JP2008174791A - Adhesive surface modification method for fluorine base synthetic resin, and article obtained thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface modification technique for obtaining high adhesive strength with metals, ceramics and the other high polymer resins in the surface of a fluorine base synthetic resin such as the lining materials of corrosion resistant tanks, rotary roller surfaces, air-tight packing surfaces, various adhesion preventive rolls and sheets using a plasma base ion implantation-film deposition process. <P>SOLUTION: Disclosed is a fluorine base synthetic resin article obtained, using a plasma base ion implantation-film deposition process, by generating argon or nitrogen plasma including argon or nitrogen of at least one or more atoms in a vacuum, and applying negative high energy high frequency pulse voltage, so as to form a fine rugged shape with a gradient structure by argon or nitrogen ion implantation. Also disclosed is a surface modification method therefor. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention provides a surface for bonding the surface of a fluorine-based synthetic resin such as a lining material of a corrosion-resistant tank, a surface of a rotating roller, an airtight packing surface, various anti-adhesion rolls, and a sheet to a metal, ceramics, or other polymer resin. The present invention relates to a surface modification method improved for the purpose of roughening and imparting adhesiveness, and an article thereof.

  Polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, polychlorotrimethyl Synthetic resins such as fluoroethylene and chlorotrifluoroethylene / ethylene copolymer are corrosion resistant tank lining materials, corrosion resistant pipe inner surfaces, corrosion resistant member surfaces, rotating roller surfaces, airtight packing surfaces, various anti-adhesion rolls, various anti-adhesion sheets and films Etc. are used a lot.

However, these fluorine-based synthetic resins alone need to be bonded to metals, ceramics, and other polymer resins due to problems of mechanical strength and functionality. Can not be used as.

Metallic sodium / ammonium salt treatment is used for fluorine-based synthetic resins, particularly polytetrafluoroethylene resin (PTFE), which are currently widely used. Since this surface treatment liquid is very oxidative and intensely corroded and the waste liquid treatment is complicated, use of the surface treatment liquid is prohibited from the viewpoint of pollution prevention. For this reason, the adhesiveness provision technique which replaces this is calculated | required early.

Currently, PTFE resin is treated with metallic sodium / ammonium salt, part of CF bond is replaced with ammonium salt, and part of it is bonded with oxygen to form carbonyl group to form epoxy resin adhesive or urethane resin adhesive. It is easy to bond with other materials. Further, in the metal sodium / ammonium salt treatment, defluorination occurs, and the PTFE surface is severely uneven. These have been put to practical use for a long time with little change over time after the surface treatment. However, early development of alternative technologies is desired due to pollution problems.

For these reasons, there have been attempts to modify the surface by various plasma treatments. As described in Japanese Patent Laid-Open No. 2000-96233, a plasma CVD apparatus capable of being processed at a low temperature as much as possible by developing a plasma generation method, applied voltage, gas composition, etc. A method for imparting adhesiveness to the surface has been proposed, and further, it has been proposed to be used for camera O-rings, automobile wiper rubbers, and the like. However, these plasma CVD methods are methods in which the introduced gas is turned into plasma at a high frequency, and activated argon or nitrogen element is chemically reacted and reacted on the component surface. Chemical bond strength is weak and adhesion may be poor.

JP 7-40442 proposes a method of increasing the adhesive strength by inserting a thermoplastic resin into the porous body at a temperature of 250 ° C. or higher in order to provide adhesion with porous PTFE. Has been. However, this method cannot provide adhesion with a non-porous material.

In the present invention, the surface of a PTFE resin is modified to a depth of 0.1 μm or more for a complex shape having irregularities from a sheet shape, a film shape, a roll shape, and a stable adhesion to an epoxy adhesive or a urethane adhesive. The present invention provides a surface modification method for a fluorine-based synthetic resin capable of imparting force.

