripper 910a is held by the polymer material 2 by the first Y-axis transfer unit 940a. In a state in which the polymer material 2 is held by the second rotary gripper 910b, the second The second rotary gripper 910b can be moved in the X-axis direction and Y-axis direction.

Furthermore, it may be considered to move the first rotary gripper 910a and the second rotary gripper 910b in the Z-axis direction (in this example, the height direction), and in this case, the first rotary gripper 910a While one of the second rotary grippers 910b performs X-Y coordinate movement, the other one may be located at a different height to expand the X-Y coordinate movement range. In addition, the above movement in the height direction can also contribute to controlling the area of the ion scanning area.

Each of the first X-axis transfer unit 920a and the second It may include a guide member 924 that guides the linear sliding movement of the slider 922 in the X-axis direction, and an X-axis driving unit (not shown) including a motor that drives the slider 922. In this embodiment, the first Y-axis transfer unit 940a and the second Y-axis transfer unit 940b each include a guide rod 942 coupled through the guide member 924 to guide the guide member 924 in the Y-axis direction, and It may include a transfer screw 944 coupled to enable screw transfer of the guide member 942 and a motor 946 that rotates the transfer screw 944.

The remaining configuration may follow the previous embodiment.

Above, an example in which gas ions were used as injection ions was mainly explained.

Hereinafter, with reference to FIGS. 9 to 12, a method for increasing the surface electrical conductivity of a polymer material by injecting one or more metal ions alone or together with gas ions into the surface of the polymer material will be described.

Referring to FIG. 9, the method according to this embodiment includes a step of preparing a polymer material 2 (S11), a step of placing the prepared polymer material 2 in a vacuum chamber (S12), and the ion generator is a gas A step of generating ions and one or more types of metal ions (S13), and a step of accelerating the complex metal ions containing the generated gas ions and one or more types of metal ions using an ion accelerator and injecting them into the prepared polymer material (S14) ) includes.

At this time, the supporting unit described in the previous embodiment can be used to support and move the polymer material. Also, the information providing unit and the control unit of the previous embodiment may be used in the same manner as described in the previous embodiment.

Unlike the previous embodiment, the ions injected in step S14 may include gas ions and complex metal ions of two or more elements. At this time, the injected composite metal ion may include metal ions of two elements with different atomic numbers. When a complex metal ion containing a metal ion with a small atomic number and a metal ion with a large atomic number is injected into the surface of a polymer material, the small-sized metal ion fills the space between the large-sized metal ions. Between elements implanted below the surface of a polymer material by two-element complex ion implantation containing a type 1 metal ion with a low atomic number, i.e., a small atomic radius, and a type 1 metal ion with a high atomic number, i.e., a large atomic radius. Density can be increased.

Alternatively, improved surface electrical conductivity can be obtained by implanting a three-element composite ion of metal 1 with a low atomic number, metal 1 with a medium atomic number, and metal 1 with a large atomic number into a polymer material. Additionally, a surface with improved electrical conductivity can be formed by implanting complex ions of four or more elements including gas and metal.

At this time, the degree of electromagnetic wave shielding on the surface of the polymer material can be controlled by changing the ion injection energy, ion injection amount, and ion injection time.

Meanwhile, metal ions are not easy to create because they have a high melting point and do not exist as atoms/molecules. To solve this, complex metal ions can be generated by sputtering method. In this case, the ion generating unit 10 is. As shown in Figure 10, a pre-manufactured composite metal sputtering target 12 is used. A composite metal sputtering target (12) is supported on a sputtering gun (14). Although not shown, damage to the sputtering gun 14 can be minimized by forming an insulating film on the outer surface of the sputtering gun 14 to prevent electric fields from being emitted. A high voltage is applied to the composite metal sputtering target 12 by the sputtering gun 14.

In addition, the ion generator 10 generates gas plasma (P) around the composite metal sputtering target 12, and generates metal ions by tearing off metal atoms through collisions with the gas plasma (P).

As shown in FIGS. 11 and 12, the composite metal sputtering target 12 includes a plurality of types of unit metal targets 122, each of which has a certain thickness and is manufactured to have a fan shape, on both the upper and lower surfaces. They can be manufactured by combining them so that they are on the same plane. The composite metal sputtering target 12 manufactured in this way is formed in the form of a pie chart-shaped disk with a certain thickness. At this time, as mentioned above, the composite metal sputtering target 12 includes a plurality of types of fan-shaped unit metal targets 122 with different atomic numbers (8 types, if different from the example) in a predetermined volume ratio, and a plurality of types. The unit metal targets 122 are manufactured to have the same thickness. When viewed from above, the vertices of each of the fan-shaped unit metal targets 122 meet at one point, and that point becomes the center of the composite metal sputtering target 12. Since the distance from the center of the composite metal sputtering target 12 to each arc of all unit metal targets 122 is constant as the radius of the composite metal sputtering target 12, the metal elements are determined according to the arc lengths of the unit metal targets 122. The ratio can be easily adjusted.

As mentioned above, controlling the ratio of multiple types of metals is achieved by adjusting the arc length ratio of the unit metal targets 122, and Figure 11 shows that the arc lengths of all unit metal targets 122 are constant, so the metal ratios are the same. This shows an example, and FIG. 12 shows an example of controlling the generated metal ion ratio by varying the arc ratio between the unit metal targets 122.

In this embodiment, the metals included in the composite metal sputtering target 12 are eight types: Cu, Al, W, Fe, Zn, Ti, Ag, and Li, but note that the types of metals can be increased or decreased.

Due to this configuration of the composite metal sputtering target 12, the ratio of specific metal elements can be increased if necessary.

Note that the present invention is not limited by the above-described embodiments and can be implemented with various modifications.

Claims

Prepare a polymer material containing a C-O bond, a C=O bond, or a C-H bond,

On the surface of the prepared polymer material, C-O bonds, C=O bonds or C-H bonds are destroyed, and inter-carbon bonds are generated and increased;

To generate and increase carbon-carbon bonds on the surface of the polymer material,

A method for improving the surface electrical conductivity of a polymer material, comprising using at least one of ion implantation, structural rearrangement by heating, radiation irradiation, electron beam irradiation, gamma ray irradiation, and chemical dissolution and recombination on the surface of the polymer material.
According to paragraph 1,

In order to generate and increase carbon-carbon bonds on the surface of the polymer material, ions are implanted into the surface of the polymer material using an ion implantation system,

The ion injection is a method of improving the surface electrical conductivity of a polymer material, characterized in that one or more types of gas ions, one or more types of metal ions, or one or more types of gas ions and one or more types of metal ions are injected into the surface of the polymer material.
According to paragraph 2,

The ion implantation system includes a vacuum chamber, an ion generator, an ion accelerator that accelerates ions generated by the ion generator into the vacuum chamber, and a polymer material that supports the polymer material in the vacuum chamber. It includes a supporting unit that moves, and for the ion implantation, the polymer material is placed in the vacuum chamber so that it is supported by the supporting unit, and the ions generated by the ion generator are introduced into the vacuum chamber by the ion accelerator. A polymer characterized in that ions are injected into the surface of the polymer material by accelerating the ions, and then the ions are injected into one area of the surface of the polymer material and then the polymer material is moved to inject the ions into another area of the surface of the polymer material. Method for improving surface electrical conductivity of materials.
According to paragraph 3,

The supporting units are located in opposite directions and are located on one side of the polymer material.

A first rotary gripper and a second rotary gripper including grip fingers for gripping an edge and an opposite edge and a motor for rotating the figure fingers, and moving the first rotary gripper and the second rotary gripper along the X-axis direction. It includes a first X-axis transfer unit and a second In a state in which the rotary gripper's grip on the polymer material is released and the second rotary gripper is moved backward to the position furthest from the polymer material by the second Y-axis transfer unit, the first rotary gripper holds the polymer material. A method of improving surface electrical conductivity of a polymer material, characterized in that the first X-axis transfer unit and the first Y-axis transfer unit move the first rotary gripper in the X-axis direction and the Y-axis direction while holding the.