  In conventional metal sodium / ammonium salt treatment, the PTFE resin surface was simply immersed in the chemical solution layer, but the present invention can also be modified by exposing the fluorine-based synthetic resin with electrodes attached to the vacuum chamber. Expensive and complicated equipment is not required. Moreover, there is no problem if the exhaust gas is exhausted through the adsorption tower without discharging the waste liquid which is a pollution problem.

In the present invention, a high voltage of 5 to 20 kV is applied in a pulsed manner to the surface of the PTFE resin to modify the surface of the PTFE to a depth of 0.1 μm or more, and a part of the CF bond is substituted with nitrogen atoms or oxygen atoms. It provides a stable adhesive surface that does not change with time.

  The present invention uses plasma-based ion implantation to generate RF plasma by an external antenna or a self-bias voltage around a fluorine-based synthetic resin (base material), which is several hundred volts to several tens of kV. A negative pulse voltage is applied, and an argon or nitrogen gradient layer is formed by injecting ions containing argon or nitrogen into the resin surface, and a polar group containing argon or nitrogen and oxygen is added to the resin while controlling the voltage. By forming on the surface layer, the above-mentioned problems are solved and the object is achieved.

Many fluorine-based synthetic resins have heat resistance compared to other polymer materials, but defluorinated fluorine gas is corrosive and the surface layer becomes brittle, so there is no arc discharge at low temperatures and high voltage. Need to be ion-implanted in a pulsed manner.

Specifically, surface modification of fluorine-based synthetic resin using equipment configured in a vacuum chamber, vacuum exhaust system, gas supply / treatment system, high-frequency plasma source, negative high-voltage pulse power supply / high-pressure introduction system and cooling system do. Since the fluorinated synthetic resin is an insulator, the electrode for applying a voltage to the base material is placed on the opposite back side where the surface is not modified or in the center where it is not treated to supply power to the high frequency plasma source. When a negative high voltage pulse voltage is applied around the injection target (fluorine-based synthetic resin) by generating a gas plasma, the electrons in the plasma are discharged, and an ion sheath is formed around the outline of the injection target. The The ion sheath is covered along the contour of the implant, and then a negative voltage is applied to the ion sheath, so that only ions are attracted and accelerated from all directions to the implant and aim at the implant. Elements are ion-implanted.

  In the insulator made of the fluorine-based synthetic resin of the present invention, a phenomenon may occur in which the treatment surface is charged and dielectric breakdown occurs due to charge-up charge. In the method of applying a high-frequency, high-voltage negative pulse voltage according to the present invention, since the pulse is a pulse, the plasma approaches the base material when there is no pulse voltage, the charge charged on the base material is released into the plasma, and the charge-up is eliminated. The Further, by optimizing the frequency and application time of the pulse for each shape, it is possible to prevent dielectric breakdown and to prevent surface modification non-uniformity due to charge-up and a decrease in the modification speed.

The parameters affecting the adhesion characteristics in the plasma-based ion implantation method include the frequency of the high-frequency plasma source, the plasma amplification voltage, the repetition frequency, the number of pulses, and the parameters on the high-voltage induced pulse power supply side include the applied voltage, current current, and repetition. There are the number of pulses, pulse width, delay time, etc., and the gas flow rate, gas pressure, etc. of the plasma generation raw material have an effect. Fluorine-based synthetic resin with improved adhesion by controlling these to form an ion sheath along the contour of the object to be injected, and implanting only ions into the fluorine-based synthetic resin that is the object to be injected A surface treatment method and a surface modified article thereof are provided.

  The surface modifying gas of the present invention uses a gas mainly composed of at least one selected from argon, hydrogen, oxygen, nitrogen, ammonia, etc., and introduces a gas into a vacuum chamber and applies a high-frequency voltage. It is preferable to generate argon, nitrogen atoms, or molecular ions by converting the gas into plasma and accelerate the ions to perform ion implantation.

  As the method for selecting the surface reforming gas, the plasma state varies depending on the ratio of argon or hydrogen atoms and nitrogen atoms, and the gas species and the mixing ratio depending on the percentage of fluorine atoms on the surface of the fluorine-based synthetic resin. Is preferably determined. Argon gas and hydrogen gas are basically used for energy for cutting the CF bond, and oxygen, nitrogen, and ammonia gas are used for bonding with carbon. It is known that oxygen contributes to the production of hydroxyl groups, carbonyl groups, and carboxyl groups, and nitrogen and ammonia contribute to the production of amino groups and ammonium, and it is desirable to select an optimum gas system for each. In particular, ammonia gas produces hydrogen and nitrogen ions when plasma decomposed, and has an advantage that more active atomic ions can be obtained than when nitrogen gas is used alone. However, in an environment where ammonia gas is difficult to use, the effect can be obtained even if nitrogen gas is used.

  As the high frequency power for generating gas plasma, it is desirable that the frequency is 0.2 MHz to 2.45 GHz, the output is 10 W to 20 kW, and the pulse width is 1.0 μsec or more. The reason is that if the frequency is lower than 0.2 MHz, the plasma decomposition of the gas is not sufficient and the surface modification rate becomes slow, and if it is higher than 2.45 GHz, the stability of plasma generation and the cost of the equipment increase. It is. This is because, when the high frequency output is 10 W or less, the plasma density is low and the surface modification cannot be performed even if ion implantation can be performed. Further, when the pulse width is 1.0 μsec or less, the substantial ion implantation time is shortened, and in the case of an insulator, it is easy to charge up.

Furthermore, not only the above plasma generation but also a high frequency pulse application power source is very important. In conventional plasma processing apparatuses, surface treatment is often performed using a DC voltage power source of 3 kV or less, and it has been used as a technique for imparting hydrophilicity temporarily. However, the frequency, pulse width, and applied voltage must be optimized as the high frequency pulse applied voltage of the present invention.

The reason is that if the frequency is 100 Hz or less, the number of ion implantations within a certain period of time decreases, and the ion implantation efficiency decreases. On the other hand, if the frequency is 5000 Hz or higher, it is necessary to improve the performance of the high-frequency pulse power supply, resulting in an increase in device cost. The pulse width is greatly related to the sheath width at the time of ion implantation. If the width is narrow, the sheath is formed along a complicated shape and is uniformly implanted, but if the width is wide, the sheath cannot be formed in the narrow gap. The injection volume is reduced. From this, if the pulse width is 1.0 μsec or less, the ion implantation time of one pulse is short, so that the ion implantation efficiency is lowered and an expensive high-frequency power source is required to form a nano-second order pulse width. Equipment cost increases. On the other hand, if the pulse width is wide and 1000 μsec or more, the plasma density supplied to the periphery of the molded product will be reduced, and not only the ion implantation efficiency will be reduced, but also high performance of the pulse power supply will be required, leading to an increase in equipment cost. Become.

A particularly preferable negative pulse voltage is preferably −7.0 to 20 kV from the viewpoint of imparting adhesion to the surface of the fluorine-based synthetic resin. If it is −7.0 kV or less, the ion implantation depth into the fluorine-based synthetic resin base material is shallow, the compound gradient structure between the carbon element and oxygen and nitrogen cannot be obtained, and it does not contribute to the improvement of the adhesive force, and −20 kV At higher voltages, the substrate and compound gradient structure will advance, but the high-frequency pulse power supply will increase in size, leading to a significant increase in equipment costs. Further, the occurrence of distortion of the plastic molded product due to heat generation becomes remarkable, and 20 kV or more is not preferable.

  The ion implantation time on the surface of the fluorine-based synthetic resin is not limited, but is preferably 5 to 60 minutes. More preferably, it is a short-time treatment from the viewpoint of productivity. However, the high-voltage ion implantation treatment of the fluorine-based synthetic resin causes the surface deterioration to become severe and the surface layer to become brittle, which may reduce the adhesive force. It is necessary to select injection conditions.

  In conventional ion implantation by mass separation, the injection current is less than mA, and in the case of high energy, it is on the order of several A. Therefore, it takes several hours to implant 1E17ions / cm2. On the other hand, in plasma-based ion implantation, a current flows into the molded product from the surroundings at a time, so a current of several A to several tens of A flows, thereby enabling argon or nitrogen ion implantation processing in a short time. Yes. In addition, since the ion implantation is performed not by direct current but by pulse, damage to the insulator due to charge-up is very small.

In the argon or nitrogen ion implantation method of the present invention, ions are implanted with an energy sufficient to sufficiently penetrate the surface contamination layer, so that an inclined structure of argon or nitrogen can be easily formed. Depth on the surface of fluorine-based synthetic resin by reacting radicals generated in the surface layer by high-energy argon or nitrogen ion implantation that breaks the bond with active nitrogen atoms or active oxygen atoms remaining in the chamber. It is possible to easily obtain a reaction layer of about 0.1 μm in the direction.

In this process, it is possible to change the thickness of the adhesive layer on the surface of the fluorinated synthetic resin by changing the energy at the time of ion implantation. Therefore, depending on the type of fluorinated synthetic resin, the resin damage can be suppressed with low energy. However, surface modification is also possible. In particular, for polymers having vinylidene double bonds, it was found that surface modification with a low energy of 10 kV or less is the optimum process for imparting adhesion.

In the surface modification method of the fluorine-based synthetic resin of the present invention, argon or nitrogen is ion-implanted by 50 nm or more from the surface of the non-treated material, and fine irregularities are formed on the surface layer portion, resulting in a surface roughness of 0.1 μm or more. It was found that the friction coefficient of the fluorine-based synthetic resin was 0.1 or more.

As a result of evaluating various changes in the high-frequency pulse voltage, pulse width, frequency, loading time, processing temperature, etc., the deeper injection of argon or nitrogen atoms from the surface of the object to be processed contributes to improved adhesion. I found out. As a result of experiments, it is preferable that ions are implanted at least 50 nm or more, and it has been found that if it is shallower than this, the contribution rate to the adhesiveness is lowered. The reason for this is that when the thickness of the reaction layer with radicals due to defluorination is several tens of atomic layers from the surface layer, it cannot be maintained over a long period of time due to oxygen and moisture in the air, and the long-term adhesion imparting effect cannot be maintained. This is because several hundred atomic layers are necessary.

  In the surface modification method for a fluorine-based synthetic resin of the present invention, a negative voltage application electrode is attached to the back surface of the resin molded product, and this is connected to a high voltage feedthrough. Radio frequency (RF) power is applied between the feedthrough and the chamber, electrons are reciprocated by the electric field change between them, and gas molecules such as argon, nitrogen, and ammonia are ionized by repeating collisions with gas molecules to generate a high-density plasma. Form. Since ions, radicals, and electrons coexist in the plasma, if a high voltage pulse voltage is applied, the ions in the plasma can be injected into the fluorine-based synthetic resin. Bolt) ions are allowed to react with the surface, and at this time, nitrogen or oxygen elements are bonded by radical polymerization to form a reaction product.

  The reactants on the surface of the fluorinated synthetic resin vary depending on the gas type, gas pressure, applied voltage, etc. used, but the resin base material does not deteriorate greatly, and it is easy to form fine fine irregularities and improve the adhesion to other materials. It is preferable to have a useful form. In the plasma-based ion implantation apparatus, the surface is preferably modified by a process of at least three steps. After cleaning the substrate surface, ion implantation is performed at a high voltage to cut the C—F bond. Thereafter, nitrogen or ammonia gas is introduced to promote the reaction for generating polar groups while applying a low voltage. Thus, it was found that the three steps of medium energy sputtering treatment, high energy ion implantation, and low energy polar group generation are advantageous for surface modification of the fluorine-based synthetic resin.

Embodiments of the present invention will be described below.
First, a schematic configuration of a plasma-based ion implantation apparatus used in the surface modification method for a fluorine-based synthetic resin substrate of the present invention will be described with reference to FIG. This apparatus includes a vacuum chamber 3 containing a frame 2 on which a fluorine-based synthetic resin sheet 1 is set. The set stand also serves as an electrode for applying a negative voltage. The inside of the vacuum chamber 3 can be maintained at a predetermined degree of vacuum by the exhaust device 4. In this apparatus, a predetermined gas is introduced through an introduction port 5 to form argon or nitrogen-based gas plasma, and if necessary, an organometallic gas introduction source for ion-implanting a special element to improve adhesion. 6 is also provided.

  The apparatus further includes a high voltage negative pulse power source 7 and a high frequency (RF) power source 8 for applying a high voltage negative charge to the fluorine-based synthetic resin sheet 1 having various shapes. The high voltage negative pulse power source 7 generates a negative charge having a predetermined energy, and applies a negative charge pulse to the fluorine-based synthetic resin sheet 1 through the high voltage feedthrough 9. This feed-through is connected to the set frame, and the set frame is in an electrically floating state with an insulator 10. Furthermore, power can be supplied from the high-voltage feedthrough 9 through the superimposing device 11 that superimposes the high voltage pulse and the high frequency, and the supply gas can be converted into plasma to form a film. A shield cover 12 is attached to the high voltage feedthrough 9 to protect the feedthrough 9.

When a negative charge pulse is applied to these fluorine-based synthetic resins, atomic ions or molecular ions in plasma generated by various introduced gases are attracted to the surface of the fluorine-based synthetic resin and ion implantation is performed. Since ions are implanted by applying a negative charge pulse along the electrode shape, an electric field is generated along the shape of the resin, even if the resin is not a flat plate but an uneven solid shape, and is almost perpendicular to this surface. Argon, hydrogen, oxygen or nitrogen ions collide.

At this time, a part of the fluorine in the fluorine-based synthetic resin can be defluorinated to form a reaction product with the remaining carbon radical and oxygen or nitrogen ions. Further, the surface of the fluorine-based synthetic resin that has been molecularly cut forms a severe microscopic uneven shape and greatly increases the adhesion surface area. At the same time, argon and hydrogen ions are also ion-implanted, which are useful for cutting C—F bonds, and after molecular cutting, argon and hydrogen in the base material are considered to diffuse and degas. It is thought that the physical properties of the are not greatly affected.
This will be described below based on examples.

  Using a plasma-based ion implantation apparatus as shown in FIG. 1, ten PTFE resin sheets 1 are attached to a flat plate electrode as shown in the figure, and plasma is generated under the following conditions to perform surface modification and perform the surface modification of PTFE. Analysis and adhesion evaluation were performed.

Material used: PTFE resin sheet 150 x 150 x 1 mm
Gas type used: Argon / hydrogen / ammonia gas mixture ratio: 1st step Argon / hydrogen = 2/1
Second step Hydrogen / ammonia = 1/2
Third Step Oxygen / Ammonia = 1/2
Pressure during ion implantation: 0.5 Pa to 1.0 Pa
Injection energy: 7keV, 12keV, 20keV
Ion implantation time: 10 minutes, 30 minutes Sample application frequency: 2000 Hz

  The treatment was performed with the above three conditions of implantation energy and two conditions of surface modification time. In the first step, the surface was cleaned using argon / hydrogen gas, and then hydrogen / ammonia gas was plasma-decomposed with high energy to implant hydrogen and nitrogen ions. Thereafter, oxygen / ammonia gas was introduced while lowering the voltage, and oxygen and ammonia gas (nitrogen) were introduced into the portion where the CF bond was cut with the high energy to cause a chemical reaction. The introduced oxygen was found to contribute to the formation of hydroxyl groups, carbonyl groups, and carboxyl groups, and nitrogen and ammonia were found to contribute to the formation of amino groups and ammonium, and were evaluated by photoelectron spectroscopy.

  FIG. 2 shows the results of measuring the element content of the surface of PTFE obtained under the present experimental conditions by photoelectron spectroscopy analysis for 30 minutes with each energy. Untreated PTFE has two fluorine elements per one carbon element, and the element content ratio is 1: 2. However, the surface contained a small amount of oxygen. On the other hand, it can be seen that in the samples implanted with high energy into PTFE, the fluorine content decreased to 10 to 30 and oxygen and nitrogen elements increased. In particular, the nitrogen content was maximum when the implantation energy was 12 kV.

  As a result of separately analyzing oxygen and nitrogen elements contained on the surface of PTFE, it is estimated that hydroxyl groups, carbonyl groups, carboxyl groups and amino groups, and ammonium salts are generated, and these greatly affect the adhesive strength. Conceivable. To what extent these compounds are changing in the depth direction was evaluated using a secondary ion mass spectrometer.

FIG. 3 shows the nitrogen concentration distribution in the depth direction from the PTFE surface, and it was found that the nitrogen layer contained up to about 150 nm. It can be seen that the nitrogen implantation depth is 7 keV up to about 80 nm, 12 keV is 120 nm, and 20 keV is 140 nm. Thus, it can be seen that the higher the applied voltage, the deeper the nitrogen enters the PTFE material, indicating an inclined structure.

  Furthermore, the following evaluation was performed in order to investigate the influence of the injection energy into PTFE and the treatment time. FIG. 4 shows the observation results of the electron microscope before and after the surface modification of PTFE, the contact angle of water after the surface modification, the measurement result of the surface roughness, and the friction coefficient before and after the surface modification of PTFE. Furthermore, in order to evaluate the adhesiveness between PTFE, a rubber material, and a metal material, they were bonded with an epoxy adhesive with a width of 1 cm, and the respective adhesive strengths were measured at three points.

As can be seen from the results of FIG. 4, untreated PTFE has a large contact angle, a smooth surface roughness, and it is understood that PTFE, rubber and metal are hardly bonded. On the other hand, it is found that the morphology of the surface-modified sample with 7 kV 10 minutes, 30 minutes, 12 kV 10 minutes, 30 minutes and 20 kV 10 minutes, 30 minutes is very uneven. In particular, it was found that the uneven surface was rough in the 12 kV treatment. The contact angle of water on the surface is reduced to 50 to 60 degrees, and thus the surface roughness is roughened to 0.2 to 0.4 μm. As a result of measuring the friction coefficient between the iron-based material and PTFE on this surface, the friction coefficient was several times. The adhesion of rubber and metal to the PTFE surface was as high as 3 to 10 kgf / cm 2, and it was found that the adhesion of 200 times or more than the conventional one was obtained.

Although not described in the experimental example, as a result of the same experiment and evaluation with respect to the PFA resin, it was confirmed that nitrogen ion implantation was confirmed up to about 130 nm with 10 keV energy, and the surface morphology was severely uneven. It was. Thus, it became clear that the pulsed ion implantation of argon or nitrogen and the subsequent low energy surface modification treatment are indispensable for the adhesion imparting technique regardless of the type of fluororesin.

As described above, according to the method of the present invention, the plasma-based ion implantation / film formation method is used to fluorinate corrosion resistant tank lining material, rotating roller surface, airtight packing surface, various anti-adhesion rolls, sheets and the like. In order to roughen the surface of the synthetic resin to adhere to metals, ceramics, and other polymer resins to give adhesion, argon, nitrogen, or ammonia ion implantation is performed, and a surface modification layer is formed with low energy. It has been found that, by forming, an excellent adhesive article between the fluorine-based synthetic resin and another material and a surface modification method thereof can be provided.

  In addition, the technology for changing the surface of the fluorine-based synthetic resin of the present invention to an excellent adhesive surface is not limited to fluorine-based synthetic resins, but for olefin-based polymers such as polyethylene, polypropylene, polyethylvinyl acetate, and cyclohexyl polyolefin. Is also effective, and has a wide range of fields such as improving the functionality in the fields of semiconductor materials, food processing equipment, medical equipment and medical equipment while taking advantage of features such as corrosion resistance, heat resistance, water repellency, mold release, and moldability It is applicable to.

It is a block diagram of the plasma base ion implantation and film-forming apparatus used for the fluorine-type synthetic resin of this invention. It is the table | surface which showed the element concentration ratio of the sample surface by the photoelectron spectroscopy analysis after the ion implantation to PTFE. It is the graph which showed the nitrogen ion implantation depth distribution to PTFE. It is the table | surface which compared the surface morphology after the ion implantation surface modification to PTFE, and adhesive evaluation with an untreated product.

Explanation of symbols

1 Fluorine-based synthetic resin sheet
2 frame
3 Vacuum chamber
4 Exhaust device
5 Hydrocarbon gas inlet
6 Organometallic gas inlet
7 High voltage negative pulse power supply
8 RF power supply
9 Feedthrough for high voltage
10 Insulator
11 Superimposing device shield cover

Claims (9)

Simultaneously generate argon or ammonia gas or argon / ammonia gas plasma in a vacuum of 0.1 to 10 Pa, expose the fluorine-based synthetic resin to this, and apply a high voltage negative pulse of 7 to 20 keV, 100 to 5000 cycles to this resin Then, a surface modification method for a fluorine-based synthetic resin, wherein argon or nitrogen ions are injected into the surface of the fluorine-based synthetic resin. A fluorine-based synthetic resin, which is an untreated product, is set in a vacuum of 0.1 to 10 Pa, and an argon / ammonia-based gas is introduced therein to generate plasma by supplying high-frequency power, and the fluorine-based synthetic resin is 1 to 30 keV, Surface modification of fluorine-based synthetic resin characterized by applying high-pressure negative pulses of 500 to 5000 cycles, ion-implanting argon or nitrogen ions from the surface of fluorine-based synthetic resin, and then reacting nitrogen element with the surface layer Method. Fluorine-based synthesis after injecting argon or nitrogen ions using a gas whose main component is at least one selected from argon, hydrogen, nitrogen, oxygen, ammonia, etc. The method for modifying the surface of a fluorine-based synthetic resin according to claim 2, wherein fluorine in the resin is replaced with nitrogen. The method for modifying the surface of a fluorine-based synthetic resin according to claim 2, wherein an applied voltage to at least the fluorine-based synthetic resin is 7 keV or more and an argon or nitrogen ion implantation time is 5 to 60 minutes. Fluorine-based synthetic resin is mainly polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, polychloro The method for surface modification of a fluorine-based synthetic resin according to any one of claims 1 to 4, comprising a synthetic resin such as trifluoroethylene or chlorotrifluoroethylene / ethylene copolymer. 6. The surface modification method for a fluorine-based synthetic resin according to claim 5, wherein an ion implantation layer of argon or nitrogen is implanted into the fluorine-based synthetic resin by 50 nm or more from the resin surface layer. The surface modification of a fluorine-based synthetic resin according to any one of claims 1 to 6, wherein the fluorine-based synthetic resin is implanted with argon or nitrogen ions, and the nitrogen concentration inside the resin surface layer is 5 at% or more. Method. 2. The fluorine-based synthetic resin according to claim 1, wherein a surface friction coefficient is set to 0.1 or more by forming at least 0.1 μm or more irregularities by implanting argon or nitrogen ions on the surface of the fluorine-based synthetic resin. Surface modification method. A fluorine-based synthetic resin article produced using the method according to claim 1.

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